WO2007126102A1 - 有機光電変換素子の製造方法及び有機光電変換素子 - Google Patents
有機光電変換素子の製造方法及び有機光電変換素子 Download PDFInfo
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- WO2007126102A1 WO2007126102A1 PCT/JP2007/059338 JP2007059338W WO2007126102A1 WO 2007126102 A1 WO2007126102 A1 WO 2007126102A1 JP 2007059338 W JP2007059338 W JP 2007059338W WO 2007126102 A1 WO2007126102 A1 WO 2007126102A1
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- Prior art keywords
- photoelectric conversion
- pigment
- organic photoelectric
- layer
- conversion element
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- 239000004576 sand Substances 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000002366 time-of-flight method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
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- 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
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- H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- H10K30/50—Photovoltaic [PV] devices
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- 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
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- 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
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- 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
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- 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
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- 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 method for producing an organic photoelectric conversion element and an organic photoelectric conversion element.
- the present invention relates to an organic photoelectric conversion element suitable for use in an organic thin film solar cell and an optical sensor.
- an optical sensor which is another organic photoelectric conversion element an image sensor in a facsimile or a copying machine can be cited.
- Such an optical sensor has been put into practical use in an image reading apparatus using a scanner based on a one-dimensional sensor using a silicon crystal.
- large-area two-dimensional sensors that do not require scanning have not been put into practical use.
- a dye-sensitized type has been studied as a wet solar cell using an organic material.
- this wet solar cell is a system using an electrolyte solution, liquid leakage or iodine loss in the liquid may occur, and it has yet to be put into practical use.
- an all-solid-state organic thin film solar cell can be mentioned.
- the heterojunction type is one in which a layer having an electron donor force and a layer having an electron acceptor force are stacked, and charge transfer caused by light induction at the junction interface is utilized.
- Non-Patent Document 3 reports a solar cell that achieves a conversion efficiency of 1% using copper phthalocyanine as an electron donor and a perylene derivative as an electron acceptor.
- condensed polycyclic aromatic compounds such as pentacene and tetracene have been studied as electron donors, and fullerene compounds such as C have been studied as electron acceptors.
- the Balta heterojunction type is an active layer formed by mixing an electron donor and an electron acceptor in an appropriate ratio, and the heterojunction type forms an active layer with a two-layer structure. Different from that.
- the junction between the electron donor and the electron acceptor exists uniformly in the Balta of the mixed active layer, and sunlight can be used effectively.
- an electron donor and an electron acceptor are co-evaporated by vacuum deposition to form an active layer, and a mixed solution of both is formed by spin coating or printing. Some are formed by coating. In vacuum deposition, copper phthalocyanine and C
- Non-patent Document 4 An active layer composed of 60 has been reported (Non-patent Document 4).
- a typical wet coating method is a system in which polythiophene, which is a conjugated polymer, and [6, 6] phenol C61-butyric acid methyl ester (abbreviation PCBM), which is a soluble derivative of fullerene, are mixed. (Non-Patent Document 5).
- a polythiophene derivative or a mixture of a Wolff-lembiylene derivative and a fullerene (C) derivative is applied as a method for manufacturing the above-mentioned Balta heterojunction type solar cell.
- Non-patent Document 7 Schottky junction type devices
- Non-patent Document 8 and Patent Documents heterojunction type devices using perylene derivatives as electron acceptor layers
- organic pigments are highly crystalline pigment materials, as typified by phthalocyanine, benzoborphyrin, quinacridone, pyropyrol, and have high durability against light irradiation. Have it!
- Patent Document 1 Japanese Patent Laid-Open No. 8-500701
- Patent Document 2 JP-A-6-179802
- Patent Document 3 Japanese Patent Application Laid-Open No. 2003-304014
- Non-patent document 1 “Latest technology of organic thin-film solar cell”, November 2005, CMC Publishing
- Non-patent document 2 “Dye-sensitized solar cell technology and the latest trends in the market”, July 2004, Toray Research Center
- Non-Patent Document 3 C. W. Tang: Appl. Phys. Lett., 48 ⁇ , 183– 185, 1986
- Patent Document 4 S. Uchida et al .: Appl. Phys. Lett., 84 ⁇ , 4218-4220, 2004
- Patent Document 5 S. E. Shaheen et al .: Appl. Phys. Lett., 78 ⁇ , 841-843, 2001
- Non-Patent Document 6 Material Reseach Society Bulletin, vol. 30, No. 1, 33 (2005)
- Non-Patent Document 7 K. Yamashita et al .: Bull. Chem. Soc. Jpn., 60 ⁇ , 803—8 05, 1987
- Non-Patent Document 8 D. Wohrle et al .: J. Mater. Chem., 5 ⁇ , 1819-1829, 1995
- Process 1 Generation of an excited state (exciton) by light absorption.
- Process 3 The ion pair is separated and reaches the electrode.
- the place (layer) where Process 1 and Process 2 occur is called an active layer.
- excitons usually have a limited range (exciton diffusion distance) within their lifetime. It has been determined. Specifically, the exciton diffusion distance is generally a small distance of about 10 nm. For this reason, the generated excitons can only be used as photovoltaic power if their location and dissociation location are within the range of movement! /.
- the organic solar cell in order to efficiently advance the process 2 (that is, a process in which excitons dissociate into ion pairs), an interface between different substances, impurities, depletion layers
- a charge transfer-prone field such as a storage layer
- the process is performed using the charge transfer-prone field. Therefore, the organic solar cell usually has a characteristic structure in each part.
- One example of the structure of these solar cells is one having an organic pigment layer.
- the organic pigment when an organic pigment is to be formed into a film for the production of a solar cell, the organic pigment usually has a high crystalline property, so that it is difficult to form the organic pigment by a method other than vacuum evaporation. there were. Therefore, film formation of a large area has become a high cost that is difficult in practice.
- the production method of a Balta heterojunction type solar cell as described in Patent Document 2 and Non-Patent Document 6 uses a conjugated polymer, although it uses a coating process. Therefore, compared to the case of using an organic pigment, durability against strong light irradiation cannot be expected, and it has been difficult to obtain a sufficiently long-life solar cell.
- the present invention was devised in view of the above problems, and a first object of the present invention is an organic photoelectric conversion element capable of producing a long-life organic photoelectric conversion element using a coating process. And an organic photoelectric conversion device having a film containing an organic pigment and inorganic particles.
- the second subject of the present invention is to provide a method for producing an organic photoelectric conversion element and an organic photoelectric conversion element, which are more excellent in photoelectric conversion characteristics than in the past.
- the present inventors have used a benzoborphyrin compound, which has also been converted into a soluble precursor force, as an electron donor of an organic photoelectric conversion element. They found that the photoelectric conversion characteristics can be improved.
- the gist of the present invention is an organic photoelectric conversion device comprising a substrate, a pair of electrodes formed on the substrate and at least one of which is transparent, and an active layer formed between the electrodes.
- the method for producing an organic photoelectric conversion element of the present invention preferably includes a step of converting a latent pigment into the pigment (claim 2).
- the latent pigment is converted into the pigment after the latent pigment is formed by a coating method (claim 3).
- the pigment exhibits semiconductor characteristics (claim 4).
- the method for producing an organic photoelectric conversion element of the present invention preferably includes a step of converting two or more kinds of the latent pigments into the pigment (claim 5).
- the pigment at least one selected from the group consisting of porphyrin, phthalocyanine, quinacridone, pyrrolopyrrole, dithioketopyrrolopyrrole and derivatives thereof is used.
- V prefers to be ⁇ (claim 7).
- the method for producing an organic photoelectric conversion element of the present invention preferably includes a step of mixing the latent pigment and a material exhibiting semiconductor characteristics in a solid state and forming a film by a coating method. (Claim 8).
- the pigment exhibits semiconductor characteristics.
- the majority carrier of the pigment and the majority carrier of the material preferably have opposite polarities (claim 9).
- the material is preferably a particle (claim 10).
- the material is more preferably inorganic particles (claim 11).
- Another gist of the present invention is a substrate, a pair of electrodes formed on the substrate, at least one of which is transparent, and an active layer containing an organic pigment and inorganic particles formed between the electrodes.
- An organic photoelectric conversion element comprising: (Claim 12).
- the organic pigment is preferably obtained by converting a latent pigment (claim 13).
- the organic pigment and the inorganic particles are phase-separated! / (Claim 14).
- the active layer includes an electron donor layer formed including an electron donor, and an electron acceptor layer formed including an electron acceptor.
- a soluble precursor of a benzoborphyrin compound represented by the following formula (I) or (II) having a bicyclo ring is converted into the benzovolphyrin compound as the electron donor by thermal conversion. It is preferable to have a step of forming the electron donor layer (claim 15).
- Z ia and Z lb (i represents an integer of 1 to 4) each independently represent a monovalent atom or atomic group, provided that z ia and z ib may be bonded to form a ring.
- I ⁇ to R 4 each independently represents a monovalent atom or atomic group.
- M represents a divalent metal atom or an atomic group in which a trivalent or higher metal is bonded to another atom.
- Z ia and Z ib (i represents an integer of 1 to 4) each independently represent a monovalent atom or atomic group, provided that z ia and z ib may be bonded to form a ring
- I ⁇ to R 4 each independently represents a monovalent atom or atomic group.
- ⁇ to ⁇ 4 each independently represents a monovalent atom or atomic group.
- ⁇ represents a divalent metal atom or an atomic group in which a trivalent or higher metal is bonded to another atom.
- a step of forming the soluble precursor layer by a coating method, and forming the electron acceptor layer on the soluble precursor layer It is preferable that the step of forming the electron donor layer is performed by the thermal conversion, and then the step of forming the electron donor layer is performed (claim 17).
- Still another subject matter of the present invention is a substrate, a pair of electrodes formed on the substrate, at least one of which is transparent, and a benzovorphyrin salt represented by the formula (I) or (II).
- An organic photoelectric conversion device comprising: an electron donor layer formed between the electrodes including a compound; and an electron acceptor layer formed between the electrodes including a fullerene compound. (Claim 18).
- Still another subject matter of the present invention is a substrate, a pair of electrodes transparent on at least one formed on the substrate, and an active layer formed including an electron acceptor and an electron donor.
- the present invention resides in an organic photoelectric conversion element (claim 19).
- Still another subject matter of the present invention is a method for producing the organic photoelectric conversion element, wherein The soluble precursor of the benzoborphyrin compound having an oral ring is converted into the benzoborphyrin compound by thermal conversion to form the benzovorphyrin compound layer. And a method for producing an organic photoelectric conversion element (claim 20).
- the soluble precursor is preferably a compound represented by the formula (III) or (IV) (claim 21).
- the organic photoelectric conversion element is preferably a solar cell (claim 22).
- the organic photoelectric conversion element of the present invention is preferably a solar cell. (Claim 23) Effect of the Invention
- a long-life organic photoelectric conversion element can be produced using a coating process, and an organic photoelectric conversion element having excellent photoelectric conversion characteristics can be obtained. At least one of the effects can be obtained. In general, a highly efficient organic photoelectric conversion element can be produced.
- the organic photoelectric conversion element which has a film
- FIG. 1 is a schematic cross-sectional view of an organic photoelectric conversion device as a first embodiment of the present invention.
- FIG. 2 is a schematic cross-sectional view of an organic photoelectric conversion device as a second embodiment of the present invention.
- FIG. 3 is a schematic cross-sectional view of an organic photoelectric conversion device as a third embodiment of the present invention.
- the organic photoelectric conversion device manufacturing method of the present invention includes an organic substrate including a substrate, a pair of electrodes formed on the substrate, at least one of which is transparent, and an active layer formed between the electrodes.
- the pigment is preferably obtained by converting a latent pigment. Therefore, the method for producing an organic photoelectric conversion element of the present invention preferably has a process (conversion step) for converting a latent pigment into a pigment.
- the specific method for producing the organic photoelectric conversion element is not particularly limited, but it is preferable to employ any one of the following methods (1) and (2).
- a method having a conversion step of converting two or more kinds of latent pigments into pigments (1) A method having a conversion step of converting two or more kinds of latent pigments into pigments.
- a latent pigment and a material exhibiting semiconductor characteristics in a solid state (hereinafter, appropriately referred to as “solid semiconductor material” t ⁇ ) are mixed, and a film is applied by coating (hereinafter referred to as “precursor film” t ⁇ as appropriate)
- a method having a film forming step of forming a film (hereinafter, appropriately referred to as “precursor film” t ⁇ as appropriate)
- the conversion step of converting the latent pigment into the pigment is usually performed, and the film containing the pigment and the solid semiconductor material (hereinafter referred to as “mixed semiconductor film” "And prefer to get u).
- the pigment that is the material of the active layer of the organic photoelectric conversion element is always in accordance with the properties of the pigment itself.
- the film formability is not good.
- the latent pigment can be easily formed by a low-cost method such as a coating method. It is possible to membrane. Utilizing this, in a preferred embodiment of the production method of the present invention, the latent pigment is formed into a film having a desired configuration such as shape, dimensions, and arrangement position, and then the latent pigment is converted into a pigment.
- An organic photoelectric conversion element is manufactured using a process for obtaining an active layer.
- the active layer and the latent pigment corresponding to the active layer are formed only by coating.
- the latent pigment according to the present invention refers to precursors having different chemical structures of pigments.
- an external stimulus such as heating or light irradiation
- the chemical structure of the latent pigment changes and is converted into a pigment.
- the latent pigment according to the present invention preferably has excellent film-forming properties. Even if the pigment does not have good film formability, it is possible to reduce the cost during film formation by forming a film in the state of a latent pigment and converting it into a force pigment.
- the latent pigment itself can be applied in a liquid state, or the latent pigment can be applied as a solution with high solubility in some solvent. Like U ⁇ .
- the solubility of the latent pigment in the solvent is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more.
- the latent pigment according to the present invention can be easily converted into a pigment.
- what kind of external stimulus is given to the latent pigment is arbitrary, but usually heat treatment, light irradiation, etc. are performed.
- the latent pigment according to the present invention is preferably converted into a pigment with a high yield through a conversion step.
- the yield of the pigment obtained by converting from a latent pigment is arbitrary unless the performance of an organic photoelectric conversion element is impaired remarkably.
- the higher the yield of the pigment capable of obtaining the latent pigment strength the more preferable it is usually 90% or more, preferably 95% or more, more preferably 99% or more.
- the pigment according to the present invention is obtained by converting the latent pigment, and is generally It refers to a material with low solubility in a solvent.
- the low solubility in a general solvent means, for example, that the solubility in toluene is usually 1% or less, preferably 0.1% or less.
- any pigment can be used depending on the constitution of the organic photoelectric conversion element, but in the present invention, an organic substance (organic pigment) is usually used as the pigment. Further, usually, since the electric charge moves through the pigment and the power generation effect of the organic photoelectric conversion element is generated, it is preferable to use a pigment exhibiting semiconductor characteristics.
- “showing semiconductor characteristics” means that, for example, the carrier mobility of the layer of the pigment alone shows a value of 10 ⁇ 7 cm 2 ZVs or more. Carrier mobility can be measured by time-of-flight method, field effect transistor characteristics, Hall effect, electrical conductivity and carrier density measurements.
- semiconductor materials use ⁇ -conjugated molecules, so those having an absorption band in the solar spectrum region are used for solar cells. Suitable as a material.
- Examples of suitable latent pigments that can be converted into pigment molecules with high yield by external stimulation include the following.
- suitable latent pigments include those described in US Pat. No. 6071989, for example. Specific examples include compounds represented by the following formula (1).
- X represents a number of 1 to 8. However, when X is 2 to 8, ⁇ may be the same or different.
- ⁇ is anthraquinone, azo, benzimidazolone, quinacridone, quinophthalone, diketopyrrolopyrrole, dioxazine, indanthrone, indigo, isoindoline.
- B represents a radical selected from the following formulas (2), (3), (4), (5a) and (5b).
- Ck (k is a natural number) indicates that the number of carbon atoms is k.
- C1 represents 1 carbon.
- m 0 or 1.
- X is an unsubstituted or C1-C6 alkyl group, R or R
- 5 6 represents an optionally substituted C2 to C5 alkylene group or a C1 to C6 alkylene group.
- R and R are each independently a hydrogen atom, C1-C6
- a phenyl group substituted with a halogen group, a cyano group, a nitro group, a C1-C6 alkyl group or a C1-C6 alkoxy group is a phenyl group substituted with a halogen group, a cyano group, a nitro group, a C1-C6 alkyl group or a C1-C6 alkoxy group.
- Q is a hydrogen atom, a C1-C6 alkyl group, CN, CC1,
- [Chemical 10] Represents a group represented by: SO 2 CH or SCH. Where R and R are as described above.
- R and R are each independently a halogen group, C1-C4
- [Chemical 11] Represents a group represented by In addition, R and R are bonded to each other to form a piperidyl group.
- R and R each independently represent a hydrogen atom, C1
- -C24 alkyl group O is inserted, S is inserted, or C1-C6 alkyl group is disubstituted, and N is inserted C1-C24 alkyl group, C3-C24 alkyl group , C3-C24 alkyl group, C4-C12 cycloalkenyl group, unsubstituted or Cl-C6 alkyl group, C1-C6 alkoxy group, halogen group, cyano group or phenyl substituted by -tro group Represents a ruthel group or a biphenyl group. Note that a group such as 0, S, or N is inserted into an alkyl group means that the group is included in the middle of the carbon chain of the alkyl group.
- R, R and R are each independently a hydrogen atom, C1-C2
- R is a hydrogen atom, a C1-C6 alkyl group, or
- R represents a C1-C6 alkyl group
- R represents a hydrogen atom or a C1-C6 alkyl group.
- R represents a hydrogen atom, a C1-C6 alkyl group, or unsubstituted or C1
- B represents the following formula:
- G is unsubstituted or substituted with a C1-C12 alkyl group, a C1-C12 alkoxy group, a C1-C12 alkylthio group, or a C2-C24 dialkylamino group, C2-C12 p, q represents an alkylene group. P and q represent different position numbers.
- one substituent may be substituted alone, or two or more substituents may be substituted.
- G represents a heteroatom selected from the group consisting of N, O and S forces.
- R and R are each independently represented by [-(C2-C12 p, q, monoalkylene group)
- the substituent of the C1-C12 alkyl group is C1-C12 alkoxy group, C1-C12 alkylthio group, C2-C24 dialkylamino group, C6-C12 aryloxy group, C6-C12 arylthio group, Examples thereof include a C7 to C24 alkylarylamino group and a C12 to C24 diallylamino group.
- one substituent may be substituted alone, or two or more substituents may be substituted.
- ii represents 1 to: the number of LOOO, and 'and' represent different position numbers.
- each R is independently N, substituted with 0, S, or a C1-C12 alkyl group.
- R 1 and R 2 may have 1 to 10 unsaturated bonds which may be saturated.
- R and R may be unsubstituted halogen.
- G— is — (CH 2) —, iv represents a number from 2 to 12, and G is S
- R is unsubstituted, saturated, O, S, N other than carbon inserted in the middle of the carbon chain
- Another example of a suitable latent pigment includes a compound represented by the following formula (6).
- At least one of X 1 and X 2 represents a group that forms a ⁇ -conjugated divalent aromatic ring, and ⁇ — ⁇ 2 is a group that can be removed by heat or light, ⁇ — Indicates that the ⁇ -conjugated compound obtained by elimination of ⁇ 2 is a pigment molecule.
- X 1 and X 2 which are not a group forming a divalent aromatic ring in which ⁇ plays a role represent a substituted or unsubstituted etylene group.
- ⁇ 1 - ⁇ 2 is eliminated by heat or light to produce a ⁇ -conjugated compound having high planarity.
- This produced ⁇ -conjugated compound is the pigment according to the present invention. In the present invention, it is preferable that this pigment exhibits semiconductor characteristics.
- pigments ( ⁇ conjugated compounds) produced by converting latent pigments include condensed aromatic hydrocarbons such as naphthacene, pentacene, pyrene, and fullerene; oligomers such as a-sexithiophene; Aromatic carboxylic acid anhydrides and imidized products such as naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide; copper phthalocyanine, perfluorocopper phthalocyanine, tetrabenzo And macrocyclic compounds such as vorphyrin and its metal salts.
- specific examples of converting the latent pigment include the following.
- the pigment obtained by converting these latent pigments is generally a highly crystalline material having crystallinity.
- ⁇ -conjugated molecules are aggregated due to strong intermolecular interaction.
- the pigment according to the present invention has a strong absorption band in the visible light region, and has semiconductor characteristics that can transport charges to some extent. Among them, U, which has high semiconductor properties is desirable.
- organic pigment materials obtained by converting latent pigments include, for example, tetrabenzoborphyrin and its metal complexes such as copper and zinc, phthalocyanine and its metal complexes, and pentacenes. Even though quinacridones are preferred, Nzoporphyrin, phthalocyanine and their metal complexes are particularly preferred!
- Pigments are classified into p-type and n-type depending on semiconductor characteristics. In general, p-type and n-type indicate the force that contributes to electrical conduction in semiconductor materials.
- pigments showing p-type and n-type include the following forces. These are not necessarily clearly classified, and the same substance may exhibit both p-type and n-type characteristics.
- examples of pigments exhibiting p-type semiconductor properties include phthalocyanine and metal complexes thereof; tetrabenzoborphyrin and metal complexes thereof; tetrathracene (naphthacene), Polyacenes such as pentacene, pyrene, and perylene; oligothiophenes such as sexithiophene; and derivatives containing these compounds as a skeleton.
- n-type pigments examples include fullerene (C); perfluoro form of p-type semiconductor; naphthalene tetracarboxylic acid-free
- Examples thereof include water, aromatic carboxylic acid anhydrides such as naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and imido compounds thereof; and derivatives containing these compounds as a skeleton.
- aromatic carboxylic acid anhydrides such as naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and imido compounds thereof; and derivatives containing these compounds as a skeleton.
- a compound in which a structure for increasing the electron affinity of the compound is introduced into the skeleton of the compound represented by the formula (7B) can be suitably used as a precursor compound of an n-type semiconductor material. be able to.
- the compound represented by the formula (7B) is a kind of pigment, and is a compound obtained by converting the compound represented by the formula (7A) which is a latent pigment.
- the following compounds or metal complexes such as copper and zinc can be mentioned.
- fluorine-substituted products and nitrogen-substituted products of the compounds represented by the formulas (8B), (9B), and (10B) can also be used as the n- type semiconductor.
- the compounds represented by the formulas (8B), (9B), and (10B) are all types of pigments, and are represented by the formulas (8A), (9A), and (10A) that are latent pigments, respectively. It is a compound obtained by converting the compound.
- an organic photoelectric conversion device of the present invention there is a method having a step of converting two or more latent pigments into a pigment as mentioned in the above method (1).
- An organic photoelectric conversion device produced by this method usually contains a p-type pigment and an n-type pigment in its active layer.
- the organic photoelectric conversion device produced by the method for producing an organic photoelectric conversion device of the present invention as a pigment, porphyrin, phthalocyanine, quinatalidone, pyrrolopyrrole, dithioketopyrrolopyrrole and It is preferable to use at least one selected from the group consisting of derivatives thereof. Among them, it is particularly preferable to use a benzoborphyrin compound as the latent pigment according to the present invention. Hereinafter, this benzoporphyrin compound will be described in detail.
- the benzoborphyrin compound according to the present invention is represented by the following formula (I) or (II).
- Z ia and Z ib (i represents an integer of 1 to 4) each independently represent a monovalent atom or atomic group, provided that z ia and z ib may be bonded to form a ring.
- I ⁇ to R 4 each independently represents a monovalent atom or atomic group.
- M represents a divalent metal atom or an atomic group in which a trivalent or higher metal is bonded to another atom.
- Z ia and Z ib are each independently
- examples of the atom include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
- the atomic group includes hydroxyl group; amino group; alkyl group, aralkyl group, alkenyl group, cyano group, acyl group, alkoxy group, alkoxycarbonyl group, aryloxy group, dialkylamino group, and dialal.
- organic groups such as a killamino group, a haloalkyl group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group.
- the carbon number of the alkyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms in the alkyl group is too large, the semiconductor properties will decrease, the solubility will increase, and redissolution will occur during lamination. Heat resistance may decrease.
- the alkyl group include a methyl group and an ethyl group.
- the carbon number of the aralkyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms in the aralkyl group is too large, the semiconductor characteristics may be deteriorated, the solubility may be increased, and redissolution may be performed during lamination, or the heat resistance may be decreased.
- the aralkyl group include a benzyl group.
- the carbon number of the alkenyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms in the alkenyl group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease. Examples of the alkenyl group include a vinyl group.
- the number of carbon atoms of the acyl group is arbitrary unless the effect of the present invention is significantly impaired. Usually, it is 12 or less, preferably 8 or less. If the number of carbon atoms in the acyl group is too large, the semiconductor characteristics may be deteriorated, the solubility may be increased, and redissolution may be performed during lamination, or the heat resistance may be decreased. Examples of this acyl group include a formyl group, a acetyl group, a benzoyl group, and the like.
- the number of carbon atoms of the alkoxy group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms of the alkoxy group is too large, the semiconductor characteristics may be deteriorated, the solubility may be increased, and redissolution may be performed during lamination, or the heat resistance may be decreased.
- the alkoxy group include a methoxy group and an ethoxy group.
- the number of carbon atoms of the alkoxycarbo group is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms of the alkoxycarbonyl group is too large, the semiconductor characteristics may be deteriorated, the solubility may be increased and redissolution may be performed during the stacking, or the heat resistance may be decreased. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and the like. [0099] Among the above organic groups, the carbon number of the aryloxy group is an arbitrary force as long as the effects of the present invention are not significantly impaired.
- the carbon number of the aryloxy group is 12 or less, preferably 8 or less. If the carbon number of the aryloxy group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and remelting may occur during lamination, or the heat resistance may decrease.
- the aryloxy group include a phenoxy group and a benzyloxy group.
- the carbon number of the dialkylamino group is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, it is 12 or less, preferably 8 or less. If the number of carbon atoms in the dialkylamino group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease. Examples of the dialkylamino group include a jetylamino group and a diisopropylamino group.
- the number of carbon atoms of the dialalkylamino group is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 12 or less, preferably 8 or less. If the number of carbon atoms in the dialalkylamino group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease.
- the diaralkylamino group include a dibenzylamino group and a diphenethylamino group.
- the carbon number of the haloalkyl group is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, it is 12 or less, preferably 8 or less. If the number of carbon atoms in the haloalkyl group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease.
- the haloalkyl group include a-haloalkyl groups such as a trifluoromethyl group.
- the number of carbon atoms of the aromatic hydrocarbon ring group is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 6 or more, preferably 10 or more, and usually 30 or less. It is preferably 20 or less. If the aromatic hydrocarbon ring group has too many carbon atoms, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease. Examples of the aromatic hydrocarbon ring group include a phenyl group and a naphthyl group.
- the carbon number of the aromatic heterocyclic group is an arbitrary force as long as the effects of the present invention are not significantly impaired. Usually 2 or more, preferably 5 or more, and usually 30 or less, preferably Is less than 20. If the number of carbon atoms in the aromatic heterocyclic group is too large, the semiconductor characteristics may deteriorate, the solubility may increase, and redissolution may occur during lamination, or the heat resistance may decrease.
- the aromatic heterocyclic group include a chael group and a pyridyl group.
- the above atomic group may have an arbitrary substituent as long as the effects of the present invention are not significantly impaired.
- substituents include a halogen atom such as a fluorine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; a methoxy carbo yl group and an ethoxy carbo ol group.
- Alkoxy group having 1 to 6 carbon atoms such as; alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group; aryloxy group such as phenoxy group and benzyloxy group; dialkyla groups such as dimethylamino group and jetylamino group A mino group; a acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group.
- substituents may be substituted alone or in plural, and two or more may be substituted in any combination and ratio.
- Zia and Zib may combine to form a ring! /.
- examples of the ring containing Z ia and Z ib include benzene Aromatic hydrocarbon ring which may have a substituent such as a ring, naphthalene ring, anthracene ring, etc .; a substituent such as a pyridine ring, a quinoline ring, a furan ring, a thiophene ring, etc. ⁇ aromatic heterocycle; non-aromatic cyclic hydrocarbon such as cyclohexane ring; and the like.
- substituents in the ring formed by combining Z ia and Z ib are optional as long as the effects of the present invention are not significantly impaired. Examples thereof include the same substituents as those exemplified as the substituent of the atomic group constituting z ia and z ib .
- 1 type may be substituted by single or multiple, and 2 or more types may be substituted by arbitrary combinations and ratios.
- a hydrogen atom is particularly preferable. This is because the crystal packing is good and high semiconductor characteristics can be expected.
- I ⁇ ⁇ R 4 each independently be Table Wa monovalent atom or atomic group.
- Examples of I ⁇ to R 4 include the same as Z ia and Z ib described above. Also, Shaku 1 ⁇ When R 4 is an atomic group, the atomic group may have an arbitrary substituent as long as the effect of the present invention is not significantly impaired. Examples of this substituent include the same substituents as Z ia and Z ib . In addition, as for this substituent, 1 type may be substituted by single or multiple, and 2 or more types may be substituted by arbitrary combinations and ratios.
- a hydrogen atom in order to improve the planarity of the molecule, a hydrogen atom, also it is preferred to selected nuclear such as a halogen atom,.
- M represents a divalent metal atom, or an atomic group in which a trivalent or higher metal is bonded to another atom.
- M is a divalent metal atom
- examples thereof include Zn, Cu, Fe, Ni, and Co.
- 1 , B 3 and B 4 represent a monovalent group such as a halogen atom, an alkyl group or an alkoxy group.
- the benzoborphyrin compound according to the present invention includes, for example, one in which two vorphyrin rings are coordinated with one atom, or two porphyrin rings have one or more atoms. May be bonded by sharing atomic groups, or by connecting 3 or more of them connected on a long chain! /.
- benzoborphyrin compounds according to the present invention are not limited to the following examples. Further, here, even an asymmetric structure based on a combination of force partial structures mainly exemplified by a highly symmetric molecular structure can be used.
- thermo conversion thermal conversion
- the soluble precursor according to the present invention can be converted to the benzoborphyrin compound according to the present invention by thermal conversion. Its structure has a bicyclo ring and is converted into the present invention by heat conversion. As long as it can be converted into such a benzoborphyrin compound, it is optional.
- the soluble precursor according to the present invention is preferably a compound represented by the following formula (III) or (IV).
- Z ia and Z ib (i represents an integer of 1 to 4) each independently represent a monovalent atom or atomic group, provided that z ia and z ib may be bonded to form a ring
- I ⁇ to R 4 each independently represents a monovalent atom or atomic group.
- ⁇ to ⁇ 4 each independently represents a monovalent atom or atomic group.
- ⁇ represents a divalent metal atom or an atomic group in which a trivalent or higher metal is bonded to another atom.
- ⁇ 4 each independently represents a monovalent atom or group of atoms.
- ⁇ 1 , ⁇ 2 , ⁇ 3 , and ⁇ 4 are the same or different. May be.
- examples of the atom include a hydrogen atom.
- examples of the atomic group include a hydroxyl group and an alkyl group.
- the carbon number of the alkyl group is arbitrary as long as the effects of the present invention are not significantly impaired, but it is usually 1 or more, and usually 10 or less, preferably 6 or less, more preferably 3 or less. If the alkyl group has too many carbon atoms, the leaving group becomes large and the leaving group volatilizes and may remain in the film.
- examples of the alkyl group include a methyl group and an ethyl group.
- the atomic group may have an arbitrary substituent as long as the effects of the present invention are not significantly impaired.
- substituents include those similar to the substituents of z ia and Z ib .
- 1 type may be substituted by single or multiple, and 2 or more types may be substituted by arbitrary combinations and ratios.
- a hydrogen atom or an alkyl group having 10 or less carbon atoms is preferable.
- the smaller the carbon number the smaller the molecular weight of the leaving group generated by the conversion, and the leaving product is more likely to volatilize out of the system.
- the solubility of the vorfilin compound is improved by introducing the alkyl group.
- the soluble precursor according to the present invention is converted into the benzoborphyrin compound according to the present invention by thermal conversion.
- the compound of the following formula (V) is formed by applying heat. Detach. This elimination reaction proceeds quantitatively. And, by this elimination reaction, the soluble precursor according to the present invention is converted into the benzovorphyrin compound according to the present invention.
- the thermal conversion will be specifically described by taking the benzoborphyrin compound BP-1 exemplified above as an example.
- a soluble precursor of Benzoborphyrin compound BP-1 For example, in the formula (III), a compound in which Z ia , Z ib , I ⁇ to R 4 and ⁇ ⁇ 4 are all hydrogen atoms (hereinafter referred to as “BP-1 precursor”) can be used.
- BP-1 precursor a compound in which Z ia , Z ib , I ⁇ to R 4 and ⁇ ⁇ 4 are all hydrogen atoms
- the soluble precursor of the benzoborphyrin compound BP-1 is not limited to this BP-1 precursor.
- the temperature condition is not limited as long as the reaction proceeds, but usually 100 ° C or higher, preferably 150 ° C or higher. If the temperature is too low, the conversion takes time, which may be undesirable in practice.
- the upper limit is arbitrary force Usually 400 ° C or lower, preferably 300 ° C or lower. This is because decomposition or sublimation may occur if the temperature is too high.
- the heating time is not limited as long as the reaction proceeds, but usually 10 seconds or longer, preferably 30. Seconds or more, and usually 100 hours or less, preferably 50 hours or less. If the heating time is too short, conversion may be insufficient, and if it is too long, it may become unpreferable for practical use.
- the atmosphere is not limited as long as the reaction proceeds, but an inert atmosphere is preferable.
- the inert gas that can be used at this time include nitrogen and rare gases. Only one inert gas may be used, or two or more inert gases may be used in any combination and ratio.
- the soluble precursor according to the present invention has high solubility in solvents such as organic solvents! ⁇ .
- the degree of general solubility depends on the type of solvent, but the solubility in black mouth form at 25 ° C. is usually at least 0.1 lgZL, preferably at least 0.5 gZL, more preferably at least lgZL. There is no limit on the upper limit, but it is usually less than lOOOgZL.
- the soluble precursor according to the present invention is highly soluble in a solvent, whereas the benzoborphyrin compound according to the present invention derived therefrom has very low solubility in a solvent such as an organic solvent. .
- a solvent such as an organic solvent.
- the structure of the soluble precursor according to the present invention is not a planar structure, and thus the solubility is high and it is difficult to crystallize, whereas the benzoborphyrin compound according to the present invention has a planar structure. It is assumed that Therefore, if such a difference in solubility in the solvent is utilized, a layer containing the benzoborphyrin compound can be easily formed by a coating method. For example, it can be produced by the following method.
- a soluble precursor according to the present invention is dissolved in a solvent to prepare a solution, and the solution is applied to form a good layer close to amorphous or amorphous. Then, this layer is heat-treated and the soluble precursor according to the present invention is converted by heat conversion, thereby providing high flatness! Thus, a layer of a benzoborphyrin compound can be obtained.
- the compound to be eliminated is an ethylene molecule. Therefore, it is suitable in terms of toxicity and safety that remain in the system.
- a known method can be arbitrarily employed without any limitation to the method for producing a soluble precursor according to the present invention.
- the BP-1 precursor as an example, it can be produced through the following synthesis route.
- Et represents an ethyl group
- t-Bu represents a t-butyl group.
- a latent pigment and a solid semiconductor material are mixed, and a precursor film is formed by a coating method.
- a method having a film forming step of forming a film contains a solid semiconductor material in its active layer.
- Solid semiconductor material refers to a material that can transport charge at least when it is in a solid state.
- the degree of semiconductor characteristics shown solid semiconductor material in the value of any a is the force carrier mobility long as they can use as a material of an organic photoelectric varying ⁇ Ko usually 10_ 7 cm 2 ZVs or more, preferably 10 _5 cm 2 More than ZVs.
- Electrical conductivity is defined by carrier mobility X carrier density, so a material with a certain amount of carrier mobility Then, if carriers are present in the material, for example, by heat, doping, or injection from an electrode, the material can transport charges. It should be noted that the carrier mobility of the solid semiconductor material is higher.
- the semiconductor material such as the solid semiconductor material according to the present invention or a pigment exhibiting semiconductor characteristics
- carriers that transport charges, electrons and holes.
- Majority carriers are usually determined by the type of semiconductor material and doping state.
- the type of semiconductor material many carriers are called n-type, those that are holes are called p-type, and those that are balanced are called i-type.
- an organic photoelectric conversion element is one that separates electrons and holes by absorption of light and takes them out, it often has an active layer containing both p-type and n-type semiconductor materials. Therefore, when the pigment according to the present invention exhibits semiconductor characteristics, the majority carrier of the pigment according to the present invention and the majority carrier of the solid semiconductor material preferably have opposite polarities. That is, in the case of the pigment strength type according to the present invention, an n-type solid semiconductor material is used, and conversely, when the pigment according to the present invention is n-type, the solid semiconductor material is p-type. It is desirable to use those.
- At least one pigment and at least one solid semiconductor material have multiple carriers of opposite polarity. May have the same polarity pigment and Z or solid semiconductor material.
- the pigment according to the present invention is pentacene or benzoporphyrin, these pigments operate as p-type, so that the solid semiconductor material with which the pigment is combined exhibits n-type. Examples thereof include naphthalene tetracarboxylic acid diimide, fullerene (C), titer, zinc oxide, and the like.
- p-type and n-type are not absolutely determined by the type of semiconductor material.
- semiconductor materials of the same type are combined, one can operate as a p-type and the other as an n-type, depending on the energy level (HOMO, LUMO level, Fermi level) and doping state. It is possible.
- the solid semiconductor material is usually present in an aggregated state such as in the form of particles or fibers.
- solid semiconductor materials are particles or It is preferably in the shape of a rubber (hereinafter also referred to as particles).
- the size of the solid semiconductor material such as the particle diameter.
- the particle size (or fiber diameter) of the solid semiconductor material is usually 2 nm or more, preferably 5 nm or more, and usually 10 ⁇ m or less, preferably 1 ⁇ m or less. It is difficult for conventional technology to disperse such small particles together with the pigment in the mixed semiconductor film, and in particular, in the mixed semiconductor film in which the organic pigment and the inorganic solid semiconductor material coexist. Was particularly difficult.
- even such a small particle size particle can be well dispersed in the mixed semiconductor film.
- the particle size of the solid semiconductor material in the mixed semiconductor film can be determined by observing with an electron microscope.
- any material can be used. Examples include naphthalene (or perylene) tetracarboxylic acid diimide, fullerene (C) and its derivatives.
- Organic semiconductors such as titania, zinc oxide, and copper oxide; compound semiconductors such as GaAs, GaP, InP, CdS, CdSe, GaN, CuInSe, and Cu (lnGa) Se;
- Examples include elemental semiconductors.
- the solid semiconductor material may be dissolved in a coating solution (described later) or dispersed in a particulate form.
- solid semiconductor materials that dissolve in a solvent include organic semiconductor materials that can be formed by a solution process, and specific examples include polythiophene, polyfluorene, poly-ethylene vinylene, polyacetylene, and poly-arine.
- Conjugated polymers alkyl-substituted oligothiophenes and the like.
- Examples of the solid semiconductor material dispersed in the form of particles include organic semiconductor particles and inorganic semiconductor particles.
- the organic semiconductor particles for example, the solubility of small crystalline organic semiconductors.
- Specific examples include naphthacene, pentacene, pyrene, condensed aromatic hydrocarbons such as fullerene; such as a-sexithiophene Chio Fen Chiofen Oligothiophenes containing 4 or more rings; a total of 4 or more thiophene rings, benzene rings, fluorene rings, naphthalene rings, anthracene rings, thiazole rings, thiadiazole rings, and benzothiazole rings Those linked above: aromatic carboxylic acid anhydrides and imidized products thereof such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, pery
- inorganic semiconductors such as the above-described oxide semiconductors, compound semiconductors, and single element semiconductors are preferable.
- Inorganic semiconductors are excellent in durability and various nanoparticles can be used.
- inorganic semiconductors are highly durable and have a large carrier mobility, so that high efficiency of organic photoelectric conversion elements can be expected.
- titania and zinc oxide are particularly preferable because of the advantage that they can be used at low cost.
- the inorganic semiconductor when used as the solid semiconductor material, is preferably particulate inorganic particles.
- the inorganic semiconductor is preferably particulate inorganic particles.
- the organic photoelectric conversion device of the present invention comprises at least a substrate, a pair of electrodes (that is, a positive electrode and a negative electrode) formed on the substrate and transparent at least one, and an electron donor (or a p-type semiconductor).
- the electron donor layer and the electron acceptor layer may be formed as separate layers, but they are formed so that a single layer functions as an electron donor layer and an electron acceptor layer. Also good.
- the active layer is composed of the electron donor layer and the electron acceptor layer. That is, the active layer refers to a layered structure composed of an electron donor layer and an electron acceptor layer when the electron donor layer and the electron acceptor layer are formed as separate layers. (Heterojunction type), and when the electron donor layer and the electron acceptor layer are formed as a single layer, they refer to the same layer as the electron donor layer and the electron acceptor layer ( Balta Heterojunction).
- the active layer contains at least one pigment according to the present invention.
- the organic photoelectric conversion element of the present invention preferably includes a p-type semiconductor layer and an n-type semiconductor layer, and includes the active layer between the P-type semiconductor layer and the n-type semiconductor layer.
- the organic photoelectric conversion element of the present invention may include components other than those described above as long as the effects of the present invention are not significantly impaired.
- the active layer may be formed containing at least one pigment.
- the latent pigment according to the present invention is converted into the pigment according to the present invention to form an active layer.
- the active layer containing a pigment can be formed by vacuum deposition or wet coating.
- the pigment is difficult to apply because of its low solubility in organic solvents.
- the latent pigment according to the present invention is used for conversion after coating film formation, it is possible to easily form an active layer having pigment strength.
- the crystallinity and shape of the obtained layer can be controlled. That is, after forming a film by a wet method using a latent pigment, the pigment with high planarity can be used in a crystalline state by converting it into a pigment by, for example, heat treatment. Thereby, since mobility can be improved, it is possible to improve the photoelectric conversion characteristics of the organic photoelectric conversion element. In addition, it is possible to improve the characteristics of the organic photoelectric conversion element by providing a pigment between the active layer and the positive electrode or the negative electrode.
- FIG. 1 shows a schematic cross-sectional view of an organic photoelectric conversion device as a first embodiment of the present invention.
- the organic photoelectric conversion device 1 of the present embodiment includes a substrate 2, a positive electrode 3, a P-type semiconductor layer 4, an electron donor layer 5, an electron acceptor layer 6, and an n-type.
- the active layer 9 is composed of the electron donor layer 5 and the electron acceptor layer 6.
- the active layer 9 is a layer composed of the electron donor layer 5 and the electron acceptor layer 6.
- the p-type semiconductor layer 4 and the n-type semiconductor layer 7 are not essential, but are preferably present.
- the substrate 2 serves as a support for the organic photoelectric conversion element 1. Therefore, the positive electrode 3, the p-type semiconductor layer 4, the active layer 9 (that is, the electron donor layer 5 and the electron acceptor layer 6), the n-type semiconductor layer 7, and the negative electrode 8 are provided on the substrate 2.
- the material of the substrate 2 is arbitrary as long as the effects of the present invention are not significantly impaired.
- a transparent material is used as the substrate material. Normally, visible light is taken into the organic photoelectric conversion element 1 even in the light. Therefore, as a transparent substrate material, the transmittance of visible light transmitted through the substrate 2 is usually 60% or more, especially 80 It is preferable to use one that is at least%.
- substrate materials include inorganic materials such as quartz, glass, sapphire, and titania; polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol Organic materials such as polyethylene vinyl alcohol copolymer, fluorine resin film, butyl chloride, polyethylene, cellulose, polysalt vinylidene, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene; Paper materials such as paper and synthetic paper; composite materials such as those obtained by coating or laminating a metal such as stainless steel, titanium or aluminum with a surface coated to provide insulation.
- inorganic materials such as quartz, glass, sapphire, and titania
- polyethylene terephthalate polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol
- Organic materials such as polyethylene vinyl alcohol copolymer,
- glass synthetic resins such as polyester, polymetatalylate, polycarbonate, and polysulfone are preferable.
- substrate material only one type of substrate material can be used. Use two or more types in any combination and ratio.
- synthetic resin it is preferable to pay attention to gas nozzle properties. If the gas barrier property of the substrate 2 is too low, the organic photoelectric conversion element 1 may be deteriorated by outside air passing through the substrate 2. For this reason, when the substrate 2 is formed of a synthetic resin, it is preferable to form a gas-nozzle layer (gas barrier layer) on one or both sides of the synthetic resin substrate. Examples of this gas layer include a dense silicon oxide film.
- the shape of the substrate 2 is not limited.
- the shape of a plate, a film, a sheet or the like can be used.
- the thickness of the substrate 2 is not limited. However, it is preferable to form it usually at least, especially 20 / zm or more, and usually 20 mm or less, especially 10 mm or less. If the substrate 2 is too thin, the strength for holding the organic photoelectric conversion element 1 may be insufficient, and if it is too thick, the cost may be high or the weight may be too heavy.
- a positive electrode 3 is formed on the substrate 2.
- the positive electrode 3 is an electrode that plays a role of receiving the positive holes separated in the active layer 9 through the p-type semiconductor layer 4.
- the material of the positive electrode 3 (positive electrode material) is optional as long as it has conductivity and does not significantly impair the effects of the present invention.
- a transparent material is used as the positive electrode material. Since visible light is usually taken into the organic photoelectric conversion element 1 even in the case of light, the transparent positive electrode material usually has a transmittance of visible light that passes through the positive electrode 3, usually 60% or more, especially 80 It is preferable to use one that is at least%.
- examples of the positive electrode material include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, norium, sodium, or alloys thereof; Metal oxides such as indium oxide and tin oxide, or alloys thereof (ITO); conductive polymers such as polyaline, polypyrrole, polythiophene, polyacetylene; the conductive polymers include hydrochloric acid, sulfuric acid, sulfonic acid Acid such as, Lewis acid such as FeCl, iodine, etc.
- metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, norium, sodium, or alloys thereof
- Metal oxides such as indium oxide and tin oxide, or alloys thereof (ITO)
- conductive polymers such as polyaline, polypyrrole, polythiophene, polyacetylene; the conductive polymers include hydrochloric acid, sulfuric acid, sulfonic acid Acid such as, Lewis acid
- dopants such as halogen atoms of sodium, sodium, potassium, etc .
- conductive particles such as metal particles, carbon black, fullerene, carbon nanotubes, etc.
- examples thereof include a conductive composite material dispersed in a matrix such as a limer binder.
- metal oxides such as indium tin oxide and indium zinc oxide are preferred as preferred examples of the positive electrode material. Only one type of positive electrode material may be used, or two or more types may be used in any combination and ratio.
- the positive electrode is formed as a transparent electrode
- examples of the material include oxides such as ITO and indium zinc oxide ( ⁇ ⁇ ); and metal thin films.
- the electrodes (positive electrode and negative electrode described later) have a function of collecting holes and electrons generated in the active layer. Therefore, an electrode material suitable for collecting holes and electrons is preferably used for the electrode. From this point of view, examples of electrode materials suitable for collecting holes include materials having a high work function such as Au and ITO.
- the thickness of the positive electrode 3 is not limited. However, it is usually preferably lOnm or more, especially 50 nm or more, and usually lOOOnm or less, especially 300 nm or less. If the positive electrode 3 is too thick, the transparency may be reduced and the cost may be increased. If the cathode 3 is too thin, the performance of increasing the series resistance may be reduced.
- the positive electrode there are no restrictions on the method of forming the positive electrode!
- it can be formed by a dry process such as vacuum deposition or sputtering.
- it can also be formed by a wet process using a conductive ink or the like.
- any conductive ink can be used.
- a conductive polymer, a metal particle dispersion, or the like can be used.
- the positive electrode may be laminated with two or more layers to improve surface treatment characteristics (such as electrical characteristics and wetting characteristics).
- a p-type semiconductor layer 4 is preferably provided on the positive electrode 3.
- the P-type semiconductor layer 4 As a material of the P-type semiconductor layer 4 (p-type semiconductor material), a material that can efficiently transport holes generated in the active layer 9 (in particular, the electron donor layer 5 in this embodiment) to the positive electrode 3 is preferable.
- the p-type semiconductor material has high hole mobility, high conductivity, a small hole injection barrier between the positive electrode 3 and the active layer 9 (especially in this embodiment). It is preferable to have properties such as a small hole injection barrier from the electron donor layer 5) to the p-type semiconductor layer 4.
- the p-type semiconductor layer is preferably transparent.
- the transmittance of visible light transmitted through the p-type semiconductor layer 4 is usually 60. It is preferable to use those that are at least%, particularly at least 80%.
- the p-type semiconductor material need only be thin enough even if it is not transparent.
- an organic semiconductor material is used as the P-type semiconductor material, and the P-type semiconductor layer is used as the P-type organic semiconductor layer. Preferred to form ,.
- preferable examples of the p-type semiconductor material include pigments, and preferable examples include Borfilin compounds and phthalocyanine compounds. These compounds may have a central metal or may be metal-free. Specific examples include 29 H, 31H-phthalocyanine, copper (II) phthalocyanine, zinc (II) phthalocyanine, titanium phthalocyanine oxide, copper ( ⁇ ) 4, 4 ', 4 ", 4, ..., one tetraaza 29H, 31H—phthalocyanine compounds such as phthalocyanine; tetrabenzoporphyrin, tetrabenzocopper porphyrin
- porphyrin compounds such as tetrabenzozinc porphyrin; and the like.
- examples of preferable p-type semiconductor materials other than pigments such as vorfilin compound and phthalocyanine compound include a system in which a dopant is mixed with a hole transporting polymer.
- examples of the hole transporting polymer include poly (ethylenedioxythiophene), polythiophene, polyarine, and polypyrrole.
- examples of dopants include iodine; acids such as poly (styrenesulfonic acid) and camphorsulfonic acid; PF, AsF, Fe
- Lewis acids such as CI
- one type of p-type semiconductor material may be used alone, or two or more types may be used in any combination and ratio.
- the thickness of the p-type semiconductor layer 4 is not limited. However, it is usually preferably 3 nm or more, especially lOnm or more, and usually 200 nm or less, especially lOOnm or less. If the p-type semiconductor layer 4 is too thick, the transmittance may decrease or the series resistance may increase. If the p-type semiconductor layer 4 is too thin, a non-uniform film may be formed.
- the method for forming the p-type semiconductor layer 4 is not limited. However, when forming the p-type semiconductor layer 4 containing a pigment, a method of applying and changing the latent pigment is preferable.
- the electron donor layer 5 is a layer formed including an electron donor, and is provided on the p-type semiconductor layer 4.
- the electron donor contained in the electron donor layer 5 has properties such as efficient absorption of visible light and high mobility to efficiently transport light-induced holes. It is preferable.
- the electron donor when considering outdoor applications, usually has a heat resistance of 100 ° C or higher, preferably 120 ° C or higher, more preferably 150 ° C or higher. Is preferred
- Examples of such an electron donor include the pigment according to the present invention.
- the pigment according to the present invention is contained in the electron donor layer 5 as an electron donor.
- the pigment according to the present invention may be used alone or in combination of two or more in any combination and ratio.
- condensed aromatic hydrocarbons such as naphthacene, pentacene, pyrene and fullerene; oligomers such as a -sexithiophene; macrocyclic compounds such as phthalocyanine and volfilin; a —sexithiophene, dialkylsexithiophene, Oligothiophenes containing four or more thiophene rings represented by the formula: Containing four or more thiophene rings, benzene rings, fluorene rings, naphthalene rings, anthracene rings, thiazole rings, thiadiazole rings, or benzothiazole rings
- a condensed thiophene such as anthradithiophene, dibenzothienobisthiophene, a, ⁇ , monobis (dithieno [3,2-b,: 2,3,1, d
- Poria diphosphate and the like are preferable.
- polymers exhibiting self-weaving and weaving properties such as regioregular polythiophene and polymers exhibiting liquid crystallinity represented by polyfluorene and copolymers thereof are preferable.
- Other electron donors may be used alone, or two or more may be used in any combination and ratio.
- the electron donor layer 5 contains the pigment according to the present invention, it is preferable to use a large amount of the pigment according to the present invention as the electron donor.
- the electron donors usually 50% by weight or more, particularly 70% by weight or more, more preferably 90% by weight or more is preferably the pigment according to the present invention, and only the pigment according to the present invention is used. Is particularly preferred. This is because the advantage of using the pigment according to the present invention is effectively exhibited.
- the thickness of the electron donor layer 5 is not limited. However, it is usually preferably 5 nm or more, especially lOnm or more, and usually 500 nm or less, especially 200 nm or less. If the electron donor layer 5 is too thick, the series resistance may increase. If the electron donor layer 5 is too thin, sufficient light absorption necessary for photoelectric conversion may not be obtained.
- the electron acceptor layer 6 is a layer formed including an electron acceptor, and is provided on the electron donor layer 5.
- the electron acceptor contained in the electron acceptor layer 6 plays a role in efficiently transporting electrons generated at the junction interface with the electron donor to the n-type semiconductor layer 7 by charge separation.
- the minimum empty orbit (LUMO) of the materials used for each electron donor layer 5 and the electron acceptor layer 6 is used.
- the relative relationship is important.
- the LUM O force of the electron donor that is the material of the electron donor layer 5 is higher than the LUMO of the electron acceptor that is the material of the electron acceptor layer 6 by a predetermined energy, in other words, the electron acceptor.
- the electron affinity of the body is larger than the electron affinity of the electron donor by a predetermined energy.
- the value of the predetermined energy varies depending on the application. Usually 0.3 leV or more, preferably 0.2 eV or more, more preferably 0.3 eV or more, and usually 0.6 eV or less, preferably 0.4 eV or less. It is.
- Examples of the electron acceptor satisfying such conditions include pigments and fullerene compounds.
- specific examples of preferable pigments and fullerene compounds include the following.
- the organic photoelectric conversion element 1 is converted into the benzoborphylline according to the present invention.
- An electron donor layer 5 containing a compound and an electron acceptor layer 6 containing a fullerene compound are provided. In this case, the photoelectric conversion characteristics are improved, which is particularly preferable.
- the electron acceptor those other than the fullerene compound may be used together with the fullerene compound, or may be used in place of the fullerene compound.
- the electron acceptor layer 6 contains a fullerene compound
- an n-type pigment may be used as the electron acceptor.
- the electron acceptor only one kind may be used, or two or more kinds may be used in any combination and in any ratio.
- the thickness of the electron acceptor layer 6 is not limited. However, it is usually preferably 5 nm or more, especially lOnm or more, and usually 500 nm or less, especially 200 nm or less. If the electron acceptor layer 6 is too thick, the series resistance may increase, and if it is too thin, the coverage may deteriorate.
- An n-type semiconductor layer 7 is preferably provided on the electron acceptor layer 6.
- the role required for the n-type semiconductor layer 7 is to transport electrons to the negative electrode, as well as the p-type semiconductor layer, and also to activate the active layer 9 (that is, the electron donor layer 5 and the electron acceptor layer 6). It is also expected to prevent the exciton (exciton) generated by absorbing the light from being quenched by the negative electrode 8.
- the material of the n-type semiconductor layer 7 preferably has an optical gap larger than the optical gap of the electron donor and electron acceptor.
- n-type semiconductor materials include organic compounds showing electron transport properties such as phenantorin derivatives and silole derivatives; inorganic semiconductors such as TiO
- n-type semiconductor materials one type may be used alone, or two or more types may be used in any combination and ratio!
- the thickness of the n-type semiconductor layer 7 is not limited. However, it is usually preferably 2 nm or more, particularly 5 nm or more, and usually 200 nm or less, especially lOOnm or less. By forming the n-type semiconductor layer 7 in such a thickness range, when light incident from the positive electrode 3 is transmitted without being absorbed by the active layer 9, it is reflected by the negative electrode 8 and returns to the active layer 9 again. It is possible to take advantage of the optical interference effect.
- a negative electrode 8 is formed on the n-type semiconductor layer 7.
- the negative electrode 8 is an electrode that plays a role of receiving electrons separated in the active layer 9 through the n-type semiconductor layer 7.
- the material of the negative electrode 8 (negative electrode material) is optional as long as it has conductivity, as long as the effects of the present invention are not significantly impaired.
- metal such as n-type semiconductor layer 7 and contact!
- suitable examples of the negative electrode material include suitable metals such as magnesium, indium, strength, aluminum, silver, or alloys thereof.
- examples of the material include oxides such as ITO and indium zinc oxide ( ⁇ ); and metal thin films.
- an electrode material suitable for collecting electrons can be exemplified as a low material such as A1.
- V a material having a work function.
- ultra-thin insulation such as LiF, MgF, LiO, etc.
- Inserting a film (0.1-5 nm) is also an effective method for improving the efficiency of the organic photoelectric conversion element 1.
- the thickness of the negative electrode 8 is not limited. However, it is usually preferably 10 nm or more, especially 50 nm or more, and usually lOOOnm or less, especially 500 nm or less. If the anode 8 is too thick, the process may be time consuming or expensive, which may be undesirable in practice, and if it is too thin, the series resistance may increase and efficiency may decrease.
- a negative electrode it can form by the method similar to a positive electrode.
- the negative electrode may be improved in characteristics (electric characteristics, wetting characteristics, etc.) due to surface treatment by laminating two or more layers.
- the organic photoelectric conversion element 1 of the present embodiment can be produced through a step of converting a latent pigment such as a soluble precursor according to the present invention into a pigment in the step of forming a pigment layer.
- a latent pigment such as a soluble precursor according to the present invention
- the electron donor layer 5 is a pigment layer.
- the organic photoelectric conversion element 1 of the present embodiment converts a latent pigment such as a soluble precursor according to the present invention into a pigment such as a benzoborphyrin compound according to the present invention. It can manufacture through the process to do.
- a specific manufacturing method is as follows, for example.
- the substrate 2 is prepared, and the positive electrode 3 is formed thereon (positive electrode forming step).
- positive electrode forming step it can form by sputtering method, a vacuum evaporation method, etc.
- the p-type semiconductor layer 4 is formed on the positive electrode 3 (p-type semiconductor layer forming step).
- the method for forming the p-type semiconductor layer 4 is not limited.
- the p-type semiconductor layer 4 can be formed by a vacuum deposition method or the like.
- a P-type semiconductor material soluble in a solvent it can be formed by a wet coating method such as spin coating or ink jet.
- the active layer 9 (that is, the electron donor layer 5 and the electron acceptor layer 6) is formed on the p-type semiconductor layer 4 by a coating method in the following manner.
- the electron donor layer 5 is formed (electron donor layer forming step).
- a latent pigment such as the soluble precursor according to the present invention is dissolved in a solvent and a coating solution (latent pigment solution; when a soluble precursor is used as the latent pigment, Prepare a “precursor solution”.
- a latent pigment corresponding to the pigment to be included in the electron donor layer 5 is used.
- the latent pigment may be used alone or in combination of two or more in any combination and ratio.
- the type of the solvent used in the coating solution is arbitrary as long as the electron donor layer 5 is obtained.
- aromatic hydrocarbons such as toluene, benzene, xylene, black benzene, methanol, Lower alcohols such as ethanol, propanol and butanol; Ketones such as acetone, methyl ketone, cyclopentanone and cyclohexanone; Esters such as ethyl acetate, butyl acetate and methyl lactate; Nitrogen-containing organic solvents such as pyridine and quinoline Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, trichloroethylene; ethers such as ethyl ether, tetrahydrofuran, dioxane; amides such as dimethylformamide, dimethylacetamide, etc. be able to. Note that only one type of solvent may be used.
- the concentration of the latent pigment in the coating solution is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually at least 0 lgZL, preferably at least 0.5 gZL, more preferably at least lgZL, and usually at most lOOOgZL. , Preferably 500 gZL or less, more preferably 200 gZL or less
- the prepared coating solution is applied to the p-type semiconductor layer 4, and a coating film (coating layer, latent pigment layer, Precursor layer) is formed.
- a coating film coating layer, latent pigment layer, Precursor layer
- a spin coating method, a dip coating method, a spray coating method, an ink jet method, or the like can be used.
- the latent pigment in the coating layer is converted into a pigment (conversion step).
- the latent pigment is one that is converted into a pigment by heat, such as when the latent pigment is a soluble precursor according to the present invention
- the coating layer is heated.
- the latent pigment is converted into the pigment according to the present invention by heat conversion, so that the coating layer can be converted into the electron donor layer 5.
- Conditions such as temperature, pressure, time and atmosphere during the conversion are as described above in the section of [2-2. Soluble Precursor of Benzoborphyrin Compound].
- the solvent may be dried and removed from the coating layer before performing conversion such as heat conversion. In that case, the coating layer is an amorphous or a good layer close to amorphous.
- the electron donor to be used in combination may be dissolved or dispersed in the above solution.
- the electron acceptor layer 6 is formed (electron acceptor layer forming step).
- the electron acceptor layer 6 As a method for forming the electron acceptor layer 6, a coating method is used. Usually, the electron acceptor is preferably formed by laminating on the electron donor layer 5 by a wet coating method.
- the wet coating method can be employed when the electron acceptor is soluble.
- this method it is preferable to form the electron acceptor layer 6 from the liquid phase by a coating method as follows. That is, first, an electron acceptor solution containing an electron acceptor is prepared.
- the type of the solvent used for the electron acceptor solution is arbitrary as long as the electron acceptor layer 6 is obtained.
- the same solvent as the solvent used for the coating solution can be used.
- only 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and a ratio.
- the concentration of the electron acceptor in the electron acceptor solution is an arbitrary force as long as the effects of the present invention are not significantly impaired.
- 0.1 lgZL or more preferably lgZL or more, more preferably 5 gZL or less.
- it is usually 1OOOgZL or less, preferably 500 gZL or less, more preferably 200 gZL or less.
- the prepared electron acceptor solution is applied to the electron donor layer 5 made of a pigment converted from the latent pigment to form a coating layer. Then, the electron acceptor layer 6 is formed by drying and removing the solvent from the coating layer.
- the thin film shape of the pigment crystallized by the conversion also has a very small crystallite force
- the electron acceptor layer 6 by the above coating method, the electron acceptor becomes each crystal of the electron donor layer 5 It is possible to intrude between the children. Accordingly, as a result, the contact area between the electron donor and the electron acceptor is increased, conversion efficiency and photocurrent can be increased, and good photoelectric conversion characteristics can be exhibited.
- the n-type semiconductor layer 7 is formed (n-type semiconductor layer forming step).
- the formation method of the n-type semiconductor layer 7 For example, it can form by the vacuum evaporation method or the wet apply
- the negative electrode 8 is formed on the n-type semiconductor layer 7 (negative electrode forming step).
- the method for forming the negative electrode 8 is not limited, but can be formed by, for example, a sputtering method, a vacuum evaporation method, or the like, similarly to the positive electrode 3.
- the organic photoelectric conversion element 1 of the present embodiment can be manufactured.
- the organic photoelectric conversion element 1 of the present embodiment Since the organic photoelectric conversion element 1 of the present embodiment is configured as described above, it can take in light, generate holes and electrons in the active layer 9, and take them out to the positive electrode 3 and the negative electrode 8. It ’s like that. In this case, the organic photoelectric conversion element 1 of the present embodiment increases the contact area between the electron donor and the electron acceptor and improves the mobility as compared with the conventional organic photoelectric conversion element. Excellent photoelectric conversion characteristics.
- the specific value of the photoelectric conversion characteristic exhibited by the organic photoelectric conversion element 1 of the present embodiment is arbitrary. However, as specific indicators, it is preferable to satisfy at least one of the following indicators, and all of them.
- the open circuit voltage (Voc) is usually 0.3 V or higher, preferably 0.4 V or higher, more preferably 0.5 V or higher. Limit to the upper limit There is no.
- the short-circuit current Cisc is usually ImAZcm 2 or more, preferably 3 mAZcm 2 or more, more preferably 5 mAZcm 2 or more. There is no limit on the upper limit.
- the energy conversion efficiency (r? P) is usually 0.5% or more, preferably 1.0% or more, more preferably 1.5% or more. It is. There is no limit on the upper limit.
- the form factor (FF) is usually 0.3 or more, preferably 0.4 or more, more preferably 0.5 or more. There is no limit on the upper limit.
- the open circuit voltage (Voc), short circuit current (Jsc), energy conversion efficiency ( ⁇ ⁇ ), and form factor (FF) are calculated using the solar simulator (AMI. 5G) light intensity of lOOmWZcm 2 It is a value measured by irradiating the organic photoelectric conversion element 1 with and measuring the voltage-current characteristics.
- the organic photoelectric conversion element 1 of the present embodiment is implemented by further modifying the above-described configuration.
- the substrate 2 may be formed on both sides of the positive electrode 3 and the negative electrode 8 which may be formed on the negative electrode 8 side.
- the positive electrode 3 and the negative electrode 8 are provided on the substrate 2 directly or indirectly through another layer.
- the p-type or n-type semiconductor layers 4 and 7 may not be provided.
- the positive electrode 3 and the negative electrode 8 serve to receive positive holes and electrons generated from the active layer 9 without passing through the p-type or n-type semiconductor layers 4 and 7.
- a force that takes in light from the positive electrode 3 side may be a side force of the negative electrode 8.
- the n-type semiconductor 7 and the negative electrode 8 are formed transparently.
- each layer constituting the organic photoelectric conversion element 1 contains one or more components other than the above-described constituent materials unless the effects of the present invention are significantly impaired. It does not matter.
- the organic photoelectric conversion element 1 has the above-described substrate 2, positive electrode 3, p-type semiconductor layer 4, electron donor layer 5, and electron acceptor layer 6 unless the effects of the present invention are significantly impaired.
- layers and components other than the n-type semiconductor layer 7 and the negative electrode 8 may be provided.
- a protective layer (not shown) may be formed so as to cover the negative electrode 8.
- the protective layer may be, for example, a polymer film such as styrene resin, epoxy resin, acrylic resin, polyurethane, polyimide, polybutyl alcohol, polyvinylidene fluoride, polyethylene polybutyl alcohol copolymer, etc .; It can be composed of an inorganic oxide film such as silicon, silicon nitride, or aluminum oxide; a nitride film; or a laminated film thereof. These protective layer materials may be used alone or in combination of two or more in any combination and ratio.
- the method for forming the protective film is not limited.
- the protective film when the protective film is a polymer film, examples thereof include a formation method by coating and drying a polymer solution, and a formation method in which a monomer is applied or evaporated to polymerize. Further, when forming the polymer film, it is possible to further perform a crosslinking treatment or to form a multilayer film.
- the protective film when the protective film is an inorganic film such as an inorganic oxide film or a nitride film, for example, a formation method in a vacuum process such as a sputtering method or a vapor deposition method, or a solution process typified by a sol-gel method. The forming method can be used.
- the organic photoelectric conversion element is a solar cell
- the conversion step of converting the latent pigment may be performed any time after the latent pigment is formed by a coating method. Therefore, in the case of this embodiment, the heat treatment for causing the latent pigment to undergo thermal conversion may be performed any time after the formation of the latent pigment layer.
- a latent pigment layer is formed on the p-type semiconductor layer 4, and then the electron acceptor layer 6, the n-type semiconductor layer 7 and the negative electrode 8 are formed thereon without performing thermal conversion. And finally, you may make it heat-process.
- FIG. 2 shows a schematic cross-sectional view of an organic photoelectric conversion device as a second embodiment of the present invention.
- the organic photoelectric conversion element 10 of the present embodiment includes a substrate 2, a positive electrode 3, a P-type semiconductor layer 4, an electron donor layer 5, a partial active layer 11, and an n-type semiconductor.
- Layer 7 and negative electrode 8 are provided. That is, the structure is the same as that of the organic photoelectric conversion element 1 of the first embodiment except that the partial active layer 11 is provided instead of the electron acceptor layer 6. That is, the active layer in this embodiment is a layer composed of an electron donor layer and a partially active layer.
- the benzovorphyrin compound according to the present invention as a pigment. Therefore, it is preferable to use the soluble precursor according to the present invention as the latent pigment corresponding to the pigment.
- the substrate 2, the positive electrode 3 and the p-type semiconductor layer 4 are the same as in the first embodiment.
- the configuration of the electron donor layer 5 is the same as that of the first embodiment. However, this electron donor layer 5 is formed as a layer different from the partially active layer 11.
- the pigment according to the present invention is used as the electron donor, as in the first embodiment.
- the electron donor layer 5 functions as a pigment layer containing the pigment according to the present invention.
- the organic photoelectric conversion element 10 includes a partial active layer 11 and a pigment layer formed between the partial active layer 11 and the positive electrode 3 (or the p-type semiconductor layer 4 when the p-type semiconductor layer 4 is provided). Will be provided.
- the partial active layer 11 of this embodiment is a layer that can be used as an active layer by itself, and includes, for example, a mixed active layer containing an electron donor and an electron acceptor in the same layer. Therefore, the partially active layer 11 functions as an electron donor layer as well as an electron acceptor layer.
- the electron acceptor used for the partially active layer 11 is the same as the electron acceptor used for the electron acceptor layer 6 of the first embodiment.
- the electron donor used for the partially active layer 11 is not limited, and any electron donor can be used. In this case, only one kind of electron donor may be used, or two or more kinds of electron donors may be used in any combination and ratio. Therefore, the pigment according to the present invention can be used as the electron donor of the partially active layer 11 as in the first embodiment.
- the partial active layer 11 is formed as a mixed layer of an electron donor and an electron acceptor.
- the partial active layer 11 is formed by forming the electron donor layer 5
- the partial active layer 11 is formed.
- the electron acceptor constituting 11 can also effectively contact the pigment in the electron donor layer 5 in addition to the electron donor in the partial active layer 11 alone. For this reason, if different types of electron donors are used in the electron donor layer 5 and the partially active layer 11, two types of electron donors having different absorption wavelength regions come into contact with the electron acceptor, and the photocurrent is reduced. This is because it is possible to increase the photoelectric conversion characteristics.
- the partially active layer 11 does not contain the pigment according to the present invention, in the present embodiment, since the electron donor layer 5 contains a pigment, The conversion element 11 contains the pigment according to the present invention in at least one layer. Therefore, in the present embodiment, the partial active layer 11 will be described on the assumption that an electron donor other than a pigment (for example, polythiophene) is used.
- a pigment for example, polythiophene
- the ratio of the mixed electron donor and electron acceptor is arbitrary as long as the effect of the present invention is not significantly impaired, but it is based on the total weight of the electron donor and the electron acceptor.
- the ratio of the electron donor is usually 5% or more, preferably 10% or more, particularly 15% or more, and usually 95% or less, particularly 90% or less, particularly 85% or less. If there are too few or too many children, the photoelectric conversion characteristics may deteriorate.
- the thickness of the partial active layer 11 is not limited. However, it is usually preferably 5 nm or more, especially lOnm or more, and usually lOOOnm or less, especially 500 nm or less. If the partial active layer 11 is too thick, the series resistance may increase, and if it is too thin, light absorption may be insufficient.
- the n-type semiconductor layer 7 and the negative active layer 11 are disposed on the partial active layer 11.
- a pole 8 is formed.
- the n-type semiconductor layer 7 and the negative electrode 8 are the same as in the first embodiment.
- the organic photoelectric conversion element 10 of the present embodiment can be manufactured through a step of converting a latent pigment such as a soluble precursor according to the present invention into a pigment in the step of forming a pigment layer.
- a latent pigment such as a soluble precursor according to the present invention
- the electron donor layer 5 is a pigment layer.
- the organic photoelectric conversion element 10 of the present embodiment is used to convert a latent pigment such as a soluble precursor according to the present invention to a benzo-borphyrin compound or the like according to the present invention. It can be manufactured through a process of converting to a pigment.
- a specific manufacturing method is as follows, for example.
- the substrate 2 is prepared, and the positive electrode 3 and the P-type semiconductor layer 4 are formed on the substrate 2 in the same manner as described in the first embodiment.
- an electron donor layer 5 that is a pigment layer is formed on the p-type semiconductor layer 4.
- a coating liquid is prepared by dissolving a latent pigment such as a soluble precursor according to the present invention in a solvent, and the prepared coating liquid is applied to the p-type semiconductor layer 4.
- the electron donor layer 5 may be formed by subjecting the obtained coating layer to a heat treatment or the like to convert a latent pigment such as a soluble precursor into a pigment.
- the partial active layer 11 is formed on the electron donor layer 5.
- the partial active layer 11 may be formed by any method, for example, an electron donor and an electron acceptor may be formed on the electron donor layer 5 by a wet coating method.
- the electron acceptor layer forming step in the first embodiment may be performed except that an electron donor contained in the partial active layer 11 is used in addition to the electron acceptor.
- the same advantage as the electron acceptor layer forming step can be obtained at the boundary between the partially active layer 11 and the electron donor layer 5. That is, according to the wet coating method, the contact area between the electron donor and the electron acceptor is increased, the conversion efficiency and the photocurrent can be increased, and good photoelectric conversion characteristics can be exhibited.
- the organic photoelectric conversion element 10 of the present embodiment can be manufactured.
- the organic photoelectric conversion element 10 of the present embodiment Since the organic photoelectric conversion element 10 of the present embodiment is configured as described above, it takes in light, generates holes and electrons in the partially active layer 11, and takes them out to the positive electrode 3 and the negative electrode 8. Has become possible. In this case, in the organic photoelectric conversion element 10 of the present embodiment, the electron acceptor and the pigment can be effectively brought into contact between the partial active layer 11 and the electron donor layer 5 that are not only inside the partial active layer 11. As a result, an increase in photocurrent occurs, resulting in excellent photoelectric conversion characteristics.
- the organic photoelectric conversion element 10 of the present embodiment also has the same open circuit voltage (Voc), short-circuit current Cisc), energy conversion efficiency (r? P), and form factor (FF) as the organic photoelectric conversion element 1 of the first embodiment. ) And the maximum value of the external quantum efficiency.
- the organic photoelectric conversion element 10 of the present embodiment can be implemented by further changing the above-described configuration. For example, the same changes as described in the first embodiment may be performed.
- the pigment according to the present invention can be used as the electron donor of the partial active layer 11.
- the pigment of the electron donor layer 5 and the pigment of the partially active layer 11 contain different types. This is to increase the photocurrent and improve the photoelectric conversion characteristics.
- the method for producing the partially active layer 11 can be performed in the same manner as the electron donor layer forming step in the first embodiment, except that the electron acceptor coexists in the precursor solution. .
- an electron acceptor layer 6 may be provided between the partial active layer 11 and the n-type semiconductor layer 7 as in the third embodiment described later.
- FIG. 3 shows a schematic cross-sectional view of an organic photoelectric conversion device as a third embodiment of the present invention.
- the organic photoelectric conversion element 12 of the present embodiment includes a substrate 2, a positive electrode 3, a P-type semiconductor layer 4, a partial active layer 13, an electron acceptor layer 6, and an n-type semiconductor. Layer 7 and negative electrode 8 are provided. That is, the first active layer 13 is provided with a partially active layer 13 instead of the electron donor layer 5.
- the configuration is the same as that of the organic photoelectric conversion element 1 of the embodiment. That is, the active layer according to the present embodiment includes the partial active layer 13 and the electron acceptor layer 6.
- the substrate 2, the positive electrode 3 and the p-type semiconductor layer 4 are the same as in the first embodiment.
- the partial active layer 13 of this embodiment is the same as the partial active layer 11 described in the second embodiment. At this time, only one type of pigment may be used, or two or more types of pigments may be used in any combination and ratio. In this case, the partially active layer 13 functions as an electron donor layer as well as an electron acceptor layer.
- the configuration of the electron acceptor layer 6 is the same as that of the first embodiment. However, the electron acceptor layer 6 is formed as a layer different from the partially active layer 13.
- the electron acceptor layer 6 formed separately from the partial active layer 13 can be formed in the same manner as described in the first embodiment. However, even in that case, it is preferable that the electron acceptor of the electron acceptor layer 6 contains a different type from the electron acceptor of the partially active layer 13.
- the partially active layer 13 is formed as a mixed layer of an electron donor and an electron acceptor. However, by forming the electron acceptor layer 6 between the n type semiconductor layer 7, the partially active layer 13 is formed. The electron donor in the layer 13 can effectively contact the electron acceptor that partially constitutes the electron acceptor layer 6 in addition to the electron acceptor in the partial active layer 13 alone.
- the electron acceptor layer 6 will be described on the assumption that a different type of electron acceptor from that of the partially active layer 13 is used as the electron acceptor.
- an n-type semiconductor layer 7 and a negative electrode are formed on the electron acceptor layer 6.
- a pole 8 is formed.
- the n-type semiconductor layer 7 and the negative electrode 8 are the same as in the first embodiment.
- the organic photoelectric conversion element 12 of the present embodiment can be manufactured through a process of converting a latent pigment such as a soluble precursor according to the present invention into a pigment.
- a pigment is used for the electron donor layer in the partial active layer 13
- a pigment may be used for the electron acceptor layer 6 and no pigment may be used for the partially active layer 13.
- the organic photoelectric conversion element 12 of the present embodiment is used to convert the latent pigment such as the soluble precursor according to the present invention into the benzovorphyrin compound according to the present invention. It can manufacture through the process of converting into pigments, such as a thing.
- the specific manufacturing method is as follows, for example.
- the substrate 2 is prepared, and the positive electrode 3 and the P-type semiconductor layer 4 are formed thereon in the same manner as described in the first embodiment.
- the partial active layer 13 is formed on the p-type semiconductor layer 4.
- the partial active layer 13 can be formed in the same manner as the electron donor layer forming step in the first embodiment except that an electron acceptor is allowed to coexist in the precursor solution.
- the electron acceptor layer 6, the n-type semiconductor layer 7 and the negative electrode 8 are formed in the same manner as described in the first embodiment.
- the organic photoelectric conversion element 10 of the present embodiment can be manufactured.
- the organic photoelectric conversion element 12 of the present embodiment is configured as described above, light is taken in, holes and electrons are generated in the partial active layer 13, and these are extracted to the positive electrode 3 and the negative electrode 8. Has become possible.
- the organic photoelectric conversion element 12 of the present embodiment can effectively contact the electron acceptor and the pigment between the partial active layer 13 and the electron acceptor layer 6 which are not only inside the partial active layer 13. As a result, an increase in photocurrent occurs, resulting in excellent photoelectric conversion characteristics.
- the organic photoelectric conversion element 12 of the present embodiment is also the organic photoelectric conversion element of the first embodiment.
- the maximum open circuit voltage (Voc), short circuit current Cisc), energy conversion efficiency (r? P), form factor (FF), and external quantum efficiency similar to those of the conversion element 1 can be realized.
- the organic photoelectric conversion element 12 of the present embodiment can be implemented by further changing the configuration described above. For example, the same changes as described in the first embodiment may be performed.
- an electron donor layer (not shown) may be provided between the partial active layer 13 and the p-type semiconductor layer 4.
- This electron donor layer may or may not contain the pigment according to the present invention. At this time, when no pigment is contained as an electron donor, or when a different type of pigment from that used in the partially active layer 13 is used, the photocurrent is reduced as in the second embodiment. This results in an increase and is preferred.
- an organic photoelectric conversion element manufactured through a process of converting two or more latent pigments into a pigment will be described. This is the same configuration as that of the first to third embodiments except that the pigment in the active layers 9, 11 and 13 is obtained by converting two or more kinds of latent pigments.
- the organic photoelectric conversion element of this embodiment is the same as the organic photoelectric conversion element of the first to third embodiments described above except for the active layer. Therefore, the description other than the active layer is omitted, and the active layer will be described below.
- the active layer is a layer formed between the pair of electrodes, and is usually a layer having two or more kinds of semiconductors, that is, an electron donor (P-type semiconductor) and an electron acceptor (n-type semiconductor). is there.
- This active layer may be composed of only a single layer or may be composed of two or more layers. Further, the active layer may contain components other than the activity as long as the effects of the present invention are not significantly impaired.
- the ratio of the two or more semiconductors used is limited.
- the limit is arbitrary as long as the effect of the present invention is not significantly impaired.
- the usage ratio of the pigment is usually 1Z99 or more, preferably 5Z95 or more, more preferably 10Z90 in terms of the volume ratio represented by “one semiconductor Z the other semiconductor”.
- it is usually 99Z1 or less, preferably 95Z5 or less, more preferably 90Z10 or less.
- the volumes of the two are not extremely different in order for each phase to be a continuous phase.
- the volume ratio is more preferably 30Z70 or more, particularly preferably 40Z60 or more, further preferably 70Z30 or less, particularly preferably 60Z40 or less.
- the specific configuration of the active layer varies depending on the type of the organic photoelectric conversion element.
- Examples of the configuration of the active layer include a Barta hetero junction type, a stacked type (hetero pn junction type), a Schottky type, and a hybrid type.
- the Balta heterojunction type includes a p-type semiconductor and an n-type semiconductor in a single layer.
- a p-type semiconductor and an n-type semiconductor are phase-separated, and carrier separation occurs at the interface between the phases, and positive charges (holes) and negative charges (electrons) are generated in each phase. Is to be transported to.
- the phase separation structure is suitable for the light absorption process, exciton diffusion process, exciton dissociation (carrier separation) process, carrier transport process, etc. There is an influence to. Therefore, it is considered that good luminous efficiency can be realized by optimizing the phase separation structure.
- the active layer is composed of two or more layers, at least one layer is formed of a p-type pigment, and the other layer is formed of an n-type semiconductor. It is what. Then, a phase interface between the p-type semiconductor and the n-type semiconductor is formed at the boundary between the p-type semiconductor force layer and the n-type semiconductor force layer, and carrier separation occurs at the phase interface. It becomes like this.
- the active layer also has a layer force of two or more, and at least one of them includes a p-type semiconductor and an n-type semiconductor so that the p-type semiconductor and the n-type semiconductor are phase-separated. It is configured as follows. In this case, the phase interface formed between the stacked layers, the p-type semiconductor and the n-type Carrier separation occurs at both the phase interface in the phase including both of the semiconductors. Alternatively, in this case, for example, it can be expected that one carrier is blocked between the stacked layers to improve the electric extraction efficiency.
- a Schottky barrier is formed in the vicinity of an electrode, and carrier separation is performed in the internal electric field of this portion.
- the active layer is optional if it comprises two or more pigments.
- any of the above-mentioned Balta heterojunction type, stacked type, and a combination of both can be adopted, and particularly high characteristics (for example, conversion efficiency, etc.) ) Can be expected.
- the active layer contains a pigment and, for example, inorganic pigment particles such as titanium and zinc oxide.
- the active layer is configured as a mixed film of an inorganic pigment and an organic pigment.
- Inorganic pigments are excellent in durability, and various nanoparticles can be used.
- the hybrid type can be expected to have high efficiency of an organic photoelectric conversion element.
- the thickness of the active layer is not particularly limited.
- the active layer has a thickness of usually 5 nm or more, preferably lOnm or more, and usually 10 m or less, preferably 5 m or less in order to sufficiently absorb light and not deactivate the charge generated by light absorption. Then form.
- the manufacturing method of the organic photoelectric conversion element of the present embodiment is the same as that of the organic photoelectric conversion elements of the first to third embodiments described above except for the method of forming the active layers 9, 11 and 13. Therefore, the description other than the method for forming the active layer is omitted, and the method for forming the active layer will be described below.
- a conversion step conversion process of converting two or more kinds of latent pigments into pigments is performed before the step of forming the active layer.
- a film forming step for forming the latent pigment hereinafter referred to as “film formation process”.
- a latent pigment is formed. Film formation is performed by a coating method. If the latent pigment is in liquid form, it can be applied as it is, but normally, a coating solution prepared by dissolving the latent pigment in an appropriate solvent is prepared, and the coating solution is applied to the coating target such as a substrate or an electrode. Then, film formation is performed.
- solvents include aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane and decane; aromatic hydrocarbons such as toluene, benzene, xylene and black benzene; methanol, ethanol, propanol Lower alcohols such as butanol; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate, butyl acetate and methyl lactate; nitrogen-containing organic solvents such as pyridine and quinoline Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene; ethers such as e
- One solvent may be used, or two or more solvents may be used in any combination and ratio.
- the coating solution should contain at least one latent pigment! It is also possible to contain two or more latent pigments.
- the type of latent pigment used at that time, and the combination and ratio of two or more types of latent pigments depend on the type of organic photoelectric conversion element and the type and ratio of pigment contained in the active layer of the organic photoelectric conversion element. You can make an appropriate choice.
- the organic photoelectric conversion element is a Balta heterojunction type
- at least one of a p-type pigment and an n-type pigment may be included in the same active layer.
- latent pigments that are precursors of p-type pigments and precursors of n-type pigments It is possible to include at least one latent pigment and a total of two or more.
- each layer constituting the active layer may contain at least one kind of pigment. Therefore, the coating liquid corresponding to each layer may be used. As long as it contains at least one latent pigment.
- At least one latent pigment is included in the coating liquid as in the case of a laminate type, and even in this case, in the method for manufacturing an organic photoelectric conversion element of this embodiment, another layer is different from another layer.
- latent pigments By constructing with latent pigments, eventually two or more types of latent pigments will be converted into pigments.
- the coating solution may contain components other than the latent pigment and the solvent as long as the effects of the present invention are not significantly impaired.
- it contains dopants that control electrical properties such as electrical conductivity, inorganic pigment particles for use in hybrid organic photoelectric conversion elements, other organic pigment particles, organic semiconductor polymers, and organic semiconductor small molecules.
- these other components may contain one kind, or two or more kinds may be used in any combination and ratio.
- the concentration of the coating solution is not limited as long as a desired latent pigment layer can be formed. Therefore, the concentrations of the latent pigment and other components in the coating solution are arbitrary. However, in order to improve the coating property, it is preferable to select a solvent or set the concentration so that the viscosity of the coating solution falls within a viscosity range suitable for coating.
- the method of applying the coating solution! / ⁇ there is no limit to the method of applying the coating solution! / ⁇ .
- spin coating, casting from a solution, dip coating, blade coating, wire bar coating, gravure coating, spray coating, and the like can be used.
- the printing method include an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, and a flexographic printing method.
- the latent pigment layer solvent may be removed as necessary. Any method such as heat drying or reduced pressure drying can be used without any limitation on the method for removing the solvent.
- the latent pigment layer is often heated. In this case, the solvent is often dried and removed with heating. Therefore, the solvent may be removed together with the conversion step.
- the latent pigment layer After forming the latent pigment layer, the latent pigment layer is externally stimulated to convert the latent pigment into a pigment. Thereby, a pigment layer can be formed to be an active layer.
- the external stimulus for converting the latent pigment into the pigment is preferably a heat treatment among forces such as heat treatment and light irradiation.
- the heat treatment temperature depends on the material used, but is generally 80 ° C or higher, preferably 100 ° C or higher, and usually 350 ° C or lower, preferably 300 ° C or lower. Latent pigments that are converted at low temperatures may be difficult to handle due to poor stability of the latent pigment itself. On the other hand, if the temperature during the heat treatment is too high, the constituent members of the organic photoelectric conversion element such as the substrate and the electrode are required to have high heat resistance and the production cost may increase.
- the time for applying the external stimulus is also arbitrary, but in consideration of the manufacturing cost, it is preferably a short time.
- the time for applying external stimulus depends on the type of external stimulus, but examples of suitable ranges include 1 nanosecond to 1 second for laser heating and 1 second for normal heating. ⁇ 1 hour to heat for 1 hour to several days.
- the latent pigments contained in each layer are converted to pigments at once after laminating all of the latent pigment layers.
- the pigment obtained by the conversion is difficult to dissolve in the solvent, so it is dissolved by the coating solution used when the layer of the latent pigment previously formed at the time of stacking is laminated later. This is because it can be suppressed.
- a Balta heterojunction organic photoelectric conversion element when manufactured using a plurality of latent pigments, it contains at least one latent pigment corresponding to p-type and n-type pigments, and a total of two or more latent pigments.
- Prepare a coating solution At this time, the mixing ratio of the latent pigment contained in the coating solution may be set so as to be the ratio of the pigment in the active layer to be formed when the latent pigment is converted into the pigment.
- the latent pigment is preferably set in consideration of the decrease because the weight, the volume, and the like decrease when the latent pigment changes.
- the desired coating solution is applied to a substrate or electrode to form a latent pigment layer (film formation process). After that, two or more kinds of latent pigments in this layer are converted into pigments by an external stimulus such as heating (conversion process) to form an active layer containing the p-type pigment and the n-type pigment in the same layer. .
- the phase separation structure in the active layer can be variously controlled by the molecular structure of the pigment to be used and the film forming process.
- the phase separation structure can be controlled by changing the mixing ratio of the latent pigment to be mixed.
- difference in conditions of conversion of latent pigments to be used difference in heat conversion temperature, etc.
- performing operations such as converting only one and then converting the other, It is also possible to control the layer structure by controlling the conditions.
- a coating liquid containing at least one latent pigment corresponding to one of p-type and n-type is prepared, and the latent liquid is applied by applying the coating liquid.
- a pigment layer is formed (film formation step), and the latent pigment in the layer is converted into a pigment (conversion process).
- prepare a coating solution containing at least one latent pigment corresponding to the other of P-type or n-type apply the coating solution to form a layer of latent pigment (film formation step), and Convert latent pigment into pigment (conversion process).
- One of the layers constituting the active layer may contain two or more kinds of pigments.
- the two or more pigments may be either p-type or n-type or both, but usually both p-type and n-type are preferred.
- two or more latent pigments may be contained in the coating solution, and the film forming process and the conversion process may be repeated in the same manner. As a result, an organic photoelectric conversion element of a combination type of a norke heterojunction type and a stacked type can be manufactured.
- a configuration in which a latent pigment is used for the electrode interface layer (that is, the above-described p-type semiconductor layer and n-type semiconductor layer) is also possible.
- a Schottky barrier is used.
- An active layer may be provided so as to be in contact with the electrode forming the electrode.
- the formation method of the active layer in this case may be the same as the active layer of the multilayer type, which may be the same as that of the above-described Balta heterojunction type active layer. This makes it possible to form an active layer in which a non-heterojunction type or stacked type and a Schottky type are combined.
- a latent pigment layer is formed by applying a coating solution containing two or more kinds of latent pigments corresponding to only one of the p-type and n-type pigments (film-forming step), and the latent pigments. This layer may be converted to a pigment. This facilitates the formation of an active layer using two or more pigments, which has been difficult in the past.
- the coating liquid contains one or both of p-type and n-type inorganic pigment particles and the other or both of p-type and n-type pigments.
- the corresponding latent pigment is contained.
- the coating liquid is applied to a substrate or an electrode to form a latent pigment layer (film formation step), and the latent pigment layer is converted to a pigment (conversion step).
- the method of forming the active layer is the same as that of the laminated active layer, except that the inorganic pigment particles are included in the coating liquid.
- the active layer can be formed by combining the Balta heterojunction type or the laminated type and the hybrid type.
- the coating liquid contains a latent pigment corresponding to one of the p-type and n-type pigments as well as the inorganic pigment particles, and the active layer contains one of the p-type and n-type pigments. May be.
- any of these types can be implemented in combination with other types.
- two or more of the pigments contained in the active layer are latently transferred even if any type of organic photoelectric conversion element is produced. It is obtained by converting the pigment power.
- the phase interface becomes large, Power generation efficiency is expected to improve.
- a production method in which two or more kinds of pigments are contained in the layer is preferred.
- two or more kinds of latent pigments are mixed to add two or more kinds to the coating liquid. It is preferable that the latent pigment is contained, the coating solution is formed into a film, and the conversion step is performed.
- the organic photoelectric conversion device is manufactured through the conversion step of converting two or more kinds of latent pigments into pigments as described above, a long-life organic photoelectric conversion device can be manufactured using a coating method.
- the latent pigment that is the precursor is formed into a film, thereby effectively utilizing the good film formation property of the latent pigment and reducing the organic photoelectric conversion element. It becomes possible to manufacture at a cost.
- the manufacturing method of the organic photoelectric conversion element of the present embodiment by using two or more kinds of latent pigments, both the p-type pigment and the n-type pigment are formed using a coating method. Therefore, it is expected that the production cost of organic photoelectric conversion elements will be greatly reduced compared to the conventional method.
- an organic photoelectric conversion element of the present embodiment it is possible to realize a microphase separation structure of P-type and n-type pigments that express the mechanism of a Balta heterojunction type organic photoelectric conversion element.
- the efficiency of the organic photoelectric conversion element can be improved.
- a latent pigment and a material exhibiting semiconductor characteristics in a solid state are mixed and manufactured through a film forming step of forming a film by a coating method.
- An organic photoelectric conversion element to be described will be described. This is the first to third embodiments except that the active layer is obtained through a film forming process in which the latent pigment and the solid semiconductor material are mixed to form a film by a coating method. It is the same composition as.
- the organic photoelectric conversion element of this embodiment is the same as the organic photoelectric conversion element of the first to third embodiments described above except for the active layer. Therefore, descriptions other than the active layer are omitted.
- the active layer will be described below.
- the active layer is a layer formed between the pair of electrodes, a layer containing a semiconductor material, and a layer that absorbs light and separates charges.
- This active layer is only a single layer film. It may be constituted by two or more laminated films. However, in the case where the active layer is formed of a single layer film, the film is formed as a mixed semiconductor film containing a pigment and a solid semiconductor material. On the other hand, when the active layer is composed of two or more films, the active layer is formed by including at least one mixed semiconductor film containing a pigment and a solid semiconductor material.
- the mixed semiconductor film may contain components other than the pigment and the solid semiconductor material as long as the effects of the present invention are not significantly impaired. In addition, each of the pigment and the solid semiconductor material may be used alone, or two or more of them may be used in any combination and ratio.
- the mixed semiconductor film preferably has a phase separation structure. This is because when a mixed semiconductor film has a phase separation structure, carrier separation occurs due to light irradiation, and after holes and electrons are generated, there is a probability that they will reach the electrode without recombination. It is the power that can be expected to be high.
- the phase separation structure is a structure in which the materials constituting the phase (for example, pigments, solid semiconductor materials, etc.) are not uniformly mixed at the molecular level, and the respective materials are in an aggregated state. There is an interface between the aggregated states.
- This phase-separated structure can be observed by using a technique such as an optical microscope, an electron microscope, an atomic force microscope (AFM), or the like to examine the local structure, or by X-ray diffraction to observe diffraction originating from the agglomerated part. Can be confirmed.
- the solid semiconductor material exists in a solid state. Therefore, in the active layer, the solid semiconductor material exists in a state exhibiting semiconductor characteristics.
- the ratio between the pigment and the solid semiconductor material is not limited, and is arbitrary depending on the type and application of the organic photoelectric conversion element.
- the use ratio of the solid semiconductor material and the pigment is a volume ratio (weight Z density ratio) represented by “solid semiconductor material Z pigment”, which is usually 1Z99 or more, preferably 5Z95 or more, more preferably 10Z90 or more. Usually, it is 99Z1 or less, preferably 95Z5 or less, more preferably 90Z10 or less.
- the volume of each phase is not extremely different.
- the volume ratio is more preferably 30Z70 or more, particularly preferably 40Z60 or more, further preferably 70Z30 or less, and particularly preferably 60Z40 or less. If the amount of one of the pigment and the solid semiconductor material is too small, an island-like isolated phase tends to be formed.
- the active layer may have a film other than the mixed semiconductor film.
- the film other than the mixed semiconductor film forming the active layer there is no limitation on the film other than the mixed semiconductor film forming the active layer, and any film containing a semiconductor material is optional as long as the effect of the present invention is not significantly impaired.
- a film for example, a film formed only of a pigment exhibiting semiconductor characteristics, a film formed only of a solid semiconductor material, one of a pigment exhibiting semiconductor characteristics and a solid semiconductor material, and other than a pigment and a solid semiconductor material You may have the film
- the specific configuration of the active layer varies depending on the type of the organic photoelectric conversion element.
- Examples of the configuration of the active layer include a Barta hetero junction type, a stacked type (hetero pn junction type), a Schottky type, and a hybrid type.
- the non-heterojunction type includes a p-type semiconductor material and an n-type semiconductor material in a single active layer.
- a p-type semiconductor material and an n-type semiconductor material have a phase separation structure in which phase separation occurs, carrier separation occurs at the interface of the phase, and V and positive charges (holes) are generated in each phase. Negative charges (electrons) are separated and transported.
- the Balta heterojunction active layer is formed with a mixed semiconductor film having a phase separation structure.
- at least one of the p-type and n-type semiconductor materials is a solid semiconductor material.
- the other of the p-type and n-type semiconductor materials may be a solid semiconductor material, but a pigment exhibiting semiconductor characteristics, preferably derived from a latent pigment, is preferred.
- phase separation structure In a Balta heterojunction active layer, the phase separation structure has an influence on the light absorption process, exciton diffusion process, exciton dissociation (carrier separation) process, carrier transport process, etc. is there. Therefore, it is considered that a good photoelectric conversion efficiency can be realized by optimizing the phase separation structure.
- the active layer is composed of two or more films, and at least One film is formed containing a p-type semiconductor material, and the other film is formed containing an n-type semiconductor material. Then, a phase interface between the p-type semiconductor material and the n-type semiconductor material is formed at the boundary between the film containing the p-type semiconductor material and the film containing the n-type semiconductor material. Carrier separation is starting to occur.
- At least one of the p-type and n-type semiconductor materials is a solid semiconductor material.
- the other of the p-type and n-type semiconductor materials may be a solid semiconductor material or a pigment exhibiting semiconductor characteristics.
- at least one of the films forming the active layer is a mixed semiconductor film formed by containing a pigment together with a solid semiconductor material. In this case, the pigment has semiconductor characteristics. What is shown is preferred.
- the active layer is composed of two or more films, and at least one of these films contains a solid semiconductor material and a pigment, and the polarity of the majority carrier of the solid semiconductor material and the majority carrier of the pigment is changed.
- one of the p-type and n-type solid semiconductor materials and the other of the p-type and n-type pigment are phase-separated.
- carrier separation occurs at both the phase interface formed between the laminated films and the phase interface between the solid semiconductor material and the pigment in the mixed semiconductor film.
- it is expected that one carrier is blocked between the laminated films to improve the electric extraction efficiency.
- a Schottky barrier is formed in the vicinity of an electrode, and carrier separation is performed in the internal electric field of this portion. If an electrode that forms a Schottky barrier is used as the electrode, the active layer is optional as long as it includes at least one mixed semiconductor film. As the specific configuration of the active layer in the Schottky type, it is possible to adopt a deviation of the above-mentioned Balta heterojunction type, laminated type, or a combination of both, and particularly high characteristics (for example, conversion efficiency) Etc.) can be expected.
- the manufacturing method of the organic photoelectric conversion element of the present embodiment is the same as that of the organic photoelectric conversion elements of the first to third embodiments described above except for the method of forming the active layers 9, 11 and 13. Therefore, Descriptions other than the method of forming the active layer are omitted, and the method of forming the active layer will be described below.
- the step of forming the active layer the film forming step of mixing the latent pigment and the solid semiconductor material and forming the precursor film by a coating method, After the film forming step, a conversion step for converting the latent pigment into the pigment is performed. Thereby, a mixed semiconductor film containing a solid semiconductor material and a pigment can be formed. This mixed semiconductor film itself is used as an active layer, or the mixed semiconductor film is combined with other films to form an active layer.
- a precursor film is formed.
- the film forming method is not particularly limited as long as the latent pigment and the solid semiconductor material are mixed to form a film by a coating method. If the latent pigment or the solid semiconductor material is in a liquid state, it is possible to mix both of them and apply it as it is, but usually the latent pigment is dissolved in an appropriate solvent and the solid semiconductor material is dissolved or dispersed in the solvent. A coating solution is prepared, and this coating solution is applied to a coating target such as a substrate and an electrode to form a film.
- the solvent for the coating solution is not limited, and any solvent that dissolves the latent pigment can be used.
- solvents include aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane and decane; aromatic hydrocarbons such as toluene, benzene, xylene and black benzene; methanol, ethanol, Lower alcohols such as propanol and butanol; Ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; Esters such as ethyl acetate, butyl acetate and methyl lactate; Nitrogen-containing organics such as pyridine and quinoline Solvents: Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene; Ethers such as e
- the coating solution may contain at least one latent pigment, but it may contain two or more latent pigments.
- the types of latent pigments used and the combination and ratio of two or more types of latent pigments depend on the type of organic photoelectric conversion element and the type and ratio of pigments contained in the active layer of the organic photoelectric conversion element. Appropriate selection should be made accordingly.
- solid semiconductor materials may also be contained in the coating solution in two or more kinds in any combination and ratio.
- the solid semiconductor material may be in any state during the manufacturing process as long as it functions as a semiconductor in a solid state in the manufactured organic photoelectric conversion element. It may be dissolved or dispersed in particulate form. At this time, when two or more kinds of solid semiconductor materials are used, only one of those dissolved or dispersed in the coating solution may be contained, or both of them may be contained. However, it is preferable to use a solid semiconductor material that is dispersed in the form of particles in the coating solution.
- the range of the particle size of the solid semiconductor material in the coating liquid is the same as the range described above as a preferable particle size of the solid semiconductor material in the active layer.
- the solid semiconductor material has a particle size in a suitable range.
- the solid semiconductor material preferably has a particle size that is treated as exemplified below if necessary. It is possible to rub it within the proper range.
- the solid semiconductor material is pulverized to produce solid semiconductor material particles.
- the solid or semiconducting material particles are produced by converting or synthesizing the precursor material in the gas phase.
- a solid semiconductor material is deposited on the oil film by vacuum deposition or sputtering, and the film is collected together with the oil film to obtain particles of the solid semiconductor material.
- the latent pigment, solid semiconductor Components other than the body material and the solvent may be contained.
- a dispersing agent such as a surfactant may be contained.
- a dopant that controls electrical properties such as electrical conductivity in the active layer may be contained.
- components other than the latent pigment and the solvent may be used alone, or two or more may be used in any combination and ratio.
- the concentration of the coating solution is not limited as long as a desired mixed semiconductor film can be formed. Therefore, the concentrations of the latent pigment, the solid semiconductor material, and other components in the coating solution are arbitrary. However, in order to improve the coating properties, it is preferable to select a solvent or set the concentration so that the viscosity of the coating solution falls within the viscosity range suitable for coating. At this time, the ratio of the latent pigment to the solid semiconductor material in the coating liquid is such that the volume ratio represented by the “solid semiconductor material Z pigment” falls within the above-described preferable range when the latent pigment is converted into the pigment. U, desired to set up.
- the latent pigment when preparing the coating liquid, there is no limitation on the mixing order of the latent pigment, the solid semiconductor material and the solvent, and other components.
- the latent pigment after dissolving or dispersing the solid semiconductor material in the solvent, the latent pigment may be dissolved in the solvent.
- the solid semiconductor material After the latent pigment is dissolved in the solvent, the solid semiconductor material may be dissolved or dispersed in the solvent. ⁇ .
- the coating liquid sufficiently disperses the solid semiconductor material by sufficiently dispersing the solid semiconductor material.
- the concentration and stirring state of the coating liquid may be controlled, or ultrasonic treatment may be performed.
- the prepared coating solution is applied to a coating target (usually a substrate or an electrode) by an appropriate coating method to form a precursor film.
- the coating method used at this time is not limited, but examples thereof include spin coating, casting from a solution, dip coating, blade coating, wire coating, gravure coating, and spray coating.
- 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.
- the solvent may be removed from the precursor film as necessary. Drying under reduced pressure and drying without limitation on solvent removal methods Any method can be used.
- the precursor film is often heated. In this case, the solvent is often dried and removed together with the heating. Therefore, the solvent may be removed together with the conversion step.
- the precursor film can be formed by the film forming process described above. At this time, even if the solid semiconductor material is dispersed in the form of particles in the coating solution, the solid semiconductor material is dispersed as well in the precursor film as in the coating film, and the latent pigment is also dispersed. Since it is once dissolved in the solvent, it is dispersed with high dispersibility. On the other hand, if the solid semiconductor material is dissolved in the coating solution! / Soot, both the latent pigment and the solid semiconductor material are once dissolved in the solvent. Each semiconductor material is highly dispersible.
- the precursor film is stimulated from the outside, and the latent pigment is converted into a pigment while maintaining the dispersed state in the precursor film. Thereby, a mixed semiconductor film containing the pigment and the solid semiconductor material can be formed. At this time, since the latent pigment is converted to the pigment while maintaining the dispersion state in the precursor film, the dispersibility of the pigment and the solid semiconductor material is kept good even in the mixed semiconductor film.
- the external stimulus for converting the latent pigment into the pigment is preferably heat treatment among forces such as heat treatment and light irradiation.
- the heat treatment temperature depends on the material used, but is generally 80 ° C or higher, preferably 100 ° C or higher, and usually 350 ° C or lower, preferably 300 ° C or lower. Latent pigments that are converted at low temperatures may be difficult to handle due to poor stability of the latent pigment itself. On the other hand, if the temperature during the heat treatment is too high, the constituent members of the organic photoelectric conversion element such as the substrate and the electrode are required to have high heat resistance and the production cost may increase.
- the time for applying the external stimulus is also arbitrary, but considering the manufacturing cost, it is preferably a short time.
- the time for applying external stimulus depends on the type of external stimulus, but examples of suitable ranges include 1 nanosecond to 1 second for laser heating and 1 second for normal heating. ⁇ 1 hour to heat for 1 hour to several days.
- the atmosphere in which the conversion process is performed can be performed in air, but the influence of oxidation and the like is suppressed. Therefore, it is preferable to carry out in an inert gas such as nitrogen or argon, or in a vacuum.
- an inert gas such as nitrogen or argon
- the crystal state of the pigment to be generated can be controlled by the heating rate or the cooling rate.
- the mixed semiconductor film can be formed by the conversion step.
- this mixed semiconductor film alone constitutes the active layer.
- each mixed semiconductor film can be formed by repeating the above-described coating process and conversion process.
- the active layer is formed by laminating two or more mixed semiconductor films, the latent pigment contained in each precursor film is converted to a pigment at a time after all the precursor films are laminated and formed.
- the pigment obtained by the conversion is usually difficult to dissolve in a solvent, so that the precursor film previously formed at the time of lamination is dissolved and disturbed by the coating solution used when the film is later laminated. It is also a force that can be suppressed.
- the active layer may include a film other than the mixed semiconductor film.
- the method for forming a film other than the mixed semiconductor film there is no limit to the method for forming a film other than the mixed semiconductor film. Therefore, for example, the electrode interface layer described above can be formed by any known method.
- a Balta heterojunction organic photoelectric conversion element when producing a Balta heterojunction organic photoelectric conversion element, if a mixed semiconductor film is formed using a pigment exhibiting semiconductor characteristics and a solid semiconductor material, first, at least p-type and n-type A coating solution containing a latent pigment corresponding to one pigment, the other solid semiconductor material of p-type and n-type, and a solvent is prepared. At this time, the mixing ratio of the latent pigment and the solid semiconductor material to be contained in the coating liquid is such that when the latent pigment is converted into the pigment, the pigment and the solid semiconductor material are suitable in the mixed semiconductor film to be formed. Set it to be within the ratio range!
- latent pigments usually have a reduced weight, volume, etc. when converted to pigments. It is preferable to set in consideration of the decrease amount of.
- the prepared coating liquid is applied to a substrate or an electrode to form a precursor layer (film formation process). Thereafter, the latent pigment in the precursor layer is converted into a pigment by an external stimulus such as heating (conversion process), and one of the p-type and n-type pigments and the other p-type and n-type solid semiconductor material A mixed semiconductor film included in the same film is formed.
- the mixed semiconductor film itself can be used as an active layer.
- the phase separation structure in the active layer can be controlled in various ways depending on the molecular structure of the pigment and the solid semiconductor material used and the film formation process.
- the phase separation structure can be controlled by changing the mixing ratio of the latent pigment to be mixed and the solid semiconductor material.
- the solid semiconductor material those dispersed as particles in the coating solution can be used, or those dissolved in the solvent can be used.
- an organic photoelectric conversion element of the present embodiment since a pigment derived from a latent pigment forms a phase separation structure with a solid semiconductor material, a Balta heterojunction type organic photoelectric conversion is performed.
- a film suitable for the element can be formed.
- pigment exhibiting semiconductor characteristics is shown, but a pigment having no semiconductor characteristics may be used depending on the use of the organic photoelectric conversion element or the like. In that case, at least one p-type and n-type solid semiconductor material is used. Examples of such pigments include those that exhibit only a sensitizing action and do not conduct electricity.
- a film containing one of the p-type and n-type solid semiconductor materials and a film containing the other p-type and n-type solid semiconductor materials is formed as a mixed semiconductor film by the film formation process and the conversion process described above.
- a coating liquid containing one of the p-type and n-type solid semiconductor materials, the latent pigment and the solvent is prepared, and this coating liquid is applied.
- a precursor film is formed (film formation process), and the latent pigment in the precursor film is converted into a pigment (conversion process).
- the pigment may or may not have semiconductor characteristics. However, if the pigment exhibits semiconductor properties, the majority carrier of the pigment and the majority carrier of the solid semiconductor material May be of the same polarity, but are preferably reversed. Thereby, the organic photoelectric conversion element of the type which combined the Balta heterojunction type and the laminated type can be manufactured.
- an active layer may be provided so as to be in contact with the electrode forming the Schottky barrier.
- the formation method of the active layer in this case may be the same as the active layer of the multilayer type, which may be the same as that of the above-described Balta heterojunction type active layer. This makes it possible to form an active layer in which a non-heterojunction type or stacked type and a Schottky type are combined.
- the method for forming a hybrid active layer is the same as that described above except that both the organic substance and the inorganic substance are contained in the mixed semiconductor film. It may be the same as the active layer of the Barta heterojunction type or the same as the stacked type active layer.
- at least two kinds of organic substances and inorganic substances are used as pigments
- at least two kinds of organic substances and inorganic substances are used as solid semiconductor materials
- organic substances are used as one of pigments and solid semiconductor materials.
- an inorganic substance may be used as the other of the pigment and the solid semiconductor material.
- use only one of the organic substance and inorganic substance as the pigment and solid semiconductor material and contain a substance other than the pigment and solid semiconductor material as the other of the organic substance and inorganic substance.
- More specific examples include, in addition to latent pigments, solid semiconductor materials and solvents, inorganic pigment particles such as titer and zinc oxide, perylene pigments, quinacridone pigments and phthalocyanines in the coating solution. What is necessary is just to mix organic pigment particles, such as a pigment. As a result, a hybrid active layer containing both an organic substance and an inorganic substance can be formed.
- the active layer is provided with a mixed semiconductor film and the mixed semiconductor is used regardless of the type of organic photoelectric conversion element.
- the film is formed through a film forming process.
- the phase interface becomes large, Improved power generation efficiency I think that. Furthermore, in the manufacturing method of the present embodiment, it is possible to form a film in which the solid semiconductor material and the pigment are well dispersed. Therefore, in the mixed semiconductor film, the majority carriers and pigments of the solid semiconductor material are mixed. It is preferable to reverse the polarity of the majority carrier.
- An active layer may be formed by providing a film other than a semiconductor film. At this time, a film other than the mixed semiconductor film may be manufactured by an arbitrary method.
- the organic photoelectric conversion element of this embodiment As described above, according to the method for manufacturing an organic photoelectric conversion element of the present embodiment, it is possible to manufacture the organic photoelectric conversion element using a coating process.
- the pigment is generally highly durable.
- the organic photoelectric conversion element of this embodiment provided with the mixed semiconductor film in which the solid semiconductor material and the pigment are dispersed in the active layer can realize a long life.
- the organic photoelectric conversion element manufactured by the method for manufacturing the organic photoelectric conversion element of the present embodiment has a good dispersion of pigment and solid semiconductor material in the mixed semiconductor film. For this reason, a high photoelectric conversion rate is realizable.
- the range of the photoelectric conversion rate is usually 3% or more, preferably 5% or more, more preferably 7% or more. Moreover, the higher the upper limit, the better.
- a mixed film of an organic pigment and particles can be obtained as a mixed semiconductor film.
- a mixed semiconductor film has been very difficult to manufacture with conventional techniques, and the ability to manufacture such a film is one of the great advantages.
- the mixed semiconductor film is a mixed film containing an organic pigment and inorganic particles, it is possible to further increase the durability of the organic photoelectric conversion element by effectively utilizing the high and durability of the inorganic particles. Therefore, it is preferable.
- inorganic particles having no semiconductor characteristics can be used together with or instead of the solid semiconductor material. Also in this case, it is possible to obtain an advantage that an organic photoelectric conversion element having a mixed film having an organic pigment and inorganic particles that has been difficult to manufacture can be easily manufactured.
- the following bicyclo compound (11A) can be converted to a planar molecule (11B) by heating to about 250 ° C.
- n-type highly doped silicon substrate with a 300 nm thermal acid-silica film formed on a chromium 5 nm, gold lOOnm electrode with a width of 10 ⁇ m and a length of 500 ⁇ m is patterned.
- This bicyclo compound (11A) was applied to form a film so as to cover the gap portion, and heat-converted at 230 ° C.
- Field effect transistor thus obtained, it showed an n-type characteristics, saturation mobility of electrons showed 1. 2 X 10 _3 C m 2 ZVs and high performance.
- the compound (7A) has the same field effect transistor structure as that described above, as described in JP-A-2004-6750, and is subjected to thermal conversion at about 200 ° C. It shows a mobility of about 0.01 to 0.1 cm 2 ZVs.
- An organic photoelectric conversion device was prepared and evaluated using two latent pigments of the compound (7A) and the bicyclo compound (11A).
- an indium stannate (ITO) transparent conductive film deposited on a glass substrate with a thickness of 145 nm (sheet resistance: 8.4 ⁇ ) is 2 mm wide using normal photolithography and hydrochloric acid etching.
- a transparent electrode was formed by patterning the stripes. The patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant, water with ultrapure water, ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally UV ozone cleaning.
- a conductive polymer poly (ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS, manufactured by Starck Vitec, product name Baytron PH), is a 40 nm film. After spin coating with a thickness, it was dried by heating at 120 ° C for 10 minutes in the air.
- the substrate was brought into the glove box and operated in a nitrogen atmosphere.
- the substrate was heat-treated at 180 ° C. for 3 minutes in a nitrogen atmosphere.
- a solution of 1% by weight of compound (7A) dissolved in 1: 1 mixed solvent (weight) of Kuroguchi Form Z Chlorobenzene is spin-coated at 1500rpm after filtration, heated at 250 ° C for 20 minutes, and compound ( 7B) was obtained. And, deposited by spin coating black port Holm bicyclo compound to 0.5 weight 0/0 dissolved also was (11A) by filtration after 1500 rpm, 250. 40 minutes at C, 280. The film of compound (11B) was laminated by heating at C for 20 minutes.
- the substrate on which the series of organic layers was formed was placed in a vacuum evaporation apparatus. Therefore, the following phenantorin phosphorus derivative (commonly referred to as BCP) was added, heated and evaporated.
- BCP phenantorin phosphorus derivative
- the vacuum degree during vapor deposition was about 10 _4 Pa, deposition rate was about InmZ seconds. This makes the film thickness 6n m films were stacked.
- an organic thin film organic photoelectric conversion element having an organic photoelectric conversion element force having a light-receiving area portion having a size of 2 mm ⁇ 2 mm was obtained.
- the organic photoelectric conversion element was irradiated with light from a solar simulator (AMI. 5G) at an irradiation intensity of lOOmWZcm 2, and the voltage-current characteristics were measured.
- the photoelectric conversion characteristics of short circuit current (Jsc) 2.9mAZcm 2 , energy conversion efficiency ( ⁇ ) 0.16%, form factor (FF) 0.40 were obtained.
- the maximum value of external quantum efficiency was 21% at a wavelength of 470 nm.
- the spectral sensitivity was expressed by the ratio of the amount of current to one photon measured by irradiating monochromatic light and measuring the intensity of the photoelectrically converted current.
- ITO indium stannate oxide
- poly (ethylenedioxythiophene) poly (Styrene sulfonic acid) (PEDOT: PSS, manufactured by Starck Vitech, product name Baytron PH) was spin-coated at a film thickness of 40 nm, and then dried by heating at 120 ° C for 10 minutes in the air.
- PEDOT poly (Styrene sulfonic acid)
- the substrate was brought into the glove box and worked in a nitrogen atmosphere.
- the substrate was heat-treated at 180 ° C. for 3 minutes in a nitrogen atmosphere.
- Chloform Form Z Chlorobenzene A 0.25 wt% solution of the following compound (12A) in a 1: 1 mixed solvent (weight) is filtered, spin-coated at 1500rpm, heated at 180 ° C for 20 minutes, A film of the compound (12B) was obtained.
- Chromium Form Z A solution of 1.2% by weight of Compound (12A) in a 1: 1 mixed solvent (weight) of chlorobenzene and PCBNB (the following compound (12C)) from Frontier Carbon Co. Prepare an 8% by weight solution, mix it at a weight ratio of 1: 1, filter, spin coat at 1500rpm, and heat at 180 ° C for 20 minutes to mix compound (12B) and compound (12C) A membrane was obtained.
- the substrate on which the series of organic layers was formed was placed in a vacuum evaporation apparatus. Therefore, the following phenantorin phosphorus derivative (commonly referred to as BCP) was added, heated and evaporated. The deposition rate was about InmZ seconds. Thereby, a film having a thickness of 6 nm was laminated.
- BCP phenantorin phosphorus derivative
- a 2 mm wide striped shadow mask was used as a mask for forming the upper electrode.
- the light electrode was placed in a separate vacuum evaporation system in close contact with the element so as to be orthogonal to the ITO stripe.
- aluminum was vapor-deposited on the BCP layer at a film thickness of 80 nm at a vapor deposition rate of 3 nm / second to form an upper electrode.
- an organic thin film solar cell having an organic photoelectric conversion element power having a light receiving area portion of 2 mm ⁇ 2 mm in size was obtained.
- the maximum value of external quantum efficiency was 56% at a wavelength of 470 nm.
- the spectral sensitivity was expressed by the ratio of the amount of current to one photon measured by irradiating monochromatic light and measuring the intensity of the photoelectrically converted current.
- Example 2 when the mixed layer of the compound (12B) and the compound (12C) was formed, the compound (12A) was added to 0.8% by weight in a 1: 1 mixed solvent (weight) of the black mouth form Z black mouth benzene. Except that the dissolved solution and a solution in which compound (12C) was dissolved by 1.2% by weight were mixed, mixed at a weight ratio of 1: 1, and annealed at 160 ° C for 20 minutes. Thus, an organic photoelectric conversion element was produced.
- PEDOT: PSS PH; 40 nm
- Clariant Japan PV— Fast Red B O. 3g Cyclohexanone 30ml with glass beads
- the mixture was stirred for 6 hours to disperse, and the glass beads were filtered to prepare a dispersion.
- a cyclohexanone solution of 0.4% by mass of the compound (12A) was prepared.
- the two solutions were mixed 1: 1. This was spin-coated at lOOOOrpm and annealed at 210 ° C to obtain a 40 nm film.
- 50 nm of aluminum was vapor-deposited to produce a sandwich type device.
- Luminace Ace LA-1 00SAE manufactured by Hayashi Watch Industry
- An organic photoelectric light emitting device having the structure shown in FIG. 1 was produced by the following method.
- a 145 nm layer of indium stannate (ITO) transparent conductive film (sheet resistance 8.4 ⁇ ) on a glass substrate [2] was used, using ordinary photolithography technology and hydrochloric acid etching.
- a transparent electrode [3] was formed by patterning into a 2 mm wide stripe. The patterned transparent electrode [3] is cleaned in the order of ultrasonic cleaning with surfactant, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally UV ozone cleaning. I did it.
- PEDOT poly (styrenesulfonic acid)
- fullerene compounds F- 4 (called PCBM) with a black hole benzene 1.2 weight 0/0 dissolved force solution, the base emission zone poly Fi electron donor layer linker also in [5] Spin coat on top. After coating, heat treatment was performed at 150 ° C. for 10 minutes, and an electron acceptor layer [6] having an average film thickness of 40 nm was laminated.
- PCBM fullerene compounds F- 4
- the substrate [2] on which the series of organic layers [4] [5] [6] was formed was placed in a vacuum deposition apparatus.
- vacuum degree of the vacuum deposition instrumentation ⁇ it was evacuated with a cryopump until 1. 9 X 10 _4 Pa.
- the following phenant mouth phosphorus derivative (commonly referred to as BCP) was placed in a metal boat arranged in a vacuum deposition apparatus and heated to deposit the phenant mouth phosphorus derivative.
- the vacuum degree during deposition was 1. 7 X 10 _4 Pa, the deposition rate was 1. OnmZ seconds.
- a 6 nm thick film was laminated on the electron acceptor layer [6] to complete the n-type semiconductor layer [7].
- a 2 mm wide stripe-shaped shadow mask is brought into close contact with the element so as to be orthogonal to the ITO stripe of the transparent electrode [3], and is placed in another vacuum deposition apparatus. installed.
- the degree of vacuum in the vacuum deposition instrumentation ⁇ was evacuated until 7. 6 X 10 _5 Pa.
- aluminum was deposited at a film thickness of 80 nm on the n-type semiconductor layer [7] at a deposition rate of 3 nm Z seconds to form the upper electrode [8].
- an organic thin-film solar cell consisting of an organic photoelectric conversion element [1] having a light-receiving area portion having a size of 2 mm ⁇ 2 mm was obtained.
- the maximum value of external quantum efficiency was 52% at a wavelength of 460 nm.
- the spectral sensitivity was expressed by the ratio of the amount of current to one photon measured by irradiating monochromatic light and measuring the intensity of the photoelectrically converted current. Absorption correction was not performed. The same applies to the following examples and comparative examples.
- An organic photoelectric conversion element was produced in the same manner as in Example 1 except that copper phthalocyanine was formed to a film thickness of 25 nm by a vacuum deposition method as the electron donor layer [5].
- the organic photoelectric conversion device was irradiated with solar simulator (AMI. 5G) light at an irradiation intensity of lOOmWZcm 2 and measured for voltage-current characteristics.
- the open circuit voltage (Voc) O. 57 V, the short-circuit current ( Jsc) 3.3mAZcm 2 , energy conversion efficiency ( ⁇ ) 0.72%, form factor (FF) 0.38 were obtained.
- the maximum value of the external quantum efficiency was 19% at a wavelength of 620 nm.
- a coating solution for the benzoborphyrin compound BP-1 use a solution prepared by dissolving 1.0% by weight of the precursor in a mixed solvent of black mouth form and black mouth benzene (mixed at a weight ratio of 1: 1).
- the organic photoelectric conversion element was fabricated in the same manner as in Example 5 except that after spin coating on the organic semiconductor layer, heating was performed at 210 ° C. for 30 minutes to obtain an electron donor layer [5] having a thickness of 85 nm. Produced.
- the organic photoelectric conversion device was irradiated with solar simulator (AMI. 5G) light at an irradiation intensity of lOOmWZcm 2 and measured for voltage-current characteristics.
- AMI. 5G solar simulator
- the shape factor (FF) 0. 50 the photoelectric conversion characteristics that were obtained.
- the maximum value of the external quantum efficiency was 54% at a wavelength of 620 nm.
- Example 7 As the coating liquid for the PCBM, using a solution prepared by dissolving in 1.2 weight 0/0 in toluene, after a spin over preparative and heated at 65 ° C 10 minutes, the electron acceptor layer having a thickness of 40nm to [6] An organic photoelectric conversion device was produced in the same manner as in Example 6 except that it was formed.
- This organic photoelectric conversion element was irradiated with light from a solar simulator (AMI. 5G) at an irradiation intensity of lOOmWZcm 2 and measured for voltage-current characteristics. As a result, the open circuit voltage (Voc) O. 55 V The photoelectric conversion characteristics of short-circuit current (Jsc) 5.6mAZcm 2 , energy conversion efficiency (p) 1.74%, form factor (FF) 0.56 were obtained.
- the maximum value of the external quantum efficiency was 50% at a wavelength of 460 nm.
- An organic photoelectric conversion device was produced in the same manner as in Example 7 except that the heat treatment after spin cording performed at the time of forming the electron acceptor layer [6] was changed to 90 ° C. for 10 minutes.
- the organic photoelectric conversion element was irradiated with solar simulator (AMI. 5G) light at an irradiation intensity of lOOmWZcm 2 and the voltage-current characteristics were measured.
- the open circuit voltage (Voc) O. 56 V, the short-circuit current ( Jsc) 6.5mAZcm 2 , energy conversion efficiency (p) 1.85%, form factor (FF) 0.51 were obtained.
- An organic photoelectric conversion device was produced in the same manner as in Example 7 except that fullerene compound F-5 was used instead of PCBM.
- the maximum value of the external quantum efficiency was 54% at a wavelength of 460 nm.
- Example 10 The organic photoelectric conversion device [10] having the structure shown in FIG. 2 in which the benzoborphyrin compound BP-1 is disposed between the p-type organic semiconductor layer [4] and the active layer [11] is prepared by the following method. Produced.
- a P-type organic semiconductor layer [4] was formed in the same manner as in Example 1 on a glass substrate [2] on which a transparent electrode [3] was formed by ITO.
- the BP-1 precursor which is a precursor of the benzoborphyrin compound BP-1
- a mixed solvent weight ratio 1: 1 of black mouth form and black mouth benzene at 0.25 wt%.
- the melted solution was spin-coated on the p-type organic semiconductor layer [4].
- heat treatment was performed on a hot plate at 210 ° C. for 30 minutes to form a crystalline benzoborphyrin compound layer [5] having an average film thickness of 20 nm.
- a film was formed at 15 nm to form a mixed active layer [11]. Furthermore, C is 30nm and BCP is 6
- the n-type semiconductor layer [7] was formed on the mixed active layer [11] by laminating by nm and vacuum deposition. Finally, as in Example 1, aluminum was formed as the upper electrode [8] to complete the organic photoelectric conversion element [10].
- the organic photoelectric conversion element [10] was irradiated with light from a solar simulator (AMI. 5G) at an irradiation intensity of lOOmW Zcm 2 and measured for voltage-current characteristics.
- the photoelectric conversion characteristics of 40V, short-circuit current (Jsc) 8.9mAZcm 2 , energy conversion efficiency (p) 1.74%, form factor (FF) O. 49 were obtained.
- the method for producing an organic photoelectric conversion element and the organic photoelectric conversion element of the present invention can be used in any industrial field.
- a photovoltaic power generation element solar cell
- an image sensor etc. It is suitable for use.
- Japanese patent application filed on November 29, 2006 Japanese Patent Application No. 2006-3214705
- Japanese patent application filed on May 1, 2007 Japanese Patent Application No. 2007-121209
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Abstract
Description
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Priority Applications (5)
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US12/299,183 US9136489B2 (en) | 2006-05-02 | 2007-05-01 | Method for producing organic photoelectric conversion device and organic photoelectric conversion device |
KR20087029231A KR101197505B1 (ko) | 2006-05-02 | 2007-05-01 | 유기 광전 변환 소자의 제조 방법 및 유기 광전 변환 소자 |
EP07742773A EP2023419A4 (en) | 2006-05-02 | 2007-05-01 | PROCESS FOR PRODUCING AN ORGANIC PHOTOELECTRIC TRANSMITTER ELEMENT AND ORGANIC PHOTOELECTRIC CONVERTER ELEMENT |
KR1020117018520A KR101165656B1 (ko) | 2006-05-02 | 2007-05-01 | 유기 광전 변환 소자의 제조 방법 및 유기 광전 변환 소자 |
CN200780015742XA CN101432904B (zh) | 2006-05-02 | 2007-05-01 | 有机光电转换元件的制造方法和有机光电转换元件 |
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JP2006321475A JP5243714B2 (ja) | 2006-11-29 | 2006-11-29 | 有機光電変換素子の製造方法及び有機光電変換素子 |
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EP (1) | EP2023419A4 (ja) |
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KR101165656B1 (ko) | 2012-07-16 |
EP2023419A4 (en) | 2013-03-13 |
EP2023419A1 (en) | 2009-02-11 |
CN101432904B (zh) | 2012-03-21 |
US9136489B2 (en) | 2015-09-15 |
KR20110106439A (ko) | 2011-09-28 |
KR101197505B1 (ko) | 2012-11-09 |
US20090308458A1 (en) | 2009-12-17 |
KR20090017552A (ko) | 2009-02-18 |
CN101432904A (zh) | 2009-05-13 |
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