WO2016136729A1 - Élément de conversion photoélectrique et cellule solaire - Google Patents

Élément de conversion photoélectrique et cellule solaire Download PDF

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WO2016136729A1
WO2016136729A1 PCT/JP2016/055238 JP2016055238W WO2016136729A1 WO 2016136729 A1 WO2016136729 A1 WO 2016136729A1 JP 2016055238 W JP2016055238 W JP 2016055238W WO 2016136729 A1 WO2016136729 A1 WO 2016136729A1
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layer
photoelectric conversion
transport layer
conversion element
electron transport
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PCT/JP2016/055238
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English (en)
Japanese (ja)
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知昭 吉岡
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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    • 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
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • 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. Among them, research results have recently been reported that solar cells using metal halides as compounds having a perovskite crystal structure (hereinafter sometimes referred to as perovskite compounds) can achieve relatively high photoelectric conversion efficiency. , Attracting attention.
  • Patent Document 1 Non-Patent Document 1
  • Non-Patent Document 2 describe solar cells in which both an electron transport layer and a hole transport layer are formed of an inorganic material.
  • Patent Documents 2 and 3 describe solar cells in which an electron transport layer is formed of an inorganic material and a hole transport layer is formed of an organic material.
  • a solar cell having a structure in which an electron transport layer and a hole transport layer are formed at opposite positions with respect to the photosensitive layer has also been proposed. That is, this solar cell has a transparent electrode layer, a hole transport layer, a photosensitive layer, an electron transport layer, and a counter electrode in this order on a transparent substrate.
  • the hole transport layer is formed of NiO
  • the electron transport layer is phenyl C 61 butyric acid methyl ester ([6,6] -Phenyl-C 61 -Butylic Acid Methyl Ester (PC 61 BM)) is described.
  • the p-type region as a hole transport layer includes an organic semiconductor layer made of poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS), and n as an electron transport layer.
  • PEDOT polystyrene sulfonate
  • a solar cell is described in which the mold region comprises an organic semiconductor layer of PC 61 BM and an inorganic semiconductor layer of titanium oxide.
  • Patent Document 4 describes that when the hole transport layer is formed of an inorganic semiconductor of NiO or V 2 O 5 instead of PEDOT: PSS, the characteristics of the photovoltaic cell are inferior (the figure in the same document). 14).
  • JP 2014-175473 A International Publication No. 2013/017520 JP 2013-055125 A International Publication No. 2014/045021
  • perovskite compounds are not sufficiently stable and are easily decomposed particularly in a high humidity environment.
  • the photoelectric conversion efficiency decreases with time in the atmosphere.
  • the photoelectric conversion efficiency rapidly decreases in a high humidity environment.
  • none of the solar cells of Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 can sufficiently suppress a decrease in photoelectric conversion efficiency over time in the atmosphere.
  • the photoelectric conversion efficiency is remarkably lowered in a high humidity environment, and the humidity resistance is not sufficient. Assuming long-term use as a solar cell, stability in the atmosphere (atmospheric stability) is required, and more desirably, moisture resistance is also required as one of durability items.
  • the present invention provides a photoelectric conversion element using a perovskite compound as a light absorber, excellent in both atmospheric stability and moisture resistance, and a solar cell using the photoelectric conversion element. This is the issue.
  • the present inventors have a layer structure in which a hole transport layer, a photosensitive layer, and an electron transport layer are provided adjacent to each other in order from the transparent substrate side. And when both a positive hole transport layer and an electron carrying layer were formed with the inorganic semiconductor, it discovered that a photoelectric conversion efficiency did not fall easily also in the time passage in air
  • the present invention has been further studied based on these findings and has been completed.
  • ⁇ 1> On a transparent substrate, a transparent electrode layer, a hole transport layer, a photosensitive layer containing a compound having at least one perovskite crystal structure as a light absorber, an electron transport layer, and a counter electrode in this order, A photoelectric conversion element in which the hole transport layer and the electron transport layer are both inorganic semiconductor layers formed of an inorganic semiconductor and are adjacent to the photosensitive layer.
  • ⁇ 3> The photoelectric conversion element according to ⁇ 1> or ⁇ 2>, wherein the inorganic semiconductor layer of the hole transport layer includes a semiconductor mixed layer formed of two or more inorganic semiconductors.
  • ⁇ 4> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic semiconductor layer of the electron transport layer has a laminated structure.
  • ⁇ 5> The photoelectric conversion element according to any one of ⁇ 1> to ⁇ 4>, wherein the inorganic semiconductor layer of the electron transport layer includes a semiconductor mixed layer formed of two or more kinds of inorganic semiconductors.
  • ⁇ 6> Any one of ⁇ 1> to ⁇ 5>, wherein at least one of the inorganic semiconductor forming the inorganic semiconductor layer of the hole transport layer and the inorganic semiconductor forming the inorganic semiconductor layer of the electron transport layer is a metal oxide
  • ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the inorganic semiconductor forming the inorganic semiconductor layer of the hole transport layer and the inorganic semiconductor forming the inorganic semiconductor layer of the electron transport layer are both metal oxides.
  • the photoelectric conversion element as described in one.
  • a compound having a perovskite crystal structure has a periodic table group 1 element or cationic organic group A, a metal atom M other than a periodic table group 1 element, and an anionic atom or atomic group X.
  • the photoelectric conversion element as described in any one of ⁇ 7>.
  • ⁇ 9> A solar cell using the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 8>.
  • 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.
  • the display of a compound is used to mean not only the compound itself but also its salt and its ion.
  • 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.
  • substituents and linking groups hereinafter referred to as substituents and the like).
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the photoelectric conversion element and solar cell of the present invention are excellent in atmospheric stability and moisture resistance while using a perovskite compound as a light absorber.
  • 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 another preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing still another preferred embodiment of the photoelectric conversion element of the present invention.
  • FIG. 4 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 the present invention has a transparent electrode layer, a hole transport layer, a photosensitive layer containing at least one perovskite compound as a light absorber, an electron transport layer, and a counter electrode in this order on a transparent substrate.
  • the hole transport layer and the electron transport layer are adjacent to the photosensitive layer.
  • both the hole transport layer and the electron transport layer are formed as an inorganic semiconductor layer formed of an inorganic semiconductor.
  • the photoelectric conversion element of the present invention in which the hole transport layer disposed on the transparent substrate side and the electron transport layer disposed on the counter electrode side are formed of an inorganic semiconductor, adjacent to the photosensitive layer, has atmospheric stability and moisture resistance. Excellent.
  • the reason is not clear in detail, but is estimated as follows. That is, when both the hole transport layer and the electron transport layer adjacent to the photosensitive layer are formed of an inorganic semiconductor, they are less susceptible to water than the layer formed of an organic semiconductor, and from the interface with the hole transport layer or the electron transport layer. Infiltration of water into the photosensitive layer can be prevented.
  • the inorganic semiconductor forming the electron transport layer functions as an oxygen scavenger, so that the light absorber in the photosensitive layer is deteriorated by the air that has permeated the counter electrode. Can be prevented.
  • the influence of the atmosphere from the transparent electrode layer side is prevented by the transparent electrode layer itself.
  • disorder of the interface state between the photosensitive layer and the electron transport layer can be suppressed, and the interface state is stabilized. By cooperating with them, the photoelectric conversion element of the present invention is considered to exhibit high atmospheric stability and high moisture resistance.
  • the photoelectric conversion element of the present invention is not particularly limited in structure other than the structure defined in the present invention, and known structures relating to the photoelectric conversion element and the solar cell can be adopted.
  • Each layer constituting the photoelectric conversion element of the present invention is designed according to the purpose, and may be formed as a single layer or a multilayer (laminated structure), for example.
  • the term “photoelectric conversion element 10” means the photoelectric conversion elements 10A to 10D unless otherwise specified. The same applies to the system 100.
  • the term “hole transport layer 13” means the hole transport layers 13A and 13B unless otherwise specified. The same applies to the electron transport layer.
  • a system 100A shown in FIG. 1 is a system applied to a battery for causing an operation circuit M (for example, an electric motor) to perform work by the external circuit 6 using the photoelectric conversion element 10A.
  • This photoelectric conversion element 10A has a transparent electrode layer 12, a hole transport layer 13A, a photosensitive layer 14, an electron transport layer 15A, and a counter electrode 16 in this order on a transparent substrate 11.
  • the hole transport layer 13A, the photosensitive layer 14, and the electron transport layer 15A are provided in contact with each other.
  • the hole transport layer 13A and the electron transport layer 15A are each formed as an inorganic semiconductor layer having a single layer structure.
  • the photoelectric conversion element 10B shown in FIG. 2 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
  • This photoelectric conversion element 10B differs from the photoelectric conversion element 10A shown in FIG. 1 in the point of the hole transport layer 13B, but is configured in the same manner as the photoelectric conversion element 10A except for this point.
  • the hole transport layer 13B is disposed on the first hole transport layer (other layer described later) 13B1 disposed on the transparent substrate 11 side, the first hole transport layer 13B1, and adjacent to the photosensitive layer 14. It has a two-layer structure having a second hole transport layer (adjacent layer described later) 13B2 disposed.
  • the photoelectric conversion element 10C shown in FIG. 3 schematically shows another preferred embodiment of the photoelectric conversion element of the present invention.
  • This photoelectric conversion element 10C differs from the photoelectric conversion element 10A shown in FIG. 1 in the point of the electron transport layer 15B, but is configured in the same manner as the photoelectric conversion element 10A except for this point.
  • the electron transport layer 15B includes a first electron transport layer (adjacent layer described later) 15B1 disposed adjacent to the photosensitive layer 14, and a second electron transport disposed on the first electron transport layer 15B1 (on the counter electrode 16 side). It has a two-layer laminated structure including a layer (other layer described later) 15B2.
  • the photoelectric conversion element 10D shown in FIG. 4 schematically shows still another preferred embodiment of the photoelectric conversion element of the present invention.
  • This photoelectric conversion element 10D differs from the photoelectric conversion element 10A shown in FIG. 1 in the hole transport layer 13B and the electron transport layer 15B, but is configured in the same manner as the photoelectric conversion element 10A except for these points.
  • the hole transport layer 13B is configured similarly to the hole transport layer 13B of the photoelectric conversion element 10B.
  • the electron transport layer 15B is configured in the same manner as the electron transport layer 15B of the photoelectric conversion element 10C.
  • 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, the light that has passed through the transparent substrate 11 and entered the photosensitive layer 14 excites the light absorber. The excited light absorber has electrons with high energy and can emit these electrons. The light absorber that has released electrons with high energy becomes an oxidant. In the photoelectric conversion element 10, electrons emitted from the light absorber move between the light absorbers and between the electron transport layers 15 (between inorganic semiconductors) and reach the counter electrode 16. The electrons that have reached the counter electrode 16 work in the external circuit 6 and then return to the photosensitive layer 14 through the transparent electrode layer 12 and the hole transport layer 13. The light absorber is reduced by the electrons returning to the photosensitive layer 14. In the photoelectric conversion element 10, the system 100 functions as a solar cell by repeating such excitation and electron transfer cycles of the light absorber.
  • the photoelectric conversion element and the solar cell of the present invention are not limited to the above-mentioned preferable forms, and the configurations and the like of the respective forms can be appropriately combined between the respective forms without departing from the gist of the present invention.
  • the material and each member used for the photoelectric conversion element or solar cell can be prepared by a conventional method.
  • Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 can be referred to.
  • it can refer also about the material and each member which are used for a dye-sensitized solar cell.
  • dye-sensitized solar cells for example, JP-A No. 2001-291534, US Pat. No. 4,927,721, US Pat. No. 4,684,537, US Pat. No. 5,084,365 Specification, US Pat. No. 5,350,644, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP-A-2004 -220974 and JP-A-2008-135197 can be referred to.
  • the transparent substrate 11 is not particularly limited as long as it can support the photosensitive layer 14 and the like.
  • Examples of the transparent substrate 11 include a glass or plastic substrate.
  • Examples of the transparent substrate 11 made of plastic include a transparent polymer film described in paragraph No. 0153 of JP-A No. 2001-291534.
  • the transparent substrate 11 is substantially transparent.
  • substantially transparent means that the transmittance of light (wavelength 300 to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more.
  • the thickness of the transparent substrate 11 is not particularly limited, and is set to an appropriate thickness.
  • the thickness is preferably 0.01 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm.
  • the film thickness of 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 transparent electrode layer 12 is formed as a conductive film on the surface of the transparent substrate 11.
  • the transparent electrode layer 12 is preferably formed by coating a conductive metal oxide.
  • a conductive metal oxide As the metal oxide, tin oxide (TO) is preferable, and fluorine-doped tin oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
  • the transparent electrode layer 12 is preferably substantially transparent.
  • the film thickness of the transparent electrode layer 12 is not particularly limited and is, for example, preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m. .
  • the coating amount of the metal oxide at this time is not particularly limited as long as it can be set to the above film thickness. For example, 0.1 to 100 g per 1 m 2 of the surface area of the transparent substrate 11 is preferable.
  • the transparent substrate 11 or the transparent electrode layer 12 may have a light management function on the surface.
  • the surface of the transparent substrate 11 or the transparent electrode layer 12 may have an antireflection film in which high refractive films and low refractive index oxide films are alternately stacked as described in JP-A-2003-123859.
  • the light guide function described in JP-A-2002-260746 may be provided.
  • the transparent substrate 11 and the transparent electrode layer 12 preferably have a configuration (also referred to as a conductive support) having a transparent substrate 11 made of glass or plastic and a transparent electrode layer 12 formed on the surface of the transparent substrate 11. More preferably, it is a conductive support in which a transparent electrode layer 12 is formed by coating the metal oxide on the surface of a transparent substrate 11 made of glass or plastic.
  • the hole transport layer 13 is formed between the transparent electrode layer 12 and the photosensitive layer 14 and adjacent to the photosensitive layer 14.
  • the hole transport layer 13 has at least a hole transport function (a function of replenishing electrons in the oxidant of the light absorber) that transports holes generated by the charge separation of the excited light absorber to the transparent electrode layer 12. If it is a layer, it will not specifically limit.
  • the hole transport layer 13 may have an electron blocking function, a hole extraction function, and the like. In the case of having these functions, the hole transport layer 13 is also referred to as an electron blocking layer or a hole extraction layer, for example.
  • the hole transport layer 13 is an inorganic semiconductor layer formed of an inorganic semiconductor described later.
  • the inorganic semiconductor layer formed of an inorganic semiconductor refers to a layer in which the inorganic semiconductor occupies 90% by mass or more of the whole.
  • the inorganic semiconductor layer may contain an organic semiconductor as long as it is less than 10% by mass.
  • an organic insulator or an inorganic insulator that does not transport charges may be contained.
  • the amount (content) of the inorganic semiconductor in the inorganic semiconductor layer functions as long as it is 90% by mass or more, but is preferably 95% or more, more preferably 98% or more.
  • the inorganic semiconductor layer to be the hole transport layer 13 may have a single layer structure (see, for example, the hole transport layer 13A) or a stacked structure (see, for example, the inorganic semiconductor layer 13B).
  • the hole transport layer 13 preferably has a laminated structure.
  • the layer adjacent to the photosensitive layer 14 also referred to as an adjacent layer
  • the layers other than the adjacent layers that constitute the stacked structure is not particularly limited.
  • Other layers include a semiconductor layer formed of a semiconductor responsible for charge (hole) transfer, an electron blocking layer that prevents electron injection from the transparent electrode layer 12, a hole extraction layer that extracts holes, and the like. May be.
  • the semiconductor layer may be a layer formed of an inorganic semiconductor, a layer formed of an organic semiconductor, or a layer formed of an inorganic semiconductor and an organic semiconductor.
  • Examples of the laminated structure of the hole transport layer 13 include a two-layer structure in which an organic semiconductor layer and an inorganic semiconductor layer are laminated, and a two-layer structure in which two inorganic semiconductor layers are laminated.
  • This laminated structure is preferably a laminated structure of two or more layers, more preferably a two-layer structure, and further preferably a two-layer structure (inorganic semiconductor layer 13B) in which two layers of inorganic semiconductors are laminated.
  • each layer when layers having the same composition are stacked adjacent to each other, these are combined into one layer. On the other hand, even if the layers have the same composition, when they are not stacked adjacent to each other, that is, when stacked through other layers, each layer is defined as one layer. When layers having different compositions are stacked, each layer is regarded as one layer regardless of whether or not they are adjacent to each other.
  • the positive hole transport layer 13 contains the semiconductor mixed layer formed with 2 or more types of the inorganic semiconductor mentioned later at the point of atmospheric stability and moisture resistance.
  • the hole transport layer 13 includes a semiconductor mixed layer when the hole transport layer 13 is a semiconductor mixed layer and when the hole transport layer 13 has a stacked structure, The case where one is a semiconductor mixed layer is included.
  • the hole transport layer 13 is an inorganic semiconductor layer having a single layer structure, the inorganic semiconductor layer can be a semiconductor mixed layer.
  • the hole transport layer 13 is an inorganic semiconductor layer having a laminated structure, at least one of the layers constituting the laminated structure, for example, an adjacent layer can be a semiconductor mixed layer.
  • the hole transport layer 13 has a single layer structure from the viewpoint of reducing manufacturing variation and productivity.
  • the inorganic semiconductor forming the semiconductor mixed layer is not particularly limited as long as it is 2 or more, but 2 or 3 is preferable and 2 is more preferable in terms of reducing manufacturing variation.
  • a preferable combination of inorganic semiconductors is not particularly limited.
  • tungsten oxide (WO) tungsten oxide
  • the content ratio (mixing ratio) of the inorganic semiconductor in the semiconductor mixed layer is not particularly limited and can be set as appropriate.
  • the mass ratio is preferably 1: 0.05 to 1:20, more preferably 1: 0.1 to 1: 5.
  • the inorganic semiconductor that forms the hole transport layer 13 may be any inorganic semiconductor that can impart at least a hole transport function to the hole transport layer 13, and includes a p-type semiconductor that can transport charges (holes).
  • p-type semiconductor, in relation to the transparent electrode layer 12 and the photosensitive layer 14, level (E VB) is the work function of the transparent electrode layer 12 level of the valence band of the photoconductive layer 14 of the valence band (E VB ) Having a characteristic of coming between.
  • level (E VB) is the work function of the transparent electrode layer 12 level of the valence band of the photoconductive layer 14 of the valence band (E VB ) Having a characteristic of coming between.
  • Such a p-type semiconductor is not particularly limited, and examples thereof include metal oxides, metal sulfides, CuI, CuNCS, and graphene oxide. Of these, metal oxides are preferable.
  • the metal oxide is preferably a compound represented by the following formula (MP). Equation (MP): M P px O py Wherein, M P represents a metal element, O represents an oxygen element. px and py each independently represent an integer of 1 or more.
  • Examples of MP include transition metal elements, Al, Zn, Cd, Hg, Ga, Ge, Sn, Sb, Tl, Pb, and Bi. Especially, each metal element of Ni, Mo, V, W, Cr, Cu, Fe, and Sn is preferable, and each metal element of Ni, Mo, V, W, Cr, and Cu is more preferable.
  • the ratio of px to py is not particularly limited, and is preferably 2: 1 to 1: 4, and more preferably 2: 1 to 1: 3.
  • px and py may each be an integer of 1 or more, preferably an integer of 1 or more that satisfies the above ratio (px: py), and is not particularly limited, but is, for example, 1 to 4.
  • Such a metal oxide is not particularly limited.
  • organic semiconductor for forming the organic semiconductor layer or the semiconductor mixed layer those used for solar cells can be used without particular limitation.
  • organic semiconductor include a conductive polymer, a spiro compound in which two rings have a tetrahedral structure such as C and Si, an aromatic amine compound such as triarylamine, a triphenylene compound, Examples thereof include nitrogen-containing heterocyclic compounds and liquid crystalline cyano compounds.
  • Examples of the conductive polymer include 2,2 ′, 7,7′-tetrakis- (N, N-di-p-methoxyphenylamine) -9,9-spirobifluorene (Spiro-OMeTAD), poly ( 3-hexylthiophene-2,5-diyl), 4- (diethylamino) benzaldehyde diphenylhydrazone, poly (3,4-ethylenedioxythiophene) (PEDOT) and the like.
  • PDOT triphenyldiamine
  • TPD triphenyldiamine
  • the film thickness of the hole transport layer 13 (when the hole transport layer 13 has a laminated structure, the total film thickness) 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. 10 nm to 1 ⁇ m is particularly preferable.
  • the film thickness of each layer constituting the laminated structure is not particularly limited as long as the total film thickness falls within the above range.
  • the thickness of each layer is preferably, for example, 1 to 400 nm, and more preferably 10 to 200 nm.
  • the ratio of the thickness of each layer constituting the laminated structure is not particularly limited, but in the case of a two-layer structure, the ratio of the thickness of the adjacent layer to the thickness of the other layer (adjacent layer: other layer) is The ratio is preferably 1: 0.01 to 1: 100, more preferably 1: 0.05 to 1:20.
  • the photosensitive layer 14 is preferably provided on the surface of the hole transport layer 13 using a perovskite compound described later as a light absorber.
  • the light absorber should just contain at least 1 type of the specific perovskite compound mentioned later, and may contain 2 or more types of perovskite compounds.
  • the photosensitive layer 14 may be a single layer or a laminate of two or more layers. When the photosensitive layer 14 has a laminated structure of two or more layers, layers made of different light absorbers may be laminated, and an intermediate layer containing a hole transport material is laminated between the photosensitive layer and the photosensitive layer. May be.
  • the photosensitive layer 14 is preferably provided so that excited electrons flow to the counter electrode 16. At this time, the photosensitive layer 14 may be provided in contact with the entire surface of each of the hole transport layer 13 and the electron transport 15 or may be provided in contact with a part of the surface.
  • the film thickness of the photosensitive layer 14 is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and particularly preferably 0.3 to 30 ⁇ m.
  • the photosensitive layer 14 includes, as light absorbers, “Group 1 element or cationic organic group A of the periodic table”, “Metal atom M other than Group 1 element of the periodic table”, and “Anionic atom or atomic group X”.
  • the cationic organic group means an organic group having a property of becoming a cation in the perovskite type crystal structure
  • the anionic atom or atomic group is an atom or atomic group having a property of becoming an anion in the perovskite type crystal structure.
  • the cation A is a cation of a group 1 element of the periodic table or an organic cation composed of a cationic organic group A.
  • the cation A is preferably an organic cation.
  • the cation of the Group 1 element of the periodic table is not particularly limited, and for example, the cation (Li + , Na + , K + of each element of lithium (Li), sodium (Na), potassium (K), or cesium (Cs). Cs + ), and a cesium cation (Cs + ) is particularly preferable.
  • the organic cation is not particularly limited as long as it is a cation of an organic group having the above properties, but is more preferably an organic cation of a cationic organic group represented by the following formula (1).
  • R 1a represents a substituent.
  • R 1a is not particularly limited as long as it is an organic group, but an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or a group that can be represented by the following formula (2) preferable.
  • an alkyl group and a group that can be represented by the following formula (2) are more preferable.
  • Xa represents NR ⁇ 1c> , an oxygen atom, or a sulfur atom.
  • R 1b and R 1c each independently represent a hydrogen atom or a substituent.
  • *** represents a bonding position with the N atom in the formula (1).
  • the organic cation of the cationic organic group A is an organic ammonium cation (R 1a —NH 3 + consisting of an ammonium cationic organic group A formed by bonding R 1a and NH 3 in the above formula (1). ) Is preferred.
  • the organic ammonium cation can have a resonance structure
  • the organic cation includes a cation having a resonance structure in addition to the organic ammonium cation.
  • X a is NH
  • R 1c is a hydrogen atom
  • an organic amidinium cation which is one of the resonance structures of the organic ammonium cation is also included.
  • Examples of the organic amidinium cation comprising an amidinium cationic organic group include a cation represented by the following formula (A am ).
  • a cation represented by the following formula (A am ) may be represented as “R 1b C ( ⁇ NH) —NH 3 ” for convenience.
  • the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.
  • methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl and the like can be mentioned.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclopentyl, and cyclohexyl.
  • the alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms.
  • the alkynyl group is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 4 carbon atoms.
  • ethynyl, butynyl, hexynyl and the like can be mentioned.
  • the aryl group is preferably an aryl group having 6 to 14 carbon atoms, for example, more preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include phenyl.
  • the heteroaryl group includes a group consisting only of an aromatic heterocycle and a group consisting of a condensed heterocycle obtained by condensing an aromatic heterocycle with another ring such as an aromatic ring, an aliphatic ring or a heterocycle.
  • a ring-constituting hetero atom constituting the aromatic hetero ring a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
  • the number of ring members of the aromatic heterocycle is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring.
  • the condensed heterocycle including a 5-membered aromatic heterocycle and a 5-membered aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a furan ring, and a thiophene ring. , Benzimidazole ring, benzoxazole ring, benzothiazole ring, indoline ring, and indazole ring.
  • Examples of the condensed heterocycle including a 6-membered aromatic heterocycle and a 6-membered aromatic heterocycle include, for example, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, and quinazoline ring. Is mentioned.
  • X a represents NR 1c , an oxygen atom or a sulfur atom, and NR 1c is preferable.
  • R 1c represents a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group, and more preferably a hydrogen atom.
  • R 1b represents a hydrogen atom or a substituent, and preferably a hydrogen atom.
  • R 1b examples include an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group.
  • the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group that R 1b and R 1c can each have the same meanings as those of R 1a above, and the preferred ones are also the same.
  • Examples of the group that can be represented by the formula (2) include (thio) acyl group, (thio) carbamoyl group, imidoyl group, and amidino group.
  • the (thio) acyl group includes an acyl group and a thioacyl group.
  • the acyl group is preferably an acyl group having 1 to 7 carbon atoms, and examples thereof include formyl, acetyl (CH 3 C ( ⁇ O) —), propionyl, hexanoyl and the like.
  • the thioacyl group is preferably a thioacyl group having 1 to 7 carbon atoms in total, and examples thereof include thioformyl, thioacetyl (CH 3 C ( ⁇ S) —), thiopropionyl and the like.
  • the (thio) carbamoyl group includes a carbamoyl group (H 2 NC ( ⁇ O) —) and a thiocarbamoyl group (H 2 NC ( ⁇ S) —).
  • the imidoyl group is a group represented by R 1b —C ( ⁇ NR 1c ) —, wherein R 1b and R 1c are each preferably a hydrogen atom or an alkyl group, and the alkyl group has the same meaning as the alkyl group of R 1a above. Is more preferable.
  • formimidoyl is preferable.
  • the amidino group as a group that can be represented by the formula (2) has a structure (—C ( ⁇ NH) NH 2 ) in which R 1b of the imidoyl group is an amino group and R 1c is a hydrogen atom.
  • the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and group that can be represented by the above formula (2), which can be taken as R 1a , may have a substituent. Good.
  • the substituent that R 1a 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, an amino group, Alkylamino group, arylamino group, acyl group, alkylcarbonyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, hydroxy group Or a carboxy group is mentioned.
  • Each substituent that R 1a may have may be further substituted with a substituent.
  • the metal cation M is not particularly limited as long as it is a cation of a metal atom M other than a group 1 element of the periodic table and a cation of a metal atom capable of taking a perovskite crystal structure.
  • metal atoms examples include calcium (Ca), strontium (Sr), cadmium (Cd), copper (Cu), nickel (Ni), manganese (Mn), iron (Fe), cobalt (Co), Metal atoms such as palladium (Pd), germanium (Ge), tin (Sn), lead (Pb), ytterbium (Yb), europium (Eu), indium (In), titanium (Ti), bismuth (Bi) It is done.
  • Ca calcium
  • Metal atoms such as palladium (Pd), germanium (Ge), tin (Sn), lead (Pb), ytterbium (Yb), europium (Eu), indium (In), titanium (Ti), bismuth (Bi) It is done.
  • the metal atom M is preferably a divalent cation, a divalent lead cation (Pb 2+ ), a divalent copper cation (Cu 2+ ), a divalent germanium cation (Ge 2+ ) and a divalent cation. Is more preferably at least one selected from the group consisting of tin cations (Sn 2+ ), more preferably Pb 2+ or Sn 2+ , and particularly preferably Pb 2+ . M may be one type of metal atom or two or more types of metal atoms. In the case of two or more kinds of metal atoms, two kinds of Pb atoms and Sn atoms are preferable. In addition, the ratio of the metal atom at this time is not specifically limited.
  • the anion X represents an anionic atom or an anion of the atomic group X.
  • This anion is preferably an anion of a halogen atom or an anion of each atomic group of NCS ⁇ , NCO ⁇ , HO ⁇ , NO 3 ⁇ , CH 3 COO ⁇ or HCOO ⁇ .
  • an anion of a halogen atom is more preferable.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.
  • the anion X may be an anion of one type of anionic atom or atomic group, or may be an anion of two or more types of anionic atom or atomic group.
  • an anion of iodine atom is preferable.
  • anions of two halogen atoms, particularly anions of bromine or chlorine atoms and anions of iodine atoms are preferred.
  • the ratio of 2 or more types of anions is not specifically limited.
  • the perovskite compound used in the present invention is preferably a perovskite compound having a perovskite crystal structure having the above-described constituent ions and represented by the following formula (I).
  • A represents a group 1 element of the periodic table or a cationic organic group.
  • M represents a metal atom other than Group 1 elements of the periodic table.
  • X represents an anionic atom or atomic group.
  • a represents 1 or 2
  • the Group 1 element of the periodic table or the cationic organic group A forms the cation A having a perovskite crystal structure. Accordingly, the Group 1 element of the periodic table and the cationic organic group A are not particularly limited as long as they are elements or groups that can form the perovskite crystal structure by becoming the cation A.
  • the Periodic Table Group 1 element or the cationic organic group A has the same meaning as the Periodic Table Group 1 element or the cationic organic group described above for the cation A, and the preferred ones are also the same.
  • the metal atom M is a metal atom that forms the metal cation M having a perovskite crystal structure. Therefore, the metal atom M is not particularly limited as long as it is an atom other than the Group 1 element of the periodic table and can form the perovskite crystal structure by becoming the metal cation M.
  • the metal atom M is synonymous with the metal atom described in the metal cation M, and the preferred ones are also the same.
  • the anionic atom or atomic group X forms the anion X having a perovskite crystal structure. Therefore, the anionic atom or atomic group X is not particularly limited as long as it is an atom or atomic group that can form the perovskite crystal structure by becoming the anion X.
  • the anionic atom or atomic group X is synonymous with the anionic atom or atomic group described in the above anion X, and preferred ones are also the same.
  • the perovskite compound represented by formula (I) is a perovskite compound represented by the following formula (I-1) when a is 1, and when a is 2, the perovskite compound represented by formula (I-2) It is a perovskite compound represented.
  • A represents a group 1 element of the periodic table or a cationic organic group, and is synonymous with A in the formula (I), and 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 or an atomic group, and is synonymous with X in the formula (I), and preferred ones are also the same.
  • the perovskite compound used in the present invention may be either a compound represented by formula (I-1) or a compound represented by formula (I-2), or a mixture thereof. Therefore, in the present invention, at least one perovskite compound only needs to be present as a light absorber, and it is not necessary to clearly distinguish which compound is strictly based on the composition formula, molecular formula, crystal structure, and the like. .
  • perovskite compounds that can be used in the present invention are illustrated below, but the present invention is not limited thereby.
  • the compound represented by the formula (I-1) and the compound represented by the formula (I-2) are described separately.
  • the compounds exemplified as the compound represented by the formula (I-1) may be a compound represented by the formula (I-2) depending on the synthesis conditions and the like.
  • the mixture is a mixture of the compound represented by -1) and the compound represented by formula (I-2).
  • the compounds exemplified as the compound represented by the formula (I-2) may be a compound represented by the formula (I-1), and may be represented by the formula (I-1).
  • the mixture is a mixture of the compound represented by formula (I-2).
  • the perovskite compound can be synthesized from a compound represented by the following formula (II) and a compound represented by the following formula (III).
  • A represents a group 1 element of the periodic table or a cationic organic group, and has the same meaning as A in the formula (I), and preferred ones are also the same.
  • X represents an anionic atom or atomic group, and is synonymous with X in formula (I), and preferred ones are also the same.
  • M represents a metal atom other than Group 1 elements of the periodic table, and has the same meaning as M in formula (I), and preferred ones are also the same.
  • X represents an anionic atom or atomic group, and is synonymous with X in formula (I), and preferred ones are also the same.
  • the perovskite compound can be synthesized from MX 2 and AX.
  • the methods described in Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 can be referred to.
  • Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka “Organometric Halide Perovskits as Visible Slight-Lights. Am. Chem. Soc. 2009, 131 (17), p.
  • the amount of the light absorber used may be an amount that covers at least a part of the surface on which light is incident out of the surface of the hole transport layer 13, and is preferably an amount that covers the entire surface.
  • the content of the perovskite compound is usually 1 to 100% by mass.
  • the electron transport layer 15 is formed between the photosensitive layer 14 and the counter electrode 16 and adjacent to the photosensitive layer 14.
  • the electron transport layer 15 is not particularly limited as long as the electron transport layer 15 has at least an electron transport function of transporting electrons generated by charge separation of the excited light absorber to the counter electrode 16.
  • the electron transport layer 15 may have a hole blocking function and an electron extraction function. In the case of having these functions, the electron transport layer 15 is also referred to as a hole blocking layer or an electron extraction layer, for example.
  • the electron transport layer 15 is an inorganic semiconductor layer formed of an inorganic semiconductor described later.
  • the inorganic semiconductor layer to be the electron transport layer 15 may have a single layer structure (see, for example, the electron transport layer 15A) or a stacked structure (see, for example, the inorganic semiconductor layer 15B).
  • the electron transport layer 15 preferably has a laminated structure.
  • the electron transport layer 15 has a laminated structure, as long as the adjacent layer adjacent to the photosensitive layer 14 is a layer formed of the above-described inorganic semiconductor, other layers other than the adjacent layer constituting the stacked structure are not particularly limited.
  • Other layers may include a semiconductor layer formed of a semiconductor responsible for charge (electron) transfer, a hole blocking layer that prevents hole injection from the counter electrode 16, an electron extraction layer that extracts electrons, and the like.
  • the semiconductor layer may be a layer formed of an inorganic semiconductor, a layer formed of an organic semiconductor, or a layer formed of an inorganic semiconductor and an organic semiconductor.
  • Examples of the laminated structure of the electron transport layer 15 include a two-layer structure in which an organic semiconductor layer and an inorganic semiconductor layer are laminated, and a two-layer structure in which two inorganic semiconductor layers are laminated.
  • This laminated structure is preferably a laminated structure of two or more layers, more preferably a two-layer structure, and further preferably a two-layer structure (inorganic semiconductor layer 15B) in which two layers of inorganic semiconductors are laminated.
  • the electron carrying layer 15 contains the semiconductor mixed layer formed with 2 or more types of the inorganic semiconductor mentioned later at the point of atmospheric stability and moisture resistance.
  • the electron transport layer 15 includes a semiconductor mixed layer.
  • the electron transport layer 15 is a semiconductor mixed layer and when the electron transport layer 15 has a stacked structure, one of the layers forming the stacked structure is a semiconductor. The case of a mixed layer is included.
  • the electron transport layer 15 is an inorganic semiconductor layer having a single layer structure, the inorganic semiconductor layer can be a semiconductor mixed layer.
  • the electron transport layer 15 is an inorganic semiconductor layer having a laminated structure, at least one of the layers constituting the laminated structure, for example, an adjacent layer can be a semiconductor mixed layer.
  • the electron transport layer 15 has a single layer structure from the viewpoint of reducing manufacturing variation and productivity.
  • the inorganic semiconductor forming the semiconductor mixed layer is not particularly limited as long as it is 2 or more, but 2 or 3 is preferable and 2 is more preferable in terms of reducing manufacturing variation. In this case, a preferable combination of inorganic semiconductors is not particularly limited.
  • the content ratio (mixing ratio) of the inorganic semiconductor in the semiconductor mixed layer is not particularly limited and can be set as appropriate.
  • the mass ratio is preferably 1: 0.01 to 1: 100, more preferably 1: 0.05 to 1:20.
  • the inorganic semiconductor that forms the electron transport layer 15 may be an inorganic semiconductor that can impart at least an electron transport function to the electron transport layer 15, and includes an n-type semiconductor that can transport charges (electrons).
  • the level of the transmission band (E CB ) is between the work function of the counter electrode 16 and the level of the transmission band of the photosensitive layer 14 (E CB ).
  • Those having characteristics are preferred.
  • Such an n-type semiconductor is not particularly limited, and examples thereof include metal oxide, LiF, and cesium carbonate. Of these, metal oxides are preferable.
  • the metal oxide is preferably a compound represented by the following formula (MN). Equation (MN): M N nx O ny
  • MN represents a metal element
  • O represents an oxygen element
  • nx and ny each independently represent an integer of 1 or more.
  • MN examples include transition metal elements, Al, Zn, Cd, Hg, Ga, Ge, Sn, Sb, Tl, Pb, and Bi. Especially, each metal element of Ti, Zn, Cu, and Cr is preferable, and each metal element of Ti and Zn is more preferable.
  • the ratio of nx to ny is not particularly limited, and is preferably 2: 1 to 1: 4, and more preferably 1: 1 to 1: 3.
  • Each of nx and ny may be an integer of 1 or more, preferably an integer of 1 or more that satisfies the above ratio (nx: ny), and is not particularly limited, but is, for example, 1 to 4.
  • Such a metal oxide is not particularly limited, and examples thereof include TiO 2 , ZnO, CrO 3 , and Cu 2 O. Of these, TiO 2 and ZnO are preferable.
  • At least one of the inorganic semiconductor forming the hole transport layer 13 and the inorganic semiconductor forming the electron transport layer 15 is a metal oxide (a metal oxide of a p-type semiconductor or a metal oxide of an n-type semiconductor). From the viewpoint of photoelectric conversion efficiency, it is preferable. More preferably, the inorganic semiconductor forming the hole transport layer 13 and the inorganic semiconductor forming the electron transport layer 15 are both metal oxides. That is, it is more preferable that the inorganic semiconductor forming the hole transport layer 13 is a metal oxide of a p-type semiconductor, and the inorganic semiconductor forming the electron transport layer 15 is a metal oxide of an n-type semiconductor.
  • organic semiconductor for forming the organic semiconductor layer constituting the electron transport layer 15 or the organic semiconductor for forming the semiconductor mixed layer those used for solar cells can be used without particular limitation.
  • organic semiconductor include fullerene compounds such as PC 61 BM, perylene compounds such as perylene tetracarboxydiimide (PTCDI), other low molecular compounds such as tetracyanoquinodimethane (TCNQ), and polymers. Compounds and the like. Although it does not specifically limit as a material which forms the said hole blocking layer, For example, a perylene compound etc. are mentioned.
  • the film thickness of the electron transport layer 15 (when the electron transport layer 15 has a laminated structure, the total film thickness) is not particularly limited, but is preferably 0.001 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
  • the film thickness of each layer constituting the laminated structure is not particularly limited as long as the total film thickness is within the above range.
  • the thickness of each layer is preferably, for example, 1 to 400 nm, and more preferably 10 to 200 nm.
  • the ratio of the thickness of each layer constituting the laminated structure is not particularly limited, but in the case of a two-layer structure, the ratio of the thickness of the adjacent layer to the thickness of the other layer (adjacent layer: other layer) is The ratio is preferably 1: 0.01 to 1: 100, more preferably 1: 0.05 to 1:20.
  • the counter electrode 16 functions as a negative electrode in the solar cell. If the counter electrode 16 has electroconductivity, it will not be specifically limited, Usually, it can be set as the same structure as the transparent substrate 11. FIG. If the strength is sufficiently maintained, the transparent substrate 11 is not necessarily required. In the solar cell of this invention, it is preferable to make sunlight inject from the transparent substrate 11 side. In this case, it is more preferable that the counter electrode 16 has a property of reflecting light.
  • Examples of the material for forming the counter electrode 16 include platinum (Pt), gold (Au), nickel (Ni), copper (Cu), silver (Ag), indium (In), ruthenium (Ru), and palladium (Pd). , Rhodium (Rh), iridium (Ir), osmium (Os), aluminum (Al), and other metals, conductive metal oxides described in the transparent electrode layer 12, carbon materials, conductive polymers, and the like.
  • 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 counter electrode 16 may be a metal thin film (including a thin film formed by vapor deposition, also referred to as a metal electrode) or a conductive metal oxide thin film (including a thin film formed by vapor deposition), or a glass substrate having these thin films. Or a plastic substrate is preferable. As the 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 counter electrode 16 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 porous layer made of an insulator or a conductive material can be provided on the transparent electrode layer 12.
  • a blocking layer, a spacer, or a separator can be used.
  • 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 6 connected to the transparent electrode layer 12 and the counter electrode 16 known ones can be used without any particular limitation.
  • the photoelectric conversion element and the solar cell of the present invention are based on known production methods, for example, the methods described in Patent Documents 1 to 4 and Non-Patent Documents 1 to 3 except for the order and conditions for forming the layers, Can be manufactured. Below, the manufacturing method of the photoelectric conversion element and solar cell of this invention is demonstrated easily.
  • the transparent electrode layer 12 is formed on the surface of the transparent substrate 11 according to the method described for the transparent electrode layer 12 or the known method described above. Moreover, a porous layer etc. can also be provided in the surface of the transparent electrode layer 12 if desired.
  • the hole transport layer 13 is formed before forming the photosensitive layer 14.
  • the hole transport layer 13 can be formed by applying a hole transport material solution (paste) containing a hole transport material that forms the hole transport layer 13 and drying it.
  • a hole transport material solution (paste) containing a hole transport material that forms the hole transport layer 13 As the hole transport material, a p-type inorganic semiconductor is usually used, but other materials such as an organic semiconductor can be used depending on a layer to be formed.
  • the hole transport layer 13 has a laminated structure, for example, it is preferable to use two or more kinds of hole transport material solutions containing different hole transport materials. Moreover, when forming a semiconductor mixed layer, it is preferable to use the positive hole transport material mixed solution containing 2 or more types of positive hole transport materials, for example.
  • the hole transport material to be used may be a semiconductor itself or a semiconductor precursor (for example, the above metal alkoxide, acetate, acetylacetonate complex, etc.).
  • the hole transport material solution and the hole transport material mixed solution preferably have a hole transport material concentration of 0.1 to 1.0 M (mol / L) from the viewpoint of excellent coatability.
  • the drying conditions for the hole transport material solution are preferably 60 to 500 ° C., more preferably 80 to 450 ° C., from the viewpoints of photoelectric conversion efficiency and manufacturing variations.
  • the method for providing the photosensitive layer 14 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 14 is prepared.
  • the light absorber solution contains AX represented by the above formula (II) and MX 2 represented by the above formula (III), which are raw materials of the perovskite compound.
  • the molar ratio of MX 2 to AX is appropriately adjusted according to the purpose.
  • the molar ratio of AX to MX 2 is preferably 1: 1 to 10: 1.
  • This light absorber solution can be prepared by mixing AX and MX 2 in a predetermined molar ratio, preferably by heating.
  • This forming liquid is usually a solution, but may be a suspension.
  • the heating conditions are not particularly limited, but the heating temperature is preferably 30 to 200 ° C, more preferably 60 to 150 ° C.
  • the heating time is preferably 0.5 to 100 hours, more preferably 1 to 3 hours.
  • the solvent or dispersion medium those described later can be used.
  • the prepared light absorber solution is brought into contact with the surface of the hole transport layer 13.
  • the perovskite compound is deposited or adsorbed on the surface of the hole transport layer 13.
  • the contact temperature is preferably 5 to 100 ° C.
  • the immersion time is preferably 5 seconds to 24 hours, more preferably 20 seconds to 1 hour.
  • the applied light absorbent solution is dried, the light absorbent solution is preferably dried by heat, and is usually dried 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.
  • any solution may be applied first, but preferably the MX 2 solution is applied first.
  • the molar ratio of AX and MX 2 put to this method, coating conditions and drying conditions are the same as the above method.
  • AX or MX 2 can be vapor-deposited instead of applying the AX solution and the MX 2 solution.
  • Still other methods include dry methods such as vacuum deposition using a compound or mixture from which the solvent of the light absorber solution has been removed. For example, the AX and the MX 2, simultaneously or sequentially, and a method of depositing. Thereby, a light absorber is formed and becomes the photosensitive layer 14.
  • the electron transport layer 15 is formed on the photosensitive layer 14 thus provided.
  • the electron transport layer 15 can be formed by applying an electron transport material solution containing the electron transport material forming the electron transport layer 15 and drying the solution.
  • the electron transport material is usually an n-type inorganic semiconductor, but other materials such as an organic semiconductor can be used depending on the layer to be formed.
  • the electron transport layer 15 has a laminated structure, for example, it is preferable to use two or more kinds of electron transport material solutions containing different electron transport materials.
  • the electron transport material to be used may be a semiconductor itself or a precursor thereof (for example, an alkoxide of the above metal, acetate, acetylacetonate complex, etc.).
  • the electron transport material solution and the electron transport material mixed solution preferably have an electron transport material concentration of 0.1 to 1.0 M (mol / L) from the viewpoint of excellent coating properties.
  • the drying conditions for the electron transport material solution are preferably 60 to 150 ° C., more preferably 80 to 130 ° C. from the viewpoint of photoelectric conversion efficiency and manufacturing variations.
  • the counter electrode 16 can be formed to manufacture a photoelectric conversion element.
  • each layer can be set by appropriately changing the concentration of each dispersion or forming solution and the number of coatings.
  • Each dispersion and forming solution may contain additives such as a dispersion aid and a surfactant, if necessary.
  • Examples of the solvent or dispersion medium used in the photoelectric conversion element and solar cell manufacturing method include, but are not limited to, the solvents described in JP-A No. 2001-291534.
  • an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, a sulfide solvent, and a mixed solvent of two or more of these are preferable.
  • a mixed solvent of an alcohol solvent and a solvent selected from an amide solvent, a nitrile solvent, or a hydrocarbon solvent is preferable.
  • methanol, ethanol, isopropyl alcohol, ⁇ -butyrolactone, n-propyl sulfide, chlorobenzene, acetonitrile, N, N-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 Various known coating methods such as printing and dipping 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 transparent electrode layer 12 and the counter electrode 16.
  • Example 1 and Comparative Example 1 [Production of Photoelectric Conversion Element (Sample No. 101)]
  • the photoelectric conversion element 10A shown in FIG. 1 was manufactured by the following procedure.
  • a fluorine-doped SnO 2 conductive film (transparent electrode layer 12, thickness 300 nm) was formed on a glass substrate (transparent substrate 11, thickness 2.2 mm) to produce a conductive support.
  • NiO powder (1 g) was dispersed in ethanol (30 mL), 10 mass% ethylcellulose ethanol solution (6 g) and terpineol (3 g) were added thereto, and after stirring, the pressure was reduced to distill off ethanol, thereby removing holes.
  • NiO paste (concentration of about 3% by mass) was prepared as a transport material solution. The obtained NiO paste was applied onto a conductive support by a spin coating method (90 seconds at 3000 rpm), and dried at 400 ° C. for 1 hour under a normal pressure in a nitrogen atmosphere to form a NiO layer ( Film thickness 50 nm, NiO content> 98 mass%).
  • ⁇ Formation of photosensitive layer 14> 1 Preparation of Ammonium Compound A 40% methanol solution of methylamine (27.86 mL) and 57% by mass of hydroiodic acid (30 mL) were stirred in a flask at 0 ° C. for 2 hours, and then concentrated to CH 3 NH. A 3 I crude was obtained. The obtained crude product of CH 3 NH 3 I was dissolved in ethanol and recrystallized from diethyl ether. The precipitated crystals were collected by filtration and dried under reduced pressure at 60 ° C. for 24 hours to obtain purified CH 3 NH 3 I. 2.
  • Tetrabutoxy titanium (IV) was diluted with isopropyl alcohol to prepare an electron transport material solution.
  • This electron transport material solution is applied onto the photosensitive layer 14 by spin coating (2000 rpm for 60 seconds), and heated at 100 ° C. for 10 minutes in a nitrogen atmosphere under normal pressure to form a TiO 2 layer (film) as the electron transport layer 15A.
  • a thickness of 100 nm and a TiO 2 content> 98% by mass) were formed.
  • the photoelectric conversion element 10B shown in FIG. 2 was manufactured as follows. That is, the NiO paste (first hole transport material solution) was applied on a conductive support produced in the same manner as in the production of the photoelectric conversion element (sample No. 101), and the atmospheric pressure was increased to 400 in a nitrogen atmosphere. It dried at 1 degreeC for 1 hour, and formed the NiO layer (film thickness of 50 nm) as 1st positive hole transport layer 13B1. Next, an MoO 3 ethanol dispersion (second hole transport material solution) was applied onto the NiO layer by spin coating (90 seconds at 3000 rpm), and dried at 150 ° C. for 1 hour in a nitrogen atmosphere under normal pressure.
  • a MoO 3 layer (film thickness 50 nm) was formed as the second hole transport layer 13B2.
  • a hole transport layer 13B film thickness 100 nm
  • the photosensitive layer 14, the electron transport layer 15A, and the counter electrode 16 were formed on the hole transport layer 13B, respectively.
  • 201 photoelectric conversion elements 10B were manufactured.
  • the second hole transport layer 13B2 is formed by using an ethanol dispersion of V 2 O 5 (second hole transport material solution) instead of the ethanol dispersion of MoO 3.
  • a photoelectric conversion element (Sample No.) except that a V 2 O 5 layer (film thickness 20 nm, layer thickness of first hole transport layer 13B1: layer thickness of second hole transport layer 13B2 1: 0.4) was formed. 201) in the same manner as in the production of Sample No. 202 photoelectric conversion elements 10B were manufactured.
  • the photoelectric conversion element 10C shown in FIG. 3 was manufactured as follows. That is, the transparent electrode layer 12, the hole transport layer 13A, and the photosensitive layer 14 were formed on the transparent substrate 11 in the same manner as in the production of the photoelectric conversion element (sample No. 101).
  • a first electron transporting material solution prepared by diluting tetrabutoxytitanium (IV) with isopropyl alcohol was applied onto the photosensitive layer 14 by spin coating (2000 rpm for 30 seconds), and was carried out at 100 ° C. in a nitrogen atmosphere under normal pressure. By heating for 10 minutes, a TiO 2 layer (film thickness: 100 nm) was formed as the first electron transport layer 15B1.
  • the first electron transport layer 15B1 is the same as the electron transport layer 15A (thickness 100 nm), and the second electron transport layer 15B2 is a 15 nm thick layer made of a LiF layer. It was.
  • the layer thickness of the first electron transport layer 15B1: the layer thickness of the second electron transport layer 15B2 was 1: 0.15.
  • the photoelectric conversion element 10D shown in FIG. 4 was manufactured as follows. In the production of the photoelectric conversion element (sample No. 201), an ethanol solution (second electron transport material solution) of zinc acetate (II) is formed on the electron transport layer (TiO 2 layer) 15A corresponding to the first electron transport layer 15B1. Photoelectric conversion element (sample No. 201) except that it was applied by spin coating (at 3000 rpm for 30 seconds) and dried at 100 ° C. for 1 hour under normal pressure in a nitrogen atmosphere to form the second electron transport layer 15B2. In the same manner as in the manufacture of Sample No. 401 photoelectric conversion element 10D was manufactured.
  • the first electron transport layer 15B1 is the same as the electron transport layer 15A (thickness 100 nm), and the second electron transport layer 15B2 is a ZnO layer having a thickness of 40 nm. did.
  • the layer thickness of the first electron transport layer 15B1: the layer thickness of the second electron transport layer 15B2 was 1: 0.4.
  • the hole transport layer 13 and the electron transport layer 15 are all inorganic semiconductor layers, and the inorganic semiconductor in each layer The content of was over 98% by mass.
  • sample No. 101 it replaced with NiO paste and used the hole transport material solution (concentration 2 mass%) containing PEDOT: PSS, and formed a positive hole transport layer (layer thickness 120nm). Except that it was formed, the sample No. was similar to the manufacture of the photoelectric conversion element (Sample No. 101). A photoelectric conversion element of c12 was produced.
  • a hole transport layer (layer thickness 120 nm) was formed using a hole transport material solution (concentration 2% by mass) containing PEDOT: PSS instead of NiO paste.
  • an electron transport layer (layer thickness: 150 nm) was formed from an electron transport material solution (concentration: 1% by mass) containing PC 61 BM instead of the electron transport material solution containing tetrabutoxytitanium (IV). Is the same as in the manufacture of the photoelectric conversion element (sample No. 101).
  • a photoelectric conversion element of c13 was produced.
  • an electron transport material layer (TiO 2 layer) is formed on the transparent electrode layer instead of the hole transport layer (NiO layer), and electron transport is performed on the photosensitive layer.
  • a hole transport layer (NiO layer) was formed instead of the material layer (TiO 2 layer)
  • sample no. A photoelectric conversion element of c14 was produced.
  • an electron transport material layer (TiO 2 layer) is formed on the transparent electrode layer instead of the hole transport layer (NiO layer), and electron transport is performed on the photosensitive layer.
  • sample No. 101 In the same manner as in the manufacture of the photoelectric conversion element (sample No. 101), except that the hole transport layer (CuSCN layer) was formed instead of the material layer (TiO 2 layer), sample no. A photoelectric conversion element of c15 was produced. These sample Nos. The photoelectric conversion element of c14 and c15 assumes the photoelectric conversion element which forms the solar cell of patent document 1, nonpatent literature 1, and nonpatent literature 2.
  • each photoelectric conversion element was allowed to stand at room temperature (20 ° C.) for 30 days in an atmosphere having a relative humidity of 5 to 10% (atmospheric stability test), and then left in the same manner as the initial photoelectric conversion efficiency (atmospheric stability).
  • the photoelectric conversion efficiency ( ⁇ /%) after the property test) was measured.
  • the measured initial photoelectric conversion efficiency is 1.0 (reference)
  • the relative value of the photoelectric conversion efficiency after standing with respect to this reference is calculated by the following formula, and the atmospheric stability (storage stability) of each photoelectric conversion element Property) was evaluated according to the following evaluation criteria.
  • the results are shown in Table 1 below.
  • Evaluation "B" is a pass level of the atmospheric stability test of this invention.
  • Relative value (photoelectric conversion efficiency after atmospheric stability test) / (initial photoelectric conversion efficiency) -Evaluation criteria for atmospheric stability tests-
  • Retention rate (photoelectric conversion efficiency after moisture resistance test) / (initial photoelectric conversion efficiency) -Evaluation criteria for moisture resistance test-
  • the decrease in photoelectric conversion efficiency was effectively suppressed when the hole transport layer or the electron transport layer was a semiconductor mixed layer containing two or more inorganic semiconductors (Sample Nos. 104 and 105). These excellent effects are considered to be achieved by using a laminated structure or a semiconductor mixed layer to increase the homogeneity of the layer.
  • the photoelectric conversion efficiency is greatly improved both in the air over time and in a high temperature environment. (Sample Nos. C11 to c13).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un élément de conversion photoélectrique (10) comprenant, sur un substrat transparent (11), dans l'ordre suivant, une couche d'électrode transparente (12), une couche de transport de trous (13), une couche photosensible (14) contenant au moins un composé pérovskite à titre d'agent absorbeur de lumière, une couche de transport d'électrons (15) et une contre-électrode (16). La couche de transport de trous (13) et la couche de transport d'électrons (15) sont des couches semi-conductrices inorganiques formées à partir de semi-conducteurs inorganiques, et sont adjacentes à la couche photosensible (14). Une cellule solaire utilisant cet élément de conversion photoélectrique (10) est également décrite.
PCT/JP2016/055238 2015-02-27 2016-02-23 Élément de conversion photoélectrique et cellule solaire WO2016136729A1 (fr)

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JP2019208010A (ja) * 2018-05-25 2019-12-05 パナソニックＩｐマネジメント株式会社 太陽電池
JP2019212702A (ja) * 2018-06-01 2019-12-12 コニカミノルタ株式会社 太陽電池及びその製造方法
CN111653674A (zh) * 2019-03-04 2020-09-11 夏普株式会社 混合粒子、光电转换元件、感光体及图像形成装置
CN112714965A (zh) * 2018-09-28 2021-04-27 夏普株式会社 发光装置、发光装置的制造方法
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CN114583011A (zh) * 2022-03-02 2022-06-03 江西沃格光电股份有限公司 一种基于全无机材料的钙钛矿太阳能电池的制作方法
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US20230298825A1 (en) * 2022-01-14 2023-09-21 The Trustees Of Princeton University Organic/inorganic composite transport layers for blocking iodine diffusion in halide perovskite electronic devices

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