WO2015046252A1 - 薄膜太陽電池、半導体薄膜、及び、半導体形成用塗布液 - Google Patents
薄膜太陽電池、半導体薄膜、及び、半導体形成用塗布液 Download PDFInfo
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- WO2015046252A1 WO2015046252A1 PCT/JP2014/075293 JP2014075293W WO2015046252A1 WO 2015046252 A1 WO2015046252 A1 WO 2015046252A1 JP 2014075293 W JP2014075293 W JP 2014075293W WO 2015046252 A1 WO2015046252 A1 WO 2015046252A1
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- WIPO (PCT)
- Prior art keywords
- thin film
- semiconductor
- sulfide
- solar cell
- photoelectric conversion
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- MYXUYXMJVQWRPU-UHFFFAOYSA-N triethoxybismuthane Chemical compound [Bi+3].CC[O-].CC[O-].CC[O-] MYXUYXMJVQWRPU-UHFFFAOYSA-N 0.000 description 1
- BUZKVHDUZDJKHI-UHFFFAOYSA-N triethyl arsorite Chemical compound CCO[As](OCC)OCC BUZKVHDUZDJKHI-UHFFFAOYSA-N 0.000 description 1
- JGOJQVLHSPGMOC-UHFFFAOYSA-N triethyl stiborite Chemical compound [Sb+3].CC[O-].CC[O-].CC[O-] JGOJQVLHSPGMOC-UHFFFAOYSA-N 0.000 description 1
- HYPTXUAFIRUIRD-UHFFFAOYSA-N tripropan-2-yl stiborite Chemical compound [Sb+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HYPTXUAFIRUIRD-UHFFFAOYSA-N 0.000 description 1
- VFWRGMGLLNCHIA-UHFFFAOYSA-N tris(2-methoxyphenyl)bismuthane Chemical compound COC1=CC=CC=C1[Bi](C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC VFWRGMGLLNCHIA-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- IDMWGAKKAOEHPM-UHFFFAOYSA-L zinc propan-2-one dichloride Chemical compound [Cl-].[Cl-].[Zn+2].CC(C)=O IDMWGAKKAOEHPM-UHFFFAOYSA-L 0.000 description 1
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Definitions
- the present invention relates to a thin-film solar cell that can exhibit high photoelectric conversion efficiency.
- the present invention also relates to a semiconductor thin film used for the thin film solar cell and a coating liquid for forming a semiconductor that can easily form the thin film solar cell with a large area and can improve manufacturing stability.
- each semiconductor functions as a P-type semiconductor or an N-type semiconductor
- photocarriers electron-hole pairs
- electrons form the N-type semiconductor.
- an electric field is generated.
- sulfides or selenide semiconductors such as antimony sulfide (Sb 2 S 3 ), bismuth sulfide (Bi 2 S 3 ), and antimony selenide have attracted attention.
- Sulfide or selenide semiconductors such as antimony sulfide, bismuth sulfide and antimony selenide have a band gap of 1.0 to 2.5 eV, and show high light absorption characteristics in the visible light region, so they are promising as photoelectric conversion materials. Is being viewed.
- sulfides or selenide semiconductors such as antimony sulfide, bismuth sulfide, and antimony selenide are also expected as visible-light-responsive photocatalytic materials.
- antimony sulfide bismuth sulfide
- antimony selenide is also expected as visible-light-responsive photocatalytic materials.
- conductivity changes due to light irradiation, it is also attracting attention as a photoconductive material.
- a thin film solar cell manufactured using a sulfide or selenide semiconductor has a problem in that the photoelectric conversion efficiency is low as compared with other photoelectric conversion elements such as a silicon solar cell and an organic thin film solar cell.
- a thin film made of a sulfide or selenide semiconductor has been conventionally formed by a method such as a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), an electrochemical deposition method (for example, Non-Patent Document 1 and 2)
- the methods such as the vacuum deposition method and the sputtering method have problems that the apparatus is not only expensive and disadvantageous in terms of cost, but also it is difficult to form a film with a large area.
- the electrochemical deposition method does not require a vacuum facility and can form a film at room temperature, but has a problem that it can be formed only on a conductive substrate.
- An object of this invention is to provide the thin film solar cell which can exhibit high photoelectric conversion efficiency.
- the present invention provides a semiconductor thin film used for the thin film solar cell, and a coating liquid for forming a semiconductor that can easily form the thin film solar cell in a large area and can improve manufacturing stability. Objective.
- the present invention is a thin-film solar cell having a photoelectric conversion layer, wherein the photoelectric conversion layer is selected from the group consisting of sulfides and / or selenides of Group 15 elements of the periodic table, rare earth elements, titanium, and zinc.
- the photoelectric conversion layer is selected from the group consisting of sulfides and / or selenides of Group 15 elements of the periodic table, rare earth elements, titanium, and zinc.
- a thin-film solar cell having a portion containing a compound containing one or more elements. The present invention is described in detail below.
- the inventor includes one or more elements selected from the group consisting of sulfides and / or selenides of Group 15 elements of the periodic table and rare earth elements, titanium, and zinc in the photoelectric conversion layer. It has been found that the photoelectric conversion efficiency can be improved by having a portion containing a compound. Moreover, when manufacturing such a thin film solar cell, this inventor is from the group which consists of a compound containing a periodic table 15 group element, a sulfur containing compound and / or a selenium containing compound, and rare earth elements, titanium, and zinc.
- a printing method can be adopted, and a thin-film solar cell that can exhibit high photoelectric conversion efficiency can be easily formed in a large area. I found it. Furthermore, the present inventor can improve the production stability of a thin-film solar cell by forming a complex between a compound containing a Group 15 element of the periodic table and a sulfur-containing compound and / or a selenium-containing compound.
- the headline and the present invention have been completed.
- the thin film solar cell of the present invention is a thin film solar cell having a photoelectric conversion layer.
- the photoelectric conversion layer is a site containing a sulfide and / or selenide of a group 15 element of the periodic table and a compound containing one or more elements selected from the group consisting of rare earth elements, titanium, and zinc (this specification) (Also referred to as sulfide and / or selenide semiconductor portion).
- the sulfide and / or selenide semiconductor portion contains a sulfide and / or selenide of a group 15 element of the periodic table. Since the sulfide and / or selenide of the Group 15 element of the periodic table has high durability, the sulfide and / or selenide of the Group 15 element of the periodic table is included in the sulfide and / or selenide semiconductor portion. Thereby, the thin film solar cell of this invention becomes the thing excellent in durability.
- the sulfide and / or selenide of the Group 15 element of the periodic table is not particularly limited, and may be used alone or in combination of two or more elements of the Group 15 element of the Periodic Table.
- It may be a composite sulfide or selenide contained in the same molecule.
- antimony sulfide, bismuth sulfide, and antimony selenide are preferable, and antimony sulfide and antimony selenide are more preferable.
- Antimony sulfide or antimony selenide has good energy level compatibility with organic semiconductors and / or inorganic semiconductors described later, and absorbs more visible light than conventional zinc oxide, titanium oxide, and the like. For this reason, when antimony sulfide or antimony selenide is contained in the sulfide and / or selenide semiconductor portion, the charge separation efficiency of the thin-film solar cell becomes extremely high, and the photoelectric conversion efficiency becomes high. In addition, when the sulfide and / or selenide semiconductor portion contains antimony sulfide or antimony selenide, the production of the thin-film solar cell is more effective than the case where the other group 15 element sulfide or selenide is contained.
- Stability increases. The reason for this is not clearly understood, but it is presumed that antimony metal hardly precipitates in antimony sulfide or antimony selenide.
- group 15 elements of the periodic table for example, bismuth has an unstable crystal structure, and bismuth metal is likely to precipitate in bismuth sulfide, resulting in a decrease in manufacturing stability (reproducibility of photoelectric conversion efficiency) of thin film solar cells. It is assumed that it is easy to do.
- production stability means reproducibility of photoelectric conversion efficiency between thin film solar cells when a plurality of thin film solar cells are produced by the same method.
- the sulfide and / or selenide semiconductor portion contains a compound containing one or more elements selected from the group consisting of rare earth elements, titanium, and zinc (also referred to as a compound containing rare earth elements in this specification). To do.
- the sulfide and / or selenide semiconductor portion contains a compound containing the rare earth element or the like in addition to the sulfide and / or selenide of the Group 15 element of the periodic table, the thin film solar cell of the present invention is , High photoelectric conversion efficiency can be exhibited.
- the compound containing the rare earth element and the like by blending the compound containing the rare earth element and the like, it is possible to suppress the change over time of the coating liquid for forming a semiconductor, which will be described later, compared to the case where the compound containing the rare earth element or the like is not blended, and to stabilize the storage of the coating liquid. The effect that property improves is also acquired.
- the rare earth element includes yttrium (Y), scandium (Sc), and an element generally called a lanthanoid.
- specific examples of the rare earth element include, in addition to yttrium (Y) and scandium (Sc), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), europium (Eu), and gadolinium.
- Examples thereof include lanthanoids such as (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
- These rare earth elements may be used independently and 2 or more types may be used together.
- trivalent is stable and not a radioisotope like antimony (Sb), yttrium (Y), scandium (Sc), lanthanum (La), neodymium (Nd), samarium (Sm), gadolinium (Gd) Terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and lutetium (Lu) are preferred.
- Sb antimony
- Y yttrium
- Sc scandium
- La lanthanum
- Nd neodymium
- Sm samarium
- Gd gadolinium
- Tb Terbium
- Dy dysprosium
- Ho holmium
- Er erbium
- Tm thulium
- Lu lutetium
- the compound containing the rare earth element or the like is not particularly limited as long as it contains one or more elements selected from the group consisting of rare earth elements, titanium and zinc, and includes compounds containing titanium (for example, titanium isopropoxide and the like).
- a compound containing titanium alkoxide) or zinc (for example, zinc chloride) may be used, but a compound containing rare earth elements (for example, chloride or nitrate of rare earth elements) is preferable.
- the rare earth element-containing compound in the sulfide and / or selenide semiconductor portion the interface resistance of the sulfide and / or selenide semiconductor portion is reduced.
- a compound containing a rare earth element and zinc is more preferable, a compound containing lanthanum and zinc, and a compound containing lutetium and zinc are particularly preferable.
- the content of the compound containing the rare earth element or the like in the sulfide and / or selenide semiconductor portion is the sum of the sulfide and / or selenide of the Group 15 element of the periodic table and the compound containing the rare earth element or the like.
- the preferable lower limit is 1 mol%
- the preferable upper limit is 50 mol%. If the said content is 1 mol% or more, the effect of adding the said rare earth elements etc. will fully be acquired, and photoelectric conversion efficiency will become high. If the said content is 50 mol% or less, the crystal structure of the said sulfide and / or selenide semiconductor site
- the minimum with said more preferable content is 2 mol%, and a more preferable upper limit is 35 mol%.
- the content of the compound containing a rare earth element or the like in the sulfide and / or selenide semiconductor site can be measured by, for example, an ICP emission spectroscopic analyzer (manufactured by SHIMAZDU, ICPS-7500).
- the sulfide and / or selenide semiconductor portion is preferably a crystalline semiconductor.
- the sulfide and / or selenide semiconductor portion is a crystalline semiconductor, electron mobility is increased and photoelectric conversion efficiency is improved.
- a crystalline semiconductor means a semiconductor that can be measured by X-ray diffraction measurement or the like and from which a scattering peak can be detected.
- crystallinity can be used as an index of crystallinity of the sulfide and / or selenide semiconductor portion.
- a preferable lower limit of the crystallinity of the sulfide and / or selenide semiconductor portion is 30%. If the said crystallinity is 30% or more, the mobility of an electron will become high and a photoelectric conversion efficiency will improve.
- a more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%.
- the crystallinity is determined by separating the scattering peak derived from the crystalline substance detected by X-ray diffraction measurement and the like from the halo derived from the amorphous part by fitting, and obtaining the intensity integral of each, It can be determined by calculating the ratio of the crystalline part.
- a method for increasing the degree of crystallinity of the sulfide and / or selenide semiconductor part in the sulfide and / or selenide semiconductor part for example, firing, laser, flash lamp or the like for the sulfide and / or selenide semiconductor part, etc.
- strong light, excimer light irradiation, plasma irradiation, etc. is mentioned.
- a method of performing irradiation with strong light, plasma irradiation, or the like is preferable because oxidation of the sulfide and / or selenide semiconductor portion can be reduced.
- the photoelectric conversion layer preferably further has a portion containing an organic semiconductor and / or an inorganic semiconductor adjacent to the sulfide and / or selenide semiconductor portion.
- a part containing an organic semiconductor also referred to as an organic semiconductor part in the present specification
- the organic semiconductor is not particularly limited, and examples thereof include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
- conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given.
- compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, and a benzoporphyrin skeleton are also included.
- the organic semiconductor is preferably a donor-acceptor type because it can absorb light in a long wavelength region.
- a donor-acceptor type compound having a thiophene skeleton is more preferable, and among the donor-acceptor type compounds having a thiophene skeleton, a thiophene-diketopyrrolopyrrole polymer is particularly preferable from the viewpoint of light absorption wavelength.
- the sulfide and / or selenide semiconductor portion is mainly an N-type semiconductor
- the organic semiconductor portion is It is presumed to work mainly as a P-type semiconductor, and by photoexcitation, photocarriers (electron-hole pairs) are generated in the P-type semiconductor or N-type semiconductor, and electrons move through the N-type semiconductor and holes move through the P-type semiconductor. An electric field is generated.
- the sulfide and / or selenide semiconductor portion may partially function as a P-type semiconductor
- the organic semiconductor portion may partially function as an N-type semiconductor.
- the photoelectric conversion layer has the sulfide and / or selenide semiconductor portion and the organic semiconductor portion
- the photoelectric conversion layer has the thin film sulfide and / or selenide semiconductor portion and the thin film shape.
- a laminate in which the organic semiconductor part is laminated may be used, or a composite film in which the sulfide and / or selenide semiconductor part and the organic semiconductor part are combined may be used.
- a composite film is preferable in that the charge separation efficiency of the organic semiconductor portion can be improved, and a laminate is preferable in that the manufacturing method is simple.
- the inorganic semiconductor is not particularly limited.
- molybdenum oxide, molybdenum sulfide, and tin sulfide are preferable because of higher stability.
- the inorganic semiconductor may contain other elements in addition to the inorganic semiconductor as the main component as described above as long as the effect of the present invention is not impaired.
- the other elements are not particularly limited, and examples thereof include copper, zinc, silver, indium, cadmium, antimony, bismuth, and gallium. These other elements may be used independently and 2 or more types may be used together. Among these, copper, indium, gallium, and zinc are preferable because of high charge mobility.
- the photoelectric conversion layer preferably has an arithmetic average roughness Ra of 5 nm or more measured on the surface in accordance with JIS B 0601-2001.
- the arithmetic average roughness Ra of the photoelectric conversion layer is a rough surface of 5 nm or more, the photoelectric conversion efficiency of the obtained thin film solar cell is further improved.
- the upper limit of the arithmetic average roughness Ra of the photoelectric conversion layer is not particularly limited, but is preferably 1 ⁇ m or less from the viewpoint of the efficiency of hole transport.
- the surface of the photoelectric conversion layer means both a portion corresponding to the interface between the photoelectric conversion layer and the hole transport layer and a portion corresponding to the interface between the photoelectric conversion layer and the electron transport layer.
- the photoelectric conversion layer as described above is formed between a pair of electrodes.
- the material of the electrode is not particularly limited, and a conventionally known material can be used.
- the anode material include metals such as gold, CuI, ITO (indium tin oxide), SnO 2 , AZO, IZO, and GZO.
- Conductive transparent materials such as, conductive transparent polymers and the like.
- cathode material examples include sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al 2 O 3 mixture, Al / LiF mixture, FTO (Fluorine-doped tin oxide) and the like. These materials may be used alone or in combination of two or more.
- the thin film solar cell of the present invention may further have a substrate, a hole transport layer, an electron transport layer, and the like.
- substrate is not specifically limited, For example, transparent glass substrates, such as soda-lime glass and an alkali free glass, a ceramic substrate, a transparent plastic substrate, etc. are mentioned.
- the material of the hole transport layer is not particularly limited, and examples thereof include a P-type conductive polymer, a P-type low molecular organic semiconductor, a P-type metal oxide, a P-type metal sulfide, and a surfactant.
- examples include polystyrene sulfonate adduct of polyethylenedioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Tin sulfide and the like, fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid and the like.
- the material of the electron transport layer is not particularly limited.
- N-type conductive polymer, N-type low molecular organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, surface activity Specific examples include, for example, cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, benzimidazole compound, naphthalene tetracarboxylic acid compound, perylene derivative, Examples include phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.
- the thin-film solar cell of the present invention has a photoelectric conversion layer which is a laminate in which the thin-film sulfide and / or selenide semiconductor portion and the thin-film organic semiconductor portion are stacked between a pair of electrodes. It is preferable to further have an electron transport layer between one electrode and the sulfide and / or selenide semiconductor portion. Furthermore, it is more preferable to further have a hole transport layer between the other electrode and the organic semiconductor part.
- An example of the thin film solar cell of the present invention having a photoelectric conversion layer which is a laminate in which a thin film sulfide and / or selenide semiconductor part and a thin film organic semiconductor part are laminated is schematically shown in FIG.
- a substrate 2 In the thin film solar cell 1 shown in FIG. 1, a substrate 2, an electrode (anode) 3, a thin film organic semiconductor region 4, a thin film sulfide and / or selenide semiconductor region 5, an electron transport layer 6, a transparent electrode ( Cathode) 7 is laminated in this order.
- a preferable lower limit of the thickness of the thin film sulfide and / or selenide semiconductor portion is 5 nm, and a preferable upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area
- the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 500 nm.
- a preferable lower limit of the thickness of the thin-film organic semiconductor portion is 5 nm, and a preferable upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area
- the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 1000 nm.
- the thin-film solar cell of the present invention has a photoelectric conversion layer which is a composite film in which the sulfide and / or selenide semiconductor portion and the organic semiconductor portion are combined between a pair of electrodes, and one electrode It is preferable to further have an electron transport layer between the electrode and the photoelectric conversion layer. Furthermore, it is preferable to further have a hole transport layer between the other electrode and the photoelectric conversion layer.
- An example of the thin film solar cell of the present invention having a photoelectric conversion layer which is a composite film in which a sulfide and / or selenide semiconductor portion and an organic semiconductor portion are combined is schematically shown in FIG. In the thin film solar cell 8 shown in FIG.
- a substrate 9 an electrode (anode) 10, a hole transport layer 11, a composite film 14 of an organic semiconductor site 12 and a sulfide and / or selenide semiconductor site 13, and an electron transport layer 15.
- the transparent electrode (cathode) 16 is laminated in this order.
- the preferable lower limit of the thickness of the composite film is 30 nm, and the preferable upper limit is 3000 nm. If the thickness is 30 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 3000 nm or less, since it becomes easy to reach
- the more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1000 nm.
- the ratio between the sulfide and / or selenide semiconductor portion and the organic semiconductor portion is very important.
- the ratio of the sulfide and / or selenide semiconductor portion to the organic semiconductor portion is preferably 1: 9 to 9: 1 (volume ratio). If the said ratio is in the said range, it will become easy for a hole or an electron to reach
- the ratio is more preferably 2: 8 to 8: 2 (volume ratio).
- the preferable lower limit of the thickness of the hole transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, electrons can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of hole transport, and a photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- the preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of electron transport, and photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- the method for producing the thin film solar cell of the present invention is not particularly limited. For example, after forming an electrode (anode) on the substrate, a photoelectric conversion layer is formed on the electrode (anode), and this photoelectric conversion is further performed. The method of forming an electrode (cathode) on a layer is mentioned. Moreover, after forming an electrode (cathode) on a board
- the method for forming the photoelectric conversion layer is not particularly limited, and may be a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), an electrochemical deposition method, or the like.
- a printing method using a coating solution for forming a semiconductor containing a sulfur-containing compound and / or a selenium-containing compound and a compound containing a rare earth element or the like is preferable.
- vacuum deposition, sputtering, gas phase reaction (CVD), electrochemical deposition, etc. it is difficult to control the content and distribution of dopants (that is, compounds containing rare earth elements, etc.). Since it becomes easy to control content and distribution of a dopant by producing a conversion layer, photoelectric conversion efficiency becomes high.
- arithmetic mean roughness Ra of the surface of the obtained photoelectric converting layer can be 5 nm or more by producing the said photoelectric converting layer by the printing method.
- the photoelectric conversion layer is formed by a conventional vacuum deposition method or the like, there is a problem of film thickness dependency that the photoelectric conversion efficiency is lowered when the film thickness of the photoelectric conversion layer is increased in the manufacturing process. It was.
- the film thickness dependency of the obtained photoelectric conversion layer can be reduced. That is, by adopting the printing method, even if the film thickness of the photoelectric conversion layer is increased during the manufacturing process, it is possible to suppress a decrease in the photoelectric conversion efficiency of the obtained thin film solar cell.
- the arithmetic average roughness Ra of the surface can be 5 nm or more, so that even when the thickness of the photoelectric conversion layer is increased, the interface between the photoelectric conversion layer and the electron transport layer and the photoelectric Since the distance between the conversion layer and the interface between the hole transport layer is unlikely to be long, it is considered that the stability of the performance with respect to the film thickness is improved.
- the method for forming the photoelectric conversion layer by the printing method is, for example, in which the photoelectric conversion layer is formed by laminating the thin-film sulfide and / or selenide semiconductor portion and the thin-film organic semiconductor portion.
- a thin film-like sulfide and / or selenide semiconductor portion is formed by a printing method such as a spin coat method using the semiconductor-forming coating solution, and the thin-film sulfide and It is preferable to form a thin organic semiconductor region on the selenide semiconductor region by a printing method such as spin coating.
- a thin film sulfide and / or selenide semiconductor region may be formed on the thin film organic semiconductor region.
- the photoelectric conversion layer is a composite film in which the sulfide and / or selenide semiconductor portion and the organic semiconductor portion are combined
- the semiconductor-forming coating liquid and the organic semiconductor are mixed. It is preferable to form a composite film using a mixed solution by a printing method such as a spin coating method.
- a coating solution for forming a semiconductor containing a compound containing a Group 15 element of the periodic table, a sulfur-containing compound and / or a selenium-containing compound, and a compound containing a rare earth element is also one aspect of the present invention.
- the semiconductor-forming coating solution of the present invention By using the semiconductor-forming coating solution of the present invention, the sulfide and / or selenide semiconductor portion of the thin film solar cell of the present invention as described above can be formed.
- a thin film solar cell that can employ a printing method and can exhibit high photoelectric conversion efficiency can be easily formed in a large area.
- the coating liquid for forming a semiconductor of the present invention contains a compound containing the rare earth element or the like, so that the change over time is small and high storage stability can be exhibited.
- Examples of the printing method include a spin coating method and a roll-to-roll method.
- the coating liquid for forming a semiconductor of the present invention contains a compound containing a group 15 element of the periodic table, a sulfur-containing compound and / or a selenium-containing compound, and a compound containing a rare earth element or the like.
- the compound containing the Group 15 element of the periodic table and the sulfur-containing compound and / or the selenium-containing compound are a sulfide and / or a selenide semiconductor site formed as described above, and the sulfide of the Group 15 element of the periodic table as described above. And / or forms a selenide.
- a metal-containing compound containing a Group 15 metal element is preferable, and examples thereof include metal salts of Group 15 metal elements, organometallic compounds, and the like.
- Examples of the metal salt of the group 15 metal element include chloride, oxychloride, nitrate, carbonate, sulfate, ammonium salt, borate, silicate, phosphorus of the group 15 metal element Examples thereof include acid salts, hydroxides, peroxides and the like.
- the metal salts of the metal elements of Group 15 of the periodic table include hydrates thereof.
- organometallic compound of the Group 15 metal element examples include, for example, carboxylic acid, dicarboxylic acid, oligocarboxylic acid, and polycarboxylic acid salt compounds of the Group 15 metal element, and more specifically, Examples thereof include salt compounds such as acetic acid, formic acid, propionic acid, octylic acid, stearic acid, oxalic acid, citric acid and lactic acid, which are group 15 metal elements.
- the compound containing the Group 15 element of the periodic table include, for example, antimony chloride, antimony acetate, antimony bromide, antimony fluoride, antimony oxyoxide, triethoxyantimony, tripropoxyantimony, bismuth nitrate, bismuth chloride, and nitric acid.
- examples thereof include bismuth hydroxide, tris (2-methoxyphenyl) bismuth, bismuth carbonate, bismuth oxycarbonate, bismuth phosphate, bismuth bromide, triethoxybismuth, triisopropoxyantimony, arsenic iodide, and triethoxyarsenic.
- These compounds containing Group 15 elements of the periodic table may be used alone or in combination of two or more.
- the preferable lower limit of the content of the compound containing the Group 15 element of the periodic table in the coating liquid for forming a semiconductor of the present invention is 0.5% by weight, and the preferable upper limit is 70% by weight. If the said content is 0.5 weight% or more, a quality sulfide and / or selenide semiconductor part can be formed easily. If the said content is 70 weight% or less, the stable coating liquid for semiconductor formation can be obtained easily.
- sulfur-containing compound examples include thiourea, thiourea derivatives, thioacetamide, thioacetamide derivatives, dithiocarbamate, xanthate, dithiophosphate, thiosulfate, and thiocyanate.
- Examples of the thiourea derivatives include 1-acetyl-2-thiourea, ethylenethiourea, 1,3-diethyl-2-thiourea, 1,3-dimethylthiourea, tetramethylthiourea, N-methylthiourea, 1-acetylthiourea, And phenyl-2-thiourea.
- Examples of the dithiocarbamate include sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, potassium dimethyldithiocarbamate, potassium diethyldithiocarbamate, and the like.
- Examples of the xanthate include sodium ethyl xanthate, potassium ethyl xanthate, sodium isopropyl xanthate, potassium isopropyl xanthate, and the like.
- Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate.
- Examples of the thiocyanate include potassium thiocyanate, potassium thiocyanate, and ammonium thiocyanate. These sulfur-containing compounds may be used alone or in combination of two or more.
- selenium-containing compound examples include hydrogen selenide, selenium chloride, selenium bromide, selenium iodide, selenophenol, selenourea, selenious acid, selenoacetamide, and the like. These selenium-containing compounds may be used alone or in combination of two or more.
- the content of the sulfur-containing compound and / or selenium-containing compound in the coating liquid for forming a semiconductor of the present invention is preferably 1 to 30 times the number of moles of the compound containing the Group 15 element of the periodic table, and preferably 2 to 20 Double is more preferred. If the said content is 1 time or more, the sulfide and / or selenide semiconductor of a stoichiometric ratio will become easy to be obtained. If the said content is 30 times or less, the stability of the coating liquid for semiconductor formation will improve more.
- the compound containing the Group 15 element of the periodic table and the sulfur-containing compound and / or the selenium-containing compound preferably form a complex, and the complex includes the Group 15 element of the periodic table and the sulfur-containing compound. And / or more preferably formed with a selenium-containing compound. Since the sulfur element in the sulfur-containing compound and the selenium element in the selenium-containing compound have a lone electron pair that is not involved in chemical bonding, an empty electron orbit (d orbit or f orbital) of the group 15 element of the periodic table ) To form a coordination bond.
- the stability of the coating liquid for forming a semiconductor is improved, and as a result, uniform high-quality sulfide and / or selenide semiconductor sites are formed, and thus the manufacturing stability is improved. . Furthermore, the electrical characteristics and semiconductor characteristics of the sulfide and / or selenide semiconductor portion are also improved, so that the performance is also improved.
- the complex formed between the Group 15 element of the periodic table and the sulfur-containing compound and / or selenium-containing compound has an absorption peak derived from the bond between the Group 15 element of the periodic table and sulfur in the infrared absorption spectrum. Alternatively, it can be confirmed by measuring an absorption peak derived from a bond between group 15 element of the periodic table and selenium. It can also be confirmed by a change in the color of the solution.
- Examples of complexes formed between the group 15 element of the periodic table and the sulfur-containing compound include, for example, bismuth-thiourea complex, bismuth-thiosulfate complex, bismuth-thiocyanate complex, antimony-thiourea complex, antimony- Examples thereof include a thiosulfuric acid complex, an antimony-thiocyanic acid complex, an antimony-dithiocarbamic acid complex, and an antimony-xanthogenic acid complex.
- Examples of the complex formed between the group 15 element of the periodic table and the selenium-containing compound include an antimony-selenourea complex, an antimony-selenoacetamide complex, and an antimony-dimethylselenourea complex.
- the compound containing the rare earth element is the same as that contained in the sulfide and / or selenide semiconductor portion of the thin film solar cell of the present invention as described above.
- the content of the compound containing the rare earth element or the like in the coating liquid for forming a semiconductor of the present invention is not particularly limited, but the molar ratio of the group 15 element of the periodic table to the rare earth element (periodic group 15 element: rare earth element or the like). ) Is preferably 10: 0.1 to 10: 5. If the molar ratio of the rare earth element or the like is 0.1 or more, the effect of adding the rare earth element or the like is sufficiently obtained, and the photoelectric conversion efficiency of the thin film solar cell formed using the coating liquid for semiconductor formation is high. Become.
- the molar ratio of the rare earth element or the like is 5 or less, the crystal structure of the sulfide and / or selenide semiconductor portion is maintained, and the photoelectric conversion efficiency is increased.
- the molar ratio of the group 15 element of the periodic table to the rare earth element is more preferably 10: 0.2 to 10: 3.5.
- the coating liquid for forming a semiconductor of the present invention preferably further contains an organic solvent.
- the organic solvent is not particularly limited, and examples thereof include methanol, ethanol, N, N-dimethylformamide, dimethyl sulfoxide, acetone, dioxane, tetrahydrofuran, isopropanol, n-propanol, chloroform, chlorobenzene, pyridine, and toluene.
- These organic solvents may be used independently and 2 or more types may be used together. Of these, methanol, ethanol, acetone, and N, N-dimethylformamide are preferable, and a sulfide and / or selenide semiconductor portion having better electrical characteristics and semiconductor characteristics is formed. Formamide is more preferred.
- the coating liquid for semiconductor formation of this invention may further contain non-organic solvent components, such as water, in the range which does not inhibit the effect of this invention.
- a semiconductor thin film containing a sulfide and / or selenide of a group 15 element of the periodic table and a compound containing a rare earth element or the like is also one aspect of the present invention.
- the sulfide and / or selenide of the Group 15 element of the periodic table and the compound containing the rare earth element or the like are included in the sulfide and / or selenide semiconductor portion of the thin film solar cell of the present invention as described above. Is the same.
- the semiconductor thin film of the present invention is useful as a photoelectric conversion material of a thin film solar cell by including a compound containing the rare earth element in addition to the sulfide and / or selenide of the group 15 element of the periodic table. Become.
- the semiconductor thin film of the present invention is useful as a photocatalytic material, a photoconductive material, or the like.
- the thin film solar cell which can exhibit high photoelectric conversion efficiency can be provided.
- a semiconductor thin film used for the thin film solar cell and a coating liquid for forming a semiconductor that can easily form the thin film solar cell in a large area and can improve manufacturing stability. be able to.
- Example 1 (Preparation of coating liquid for semiconductor formation) After adding 20 parts by weight of antimony (III) chloride to 100 parts by weight of N, N-dimethylformamide, it was dissolved by stirring. After adding 20 parts by weight of thiourea (CS (NH 2 ) 2 ) to 100 parts by weight of N, N-dimethylformamide, the mixture was dissolved by stirring. To 50 parts by weight of an antimony chloride N, N-dimethylformamide solution, 40 parts by weight of a thiourea N, N-dimethylformamide solution was gradually added with stirring. At that time, the solution changed from colorless and transparent to yellow and transparent before mixing. Moreover, the infrared absorption spectrum was measured about the solution, and formation of the complex was confirmed.
- CS thiourea
- a stock solution containing antimony chloride and thiourea was prepared by stirring for another 30 minutes after the end of the addition. After adding 20 parts by weight of yttrium nitrate n-hydrate Y (NO 3 ) 3 nH 2 O to 100 parts by weight of N, N-dimethylformamide, the mixture was dissolved by stirring. A stock solution containing yttrium nitrate was prepared by stirring for another 30 minutes after completion of the addition. After adding 5 parts by weight of a stock solution containing yttrium nitrate to 95 parts by weight of a stock solution containing antimony chloride and thiourea, the mixture was dissolved by stirring to prepare a coating solution for forming a semiconductor. In the obtained coating liquid for forming a semiconductor, the molar ratio of antimony: sulfur: yttrium was 10: 24: 0.5.
- aqueous hydroxycarboxylic acid titanium compound solution was applied on an FTO glass substrate by a spin coating method under the condition of a rotational speed of 3000 rpm. After the application, it was baked in the atmosphere at 550 ° C. for 10 minutes. A paste containing TiO 2 nanoparticles (particle size: 30 nm) was applied on the obtained film, and then fired at 550 ° C. for 10 minutes in the air to form a porous electron transport layer. A coating solution for forming a semiconductor was applied on the obtained porous electron transport layer by a spin coating method under the condition of a rotation speed of 1500 rpm.
- the sample was placed in a vacuum furnace and baked at 260 ° C. for 10 minutes while being evacuated to obtain a sulfide semiconductor thin film (thin film-like sulfide semiconductor portion) (thickness 120 nm, band gap 1.7 eV). ).
- the sulfide semiconductor thin film taken out from the vacuum furnace was black.
- the thickness of the sulfide semiconductor thin film was measured as an average film thickness using a film thickness meter (KLA-TENCOR, P-16 +), and the band gap of the sulfide semiconductor thin film was measured using a spectrophotometer (manufactured by Hitachi High-Tech, It was estimated from the absorption spectrum measured using U-4100).
- the obtained sulfide semiconductor thin film was measured by an ICP emission spectroscopic analyzer (manufactured by SHIMAZDU, ICPS-7500). As a result, the content of antimony sulfide and yttrium nitrate was 92% when the total content was 100 mol%. Mole% and 8 mol%.
- poly (3-hexylthiophene) P3HT was formed to a thickness of 100 nm as an organic semiconductor thin film (thin film-like organic semiconductor portion) by spin coating. Thereafter, polyethylene dioxide thiophene: polystyrene sulfonate (PEDOT: PSS) was formed as a hole transport layer on the organic semiconductor thin film to a thickness of 100 nm by a spin coating method. Next, a thin film solar cell was fabricated by forming a gold electrode having a thickness of 80 nm on the hole transport layer by vacuum deposition.
- P3HT poly (3-hexylthiophene)
- Example 1 except that the compound (or other compound) containing a group 15 element, a sulfur-containing compound or a selenium-containing compound, a rare earth element, etc. in the periodic table was changed to the compounds and contents shown in Table 1 and Table 2.
- the coating liquid for semiconductor formation and the thin film solar cell were produced by the same method.
- Example 28 An aqueous hydroxycarboxylic acid titanium compound solution was applied on an FTO glass substrate by a spin coating method under the condition of a rotational speed of 1500 rpm. After the application, it was baked for 10 minutes at 550 ° C. in the air to form a flat electron transport layer having an arithmetic average roughness Ra of about 1 nm.
- Thin film solar cells were produced in the same manner as in Examples 8 and 15, except that a semiconductor forming coating solution was applied onto the obtained flat electron transport layer to form a sulfide semiconductor thin film.
- Example 30 and 31 (Production of thin film solar cells) A thin film solar cell was produced in the same manner as in Example 1 except that the chemical deposition method shown below was used instead of using the semiconductor-forming coating solution.
- Example 30 After removing the obtained sample from the solution, the excess is washed away with ion-exchanged water, and the sample is placed in a vacuum furnace and baked at 260 ° C. for 10 minutes while being evacuated to form a sulfide semiconductor thin film (thin film-like sulfide). (Semiconductor part) was obtained.
- Example 30 2.5 mL of 0.05 M titanium chloride acetone solution was used instead of 2.5 mL of 1 M SbCl 3 acetone solution, and the same as the above except that the sample on which the sulfide semiconductor thin film was formed was immersed. In this method, titanium was added at 4 mol%.
- Example 31 the same method as described above except that 2.5 mL of 0.05 M zinc chloride acetone solution was used instead of 2.5 mL of 1 M SbCl 3 acetone solution and the sample on which the sulfide semiconductor thin film was formed was immersed. Then, zinc was added at 4 mol%.
- Example 32 and 33 An aqueous hydroxycarboxylic acid titanium compound solution was applied on an FTO glass substrate by a spin coating method under the condition of a rotational speed of 1500 rpm. After the application, it was baked at 550 ° C. for 10 minutes in the atmosphere to form a flat electron transport layer. Thin film solar cells were produced in the same manner as in Examples 30 and 31 except that the obtained flat electron transport layer was used.
- Example 34 An aqueous hydroxycarboxylic acid titanium compound solution was applied on an FTO glass substrate by a spin coating method under the condition of a rotational speed of 1500 rpm. After the application, it was baked at 550 ° C. for 10 minutes in the atmosphere to form a flat electron transport layer.
- a thin film solar cell was produced in the same manner as in Example 1 except that a semiconductor thin film was formed by co-evaporating antimony sulfide and zinc on the obtained flat electron transport layer by a co-evaporation method.
- ⁇ Surface arithmetic average roughness Ra is 0 nm or more and less than 5 nm ⁇ : Surface arithmetic average roughness Ra is 5 nm or more and less than 10 nm ⁇ : Surface arithmetic average roughness Ra is 10 nm or more and less than 20 nm ⁇ : Surface arithmetic Average roughness Ra is 20 nm or more
- the photoelectric conversion efficiency of the thin film solar cell obtained in Example 27 was normalized by setting the photoelectric conversion efficiency of the thin film solar cell obtained in Comparative Example 15 to 1.0 (in the case of antimony selenide thin film). ).
- the thickness of the sulfide semiconductor thin film was 120 nm and 150 nm by the same method.
- An evaluation cell was prepared so that The relative conversion efficiency of the solar cell of the evaluation cell was determined in the same manner as (2) above.
- the conversion efficiency at a thickness of 120 nm was standardized by setting the conversion efficiency at a thickness of 120 nm to 1.0, and the film thickness dependency was evaluated according to the following criteria.
- ⁇ The standard value exceeded 0.5 and was 0.8 or less.
- ⁇ The standard value was 0.5 or less.
- the photoelectric conversion efficiency of a thin film solar cell produced by the same method as in Comparative Example 1 is 1.0
- the value obtained by standardizing the photoelectric conversion efficiency of a thin film solar cell produced by the same method as in Comparative Example 1 using the coating liquid for semiconductor formation after storage at 25 ° C. for 1 day was defined as E1.
- the photoelectric conversion efficiency of a thin film solar cell produced by the same method as in Examples 1 to 26 and 28 to 29 using the semiconductor-forming coating solution immediately after preparation was set to 1.0, in the atmosphere at 25 ° C. for 1 day.
- a value obtained by standardizing the photoelectric conversion efficiency of a thin film solar cell produced by the same method as in Examples 1 to 26 and 28 to 29 using the coating liquid for forming a semiconductor after storage was defined as E3.
- the value which normalized the photoelectric conversion efficiency of the thin film solar cell produced by the method similar to the comparative example 15 using the liquid was set to E2.
- the coating liquid for semiconductor formation immediately after the preparation the semiconductor conversion after storage for 1 day at 25 ° C.
- a value obtained by standardizing the photoelectric conversion efficiency of the thin-film solar cell manufactured by the same method as in Example 27 using the coating liquid for coating was E4.
- the photoelectric conversion efficiency was measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2 by connecting a power source (manufactured by KEITHLEY, 236 model) between the electrodes of the thin film solar cell.
- the storage stability was evaluated according to the following criteria using each obtained value. ⁇ : E3 / E1 is greater than 1.01, or E4 / E2 is greater than 1.01
- the thin film solar cell which can exhibit high photoelectric conversion efficiency can be provided.
- a semiconductor thin film used for the thin film solar cell and a coating liquid for forming a semiconductor that can easily form the thin film solar cell in a large area and can improve manufacturing stability. be able to.
Abstract
Description
また硫化物又はセレン化物半導体からなる薄膜は、従来、真空蒸着法、スパッタ法、気相反応法(CVD)、電気化学沈積法等の方法により形成されてきたが(例えば、非特許文献1及び2)、真空蒸着法やスパッタ法等の方法は、装置が高価でコスト面で不利であるだけでなく、大面積の成膜が困難であるという問題点があった。また、電気化学沈積法は、真空設備を必要せず、常温で成膜できるが、導電性の基板にしか成膜できないという問題点があった。
以下、本発明を詳述する。
また、本発明者は、このような薄膜太陽電池を製造する際に、周期表15族元素を含む化合物と、硫黄含有化合物及び/又はセレン含有化合物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有する半導体形成用塗布液を用いることにより、印刷法を採用でき、高い光電変換効率を発揮できる薄膜太陽電池を大面積で簡易に形成できることを見出した。更に、本発明者は、周期表15族元素を含む化合物と、硫黄含有化合物及び/又はセレン含有化合物とが錯体を形成していることで薄膜太陽電池の製造安定性を向上させることができることを見出し、本発明を完成させるに至った。
上記光電変換層は、周期表15族元素の硫化物及び/又はセレン化物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有する部位(本明細書中、硫化物及び/又はセレン化物半導体部位ともいう)を有する。
上記周期表15族元素の硫化物及び/又はセレン化物は特に限定されず、単独で用いられてもよく、2種以上が併用されてもよく、周期表15族元素の2種以上の元素を同一の分子に含有する複合硫化物又はセレン化物であってもよい。なかでも、硫化アンチモン、硫化ビスマス、セレン化アンチモンが好ましく、硫化アンチモン、セレン化アンチモンがより好ましい。
更に、上記硫化物及び/又はセレン化物半導体部位に硫化アンチモン又はセレン化アンチモンが含まれることにより、他の周期表15族元素の硫化物又はセレン化物が含まれる場合よりも、薄膜太陽電池の製造安定性(光電変換効率の再現性)が高くなる。この理由ははっきりとは判っていないが、アンチモン金属が硫化アンチモン又はセレン化アンチモン中に析出しにくいためと推測される。一方、周期表15族元素のなかでも、例えばビスマスは結晶構造が不安定であり、ビスマス金属が硫化ビスマス中に析出しやすく、薄膜太陽電池の製造安定性(光電変換効率の再現性)が低下しやすいと推測される。
なお、製造安定性(光電変換効率の再現性)とは、同一の方法で薄膜太陽電池を複数個作製したときの各薄膜太陽電池間での光電変換効率の再現性を意味する。
上記希土類元素として、具体的には例えば、イットリウム(Y)、スカンジウム(Sc)に加えて、ランタン(La)、セリウム(Ce)、ネオジム(Nd)、サマリウム(Sm)、ユーロピウム(Eu)、ガドリニウム(Gd)、テルビウム(Tb)、ジスプロシウム(Dy)、ホルミウム(Ho)、エルビウム(Er)、ツリウム(Tm)、イッテルビウム(Yb)、ルテチウム(Lu)等のランタノイドが挙げられる。これらの希土類元素は単独で用いられてもよく、2種以上が併用されてもよい。なかでも、アンチモン(Sb)と同じく3価が安定で放射性同位元素でないことから、イットリウム(Y)、スカンジウム(Sc)、ランタン(La)、ネオジム(Nd)、サマリウム(Sm)、ガドリニウム(Gd)、テルビウム(Tb)、ジスプロシウム(Dy)、ホルミウム(Ho)、エルビウム(Er)、ツリウム(Tm)、ルテチウム(Lu)が好ましい。
なお、硫化物及び/又はセレン化物半導体部位における希土類元素等を含む化合物の含有量は、例えば、ICP発光分光分析装置(SHIMAZDU社製、ICPS-7500)等により測定することができる。
なお、結晶性半導体とは、X線回折測定等で測定し、散乱ピークが検出できる半導体を意味する。
なお、結晶化度は、X線回折測定等により検出された結晶質由来の散乱ピークと、非晶質部由来のハローとをフィッティングにより分離し、それぞれの強度積分を求めて、全体のうちの結晶質部分の比を算出することにより求めることができる。
上記有機半導体は特に限定されず、例えば、ポリ(3-アルキルチオフェン)等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格等を有する化合物も挙げられる。なかでも、比較的耐久性が高いことから、チオフェン骨格、フタロシアニン骨格、ナフタロシアニン骨格、ベンゾポルフィリン骨格を有する化合物が好ましい。
また、上記光電変換層が上記硫化物及び/又はセレン化物半導体部位と上記有機半導体部位とを有する場合、上記光電変換層は、薄膜状の上記硫化物及び/又はセレン化物半導体部位と薄膜状の上記有機半導体部位とを積層した積層体であってもよいし、上記硫化物及び/又はセレン化物半導体部位と上記有機半導体部位とを複合化した複合膜であってもよい。上記有機半導体部位の電荷分離効率を向上させることができる点では複合膜が好ましく、製法が簡便である点では積層体が好ましい。
従来の真空蒸着法やスパッタ法等では、このような粗面の光電変換層を形成することは困難であったが、本発明においては、周期表15族元素を含む化合物と、硫黄含有化合物及び/又はセレン含有化合物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有する半導体形成用塗布液を用い、印刷法により光電変換層を形成することにより、算術平均粗さRaが5nm以上の光電変換層を容易に形成することができる。
上記光電変換層の算術平均粗さRaの上限は特に限定されないが、ホール輸送の効率の観点から1μm以下であることが好ましい。
なお、本明細書において光電変換層の表面は、光電変換層とホール輸送層の界面にあたる部分、光電変換層と電子輸送層の界面にあたる部分のいずれをも意味する。
上記電極の材料は特に限定されず、従来公知の材料を用いることができるが、陽極材料として、例えば、金等の金属、CuI、ITO(インジウムスズ酸化物)、SnO2、AZO、IZO、GZO等の導電性透明材料、導電性透明ポリマー等が挙げられる。また、陰極材料として、例えば、ナトリウム、ナトリウム-カリウム合金、リチウム、マグネシウム、アルミニウム、マグネシウム-銀混合物、マグネシウム-インジウム混合物、アルミニウム-リチウム合金、Al/Al2O3混合物、Al/LiF混合物、FTO(フッ素ドープスズ酸化物)等が挙げられる。これらの材料は単独で用いられてもよく、2種以上が併用されてもよい。
薄膜状の硫化物及び/又はセレン化物半導体部位と薄膜状の有機半導体部位とを積層した積層体である光電変換層を有する本発明の薄膜太陽電池の一例を、図1に模式的に示す。図1に示す薄膜太陽電池1においては、基板2、電極(陽極)3、薄膜状の有機半導体部位4、薄膜状の硫化物及び/又はセレン化物半導体部位5、電子輸送層6、透明電極(陰極)7がこの順で積層されている。
硫化物及び/又はセレン化物半導体部位と有機半導体部位とを複合化した複合膜である光電変換層を有する本発明の薄膜太陽電池の一例を、図2に模式的に示す。図2に示す薄膜太陽電池8においては、基板9、電極(陽極)10、ホール輸送層11、有機半導体部位12と硫化物及び/又はセレン化物半導体部位13との複合膜14、電子輸送層15、透明電極(陰極)16がこの順で積層されている。
また、印刷法で上記光電変換層を作製することにより、得られる光電変換層の表面の算術平均粗さRaを5nm以上とすることができる。
更に、従来の真空蒸着法等により光電変換層を形成したときには、製造工程で光電変換層の膜厚が厚くなった場合に光電変換効率が低下してしまうという、膜厚依存性の問題があった。印刷法で光電変換層を作製することにより、得られる光電変換層の膜厚依存性を小さくすることができる。即ち、印刷法を採用することにより、たとえ製造過程で光電変換層の膜厚が厚くなったとしても、得られる薄膜太陽電池の光電変換効率の低下を抑制することができる。これは、印刷法によれば表面の算術平均粗さRaを5nm以上とすることができることにより、光電変換層の膜厚が厚くなった場合にでも、光電変換層と電子輸送層の界面と光電変換層とホール輸送層の界面との距離が長くなりにくくなることから、膜厚に対する性能の安定性が向上するためではないかと考えられる。
また、例えば、上記光電変換層が上記硫化物及び/又はセレン化物半導体部位と上記有機半導体部位とを複合化した複合膜である場合には、上記半導体形成用塗布液と有機半導体とを混合した混合液を用いてスピンコート法等の印刷法により複合膜を成膜することが好ましい。
本発明の半導体形成用塗布液を用いることにより、上述したような本発明の薄膜太陽電池の硫化物及び/又はセレン化物半導体部位を形成することができる。本発明の半導体形成用塗布液を用いることにより、印刷法を採用でき、高い光電変換効率を発揮できる薄膜太陽電池を大面積で簡易に形成することができる。また、本発明の半導体形成用塗布液は、上記希土類元素等を含む化合物を含有することにより、経時変化が小さく、高い保存安定性を発揮することができる。
上記印刷法として、例えば、スピンコート法、ロールtoロール法等が挙げられる。
上記周期表15族元素を含む化合物と、上記硫黄含有化合物及び/又はセレン含有化合物とは、形成される硫化物及び/又はセレン化物半導体部位において、上述したような周期表15族元素の硫化物及び/又はセレン化物を形成するものである。上記周期表15族元素を含む化合物として、周期表15族の金属元素を含む金属含有化合物が好ましく、例えば、周期表15族の金属元素の金属塩、有機金属化合物等が挙げられる。
上記周期表15族の金属元素の有機金属化合物として、例えば、周期表15族の金属元素のカルボン酸、ジカルボン酸、オリゴカルボン酸、ポリカルボン酸の塩化合物が挙げられ、より具体的には、周期表15族の金属元素の酢酸、ギ酸、プロピオン酸、オクチル酸、ステアリン酸、シュウ酸、クエン酸、乳酸等の塩化合物等が挙げられる。
このような錯体が形成されることで、半導体形成用塗布液の安定性が向上し、その結果、均一な良質の硫化物及び/又はセレン化物半導体部位が形成されるため製造安定性が向上する。更に、硫化物及び/又はセレン化物半導体部位の電気的な特性及び半導体特性も向上するため性能も向上する。
なお、周期表15族元素と、硫黄含有化合物及び/又はセレン含有化合物との間に形成された錯体は、赤外吸収スペクトルにて、周期表15族元素-硫黄間の結合に由来する吸収ピーク又は周期表15族元素-セレン間の結合に由来する吸収ピークを測定することで確認することができる。また、溶液の色の変化で確認することもできる。
上記周期表15族元素と、上記セレン含有化合物との間に形成された錯体として、例えば、アンチモン-セレノ尿素錯体、アンチモン-セレノアセトアミド錯体、アンチモン―ジメチルセレノ尿素錯体等が挙げられる。
本発明の半導体形成用塗布液における上記希土類元素等を含む化合物の含有量は特に限定されないが、上記周期表15族元素と上記希土類元素等とのモル比(周期表15族元素:希土類元素等)が10:0.1~10:5が好ましい。上記希土類元素等のモル比が0.1以上であれば、上記希土類元素等を添加する効果が充分に得られ、半導体形成用塗布液を用いて形成された薄膜太陽電池の光電変換効率が高くなる。上記希土類元素等のモル比が5以下であれば、上記硫化物及び/又はセレン化物半導体部位の結晶構造が保たれ、光電変換効率が高くなる。上記周期表15族元素と上記希土類元素等とのモル比(周期表15族元素:希土類元素等)は10:0.2~10:3.5がより好ましい。
上記有機溶媒を適宜選択することで、上述したような錯体を形成させやすくすることができる。上記有機溶媒は特に限定されず、例えば、メタノール、エタノール、N,N-ジメチルホルムアミド、ジメチルスルホキシド、アセトン、ジオキサン、テトラヒドロフラン、イソプロパノール、n-プロパノール、クロロホルム、クロロベンゼン、ピリジン、トルエン等が挙げられる。これらの有機溶媒は単独で用いられてもよく、2種以上が併用されてもよい。なかでも、メタノール、エタノール、アセトン、N,N-ジメチルホルムアミドが好ましく、電気的な特性及び半導体特性のより優れた硫化物及び/又はセレン化物半導体部位が形成されることから、N,N-ジメチルホルムアミドがより好ましい。
上記周期表15族元素の硫化物及び/又はセレン化物と、上記希土類元素等を含む化合物とは、上述したような本発明の薄膜太陽電池の硫化物及び/又はセレン化物半導体部位に含まれるものと同じである。上記周期表15族元素の硫化物及び/又はセレン化物に加えて、上記希土類元素等を含む化合物が含まれることにより、本発明の半導体薄膜は、薄膜太陽電池の光電変換材料として有用なものとなる。更に、本発明の半導体薄膜は、光触媒材料、光導電材料等としても有用である。
(半導体形成用塗布液の作製)
N,N-ジメチルホルムアミド100重量部に、塩化アンチモン(III)20重量部を添加した後、攪拌することによって溶解した。N,N-ジメチルホルムアミド100重量部に、チオ尿素(CS(NH2)2)20重量部を添加した後、攪拌することによって溶解した。塩化アンチモンのN,N-ジメチルホルムアミド溶液50重量部に、チオ尿素のN,N-ジメチルホルムアミド溶液40重量部を攪拌しながら徐々に添加した。その際、溶液は混合前の無色透明から黄色透明に変わった。また、溶液について赤外吸収スペクトルを測定し、錯体の形成を確認した。添加終了後に更に30分間攪拌することによって、塩化アンチモンとチオ尿素とを含有するストック溶液を作製した。
N,N-ジメチルホルムアミド100重量部に、硝酸イットリウムn水和物Y(NO3)3nH2Oを20重量部添加した後、攪拌することによって溶解した。添加終了後に更に30分間攪拌することによって、硝酸イットリウムを含有するストック溶液を作製した。
塩化アンチモンとチオ尿素とを含有するストック溶液95重量部に対し、硝酸イットリウムを含有するストック溶液5重量部を添加した後、攪拌することによって溶解し、半導体形成用塗布液を作製した。得られた半導体形成用塗布液において、アンチモン:硫黄:イットリウムのモル比は10:24:0.5であった。
FTOガラス基板上に、ヒドロキシカルボン酸チタン化合物水溶液を、回転数3000rpmの条件でスピンコート法により塗布した。塗布後、大気中550℃で10分間焼成した。得られた膜上にTiO2ナノ粒子(粒径:30nm)を含むペーストを塗布した後、大気中550℃で10分間焼成し、多孔質電子輸送層を形成した。
得られた多孔質電子輸送層上に半導体形成用塗布液を、回転数1500rpmの条件でスピンコート法により塗布した。塗布後、サンプルを真空炉に入れ、真空に引きながら260℃で10分間焼成することによって硫化物半導体薄膜(薄膜状の硫化物半導体部位)を得た(厚みが120nm、バンドギャップが1.7eV)。真空炉から取出した硫化物半導体薄膜は黒色であった。なお、硫化物半導体薄膜の厚みは、膜厚計(KLA-TENCOR、P-16+)を用いて平均膜厚として測定し、硫化物半導体薄膜のバンドギャップは、分光光度計(日立ハイテック社製、U-4100)を用いて測定した吸収スペクトルから見積もった。得られた硫化物半導体薄膜についてICP発光分光分析装置(SHIMAZDU社製、ICPS-7500)により測定したところ、硫化アンチモン、硝酸イットリウムの含有量は、これらの合計を100モル%としたとき、それぞれ92モル%、8モル%であった。
周期表15族元素を含む化合物、硫黄含有化合物又はセレン含有化合物、希土類元素等を含む化合物(又はその他の化合物)を表1及び表2に示す化合物及び含有量に変更した以外は、実施例1と同様の方法で半導体形成用塗布液及び薄膜太陽電池を作製した。
FTOガラス基板上に、ヒドロキシカルボン酸チタン化合物水溶液を、回転数1500rpmの条件でスピンコート法により塗布した。塗布後、大気中550℃で10分間焼成し、算術平均粗さRaが約1nmである平坦電子輸送層を形成した。
得られた平坦電子輸送層上に半導体形成用塗布液を塗布して硫化物半導体薄膜を形成した以外は、実施例8、15と同様の方法で薄膜太陽電池を作製した。
(薄膜太陽電池の作製)
半導体形成用塗布液を用いる代わりに以下に示す化学析出法を用いたこと以外は、実施例1と同様の方法で薄膜太陽電池を作製した。
[化学析出法]
1MのNa2S2O3水溶液25mL(溶液温度5~10℃)にイオン交換水(水温度5~10℃)72.5mLを加え、更に、1MのSbCl3アセトン溶液2.5mLを加えた。得られた溶液を1分間攪拌した後、ブロッキング層を形成した多孔質酸化チタン膜を溶液に浸漬し、冷蔵庫(温度5~10℃)で3時間成膜した。得られたサンプルを溶液から取り出した後、イオン交換水で余分なものを洗い流し、サンプルを真空炉に入れ、真空に引きながら260℃で10分間焼成することによって硫化物半導体薄膜(薄膜状の硫化物半導体部位)を得た。
次いで、実施例30では、1MのSbCl3アセトン溶液2.5mLの代わりに0.05Mの塩化チタンアセトン溶液2.5mLを用い、硫化物半導体薄膜が形成されたサンプルを浸漬した以外は上記と同様の方法で、チタンを4モル%で添加した。実施例31では、1MのSbCl3アセトン溶液2.5mLの代わりに0.05Mの塩化亜鉛アセトン溶液2.5mLを用い、硫化物半導体薄膜が形成されたサンプルを浸漬した以外は上記と同様の方法で、亜鉛を4モル%で添加した。
FTOガラス基板上に、ヒドロキシカルボン酸チタン化合物水溶液を、回転数1500rpmの条件でスピンコート法により塗布した。塗布後、大気中550℃で10分間焼成し、平坦電子輸送層を形成した。
得られた平坦電子輸送層を用いた以外は、実施例30、31と同様の方法で薄膜太陽電池を作製した。
FTOガラス基板上に、ヒドロキシカルボン酸チタン化合物水溶液を、回転数1500rpmの条件でスピンコート法により塗布した。塗布後、大気中550℃で10分間焼成し、平坦電子輸送層を形成した。
得られた平坦電子輸送層上に、共蒸着法によって硫化アンチモンと亜鉛を共蒸着させて半導体薄膜を形成したこと以外は、実施例1と同様の方法で薄膜太陽電池を作製した。
実施例及び比較例で得られた薄膜太陽電池について、以下の評価を行った。また、実施例及び比較例において調製した半導体形成用塗布液について、以下の評価を行った。
結果を表1及び表2に示した。
BRUKER社製、DIMENSION ICON AFMを用いて得られた硫化物半導体薄膜の表面形状を測定し、JIS B 0601-2001に準じた方法により表面の算術平均粗さRaを算出した。硫化物半導体薄膜の表面粗さを以下の基準により評価した。
×:表面の算術平均粗さRaが0nm以上、5nm未満
△:表面の算術平均粗さRaが5nm以上、10nm未満
〇:表面の算術平均粗さRaが10nm以上、20nm未満
◎:表面の算術平均粗さRaが20nm以上
実施例及び比較例で得られた薄膜太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて薄膜太陽電池の光電変換効率を測定した。
比較例1で得られた薄膜太陽電池の光電変換効率を1.0として実施例1~26、28~34、比較例2~14で得られた薄膜太陽電池の光電変換効率を規格化し(硫化アンチモン薄膜の場合)、比較例15で得られた薄膜太陽電池の光電変換効率を1.0として実施例27で得られた薄膜太陽電池の光電変換効率を規格化した(セレン化アンチモン薄膜の場合)。
実施例及び比較例における薄膜太陽電池の作製方法と同じ方法で、評価用セルをそれぞれ4個ずつ作製した。4個の評価用セルの相対光電変換効率を上記(2)と同様にしてそれぞれ測定し、製造安定性を以下の基準により評価した。
△:相対光電変換効率の最大値と最小値との差が、最大値の20%より大きかった
○:相対光電変換効率の最大値と最小値との差が、最大値の20%以下であった
平坦電子輸送層を用いた実施例28、29、32、33、34について、同様の方法により硫化物半導体薄膜の厚みが120nmと150nmになるよう評価用セルを作製した。評価用セルの太陽電池の相対変換効率を上記(2)と同様にして求めた。厚み120nmの変換効率を1.0として厚み150nmの変換効率を規格化し、以下の基準により膜厚依存性を評価した。
◎:規格値が0.8を超えていた
○:規格値が0.5を超え、0.8以下であった
△:規格値が0.5以下であった
調製直後の半導体形成用塗布液を用い、比較例1と同様の方法により作製した薄膜太陽電池の光電変換効率を1.0として、大気中、25℃で1日間保管した後の半導体形成用塗布液を用い、比較例1と同様の方法により作製した薄膜太陽電池の光電変換効率を規格化した値をE1とした。一方、調製直後の半導体形成用塗布液を用い、実施例1~26、28~29と同様の方法により作製した薄膜太陽電池の光電変換効率を1.0として、大気中、25℃で1日間保管した後の半導体形成用塗布液を用い、実施例1~26、28~29と同様の方法により作製した薄膜太陽電池の光電変換効率を規格化した値をE3とした。
調製直後の半導体形成用塗布液を用い、比較例15と同様の方法により作製した薄膜太陽電池の光電変換効率を1.0として、大気中、25℃で1日間保管した後の半導体形成用塗布液を用い、比較例15と同様の方法により作製した薄膜太陽電池の光電変換効率を規格化した値をE2とした。一方、調製直後の半導体形成用塗布液を用い、実施例27と同様の方法により作製した薄膜太陽電池の光電変換効率を1.0として、大気中、25℃で1日間保管した後の半導体形成用塗布液を用い、実施例27と同様の方法により作製した薄膜太陽電池の光電変換効率を規格化した値をE4とした。
なお、光電変換効率は、薄膜太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて測定した。
得られた各値を用い、下記の基準で保存安定性を評価した。
○:E3/E1が1.01より大きい、又はE4/E2が1.01より大きい
2 基板
3 電極(陽極)
4 薄膜状の有機半導体部位
5 薄膜状の硫化物及び/又はセレン化物半導体部位
6 電子輸送層
7 透明電極(陰極)
8 薄膜太陽電池
9 基板
10 電極(陽極)
11 ホール輸送層
12 有機半導体部位
13 硫化物及び/又はセレン化物半導体部位
14 複合膜
15 電子輸送層
16 透明電極(陰極)
Claims (8)
- 光電変換層を有する薄膜太陽電池であって、
前記光電変換層は、周期表15族元素の硫化物及び/又はセレン化物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有する部位を有する
ことを特徴とする薄膜太陽電池。 - 光電変換層は、更に、有機半導体を含有する部位を有することを特徴とする請求項1記載の薄膜太陽電池。
- 光電変換層は、表面のJIS B 0601-2001に準拠して測定された算術平均粗さRaが5nm以上であることを特徴とする請求項1又は2記載の薄膜太陽電池。
- 一対の電極間に光電変換層が形成されていることを特徴とする請求項1、2又は3記載の薄膜太陽電池。
- 周期表15族元素の硫化物及び/又はセレン化物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有することを特徴とする半導体薄膜。
- 周期表15族元素を含む化合物と、硫黄含有化合物及び/又はセレン含有化合物と、希土類元素、チタン及び亜鉛からなる群から選択される1種以上の元素を含む化合物とを含有することを特徴とする半導体形成用塗布液。
- 周期表15族元素を含む化合物と、硫黄含有化合物及び/又はセレン含有化合物とが、錯体を形成していることを特徴とする請求項6記載の半導体形成用塗布液。
- 更に、有機溶媒を含有することを特徴とする請求項6又は7記載の半導体形成用塗布液。
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