WO2016143526A1 - 光電変換素子、太陽電池および組成物 - Google Patents
光電変換素子、太陽電池および組成物 Download PDFInfo
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- WO2016143526A1 WO2016143526A1 PCT/JP2016/055520 JP2016055520W WO2016143526A1 WO 2016143526 A1 WO2016143526 A1 WO 2016143526A1 JP 2016055520 W JP2016055520 W JP 2016055520W WO 2016143526 A1 WO2016143526 A1 WO 2016143526A1
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- H—ELECTRICITY
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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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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L2031/0344—Organic materials
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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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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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
- H10K30/50—Photovoltaic [PV] devices
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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
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photoelectric conversion element, a solar cell, and a composition.
- Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like. Solar cells are expected to be put into full-scale practical use as non-depleting solar energy. Among these, a dye-sensitized solar cell using an organic dye or a Ru bipyridyl complex as a sensitizer has been actively researched and developed, and the photoelectric conversion efficiency has reached about 11%.
- a photoelectric conversion element or a solar cell using a compound having a perovskite crystal structure (hereinafter also referred to as “perovskite compound”) has achieved certain results in improving photoelectric conversion efficiency.
- perovskite compound a compound having a perovskite crystal structure
- photoelectric conversion elements or solar cells using perovskite compounds have attracted attention in recent years, and little is known about battery performance other than photoelectric conversion efficiency.
- the photoelectric conversion element and the solar cell are required to have durability capable of maintaining initial performance in the field environment where they are actually used.
- perovskite compounds are susceptible to damage in a high humidity environment.
- photoelectric conversion elements or solar cells using a perovskite compound as a light absorber often have a significant decrease in photoelectric conversion efficiency in a high humidity environment.
- An object of the present invention is to provide a photoelectric conversion element using a perovskite compound as a light absorber in a photosensitive layer and having excellent moisture resistance.
- this invention makes it a subject to provide the solar cell using the said photoelectric conversion element.
- this invention makes it a subject to provide a composition suitable for forming the photosensitive layer of the said photoelectric conversion element.
- the present inventors have an organic compound having a silyl group as at least a part of the organic cation. It has been found that by using a cation, a photoelectric conversion element or a solar cell can be obtained in which the photoelectric conversion efficiency is hardly lowered even in a high humidity environment.
- the present invention has been further studied based on these findings and has been completed.
- the light absorber includes a compound having a perovskite crystal structure having an organic cation, a cation of a metal atom other than the Group 1 element of the periodic table, and an anion, and at least a part of the organic cation constituting the compound
- a photoelectric conversion element in which is an organic cation having a silyl group is represented by the following formula (1).
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group.
- R 2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group.
- L represents a divalent linking group.
- R 1 is an alkyl group, an aryl group, or a heteroaryl group.
- L is a divalent linking group selected from an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, —O—, —S—, and —NR L —, or The photoelectric conversion element according to [2] or [3], which is a divalent linking group formed by combining two or more types of these linking groups.
- R L represents a hydrogen atom or an alkyl group.
- a composition comprising a compound represented by the following formula (1a) and a metal halide.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group.
- R 2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group.
- L represents a divalent linking group.
- Hal represents a halogen atom.
- each chemical formula may be expressed as a descriptive formula in order to understand the chemical structure of the perovskite compound. Accordingly, in each chemical formula, the partial structure is referred to as a (substituted) group, ion, atom, or the like. In this specification, these are represented by the above formula in addition to the (substituted) group, ion, atom, or the like. It may mean an element group or an element constituting a (substituent) group or ion.
- the term “compound” is used to mean not only the compound itself but also its salt and its ion. Furthermore, a group or compound that does not clearly indicate substitution or non-substitution is meant to include a group or compound having an arbitrary substituent as long as a desired effect is obtained.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the photoelectric conversion element and the solar cell of the present invention are excellent in moisture resistance while having a structure containing a perovskite compound as a light absorber.
- the composition of the present invention can be suitably used for forming a photosensitive layer in the production of the photoelectric conversion element of the present invention.
- the photoelectric conversion element of the present invention has a first electrode having a conductive support, a photosensitive layer containing a light absorber, and a second electrode facing the first electrode.
- the first electrode and the second electrode face each other means that the first electrode and the second electrode are stacked in contact with each other, and the first electrode and the second electrode are stacked via another layer. (That is, a form in which the first electrode and the second electrode are provided facing each other across another layer).
- the photoelectric conversion element of the present invention preferably has a hole transport layer provided between the first electrode and the second electrode.
- the photosensitive layer and the second electrode are provided on the conductive support in this order.
- the photoelectric conversion element has a hole transport layer
- the photosensitive layer, the hole transport layer, and the second electrode are provided on the conductive support in this order.
- the hole transport layer may be provided between the conductive support and the photosensitive layer.
- the hole transport layer, the photosensitive layer, and the second electrode are provided on the conductive support in this order.
- the light absorber contains at least one perovskite compound described later.
- the light absorber may contain a light absorber other than the perovskite compound in combination with the perovskite compound. Examples of the light absorber other than the perovskite compound include metal complex dyes and organic dyes.
- “having a photosensitive layer on a conductive support” means an embodiment having a photosensitive layer in contact with the surface of the conductive support, and another layer above the surface of the conductive support. It is meant to include embodiments having a photosensitive layer.
- examples of other layers provided between the conductive support and the photosensitive layer include a porous layer, a blocking layer, and an electron.
- examples include a transport layer and a hole transport layer.
- the photosensitive layer is provided in the form of a thin film on the surface of the porous layer (see FIG. 1). ), An embodiment provided thick on the surface of the porous layer (see FIG. 2), an embodiment provided thin on the surface of the blocking layer, an embodiment provided on the surface of the blocking layer in a thick film form (see FIG. 3), an electron transport layer Examples include a mode in which a thin film or a thick film (see FIG.
- the photosensitive layer may be provided in a linear or dispersed form, but is preferably provided in a film form.
- the photoelectric conversion element of the present invention is not particularly limited in structure other than the structure defined in the present invention, and known structures relating to the photoelectric conversion element and the solar cell can be adopted.
- Each layer constituting the photoelectric conversion element of the present invention is designed according to the purpose, and may be formed in a single layer or multiple layers, for example.
- 1 to 5 the same reference numerals mean the same components (members). 1 and 2 show the size of the fine particles forming the porous layer 12 with emphasis. These fine particles are preferably clogged (deposited or adhered) in the horizontal and vertical directions with respect to the conductive support 11 to form a porous structure.
- photoelectric conversion element 10 means the photoelectric conversion elements 10A, 10B, 10C, 10D, and 10E unless otherwise specified.
- photosensitive layer 13 means the photosensitive layers 13A, 13B and 13C unless otherwise specified.
- hole transport layer 3 means the hole transport layers 3A and 3B unless otherwise specified.
- a photoelectric conversion element 10A shown in FIG. 1 A system 100A shown in FIG. 1 is a system applied to a battery for causing an operation circuit M (for example, an electric motor) to perform work by the external circuit 6 using the photoelectric conversion element 10A.
- This photoelectric conversion element 10A has a first electrode 1A, a second electrode 2, and a hole transport layer 3A containing a hole transport material described later between the first electrode 1A and the second electrode 2. Yes.
- the first electrode 1A has a conductive support 11 composed of a support 11a and a transparent electrode 11b, a porous layer 12, and a photosensitive layer 13A on the porous layer 12.
- the blocking layer 14 is provided on the transparent electrode 11 b, and the porous layer 12 is formed on the blocking layer 14.
- the photoelectric conversion element 10A having the porous layer 12 improves the charge separation and charge transfer efficiency because the surface area of the photosensitive layer 13A is increased.
- the photoelectric conversion element 10B shown in FIG. 2 schematically shows a preferred embodiment in which the photosensitive layer 13A of the photoelectric conversion element 10A shown in FIG. In the photoelectric conversion element 10B, the hole transport layer 3B is thinly provided.
- the photoelectric conversion element 10B differs from the photoelectric conversion element 10A shown in FIG. 1 in the film thicknesses of the photosensitive layer 13B and the hole transport layer 3B, but is configured in the same manner as the photoelectric conversion element 10A except for these points. ing.
- a photoelectric conversion element 10C shown in FIG. 3 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
- the photoelectric conversion element 10C is different from the photoelectric conversion element 10B illustrated in FIG. 2 in that the porous layer 12 is not provided, but is configured in the same manner as the photoelectric conversion element 10B except for this point. That is, in the photoelectric conversion element 10 ⁇ / b> C, the photosensitive layer 13 ⁇ / b> C is formed in a thick film shape on the surface of the blocking layer 14.
- a photoelectric conversion element 10D shown in FIG. 4 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
- This photoelectric conversion element 10D is different from the photoelectric conversion element 10C shown in FIG. 3 in that an electron transport layer 15 is provided instead of the blocking layer 14, but is otherwise configured in the same manner as the photoelectric conversion element 10C.
- the first electrode 1 ⁇ / b> D includes a conductive support 11 and an electron transport layer 15 and a photosensitive layer 13 ⁇ / b> C that are sequentially formed on the conductive support 11.
- This photoelectric conversion element 10D is preferable in that each layer can be formed of an organic material. As a result, the productivity of the photoelectric conversion element is improved, and it is possible to make it thinner or flexible.
- the photoelectric conversion element 10E shown in FIG. 5 schematically shows still another preferred embodiment of the photoelectric conversion element of the present invention.
- a system 100E including the photoelectric conversion element 10E is a system applied to battery use as in the system 100A.
- the photoelectric conversion element 10 ⁇ / b> E has a first electrode 1 ⁇ / b> E, a second electrode 2, and an electron transport layer 4 between the first electrode 1 ⁇ / b> E and the second electrode 2.
- the first electrode 1 ⁇ / b> E includes a conductive support 11 and a hole transport layer 16 and a photosensitive layer 13 ⁇ / b> C, which are sequentially formed on the conductive support 11.
- This photoelectric conversion element 10E is preferable in that each layer can be formed of an organic material, like the photoelectric conversion element 10D.
- the system 100 to which the photoelectric conversion element 10 is applied functions as a solar cell as follows. That is, in the photoelectric conversion element 10A, light that has passed through the conductive support 11 or passed through the second electrode 2 and entered the photosensitive layer 13 excites the light absorber. The excited light absorber has electrons with high energy and can emit these electrons. The light absorber that has released electrons with high energy becomes an oxidant.
- the photoelectric conversion elements 10A to 10D electrons emitted from the light absorber move between the light absorbers and reach the conductive support 11. At this time, the light absorber that has released electrons with high energy is an oxidant. After the electrons that have reached the conductive support 11 work in the external circuit 6, they pass through the second electrode 2 (if there is a hole transport layer 3, further via the hole transport layer 3), and then the photosensitive layer Return to 13. The light absorber is reduced by the electrons returning to the photosensitive layer 13.
- the electrons emitted from the light absorber reach the second electrode 2 from the photosensitive layer 13C through the electron transport layer 4, and after working in the external circuit 6, the conductive support 11 Then, the process returns to the photosensitive layer 13.
- the light absorber is reduced by the electrons returning to the photosensitive layer 13.
- the system 100 functions as a solar cell by repeating such excitation and electron transfer cycles of the light absorber.
- the way in which electrons flow from the photosensitive layer 13 to the conductive support 11 varies depending on the presence / absence of the porous layer 12 and the type thereof.
- the porous layer 12 can be formed with an insulator other than the conventional semiconductor.
- the porous layer 12 is formed of a semiconductor, electron conduction in which electrons move inside or between the semiconductor particles of the porous layer 12 also occurs.
- the porous layer 12 is formed of an insulator, electron conduction in the porous layer 12 does not occur.
- the porous layer 12 is formed of an insulator
- a relatively high electromotive force (Voc) can be obtained by using aluminum oxide (Al 2 O 3 ) particles as the insulator particles.
- Al 2 O 3 aluminum oxide
- the blocking layer 14 as the other layer is formed of a conductor or a semiconductor, electron conduction in the blocking layer 14 occurs. Also, electron conduction occurs in the electron transport layer 15.
- the photoelectric conversion element and the solar cell of the present invention are not limited to the above-described preferred embodiments, and the configuration of each embodiment can be appropriately combined between the respective embodiments without departing from the spirit of the present invention.
- Non-Patent Document 1 materials and members used for the photoelectric conversion element or solar cell can be prepared by a conventional method except for the light absorber.
- a photoelectric conversion element or a solar cell using a perovskite compound for example, Non-Patent Document 1 can be referred to.
- dye-sensitized solar cells for example, Japanese Patent Application Laid-Open No. 2001-291534, US Pat. No. 4,927,721, US Pat. No. 4,684,537, US Pat. No. 5,084, 365, US Pat. No. 5,350,644, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP 2004-220974 A and JP 2008-135197 A can be referred to.
- the first electrode 1 has a conductive support 11 and a photosensitive layer 13 and functions as a working electrode in the photoelectric conversion element 10. As shown in FIGS. 1 to 5, the first electrode 1 preferably has at least one of a porous layer 12, a blocking layer 14, an electron transport layer 15, and a hole transport layer 16. The first electrode 1 preferably has at least the blocking layer 14 in terms of prevention of short circuit, and more preferably has the porous layer 12 and the blocking layer 14 in terms of light absorption efficiency and prevention of short circuit. Moreover, it is preferable that the 1st electrode 1 has the electron carrying layer 15 or the positive hole transport layer 16 at the point which can be formed with an organic material.
- the conductive support 11 is not particularly limited as long as it has conductivity and can support the photosensitive layer 13 and the like.
- the conductive support 11 includes a conductive material such as a metal, or a glass or plastic support 11a and a transparent electrode 11b as a conductive film formed on the surface of the support 11a. The structure which has is preferable.
- a conductive support 11 in which a transparent metal electrode 11b is formed by coating a conductive metal oxide on the surface of a glass or plastic support 11a is more preferable.
- the support 11a formed of plastic include a transparent polymer film described in paragraph No. 0153 of JP-A-2001-291534.
- ceramic Japanese Patent Laid-Open No. 2005-135902
- conductive resin Japanese Patent Laid-Open No. 2001-160425
- tin oxide As the metal oxide, tin oxide (TO) is preferable, and fluorine-doped tin oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
- the coating amount of the metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the surface area of the support 11a. When the conductive support 11 is used, light is preferably incident from the support 11a side.
- the conductive support 11 is preferably substantially transparent.
- “substantially transparent” means that the transmittance of light (wavelength 300 to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more.
- the thicknesses of the support 11a and the conductive support 11 are not particularly limited, and are set to appropriate thicknesses.
- the thickness is preferably 0.01 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm.
- the film thickness of the transparent electrode 11b is not particularly limited, and is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and more preferably 0.05 to 20 ⁇ m. It is particularly preferred that
- the conductive support 11 or the support 11a may have a light management function on the surface.
- the surface of the conductive support 11 or the support 11a may have an antireflection film in which high refractive films and low refractive index oxide films are alternately stacked as described in JP-A-2003-123859.
- the light guide function described in JP-A-2002-260746 may be provided.
- the blocking layer 14 is provided.
- the blocking layer 14 functions to prevent this reverse current.
- the blocking layer 14 is also referred to as a short circuit prevention layer.
- This blocking layer may be provided also when a photoelectric conversion element has an electron carrying layer.
- the photoelectric conversion element 10D it may be provided between the conductive support 11 and the electron transport layer 15, and in the case of the photoelectric conversion element 10E, it is provided between the second electrode 2 and the electron transport layer 4. May be.
- the material for forming the blocking layer 14 is not particularly limited as long as it is a material capable of fulfilling the above function, but is a substance that transmits visible light and is an insulating substance for the conductive support 11 (transparent electrode 11b).
- the “insulating substance with respect to the conductive support 11 (transparent electrode 11b)” specifically refers to a material whose conduction band energy level forms the conductive support 11 (metal oxide forming the transparent electrode 11b).
- a compound (n-type semiconductor compound) that is higher than the energy level of the conduction band of the material and lower than the energy level of the conduction band of the material constituting the porous layer 12 and the ground state of the light absorber.
- Examples of the material for forming the blocking layer 14 include silicon oxide, magnesium oxide, aluminum oxide, calcium carbonate, polyvinyl alcohol, and polyurethane.
- the material generally used for the photoelectric conversion material may be used, and examples thereof include titanium oxide, tin oxide, niobium oxide, and tungsten oxide. Of these, titanium oxide, tin oxide, magnesium oxide, aluminum oxide and the like are preferable.
- the thickness of the blocking layer 14 is preferably 0.001 to 10 ⁇ m, more preferably 0.005 to 1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m.
- the thickness of each layer can be measured by observing the cross section of the photoelectric conversion element 10 using a scanning electron microscope (SEM) or the like.
- the porous layer 12 is preferably provided on the transparent electrode 11b.
- the porous layer 12 is preferably formed on the blocking layer 14.
- the porous layer 12 is a layer that functions as a scaffold for carrying the photosensitive layer 13 on the surface.
- the porous layer 12 is preferably a fine particle layer having pores, in which fine particles of the material forming the porous layer 12 are deposited or adhered.
- the porous layer 12 may be a fine particle layer in which two or more kinds of multi-fine particles are deposited.
- the amount of light absorbent supported (adsorption amount) can be increased.
- the surface area of the porous layer 12 it is preferable to increase the surface area of the individual fine particles constituting the porous layer 12.
- the surface area of the fine particles is preferably 10 times or more, more than 100 times the projected area. It is more preferable.
- the particle diameter of the fine particles forming the porous layer 12 is preferably 0.001 to 1 ⁇ m as the primary particle in the average particle diameter using the diameter when the projected area is converted into a circle.
- the average particle diameter of the fine particles is preferably 0.01 to 100 ⁇ m as the average particle diameter of the dispersion.
- the material for forming the porous layer 12 is not particularly limited with respect to conductivity, and may be an insulator (insulating material), a conductive material, or a semiconductor (semiconductive material). .
- Examples of the material for forming the porous layer 12 include metal chalcogenides (eg, oxides, sulfides, selenides, etc.), compounds having a perovskite crystal structure (excluding a light absorber described later), and oxidation of silicon.
- An object for example, silicon dioxide, zeolite), or carbon nanotube (including carbon nanowire and carbon nanorod) can be used.
- the metal chalcogenide is not particularly limited, but is preferably titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, aluminum or tantalum oxide, cadmium sulfide. , Cadmium selenide and the like.
- Examples of the crystal structure of the metal chalcogenide include an anatase type, brookite type and rutile type, and anatase type and brookite type are preferable.
- the compound having a perovskite crystal structure is not particularly limited, and examples thereof include transition metal oxides.
- transition metal oxides For example, strontium titanate, calcium titanate, barium titanate, lead titanate, barium zirconate, barium stannate, lead zirconate, strontium zirconate, strontium tantalate, potassium niobate, bismuth ferrate, strontium barium titanate , Barium lanthanum titanate, calcium titanate, sodium titanate, bismuth titanate.
- strontium titanate, calcium titanate and the like are preferable.
- the carbon nanotube has a shape obtained by rounding a carbon film (graphene sheet) into a cylindrical shape.
- Carbon nanotubes are single-walled carbon nanotubes (SWCNT) in which one graphene sheet is wound in a cylindrical shape, double-walled carbon nanotubes (DWCNT) in which two graphene sheets are wound in a concentric shape, and multiple graphene sheets are concentric
- SWCNT single-walled carbon nanotubes
- DWCNT double-walled carbon nanotubes
- MWCNT multi-walled carbon nanotubes
- any carbon nanotube is not particularly limited and can be used.
- the material for forming the porous layer 12 is preferably titanium, tin, zinc, zirconium, aluminum or silicon oxide, or carbon nanotube, more preferably titanium oxide or aluminum oxide.
- the porous layer 12 may be formed of at least one of the above-described metal chalcogenide, compound having a perovskite crystal structure, silicon oxide, and carbon nanotube, and may be formed of a plurality of types. .
- the film thickness of the porous layer 12 is not particularly limited, but is usually in the range of 0.1 to 100 ⁇ m. When used as a solar cell, 0.1 to 50 ⁇ m is preferable, and 0.2 to 30 ⁇ m is more preferable.
- the electron transport layer 15 is preferably provided on the surface of the transparent electrode 11b.
- the electron transport layer 15 has a function of transporting electrons generated in the photosensitive layer 13 to the conductive support 11.
- the electron transport layer 15 is formed of an electron transport material that can exhibit this function.
- the electron transport material is not particularly limited, but an organic material (organic electron transport material) is preferable.
- the organic electron transport material examples include fullerene compounds such as [6,6] -phenyl-C61-Butylic Acid Methyl Ester (PCBM), perylene compounds such as perylenetetracarboxydiimide (PTCDI), and other tetracyanoquinodimethane (TCNQ). ) And the like, or high molecular compounds.
- the thickness of the electron transport layer 15 is not particularly limited, but is preferably 0.001 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
- the hole transport layer 16 is preferably provided on the surface of the transparent electrode 11b.
- the hole transport layer 16 is the same as the hole transport layer 3 described later except that the position where it is formed is different.
- the perovskite compound described later is preferably a porous layer 12 (photoelectric conversion elements 10A and 10B) or a blocking layer 14 (photoelectric conversion element 10C)) or an electron transport layer 15 (photoelectric conversion) as a light absorber. Element 10D) or the surface of each layer of hole transport layer 16 (photoelectric conversion element 10E) (including the inner surface when the surface on which photosensitive layer 13 is provided is uneven).
- the light absorber only needs to contain at least one perovskite compound described below, and may contain two or more perovskite compounds.
- the photosensitive layer 13 may be a single layer or a laminate of two or more layers. When the photosensitive layer 13 has a laminated structure of two or more layers, layers composed of different light absorbers may be laminated, and an intermediate layer containing a hole transport material is laminated between the photosensitive layer and the photosensitive layer. May be.
- the form having the photosensitive layer 13 on the conductive support 11 is as described above.
- the photosensitive layer 13 is preferably provided on the surface of each of the layers so that excited electrons flow through the conductive support 11. At this time, the photosensitive layer 13 may be provided on the entire surface of each of the above layers, or may be provided on a part of the surface.
- the film thickness of the photosensitive layer 13 is appropriately set according to the mode having the photosensitive layer 13 on the conductive support 11 and is not particularly limited.
- the film thickness of the photosensitive layer 13 (when the porous layer 12 is provided, the total film thickness with the porous layer 12) is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and 0 2 to 30 ⁇ m is particularly preferable.
- the light absorber contained in the photosensitive layer may function as a hole transport material.
- the photosensitive layer 13 includes a perovskite compound having an organic cation, a cation of a metal atom other than the Group 1 element of the periodic table, and an anion as a light absorber.
- the organic cation constituting the perovskite compound used in the present invention includes an organic cation having a silyl group.
- the perovskite compound has an organic cation having a silyl group in its crystal structure, the moisture resistance of the obtained photoelectric conversion element can be greatly increased. The reason is not clear, but it is presumed that the silyl group becomes a hydrophobic component and effectively exhibits a barrier action against moisture.
- the organic cation having a silyl group is preferably represented by the following formula (1).
- R 1 represents a group selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group.
- the alkyl group that can be adopted as R 1 includes a linear alkyl group and a branched alkyl group.
- the alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- Preferable specific examples of the alkyl group include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, and hexyl.
- two R 1 that are connected to Si atoms and are adjacent to each other may be connected to each other to form a ring. In this case, the formed ring may have a hetero atom as a ring constituent atom.
- the cycloalkyl group that can be employed as R 1 preferably has 3 to 8 carbon atoms.
- Preferable specific examples of this cycloalkyl group include, for example, cyclopropyl, cyclopentyl, and cyclohexyl.
- Alkenyl groups that can be employed as R 1 include straight-chain alkenyl groups and branched alkenyl groups.
- the alkenyl group preferably has 2 to 18 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms.
- Preferable specific examples of this alkenyl group include, for example, vinyl, allyl, butenyl and hexenyl.
- Alkynyl groups that can be employed as R 1 include straight-chain alkynyl groups and branched alkynyl groups.
- the alkynyl group preferably has 2 to 18 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms.
- Preferable specific examples of the alkynyl group include ethynyl, butynyl and hexynyl.
- the alkoxy group which can be taken as R 1 includes a linear alkoxy group and a branched alkoxy group.
- the alkyl part of the alkoxy group is synonymous with the alkyl group which can be taken as R 1 described above, and the preferred form is also the same.
- the aryl group that can be used as R 1 preferably has 6 to 14 carbon atoms.
- Preferable specific examples of the aryl group include phenyl and naphthyl, and phenyl is more preferable.
- the heteroaryl group which can be taken as R 1 includes a group consisting only of an aromatic heterocycle and a group consisting of a condensed heterocycle obtained by condensing an aromatic heterocycle with another ring such as an aromatic ring, an aliphatic ring or a heterocycle. Is included.
- a ring-constituting hetero atom constituting the aromatic hetero ring a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
- the number of ring members of the aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.
- Examples of the condensed heterocycle including a 5-membered aromatic heterocycle and a 5-membered aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a furan ring, and a thiophene ring. , Benzimidazole ring, benzoxazole ring, benzothiazole ring, indoline ring, and indazole ring.
- Examples of the condensed heterocycle including a 6-membered aromatic heterocycle and a 6-membered aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a quinoline ring, and a quinazoline ring. .
- the aliphatic heterocyclic group that can be adopted as R 1 preferably has 0 to 24 carbon atoms, and more preferably 1 to 18 carbon atoms.
- Preferable specific examples of the aliphatic heterocyclic ring of this aliphatic heterocyclic group include pyrrolidine ring, oxolane ring, thiolane ring, piperidine ring, oxane ring, thiane ring, piperazine ring, morpholine ring, quinuclidine ring, pyrrolidine ring, azetidine ring.
- R 1 may further have a substituent, and examples of this substituent include the substituents that can be adopted as R 1 described above.
- the substituent that R 1 may have is also preferably —L—NR 2 3 + in formula (1).
- R 1 is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group, from the viewpoint of more effectively expressing a barrier action against moisture.
- R 2 represents a group selected from a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group.
- Alkyl group which may take as R 2 a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group, an alkyl group which may respectively take as the R 1, cycloalkyl group, alkenyl group, alkynyl It is synonymous with group, an aryl group, heteroaryl group, and an aliphatic heterocyclic group, and its preferable form is also the same.
- Two R 2 s that are linked to an N atom and are adjacent to each other may be linked to each other to form a ring. In this case, the formed ring may have a hetero atom as a ring constituent atom.
- R 2 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
- L is a divalent linking group.
- L is a divalent linking group selected from an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, —O—, —S—, and —NR L —, or an alkylene group,
- a divalent linking group formed by combining divalent linking groups selected from a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, —O—, —S—, and —NR L — is preferable.
- R L is a hydrogen atom or an alkyl group, and this alkyl group has the same meaning as the alkyl group that can be adopted as R 1 described above, and the preferred form is also the same.
- the alkylene group that can be taken as L or a part of L includes a linear alkylene group and a branched alkylene group.
- the alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 5, and still more preferably 1 to 3.
- Preferable specific examples of this alkylene group include, for example, methylene, ethylene, propylene, butylene, pentylene and hexylene.
- the cycloalkylene group that can be taken as L or a part of L preferably has 3 to 8 carbon atoms.
- Preferable specific examples of the cycloalkylene group include, for example, cyclopropylene, cyclopentylene, and cyclohexylene.
- Alkenylene groups that can be taken as L or a part of L include linear alkenylene groups and branched alkenylene groups.
- the alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 5, and still more preferably 2 to 3.
- Alkynylene groups that can be taken as L or part of L include straight-chain alkynylene groups and branched alkynylene groups.
- the alkynylene group has preferably 2 to 20, more preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 5, and particularly preferably 2 to 4 carbon atoms.
- the arylene group that can be taken as L or a part of L preferably has 6 to 14 carbon atoms.
- the arylene group is preferably phenylene or naphthylene, more preferably phenylene.
- the heteroarylene group that can be taken as L or a part of L preferably has 0 to 24 carbon atoms, more preferably 1 to 18 carbon atoms.
- the ring constituting the heteroarylene group is a 5-membered aromatic heterocycle or a fused heterocycle containing a 5-membered aromatic heterocycle, or a 6-membered aromatic heterocycle or a 6-membered aromatic ring. Fused heterocycles including heterocycles are preferred.
- this 5-membered aromatic heterocycle and fused heterocycles containing 5-membered aromatic heterocycles and fused heterocycles containing 6-membered aromatic heterocycles and 6-membered aromatic heterocycles
- L is an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group or a heteroarylene group, or an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, and a heteroarylene group.
- a divalent linking group formed by combining two or more (preferably two) groups selected is preferable.
- L is more preferably an alkylene group or an arylene group, or a divalent linking group formed by combining an alkylene group and an arylene group.
- the organic cation having the silyl group represented by the above formula (1) has an alkylene group in the L
- the L and the NR 2 3 + are connected by the alkylene group. That is, when the organic cation having the silyl group represented by the above formula (1) has an alkylene group in L, the organic cation is R 1 3 Si-L 1 -L 2 -NR 2 3 +
- L 1 represents a single bond, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, —O—, —S—, and —NR L —
- L 2 represents an alkylene group.
- R 1 , R 2 and RL are synonymous with R 1 , R 2 and RL described above, respectively, and preferred forms are also the same. Further, preferred forms of the alkylene group L 2 are the same as the preferred form of the alkylene group can be taken as L as described above.
- the organic cation having the silyl group is preferably an organic cation represented by the following formula (RI) in addition to the organic cation represented by the above formula (1).
- R 1 and R 2 have the same meanings as R 1 and R 2 in formula (1), respectively, and the preferred forms are also the same.
- the organic cation constituting the perovskite compound used in the present invention preferably contains an organic cation having no silyl group in addition to an organic cation having a silyl group.
- the organic cation having no silyl group is preferably an organic cation represented by the following formula (2).
- R A is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or a group that can be represented by the following formula (3).
- an alkyl group and a group that can be represented by the following formula (3) are more preferable, and an alkyl group is more preferable.
- An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group that can be taken as R A are, respectively, an alkyl group, a cycloalkyl group, an alkenyl group that can be taken by R 1 in the above formula (1), It is synonymous with an alkynyl group, an aryl group, and a heteroaryl group, and its preferable range is also the same.
- Xa represents NR ⁇ 1c> , an oxygen atom, or a sulfur atom.
- R 1b and R 1c each independently represent a hydrogen atom or a substituent. * Represents a bonding position with the N atom in the formula (2).
- the organic ammonium cation having no silyl group is an organic ammonium cation formed by bonding R A and NH 3 + in the above formula (2)
- the organic ammonium cation can take a resonance structure.
- the organic cation having no silyl group is an organic ammonium cation formed by bonding R A and NH 3 + in the above formula (2)
- the organic ammonium cation can take a resonance structure.
- the organic cation having no silyl group is an organic ammonium cation formed by bonding R A and NH 3 + in the above formula (2)
- the organic ammonium cation can take a resonance structure.
- the organic ammonium cation when X a is NH (R 1c is a hydrogen atom), the organic cation has a group that can be represented by the above formula (3) and NH 3 +.
- an organic amidinium cation which is one of the resonance structures of the organic ammonium cation is also included.
- X a represents NR 1c , an oxygen atom or a sulfur atom, and NR 1c is preferable.
- R 1c represents a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom.
- R 1b represents a hydrogen atom or a substituent, and preferably a hydrogen atom.
- R 1b examples include an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group.
- An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group, which can be each taken by R 1b and R 1c, are an alkyl group, a cycloalkyl group, each of which can be taken as R 1 in the above formula (1), It is synonymous with an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group, and its preferable form is also the same.
- Examples of the group that can be represented by the formula (3) include (thio) acyl group, (thio) carbamoyl group, imidoyl group, and amidino group.
- the (thio) acyl group includes an acyl group and a thioacyl group.
- the acyl group is preferably an acyl group having 1 to 7 carbon atoms, and examples thereof include formyl, acetyl (CH 3 C ( ⁇ O) —), propionyl, hexanoyl and the like.
- the thioacyl group is preferably a thioacyl group having 1 to 7 carbon atoms in total, and examples thereof include thioformyl, thioacetyl (CH 3 C ( ⁇ S) —), thiopropionyl and the like.
- the (thio) carbamoyl group includes a carbamoyl group (H 2 NC ( ⁇ O) —) and a thiocarbamoyl group (H 2 NC ( ⁇ S) —).
- the amidino group as a group that can be represented by the formula (3) has a structure (—C ( ⁇ NH) NH 2 ) in which R 1b of the imidoyl group is an amino group and R 1c is a hydrogen atom.
- the molar ratio of the organic cation having no silyl group to the organic cation having a silyl group preferably satisfies the following formula (i), and more preferably satisfies the formula (ii). It is preferable that the mathematical formula (iii) is satisfied.
- the moisture resistance of the photoelectric conversion element can be further improved.
- the perovskite compound used in the present invention has a cation of a metal atom other than the Group 1 element of the periodic table in its crystal structure.
- metal atoms other than Group 1 elements of the periodic table include calcium (Ca), strontium (Sr), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), iron (Fe), Cobalt (Co), palladium (Pd), germanium (Ge), tin (Sn), lead (Pb), ytterbium (Yb), europium (Eu), indium (In), titanium (Ti), bismuth (Bi), etc.
- the perovskite compound used in the present invention may have one kind of cation of a metal atom other than the Group 1 element of the periodic table in its crystal structure, or two or more kinds. In the case of having two or more kinds of cations of metal atoms other than Group 1 elements of the periodic table, it is preferable to have two kinds of Pb atoms and Sn atoms.
- the perovskite compound has two or more kinds of cations of metal atoms other than Group 1 elements of the periodic table, the abundance ratio of these two or more kinds of cations is not particularly limited.
- the anion constituting the perovskite compound used in the present invention may be a monoatomic anion or a polyatomic anion.
- the monoatomic anion include a halogen atom anion.
- the polyatomic anion include NCS ⁇ , NCO ⁇ , HO ⁇ , NO 3 ⁇ and COO ⁇ .
- the anion which comprises a perovskite compound is an anion of a halogen atom.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A bromine atom or an iodine atom is preferable.
- the anion constituting the perovskite compound used in the present invention may be one kind of anion or two or more kinds of anions.
- an anion of iodine atom is preferable.
- a form having two or more types of anions of halogen atoms is preferable, and a form having two types of anions of chlorine atoms and anions of iodine atoms is more preferable.
- the perovskite compound has two or more types of anions, the ratio is not particularly limited.
- the perovskite compound used in the present invention may have a cation of a group 1 element of the periodic table in its structure.
- a cation of the periodic table first group element lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), and cesium ion (Cs + ) are preferable, and Cs + is more preferable.
- the perovskite compound used in the present invention has a perovskite crystal structure having each of the above constituent ions.
- the perovskite compound used in the present invention is preferably a perovskite compound represented by the following formula (I).
- A represents a group 1 element of the periodic table or a cationic organic group.
- M represents a metal atom other than Group 1 elements of the periodic table.
- X represents an anionic atom or anionic atom group.
- a represents 1 or 2
- a cationic organic group means an organic group that exists as a cation in a perovskite crystal structure
- an anionic atom means an atom that exists as a monoatomic anion in a perovskite crystal structure
- An atomic group means an atomic group that exists as a polyatomic anion in a perovskite crystal structure.
- the first group element A of the periodic table exists as a cation in the perovskite type crystal structure.
- the cationic organic group A exists as the organic cation described above in the perovskite crystal structure.
- the metal atom M exists in the perovskite crystal structure as a cation of a metal atom other than the first group element of the periodic table described above.
- the anionic atom X exists as the above-described monoatomic anion in the perovskite crystal structure.
- the anionic atomic group X exists as the above-mentioned polyatomic anion in the perovskite crystal structure.
- at least a part of A is a cationic organic group having a silyl group.
- the perovskite compound used in the present invention may be a mixture of a perovskite compound in which a is 1 in the above formula (I) and a perovskite compound in which a is 2.
- the perovskite compound can be synthesized from MX 2 and AX.
- a perovskite compound can be synthesized with reference to Non-Patent Document 1 above.
- Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka “Organometric Halide Perovskits as Visible Slight-Lights. Am. Chem. Soc. , 2009, 131 (17), 6050-6051 as appropriate, a perovskite compound can be synthesized.
- the perovskite compound used in the present invention is composed of an organic cation represented by the above formula (1), an organic cation represented by the above formula (RI), and the above formula (2) with respect to the total molar amount of cations constituting the perovskite compound.
- the ratio of the total molar amount of the organic cation represented by the above and the cation of the metal atom other than the Group 1 element of the periodic table is preferably 90 to 100 mol%, more preferably 95 to 100 mol%. .
- the ratio of the total molar amount of anions of halogen atoms to the total molar amount of anions constituting the perovskite compound is preferably 90 to 100 mol%, preferably 95 to 100 mol. % Is more preferable, and 98 to 100 mol% is more preferable.
- the amount of the light absorber used may be an amount that covers at least a part of the surface of the porous layer 12 or the blocking layer 14 on which light is incident, and is preferably an amount that covers the entire surface.
- the content of the perovskite compound is usually 1 to 100% by mass.
- the photoelectric conversion element of the present invention preferably has a hole transport layer 3 between the first electrode and the second electrode.
- the hole transport layer 3 has a function of replenishing electrons to the oxidant of the light absorber, and is preferably a solid layer.
- the hole transport layer 3 is preferably provided between the photosensitive layer 13 of the first electrode 1 and the second electrode 2.
- the hole transport material for forming the hole transport layer 3 is not particularly limited, but inorganic materials such as CuI and CuNCS, and organic hole transport materials described in Paragraph Nos. 0209 to 0212 of JP-A-2001-291534 Etc.
- the organic hole transport material is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole and polysilane, a spiro compound in which two rings share a tetrahedral structure such as C and Si, and triarylamine. And aromatic amine compounds such as triphenylene compounds, nitrogen-containing heterocyclic compounds, and liquid crystalline cyano compounds.
- the hole transporting material is preferably an organic hole transporting material that can be applied by solution and becomes solid.
- 2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenyl) Amine) -9,9-spirobifluorene also referred to as Spiro-OMeTAD
- 4- (diethylamino) benzaldehyde diphenylhydrazone polyethylenedioxythiophene (PEDOT), etc.
- the thickness of the hole transport layer 3 is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 1 nm to 10 ⁇ m, further preferably 5 nm to 5 ⁇ m, and particularly preferably 10 nm to 1 ⁇ m.
- the total film thickness of the porous layer 12, the photosensitive layer 13, and the hole transport layer 3 is not particularly limited, but is preferably 0.1 to 200 ⁇ m, for example, 1 to 50 ⁇ m is more preferable, and 0.2 to 5 ⁇ m is more preferable.
- the electron transport layer 4 is preferably provided between the photosensitive layer 13C and the second electrode 2.
- the electron transport layer 4 is the same as the electron transport layer 15 except that the electron transport destination is the second electrode and the position where the electron transport layer 4 is formed is different.
- the second electrode 2 functions as a positive electrode in the solar cell.
- the 2nd electrode 2 will not be specifically limited if it has electroconductivity, Usually, it can be set as the same structure as the electroconductive support body 11. FIG. If the strength is sufficiently maintained, the support 11a is not necessarily required.
- the structure of the second electrode 2 is preferably a structure having a high current collecting effect. In order for light to reach the photosensitive layer 13, at least one of the conductive support 11 and the second electrode 2 must be substantially transparent. In the solar cell of this invention, it is preferable that the electroconductive support body 11 is transparent and sunlight is entered from the support body 11a side. In this case, it is more preferable that the second electrode 2 has a property of reflecting light.
- Examples of the material for forming the second electrode 2 include platinum (Pt), gold (Au), nickel (Ni), copper (Cu), silver (Ag), indium (In), ruthenium (Ru), palladium ( Examples thereof include metals such as Pd), rhodium (Rh), iridium (Ir), osnium (Os), and aluminum (Al), the above-described conductive metal oxides, carbon materials, and conductive polymers.
- the carbon material may be any conductive material formed by bonding carbon atoms, and examples thereof include fullerene, carbon nanotube, graphite, graphene, and carbon black.
- the second electrode 2 is preferably a metal or conductive metal oxide thin film (including a thin film formed by vapor deposition), or a glass substrate or a plastic substrate having this thin film.
- a metal or conductive metal oxide thin film including a thin film formed by vapor deposition
- a glass substrate or a plastic substrate having this thin film.
- glass substrate or plastic substrate glass having a thin film of gold or platinum or glass on which platinum is deposited is preferable.
- the film thickness of the second electrode 2 is not particularly limited, but is preferably 0.01 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m, and particularly preferably 0.01 to 1 ⁇ m.
- a spacer or a separator can be used instead of the blocking layer 14 or the like or together with the blocking layer 14 or the like.
- a hole blocking layer may be provided between the second electrode 2 and the hole transport layer 3.
- the solar cell of this invention is comprised using the photoelectric conversion element of this invention.
- a photoelectric conversion element 10 provided with an external circuit 6 can be used as a solar cell.
- the external circuit connected to the first electrode 1 (conductive support 11) and the second electrode 2 can be used without particular limitation.
- the photoelectric conversion element and solar cell of the present invention can be produced according to a known production method, for example, the method described in Non-Patent Document 1 or the like. Below, the manufacturing method of the photoelectric conversion element and solar cell of this invention is demonstrated easily.
- a blocking layer 14 is formed on the surface of the conductive support 11.
- the blocking layer 14 can be formed by, for example, a method of applying a dispersion containing the insulating material or a precursor compound thereof to the surface of the conductive support 11 and baking it, or a spray pyrolysis method.
- the material forming the porous layer 12 is preferably used as fine particles, and more preferably used as a dispersion containing fine particles.
- the method for forming the porous layer 12 is not particularly limited, and examples thereof include a wet method, a dry method, and other methods (for example, a method described in Chemical Review, Vol. 110, page 6595 (2010)). It is done.
- the dispersion (paste) is preferably applied to the surface of the conductive support 11 or the surface of the blocking layer 14 and then baked at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours. Thereby, microparticles
- the firing temperature other than the last firing is preferably performed at a temperature lower than the last firing temperature (the last firing temperature).
- the firing temperature other than the last can be set within a range of 50 to 300 ° C.
- the final firing temperature can be set to be higher than the firing temperature other than the last within the range of 100 to 600 ° C.
- the firing temperature is preferably 60 to 500 ° C.
- the amount of the porous material applied when forming the porous layer 12 is appropriately set according to the thickness of the porous layer 12 and the number of times of application, and is not particularly limited.
- the coating amount of the porous material per 1 m 2 of the surface area of the conductive support 11 is preferably 0.5 to 500 g, and more preferably 5 to 100 g.
- the electron transport layer 15 or the hole transport layer 16 When the electron transport layer 15 or the hole transport layer 16 is provided, it can be formed in the same manner as the hole transport layer 3 or the electron transport layer 4 described later.
- the method for providing the photosensitive layer 13 includes a wet method and a dry method, and is not particularly limited.
- a wet method is preferred, and for example, a method of contacting with a light absorbent solution containing an absorbent is preferred.
- a light absorbent solution for forming the photosensitive layer 13 is prepared.
- the light absorber solution contains MX 2 and AX, which are raw materials for the perovskite compound.
- A, M and X have the same meanings as A, M and X in the above formula (I).
- the molar ratio of MX 2 to AX is appropriately adjusted according to the purpose.
- the molar ratio of AX to MX 2 is preferably 1: 1 to 10: 1.
- This light absorber solution can be prepared by mixing AX and MX 2 in a predetermined molar ratio, preferably by heating.
- This forming liquid is usually a solution, but may be a suspension.
- the heating conditions are not particularly limited, but the heating temperature is preferably 30 to 200 ° C, more preferably 60 to 150 ° C.
- the heating time is preferably 0.5 to 100 hours, more preferably 1 to 3 hours.
- the solvent or dispersion medium those described later can be used.
- the prepared light absorber solution is a layer that forms the photosensitive layer 13 on the surface (in the photoelectric conversion element 10, any one of the porous layer 12, the blocking layer 14, the electron transport layer 15 and the hole transport layer 16).
- the surface of the layer). Specifically, it is preferable to apply or immerse the light absorbent solution.
- a perovskite compound is formed on the surface of the porous layer 12, the blocking layer 14, the electron transport layer 15 or the hole transport layer 16.
- the contact temperature is preferably 5 to 100 ° C.
- the immersion time is preferably 5 seconds to 24 hours, more preferably 20 seconds to 1 hour.
- the above drying is preferably performed by heating, and is usually performed by heating to 20 to 300 ° C., preferably 50 to 170 ° C.
- the photosensitive layer can also be formed according to the method for synthesizing the perovskite compound.
- the AX solution containing the AX, and MX 2 solution containing the MX 2 and separately applied (including immersion method), and a method of drying if necessary.
- any solution may be applied first, but preferably the MX 2 solution is applied first.
- the molar ratio of AX and MX 2 put to this method, coating conditions and drying conditions are the same as the above method.
- AX or MX 2 can be vapor-deposited instead of applying the AX solution and the MX 2 solution.
- Still other methods include dry methods such as vacuum deposition using a compound or mixture from which the solvent of the light absorber solution has been removed. For example, the AX and the MX 2, simultaneously or sequentially, and a method of depositing. As a result, a light absorber is formed and becomes the photosensitive layer 13.
- the hole transport layer 3 or the electron transport layer 4 is preferably formed on the photosensitive layer 13 thus provided.
- the hole transport layer 3 can be formed by applying a hole transport material solution containing a hole transport material and drying it.
- the hole transport material solution has an excellent coating property, and when it has the porous layer 12 and there are voids, it easily penetrates into the pores of the porous layer 12. It is preferably 01 to 1.0 M (mol / L).
- the electron transport layer 4 can be formed by applying an electron transport material solution containing an electron transport material and drying it.
- the second electrode 2 After forming the hole transport layer 3 or the electron transport layer 4, the second electrode 2 is formed, and a photoelectric conversion element and a solar cell are manufactured.
- the film thickness of each layer can be adjusted by appropriately changing the concentration of each dispersion or solution and the number of coatings. For example, when the photosensitive layers 13B and 13C having a large film thickness are provided, the light absorber solution may be applied and dried a plurality of times.
- Each of the above-mentioned dispersions and solutions may contain additives such as a dispersion aid and a surfactant as necessary.
- Examples of the solvent or dispersion medium used in the photoelectric conversion element and solar cell manufacturing method include, but are not limited to, the solvents described in JP-A No. 2001-291534.
- an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, a sulfide solvent, and a mixed solvent of two or more of these are preferable.
- a mixed solvent of an alcohol solvent and a solvent selected from an amide solvent, a nitrile solvent, or a hydrocarbon solvent is preferable.
- methanol, ethanol, isopropanol, ⁇ -butyrolactone, chlorobenzene, acetonitrile, dimethylformamide (DMF) or dimethylacetamide, or a mixed solvent thereof is preferable.
- the application method of the solution or dispersant forming each layer is not particularly limited, and spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, inkjet
- a known coating method such as a printing method or a dipping method can be used. Of these, spin coating, screen printing, dipping, and the like are preferable.
- the photoelectric conversion element produced as described above can be used as a solar cell by connecting the external circuit 6 to the first electrode 1 and the second electrode 2.
- composition of the present invention comprises a compound represented by the following formula (1a) and a metal halide.
- R 1 3 Si—L—NR 2 3 Hal Formula (1a) Wherein, R 1, R 2 and L are each the same as R 1, R 2 and L in the formula (1), a preferred form also the same.
- Hal represents a halogen atom (preferably an iodine atom, a chlorine atom, or a bromine atom).
- the composition of the present invention may contain one type of compound represented by the above formula (1a), or may contain two or more types.
- the above-described perovskite compound used in the present invention has a halide of metal atom M other than the Group 1 element of the periodic table (that is, M (Hal) 2 A compound represented by the formula, Hal represents a halogen atom.), More preferably at least one selected from a halide of Pb and a halide of Sn, and more preferably an iodide or chlorinate of Pb. And at least one selected from iodinated or chlorinated Sn, particularly preferably at least one selected from PbI 2 and SnI 2 .
- the composition of the present invention may be solid (powder, granular, etc.) or a solution.
- the medium used is preferably an organic solvent.
- Alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, or the mixed solvent of 2 or more types of these solvents is mentioned.
- the organic solvent that can be used in the composition of the present invention is more preferably methanol, ethanol, isopropanol, ⁇ -butyrolactone, chlorobenzene, acetonitrile, DMF, dimethylacetamide, dimethyl sulfoxide, or a mixed solvent thereof.
- composition of the present invention may further contain other components in addition to the compound represented by the above formula (1a) and the metal halide.
- the composition of the present invention preferably contains at least one compound represented by R A —NH 3 Hal as the other component (R A has the same meaning as R A in the above formula (2), Preferred forms are also the same: Hal represents a halogen atom, preferably an iodine atom, a chlorine atom or a bromine atom). More preferably, R A —NH 3 Hal is CH 3 NH 3 Hal or CH 3 CH 2 NH 3 Hal.
- the molar ratio between the content a of the compound represented by the formula (1a) and the content b of the metal halide is preferably 0.001 ⁇ a / b ⁇ 10, and 0.01 ⁇ a / b ⁇ 10 is more preferable, and 0.01 ⁇ a / b ⁇ 3 is more preferable.
- composition of the present invention contains R A —NH 3 Hal
- the molar ratio of c is preferably 4 ⁇ c / a ⁇ 999, more preferably 19 ⁇ c / a ⁇ 499, and particularly preferably 49 ⁇ c / a ⁇ 199.
- the composition of the present invention contains the compound represented by the above formula (1a) and the above R A —NH 3 Hal
- the metal halide content b in the composition of the present invention and the above
- the total molar ratio of the content a of the compound represented by the formula (1a) and the content c of R A —NH 3 Hal is preferably 1 ⁇ (a + c) / b ⁇ 10, and 1 ⁇ (a + c) / B ⁇ 5 is more preferable.
- composition of the present invention may contain a halide of a Group 1 element of the periodic table as the other component.
- the composition of the present invention can be suitably used as a supply source of the above-described MX 2 and AX in the formation of the photosensitive layer of the photoelectric conversion element of the present invention.
- the composition of the present invention is in the form of powder, granules, etc.
- the composition of the present invention is dissolved in a solvent to prepare a solution with an appropriate concentration, and after filtration, purification, etc., if necessary, the light absorber described above It can be used as a solution.
- the composition of the present invention is a solution, it can be used as it is or after concentration, dilution, filtration, purification, etc., as the above-described light absorbent solution. That is, the composition of the present invention can be suitably used for forming a photosensitive layer in the production of the photoelectric conversion device of the present invention.
- the photoelectric conversion element 10A shown in FIG. 1 was manufactured by the following procedure.
- the film thickness of the photosensitive layer 13 is large, it corresponds to the photoelectric conversion element 10B shown in FIG.
- conductive support 11 A fluorine-doped SnO 2 conductive film (transparent electrode 11b) was formed on a glass substrate (support 11a, thickness 2.2 mm) to produce a conductive support 11.
- a blocking layer 14 (thickness 50 nm) made of titanium oxide is formed on the SnO 2 conductive film of the conductive support 11 at 450 ° C. by spray pyrolysis using the prepared 0.02M blocking layer solution. did.
- ⁇ Formation of porous layer 12> The prepared titanium oxide paste was applied onto the blocking layer 14 by screen printing and baked. The application and firing of the titanium oxide paste was repeated again. The first firing was performed at 130 ° C. for 1 hour, and the second firing was performed at 500 ° C. for 1 hour. The obtained titanium oxide fired body was immersed in a 40 mM TiCl 4 aqueous solution, heated at 60 ° C. for 1 hour, and then heated at 500 ° C. for 30 minutes to form a porous layer 12 (thickness of TiO 2). 250 nm).
- the prepared light absorbent solution A was applied onto the porous layer 12 by spin coating (2000 rpm for 60 seconds), and the applied light absorbent solution A was dried on a hot plate at 100 ° C. for 90 minutes to obtain a perovskite compound.
- a photosensitive layer A (thickness 300 nm (including the thickness of the porous layer 12 of 250 nm)) was formed as a photosensitive layer 13 ⁇ / b> A. In this way, the first electrode 1 was produced.
- a hole transport material solution is applied onto the photosensitive layer 13 of the first electrode 1 by spin coating, and the applied hole transport material solution is dried to form a hole transport layer 3 (thickness 0.1 ⁇ m). ) Was formed.
- Sample No. In the same manner as in the production of the photoelectric conversion element 101, the sample No. The photoelectric conversion elements 10 of 106 to 133 were manufactured. Purified CH 3 NH 3 I and compound (b2), (g2), (s2), (w2), (x2), (y2), (z2), (aa2), (bb2), (cc2) or and total amount of the (dd2), the mixing molar ratio of PbI 2, the sample No. Similar to the manufacture of 101, the ratio was 2: 1.
- the prepared light absorber solution B was applied onto the porous layer 12 by a spin coating method (2000 rpm for 60 seconds, followed by 3000 rpm for 60 seconds). It was dried for a minute to form a photosensitive layer A (film thickness 600 nm (including the film thickness 500 nm of the porous layer 12)) as the photosensitive layer 13A having a perovskite compound.
- Photoelectric conversion efficiency was evaluated as follows. Each sample No. Three photoelectric conversion elements were manufactured. A battery characteristic test was performed for each of the three specimens, and the photoelectric conversion efficiency ( ⁇ /%) was measured. Then, the average value of these three specimens is assigned to each sample No. The initial photoelectric conversion efficiency ( ⁇ /%) of the photoelectric conversion element was determined. The battery characteristic test was performed by irradiating 1000 W / m 2 of simulated sunlight from a xenon lamp through an AM1.5 filter using a solar simulator “WXS-85H” (manufactured by WACOM). The current-voltage characteristics were measured using an IV tester to determine the photoelectric conversion efficiency ( ⁇ /%).
- the moisture resistance of the photoelectric conversion element was evaluated as follows. Each sample No. Each of the three specimens was stored in a constant temperature and humidity chamber at a temperature of 25 ° C. and a humidity of 60% RH for 24 hours, and then a battery characteristic test was performed in the same manner as described above to measure photoelectric conversion efficiency ( ⁇ /%). . The average value of the three samples was assigned to each sample No. The photoelectric conversion efficiency ( ⁇ /%) after storage of the photoelectric conversion element was determined. The moisture resistance of the photoelectric conversion element was evaluated according to the following evaluation criteria from the rate of decrease in photoelectric conversion efficiency calculated by the following formula.
- Decreasing rate (%) 100 ⁇ ⁇ 100 ⁇ (photoelectric conversion efficiency after storage) / (initial photoelectric conversion efficiency) ⁇ -Evaluation criteria for moisture resistance-
- [A], [B], [C], and [D] are acceptable levels, preferably [A], [B], and [C], more preferably [A ].
- [E] has a large decrease rate and does not reach the pass level (required level) of the present invention.
- Table 1 The results are shown in Table 1 below.
- [A2] / [A1] shown in the following Table 1 corresponds to the molar ratio of the organic cation having no silyl group to the organic cation having a silyl group constituting the perovskite compound.
- the photoelectric conversion element has a significant decrease in photoelectric conversion efficiency under high humidity conditions. As a result.
- the perovskite compound in the light absorber contains an organic cation having a silyl group in its crystal structure, the photoelectric conversion element is less likely to have a reduced photoelectric conversion efficiency even under the above-described high humidity conditions, and is thus moisture resistant. I found it excellent.
- the photoelectric conversion element or solar cell of the present invention exhibits excellent moisture resistance.
- Electron transport layer 16 Hole transport layer 2 Second electrode 3A, 3B Hole transport layer 4 Electron transport layer 6 External circuit (lead) 10A, 10B, 10C, 10D, 10E Photoelectric conversion elements 100A, 100B, 100C, 100D, 100E A system M electric motor using photoelectric conversion elements for battery applications
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Abstract
Description
しかし、ペロブスカイト化合物は高湿環境下で損傷を受けやすいことが知られている。実際、ペロブスカイト化合物を光吸収剤として用いた光電変換素子ないし太陽電池は、高湿環境下において光電変換効率が大きく低下することが多い。
本発明は、感光層中にペロブスカイト化合物を光吸収剤として用いた光電変換素子であって、耐湿性に優れた光電変換素子を提供することを課題とする。また本発明は、上記光電変換素子を用いた太陽電池を提供することを課題とする。また本発明は、上記光電変換素子の感光層を形成するのに好適な組成物を提供することを課題とする。
〔1〕
光吸収剤を含む感光層を導電性支持体上に有する第一電極と、第一電極に対向する第二電極とを有する光電変換素子であって、
上記光吸収剤が、有機カチオンと、周期表第一族元素以外の金属原子のカチオンと、アニオンとを有するペロブスカイト型結晶構造を持つ化合物を含み、この化合物を構成する上記有機カチオンの少なくとも一部がシリル基を有する有機カチオンである、光電変換素子。
〔2〕
上記のシリル基を有する有機カチオンが下記式(1)で表される、〔1〕に記載の光電変換素子。
R1 3Si-L-NR2 3 + 式(1)
式中、R1は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。R2は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。Lは2価の連結基を示す。
〔3〕
上記R1がアルキル基、アリール基またはヘテロアリール基である、〔2〕に記載の光電変換素子。
〔4〕
上記Lがアルキレン基、シクロアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、ヘテロアリーレン基、-O-、-S-、および-NRL-から選ばれる2価の連結基であるか、または、これらの連結基の2種以上の基を組み合わせてなる2価の連結基である、〔2〕または〔3〕に記載の光電変換素子。
RLは水素原子またはアルキル基を示す。
〔5〕
上記Lがアルキレン基もしくはアリーレン基であるか、または、アルキレン基およびアリーレン基を組み合わせてなる2価の連結基である、〔4〕に記載の光電変換素子。
〔6〕
上記式(1)で表されるシリル基を有する有機カチオンが、上記L中にアルキレン基を有し、このアルキレン基により上記Lと上記NR2 3 +とが連結している、〔2〕~〔5〕のいずれか1つに記載の光電変換素子。
〔7〕
上記のペロブスカイト型結晶構造を持つ化合物が、シリル基を有しない有機カチオンを有する、〔1〕~〔6〕のいずれか1つに記載の光電変換素子。
〔8〕
上記のペロブスカイト型結晶構造を持つ化合物中、上記のシリル基を有する有機カチオンに対する上記のシリル基を有しない有機カチオンのモル比が下記式を満たす、〔7〕に記載の光電変換素子。
19≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦499
〔9〕
上記のペロブスカイト型結晶構造を持つ化合物中、上記のシリル基を有する有機カチオンに対する上記のシリル基を有しない有機カチオンのモル比が下記式を満たす、〔8〕に記載の光電変換素子。
49≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦199
〔10〕
〔1〕~〔9〕のいずれか1つに記載の光電変換素子を用いた太陽電池。
〔11〕
下記式(1a)で表される化合物と、ハロゲン化金属とを含有する組成物。
R1 3Si-L-NR2 3Hal 式(1a)
式中、R1は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。R2は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。Lは2価の連結基を示す。Halはハロゲン原子を示す。
〔12〕
〔1〕~〔9〕のいずれか1つに記載の光電変換素子の製造における感光層の形成に用いる、〔11〕に記載の組成物。
本発明の上記および他の特徴および利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。
本発明の光電変換素子は、導電性支持体と、光吸収剤を含む感光層とを有する第一電極と、第一電極に対向する第二電極とを有する。ここで、第一電極と第二電極が対向するとは、第一電極と第二電極が互いに接した状態で積層された形態、第一電極と第二電極とが他の層を介して積層された形態(すなわち第一電極と第二電極が他の層を挟んで互いに対向して設けられた形態)の両形態を含む意味である。
本発明の光電変換素子は好ましくは、第一電極と第二電極の間に設けられた正孔輸送層を有する。感光層および第二電極はこの順で導電性支持体上に設けられている。すなわち光電変換素子が正孔輸送層を有する場合には、感光層、正孔輸送層および第二電極はこの順で導電性支持体上に設けられていることが好ましい。
また、正孔輸送層は導電性支持体と感光層との間に設けられていてもよい。この場合、正孔輸送層、感光層および第二電極はこの順で導電性支持体上に設けられている。
光吸収剤は、後述するペロブスカイト化合物を少なくとも1種含んでいる。光吸収剤は、ペロブスカイト化合物と併せて、ペロブスカイト化合物以外の光吸収剤を含んでいてもよい。ペロブスカイト化合物以外の光吸収剤としては、例えば金属錯体色素および有機色素が挙げられる。
本発明において、導電性支持体の表面上方に他の層を介して感光層を有する態様としては、例えば、感光層が、多孔質層の表面に薄い膜状等に設けられる態様(図1参照)、多孔質層の表面に厚く設けられる態様(図2参照)、ブロッキング層の表面に薄く設けられる態様、ブロッキング層の表面に厚い膜状に設けられる態様(図3参照)、電子輸送層の表面に薄い膜状または厚い膜状(図4参照)に設けられる態様、および、正孔輸送層の表面に薄い膜状または厚い膜状(図5参照)に設けられる態様が挙げられる。感光層は、線状または分散状に設けられてもよいが、好ましくは膜状に設けられる。
図1~図5において、同じ符号は同じ構成要素(部材)を意味する。
なお、図1および図2は、多孔質層12を形成する微粒子の大きさを強調して示してある。これらの微粒子は、好ましくは、導電性支持体11に対して水平方向および垂直方向に詰まり(堆積または密着して)、多孔質構造を形成している。
この光電変換素子10Aは、第一電極1Aと、第二電極2と、第一電極1Aと第二電極2の間に、後述する正孔輸送材料を含む正孔輸送層3Aとを有している。
第一電極1Aは、支持体11aおよび透明電極11bからなる導電性支持体11と、多孔質層12と、多孔質層12上に感光層13Aとを有している。また透明電極11b上にブロッキング層14を有し、ブロッキング層14上に多孔質層12が形成される。このように多孔質層12を有する光電変換素子10Aは、感光層13Aの表面積が大きくなるため、電荷分離および電荷移動効率が向上すると推測される。
光電変換素子10Eは、第一電極1Eと、第二電極2と、第一電極1Eおよび第二電極2の間に電子輸送層4とを有している。第一電極1Eは、導電性支持体11と、導電性支持体11上に順に形成された、正孔輸送層16および感光層13Cとを有している。この光電変換素子10Eは、光電変換素子10Dと同様に、各層を有機材料で形成できる点で、好ましい。
すなわち、光電変換素子10Aにおいて、導電性支持体11を透過して、または第二電極2を透過して感光層13に入射した光は光吸収剤を励起する。励起された光吸収剤はエネルギーの高い電子を有しており、この電子を放出できる。エネルギーの高い電子を放出した光吸収剤は酸化体となる。
一方、光電変換素子10Eにおいては、光吸収剤から放出された電子は、感光層13Cから電子輸送層4を経て第二電極2に到達し、外部回路6で仕事をした後に導電性支持体11を経て、感光層13に戻る。感光層13に戻った電子により光吸収剤が還元される。
光電変換素子10において、このような、上記光吸収剤の励起および電子移動のサイクルを繰り返すことにより、システム100が太陽電池として機能する。
なお、上記他の層としてのブロッキング層14が導体または半導体により形成された場合もブロッキング層14での電子伝導が起こる。
また、電子輸送層15でも、電子伝導が起こる。
第一電極1は、導電性支持体11と感光層13とを有し、光電変換素子10において作用電極として機能する。
第一電極1は、図1~5に示されるように、多孔質層12、ブロッキング層14、電子輸送層15および正孔輸送層16の少なくとも1つの層を有することが好ましい。
第一電極1は、短絡防止の点で少なくともブロッキング層14を有することが好ましく、光吸収効率の点および短絡防止の点で多孔質層12およびブロッキング層14を有していることがさらに好ましい。
また、第一電極1は、有機材料で形成できる点で、電子輸送層15または正孔輸送層16を有することが好ましい。
導電性支持体11は、導電性を有し、感光層13等を支持できるものであれば特に限定されない。導電性支持体11は、導電性を有する材料、例えば金属で形成された構成、または、ガラスもしくはプラスチックの支持体11aとこの支持体11aの表面に形成された導電膜としての透明電極11bとを有する構成が好ましい。
支持体11aおよび導電性支持体11の厚みは、特に限定されず、適宜の厚みに設定される。例えば、0.01μm~10mmであることが好ましく、0.1μm~5mmであることがさらに好ましく、0.3μm~4mmであることが特に好ましい。
透明電極11bを設ける場合、透明電極11bの膜厚は、特に限定されず、例えば、0.01~30μmであることが好ましく、0.03~25μmであることがさらに好ましく、0.05~20μmであることが特に好ましい。
本発明においては、光電変換素子10A~10Cのように、好ましくは、透明電極11bの表面に、すなわち、導電性支持体11と、多孔質層12、感光層13または正孔輸送層3等との間に、ブロッキング層14を有している。
光電変換素子および太陽電池において、例えば感光層13または正孔輸送層3と、透明電極11bとが電気的に接続すると逆電流を生じる。ブロッキング層14は、この逆電流を防止する機能を果たす。ブロッキング層14は短絡防止層ともいう。
このブロッキング層は、光電変換素子が電子輸送層を有する場合にも設けられてもよい。例えば、光電変換素子10Dの場合、導電性支持体11と電子輸送層15との間に設けられてもよく、光電変換素子10Eの場合、第二電極2と電子輸送層4との間に設けられてもよい。
ブロッキング層14を形成する材料は、例えば、酸化ケイ素、酸化マグネシウム、酸化アルミニウム、炭酸カルシウム、ポリビニルアルコール、ポリウレタン等が挙げられる。また、一般的に光電変換材料に用いられる材料でもよく、例えば、酸化チタン、酸化スズ、酸化ニオブ、酸化タングステン等も挙げられる。なかでも、酸化チタン、酸化スズ、酸化マグネシウム、酸化アルミニウム等が好ましい。
ブロッキング層14の膜厚は、0.001~10μmが好ましく、0.005~1μmがさらに好ましく、0.01~0.1μmが特に好ましい。
本発明において、光電変換素子10Aおよび10Bのように、好ましくは、透明電極11b上に多孔質層12を有している。ブロッキング層14を有している場合、多孔質層12はブロッキング層14上に形成されることが好ましい。
多孔質層12は、表面に感光層13を担持する足場として機能する層である。太陽電池において、光吸収効率を高めるためには、少なくとも太陽光等の光を受ける部分の表面積を大きくすることが好ましく、多孔質層12の全体としての表面積を大きくすることが好ましい。
多孔質層12の表面積を大きくするには、多孔質層12を構成する個々の微粒子の表面積を大きくすることが好ましい。本発明では、多孔質層12を形成する微粒子を導電性支持体11等に塗設した状態で、この微粒子の表面積が投影面積に対して10倍以上であることが好ましく、100倍以上であることがより好ましい。この上限には特に制限はないが、通常5000倍程度である。多孔質層12を形成する微粒子の粒径は、投影面積を円に換算したときの直径を用いた平均粒径において、1次粒子として0.001~1μmが好ましい。微粒子の分散物を用いて多孔質層12を形成する場合、微粒子の上記平均粒径は、分散物の平均粒径として0.01~100μmが好ましい。
多孔質層12を形成する材料としては、例えば、金属のカルコゲニド(例えば酸化物、硫化物、セレン化物等)、ペロブスカイト型結晶構造を有する化合物(後述する光吸収剤を除く。)、ケイ素の酸化物(例えば、二酸化ケイ素、ゼオライト)、またはカーボンナノチューブ(カーボンナノワイヤおよびカーボンナノロッド等を含む)を用いることができる。
本発明においては、光電変換素子10Dのように、好ましくは、透明電極11bの表面に電子輸送層15を有している。
電子輸送層15は、感光層13で発生した電子を導電性支持体11へと輸送する機能を有する。電子輸送層15は、この機能を発揮することができる電子輸送材料で形成される。電子輸送材料としては、特に限定されないが、有機材料(有機電子輸送材料)が好ましい。有機電子輸送材料としては、[6,6]-Phenyl-C61-Butyric Acid Methyl Ester(PCBM)等のフラーレン化合物、ペリレンテトラカルボキシジイミド(PTCDI)等のペリレン化合物、その他、テトラシアノキノジメタン(TCNQ)等の低分子化合物、または、高分子化合物等が挙げられる。
電子輸送層15の膜厚は、特に限定されないが、0.001~10μmが好ましく、0.01~1μmがより好ましい。
本発明においては、光電変換素子10Eのように、好ましくは、透明電極11bの表面に正孔輸送層16を有している。
正孔輸送層16は、形成される位置が異なること以外は、後述する正孔輸送層3と同じである。
感光層13は、好ましくは、後述するペロブスカイト化合物が、光吸収剤として多孔質層12(光電変換素子10Aおよび10B)、もしくはブロッキング層14(光電変換素子10C))、電子輸送層15(光電変換素子10D)、または、正孔輸送層16(光電変換素子10E)の各層の表面(感光層13が設けられる表面が凹凸の場合の内表面を含む。)に設けられる。
本発明において、光吸収剤は、後述するペロブスカイト化合物を少なくとも1種含有していればよく、2種以上のペロブスカイト化合物を含有してもよい。
感光層13は、単層であっても2層以上の積層であってもよい。感光層13が2層以上の積層構造である場合、互いに異なった光吸収剤からなる層を積層してもよく、また感光層と感光層の間に正孔輸送材料を含む中間層を積層してもよい。
本発明において、感光層を厚い膜状に設ける場合(感光層13Bおよび13C)、この感光層に含まれる光吸収剤は正孔輸送材料として機能することもある。
感光層13は、光吸収剤として、有機カチオンと、周期表第一族元素以外の金属原子のカチオンと、アニオンとを有するペロブスカイト化合物を含む。
式(1)においては、Si原子に連結し、隣接して存在する2つのR1は互いに連結して環を形成してもよい。この場合、形成された環は、環構成原子としてヘテロ原子を有してもよい。
芳香族ヘテロ環を構成する環構成ヘテロ原子としては、窒素原子、酸素原子、硫黄原子が好ましい。また、芳香族ヘテロ環の環員数としては、5員環または6員環が好ましい。
5員環の芳香族ヘテロ環および5員環の芳香族ヘテロ環を含む縮合ヘテロ環としては、例えば、ピロール環、イミダゾール環、ピラゾール環、オキサゾール環、チアゾール環、トリアゾール環、フラン環、チオフェン環、ベンゾイミダゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、インドリン環、およびインダゾール環が挙げられる。また、6員環の芳香族ヘテロ環および6員環の芳香族ヘテロ環を含む縮合ヘテロ環としては、例えば、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、キノリン環、およびキナゾリン環が挙げられる。
R2として採り得るアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基および脂肪族ヘテロ環基は、それぞれ上記R1として採り得るアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基および脂肪族ヘテロ環基と同義であり、好ましい形態も同じである。N原子に連結し、隣接して存在する2つのR2は互いに連結して環を形成してもよい。この場合、形成された環は、環構成原子としてヘテロ原子を有してもよい。
上記式(1)で表されるシリル基を有する有機カチオンが、上記L中にアルキレン基を有する場合、このアルキレン基により上記Lと上記NR2 3 +とが連結していることが好ましい。すなわち、上記式(1)で表されるシリル基を有する有機カチオンが、上記L中にアルキレン基を有する場合には、この有機カチオンはR1 3Si-L1-L2-NR2 3 +で表されることが好ましい。ここで、L1は単結合、シクロアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、ヘテロアリーレン基、-O-、-S-、および-NRL-から選ばれる2価の連結基を示し、L2はアルキレン基を示す。R1、R2およびRLは、それぞれ上記で説明したR1、R2およびRLと同義であり、好ましい形態も同じである。また、アルキレン基L2の好ましい形態は、上述したLとして採り得るアルキレン基の好ましい形態と同じである。
RAとして採り得るアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、およびヘテロアリール基は、それぞれ、上記式(1)のR1が採り得るアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、およびヘテロアリール基と同義であり、好ましい範囲も同じである。
R1bは、水素原子または置換基を表し、水素原子が好ましい。R1bとして採り得る置換基は、アミノ基、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基が挙げられる。
R1bおよびR1cがそれぞれとり得る、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基およびヘテロアリール基は、それぞれ上記式(1)におけるR1として採り得るアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基およびヘテロアリール基と同義であり、好ましい形態も同じである。
式(3)で表すことができる基としては、(チオ)アシル基、(チオ)カルバモイル基、イミドイル基またはアミジノ基が挙げられる。
(チオ)アシル基は、アシル基およびチオアシル基を包含する。アシル基は、総炭素数が1~7のアシル基が好ましく、例えば、ホルミル、アセチル(CH3C(=O)-)、プロピオニル、ヘキサノイル等が挙げられる。チオアシル基は、総炭素数が1~7のチオアシル基が好ましく、例えば、チオホルミル、チオアセチル(CH3C(=S)-)、チオプロピオニル等が挙げられる。
(チオ)カルバモイル基は、カルバモイル基(H2NC(=O)-)およびチオカルバモイル基(H2NC(=S)-)を包含する。
イミドイル基は、R1b-C(=NR1c)-で表される基であり、R1bおよびR1cはそれぞれ水素原子またはアルキル基が好ましく、アルキル基は上記R1aのアルキル基と同義であるのがより好ましい。例えば、ホルムイミドイル(HC(=NH)-)、アセトイミドイル(CH3C(=NH)-)、プロピオンイミドイル(CH3CH2C(=NH)-)等が挙げられる。中でも、ホルムイミドイルが好ましい。
式(3)で表すことができる基としてのアミジノ基は、上記イミドイル基のR1bがアミノ基でR1cが水素原子である構造(-C(=NH)NH2)を有する。
4≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦999
19≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦499
49≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦199
本発明に用いるペロブスカイト化合物を構成するアニオンは、1種のアニオンであってもよく、2種以上のアニオンであってもよい。ペロブスカイト化合物を構成するアニオンが1種の場合、ヨウ素原子のアニオンが好ましい。また、ペロブスカイト化合物を構成するアニオンが2種以上の場合、2種以上のハロゲン原子のアニオンを有する形態が好ましく、なかでも塩素原子のアニオンおよびヨウ素原子のアニオンの2種を有する形態がより好ましい。ペロブスカイト化合物が2種以上のアニオンを有する場合、その割合に特に制限はない。
式中、Aは周期表第一族元素またはカチオン性有機基を表す。Mは周期表第一族元素以外の金属原子を表す。Xはアニオン性原子またはアニオン性原子群を表す。
aは1または2を表し、mは1を表し、a、mおよびxはa+2m=xを満たす。
本明細書において、カチオン性有機基とは、ペロブスカイト型結晶構造においてカチオンとして存在する有機基を意味し、アニオン性原子とは、ペロブスカイト型結晶構造において単原子アニオンとして存在する原子を意味し、アニオン性原子群とは、ペロブスカイト型結晶構造において多原子アニオンとして存在する原子群を意味する。
式(I)において、カチオン性有機基Aは、ペロブスカイト型結晶構造中において上述した有機カチオンとして存在する。
式(I)において、金属原子Mは、ペロブスカイト型結晶構造中において、上述した周期表第一族元素以外の金属原子のカチオンとして存在している。
式(I)において、アニオン性原子Xは、ペロブスカイト型結晶構造中において、上述した単原子アニオンとして存在する。
式(I)において、アニオン性原子群Xは、ペロブスカイト型結晶構造中において、上述した多原子アニオンとして存在する。
式(I)で表されるペロブスカイト化合物において、Aの少なくとも一部は、シリル基を有するカチオン性有機基である。
本発明の光電変換素子は、第一電極と第二電極との間に正孔輸送層3を有することが好ましい。
正孔輸送層3は、光吸収剤の酸化体に電子を補充する機能を有し、好ましくは固体状の層である。正孔輸送層3は、好ましくは第一電極1の感光層13と第二電極2の間に設けられる。
正孔輸送材料は、溶液塗布可能で固体状になる有機正孔輸送材料が好ましく、具体的には、2,2’,7,7’-テトラキス-(N,N-ジ-p-メトキシフェニルアミン)-9,9-スピロビフルオレン(Spiro-OMeTADともいう)、ポリ(3-ヘキシルチオフェン-2,5-ジイル)、4-(ジエチルアミノ)ベンゾアルデヒド ジフェニルヒドラゾン、ポリエチレンジオキシチオフェン(PEDOT)等が挙げられる。
本発明においては、光電変換素子10Eのように、好ましくは、感光層13Cと第二電極2との間に電子輸送層4を有している。
電子輸送層4は、電子の輸送先が第二電極である点、および、形成される位置が異なること以外は、上記電子輸送層15と同じである。
第二電極2は、太陽電池において正極として機能する。第二電極2は、導電性を有していれば特に限定されず、通常、導電性支持体11と同じ構成とすることができる。強度が十分に保たれる場合は、支持体11aは必ずしも必要ではない。
第二電極2の構造としては、集電効果が高い構造が好ましい。感光層13に光が到達するためには、導電性支持体11と第二電極2との少なくとも一方は実質的に透明でなければならない。本発明の太陽電池においては、導電性支持体11が透明であって太陽光を支持体11a側から入射させるのが好ましい。この場合、第二電極2は光を反射する性質を有することがさらに好ましい。
第二電極2としては、金属もしくは導電性の金属酸化物の薄膜(蒸着してなる薄膜を含む)、または、この薄膜を有するガラス基板もしくはプラスチック基板が好ましい。ガラス基板もしくはプラスチック基板としては、金もしくは白金の薄膜を有するガラス、または、白金を蒸着したガラスが好ましい。
本発明では、第一電極1と第二電極2との接触を防ぐために、ブロッキング層14等に代えて、または、ブロッキング層14等とともに、スペーサーやセパレータを用いることもできる。
また、第二電極2と正孔輸送層3の間に正孔ブロッキング層を設けてもよい。
本発明の太陽電池は、本発明の光電変換素子を用いて構成される。例えば図1~図5に示されるように、外部回路6を設けて構成した光電変換素子10を太陽電池として用いることができる。第一電極1(導電性支持体11)および第二電極2に接続される外部回路は、公知のものを特に制限されることなく、用いることができる。
本発明の太陽電池は、構成物の劣化および蒸散等を防止するために、側面をポリマーや接着剤等で密封することが好ましい。
本発明の光電変換素子および太陽電池は、公知の製造方法、例えば非特許文献1等に記載の方法に準拠して、製造できる。
以下に、本発明の光電変換素子および太陽電池の製造方法を簡単に説明する。
ブロッキング層14は、例えば、上記絶縁性物質またはその前駆体化合物等を含有する分散物を導電性支持体11の表面に塗布し、焼成する方法またはスプレー熱分解法等によって、形成できる。
多孔質層12を形成する方法としては、特に限定されず、例えば、湿式法、乾式法、その他の方法(例えば、Chemical Review,第110巻,6595頁(2010年刊)に記載の方法)が挙げられる。これらの方法において、導電性支持体11の表面またはブロッキング層14の表面に分散物(ペースト)を塗布した後に、100~800℃の温度で10分~10時間焼成することが好ましい。これにより、微粒子同士を密着させることができる。
焼成を複数回行う場合、最後の焼成以外の焼成の温度(最後以外の焼成温度)を、最後の焼成の温度(最後の焼成温度)よりも低い温度で行うのがよい。例えば、酸化チタンペーストを用いる場合、最後以外の焼成温度を50~300℃の範囲内に設定することができる。また、最後の焼成温度を、100~600℃の範囲内において、最後以外の焼成温度よりも高くなるように、設定することができる。支持体11aとしてガラス支持体を用いる場合、焼成温度は60~500℃が好ましい。
感光層13を設ける方法は、湿式法および乾式法が挙げられ、特に限定されない。本発明においては、湿式法が好ましく、例えば、吸収剤を含有する光吸収剤溶液に接触させる方法が好ましい。この方法においては、まず、感光層13を形成するための光吸収剤溶液を調製する。光吸収剤溶液は、上記ペロブスカイト化合物の原料であるMX2とAXとを含有する。ここで、A、MおよびXは上記式(I)のA、MおよびXと同義である。この光吸収剤溶液において、MX2とAXとのモル比は目的に応じて適宜に調整される。光吸収剤としてペロブスカイト化合物を形成する場合、AXとMX2とのモル比は、1:1~10:1であることが好ましい。この光吸収剤溶液は、AXとMX2とを所定のモル比で混合した後に好ましくは加熱することにより、調製できる。この形成液は通常溶液であるが、懸濁液でもよい。加熱する条件は、特に限定されないが、加熱温度は30~200℃が好ましく、60~150℃がさらに好ましい。加熱時間は0.5~100時間が好ましく、1~3時間がさらに好ましい。溶媒または分散媒は後述するものを用いることができる。
次いで、調製した光吸収剤溶液を、その表面に感光層13を形成する層(光電変換素子10においては、多孔質層12、ブロッキング層14、電子輸送層15または正孔輸送層16のいずれかの層)の表面に接触させる。具体的には、光吸収剤溶液を塗布または浸漬することが好ましい。これにより、ペロブスカイト化合物が多孔質層12、ブロッキング層14、電子輸送層15または正孔輸送層16の表面に形成される。接触させる温度は5~100℃であることが好ましく、浸漬時間は5秒~24時間であるのが好ましく、20秒~1時間がより好ましい。塗布した光吸収剤溶液を乾燥させる場合、上記乾燥は熱による乾燥が好ましく、通常は、20~300℃、好ましくは50~170℃に加熱することで乾燥させる。
また、上記ペロブスカイト化合物の合成方法に準じて感光層を形成することもできる。
さらに、上記AXを含有するAX溶液と、上記MX2を含有するMX2溶液とを、別々に塗布(浸漬法を含む)し、必要により乾燥する方法も挙げられる。この方法では、いずれの溶液を先に塗布してもよいが、好ましくはMX2溶液を先に塗布する。この方法におけAXとMX2とのモル比、塗布条件および乾燥条件は、上記方法と同じである。この方法では、上記AX溶液および上記MX2溶液の塗布に代えて、AXまたはMX2を、蒸着させることもできる。
さらに他の方法として、上記光吸収剤溶液の溶剤を除去した化合物または混合物を用いた、真空蒸着等の乾式法が挙げられる。例えば、上記AXおよび上記MX2を、同時または順次、蒸着させる方法も挙げられる。
これにより、光吸収剤が形成され、感光層13となる。
正孔輸送層3は、正孔輸送材料を含有する正孔輸送材料溶液を塗布し、乾燥して、形成することができる。正孔輸送材料溶液は、塗布性に優れる点、および多孔質層12を有しかつ空隙がある場合は多孔質層12の孔内部まで侵入しやすい点で、正孔輸送材料の濃度が0.01~1.0M(モル/L)であるのが好ましい。
電子輸送層4は、電子輸送材料を含有する電子輸送材料溶液を塗布し、乾燥して、形成することができる。
本発明の組成物は、下記式(1a)で表される化合物と、ハロゲン化金属とを含有してなる。
R1 3Si-L-NR2 3Hal 式(1a)
式中、R1、R2およびLは、それぞれ上記式(1)におけるR1、R2およびLと同義であり、好ましい形態も同じである。Halはハロゲン原子(好ましくはヨウ素原子、塩素原子、または臭素原子)を示す。
本発明の組成物は、上記式(1a)で表される化合物を1種含むものであってもよく、2種以上含んでもよい。
本発明の組成物は、固形(紛体、粒状等)であってもよく、溶液であってもよい。本発明の組成物が溶液である場合、用いる媒体としては有機溶媒が好ましい。この有機溶媒に特に制限はなく、アルコール溶媒、アミド溶媒、ニトリル溶媒、炭化水素溶媒、ラクトン溶媒、ハロゲン溶媒、またはこれらのうち2種以上の溶媒の混合溶媒が挙げられる。本発明の組成物に用いうる有機溶媒は、より好ましくは、メタノール、エタノール、イソプロパノール、γ-ブチロラクトン、クロロベンゼン、アセトニトリル、DMF、ジメチルアセトアミド、ジメチルスルホキシドまたはこれらの混合溶媒である。
また、本発明の組成物がRA-NH3Halを含有する場合、本発明の組成物中、上記式(1a)で表される化合物の含有量aとRA-NH3Halの含有量cのモル比は、4≦c/a≦999が好ましく、19≦c/a≦499がより好ましく、49≦c/a≦199が特に好ましい。
すなわち本発明の組成物は、本発明の光電変換素子の製造において、感光層の形成に好適に用いることができる。
[光電変換素子(試料No.101)の製造]
以下に示す手順により、図1に示される光電変換素子10Aを製造した。なお、感光層13の膜厚が大きい場合は、図2に示される光電変換素子10Bに対応することになる。
ガラス基板(支持体11a、厚さ2.2mm)上にフッ素ドープされたSnO2導電膜(透明電極11b)を形成し、導電性支持体11を作製した。
チタニウム ジイソプロポキシド ビス(アセチルアセトナート)の15質量%イソプロパノール溶液(アルドリッチ社製)を1-ブタノールで希釈して、0.02Mのブロッキング層用溶液を調製した。
調製した0.02Mのブロッキング層用溶液を用いてスプレー熱分解法により、450℃にて、導電性支持体11のSnO2導電膜上に酸化チタンからなるブロッキング層14(膜厚50nm)を形成した。
酸化チタン(アナターゼ、平均粒径20nm)のエタノール分散液に、エチルセルロース、ラウリン酸およびテルピネオールを加えて、酸化チタンペーストを調製した。
調製した酸化チタンペーストをブロッキング層14の上にスクリーン印刷法で塗布し、焼成した。この酸化チタンペーストの塗布および焼成を再度繰り返した。なお、1回目の焼成を130℃で1時間行い、2回目の焼成を500℃で1時間行った。得られた酸化チタンの焼成体を、40mMのTiCl4水溶液に浸した後、60℃で1時間加熱し、続けて500℃で30分間加熱して、TiO2からなる多孔質層12(膜厚250nm)を形成した。
(CH3NH3Iの合成)
メチルアミンの40%メタノール溶液(27.86mL)と、57質量%のヨウ化水素の水溶液(ヨウ化水素酸、30mL)を、フラスコ中、0℃で2時間攪拌した後、濃縮して、CH3NH3Iの粗体を得た。得られたCH3NH3Iの粗体をエタノールに溶解し、ジエチルエーテルで再結晶した。析出した結晶をろ取し、60℃で24時間減圧乾燥して、精製CH3NH3Iを得た。
(化合物(a1)の合成)
下記合成スキームに示すように、化合物(a1)を合成した。
(化合物(a2)の合成)
上記で合成した化合物(a1)の10%エタノール溶液(117g)と57質量%のヨウ化水素の水溶液(23g)を、フラスコ中、0℃で2時間攪拌した後、濃縮により溶媒を除去した後、さらに60℃で24時間減圧乾燥し下記化合物(a2)を得た。
(光吸収剤溶液Aの調製)
次いで、精製CH3NH3Iと化合物(a2)とPbI2を、モル比で99.8:0.2:50とし、ジメチルホルムアミド(DMF)中、60℃で12時間攪拌して混合した後、ポリテトラフルオロエチレン(PTFE)シリンジフィルターでろ過して、40質量%の光吸収剤溶液Aを調製した。
このようにして、第一電極1を作製した。
正孔輸送材料としてのSpiro-OMeTAD(180mg)をクロロベンゼン(1mL)に溶解させた。このクロロベンゼン溶液に、リチウム-ビス(トリフルオロメタンスルホニル)イミド(170mg)をアセトニトリル(1mL)に溶解させたアセトニトリル溶液(37.5μL)と、t-ブチルピリジン(TBP、17.5μL)とを加えて混合し、正孔輸送材料溶液を調製した。
次いで、正孔輸送材料溶液を、スピンコート法により、第一電極1の感光層13上に塗布し、塗布した正孔輸送材料溶液を乾燥して、正孔輸送層3(膜厚0.1μm)を形成した。
蒸着法により金(膜厚0.1μm)を正孔輸送層3上に蒸着して、第二電極2を作製した。
このようにして、試料No.101の光電変換素子10を製造した。
上述した試料No.101の光電変換素子の製造における、<感光層13Aの形成>において、精製CH3NH3Iと化合物(a2)との混合モル比を下表に示すとおりに変更したこと以外は、試料No.101の光電変換素子の製造と同様にして、試料No.102~104の光電変換素子10を製造した。なお、精製CH3NH3Iと化合物(a2)の総量と、PbI2との混合モル比は、試料No.101の製造と同様に2:1とした。
上述した試料No.101の光電変換素子の製造における、<感光層13Aの形成>において、メチルアミンをエチルアミンに変更し、且つ、精製CH3CH2NH3Iと化合物(a2)とPbI2のモル比を98:2:50としたこと以外は、試料No.101の光電変換素子の製造と同様にして、試料No.105の光電変換素子10を製造した。
上述した試料No.101の光電変換素子の製造における、<感光層13Aの形成>において、化合物(a1)に代えて化合物(b1)、(g1)、(s1)、(w1)、(x1)、(y1)、(z1)、(aa1)、(bb1)、(cc1)または(dd1)を用いることにより、下記化合物(b2)、(g2)、(s2)、(w2)、(x2)、(y2)、(z2)、(aa2)、(bb2)、(cc2)または(dd2)をそれぞれ得、これらの化合物と精製CH3NH3Iとの混合モル比を下表に示すとおりとしたこと以外は、試料No.101の光電変換素子の製造と同様にして、試料No.106~133の各光電変換素子10を製造した。なお、精製CH3NH3Iと化合物(b2)、(g2)、(s2)、(w2)、(x2)、(y2)、(z2)、(aa2)、(bb2)、(cc2)または(dd2)との総量と、PbI2との混合モル比は、試料No.101の製造と同様に2:1とした。
上述した試料No.101の光電変換素子の製造における<感光層13Aの形成>を下記の通りとしたこと以外は、試料No.101の光電変換素子の製造と同様にして、試料No.201の光電変換素子10を製造した。
メチルアミンの40%メタノール溶液(27.86mL)と57質量%のヨウ化水素の水溶液(ヨウ化水素酸、30mL)を、フラスコ中、0℃で2時間攪拌した後、濃縮して、CH3NH3Iの粗体を得た。得られたCH3NH3Iの粗体をエタノールに溶解し、ジエチルエーテルで再結晶した。析出した結晶をろ取し、60℃で24時間減圧乾燥して、精製CH3NH3Iを得た。
次いで、精製CH3NH3IとPbI2を、モル比で2:1とし、γ-ブチロラクトン中、60℃で12時間攪拌して混合した後、ポリテトラフルオロエチレン(PTFE)シリンジフィルターでろ過して、40質量%の光吸収剤溶液Bを調製した。
上述した試料No.201の光電変換素子の製造における、<感光層13Aの形成>において、メチルアミンを、メチルアミンとエチルアミンの混合物(メチルアミン/エチルアミン=9(モル比)とし、光吸収剤溶液Bの調製に際して、CH3NH3I:CH3CH2NH3I:PbI2=1.8:0.2:1(モル比)として混合したこと以外は、試料No.201の光電変換素子の製造と同様にして、試料No.202の光電変換素子10を製造した。
<初期の光電変換効率の測定>
光電変換効率を以下のようにして評価した。
各試料No.の光電変換素子を3検体ずつ製造した。3検体それぞれについて、電池特性試験を行って、光電変換効率(η/%)を測定した。そして、それら3検体の平均値を各試料No.の光電変換素子の初期の光電変換効率(η/%)とした。電池特性試験は、ソーラーシミュレーター「WXS-85H」(WACOM社製)を用いて、AM1.5フィルタを通したキセノンランプから1000W/m2の擬似太陽光を照射することにより行った。I-Vテスターを用いて電流-電圧特性を測定し、光電変換効率(η/%)を求めた。
光電変換素子の耐湿性を以下のようにして評価した。
各試料No.の3検体それぞれを、温度25℃、湿度60%RHの恒温恒湿槽に24時間保存してから、上記と同様にして電池特性試験を行って、光電変換効率(η/%)を測定した。3検体の平均値を各試料No.の光電変換素子の、保存後の光電変換効率(η/%)とした。
光電変換素子の耐湿性は、下記式によって算出される光電変換効率の低下率から下記評価基準に沿って評価した。
低下率(%)=100-{100×(保存後の光電変換効率)/(初期の光電変換効率)}
- 耐湿性評価基準 -
A: 低下率が25%未満
B: 低下率が25%以上29%未満
C: 低下率が29%以上33%未満
D: 低下率が33%以上37%未満
E: 低下率が37%以上
耐湿性評価基準において、〔A〕、〔B〕、〔C〕、および〔D〕が合格レベルであり、好ましくは〔A〕、〔B〕、および〔C〕であり、より好ましくは〔A〕である。一方、〔E〕は低下率が大きく、本発明の合格レベル(要求レベル)に到達しない。
結果を下記表1に示す。
なお、下記表1に示される[A2]/[A1]は、ペロブスカイト化合物を構成するシリル基を有する有機カチオンに対するシリル基を有しない有機カチオンのモル比に相当する。
これに対し、光吸収剤中のペロブスカイト化合物が、その結晶構造中にシリル基を有する有機カチオンを含む場合、光電変換素子は上記高湿条件下においても光電変換効率が低下しにくく、耐湿性に優れることがわかった。
11 導電性支持体
11a 支持体
11b 透明電極
12 多孔質層
13A、13B、13C 感光層
14 ブロッキング層
15 電子輸送層
16 正孔輸送層
2 第二電極
3A、3B 正孔輸送層
4 電子輸送層
6 外部回路(リード)
10A、10B、10C、10D、10E 光電変換素子
100A、100B、100C、100D、100E 光電変換素子を電池用途に応用したシステム
M 電動モーター
Claims (12)
- 光吸収剤を含む感光層を導電性支持体上に有する第一電極と、第一電極に対向する第二電極とを有する光電変換素子であって、
前記光吸収剤が、有機カチオンと、周期表第一族元素以外の金属原子のカチオンと、アニオンとを有するペロブスカイト型結晶構造を持つ化合物を含み、該化合物を構成する前記有機カチオンの少なくとも一部がシリル基を有する有機カチオンである、光電変換素子。 - 前記のシリル基を有する有機カチオンが下記式(1)で表される、請求項1に記載の光電変換素子。
R1 3Si-L-NR2 3 + 式(1)
式中、R1は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。R2は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。Lは2価の連結基を示す。 - 前記R1がアルキル基、アリール基またはヘテロアリール基である、請求項2に記載の光電変換素子。
- 前記Lがアルキレン基、シクロアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、ヘテロアリーレン基、-O-、-S-、および-NRL-から選ばれる2価の連結基であるか、または、これらの連結基の2種以上を組み合わせてなる2価の連結基である、請求項2または3に記載の光電変換素子。
RLは水素原子またはアルキル基を示す。 - 前記Lがアルキレン基もしくはアリーレン基であるか、または、アルキレン基およびアリーレン基を組み合わせてなる2価の連結基である、請求項4に記載の光電変換素子。
- 前記式(1)で表されるシリル基を有する有機カチオンが、前記L中にアルキレン基を有し、該アルキレン基により前記Lと前記NR2 3 +とが連結している、請求項2~5のいずれか1項に記載の光電変換素子。
- 前記のペロブスカイト型結晶構造を持つ化合物が、シリル基を有しない有機カチオンを有する、請求項1~6のいずれか1項に記載の光電変換素子。
- 前記のペロブスカイト型結晶構造を持つ化合物中、前記のシリル基を有する有機カチオンに対する前記のシリル基を有しない有機カチオンのモル比が下記式を満たす、請求項7に記載の光電変換素子。
19≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦499 - 前記のペロブスカイト型結晶構造を持つ化合物中、前記のシリル基を有する有機カチオンに対する前記のシリル基を有しない有機カチオンのモル比が下記式を満たす、請求項8に記載の光電変換素子。
49≦[シリル基を有しない有機カチオン]/[シリル基を有する有機カチオン]≦199 - 請求項1~9のいずれか1項に記載の光電変換素子を用いた太陽電池。
- 下記式(1a)で表される化合物と、ハロゲン化金属とを含有する組成物。
R1 3Si-L-NR2 3Hal 式(1a)
式中、R1は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。R2は水素原子、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基または脂肪族ヘテロ環基を示す。Lは2価の連結基を示す。Halはハロゲン原子を示す。 - 請求項1~9のいずれか1項に記載の光電変換素子の製造における感光層の形成に用いる、請求項11に記載の組成物。
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"Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting", ANGEWANDTE CHEMIE, vol. 53, 2014, pages 3151 - 3157, XP055162823 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017169191A1 (ja) * | 2016-03-30 | 2017-10-05 | 富士フイルム株式会社 | 光電変換素子、太陽電池、光電変換素子の製造方法、表面処理剤、表面処理用組成物および表面処理液 |
JPWO2017169191A1 (ja) * | 2016-03-30 | 2018-07-05 | 富士フイルム株式会社 | 光電変換素子、太陽電池、光電変換素子の製造方法、表面処理剤、表面処理用組成物および表面処理液 |
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CN107210370A (zh) | 2017-09-26 |
EP3267504A4 (en) | 2018-10-31 |
EP3267504A1 (en) | 2018-01-10 |
KR20170108109A (ko) | 2017-09-26 |
US20190304707A1 (en) | 2019-10-03 |
US20170330694A1 (en) | 2017-11-16 |
JP6229991B2 (ja) | 2017-11-15 |
JPWO2016143526A1 (ja) | 2017-07-20 |
US10418186B2 (en) | 2019-09-17 |
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