WO2022176335A1 - 太陽電池 - Google Patents

太陽電池 Download PDF

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WO2022176335A1
WO2022176335A1 PCT/JP2021/045240 JP2021045240W WO2022176335A1 WO 2022176335 A1 WO2022176335 A1 WO 2022176335A1 JP 2021045240 W JP2021045240 W JP 2021045240W WO 2022176335 A1 WO2022176335 A1 WO 2022176335A1
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layer
photoelectric conversion
solar cell
electrode
conversion layer
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French (fr)
Japanese (ja)
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健之 関本
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2023500562A priority Critical patent/JP7539051B2/ja
Publication of WO2022176335A1 publication Critical patent/WO2022176335A1/ja
Priority to US18/357,112 priority patent/US12200948B2/en
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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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • 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
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • 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
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • 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

  • This disclosure relates to solar cells.
  • perovskite-type crystals represented by the chemical formula ABX 3 (A is a monovalent cation, B is a divalent cation, and X is a halogen anion) and similar structures (hereinafter referred to as “perovskite compounds”) have been photovoltaic.
  • A is a monovalent cation
  • B is a divalent cation
  • X is a halogen anion
  • perovskite compounds similar structures
  • Patent Documents 1 to 3 disclose that the stability of the perovskite compound against humidity and oxygen is improved by passivating the defective sites of the perovskite compound.
  • Patent Documents 1 to 3 disclose that molecules of passivating agents, which are organic compounds, chemically bond with anions or cations in the perovskite compound, thereby terminating defect sites in the bulk of the perovskite compound. It is Patent Documents 1 to 3 also disclose cases where the passivating agent contains non-polar organic molecules such as naphthalene or anthracene. Non-polar organic molecules are not chemically bound to the anions or cations in the perovskite. However, the non-polar organic molecules block the anion-cation Coulomb interaction at the grain boundary, so that the grain boundary defect sites are passivated.
  • Non-Patent Document 1 reports the results of analyzing photo-induced chemical changes in perovskite compounds by combining visible light irradiation and photoelectron spectroscopy.
  • X ions partially migrate under light irradiation, the concentrations of iodine ions (I ⁇ ) and lead ions (Pb 2+ ) decrease on the surface, and the concentration of bromine ions (Br ⁇ ) decreases. Phase separation occurs with increasing concentrations. This phase separation reverses in the dark.
  • Partially reversible zero-valent lead (Pb 0 ) is also formed in perovskite compounds under photoirradiation, and a photoinduced electron transport mechanism from I ⁇ to Pb 2+ has been proposed.
  • Non-Patent Document 2 changes in the chemical bonding state of the electron transport layer/perovskite compound layer interface and the perovskite compound layer/hole transport layer interface of perovskite solar cells before and after light irradiation were analyzed using hard X-ray photoelectron spectroscopy. results have been reported.
  • zerovalent iodine I 0 or I 2
  • Pb 0 accumulates at the electron transport layer/perovskite compound layer interface.
  • a model has been proposed in which iodine vacancies are accumulated in the vicinity of the electron transport layer/perovskite compound layer interface as iodine accumulates in the vicinity of the perovskite compound layer/hole transport layer interface.
  • Non-Patent Document 3 reports that perovskite compounds are partially reversibly decomposed by heat or light irradiation even in the absence of oxygen and moisture.
  • CH3NH3PbI3 decomposes to PbI2 and CH3NH3I , PbI2 to Pb0 and I2 , CH3NH3I to CH3I , NH3 , and several other compounds. , the process of decomposition is shown.
  • An object of the present disclosure is to provide a solar cell with improved heat durability.
  • the solar cell of the present disclosure includes a first electrode, a photoelectric conversion layer, an intermediate layer, and a second electrode in this order,
  • the photoelectric conversion layer contains a perovskite compound
  • the intermediate layer contains a heterocyclic compound
  • the heterocyclic compound includes one or more and three or less six-membered rings, and at least one of the six-membered rings has an element having a lone pair at the 1- and 4-positions.
  • the present disclosure provides a solar cell with improved thermal durability.
  • FIG. 1 schematically shows the BX6 lattice in the absence of X-site vacancies in perovskite compounds.
  • Figure 2 schematically shows the BX6 lattice when there are X-site vacancies in perovskite compounds.
  • FIG. 3 schematically shows the BX 6 lattice when the X-site vacancies in the perovskite compound are terminated by the heteroaromatic compound phenazine.
  • FIG. 4 schematically shows a cross-sectional view of the solar cell 100 according to the first embodiment.
  • FIG. 5 schematically shows a cross-sectional view of a solar cell 200 according to the second embodiment.
  • FIG. 6 schematically shows a cross-sectional view of a solar cell 300 according to the third embodiment.
  • Types of defects in perovskite compounds can include atomic vacancies, interstitial atoms, and interstitial substitutions at each site of ABX 3 (ie, A, B, and X).
  • the types of defects generated and their generation locations depend not only on the composition of the perovskite compound and the method of preparation, but also on factors such as thermal stress, light irradiation, oxygen, and moisture, as shown in Non-Patent Documents 1 to 3. It may also change depending on factors such as the surrounding environment.
  • FIG. 1 schematically shows the BX 6 -lattice in the absence of X-site vacancies in perovskite compounds.
  • FIG. 2 also schematically shows the BX 6 -lattice when there are X-site vacancies in the perovskite compound.
  • reference numeral 1 indicates B ions
  • reference numeral 2 indicates X ions
  • reference numeral 3 indicates X site vacancies. That is, when X-site vacancies 3 are formed, the BX6 lattice of the perovskite compound is distorted from the state shown in FIG. 1 to the state shown in FIG.
  • the structure of the perovskite compound near the interface between the perovskite compound layer and the hole-transporting layer becomes distorted and becomes unstable, and at high temperatures, the X-site vacancies Thermal desorption of gas and/or iodine derived from the A-site organic cation proceeds.
  • the structure of the perovskite compound is unstable, the local structure around the vacancies is likely to change, so the perovskite compound can undergo lattice deformation so as to facilitate gas desorption.
  • the X-site vacancies are terminated to relax the structural distortion of the perovskite compound due to the X-site vacancies near the interface between the perovskite compound layer and the hole transport layer. It is necessary to suppress gas desorption from the X-site vacancies by stabilizing . At the ends of these X-site vacancies, it is necessary to select an organic molecule with an optimal structure as a passivating agent and place it appropriately.
  • Patent Documents 1 to 3 show as examples the use of organic molecules containing one heteroatom, such as pyridine or thiophene, as passivating agents.
  • passivators such as these, there is one element with a lone pair of electrons. Therefore, when the X-site vacancies are terminated using a passivating agent such as these, the bond with the cation located in the nearby B-site (hereinafter referred to as "B ion”) is insufficient, resulting in a perovskite structure.
  • B ions are, for example, B 2+ .
  • Patent Documents 1 to 3 describe the use of non-polar molecules such as anthracene to passivate grain boundary defects.
  • these non-polar molecules do not contain elements with lone pairs of electrons. Therefore, when these non-polar molecules are used as passivators, there is no bond between the passivator terminating the X-site vacancies and the B ions in its vicinity, and the passivator is a weak hydrogen It combines with the elements of the perovskite compound only by bonding. Therefore, the use of non-polar molecules to passivate grain boundary defects has the problem that the structure of the perovskite compound is not sufficiently stabilized.
  • the ionic radius of I ⁇ one of the X ions, is 220 pm, and the ionic radius of Pb 2+ , one of the B ions, is 119 pm. to 636 pm). Therefore, it is predicted that the size limit in one direction of molecules that can enter iodine vacancies and terminate defects is at least around 430 pm, which is the distance between Pb 2+ -Pb 2+ . Also, there is a limit to the size in the direction perpendicular to the above directions. Therefore, the number of six-membered rings contained in a molecule that can enter X-site vacancies and terminate defects is three or less.
  • FIG. 3 schematically shows the BX 6 lattice when the X-site vacancies in the perovskite compound are terminated by a heterocyclic aromatic compound, phenazine.
  • reference numeral 4 indicates a lone electron pair
  • reference numeral 5 indicates a phenazine molecule.
  • Phenazines are heteroaromatic compounds containing three six-membered rings. As shown in FIG. 3, the phenazine molecule 5 can fit into the X-site vacancies within the structure of perovskite compounds.
  • the present inventor found the following. Heat resistance of perovskite solar cells by inserting a layer containing a heterocyclic compound containing a six-membered ring having an element having a lone pair at the 1- and 4-positions, for example, at the perovskite compound layer/hole transport layer interface is greatly improved.
  • the heterocyclic compound partially terminates the X-site vacancies of the perovskite compound.
  • the B ions of the perovskite compound are located on the lone pair sides of both the 1- and 4-positions of the heterocyclic compound.
  • the lone electron pair and the B ion are strongly bonded.
  • the structure of the perovskite compound is stabilized, thereby improving the thermal durability of the perovskite solar cell.
  • a solar cell according to the first embodiment includes a first electrode, a photoelectric conversion layer, an intermediate layer, and a second electrode in this order.
  • the photoelectric conversion layer contains a perovskite compound.
  • the intermediate layer contains a heterocyclic compound. Heterocyclic compounds contain from one to three six-membered rings, and at least one of the six-membered rings has a lone pair of electrons at the 1- and 4-positions. Note that the photoelectric conversion layer and the intermediate layer may be arranged in contact with each other. Further, another layer may be provided between the photoelectric conversion layer and the intermediate layer.
  • the heterocyclic compound contained in the intermediate layer partially terminates the defective sites of the perovskite compound contained in the photoelectric conversion layer.
  • the B ions of the perovskite compound are positioned on the two lone pair sides of the 1- and 4-positions of the six-membered ring constituting the heterocyclic compound. . Therefore, the lone pair of electrons at the 1st and 4th positions of the six-membered ring are each bonded to the B ion, and the two bonds of the lone pair and the B ion are aligned in a straight line, for example, as shown in FIG. For this reason, the lone electron pair and the B ion are strongly bonded, and the structure of the perovskite compound constituting the photoelectric conversion layer is stabilized. Therefore, the solar cell according to the first embodiment has high thermal durability.
  • Perovskite compounds have a high light absorption coefficient and high carrier mobility in the wavelength region of the sunlight spectrum. Since the solar cell according to the first embodiment contains a perovskite compound, it has high photoelectric conversion efficiency.
  • An element with a lone pair of electrons in a heterocyclic compound may have a larger atomic radius (or covalent bond radius) than oxygen.
  • the distance between the element having a lone pair of electrons and the B ion becomes shorter, so that the bond becomes stronger and the structure of the perovskite compound constituting the photoelectric conversion layer becomes more stable.
  • the atomic radius of oxygen is, for example, the atomic radius (65 pm) of oxygen contained in 1,4-dioxin.
  • the atomic radius of an element having a lone pair of electrons can be determined, for example, by measuring the bond distance between carbon and an element having a lone pair of electrons from a measurement using X-ray diffraction or microwave spectroscopy, and then calculating the bond distance from the atom of carbon. It is found by subtracting the radius.
  • the atomic radius of carbon is obtained from the bond distance between carbon atoms.
  • the element having a lone pair of electrons in the heterocyclic compound may be at least one selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus. According to the above configuration, it is possible to further improve the thermal durability of the solar cell.
  • the element with the lone pair may contain sulfur.
  • only the element having a lone pair at the 1st position may be sulfur, and only the element having a lone pair at the 4th position may be sulfur. and the element with a lone pair at the 4-position may both be sulfur.
  • the heterocyclic compound is at least selected from the group consisting of phenazine, thianthrene, oxantrene, phenoxathiin, pyrazine, 1,4-dioxine, 1,4-dioxane, 1,4-dithiine, and 1,4-dithiane. It may be one. According to the above configuration, it is possible to further improve the thermal durability of the solar cell.
  • the heterocyclic compound contained in the intermediate layer may be a heterocyclic aromatic compound.
  • the heterocyclic aromatic compound may be, for example, at least one selected from the group consisting of phenazine, thianthrene, oxanthrene, phenoxathiin, pyrazine, 1,4-dioxin, and 1,4-dithiine. According to the above configuration, it is possible to further improve the thermal durability of the solar cell.
  • FIG. 4 schematically shows a cross-sectional view of the solar cell 100 according to the first embodiment.
  • a solar cell 100 includes a substrate 6, a first electrode 7, an electron transport layer 8, a photoelectric conversion layer 9, an intermediate layer 10, and a second electrode 11 in this order.
  • the photoelectric conversion layer 9 contains a perovskite compound.
  • the intermediate layer 10 contains a heterocyclic compound.
  • Heterocyclic compounds contain from one to three six-membered rings, and at least one of the six-membered rings has a lone pair of electrons at the 1- and 4-positions.
  • the solar cell 100 has high thermal durability.
  • the solar cell 100 may not have the substrate 6.
  • the solar cell 100 may not have the electron transport layer 8.
  • the photoelectric conversion layer 9 absorbs the light and generates excited electrons and holes.
  • the excited electrons move through the electron transport layer 8 to the first electrode 7 .
  • holes generated in the photoelectric conversion layer 9 move to the second electrode 11 through the intermediate layer 10 .
  • the solar cell 100 can extract current from the first electrode 7 and the second electrode 11 . If the surface of the photoelectric conversion layer 9 has a portion that terminates or is not covered with the intermediate layer 10 , the excited electrons may move directly to the second electrode 11 .
  • the first electrode 7 is, for example, a positive electrode.
  • the second electrode is the negative electrode.
  • the solar cell 100 can be produced, for example, by the following method.
  • the first electrode 7 is formed on the surface of the substrate 6 by chemical vapor deposition, sputtering, or the like.
  • an electron transport layer 8 is formed by a chemical vapor deposition method, a sputtering method, a solution coating method, or the like.
  • a photoelectric conversion layer 9 is formed on the electron transport layer 8 .
  • a perovskite compound may be cut into a predetermined thickness to form the photoelectric conversion layer 9 and placed on the first electrode 7 .
  • an intermediate layer 10 is formed on the photoelectric conversion layer 9 by a chemical vapor deposition method, a solution coating method, or the like.
  • the second electrode 11 is formed on the intermediate layer 10 by chemical vapor deposition, sputtering, or the like.
  • Solar cell 100 can be obtained as described above.
  • the solar cell according to the second embodiment has a porous layer in addition to the structure of the solar cell according to the first embodiment.
  • a porous layer is disposed between the electron transport layer and the photoelectric conversion layer.
  • the material of the photoelectric conversion layer penetrates into the voids of the porous layer, and the porous layer serves as a scaffold for the photoelectric conversion layer. Therefore, it is difficult for the material of the photoelectric conversion layer to repel or agglomerate on the surface of the porous layer. Therefore, the photoelectric conversion layer can be easily formed as a uniform film. Furthermore, an effect of increasing the optical path length of light passing through the photoelectric conversion layer is expected due to light scattering caused by the porous layer.
  • FIG. 5 schematically shows a cross-sectional view of a solar cell 200 according to the second embodiment.
  • a solar cell 200 includes a substrate 6, a first electrode 7, an electron transport layer 8, a porous layer 12, a photoelectric conversion layer 9, an intermediate layer 10, and a second electrode 11 in this order.
  • the porous layer 12 contains a porous body.
  • the porous body contains voids.
  • the solar cell 200 may not have the substrate 6.
  • the solar cell 200 may not have the electron transport layer 8.
  • the solar cell according to the third embodiment has a hole transport layer in addition to the structure of the cell according to the first embodiment.
  • a hole transport layer is disposed between the intermediate layer and the second electrode.
  • the solar cell according to the third embodiment can efficiently extract current. Furthermore, since the intermediate layer is arranged between the photoelectric conversion layer and the hole transport layer, the defective sites in the structure of the perovskite compound constituting the photoelectric conversion layer are terminated, and the two lone electron pairs of the heterocyclic compound are terminated. Since the B ions are arranged on the side, the lone pair and the B ions are strongly bonded. As a result, the structure of the perovskite compound forming the photoelectric conversion layer is stabilized. Therefore, the solar cell according to the third embodiment has high heat resistance.
  • FIG. 6 schematically shows a cross-sectional view of a solar cell 300 according to the third embodiment.
  • a solar cell 300 includes a substrate 6, a first electrode 7, an electron transport layer 8, a porous layer 12, a photoelectric conversion layer 9, an intermediate layer 10, a hole transport layer 13, and a second electrode 11 in this order.
  • the solar cell 300 has high thermal durability.
  • the solar cell 300 may not have the substrate 6.
  • the solar cell 300 may not have the electron transport layer 8.
  • the solar cell 300 may not have the porous layer 12.
  • the photoelectric conversion layer 9 absorbs the light and generates excited electrons and holes.
  • the excited electrons move to the electron transport layer 8 .
  • holes generated in the photoelectric conversion layer 9 move to the hole transport layer 13 via the intermediate layer 10 .
  • the electron transport layer 8 is connected to the first electrode 7 and the hole transport layer 13 is connected to the second electrode 11 .
  • the solar cell 300 can extract current from the first electrode 7 and the second electrode 11 .
  • Substrate 6 is an additional component.
  • a substrate 6 serves to hold the layers of the solar cell.
  • Substrate 6 may be formed from a transparent material.
  • the substrate 6 for example, a glass substrate or a plastic substrate can be used.
  • the plastic substrate may be, for example, a plastic film.
  • the material of the substrate 6 may be a material that does not have translucency.
  • the material of the substrate 6 can be metal, ceramics, or a resin material with low translucency. If the first electrode 7 has sufficient strength, each layer can be held by the first electrode 7, so the substrate 6 may not be provided.
  • the first electrode 7 has conductivity. If the solar cell does not have an electron-transporting layer 8 , the first electrode 7 is made of a material that does not form an ohmic contact with the photoelectric conversion layer 9 . Furthermore, the first electrode 7 has a property of blocking holes from the photoelectric conversion layer 9 . The property of blocking holes from the photoelectric conversion layer 9 is a property of allowing only electrons generated in the photoelectric conversion layer 9 to pass through and not allowing holes to pass through. A material having such properties is a material whose Fermi energy is higher than the energy at the top of the valence band of the photoelectric conversion layer 9 . The above material may be a material whose Fermi energy is higher than the Fermi energy of the photoelectric conversion layer 9 .
  • a specific material is aluminum.
  • the solar cell comprises an electron transport layer 8 between the first electrode 7 and the photoelectric conversion layer 9, the first electrode 7 does not have the property of blocking holes migrating from the photoelectric conversion layer 9.
  • the first electrode 7 may be made of a material capable of forming an ohmic contact with the photoelectric conversion layer 9 .
  • the first electrode 7 has translucency. For example, it transmits light in the visible region to the near-infrared region.
  • the first electrode 7 can be formed using, for example, a transparent and conductive metal oxide and/or metal nitride. Examples of such materials include titanium oxide doped with at least one selected from the group consisting of lithium, magnesium, niobium, and fluorine, and oxide doped with at least one selected from the group consisting of tin and silicon.
  • the first electrode 7 can be formed by using a non-transparent material and providing a pattern through which light can pass.
  • the light-transmitting pattern include a linear pattern, a wavy pattern, a lattice pattern, and a punching metal pattern in which a large number of fine through holes are regularly or irregularly arranged.
  • Non-transparent electrode materials can include, for example, platinum, gold, silver, copper, aluminum, rhodium, indium, titanium, iron, nickel, tin, zinc, or alloys containing any of these.
  • a conductive carbon material can also be used.
  • the light transmittance of the first electrode 7 may be, for example, 50% or more, or may be 80% or more.
  • the wavelength of light to be transmitted depends on the absorption wavelength of the photoelectric conversion layer 9 .
  • the thickness of the first electrode 7 is, for example, 1 nm or more and 1000 nm or less.
  • the electron transport layer 8 contains a semiconductor.
  • the electron transport layer 8 may be a semiconductor with a bandgap of 3.0 eV or more. Visible light and infrared light can be transmitted to the photoelectric conversion layer 9 by forming the electron transport layer 8 with a semiconductor having a bandgap of 3.0 eV or more. Examples of semiconductors include inorganic n-type semiconductors.
  • metal element oxides for example, metal element oxides, metal element nitrides and perovskite oxides can be used.
  • oxides of metal elements include Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si, and Cr oxides can be used. More specific examples include TiO2 or SnO2 .
  • Nitrides of metal elements include, for example, GaN.
  • perovskite oxides include SrTiO3 or CaTiO3 .
  • the electron transport layer 8 may be made of a substance with a bandgap greater than 6.0 eV.
  • Substances with a bandgap greater than 6.0 eV include halides of alkali metals or alkaline earth metals such as lithium fluoride and calcium fluoride, alkali metal oxides such as magnesium oxide, and silicon dioxide.
  • the electron transport layer 8 is configured with a thickness of, for example, 10 nm or less.
  • the electron transport layer 8 may include multiple layers made of different materials.
  • Photoelectric conversion layer 9 contains a perovskite compound.
  • Perovskite compounds may be represented by the chemical formula ABX3 .
  • A is a monovalent cation.
  • monovalent cations include monovalent cations such as alkali metal cations and organic cations. More specifically, methylammonium cation (CH 3 NH 3 + ), formamidinium cation (HC(NH 2 ) 2 + ), ethylammonium cation (CH 3 CH 2 NH 3 + ), guanidinium cation (CH 6 N 3 + ), potassium cation (K + ), cesium cation (Cs + ), and rubidium cation (Rb + ).
  • B is a divalent lead cation (Pb 2+ ) and a tin cation (Sn 2+ ).
  • X is a monovalent anion such as a halogen anion.
  • Each of the A, B, and X sites may be occupied by multiple types of ions.
  • the thickness of the photoelectric conversion layer 9 is, for example, 50 nm or more and 10 ⁇ m or less.
  • the photoelectric conversion layer 9 can be formed using a coating method using a solution, a printing method, a vapor deposition method, or the like.
  • the photoelectric conversion layer 9 may be formed by cutting out a perovskite compound.
  • the photoelectric conversion layer 9 may mainly contain a perovskite compound represented by the chemical formula ABX3 .
  • the photoelectric conversion layer 9 mainly contains a perovskite compound represented by the chemical formula ABX 3 means that the photoelectric conversion layer 9 contains 90% by mass or more of the perovskite compound represented by the chemical formula ABX 3 . .
  • the photoelectric conversion layer 9 may contain 95% by mass or more of the perovskite compound represented by the chemical formula ABX3 .
  • the photoelectric conversion layer 9 may consist of a perovskite compound represented by the chemical formula ABX3 .
  • the photoelectric conversion layer 9 only needs to contain the perovskite compound represented by the chemical formula ABX 3 , and may contain defects or impurities.
  • the photoelectric conversion layer 9 may further contain other compounds different from the perovskite compound represented by the chemical formula ABX3 .
  • Other different compounds include, for example, compounds having a Ruddlesden-Popper type layered perovskite structure.
  • Intermediate layer 10 contains a heterocyclic compound.
  • a heterocyclic compound contains one or more and three or less six-membered rings, and at least one of the six-membered rings has an element having a lone pair at the 1- and 4-positions.
  • the element having the lone pair of electrons may be at least one selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus.
  • heterocyclic compounds include, for example, phenazine, thianthrene, oxantrene, phenoxathiin, pyrazine, 1,4-dioxin, 1,4-dioxane, 1,4-dithiine, or 1,4-dithiane. be done.
  • the heterocyclic compound may be a heterocyclic aromatic compound.
  • the intermediate layer 10 may mainly contain the heterocyclic compound.
  • the intermediate layer 10 mainly contains the heterocyclic compound means that the intermediate layer 10 contains 90% by mass or more of the heterocyclic compound.
  • the intermediate layer 10 may contain 95% by mass or more of the heterocyclic compound.
  • the intermediate layer 10 may consist only of the above heterocyclic compound.
  • the intermediate layer 10 only needs to contain the above heterocyclic compound, and may contain impurities.
  • the intermediate layer 10 may further contain a heterocyclic compound different from the above heterocyclic compound.
  • intermediate layer 10 may further include a heterocyclic compound containing four or more six-membered rings.
  • at least one of the six-membered rings may have an element having a lone pair at the 1- and 4-positions.
  • the intermediate layer 10 is a heterocyclic compound A containing one or more and three or less six-membered rings, and at least one of the six-membered rings has an element having a lone pair at the 1- and 4-positions; , a heterocyclic compound B containing four or more six-membered rings, and at least one of the six-membered rings having an element having a lone pair at the 1- and 4-positions.
  • a heterocyclic compound B When multiple X-site defects in a perovskite compound are connected to form a large X-site vacancy, the heterocyclic compound B effectively terminates such large X-site vacancies and The structure of the compound can be further stabilized.
  • the thermal durability of the solar cell can be further improved.
  • the content of the heterocyclic compound A in the intermediate layer 10 is, for example, higher than the content of the heterocyclic compound B in mass ratio.
  • the intermediate layer 10 is formed on the photoelectric conversion layer 9 by, for example, a chemical vapor deposition method or a solution coating method. Part of the heterocyclic compound contained in intermediate layer 10 terminates grain boundaries and/or surface defects of photoelectric conversion layer 9 . If the intermediate layer 10 does not sufficiently cover the surface of the photoelectric conversion layer 9 , there may be a portion where the hole transport layer 13 or the second electrode 11 and the photoelectric conversion layer 9 are in contact with each other. The intermediate layer 10 does not hinder hole transfer from the photoelectric conversion layer 9 to the hole transport layer 13 or the second electrode 11 .
  • the solution is obtained by dissolving the heterocyclic compound in an organic solvent.
  • an organic solvent For example, 2-propanol is used as the organic solvent.
  • the concentration of the heterocyclic compound may be, for example, greater than or equal to 0.01 g/L and less than or equal to 10 g/L.
  • Application methods include, for example, a doctor blade method, a bar coating method, a spray method, a dip coating method, and a spin coating method.
  • Annealing is then performed.
  • annealing treatment for example, annealing is performed on a hot plate at a temperature of 85° C. to 115° C. for 10 seconds to 30 minutes.
  • the substrate 6 having the intermediate layer 10 formed on the photoelectric conversion layer 9 is obtained by naturally cooling to room temperature. Thus, the intermediate layer 10 is formed.
  • the porous layer 12 is formed on the electron transport layer 8 by, for example, a coating method. If the solar cell does not comprise an electron transport layer 8, it is formed over the first electrode 7. FIG.
  • the pore structure introduced by the porous layer 12 serves as a foundation for forming the photoelectric conversion layer 9 .
  • the porous layer 12 does not hinder light absorption by the photoelectric conversion layer 9 and electron transfer from the photoelectric conversion layer 9 to the electron transport layer 8 .
  • the porous layer 12 contains a porous body.
  • the porous body include a porous body in which insulating or semiconductor particles are connected.
  • the insulating particles for example, particles of aluminum oxide or silicon oxide can be used.
  • Inorganic semiconductor particles can be used as the semiconductor particles.
  • an oxide of a metal element, a perovskite oxide of a metal element, a sulfide of a metal element, or a metal chalcogenide can be used as the semiconductor particles.
  • oxides of metal elements include Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, Si, Alternatively, an oxide of Cr may be mentioned.
  • a more specific example is TiO2 .
  • perovskite oxides of metallic elements include SrTiO3 or CaTiO3 .
  • sulfides of metallic elements include CdS, ZnS , In2S3 , PbS , Mo2S , WS2 , Sb2S3 , Bi2S3 , ZnCdS2 , or Cu2S .
  • metal chalcogenides include CsSe , In2Se3 , WSe2 , HgS, PbSe, or CdTe.
  • the thickness of the porous layer 12 may be 0.01 ⁇ m or more and 10 ⁇ m or less, or may be 0.05 ⁇ m or more and 1 ⁇ m or less.
  • the surface roughness coefficient given by effective area/projected area may be 10 or more, or 100 or more.
  • the projected area is the area of the shadow behind the object when it is illuminated directly from the front.
  • Effective area is the actual surface area of an object.
  • the effective area can be calculated from the volume determined from the projected area and thickness of the object, and the specific surface area and bulk density of the material forming the object.
  • the specific surface area is measured, for example, by a nitrogen adsorption method.
  • the voids in the porous layer 12 are connected to the portion in contact with the photoelectric conversion layer 9 and the portion in contact with the electron transport layer 8 . That is, the voids of the porous layer 12 are connected from one main surface of the porous layer 12 to the other main surface. Thereby, the material of the photoelectric conversion layer 9 can fill the voids of the porous layer 12 and reach the surface of the electron transport layer 8 . Therefore, since the photoelectric conversion layer 9 and the electron transport layer 8 are in direct contact with each other, electron transfer is possible.
  • the effect that the photoelectric conversion layer 9 can be easily formed can be obtained.
  • the material of the photoelectric conversion layer 9 penetrates into the voids of the porous layer 12 , and the porous layer 12 serves as a scaffold for the photoelectric conversion layer 9 . Therefore, it is difficult for the material of the photoelectric conversion layer 9 to repel or agglomerate on the surface of the porous layer 12 . Therefore, the photoelectric conversion layer 9 can be easily formed as a uniform film.
  • the photoelectric conversion layer 9 can be formed by the above coating method, printing method, vapor deposition method, or the like.
  • the light scattering caused by the porous layer 12 is expected to increase the optical path length of the light passing through the photoelectric conversion layer 9 . It is expected that the amount of electrons and holes generated in the photoelectric conversion layer 9 will increase as the optical path length increases.
  • Hole transport layer 13 includes a hole transport material.
  • a hole-transporting material is a material that transports holes.
  • the hole transport layer 13 is composed of a hole transport material such as an organic substance or an inorganic semiconductor.
  • Typical examples of organic substances used as hole transport materials include 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene, poly[bis(4 -phenyl)(2,4,6-trimethylphenyl)amine] (hereinafter sometimes abbreviated as "PTAA”), poly(3-hexylthiophene-2,5-diyl), poly(3,4-ethylenedioxythiophene), or copper phthalocyanine.
  • PTAA 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene
  • PTAA poly[bis(4 -phenyl)(2,4,6-trimethylphenyl)amine]
  • Inorganic semiconductors used as hole transport materials are p-type semiconductors.
  • Examples of inorganic semiconductors are Cu2O, CuGaO2 , CuSCN , CuI, NiOx , MoOx , V2O5 , or carbon materials such as graphene oxide.
  • the hole transport layer 13 may include multiple layers made of different materials. For example, by laminating a plurality of layers so that the ionization potential of the hole transport layer 13 becomes smaller than the ionization potential of the photoelectric conversion layer 9, the hole transport characteristics are improved.
  • the thickness of the hole transport layer 13 may be 1 nm or more and 1000 nm or less, or may be 10 nm or more and 50 nm or less. Within this range, a sufficient hole transport property can be exhibited and a low resistance can be maintained, so that photovoltaic power generation can be performed with high efficiency.
  • a coating method, a printing method, a vapor deposition method, or the like can be adopted. This is similar to the photoelectric conversion layer 9 .
  • Application methods include, for example, a doctor blade method, a bar coating method, a spray method, a dip coating method, and a spin coating method.
  • the printing method includes, for example, a screen printing method. If necessary, a plurality of materials may be mixed to form the hole transport layer 13, and pressurized or baked.
  • the hole transport layer 13 can also be produced by a vacuum deposition method.
  • the hole transport layer 13 may contain a supporting electrolyte and a solvent.
  • the supporting electrolyte and solvent have the effect of stabilizing the holes in the hole transport layer 13 .
  • Examples of supporting electrolytes include ammonium salts and alkali metal salts.
  • Ammonium salts include, for example, tetrabutylammonium perchlorate, tetraethylammonium hexafluorophosphate, imidazolium salts, or pyridinium salts.
  • Alkali metal salts include, for example, lithium perchlorate or potassium boron tetrafluoride.
  • the solvent contained in the hole transport layer 13 may have excellent ion conductivity. Both aqueous and organic solvents may be used.
  • the solvent contained in the hole transport layer 13 may be an organic solvent in order to stabilize the solute more. Specific examples include heterocyclic compound solvents such as tert-butylpyridine, pyridine and n-methylpyrrolidone.
  • the ionic liquid may be used alone, or may be used by being mixed with other kinds of solvents. Ionic liquids are desirable because of their low volatility and high flame retardancy.
  • the ionic liquid examples include imidazolium-based, such as 1-ethyl-3-methylimidazolium tetracyanoborate, pyridine-based, alicyclic amine-based, aliphatic amine-based, or azonium amine-based ionic liquids. be able to.
  • the second electrode 11 has conductivity. If the solar cell does not have the hole transport layer 13 , the second electrode 11 is made of a material that does not make ohmic contact with the photoelectric conversion layer 9 . Furthermore, the second electrode 11 has a property of blocking electrons from the photoelectric conversion layer 9 .
  • the property of blocking electrons from the photoelectric conversion layer 9 means the property of allowing only holes generated in the photoelectric conversion layer 9 to pass therethrough and not allowing electrons to pass therethrough.
  • a material having such properties is a material whose Fermi energy is lower than the energy at the bottom of the conduction band of the photoelectric conversion layer 9 .
  • the above material may be a material having a Fermi energy lower than the Fermi energy of the photoelectric conversion layer 9 .
  • Specific materials include platinum, gold, or carbon materials such as graphene.
  • the second electrode 11 does not have to block electrons from the photoelectric conversion layer 9 . That is, the material of the second electrode 11 may be a material that makes ohmic contact with the photoelectric conversion layer 9 . Therefore, the second electrode 11 can be formed to have translucency.
  • the electrode on the light incident side only needs to be translucent. Therefore, one of the first electrode 7 and the second electrode 11 does not have to be translucent. In other words, one of the first electrode 7 and the second electrode 11 may not use a light-transmitting material, or may not have a pattern including openings that transmit light.
  • solar cells were produced using perovskite compounds, and the initial characteristics of the solar cells and the characteristics after the heat resistance test were evaluated.
  • Each configuration of the solar cells of Examples 1 to 3 and Comparative Examples 1 to 3 is as follows.
  • the solar cells of Examples 1 to 3, Comparative Example 1, and Comparative Example 2 had the same structure as the solar cell 300 shown in FIG.
  • the solar cell of Comparative Example 1 had a structure in which the intermediate layer 10 was removed from the solar cell 300 .
  • Substrate 6 glass substrate (thickness: 0.7 mm) ⁇ First electrode 7: transparent conductive layer indium-tin composite oxide layer (thickness: 200 nm) - Electron transport layer 8: titanium oxide ( TiO2 ) (thickness: 10 nm) ⁇ Porous layer 12: Mesoporous structure titanium oxide (TiO 2 ) Photoelectric conversion layer 9: a layer mainly containing HC(NH 2 ) 2 PbI 3 (thickness: 500 nm) - Intermediate layer 10: phenazine, thianthrene, pyrazine, acridine, or anthracene (all manufactured by Tokyo Kasei Kogyo Co., Ltd.) Hole transport layer 13: layer containing n-butylammonium bromide (manufactured by greatcell Solar) / layer mainly containing PTAA (however, tris (pentafluorophenyl) borane (manufactured by
  • Example 1 a substrate 6 having a transparent conductive layer functioning as a first electrode 7 on its surface was prepared.
  • a glass substrate having a thickness of 0.7 mm was used as the substrate 6 .
  • an indium-tin composite oxide layer was formed on the substrate 6 by sputtering.
  • a layer of titanium oxide was formed on the first electrode 7 by sputtering.
  • Titanium oxide with a mesoporous structure was used as the porous layer 12 .
  • 30NR-D manufactured by Great Cell Solar
  • a raw material solution of a photoelectric conversion material was applied by spin coating to form a photoelectric conversion layer 9 containing a perovskite compound.
  • the raw material solution contains 0.92 mol/L lead (II) iodide (manufactured by Tokyo Chemical Industry), 0.17 mol/L lead (II) bromide (manufactured by Tokyo Chemical Industry), 0.83 mol/L iodine Formamidinium chloride (manufactured by GreatCell Solar), 0.17 mol/L methylammonium bromide (manufactured by GreatCell Solar), 0.05 mol/L cesium iodide (manufactured by Iwatani Corporation), and 0.05 mol/L iodide It was a solution containing rubidium (manufactured by Iwatani Corporation).
  • the solvent of the solution was a mixture of dimethylsulfoxide (manufactured by acros) and N,N-dimethylformamide (manufactured by acros).
  • the mixing ratio (DMSO:DMF) of dimethylsulfoxide (DMSO) and N,N-dimethylformamide (DMF) in the raw material solution was 1:4 by volume.
  • a heterocyclic compound solution was applied onto the photoelectric conversion layer 9 by spin coating, and then annealed on a hot plate at 100° C. for 5 minutes to form an intermediate layer 10 containing a heterocyclic compound.
  • phenazine was used as the solute of the heterocyclic compound solution
  • 2-propanol was used as the solvent
  • concentration of the solution was adjusted to 6.5 mM.
  • a hole-transporting layer 13 containing PTAA was formed on the intermediate layer 10 by applying a raw material solution of the hole-transporting material by spin coating.
  • the solvent of the stock solution was toluene (manufactured by Acros), and the solution contained 10 g/L of PTAA.
  • a second electrode 11 was formed by depositing a gold (Au) film on the hole transport layer 13 by vacuum evaporation.
  • Au gold
  • Example 2 In Example 2, thianthrene was used as the solute of the heterocyclic compound solution. A solar cell of Example 2 was obtained in the same manner as in Example 1 except for the above.
  • Example 3 In Example 3, pyrazine was used as the solute of the heterocyclic compound solution. A solar cell of Example 3 was obtained in the same manner as in Example 1 except for the above.
  • Comparative example 1 In Comparative Example 1, the intermediate layer 10 was not formed. A solar cell of Comparative Example 1 was obtained in the same manner as in Example 1 except for the above.
  • Comparative example 2 In Comparative Example 2, acridine was used as the solute of the heterocyclic compound solution. A solar cell of Comparative Example 2 was obtained in the same manner as in Example 1 except for the above.
  • Comparative Example 3 Comparative Example 3, anthracene was used as the solute of the heterocyclic compound solution.
  • a solar cell of Comparative Example 3 was obtained in the same manner as in Example 1 except for the above.
  • the photoelectric conversion efficiency of the solar cell was measured using an electrochemical analyzer (ALS440B, manufactured by BAS) and a xenon light source (BPS X300BA, manufactured by Spectroscopy Instruments). Before measurement, the light intensity was calibrated to 1 Sun (100 mW/cm 2 ) using a silicon photodiode. The voltage sweep speed was 100 mV/s. No preconditioning, such as light irradiation and long-term forward bias application, was performed before the start of the measurement. In order to fix the effective area and reduce the influence of scattered light, light was irradiated from the mask/substrate 6 side while the solar cell was masked with a black mask having an opening of 0.1 cm 2 . Photoelectric conversion efficiency measurements were performed at room temperature under dry air ( ⁇ 2% RH). Table 1 shows the initial efficiencies of the solar cells of Examples 1 to 3 and Comparative Examples 1 to 3 measured as described above.
  • ⁇ Heat resistance test> The solar cells of Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to a heat resistance test by the following method. First, the solar cell was sealed under a nitrogen atmosphere with a UV curable resin using a sealing glass with a moisture and oxygen getter stuck inside. After that, the solar cell sealed with the sealing glass was held at 85° C. for 232 hours in a constant temperature bath. Photoelectric conversion efficiency was measured before and after this heat resistance test.
  • an intermediate layer 10 containing phenazine, thianthrene, or pyrazine which is a heterocyclic compound containing one six-membered ring having an element with a lone pair of electrons at the 1- and 4-positions. It was inserted between the photoelectric conversion layer 9 and the hole transport layer 13 .
  • the photovoltaic conversion efficiency after the heat resistance test was significantly increased, and the heat deterioration occurred. rate improved. Therefore, by inserting the intermediate layer 10 between the photoelectric conversion layer 9 and the hole transport layer 13, a solar cell having high durability can be obtained.
  • the acridine used as the heterocyclic compound in Comparative Example 2 contains one six-membered ring having nitrogen having a lone pair of electrons only at the 1-position.
  • Anthracene used as the heterocyclic compound in Comparative Example 3 does not contain any six-membered ring having an element with a lone pair of electrons.
  • Table 1 the photoelectric conversion efficiencies and thermal deterioration rates of the solar cells of Comparative Examples 2 and 3 after the heat resistance test were significantly lower than those of the solar cells of Examples 1-3.
  • the solar cells of Comparative Examples 2 and 3 had lower photoelectric conversion efficiencies after the heat resistance test than the solar cells of Comparative Example 1, which did not have the intermediate layer 10, and showed no significant improvement in heat resistance. I didn't.
  • the solar cell of Comparative Example 3 had a higher thermal deterioration rate than the solar cell of Comparative Example 1, in which the intermediate layer 10 was not present.
  • Phenazines and pyrazines contain one six-membered ring with a nitrogen having a lone pair at the 1 and 4 positions.
  • Thiantrene contains one six-membered ring with sulfur having a lone pair of electrons at the 1 and 4 positions.
  • acridine and anthracene have 0 to 1 element with a lone pair of electrons.
  • the present disclosure is a solar cell having an intermediate layer comprising a heterocyclic compound, which, when interposed, for example, between the photoelectric conversion layer and the hole transport layer of the solar cell, reduces the thermal energy of the solar cell.
  • the durability can be greatly improved, and it can be said that the possibility of industrial application is extremely high.

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