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WO2017169151A1 - Élément de conversion photoélectrique, cellule solaire et composition - Google Patents

Élément de conversion photoélectrique, cellule solaire et composition Download PDF

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Publication number
WO2017169151A1
WO2017169151A1 PCT/JP2017/004596 JP2017004596W WO2017169151A1 WO 2017169151 A1 WO2017169151 A1 WO 2017169151A1 JP 2017004596 W JP2017004596 W JP 2017004596W WO 2017169151 A1 WO2017169151 A1 WO 2017169151A1
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group
photoelectric conversion
conversion element
atom
formula
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English (en)
Japanese (ja)
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研史 白兼
寛敬 佐藤
伊勢　俊大
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2018508508A priority Critical patent/JP6442644B2/ja
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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

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%.
  • Non-Patent Document 1 describes a solar cell using a metal halide represented by CH 3 NH 3 PbI 2 Cl as a light absorber.
  • Patent Document 1 and Non-Patent Document 2 describe solar cells using a layered perovskite represented by (PEA) 2 (MA) 2 [Pb 3 I 10 ].
  • PEA represents C 6 H 5 (CH 2 ) 2 NH 3 +
  • MA represents CH 3 NH 3 + .
  • Non-Patent Document 3 describes a perovskite solar cell having a three-layer structure of a TiO 2 layer, a ZrO 2 layer, and a layer made of (5-AVA) x (MA) 1-x PbI 3. Yes.
  • 5-AVA represents a 5-aminovaleric acid cation
  • MA represents a methylammonium cation.
  • a photoelectric conversion element and a solar cell using a compound having a perovskite crystal structure have achieved certain results in improving photoelectric conversion efficiency.
  • Such photoelectric conversion elements and solar cells exhibit high photoelectric conversion efficiency even in the field environment where they are actually used, for example, in an environment where light from a light-emitting diode (LED) is irradiated indoors. Is required.
  • LED light-emitting diode
  • conventional photoelectric conversion elements and solar cells using a perovskite compound as a light absorber have a low photoelectric conversion efficiency in a low illuminance environment such as indoor LED light.
  • An object of the present invention is to provide a photoelectric conversion element using a perovskite compound as a light absorber and exhibiting high photoelectric conversion efficiency even in a low illuminance environment. Moreover, this invention makes it a subject to provide the solar cell using the said photoelectric conversion element. Furthermore, this invention makes it a subject to provide the composition suitable for forming the photosensitive layer of the said photoelectric conversion element.
  • the present inventors use two kinds of organic cations together, and 2 It has been found that a photoelectric conversion element and a solar cell exhibiting high photoelectric conversion efficiency can be obtained even in a low illuminance environment such as indoor LED light by setting the kind of organic cation to a specific ratio.
  • the present invention has been further studied based on these findings and has been completed.
  • a photoelectric conversion element having a first electrode having a photosensitive layer containing a light absorber on a conductive support, and a second electrode facing the first electrode,
  • the light absorber comprises a compound having a perovskite crystal structure having an organic cation, a cation of a metal atom, and an anion atom or an anion of an atomic group;
  • the organic cation includes a first organic cation represented by the following formula (1) and a second organic cation represented by the following formula (2),
  • the photoelectric conversion in which the content [A1] of the first organic cation and the content [A2] of the second organic cation satisfy the relationship of the molar ratio defined by 999 ⁇ [A2] / [A1] ⁇ 999999 element.
  • R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group.
  • R 1 represents an alkyl group having 1 or 2 carbon atoms
  • the alkyl group has a substituent selected from the following substituent group Z.
  • R 2 represents a methyl group, an ethyl group, or a group represented by the following formula (2a).
  • R 1a and R 2a each independently 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.
  • X a represents NR 2c, oxygen atom or sulfur atom.
  • R 2b and R 2c each independently represent a hydrogen atom or a substituent.
  • *** represents a bonding position with the N atom in the formula (2).
  • Substituent group Z alkenyl group, alkynyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylthio Carbonyl group, arylthiocarbonyl group, heteroarylthiocarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonyloxy group, alkylcarbonylthio group, arylcarbonylthio group, heteroarylcarbonylthio group, hydroxy group, mercapto Group, acyl group, halogen atom, cyano group, heteroaryl group and silyl group.
  • R 1 represents an alkyl group having 5 or more carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group.
  • R 1 represents a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group.
  • ⁇ 5> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 4>, wherein the ClogP value of the site represented by R 1 is 2.3 to 15.
  • ⁇ 6> A solar cell using the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 5>.
  • R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group.
  • R 1 represents an alkyl group having 1 or 2 carbon atoms
  • the alkyl group has a substituent selected from the following substituent group Z.
  • R 2 represents a methyl group, an ethyl group, or a group that can be represented by the following formula (2a).
  • R 1a and R 2a each independently 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.
  • Hal represents a halogen atom.
  • X a represents NR 2c, oxygen atom or sulfur atom.
  • R 2b and R 2c each independently represent a hydrogen atom or a substituent.
  • *** represents a bonding position with the N atom in the formula (2b).
  • Substituent group Z alkenyl group, alkynyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, alkylthio Carbonyl group, arylthiocarbonyl group, heteroarylthiocarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonyloxy group, alkylcarbonylthio group, arylcarbonylthio group, heteroarylcarbonylthio group, hydroxy group, mercapto Group, acyl group, halogen atom, cyano group, heteroaryl group and silyl group.
  • composition according to ⁇ 7> further comprising a metal halide.
  • composition according to ⁇ 7> or ⁇ 8> which is used for forming a photosensitive layer of the photoelectric conversion device according to any one of ⁇ 1> to ⁇ 5>.
  • the photoelectric conversion element and solar cell of the present invention exhibit high photoelectric conversion efficiency even in a low illumination environment.
  • the composition of this invention can be used suitably for formation of the photosensitive layer of the photoelectric conversion element of this invention.
  • FIG. 1A is a cross-sectional view schematically showing a preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 1B is an enlarged view of the circled portion of FIG. 1A.
  • FIG. 2 is a cross-sectional view schematically showing a preferred embodiment having a thick photosensitive layer of the photoelectric conversion element of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing another preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 4 is a sectional view schematically showing still another preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing still another preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing still another preferred embodiment of the photoelectric conversion element of the present invention.
  • each formula may be expressed as a sexual formula in order to understand the chemical structure of the compound. Accordingly, in each 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 atomic group or element constituting a (substituted) group or ion.
  • the display of a compound is used to mean not only the compound itself but also its salt and its ion. Moreover, about the compound which does not specify substituted or unsubstituted, it is the meaning containing the compound which has arbitrary substituents in the range which does not impair the target effect. The same applies to substituents and linking groups (hereinafter referred to as substituents and the like).
  • 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 of this invention has the 1st electrode which has the photosensitive layer containing a light absorber on a conductive support body, and the 2nd electrode facing a 1st electrode.
  • having a photosensitive layer on a conductive support means an embodiment in which a photosensitive layer is provided (directly provided) in contact with the surface of the conductive support, and another layer is provided above the surface of the conductive support. It includes a mode in which a photosensitive layer is provided.
  • the other layer provided between the conductive support and the photosensitive layer does not deteriorate the battery performance of the solar cell.
  • a porous layer, a blocking layer, an electron transport layer, a hole transport layer, and the like can be given.
  • the photosensitive layer may have a thin film shape (see FIG. 1A) or a thick film shape on the surface of the porous layer. (Refer to FIG. 2 and FIG. 6), an aspect (refer to FIG. 3) provided on the surface of the blocking layer in the form of a thin film or thick film, and a thin film or thick film on the surface of the electron transport layer (see FIG. 4) and a mode provided on the surface of the hole transport layer in a thin film shape or a thick film shape (see FIG. 5).
  • the photosensitive layer may be provided in a linear or dispersed form, but is preferably provided in a film form.
  • the perovskite compound as a light absorber has a perovskite crystal structure having two organic cations, a metal atom cation, and an anion atom or an anion of an atomic group. .
  • a photoelectric conversion element shows high photoelectric conversion efficiency also under irradiation of LED light indoors.
  • the structure other than the structure defined in the present invention is not particularly limited, 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.
  • a porous layer can be provided between the conductive support and the photosensitive layer (see FIGS. 1A, 2 and 6).
  • FIG. 1A, FIG. 1B, and FIGS. 2 to 6 the same reference numerals mean the same components (members).
  • 1A, 2 and 6 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.
  • the term “photoelectric conversion element 10” means the photoelectric conversion elements 10A to 10F unless otherwise specified.
  • the simple term “photosensitive layer 13” means the photosensitive layers 13A to 13C unless otherwise specified.
  • the hole transport layer 3 means the hole transport layers 3A and 3B unless otherwise specified.
  • a preferred embodiment of the photoelectric conversion element of the present invention includes, for example, a photoelectric conversion element 10A shown in FIG. 1A.
  • a system 100A shown in FIG. 1A is a system applied to a battery for causing the operation means M (for example, an electric motor) to work with the external circuit 6 using the photoelectric conversion element 10A.
  • the operation means M for example, an electric motor
  • the photoelectric conversion element 10A includes a first electrode 1A, a second electrode 2, and a hole transport layer 3A between the first electrode 1A and the second electrode 2.
  • 1st electrodes have the electroconductive support body 11 which consists of the support body 11a and the transparent electrode 11b, the porous layer 12, and the photosensitive layer 13A containing a perovskite type light absorber.
  • the photosensitive layer 13A is provided on the surface of the porous layer 12.
  • the blocking layer 14 is formed on the transparent electrode 11 b and the porous layer 12 is formed on the blocking layer 14.
  • the photoelectric conversion element 10B shown in FIG. 2 schematically shows a preferable embodiment in which the photosensitive layer 13A of the photoelectric conversion element 10A shown in FIG. 1A is provided thick.
  • the hole transport layer 3B is thinly provided.
  • the photoelectric conversion element 10B differs from the photoelectric conversion element 10A shown in FIG. 1A 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. In the photoelectric conversion element 10 ⁇ / b> C, the hole transport layer 3 ⁇ / b> B can be provided thick like the hole transport layer 3 ⁇ / b> A.
  • 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.
  • a 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.
  • a photoelectric conversion element 10F shown in FIG. 6 schematically shows still another preferred embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10F is different from the photoelectric conversion element 10B illustrated in FIG. 2 in that the hole transport layer 3B is not provided, but is configured in the same manner as the photoelectric conversion element 10B except for this point.
  • the system 100 to which the photoelectric conversion element 10 is applied functions as a solar cell as follows.
  • the photoelectric conversion element 10 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 (cation).
  • the electrons emitted from the light absorber move between the light absorbers and reach the conductive support 11. 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 differs depending on the presence and type of the porous layer 12 and the like.
  • the porous layer 12 can be formed of an insulator other than a 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.
  • a relatively high electromotive force (Voc) can be obtained by using aluminum oxide (Al 2 O 3 ) particles as the insulator particles.
  • the blocking layer 14 as the other layer is formed of a conductor or a semiconductor, electron conduction in the blocking layer 14 occurs. Electron conduction also 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.
  • a configuration in which the hole transport layer 3B is not provided as in the photoelectric conversion element 10F with respect to the photoelectric conversion element 10C or 10D may be employed.
  • 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 perovskite compound for example, Non-Patent Documents 1 to 3 can be referred to. And J.A. Am. Chem. Soc. 2009, 131 (17), p. 6050-6051 and Science, 338, p. 643 (2012).
  • the material and each member which are used for a dye-sensitized solar cell can refer also to the material and each member which are used for a dye-sensitized solar cell.
  • the dye-sensitized solar cell 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. 5,0843,65. Specification, US Pat. No. 5,350,644, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP-A-2004 -220974 and JP-A-2008-135197 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.
  • 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 as shown in FIG. 1A and FIGS.
  • the first electrode 1 preferably has at least a blocking layer 14 in terms of prevention of short circuit, and more preferably has a porous layer 12 and a blocking layer 14 in terms of light absorption efficiency and prevention of short circuit.
  • the first electrode 1 preferably has an electron transport layer 15 or a hole transport layer 16 formed of an organic material from the viewpoint of improving the productivity of the photoelectric conversion element, making it thin or flexible.
  • 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 is composed of a conductive material, for example, 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 having is preferable.
  • a conductive support 11 in which a conductive metal oxide is coated on the surface of a glass or plastic support 11a to form a transparent electrode 11b 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, indium-tin oxide (indium tin oxide; ITO), fluorine-doped tin oxide (FTO). Particularly preferred are fluorine-doped tin oxides such as
  • 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 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 thickness of the support 11a and the conductive support 11 is not particularly limited, and is set to an appropriate thickness.
  • 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.
  • a blocking layer 14 is provided on the surface of the transparent electrode 11b, that is, the conductive support 11, the porous layer 12, the photosensitive layer 13, or the hole transport layer 3 Etc.
  • the blocking layer 14 functions to prevent this reverse current.
  • the blocking layer 14 is also referred to as a short circuit prevention layer.
  • the blocking layer 14 can also function as a scaffold carrying a light absorber.
  • the blocking layer 14 may also be provided when the photoelectric conversion element has an electron transport 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. Also good.
  • the material for forming the blocking layer 14 is not particularly limited as long as it is a material that can perform the above function, and is a substance that transmits visible light, and is an insulating substance for the conductive support 11 (transparent electrode 11b) and the like. It is preferable that Specifically, 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, cesium 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, zinc oxide, niobium oxide, and tungsten oxide. Of these, titanium oxide, tin oxide, magnesium oxide, aluminum oxide and the like are preferable.
  • the film 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 a 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.
  • it is preferable to increase the surface area of at least a portion that receives light such as sunlight, and it is preferable to increase the entire surface area of the porous layer 12.
  • 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 fine particles are deposited.
  • the amount of light absorbent supported (adsorption amount) can be increased.
  • the surface area of the fine particles is preferably 10 times or more, more than 100 times the projected area. It is more preferable. This upper limit is not particularly limited, and is usually about 5000 times.
  • 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 perovskite compounds used as light absorbers), silicon. These oxides (for example, silicon dioxide, zeolite) or carbon nanotubes (including carbon nanowires and carbon nanorods) can be used.
  • metal chalcogenides eg, oxides, sulfides, selenides, etc.
  • compounds having a perovskite crystal structure excluding perovskite compounds used as light absorbers
  • silicon for example, silicon dioxide, zeolite
  • carbon nanotubes including carbon nanowires and carbon nanorods
  • the metal chalcogenide is not particularly limited, and preferably titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, aluminum or tantalum oxide, cadmium sulfide, selenium. Examples thereof include cadmium iodide. 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 a single graphene sheet is rolled into a cylindrical shape, and double-walled carbon nanotubes (double-walled in which two graphene sheets are wound in a concentric shape).
  • carbon nanotube (DWCNT) which is classified into multi-walled carbon nanotube (MWCNT) in which a plurality of graphene sheets are concentrically wound.
  • MWCNT multi-walled carbon nanotube
  • 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 thickness of the porous layer 12 is not particularly limited, and is usually in the range of 0.05 to 100 ⁇ m, preferably in the range of 0.1 to 100 ⁇ m. When used as a solar cell, the thickness is preferably 0.1 to 50 ⁇ m, more preferably 0.2 to 30 ⁇ m.
  • 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, and an organic material (organic electron transport material) is preferable.
  • the organic electron transporting material include fullerene compounds such as [6,6] -phenyl-C61-Butylic Acid Methyl Ester (PC 61 BM), perylene compounds such as perylene tetracarboxylic diimide (PTCDI), and other tetra Examples thereof include a low molecular compound such as cyanoquinodimethane (TCNQ) or a high molecular compound.
  • the film 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 may be 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 photosensitive layer 13 is preferably a porous layer 12 (photoelectric conversion elements 10A, 10B and 10F), a blocking layer 14 (photoelectric conversion element 10C), an electron transport layer 15 (photoelectric conversion element 10D), or a hole transport layer 16. (Photoelectric conversion element 10E) is provided on the surface of each layer (including the inner surface of the recess when the surface on which the photosensitive layer 13 is provided is uneven).
  • the light absorber is represented by the first organic cation represented by the following formula (1) (hereinafter sometimes referred to as the first organic cation (A1)) and the formula (2). It is only necessary to contain a perovskite compound having at least one second organic cation (hereinafter sometimes referred to as a second organic cation (A2)).
  • 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.
  • the ratio of the perovskite compound to other light absorbers is not particularly limited.
  • the photosensitive layer 13 may be a single layer or a laminate of two or more layers.
  • the photosensitive layer 13 may be a laminated structure in which layers made of different light absorbers are laminated, and an intermediate including a hole transport material between the photosensitive layer and the photosensitive layer.
  • a laminated structure having layers may also be used.
  • the photosensitive layer 13 has a laminated structure of two or more layers, the first organic cation (A1) and the second organic cation (A2) are included in at least one layer (any layer or all layers). As long as it has at least one perovskite compound.
  • the aspect 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 to the conductive support 11 or the second electrode 2.
  • 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. Usually, the film thickness is, for example, preferably 0.001 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m, and particularly preferably 0.01 to 5 ⁇ m.
  • the total film thickness with the porous layer 12 is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, further preferably 0.1 ⁇ m or more, and 0.3 ⁇ m or more. Particularly preferred. Further, the total film thickness is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less. The total film thickness can be in a range where the above values are appropriately combined.
  • the thickness of the photosensitive layer 13 is the interface with the porous layer 12 along the direction perpendicular to the surface of the porous layer 12. This is the distance from the interface with the hole transport layer 3 described later.
  • the total film thickness of the porous layer 12, the photosensitive layer 13, and the hole transport layer 3 is not particularly limited. 01 ⁇ m or more is preferable, 0.05 ⁇ m or more is more preferable, 0.1 ⁇ m or more is further preferable, and 0.3 ⁇ m or more is particularly preferable.
  • the total film thickness is preferably 200 ⁇ m or less, preferably 50 ⁇ m or less, preferably 30 ⁇ m or less, and preferably 5 ⁇ m or less.
  • the total film thickness can be in a range where the above values are appropriately combined.
  • the light absorber contained in the photosensitive layer may function as a hole transport material.
  • the photosensitive layer 13 includes a perovskite compound (also referred to as a perovskite light absorber) having “cationic organic group A”, “metal atom M”, and “anionic atom or atomic group X” as a light absorber. contains.
  • the cationic organic group A, the metal atom M, and the anionic atom or atomic group X of the perovskite compound each have an organic cation (sometimes referred to as an organic cation A for convenience), a metal cation (for convenience, a metal for a perovskite crystal structure). It is present as each constituent ion of a cation M) and an anion (sometimes referred to as an anion X for convenience).
  • the cationic organic group means an organic group having a property of becoming an organic cation A in a perovskite crystal structure.
  • the cationic organic group A includes at least two kinds of organic groups that respectively become first and second organic cations described later.
  • An anionic atom or atomic group means an atom or atomic group having a property of becoming an anion in a perovskite crystal structure.
  • the perovskite compound as the light absorber includes two kinds of a first organic cation (A1) having a specific organic group and a second organic cation (A2) having a specific organic group.
  • A1 a first organic cation
  • A2 a second organic cation
  • Having a perovskite crystal structure having a cation of a metal atom and an anion of an anionic atom or atomic group, and the content of the first organic cation [A1] and the content of the second organic cation [ A2] satisfies the molar ratio relationship defined by 999 ⁇ [A2] / [A1] ⁇ 999,999.
  • a photoelectric conversion element and a solar cell satisfying these conditions exhibit high photoelectric conversion efficiency under irradiation of LED light at room temperature.
  • the first organic cation which is a minor component, has substantially the same potential as the second organic cation.
  • the first organic cation that is unevenly distributed at the grain boundary is a trap for charges.
  • the organic cation (A1) is represented by the following formula (1).
  • Formula (1) R 1 —N (R 1a ) 3 +
  • R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group.
  • R 1 is an alkyl group having 1 or 2 carbon atoms
  • each alkyl group has a substituent selected from the following substituent group Z.
  • 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 30 carbon atoms, more preferably 5 to 18 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
  • Preferable specific examples of this alkyl group include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, decyl and octadecyl.
  • each alkyl group has a substituent selected from the following substituent group Z.
  • substituent group Z In the substituent each of the alkyl group having 1 or 2 carbon atoms, the preferable group and the preferable range of each group are the same as the preferable group and the range described in the substituent group Z described later.
  • the cycloalkyl group that can be used 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, propynyl, butynyl, hexynyl and octynyl.
  • 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 is a group consisting of only an aromatic heterocycle and a group consisting of a condensed heterocycle obtained by condensing an aromatic heterocycle with another ring, for example, an aromatic ring, an aliphatic ring or a heterocycle. Including.
  • the 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 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring.
  • the aromatic hetero ring preferably has 0 to 20 carbon atoms, more preferably 0 to 18 carbon atoms.
  • 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 or 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 taken as R 1 includes a group consisting of only an aliphatic heterocyclic ring and a group consisting of an aliphatic heterocyclic ring and another ring, for example, an aliphatic condensed heterocyclic ring in which an aliphatic ring is condensed.
  • a ring-constituting hetero atom constituting the aliphatic hetero ring a nitrogen atom, an oxygen atom, and a sulfur atom are preferable.
  • the number of ring members of the aliphatic heterocycle is preferably a 3 to 8 membered ring, more preferably a 5 or 6 membered ring.
  • the number of carbon atoms in the aliphatic heterocycle is preferably 0 to 24, and more preferably 1 to 18.
  • aliphatic heterocycle examples include pyrrolidine ring, oxolane ring, thiolane ring, piperidine ring, tetrahydrofuran ring, oxane ring, thiane ring, piperazine ring, morpholine ring, quinuclidine ring, pyrrolidine ring, azetidine ring, oxetane ring, Examples thereof include an aziridine ring, a dioxane ring, a pentamethylene sulfide ring, and ⁇ -butyrolactone.
  • R 1 is preferably an alkyl group having 5 or more carbon atoms, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group, and a cycloalkyl group, an alkenyl group, an alkynyl group.
  • a group, an aryl group, a heteroaryl group or an aliphatic heterocyclic group is more preferable.
  • R 1 may have a substituent.
  • the substituent in this case is not particularly limited, and an alkyl group or a substituent selected from the following substituent group Z is preferable.
  • Embodiment R 1 has a substituent is not particularly limited, for example, the embodiments having R 1 substituent, and embodiments having complex substituent R 1 is a combination of 2 or more substituents, R 1 is a substituted And embodiments having multiple substituents.
  • R 1 when having R 1 substituent, R 1, then the substituents directly bonded to R 1, such that many carbon atoms in the order of, determining R 1 and substituents. Similarly, in the case of a composite substituent, each substituent is determined so that the substituent closer to R 1 has a larger number of carbon atoms.
  • Substituent group Z includes alkenyl group, alkynyl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, Alkylthiocarbonyl group, arylthiocarbonyl group, heteroarylthiocarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, heteroarylcarbonyloxy group, alkylcarbonylthio group, arylcarbonylthio group, heteroarylcarbonylthio group, hydroxy group, Including a mercapto group, an acyl group, a halogen atom, a cyano group, a teloaryl group, and a silyl group.
  • an alkyl group when an alkyl group is described separately from a cycloalkyl group, the alkyl group is used to include a linear alkyl group and a branched alkyl group.
  • an alkyl group when simply described as an alkyl group), and unless otherwise specified, an alkyl group is a linear alkyl group or a branched alkyl group And cycloalkyl group.
  • the acyl group preferably has 1 to 19 carbon atoms, and more preferably 2 to 19 carbon atoms.
  • Preferable specific examples of the acyl group include, for example, formyl, acetyl, propionyl, octadecanoyl, benzoyl or acrylyl.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and an iodine atom or a bromine atom is preferable.
  • a carbonyl group, an arylthiocarbonyl group, a heteroarylthiocarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a heteroarylcarbonyloxy group, an alkylcarbonylthio group, an arylcarbonylthio group, and a heteroarylcarbonylthio group are as follows: It can be represented by any one of formulas (W-1) to (W-6).
  • * represents the bonding position with the N atom in the above formula (1) or another substituent selected from the substituent group Z.
  • Rw represents any of an alkyl group, an aryl group, and a heteroaryl group.
  • the preferred ranges of the alkyl group, aryl group and heteroaryl group are the same as the preferred ranges of the alkyl group (including cycloalkyl group), aryl group and heteroaryl group of R 1 above.
  • Table 1 below shows the correspondence between each of the substituents contained in the substituent group Z and the groups represented by the above formulas (W-1) to (W-6).
  • R 1 has, it is preferable that at least one is a silyl group.
  • the substituent selected from the substituent group Z may further have a substituent (an embodiment having a composite substituent).
  • the substituent that may be further included is not particularly limited, and preferably includes an alkyl group or a substituent selected from the above substituent group Z.
  • the preferred range of the substituent which may be present is the same as the preferred range of R 1 or the substituent group Z.
  • the combination of a plurality of substituents selected from an alkyl group or substituent group Z is not particularly limited, and includes, for example, a combination of a halogen atom and another substituent, an alkyl group and another substituent, , A combination of an alkylthio group and another substituent, or a combination of a silyl group and another substituent.
  • halogen atoms and other substituents examples include alkoxy groups and halogen atoms, aryloxy groups and halogen atoms, heteroaryloxy groups and halogen atoms, alkylthio groups and halogen atoms, arylthio groups and halogen atoms, and heteroaryls.
  • Examples include a combination of a ruthio group and a halogen atom, an acyl group and a halogen atom, or a heteroaryl group and a halogen atom.
  • alkyl groups and other substituents examples include aryloxy groups and alkyl groups, heteroaryloxy groups and alkyl groups, arylthio groups and alkyl groups, heteroarylthio groups and alkyl groups, aryloxycarbonyl groups and alkyl groups.
  • heteroaryloxycarbonyl group and alkyl group arylthiocarbonyl group and alkyl group, heteroarylthiocarbonyl group and alkyl group, arylcarbonyloxy group and alkyl group, heteroarylcarbonyloxy group and alkyl group, arylcarbonylthio group and Examples include an alkyl group, a heteroarylcarbonylthio group and an alkyl group, or a combination of a heteroaryl group and an alkyl group, a silyl group and an alkyl group.
  • alkylthio groups and other substituents examples include aryloxy groups and alkylthio groups, heteroaryloxy groups and alkylthio groups, arylthio groups and alkylthio groups, heteroarylthio groups and alkylthio groups, aryloxycarbonyl groups and alkylthio groups.
  • heteroaryloxycarbonyl group and alkylthio group arylthiocarbonyl group and alkylthio group, heteroarylthiocarbonyl group and alkylthio group, arylcarbonyloxy group and alkylthio group, heteroarylcarbonyloxy group and alkylthio group, arylcarbonylthio group and Examples include alkylthio groups, heteroarylcarbonylthio groups and alkylthio groups, acyl groups and alkylthio groups, or heteroaryl groups and alkylthio groups.
  • the number of substituents that R 1 can have is not particularly limited in any of the above embodiments, and is preferably set appropriately depending on the type of the substituent.
  • the number of substituents is preferably 1 to 37 (in the case of a composite substituent, 2 to 37), preferably 1 to 19 (of the composite substituent). More preferably 1 to 13 (2 to 13 in the case of a composite substituent), and further preferably 1 to 7 (2 to 19 in the case of a composite substituent). 7) is particularly preferable.
  • the number of substituents is preferably 1 to 8 (2 to 8 in the case of a composite substituent), preferably 1 to 4 ( More preferably, it is 2 to 4 in the case of a composite substituent.
  • the number of substituents may be 1 to 6 (2 to 6 in the case of a composite substituent) It is preferably 1 to 3 (more preferably 2 or 3 in the case of a composite substituent).
  • the ClogP value of R 1 is preferably 2.3 to 15 from the viewpoint of the stability of the photoelectric conversion element.
  • the ClogP value is known as an index of the fat solubility of the compound.
  • the ClogP value is a value obtained by calculating the common logarithm logP of the distribution coefficient P between 1-octanol and water of the compound.
  • the measurement of the octanol-water partition coefficient (log P value) can be generally carried out by a flask soaking method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement.
  • Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987)
  • Viswanadhan's fragmentation method J. Chem. Inf. Comput. Sci., 29, 163). (1989)
  • Broto's fragmentation method Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984) and the like are known.
  • R 1a 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.
  • R 1a An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group and an aliphatic heterocyclic group that can be taken as R 1a are respectively an alkyl group, a cycloalkyl group, and an alkenyl that can be taken as R 1.
  • Each group, alkynyl group, aryl group, heteroaryl group and aliphatic heterocyclic group have the same meaning and preferred ranges are also the same.
  • Two R 1a that are adjacent to each other and connected to the N atom 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.
  • R 1a is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • first organic cation (A1) that the perovskite compound used in the present invention can have are shown below, but the present invention is not limited thereto.
  • Particularly preferred first organic cations (A1) are organic cations a3, a4, a5, a6 and a59.
  • the second organic cation (A2) is represented by the following formula (2).
  • R 2a 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.
  • An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group and an aliphatic heterocyclic group that can be taken as R 2a are each an alkyl group, a cycloalkyl group, an alkenyl that can be taken as R 1. It is synonymous with a group, an alkynyl group, an aryl group, a heteroaryl group and an aliphatic heterocyclic group, and the preferred range is also the same.
  • Two R 2a that are connected to an N atom 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.
  • R 2a is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • R 2 represents a methyl group, an ethyl group or a group represented by the following formula (2a).
  • X a represents NR 2c , an oxygen atom or a sulfur atom, and NR 2c is preferable.
  • R 2c represents a hydrogen atom or a substituent.
  • the substituent that can be adopted as R 2c is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group.
  • R 2c is preferably a hydrogen atom.
  • R 2b represents a hydrogen atom or a substituent, and preferably a hydrogen atom.
  • the substituent which can be taken as R 2b is not particularly limited, examples thereof include an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group.
  • An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group, which R 2b and R 2c can each take, are each taken as R 1 in the above formula (1).
  • the obtained alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aliphatic group have the same definitions, and preferred ranges are also the same.
  • Examples of the group that can be represented by the formula (2a) 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 imidoyl group is a group represented by R 2b —C ( ⁇ NR 2c ) —, and R 2b and R 2c are each preferably a hydrogen atom or an alkyl group.
  • Alkyl group has the same meaning as the above alkyl group R 1.
  • formimidoyl is preferable.
  • the amidino group as a group that can be represented by the formula (2) has a structure (—C ( ⁇ NH) NH 2 ) in which R 2b of the imidoyl group is an amino group and R 2c is a hydrogen atom.
  • the second organic cation (A2) is an organic ammonium cation formed by combining R 2 of the above formula (2) and NH 3 + Become.
  • the organic ammonium cation can take a resonance structure
  • the second organic cation (A2) includes a cation having a resonance structure in addition to the organic ammonium cation.
  • the organic cation is one of the resonance structures of the organic ammonium cation in addition to the organic ammonium cation.
  • organic amidinium cations are also included.
  • Examples of the organic amidinium cation include a cation represented by the following formula (A am ).
  • a cation represented by the following formula (A am ) may be expressed as “R 2b C ( ⁇ NH) —NH 3 + ” for convenience.
  • the content [A2] of the second organic cation (A2) with respect to the content [A1] of the first organic cation (A1) is defined by the following formula (i) as a molar ratio. It is preferable to satisfy the relationship defined by the following formula (ii), and it is more preferable to satisfy the relationship defined by the following formula (iii).
  • [A1] represents the content of the first organic cation (A1)
  • [A2] represents the content of the second organic cation (A2) in molar amounts.
  • the cation of the metal atom M is preferably a cation of a metal atom other than the Group 1 element of the periodic table.
  • the metal atom M include calcium (Ca), strontium (Sr), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), iron (Fe), cobalt (Co), palladium ( Metals such as Pd), germanium (Ge), tin (Sn), lead (Pb), ytterbium (Yb), europium (Eu), indium (In), titanium (Ti), bismuth (Bi), thallium (Tl) Atom.
  • Pb atom, Cu atom, Ge atom or Sn atom is particularly preferable.
  • the cation of the metal atom M may be a single cation or two or more cations. In the case of two or more kinds of cations, these ratios (content ratios) are not particularly limited.
  • the anion X represents an anionic atom or an anion of the atomic group X.
  • This anion is preferably an anion of a halogen atom or an anion of each atomic group of NCS ⁇ , NCO ⁇ , OH ⁇ , NO 3 ⁇ , CH 3 COO ⁇ or HCOO ⁇ .
  • an anion of a halogen atom is more preferable.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.
  • the anion X may be an anion of one type of anionic atom or atomic group, or may be an anion of two or more types of anionic atom or atomic group.
  • an anion of iodine atom is preferable.
  • two types of anions of halogen atoms, particularly anions of chlorine atoms and iodine atoms are preferred.
  • the ratio (content ratio) of two or more types of anions is not particularly limited.
  • the perovskite compound used in the present invention has a perovskite crystal structure having each of the above constituent ions, and for example, a perovskite compound represented by the following formula (I) is preferable.
  • A represents a cationic organic group.
  • M represents a metal atom.
  • X represents an anionic atom or atomic group.
  • a represents 1 or 2
  • the cationic organic group forms the organic cation A having a perovskite crystal structure.
  • the cationic organic group includes one or more cationic organic groups that generate the first organic cation (A1) and one or more cationic organic groups that generate the second organic cation (A2). These cationic organic groups, molar ratios, etc. are synonymous with what was demonstrated with the said organic cation A, and a preferable thing is also the same.
  • the metal atom M is a metal atom that forms the metal cation M having a perovskite crystal structure. Therefore, the metal atom M is not particularly limited as long as it is an atom that can form the perovskite crystal structure by becoming the metal cation M.
  • the metal atom M is synonymous with the metal atom described in the metal cation M, and the preferred ones are also the same.
  • the anionic atom or atomic group X forms the anion X having a perovskite crystal structure. Therefore, the anionic atom or atomic group X is not particularly limited as long as it is an atom or atomic group that can form the perovskite crystal structure by becoming the anion X.
  • the anionic atom or atomic group X is synonymous with the anionic atom or atomic group described in the above anion X, and preferred ones are also the same.
  • the perovskite compound represented by formula (I) is a perovskite compound represented by the following formula (I-1) when a is 1, and when a is 2, the perovskite compound represented by formula (I-2) It is a perovskite compound represented.
  • A represents a cationic organic group and is synonymous with the cationic organic group A of the above formula (I), and preferred ones are also the same.
  • M represents a metal atom and is synonymous with the metal atom M of the above formula (I), and preferred ones are also the same.
  • X represents an anionic atom or atomic group, and is synonymous with the anionic atom or atomic group X of the above formula (I), and preferred ones are also the same.
  • the perovskite compound further has, as a cation, an organic cation other than a cationic organic group that becomes a cation of a group 1 element of the periodic table or a first organic cation (A1) and a second organic cation (A2). May be.
  • the cation of the Group 1 element of the periodic table is not particularly limited.
  • the cation of each element of lithium (Li), sodium (Na), potassium (K), or cesium (Cs) (Li + , Na + , K + , Cs + ), and a cesium cation (Cs + ) is particularly preferable.
  • the organic cation other than the first organic cation (A1) and the second organic cation (A2) is not particularly limited as long as it is a cation having the above properties.
  • the perovskite compound used in the present invention is a total molar amount of the first organic cation (A1), the second organic cation (A2), and the cation of the metal atom M with respect to the total molar amount of cations constituting the perovskite crystal structure. 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 type crystal structure is preferably 90 to 100 mol%, and 95 to 100 More preferably, it is mol%, more preferably 98 to 100 mol%.
  • the perovskite compound can be synthesized from, for example, a compound represented by the following formula (II) and a compound represented by the following formula (III).
  • Formula (II) AX Formula (III) MX 2
  • A represents a cationic organic group, and is synonymous with the cationic organic group A of formula (I), and preferred ones are also the same.
  • X represents an anionic atom or atomic group, and has the same meaning as that of the anionic atom or atomic group X of the formula (I), and preferred examples thereof are also the same.
  • M represents a metal atom and has the same meaning as that of the metal atom M in the formula (I), and preferred examples thereof are also the same.
  • X represents an anionic atom or atomic group, and is synonymous with the anionic atom or atomic group X of formula (I), and the preferred ones are also the same.
  • Examples of the synthesis method of the perovskite compound include Non-Patent Documents 1 to 3 described above.
  • Akihiro Kojima, Kenjiro Teshima, Yasushio Shirai, and Tsutomu Miyasaka, “Organal Halide Perovskitsu asVisibleSports-PrivateSport. Am. Chem. Soc. 2009, 131 (17), p. 6050-6051 may also be mentioned.
  • the light absorber may be used in an amount that covers at least part of the surface of the layer provided adjacent to the photosensitive layer, and is preferably an amount that covers the entire surface.
  • the content of the perovskite compound is usually 1 to 100% by mass.
  • the hole transport layer 3 is provided between the first electrode 1 and the second electrode 2 as in the photoelectric conversion elements 10A to 10D.
  • the hole transport layer 3 is preferably in contact (laminated) with the photosensitive layer 13.
  • 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 layer 3 has a function of replenishing electrons to the oxidant of the light absorber, and is preferably a solid layer (solid hole transport layer).
  • the hole transport material forming the hole transport layer 3 may be a liquid material or a solid material, and is not particularly limited. Examples thereof include inorganic materials such as CuI and CuNCS, and organic hole transport materials described in paragraph numbers 0209 to 0212 of JP-A No. 2001-291534, for example.
  • the organic hole transport material is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole and polysilane, a spiro compound in which two rings have a tetrahedral structure such as C or Si, a 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) Amino) -9,9′-spirobifluorene (2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenylamine) -9,9′-spirobifluorene: also referred to as spiro-MeOTAD
  • poly (3-hexylthiophene-2,5-diyl) 4- (diethylamino) benzaldehyde, diphenylhydrazone, poly (3,4-ethylenedioxythiophene) (PEDOT), and the like. .
  • the film thickness of the hole transport layer 3 is not particularly limited, 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 film thickness of the hole transport layer 3 corresponds to the average distance between the second electrode 2 and the surface of the photosensitive layer 13, and the cross section of the photoelectric conversion element using a scanning electron microscope (SEM) or the like. Can be measured by observing.
  • the photoelectric conversion element of this invention has the electron carrying layer 4 between the 1st electrode 1 and the 2nd electrode 2 like the photoelectric conversion element 10E.
  • the electron transport layer 4 is preferably in contact (laminated) with the photosensitive layer 13.
  • 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 it 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 a structure having a high current collecting effect is preferable.
  • at least one of the conductive support 11 and the second electrode 2 must be substantially transparent.
  • the electroconductive support body 11 is transparent and sunlight etc. are entered from the support body 11a side.
  • 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 a conductive material formed by bonding carbon atoms to each other, and examples thereof include fullerene, carbon nanotube, graphite, and graphene.
  • 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 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 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 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 configured to cause the external circuit 6 to work can be used as a solar cell.
  • the external circuit 6 connected to the first electrode 1 (conductive support 11) and the second electrode 2 a known one can be used without particular limitation.
  • Non-Patent Documents 1 to 3 J. Am. Chem. Soc. 2009, 131 (17), p. 6050-6051 and Science, 338, p. 643 (2012).
  • the side surface it is preferable to seal the side surface with a polymer, an adhesive, or the like in order to prevent deterioration of the components and transpiration.
  • the photoelectric conversion element and solar cell of the present invention can be produced by a known production method other than the formation of a photosensitive layer, for example, Non-Patent Documents 1 to 3, Am. Chem. Soc. 2009, 131 (17), p. 6050-6051, Science, 338, p. 643 (2012) or the like.
  • the manufacturing method of the photoelectric conversion element and solar cell of this invention is demonstrated easily.
  • the production method of the present invention first, at least one of the blocking layer 14, the porous layer 12, the electron transport layer 15, and the hole transport layer 16 is formed on the surface of the conductive support 11 as desired.
  • 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 on the surface of the conductive support 11 and baking, or a spray pyrolysis method.
  • the material forming the porous layer 12 is preferably used as fine particles, more preferably 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)).
  • the dispersion (paste) is applied to the surface of the conductive support 11 or the surface of the blocking layer 14, and then fired at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours, for example, in air. preferable. 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 photosensitive layer 13 is provided.
  • a compound capable of synthesizing a perovskite compound is used.
  • compounds that can synthesize a perovskite compound include the compound AX represented by the above formula (II) and the compound MX 2 represented by the above formula (III). Each of these compounds may be used alone or as a composition (including solutions, suspensions, pastes, etc.).
  • the photosensitive layer 13 can be formed using a light absorbent composition containing all of the above compounds. Further, a composition containing the first halide represented by the following formula (1b) and the second halide represented by the following formula (2b) (the composition of the present invention, a light absorber composition). For the sake of distinction, the photosensitive layer 13 may be formed using the compound MX 2 for convenience) and the compound MX2.
  • A, M and X have the same meanings as A, M and X in the above formula (I). .
  • R 1 —N (R 1a ) 3 X and the compound R 2 —N (R 2a ) 3 X are preferable to use as the compound AX.
  • R 1, R 2, R 1a and R 2a, respectively, the equation (1) and (2) have the same meanings as R 1, R 2, R 1a and R 2a in a preferred also the same .
  • X is preferably a halogen atom.
  • both the above compounds are the first and second halides represented by the following formulas (1b) and (2b), respectively, and preferable ones are also the same. is there.
  • R 1, R 2, R 1a and R 2a respectively, have the same meanings as R 1, R 2, R 1a and R 2a in the formula (1) and (2), it is preferable also the same .
  • Hal represents a halogen atom, preferably an iodine atom, a chlorine atom or a bromine atom.
  • Light absorbent composition comprising a compound AX and Compound MX 2.
  • the light absorbent composition by heating the compound AX and Compound MX 2 were mixed in a predetermined molar ratio, it can be prepared.
  • This forming liquid is usually a solution (light absorber solution), but may be a suspension.
  • the conditions for heating are not particularly limited.
  • the heating temperature is preferably 30 to 200 ° C, more preferably 70 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 ammonium salt composition only needs to contain one kind each of the first halide represented by the formula (1b) and the second halide represented by the formula (2b). You may go out.
  • the ammonium salt composition may contain compound MX 2 , preferably a metal halide (when X is a halogen atom).
  • the ammonium salt composition is a preferred embodiment of the light absorber composition.
  • the metal halide examples include halides of the metal atom M (that is, a compound represented by M (Hal) 2 , Hal represents a halogen atom) included in the perovskite compound used in the present invention. it can. Preferably, it is at least one selected from halides of Pb and halides of Sn, and more preferably, at least one selected from iodides of Pb, chlorides of Pb, iodides of Sn and chlorides of Sn. And particularly preferably at least one selected from PbI 2 and SnI 2 .
  • ammonium salt composition does not contain compounds MX 2
  • compounds MX 2 is preferably used a metal salt composition containing a metal halide.
  • This metal salt composition is preferably a solution, and is prepared by heating if necessary.
  • the conditions for heating are not particularly limited.
  • the heating temperature is preferably 30 to 200 ° C, more preferably 50 to 120 ° C.
  • the heating time is preferably 5 minutes to 48 hours, more preferably 0.5 to 24 hours.
  • the light absorber composition, the ammonium salt composition, and the metal salt composition may all be solid (powder, granular, etc.) and are preferably solutions.
  • an organic solvent is preferable as a medium to be used. The organic solvent will be described later.
  • compositions may contain other components in addition to the above compounds.
  • examples of other components include halides of Group 1 elements of the periodic table.
  • compositions are both in the formation of the photosensitive layer in the photoelectric conversion element of the present invention can be suitably used as a source of the compound AX and Compound MX 2.
  • these compositions are powders, granules, etc., they can be used after dissolving the composition in a solvent to prepare a solution with an appropriate concentration and, if necessary, carrying out filtration, purification and the like.
  • the composition is a solution, it can be used as it is or after concentration, dilution, filtration, purification, or the like.
  • compositions can be suitably used for forming a photosensitive layer in the production of the photoelectric conversion device of the present invention.
  • the light absorber composition and the ammonium salt composition each have a first halide content [a1] represented by R 1 —N (R 1a ) 3 Hal and R 2 —N (R 2a ) 3.
  • the content [a2] of the second halide represented by Hal satisfies the relationship of the molar ratio defined by the following formula (r1-1), and the molar ratio defined by the following formula (r1-2) It is more preferable to satisfy this relationship, and it is particularly preferable to satisfy the relationship of the molar ratio defined by the following formula (r1-3).
  • Formula (r1-1) 999 ⁇ [a2] / [a1] ⁇ 99999
  • Formula (r1-2) 999 ⁇ [a2] / [a1] ⁇ 49999
  • Formula (r1-3) 1999 ⁇ [a2] / [a1] ⁇ 9999
  • the content [a1] of the first halide represented by R 1 —N (R 1a ) 3 Hal, respectively, , R 2 —N (R 2a ) 3 Hal represented by the content [a2] of the second halide and the content [c] of the compound MX 2 are within a range where a perovskite compound can be formed. Is set.
  • the perovskite compound When the perovskite compound is formed, it is usually set so that the total content of the content [a1] and the content [a2] is excessive with respect to the content [c]. Depending on the method of applying the ammonium salt composition and the metal salt composition separately, the specific amount used may not be specified.
  • the content [c] when the content [c] can be specified, the content [a1], [a2] and [c] satisfy the relationship of the molar ratio defined by the following formula (r2-1). It is more preferable that the molar ratio relationship defined by the following formula (r2-2) is satisfied.
  • the content [a1] of the first halide represented by R 1 —N (R 1a ) 3 Hal R The molar ratio a1: a2: c between the content [a2] of the second halide represented by 2- N (R 2a ) 3 Hal and the content [c] of the compound MX 2 is represented by the formula (r1 -1) to (r1-3) and the above formulas (r2-1) and (r2-2) can be set in appropriate combinations.
  • the solid content concentrations of the light absorber composition, the ammonium salt composition, and the metal salt composition are not particularly limited.
  • the solid content concentration of the light absorber composition is preferably 0.1 to 99% by mass, and more preferably 1 to 70% by mass.
  • the solid content concentration of the ammonium salt composition is preferably 0.05 to 90% by mass, and more preferably 0.1 to 55% by mass.
  • the solid content concentration of the metal salt composition is preferably 0.05 to 95% by mass, and more preferably 0.1 to 80% by mass.
  • the method for providing the photosensitive layer 13 includes a wet method and a dry method, and is not particularly limited. In the present invention, a wet method is preferable. For example, 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). A method of bringing the light absorber composition or the ammonium salt composition into contact with the surface of the layer) is preferable.
  • the method of bringing the light absorbent composition into contact with the surface preferably coats or immerses the light absorbent composition on the surface.
  • 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.
  • drying the applied light absorber composition drying by heat is preferable, and drying 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 method of bringing the ammonium salt composition into contact with the surface preferably includes a method in which the ammonium salt composition and the metal salt composition are separately applied (including a dipping method) and dried if necessary.
  • any composition may be applied to the surface first, and preferably the metal salt composition is applied to the surface first.
  • the coating conditions and drying conditions in this method are the same as the methods for bringing the light absorbent composition into contact with the surface.
  • an ammonium salt composition or a metal salt composition can be deposited instead of applying the ammonium salt composition and the metal salt composition.
  • Yet another method includes a dry method such as vacuum deposition using a mixture from which the solvent of the light absorber composition has been removed.
  • a dry method such as vacuum deposition using a mixture from which the solvent of the light absorber composition has been removed.
  • the compound AX and the compound MX 2 simultaneously or sequentially, and a method of depositing.
  • the perovskite compound is formed as a photosensitive layer on the surface of the porous layer 12, the blocking layer 14, the electron transport layer 15 or the hole transport layer 16.
  • 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 a coating solution concentration of 0.1 to 1.0 M in that it has excellent coating properties, and if it has the porous layer 12, it easily penetrates into the pores of the porous layer 12. (Mol / L) is preferred.
  • 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 is 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 thick photosensitive layers 13B and 13C are provided, the light absorber composition, the ammonium salt composition or the metal salt composition 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 method for producing a photoelectric conversion element include the solvents described in JP-A-2001-291534, but are not particularly limited thereto.
  • an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, and a mixed solvent of two or more of these are preferable.
  • the mixed solvent 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, N, N-dimethylformamide (DMF), 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 and screen printing are preferred.
  • the photoelectric conversion element of the present invention may be subjected to an efficiency stabilization treatment such as annealing, light soaking, and leaving in an oxygen atmosphere as necessary.
  • 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.
  • Example 1 The photoelectric conversion element 10A shown in FIG. 1A was manufactured by the following procedure. When the film thickness of the photosensitive layer 13 is large, it corresponds to the photoelectric conversion element 10B shown in FIG.
  • a blocking layer 14 made of titanium oxide having a thickness of 100 nm was 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. .
  • the prepared titanium oxide paste was applied onto the blocking layer 14 by screen printing and baked.
  • the titanium oxide paste was applied and fired twice. The first firing was performed at 130 ° C. for 0.5 hours, and the second firing was performed at 500 ° C. for 1 hour.
  • the obtained sintered body of titanium oxide was immersed in a 40 mM TiCl 4 aqueous solution, then heated at 60 ° C. for 1 hour, and subsequently heated at 500 ° C. for 30 minutes to form a porous layer 12 made of TiO 2 having a thickness of 250 nm. Formed.
  • the prepared light absorbent solution A was applied on the porous layer 12 at a coating temperature of 60 ° C. by spin coating under the conditions of 2000 rpm and 60 seconds.
  • the applied light absorbent solution A was dried at 100 ° C. for 90 minutes by a hot plate to form a photosensitive layer 13A having a perovskite compound.
  • the film thickness of the porous layer 12 was 250 nm, and the total film thickness of the porous layer 12 and the photosensitive layer 13A was 300 nm. In this way, the first electrode 1 was produced.
  • ⁇ Preparation of hole transport material solution 180 mL of 2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9′-spirobifluorene (spiro-OMeTAD) as 1 mL of chlorobenzene as a hole transport material Dissolved in. Also, 170 mg of lithium-bis (trifluoromethanesulfonyl) imide was dissolved in 1 mL of acetonitrile to prepare an acetonitrile solution. To the chlorobenzene solution, 37.5 ⁇ L of the obtained acetonitrile solution and 17.5 ⁇ L of t-butylpyridine (TBP) were added and mixed to prepare a hole transport material solution.
  • TBP t-butylpyridine
  • a hole transport material solution was applied onto the photosensitive layer 13 by a spin coating method and dried to form a hole transport layer 3 having a thickness of 100 nm.
  • Table 2 shows the mixing molar ratio ([a2] / [a1]) of purified n-C 4 H 9 NH 3 I and purified CH 3 NH 3 I in the production of the photoelectric conversion element of sample number 105 described above.
  • the photoelectric conversion elements 10 of sample numbers 101 to 104 and 106 to 111 were manufactured in the same manner as the manufacture of the photoelectric conversion element of sample number 105 except that the values were changed.
  • each compound c1 to c6, c8 synthesized from compounds b1 to b6, b8 to b11, b13, b14, b16, b32, b40, b43, b44, b46 or b54 was used.
  • C11, c13, c14, c16, c32, c40, c43, c44, c46 or c54 can be used.
  • c7, c48, c50, c59 or c60 to c66 can be used.
  • Me represents methyl.
  • the molar ratio ([A2]) of the content [A2] of the second organic cation to the content [A1] of the first organic cation forming the perovskite crystal structure. / [A1]) can be replaced by a mixed molar ratio ([a2] / [a1]) of the light absorber solution A or the ammonium salt composition.
  • the molar ratio of the content [A2] of the second organic cation to the content [A1] of the first organic cation in the photosensitive layer is the first halide ( It almost coincided with the mixing molar ratio of 1b) to the second halide (2b).
  • the analysis means at this time was gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • a sample can be treated with a base and detected as an amine or derivatized and detected as necessary. If analysis is difficult even with these means, X-ray diffraction (XRD) or liquid chromatograph mass spectrometry (LC-MS) can be used instead.
  • the molar ratio (([A1] + [A2]) / [PbI 2 ]) is the mixing molar ratio of the light absorbent solution A (([a1] + [ a2]) / [c]).
  • the molar ratio [A2]: [A1]: [PbI 2 ] can be measured in the same manner by using ion chromatography (ICP) in addition to these methods as necessary, and the mixed molar ratio [a1] : [A2]: Almost consistent with [c].
  • each photoelectric conversion element (sample numbers 101 to 137) of the present invention the first organic cation (A1), the second organic cation (A2), and the metal cation with respect to the total molar amount of cations constituting the perovskite crystal structure
  • the ratio of the total molar amount of each was 100 mol%.
  • the ratio of the molar amount of the anion of the halogen atom to the total molar amount of the anion constituting the perovskite crystal structure was 100 mol% in all cases.
  • a battery characteristic test in a low illuminance environment was performed using each manufactured photoelectric conversion element.
  • the battery characteristic test was performed using a white LED manufactured by Toshiba (model number: LDA8N-GK / D / 60W).
  • the illuminance of the white LED was adjusted to 300 ⁇ W / cm 2 (1000 lux) using ND filters (ND1 to ND80) sold by Shibuya Engineering. It was confirmed that the target illuminance was adjusted by measuring the illuminance of the white LED using a spectroscope USB4000 manufactured by Ocean Photonics.
  • the current-voltage characteristics were measured using an IV tester, and the photoelectric conversion efficiency under the irradiation of LED light at room temperature was determined.
  • Table 2 (Sample Nos. 101 to 113) and Table 3 (Sample Nos. 114 to 137) show the results of photoelectric conversion efficiency under irradiation of LED light at room temperature.
  • Evaluation criteria for photoelectric conversion efficiency are as follows. AAA: 1.30 times or more with respect to the photoelectric conversion efficiency of the sample number 112 AA: 1.25 times or more and less than 1.30 times with respect to the photoelectric conversion efficiency of the sample number 112 A: With respect to the photoelectric conversion efficiency of the sample number 112 On the other hand, 1.2 times or more and less than 1.25 times B: 1.1 times or more and less than 1.2 times the photoelectric conversion efficiency of the sample number 112 C: 1.
  • [a2] / [a1] is the molar ratio of the content [a2] of the second halide to the content [a1] of the first halide, which is [A2] / [A1 That is, the molar ratio of the content [A2] of the second organic cation to the content [A1] of the first organic cation is substantially the same.
  • the molar ratio [A2] / [A1] of the content [A2] of the second organic cation to the content [A1] of the first organic cation satisfies the relationship of 999 ⁇ [A2] / [A1] ⁇ 999999.
  • the photoelectric conversion elements of Samples 105 to 110 showed higher photoelectric conversion efficiency under irradiation of LED light at room temperature than the photoelectric conversion element of Sample No. 112 as a reference.
  • the photoelectric conversion of samples 101 to 104 in which the molar ratio [A2] / [A1] of the content [A2] of the second organic cation to the content [A1] of the first organic cation is less than 999
  • the photoelectric conversion element of the sample 111 in which the element, the molar ratio [A2] / [A1] exceeds 99999, and the photoelectric conversion element of the sample 113 using only the second organic cation are the photoelectric of the sample number 112 as a reference.
  • the photoelectric conversion efficiency under irradiation of LED light at room temperature was equal to or less.
  • R 1 is an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, or aliphatic heterocyclic group having 5 or more carbon atoms. It is preferable to use what is.
  • R 1 is a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aliphatic heterocyclic group is more used. preferable.
  • R 1 of the first halide (first organic cation) has a silyl group as a substituent.
  • the first halide (first organic cation) those having a ClogP value of 2.3 to 15 at the site represented by R 1 are also preferred.
  • First electrode 11 Conductive support 11a Support 11b Transparent electrode 12 Porous layer 13A to 13C Photosensitive layer 14 Blocking layer 2 Second electrode 3A, 3B, 16 Hole transport layer 4, 15 Electron transport layer 6 External Circuit (Lead) 10A to 10F Photoelectric conversion element 100A to 100F System using solar cell M Electric motor

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Abstract

L'invention concerne un élément de conversion photoélectrique qui présente un rendement de conversion photoélectrique élevé, même sous un éclairage intérieur par lampes à diodes électroluminescentes (DEL), une cellule solaire utilisant l'élément de conversion photoélectrique, et une composition. L'élément de conversion photoélectrique (10A) comprend une première électrode (1A) qui comprend, sur un élément de support conducteur (11), une couche photosensible (13A) comprenant un agent absorbant la lumière; une seconde électrode (2) à l'opposé de la première électrode (1A). L'agent absorbant la lumière comprend un composé à structure cristalline du type pérovskite ayant un cation organique, un cation d'un atome métallique et un anion. Le cation organique comprend un premier cation organique exprimé par une formule (1) R1-N(R1a)3 + et un second cation organique exprimé par une formule (2) R2-N(R2a)3 +, la teneur [A1] du premier cation organique et la teneur [A2] du second cation organique satisfaisant une relation de rapport molaire définie par 999 < [A2]/[A1] ≤ 99.999.
PCT/JP2017/004596 2016-03-30 2017-02-08 Élément de conversion photoélectrique, cellule solaire et composition Ceased WO2017169151A1 (fr)

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JP2020053616A (ja) * 2018-09-28 2020-04-02 株式会社リコー 太陽電池モジュール

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015119102A (ja) * 2013-12-19 2015-06-25 アイシン精機株式会社 ハイブリッド型太陽電池
WO2015159952A1 (fr) * 2014-04-18 2015-10-22 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire l'utilisant et procédé de fabrication d'élément de conversion photoélectrique
JP2016502282A (ja) * 2012-12-20 2016-01-21 イッサム リサーチ ディベロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム リミテッドＹｉｓｓｕｍ Ｒｅｓｅａｒｃｈ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ Ｏｆ Ｔｈｅ Ｈｅｂｒｅｗ Ｕｎｉｖｅｒｓｔｙ Ｏｆ Ｊｅｒｕｓａｌｅｍ Ｌｔｄ． ペロブスカイトショットキー型太陽電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2566914T3 (es) * 2012-05-18 2016-04-18 Isis Innovation Limited Dispositivo fotovoltaico que comprende perovskitas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016502282A (ja) * 2012-12-20 2016-01-21 イッサム リサーチ ディベロップメント カンパニー オブ ザ ヘブライ ユニバーシティー オブ エルサレム リミテッドＹｉｓｓｕｍ Ｒｅｓｅａｒｃｈ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ Ｏｆ Ｔｈｅ Ｈｅｂｒｅｗ Ｕｎｉｖｅｒｓｔｙ Ｏｆ Ｊｅｒｕｓａｌｅｍ Ｌｔｄ． ペロブスカイトショットキー型太陽電池
JP2015119102A (ja) * 2013-12-19 2015-06-25 アイシン精機株式会社 ハイブリッド型太陽電池
WO2015159952A1 (fr) * 2014-04-18 2015-10-22 富士フイルム株式会社 Élément de conversion photoélectrique, cellule solaire l'utilisant et procédé de fabrication d'élément de conversion photoélectrique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PELLET, NORMAN ET AL.: "Mixed-Organic-Cation Perovskite Photovoltaics for Enhanced Solar- Light Harvesting", ANGEWANDTE CHEMIE, vol. 53, no. 12, 17 March 2014 (2014-03-17), pages 3151 - 3157, XP055162823, Retrieved from the Internet <URL:doi:10.1002/anie.201309361> *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020053616A (ja) * 2018-09-28 2020-04-02 株式会社リコー 太陽電池モジュール
CN112740433A (zh) * 2018-09-28 2021-04-30 株式会社理光 太阳能电池模块
EP3857623A4 (fr) * 2018-09-28 2021-12-22 Ricoh Company, Ltd. Module de cellules solaires

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