WO2016072439A1 - Élément de conversion photoélectrique et cellule solaire - Google Patents

Élément de conversion photoélectrique et cellule solaire Download PDF

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WO2016072439A1
WO2016072439A1 PCT/JP2015/081119 JP2015081119W WO2016072439A1 WO 2016072439 A1 WO2016072439 A1 WO 2016072439A1 JP 2015081119 W JP2015081119 W JP 2015081119W WO 2016072439 A1 WO2016072439 A1 WO 2016072439A1
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photoelectric conversion
conversion element
ring
formula
nitrogen
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PCT/JP2015/081119
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English (en)
Japanese (ja)
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渡辺　康介
寛敬 佐藤
小林　克
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富士フイルム株式会社
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Priority to JP2016557789A priority Critical patent/JP6222641B2/ja
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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion element and a solar cell.
  • 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. In particular, research and development of dye-sensitized solar cells using organic dyes or Ru bipyridyl complexes as sensitizers has been actively promoted, and the photoelectric conversion efficiency has reached about 11%.
  • Patent Document 1 describes a photovoltaic device having a perovskite including a first cation, a second cation, and at least one halide anion or chalcogenide anion.
  • R 1 to R 8 each independently represents a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, or a substituted or unsubstituted aryl group.
  • Patent Document 2 describes a solid-state solar cell having an organic-inorganic perovskite layer containing a perovskite structure having an imidazolium salt as an organic cation.
  • a solar cell using a perovskite compound exhibits high photoelectric conversion efficiency after production as described above.
  • the photoelectric conversion efficiency gradually decreases with time, and stable battery characteristics cannot be exhibited. This problem is not solved even in the photovoltaic device described in Patent Document 1 and the solid-state solar cell described in Patent Document 2.
  • An object of the present invention is to provide a photoelectric conversion element excellent in durability and a solar cell using the photoelectric conversion element.
  • the present inventors have a great influence on the durability of the photoelectric conversion element and the solar cell. Found to affect. As a result of further investigation, when an ammonium cation having a specific nitrogen-containing ring structure is used as the ammonium cation, a decrease in photoelectric conversion efficiency over time is suppressed, and the photoelectric conversion element and the solar cell exhibit stable battery performance. I found out. The present invention has been completed based on these findings.
  • 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,
  • R 11 , R 12 and R 21 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Q 11 represents an atomic group that combines with a nitrogen atom to form a nitrogen-containing aliphatic ring.
  • Q 21 represents an atomic group that forms a nitrogen-containing heterocycle other than an imidazole ring by bonding to a —N + (R 21 ) ⁇ C— group.
  • X 11 and X 21 each independently represent an anion.
  • M 31 represents a metal cation and X 31 represents an anion.
  • ⁇ 2> The photoelectric conversion element according to ⁇ 1>, wherein an ammonium cation forming an ammonium salt has a CLogP value of 0.4 or more and 10 or less.
  • ⁇ 3> The photoelectric conversion element according to ⁇ 1> or ⁇ 2>, wherein X 11 or X 21 is an anion of a halogen atom.
  • ⁇ 4> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 3>, wherein M 31 is Pb 2+ or Sn 2+ .
  • ⁇ 5> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 4>, wherein the nitrogen-containing aliphatic ring is a nitrogen-containing saturated aliphatic ring.
  • ⁇ 6> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 5>, wherein the nitrogen-containing aliphatic ring is a 5-membered ring or a 6-membered ring.
  • ⁇ 7> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 4>, wherein the nitrogen-containing heterocycle is a nitrogen-containing aliphatic heterocycle or a nitrogen-containing aromatic heterocycle other than an imidazole ring.
  • ⁇ 8> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 4> and ⁇ 7>, wherein the nitrogen-containing heterocycle is a 5-membered ring or a 6-membered ring.
  • ⁇ 9> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 4>, ⁇ 7>, and ⁇ 8>, wherein the ammonium salt represented by the formula (2) is represented by the following formula (2A) .
  • R 22 and R 23 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Q 22 represents an atomic group that forms a 5-membered nitrogen-containing aromatic heterocycle by bonding to the —N (R 22 ) —NH + ⁇ C (R 23 ) — group.
  • X 22 represents an anion.
  • R 22 and R 23 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • X 22 represents an anion.
  • ⁇ 11> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 10>, which has a porous layer between the conductive support and the photosensitive layer.
  • ⁇ 12> The photoelectric conversion device according to any one of ⁇ 1> to ⁇ 11>, which has a hole transport layer between the first electrode and the second electrode.
  • ⁇ 13> A solar cell using the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 12>.
  • the display of a compound is used to mean not only the compound itself but also its salt and its ion. Moreover, it is the meaning including what changed a part of structure in the range which does not impair the target effect. Furthermore, a compound that does not specify substitution or non-substitution is meant to include a compound having an arbitrary substituent as long as the intended effect is not impaired. The same applies to substituents and linking groups (hereinafter referred to as substituents and the like).
  • 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, or atom. In this specification, these are represented by the above formula in addition to the (substituted) group, ion, atom, or the like. It may mean an element group or an element constituting a (substituted) group or ion.
  • 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.
  • FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the photoelectric conversion element of the present invention.
  • 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.
  • 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.
  • the photosensitive layer and the second electrode are provided on the conductive support in this order.
  • “having a photosensitive layer on a conductive support” means an embodiment having a photosensitive layer in contact with the surface of the conductive support, and another layer above the surface of the conductive support. It is meant to include embodiments having a photosensitive layer.
  • 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 is provided in the form of a thin film on the surface of the porous layer (see FIG. 1). ), A mode (see FIGS. 2 and 6) provided on the surface of the porous layer (see FIG. 2 and FIG. 6), a mode provided on the surface of the blocking layer as a thin film, and a thick film on the surface of the blocking layer Aspect (see FIG.
  • the photosensitive layer may be provided in a linear or dispersed form, but is preferably provided in a film form.
  • the light absorber contained in the photosensitive layer is formed from an ammonium salt represented by the above formula (1) or the above formula (2) and a metal salt represented by the above formula (3).
  • the photoelectric conversion element of the present invention is not particularly limited in structure other than the structure defined in the present invention, and a known structure relating to the photoelectric conversion element and the solar cell can be adopted.
  • Each layer constituting the photoelectric conversion element of the present invention may be formed in a single layer or multiple layers depending on the purpose.
  • the same reference numerals mean the same components (members). 1, 2, and 6 emphasize the size of the fine particles forming the porous layer 12. 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, 10B, 10C, 10D, 10E, and 10F unless otherwise specified.
  • the term “photosensitive layer 13” means the photosensitive layers 13A, 13B, and 13C unless otherwise specified.
  • the hole transport layer 3 means the hole transport layers 3A and 3B unless otherwise specified.
  • a photoelectric conversion element 10A shown in FIG. A system 100A shown in FIG. 1 is a system applied to a battery for causing an operation circuit M (for example, an electric motor) to perform work by the external circuit 6 using the photoelectric conversion element 10A.
  • This photoelectric conversion element 10 ⁇ / b> A has a first electrode 1 ⁇ / b> A, a second electrode 2, and a hole transport layer 3 ⁇ / b> A between the first electrode 1 ⁇ / b> A and the second electrode 2.
  • the first electrode 1A has a conductive support 11 composed of a support 11a and a transparent electrode 11b, a porous layer 12, and a photosensitive layer 13A on the porous layer 12.
  • the blocking layer 14 is provided on the transparent electrode 11 b, and the porous layer 12 is formed on the blocking layer 14.
  • the photoelectric conversion element 10A having the porous layer 12 improves the charge separation and charge transfer efficiency because the surface area of the photosensitive layer 13A is increased.
  • the photoelectric conversion element 10B shown in FIG. 2 schematically shows a preferred embodiment in which the photosensitive layer 13A of the photoelectric conversion element 10A shown in FIG. In the photoelectric conversion element 10B, the hole transport layer 3B is thinly provided.
  • the photoelectric conversion element 10B differs from the photoelectric conversion element 10A shown in FIG. 1 in the film thicknesses of the photosensitive layer 13B and the hole transport layer 3B, but is configured in the same manner as the photoelectric conversion element 10A except for these points. ing.
  • a photoelectric conversion element 10C shown in FIG. 3 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10C is different from the photoelectric conversion element 10B illustrated in FIG. 2 in that the porous layer 12 is not provided, but is configured in the same manner as the photoelectric conversion element 10B except for this point.
  • the photosensitive layer 13 ⁇ / b> C is formed in a thick film shape on the surface of the blocking layer 14.
  • a photoelectric conversion element 10D shown in FIG. 4 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
  • This photoelectric conversion element 10D is different from the photoelectric conversion element 10C shown in FIG. 3 in that an electron transport layer 15 is provided instead of the blocking layer 14, but is otherwise configured in the same manner as the photoelectric conversion element 10C.
  • the first electrode 1 ⁇ / b> D includes a conductive support 11 and an electron transport layer 15 and a photosensitive layer 13 ⁇ / b> C that are sequentially formed on the conductive support 11.
  • This photoelectric conversion element 10D is preferable in that each layer can be formed of an organic material. As a result, the productivity of the photoelectric conversion element is improved, and it is possible to make it thinner or flexible.
  • 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. That is, in the photoelectric conversion element 10, light that has passed through the conductive support 11 or passed through the second electrode 2 and entered the photosensitive layer 13 excites the light absorber. The excited light absorber has high-energy electrons and can emit these electrons. The light absorber that has released electrons with high energy becomes an oxidant.
  • the electrons emitted from the light absorber move between the light absorbers and reach the conductive support 11 from the photosensitive layer 13.
  • the electrons that have reached the conductive support 11 work in the external circuit 6 and then pass through the second electrode 2 (if the hole transport layer 3 is present, further via the hole transport layer 3), Return to the photosensitive layer 13.
  • the light absorber is reduced by the electrons returning to the photosensitive layer 13.
  • the photoelectric conversion element 10E 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 with an insulator other than the conventional semiconductor.
  • the porous layer 12 is formed of a semiconductor, electron conduction in which electrons move inside or between the semiconductor particles of the porous layer 12 also occurs.
  • the porous layer 12 is formed of an insulator, electron conduction in the porous layer 12 does not occur.
  • a relatively high electromotive force can be obtained by using aluminum oxide (Al 2 O 3 ) particles as the insulator particles.
  • Al 2 O 3 aluminum oxide
  • the blocking layer 14 as the other layer is formed of a conductor or a semiconductor, electron conduction in the blocking layer 14 occurs. Also, electron conduction occurs in the electron transport layer 15.
  • the photoelectric conversion element and the solar cell of the present invention are not limited to the above-described preferred embodiments, and the configuration of each embodiment can be appropriately combined between the respective embodiments without departing from the spirit of the present invention.
  • the photoelectric conversion element 10C or 10D may have a configuration in which the hole transport layer 3B is not provided as in the photoelectric conversion element 10F.
  • materials and members used for the photoelectric conversion element or the solar cell can be prepared by ordinary methods using ordinary materials except for the light absorber.
  • Patent Documents 1 and 2 can be referred to.
  • dye-sensitized solar cells for example, Japanese Patent Application Laid-Open No. 2001-291534, US Pat. No. 4,927,721, US Pat. No. 4,684,537, US Pat. No. 5,084, 365, US Pat. No. 5,350,644, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP 2004-220974 A and JP 2008-135197 A can be referred to.
  • the first electrode 1 has a conductive support 11 and a photosensitive layer 13 and functions as a working electrode in the photoelectric conversion element 10. As shown in FIGS. 1 to 6, the first electrode 1 preferably has at least one of a porous layer 12, a blocking layer 14, an electron transport layer 15 and a hole transport layer 16. The first electrode 1 preferably has at least the blocking layer 14 in terms of prevention of short circuit, and more preferably has the porous layer 12 and the blocking layer 14 in terms of light absorption efficiency and prevention of short circuit. Moreover, it is preferable that the 1st electrode 1 has the electron carrying layer 15 or the positive hole transport layer 16 at the point which can be formed with an organic material.
  • the conductive support 11 is not particularly limited as long as it has conductivity and can support the photosensitive layer 13 and the like.
  • the conductive support 11 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. When the strength of the conductive support 11 is sufficiently maintained, the support 11a is not necessarily required.
  • a conductive support 11 in which a transparent metal electrode 11b is formed by coating a conductive metal oxide on the surface of a glass or plastic support 11a is more preferable.
  • the support 11a formed of plastic include a transparent polymer film described in paragraph No. 0153 of JP-A-2001-291534.
  • ceramic Japanese Patent Laid-Open No. 2005-135902
  • conductive resin Japanese Patent Laid-Open No. 2001-160425
  • tin oxide As the conductive metal oxide, tin oxide (TO) is preferable, and fluorine-doped tin oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
  • the coating amount of the metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the surface area of the support 11a. When the conductive support 11 is used, light is preferably incident from the support 11a side.
  • the conductive support 11 is preferably substantially transparent.
  • “substantially transparent” means that the transmittance of light (wavelength 300 to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more.
  • the thicknesses of the support 11a and the conductive support 11 are not particularly limited, and are set to appropriate thicknesses.
  • the thickness is preferably 0.01 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm.
  • the film thickness of the transparent electrode 11b is not particularly limited, and is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and more preferably 0.05 to 20 ⁇ m. It is particularly preferred that
  • the conductive support 11 or the support 11a may have a light management function on the surface.
  • the surface of the conductive support 11 or the support 11a may have an antireflection film in which high refractive films and low refractive index oxide films are alternately stacked as described in JP-A-2003-123859.
  • the light guide function described in JP-A-2002-260746 may be provided.
  • -Blocking layer 14- In the present invention, like the photoelectric conversion elements 10A to 10C and 10F, preferably on the surface of the transparent electrode 11b, that is, the conductive support 11, the porous layer 12, the photosensitive layer 13, the hole transport layer 3, etc. Between the two, a blocking layer 14 is provided.
  • a photoelectric conversion element and a solar cell for example, when the photosensitive layer 13 or the hole transport layer 3 and the transparent electrode 11b or the like are in electrical contact, a reverse current is generated.
  • the blocking layer 14 functions to prevent this reverse current.
  • the blocking layer 14 is also referred to as a short circuit prevention layer.
  • This blocking layer may be provided also when a photoelectric conversion element has an electron carrying layer. For example, in the case of the photoelectric conversion element 10D, it may be provided between the conductive support 11 and the electron transport layer 15, and in the case of the photoelectric conversion element 10E, it is provided between the second electrode 2 and the electron transport layer 4. May be.
  • the material for forming the blocking layer 14 is not particularly limited as long as it is a material capable of fulfilling the above functions, but 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 equal to or higher than the energy level of the conduction band of the material and the like and lower than the energy level of the conduction band of the material constituting the porous layer 12 or 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 thickness of the blocking layer 14 is preferably 0.001 to 10 ⁇ m, more preferably 0.005 to 1 ⁇ m, and particularly preferably 0.01 to 0.1 ⁇ m.
  • the thickness of each layer can be measured by observing the cross section of the photoelectric conversion element 10 using a scanning electron microscope (SEM) or the like.
  • the porous layer 12 is preferably provided on the transparent electrode 11b.
  • the porous layer 12 is preferably formed on the blocking layer 14.
  • the porous layer 12 is a layer that functions as a scaffold for carrying the photosensitive layer 13 on the surface.
  • the porous layer 12 is preferably a fine particle layer having pores, in which fine particles of the material forming the porous layer 12 are deposited or adhered.
  • the porous layer 12 may be a fine particle layer in which two or more kinds of fine particles are deposited.
  • the amount of light absorbent supported (adsorption amount) can be increased.
  • the surface area of the porous layer 12 it is preferable to increase the surface area of the individual fine particles constituting the porous layer 12.
  • the surface area of the fine particles is preferably 10 times or more, more than 100 times the projected area. It is more preferable.
  • the particle diameter of the fine particles forming the porous layer 12 is preferably 0.001 to 1 ⁇ m as the primary particle in the average particle diameter using the diameter when the projected area is converted into a circle.
  • the average particle diameter of the fine particles is preferably 0.01 to 100 ⁇ m as the average particle diameter of the dispersion.
  • the material for forming the porous layer 12 is not particularly limited with respect to conductivity, and may be an insulator (insulating material), a conductive material, or a semiconductor (semiconductive material).
  • Examples of the material for forming the porous layer 12 include metal chalcogenides (eg, oxides, sulfides, selenides, etc.), perovskite compounds, silicon oxides (eg, silicon dioxide, zeolite), or carbon nanotubes (carbon Nanowires, carbon nanorods and the like) can be used.
  • the metal chalcogenide is not particularly limited, but is preferably titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, aluminum or tantalum oxide, cadmium sulfide. , Cadmium selenide and the like.
  • Examples of the crystal structure of the metal chalcogenide include an anatase type, brookite type and rutile type, and anatase type and brookite type are preferable.
  • the perovskite compound is not particularly limited, and examples thereof include transition metal oxides.
  • transition metal oxides For example, strontium titanate, calcium titanate, barium titanate, lead titanate, barium zirconate, barium stannate, lead zirconate, strontium zirconate, strontium tantalate, potassium niobate, bismuth ferrate, strontium barium titanate , Barium lanthanum titanate, calcium titanate, sodium titanate, bismuth titanate.
  • strontium titanate, calcium titanate and the like are preferable.
  • the carbon nanotube has a shape obtained by rounding a carbon film (graphene sheet) into a cylindrical shape.
  • Carbon nanotubes are single-walled carbon nanotubes (SWCNT) in which one graphene sheet is wound in a cylindrical shape, double-walled carbon nanotubes (DWCNT) in which two graphene sheets are wound in a concentric shape, and multiple graphene sheets are concentric
  • SWCNT single-walled carbon nanotubes
  • DWCNT double-walled carbon nanotubes
  • MWCNT multi-walled carbon nanotubes
  • any carbon nanotube is not particularly limited and can be used.
  • the material for forming the porous layer 12 is preferably titanium, tin, zinc, zirconium, aluminum or silicon oxide, or carbon nanotube, more preferably titanium oxide or aluminum oxide.
  • the porous layer 12 may be formed of at least one of the above-described metal chalcogenides, perovskite compounds, silicon oxides, and carbon nanotubes, and may be formed of a plurality of types.
  • the thickness of the porous layer 12 is not particularly limited, but 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 0.1 to 50 ⁇ m. More preferably, 0.2 to 30 ⁇ m is more preferable, and 0.3 to 30 ⁇ m is particularly preferable.
  • the electron transport layer 15 is preferably provided on the surface of the transparent electrode 11b.
  • the electron transport layer 15 has a function of transporting electrons generated in the photosensitive layer 13 to the conductive support 11.
  • the electron transport layer 15 is formed of an electron transport material that can exhibit this function.
  • the electron transport material is not particularly limited, but an organic material (organic electron transport material) is preferable.
  • the organic electron transport material examples include fullerene compounds such as [6,6] -Phenyl-C61-Butylic Acid Methyl Ester (PC 61 BM), perylene compounds such as perylene tetracarboxydiimide (PTCDI), and other tetracyanoquinodimethanes. Examples thereof include a low molecular compound such as (TCNQ) or a high molecular compound.
  • the thickness of the electron transport layer 15 is not particularly limited, but is preferably 0.001 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
  • the hole transport layer 16 is preferably provided on the surface of the transparent electrode 11b.
  • the hole transport layer 16 is the same as the hole transport layer 3 described later, except that the position where it is formed is different.
  • the 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 photosensitive layer 13 contains at least one light absorber formed from an ammonium salt represented by the following formula (1) or (2) and a metal salt represented by the following formula (3). What is necessary is just to contain 2 or more types. In the present invention, the photosensitive layer 13 may contain a light absorber different from this light absorber. Examples of different light absorbers include metal complex dyes or organic dyes.
  • the photosensitive layer 13 may be a single layer or a laminate of two or more layers.
  • a laminated structure in which layers made of different light absorbers are laminated may be used, and a hole transport material is included between the photosensitive layer and the photosensitive layer.
  • a laminated structure having an intermediate layer may also be used.
  • the form having the photosensitive layer 13 on the conductive support 11 is as described above.
  • the photosensitive layer 13 is preferably provided on the surface of each of the layers so that excited electrons flow 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. For example, 0.001 to 100 ⁇ m is preferable, 0.01 to 10 ⁇ m is more preferable, and 0.01 to 5 ⁇ m is particularly preferable.
  • 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. For example, 0.1 to 100 ⁇ m is preferable, 0.1 to 50 ⁇ m is more preferable, and 0.3 to 30 ⁇ m is particularly preferable.
  • the film 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 photosensitive layer when the photosensitive layer is provided in the form of a thick film (photosensitive layers 13B and 13C), the light absorber contained in the photosensitive layer may function as a hole transport material.
  • the amount of the perovskite compound used is preferably an amount covering at least a part of the surface of the first electrode 1, and more preferably an amount covering the entire surface.
  • the light absorber contained in the photosensitive layer 13 is formed from an ammonium salt represented by the following formula (1) or the following formula (2) and a metal salt represented by the following formula (3).
  • R 11 , R 12 and R 21 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Q 11 represents an atomic group that combines with a nitrogen atom to form a nitrogen-containing aliphatic ring.
  • Q 21 represents an atomic group that forms a nitrogen-containing heterocycle other than an imidazole ring by bonding to the —N + (R 21 ) ⁇ C— group.
  • X 11 and X 21 each independently represent an anion.
  • M 31 represents a metal cation and X 31 represents an anion.
  • a ring formed by bonding of Q 11 to a nitrogen atom (referred to as a ring formed by Q 11 ) or Q 21 is bonded to a —N + (R 21 ) ⁇ C— group.
  • a ring formed by Q 21 Formed by an ammonium cation having a ring formed by Q 21 (referred to as a ring formed by Q 21 ) and an anion X 11 or X 21 .
  • the ammonium cation is preferably a monovalent or divalent cation, and more preferably a monovalent cation.
  • the ring formed by Q 11 and Q 21 is a ring containing at least one quaternary nitrogen atom, but in the present specification, for the sake of convenience, it will be described as an electrically neutral ring.
  • Q 11 is preferably an atomic group selected from a ring-constituting nonmetallic atomic group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom.
  • Ring Q 11 is formed may be a nitrogen-containing aliphatic ring containing at least one quaternary nitrogen atom as a ring-constituting atom, a nitrogen-containing saturated alicyclic ring, nitrogen-containing unsaturated aliphatic exhibiting no aromaticity A ring is mentioned.
  • nitrogen-containing unsaturated aliphatic ring are different rings and ring Q 21 is formed.
  • Ring Q 11 is formed, a nitrogen-containing saturated alicyclic ring are preferred.
  • the ring formed by Q 11 is preferably a 5-membered ring or a 6-membered ring.
  • the ring formed by Q 11 may be a single ring, a condensed ring, or a spiro ring, and is preferably a single ring.
  • Examples of the ring Q 11 is formed, for example, pyrrolidine ring, and an imidazolidine ring, a pyrazolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, quinuclidine ring, a nitrogen-containing saturated alicyclic ring such as indoline ring .
  • examples of the ring formed by Q 11 include nitrogen-containing unsaturated aliphatic rings such as a 2-pyrroline ring, a 2-imidazoline ring, and a 3-pyrazolin ring. Of these, a pyrrolidine ring, a piperidine ring, a piperazine ring or a thiomorpholine ring is preferable.
  • the nitrogen-containing aliphatic ring may have a substituent.
  • the substituent that the nitrogen-containing aliphatic ring may have is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group, Amino group, alkylamino group, arylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, hydroxy group or carboxy group . Each of these substituents may be further substituted with a substituent.
  • R 11 and R 12 are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • the aliphatic hydrocarbon group may be a linear hydrocarbon group, a branched hydrocarbon group, or a cyclic hydrocarbon group.
  • the aliphatic hydrocarbon group includes a saturated hydrocarbon group and an unsaturated hydrocarbon group, and a saturated hydrocarbon group is preferable.
  • the saturated hydrocarbon group includes an alkyl group and a cycloalkyl group, and an alkyl group is preferable.
  • Unsaturated hydrocarbon groups include alkenyl, alkynyl and cycloalkenyl groups.
  • the alkyl group may be an alkyl group having 1 to 12 carbon atoms, and the carbon number thereof is preferably 1 to 10, and more preferably 1 to 8.
  • Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl. Of these, methyl, ethyl, propyl, butyl, hexyl and octyl are preferred.
  • the cycloalkyl group may be a cycloalkyl group having 3 to 12 carbon atoms, and the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 8. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
  • the alkenyl group may be an alkenyl group having 2 to 12 carbon atoms, and the carbon number thereof is preferably 2 to 10, more preferably 2 to 8.
  • Examples of the alkenyl group include ethenyl (vinyl), allyl, butenyl, and hexenyl.
  • the cycloalkenyl group may be a cycloalkenyl group having 4 to 12 carbon atoms, and examples thereof include cyclopentenyl and cyclohexenyl.
  • the alkynyl group may be an alkynyl group having 2 to 12 carbon atoms, and the carbon number is preferably 2 to 10 and more preferably 2 to 8. Examples of the alkynyl group include ethynyl, butynyl, and hexynyl.
  • R 11 and R 12 are each preferably a hydrogen atom or an alkyl group, and more preferably at least one is a hydrogen atom.
  • R 11 and R 12 may be bonded to atoms contained in the atomic group of Q 11 to form a ring.
  • the ring Q 11 is formed, a bridged ring.
  • Examples of such a bridged ring formed by R 11 or R 12 and Q 11 include a triethylenediamine (1,4-diazabicyclo [2.2.2] octane) ring.
  • R 11 and R 12 may each have a substituent.
  • the substituent that R 11 and R 12 may have is the same as the substituent that the nitrogen-containing aliphatic ring may have.
  • X 11 represents an anion paired with an ammonium cation having a ring formed by Q 11 , and when the ammonium cation is multivalent, this valence and the total valence of X 11 may be the same valence. preferable.
  • X 11 is preferably a monovalent anion, and includes an anion of a halogen atom or an anion of each atomic group of NCS ⁇ , NCO ⁇ , CH 3 COO ⁇ or HCOO ⁇ . Of these, an anion of a halogen atom is more preferable.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
  • Anion X 11 may be a one anion, it may be two or more anionic. When X 11 is one of the anion is the anion of an iodine atom. On the other hand, in the case of two or more types of anions, two types of halogen atom anions, particularly bromine atom anions and iodine atom anions are preferred. The ratio of two or more types of anions is not particularly limited.
  • Q 21 is preferably an atomic group selected from a ring-constituting nonmetallic atom group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
  • the ring formed by Q 21 may be a nitrogen-containing heterocycle (excluding an imidazole ring) containing a quaternary nitrogen atom and a carbon atom bonded to this atom through a double bond as a ring constituent atom. Examples include a heterocycle or a nitrogen-containing aromatic heterocycle other than an imidazole ring.
  • the nitrogen-containing aliphatic heterocycle may be an unsaturated ring that does not exhibit aromaticity, and is also referred to as a nitrogen-containing unsaturated aliphatic heterocycle.
  • the ring formed by Q 21 is preferably a 5-membered ring or a 6-membered ring.
  • the ring formed by Q 21 may be any of a single ring, a condensed ring, or a spiro ring, and a single ring is preferable.
  • Examples of the ring formed by Q 21 include nitrogen-containing unsaturated aliphatic heterocycles such as 1,4,5,6-tetrahydropyrimidine and 1,2,3,4-tetrahydropyridine.
  • the ring formed by Q 21 includes 2H-pyrrole ring, pyrazole ring, triazole ring, thiazole ring, oxazole ring, thiadiazole ring, oxadiazole ring, benzopyrazole ring, benzotriazole ring, benzoxazole ring, benzothiazole.
  • nitrogen-containing aromatic heterocycles such as a ring, benzothiadiazole ring, benzooxadiazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, tetrazine ring, quinoline ring, isoquinoline ring or quinazoline ring.
  • a pyrazole ring is preferable.
  • the ring formed by Q 21 is preferably a 1,4,5,6-tetrahydropyrimidine ring or a pyrazole ring.
  • the nitrogen-containing heterocycle may have a substituent.
  • the substituent that the nitrogen-containing heterocycle may have is the same as the substituent that the nitrogen-containing aliphatic ring may have.
  • R 21 has the same meaning as R 11 and R 12 , and preferred ones are also the same.
  • R 21 may have a substituent.
  • the substituent that R 21 may have is the same as the substituent that the nitrogen-containing aliphatic ring may have.
  • X 21 represents an anion, which is synonymous with X 11 , and preferred ones are also the same.
  • ammonium salt represented by the formula (2) is preferably an ammonium salt represented by the following formula (2A).
  • R 22 and R 23 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Q 22 represents an atomic group that forms a 5-membered nitrogen-containing aromatic heterocycle by bonding to the —N (R 22 ) —NH + ⁇ C (R 23 ) — group.
  • X 22 represents an anion.
  • R 22 and R 23 are respectively synonymous with R 21 , and preferred ones are also the same.
  • R 22 and R 23 may be the same group or different groups.
  • Q 22 is synonymous with Q 21 except that it is bonded to a —N (R 22 ) —NH + ⁇ C (R 23 ) — group to form a 5-membered nitrogen-containing aromatic heterocycle, and is preferable Is the same.
  • examples of the ring formed by Q 22 include nitrogen-containing aromatics such as a pyrazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a benzopyrazole ring, a benzotriazole ring, a benzooxadiazole ring, and a benzothiadiazole ring.
  • a heterocycle is mentioned. Of these, a pyrazole ring is preferable.
  • X 22 has the same meaning as X 21 , and preferred ones are also the same.
  • ammonium salt represented by the formula (2) is more preferably an ammonium salt represented by the following formula (2a).
  • R 22 and R 23 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different.
  • R 22 and R 23 has the same meaning as R 22 and R 23 of formula (2A), it is preferable also the same.
  • X 22 represents an anion, which has the same meaning as X 22 in formula (2A), and preferred examples thereof are also the same.
  • ammonium salt represented by the formula (2) is also preferably an ammonium salt represented by the following formula (2B).
  • R 24 , R 25 and R 26 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • Q 23 represents an atomic group that forms a 6-membered nitrogen-containing heterocycle by combining with a —N + (R 24 ) ⁇ C (R 25 ) —N (R 26 ) — group.
  • X 23 represents an anion.
  • R 24 , R 25 and R 26 have the same meanings as R 22 and R 23 in formula (2A), and preferred ones are also the same.
  • R 25 and R 26 may combine with each other to form a ring.
  • examples of the ring formed by R 25 and R 26 include a pyrrolidine ring, a piperidine ring, and a hexamethyleneimine (azacycloheptane) ring.
  • Q 23 has the same meaning as Q 21 except that it is bonded to a —N + (R 24 ) ⁇ C (R 25 ) —N (R 26 ) — group to form a 6-membered nitrogen-containing heterocycle, The preferred ones are the same.
  • the ring Q 23 forms includes a nitrogen-containing aliphatic hetero ring and nitrogen-containing aromatic heterocyclic ring, for example, 1,4,5,6-tetrahydropyrimidine ring, a pyrimidine ring, a triazine ring, tetrazine ring, quinazoline A ring etc. are mentioned.
  • Ring Q 23 is formed, preferably a nitrogen-containing aliphatic hetero ring, more preferably 1,4,5,6-tetrahydropyrimidine ring.
  • X 23 has the same meaning as X 21 , and preferred ones are also the same.
  • ammonium salt represented by the formula (2) is more preferably an ammonium salt represented by the following formula (2b).
  • each of R 24 , R 25 and R 26 independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other.
  • R 24 , R 25 and R 26 have the same meanings as R 24 , R 25 and R 26 in formula (2B), respectively, and preferred ones are also the same.
  • X 23 represents an anion, which is synonymous with X 23 in formula (2B), and preferred examples thereof are also the same.
  • the ammonium cation forming the ammonium salt preferably has a CLogP value of 0.4 or more and 10 or less.
  • the CLogP value means a common logarithm of a distribution coefficient P (Partition Coefficient). Specifically, it is a physical property value that expresses how a chemical substance is distributed in a two-phase equilibrium of oil (generally 1-octanol) and water as a quantitative value. Is done.
  • CLogP Log (C oil / C water )
  • C oil represents the molar concentration in the oil phase
  • C water represents the molar concentration in the aqueous phase.
  • CLogP value is positively increased, the oil solubility is increased.
  • ClogP value is negative and the absolute value is increased, the water solubility is increased.
  • the CLogP value has a negative correlation with the water solubility of chemical substances, and is widely used as a parameter for estimating hydrophilicity / hydrophobicity. In principle, it is actually measured in a distribution experiment considering its definition, but estimation from the structural formula is an effective means. For this reason, the calculated CLogP value is frequently used.
  • the CLogP value is measured by ChemDrawPro ver. Manufactured by CambridgeSoft. It is a value calculated by 12.0.
  • ammonium cation which forms the ammonium salt represented by Formula (1) and Formula (2) below is shown with a CLogP value, this invention is not limited to these.
  • A1 is given as a compound number to specific examples of ammonium cations that form the ammonium salt represented by the formula (1).
  • A2 is given as a compound number to specific examples of the ammonium cation forming the ammonium salt represented by the formula (2).
  • the metal cation M 31 forming the metal salt is not particularly limited, but a cation of a metal atom other than the Group 1 element of the periodic table is preferable.
  • the metal cation M 31 is preferably a divalent cation, particularly preferably Pb 2+ (Pb metal salt) or Sn 2+ (Sn metal salt).
  • M 31 may be one type of metal cation or two or more types of metal cations. In the case of two or more kinds of metal cations, two kinds of Pb 2+ and Sn 2+ are preferable.
  • the ratio of the metal cation at this time is not specifically limited.
  • the anion X 31 is synonymous with the anion X 11 .
  • X 31 is one kind of anion, it is the same as that of the anion X 11 except that an anion of a chlorine atom is preferable.
  • the light absorber formed from the ammonium salt and the metal salt is preferably a compound represented by the following formula (I).
  • A represents a cationic organic group.
  • M represents a metal atom other than Group 1 elements of the periodic table.
  • X represents an anionic atom (atomic group).
  • a represents 1 or 2
  • the cationic organic group A is an organic group that becomes an ammonium cation that forms an ammonium salt represented by the formulas (1) and (2). Preferred examples of the cationic organic group A are the same as those of the ammonium cation.
  • Metal atom M has the same meaning as the metal atom described metal cation M 31, it is preferable also the same.
  • the anionic atom X is an anionic atom (atomic group) which becomes the anion X 11 , X 21 or the anion X 31 .
  • Preferred anionic atoms X are the same as the preferred anions X 11 , X 21 or anions X 31 .
  • the compound represented by the formula (I) is a compound represented by the following formula (I-1) when a is 1, and is represented by the following formula (I-2) when a is 2. It is a compound.
  • A represents a cationic organic group and has the same meaning as A in the formula (I), and the preferred ones are also the same.
  • M represents a metal atom other than the Group 1 element of the periodic table, and is synonymous with M in the above formula (I), and preferred ones are also the same.
  • X represents an anionic atom (atomic group) and is synonymous with X in the formula (I), and preferred ones are also the same.
  • Examples of the compound represented by the formula (I) include perovskite compounds.
  • the compound represented by formula (I) may be either a compound represented by formula (I-1), a compound represented by formula (I-2), or a mixture thereof. Therefore, the light absorber preferably contains at least one compound represented by the formula (I), and it is necessary to clearly distinguish which compound is strictly based on the composition formula, molecular formula, crystal structure, and the like. Absent.
  • the light absorber can be synthesized by heating an ammonium salt and a metal salt, for example.
  • a synthesis method Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka, “Organal Halide Perovskits as Visible-Lisgit-Ligitt-Lift-Slit. Am. Chem. Soc. 2009, 131 (17), 6050-6051.
  • the hole transport layer 3 has a function of replenishing electrons to the oxidant of the light absorber.
  • the hole transport layer 3 may be a liquid layer such as a liquid electrolyte, or may be a solid layer (solid layer). In the present invention, a solid layer is preferable.
  • the hole transport layer 3 is preferably provided between the photosensitive layer 13 of the first electrode 1 and the second electrode 2 as in the photoelectric conversion elements 10A to 10D.
  • the hole transport material for forming the hole transport layer 3 is not particularly limited, and examples thereof include inorganic materials such as CuI, CuNCS, graphene oxide (GO), and paragraph numbers 0209-0212 of JP-A-2001-291534. And the organic hole transport material described in the above.
  • the organic hole transport material is preferably a conductive polymer such as polythiophene, polyaniline, polypyrrole and polysilane, a spiro compound in which two rings share a tetrahedral structure such as C and Si, and triarylamine. And aromatic amine compounds such as triphenylene compounds, nitrogen-containing heterocyclic compounds, and liquid crystalline cyano compounds.
  • the hole transporting material is preferably an organic hole transporting material that can be applied by solution and becomes solid.
  • organic hole transporting material Specifically, 2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenyl) Amine) -9,9-spirobifluorene (Spiro-OMeTAD), poly (3-hexylthiophene-2,5-diyl), 4- (diethylamino) benzaldehyde diphenylhydrazone, polyethylenedioxythiophene (PEDOT), etc. It is done.
  • the thickness of the hole transport layer 3 is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 1 nm to 10 ⁇ m, further preferably 5 nm to 5 ⁇ m, and particularly preferably 10 nm to 1 ⁇ m.
  • the total film thickness of the porous layer 12, the photosensitive layer 13, and the hole transport layer 3 is not particularly limited, but is preferably 0.1 to 200 ⁇ m, for example, 5 to 50 ⁇ m is more preferable, and 0.5 to 5 ⁇ m is more preferable.
  • the photoelectric conversion element 10 ⁇ / b> E has an electron transport layer 4 between the photosensitive layer 13 ⁇ / b> C and the second electrode 2.
  • the electron transport layer 4 is the same as the electron transport layer 15 except that the electron transport destination is the second electrode and the position where the electron transport layer 4 is formed is different.
  • the second electrode 2 functions as a positive electrode in the solar cell.
  • the 2nd electrode 2 will not be specifically limited if it has electroconductivity, Usually, it can be set as the same structure as the electroconductive support body 11. FIG. If the strength is sufficiently maintained, the support 11a is not necessarily required.
  • the structure of the second electrode 2 is preferably a structure having a high current collecting effect. In order for light to reach the photosensitive layer 13, at least one of the conductive support 11 and the second electrode 2 must be substantially transparent. In the solar cell of this invention, it is preferable that the electroconductive support body 11 is transparent and sunlight is entered from the support body 11a side. In this case, it is more preferable that the second electrode 2 has a property of reflecting light.
  • Examples of the material for forming the second electrode 2 include platinum (Pt), gold (Au), nickel (Ni), copper (Cu), silver (Ag), indium (In), ruthenium (Ru), palladium ( Examples thereof include metals such as Pd), rhodium (Rh), iridium (Ir), osnium (Os), and aluminum (Al), the above-described conductive metal oxides, carbon materials, and conductive polymers.
  • the carbon material may be 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 a plastic substrate having this thin film.
  • a metal or conductive metal oxide thin film including a thin film formed by vapor deposition
  • a glass substrate or a plastic substrate having this thin film.
  • glass substrate or plastic substrate glass having a thin film of gold or platinum or glass on which platinum is deposited is preferable.
  • the film thickness of the second electrode 2 is not particularly limited, but is preferably 0.01 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m, and particularly preferably 0.01 to 1 ⁇ m.
  • a spacer or a separator can be used instead of the blocking layer 14 or the like or together with the blocking layer 14 or the like.
  • a hole blocking layer may be provided between the second electrode 2 and the hole transport layer 3.
  • the solar cell of this invention is comprised using the photoelectric conversion element of this invention.
  • a photoelectric conversion element 10 provided with an external circuit 6 can be used as a solar cell.
  • the external circuit connected to the first electrode 1 (conductive support 11) and the second electrode 2 can be used without particular limitation.
  • the solar cell to which the photoelectric conversion element of the present invention is applied is not particularly limited, and examples thereof include solar cells described in Patent Documents 1 and 2.
  • the photoelectric conversion element and the solar cell of the present invention have a photosensitive layer containing the above light absorber. Thereby, durability is high and the stable battery performance is exhibited.
  • the photoelectric conversion element and solar cell of the present invention can be produced according to known production methods, for example, the methods described in Patent Documents 1 and 2, etc. Below, the manufacturing method of the photoelectric conversion element and solar cell of this invention is demonstrated easily.
  • a blocking layer 14 is formed on the surface of the conductive support 11.
  • the blocking layer 14 can be formed by, for example, a method of applying a dispersion containing the insulating material or a precursor compound thereof to the surface of the conductive support 11 and baking it, or a spray pyrolysis method.
  • the material forming the porous layer 12 is preferably used as fine particles, and more preferably used as a dispersion containing fine particles.
  • the method for forming the porous layer 12 is not particularly limited, and examples thereof include a wet method, a dry method, and other methods (for example, a method described in Chemical Review, Vol. 110, page 6595 (2010)). It is done. In these methods, 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 method for providing the photosensitive layer 13 includes a wet method and a dry method, and is not particularly limited.
  • a wet method is preferred, and for example, a method of contacting with a light absorbent solution containing an absorbent is preferred.
  • a light absorbent solution for forming the photosensitive layer 13 is prepared.
  • the light absorber solution contains an ammonium salt represented by the above formula (1) or formula (2) and a metal salt represented by formula (3). In this light absorber solution, the molar ratio between the ammonium salt and the metal salt is appropriately determined according to the light absorber to be formed.
  • the molar ratio of the ammonium salt to the metal salt is preferably 1: 1 to 10: 1.
  • This light absorber solution can be prepared by preferably heating after mixing an ammonium salt and a metal salt in a predetermined molar ratio.
  • This forming liquid is usually a solution, but may be a suspension.
  • the heating conditions are not particularly limited, but the heating temperature is preferably 30 to 200 ° C, more preferably 60 to 150 ° C.
  • the heating time is preferably 0.5 to 100 hours, more preferably 1 to 3 hours.
  • the solvent or dispersion medium those described later can be used.
  • the light absorber solution thus prepared is a layer for forming the photosensitive layer 13 on the surface thereof (in the photoelectric conversion element 10, any one of the porous layer 12, the blocking layer 14, the electron transport layer 15 and the hole transport layer 16).
  • the surface of the layer). Specifically, it is preferable to apply or immerse the light absorbent solution.
  • 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 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.
  • ammonium salt solution containing the said ammonium salt and the metal salt solution containing the said metal salt are apply
  • any solution may be applied first, but a metal salt solution is preferably applied first.
  • the molar ratio of ammonium salt to metal salt, coating conditions and drying conditions in this method are the same as in the above method.
  • an ammonium salt or a metal salt can be deposited.
  • Still other methods include dry methods such as vacuum deposition using a compound or mixture from which the solvent of the light absorber solution has been removed.
  • a method in which the ammonium salt and the metal salt are vapor-deposited simultaneously or sequentially is also included. As a result, a light absorber is formed and becomes the photosensitive layer 13.
  • the hole transport layer 3 or the electron transport layer 4 is preferably formed on the photosensitive layer 13 thus provided.
  • the hole transport layer 3 can be formed by applying a hole transport material solution containing a hole transport material and drying it.
  • the hole transport material solution has 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 photosensitive layers 13B and 13C having a large film thickness are provided, the light absorber solution may be applied and dried a plurality of times.
  • Each of the above-mentioned dispersions and solutions may contain additives such as a dispersion aid and a surfactant as necessary.
  • Examples of the solvent or dispersion medium used in the photoelectric conversion element and solar cell manufacturing method include, but are not limited to, the solvents described in JP-A No. 2001-291534.
  • an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, 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, dimethylformamide (DMF) or dimethylacetamide, or a mixed solvent thereof is preferable.
  • the application method of the solution or dispersant forming each layer is not particularly limited, and spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, inkjet
  • a known coating method such as a printing method or a dipping method can be used. Of these, spin coating, screen printing, dipping, and the like are preferable.
  • the photoelectric conversion element produced as described above can be used as a solar cell by connecting the external circuit 6 to the first electrode 1 (transparent electrode 11b) and the second electrode 2.
  • Example 1 (Production of photoelectric conversion elements (sample numbers 101 to 104 and sample numbers c1 and c2))
  • the photoelectric conversion element 10A shown in FIG. 1 was manufactured by the following procedure.
  • the film thickness of the photosensitive layer 13 is large, it corresponds to the photoelectric conversion element 10B shown in FIG.
  • conductive support 11 A fluorine-doped SnO 2 conductive film (transparent electrode 11b, film thickness 300 nm) was formed on a glass substrate (support 11a, thickness 2.2 mm) to produce a conductive support 11.
  • a blocking layer 14 (thickness: 100 nm) made of titanium oxide is formed on the SnO 2 conductive film of the conductive support 11 at 450 ° C. by spray pyrolysis using the prepared 0.02M blocking layer solution. did.
  • 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.
  • As the firing temperature the first firing was performed at 130 ° C., and the second firing was performed at 500 ° C. for 1 hour.
  • the obtained titanium oxide fired body was immersed in a 40 mM TiCl 4 aqueous solution, heated at 60 ° C. for 1 hour, and then heated at 500 ° C. for 30 minutes to form a porous layer 12 (thickness of TiO 2). 500 nm).
  • ammonium salt of sample number c1 methylammonium iodide is an ammonium salt described in Examples of Patent Document 1.
  • dimethylimidazolium cation of the ammonium salt of sample number c2 is a cation represented by the formula (30) of Patent Document 2 (both R 1 and R 4 are methyl).
  • each purified ammonium salt and PbCl 2 as a metal salt were mixed at a molar ratio of 2: 1 and stirred and mixed in ⁇ -butyrolactone at 60 ° C. for 12 hours, and then a polytetrafluoroethylene (PTFE) syringe filter. Filtration was performed to prepare a light absorber solution having a concentration of 40% by mass.
  • PTFE polytetrafluoroethylene
  • Each light absorber solution thus prepared was applied onto the porous layer 12 by a spin coating method (2000 rpm for 60 seconds, followed by 3000 rpm for 60 seconds).
  • the applied light absorbent solution was dried with a hot plate under normal pressure in a nitrogen atmosphere at 100 ° C. for 40 minutes to synthesize a light absorbent.
  • a part of the light absorber contained a perovskite compound.
  • the photosensitive layer 13 containing the light absorber film thickness 600 nm (including the thickness of the porous layer 12 of 500 nm) was provided on the porous layer 12 to produce the first electrode 1.
  • the prepared hole transporting material solution is applied onto the photosensitive layer 13 of the first electrode 1 by spin coating, and the applied hole transporting material solution is dried to form a solid hole transporting layer 3 (film). A thickness of 0.5 ⁇ m) was formed.
  • the photoelectric conversion element of each sample number was subjected to a battery characteristic test within 1 hour after production.
  • the battery characteristic test is performed by irradiating each photoelectric conversion element with 1000 W / m 2 of pseudo-sunlight from a xenon lamp through an AM1.5 filter using a solar simulator “WXS-85H” (manufactured by WACOM). It was.
  • the current-voltage characteristic was measured using an IV tester to determine the initial photoelectric conversion efficiency ⁇ 1 (%).
  • the durability of the photoelectric conversion element was evaluated according to the following evaluation criteria based on the calculated conversion efficiency ratio.
  • “B” is a passing level of this test, and “A” is an excellent level.
  • “C” has a large decrease in conversion efficiency, and does not reach the pass level (required level) of this test.
  • the ratio of photoelectric conversion efficiency is A: 0.6 or more and 1.0 or less B: 0.4 or more and less than 0.6 C: Less than 0.4
  • photoelectric conversion elements 10C to 10E were manufactured in the same manner as in Example 1 except that the form of the photoelectric conversion element was changed to each form shown in FIGS. .
  • the obtained photoelectric conversion elements were evaluated for durability in the same manner as in Example 1. As a result, all of the photoelectric conversion elements were as excellent as the photoelectric conversion elements of Sample Nos. 101 to 104 in Example 1.
  • Electron transport layer 16 Hole transport layer 2 First Two electrodes 3A, 3B Hole transport layer 4
  • Electron transport layer 6 External circuit (lead) 10A, 10B, 10C, 10D, 10E, 10F Photoelectric conversion elements 100A, 100B, 100C, 100D, 100E, 100F System M that applies photoelectric conversion elements to battery applications Electric motor

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  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention porte sur un élément de conversion photoélectrique qui comprend une première électrode, qui présente une couche photosensible contenant un absorbeur de lumière sur un corps de support conducteur, et une seconde électrode, qui fait face à la première électrode, l'absorbeur de lumière étant formé d'un sel d'ammonium représenté par la formule (1) ou la formule (2) et d'un sel métallique représenté par la formule (3) ; sur une cellule solaire qui utilise cet élément de conversion photoélectrique. Dans la formule (1) et la formule (2), R11, R12 et R21 représentent chacun indépendamment un atome d'hydrogène ou un groupe hydrocarbure aliphatique contenant de 1 à 12 atomes de carbone ; Q11 représente un groupe atomique qui se combine avec un atome d'azote et forme un cycle aliphatique contenant de l'azote ; Q21 représente un groupe atomique qui se combine avec un groupe -N+(R21)=C- et forme un cycle hétérocyclique contenant de l'azote autre qu'un cycle imidazole ; X11 et X21 représentent chacun indépendamment un anion. Dans la formule (3), M31 représente un cation métallique et X31 représente un anion.
PCT/JP2015/081119 2014-11-07 2015-11-05 Élément de conversion photoélectrique et cellule solaire WO2016072439A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10388465B2 (en) 2017-03-07 2019-08-20 Kabushiki Kaisha Toshiba Semiconductor elements and method for manufacturing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007053102A (ja) * 2005-08-18 2007-03-01 Samsung Sdi Co Ltd 色素増感太陽電池用色素および色素増感太陽電池
JP2009530847A (ja) * 2006-03-20 2009-08-27 ゼネラル・エレクトリック・カンパニイ 向上した効率を示す光電子デバイス
JP2013058400A (ja) * 2011-09-08 2013-03-28 Japan Carlit Co Ltd:The 色素増感太陽電池用電解液およびそれを用いた色素増感太陽電池
EP2693503A1 (fr) * 2012-08-03 2014-02-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Cellule solaire à hétérojonction comprenant une couche pérovskite d'halogénures organo-métalliques et sa fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007053102A (ja) * 2005-08-18 2007-03-01 Samsung Sdi Co Ltd 色素増感太陽電池用色素および色素増感太陽電池
JP2009530847A (ja) * 2006-03-20 2009-08-27 ゼネラル・エレクトリック・カンパニイ 向上した効率を示す光電子デバイス
JP2013058400A (ja) * 2011-09-08 2013-03-28 Japan Carlit Co Ltd:The 色素増感太陽電池用電解液およびそれを用いた色素増感太陽電池
EP2693503A1 (fr) * 2012-08-03 2014-02-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Cellule solaire à hétérojonction comprenant une couche pérovskite d'halogénures organo-métalliques et sa fabrication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10388465B2 (en) 2017-03-07 2019-08-20 Kabushiki Kaisha Toshiba Semiconductor elements and method for manufacturing the same

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