WO2023190182A1 - Method for manufacturing perovskite thin film-based solar cell, and perovskite thin film-based solar cell - Google Patents
Method for manufacturing perovskite thin film-based solar cell, and perovskite thin film-based solar cell Download PDFInfo
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- WO2023190182A1 WO2023190182A1 PCT/JP2023/011867 JP2023011867W WO2023190182A1 WO 2023190182 A1 WO2023190182 A1 WO 2023190182A1 JP 2023011867 W JP2023011867 W JP 2023011867W WO 2023190182 A1 WO2023190182 A1 WO 2023190182A1
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- thin film
- electrode layer
- solar cell
- transport layer
- perovskite thin
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 20
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
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- 239000010408 film Substances 0.000 claims description 28
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- 239000002184 metal Substances 0.000 claims description 17
- 238000010306 acid treatment Methods 0.000 claims description 10
- 238000002834 transmittance Methods 0.000 claims description 5
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- 229910052718 tin Inorganic materials 0.000 description 9
- 239000000969 carrier Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
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- 125000005843 halogen group Chemical group 0.000 description 5
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- 238000005240 physical vapour deposition Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- FZHSXDYFFIMBIB-UHFFFAOYSA-L diiodolead;methanamine Chemical compound NC.I[Pb]I FZHSXDYFFIMBIB-UHFFFAOYSA-L 0.000 description 3
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- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- XIOYECJFQJFYLM-UHFFFAOYSA-N 2-(3,6-dimethoxycarbazol-9-yl)ethylphosphonic acid Chemical compound COC=1C=CC=2N(C3=CC=C(C=C3C=2C=1)OC)CCP(O)(O)=O XIOYECJFQJFYLM-UHFFFAOYSA-N 0.000 description 2
- KIMPAVBWSFLENS-UHFFFAOYSA-N 2-carbazol-9-ylethylphosphonic acid Chemical compound C1=CC=CC=2C3=CC=CC=C3N(C1=2)CCP(O)(O)=O KIMPAVBWSFLENS-UHFFFAOYSA-N 0.000 description 2
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
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- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OBKVURADRVPPKM-UHFFFAOYSA-L [Pb](I)I.N Chemical compound [Pb](I)I.N OBKVURADRVPPKM-UHFFFAOYSA-L 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000013545 self-assembled monolayer Substances 0.000 description 1
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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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—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
- 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
- H10K30/83—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes comprising arrangements for extracting the current from the cell, e.g. metal finger grid systems to reduce the serial resistance of transparent electrodes
Definitions
- the present invention relates to a method for manufacturing a perovskite thin film solar cell and a perovskite thin film solar cell.
- crystalline silicon solar cells that use a crystalline silicon substrate for the photoelectric conversion part and thin film solar cells that use an inorganic thin film such as an amorphous silicon thin film for the photoelectric conversion part are known.
- a thin film solar cell a perovskite thin film solar cell is known in which a perovskite thin film, which is an organic thin film (specifically, an organic/inorganic hybrid thin film), is used in the photoelectric conversion portion.
- Patent Documents 1 and 2 disclose perovskite thin film solar cells.
- a perovskite thin film solar cell consists of a first electrode layer (anode electrode or cathode electrode), which is a transparent conductive film, and a first carrier transport layer (hole transport film or cathode electrode), which are sequentially formed on a base material such as glass or resin.
- a transparent conductive oxide (TCO) film for example, an ITO (Indium Tin Oxide) thin film in which tin is added to indium oxide, can be used as the first electrode layer.
- TCO transparent conductive oxide
- ITO Indium Tin Oxide
- the crystallinity of the ITO thin film may be increased by high-temperature film formation or room temperature film formation + annealing.
- An object of the present invention is to provide a method for manufacturing a perovskite thin film solar cell and a perovskite thin film solar cell that further improves the performance of the perovskite thin film solar cell.
- the method for manufacturing a perovskite thin film solar cell according to the present invention includes forming a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer on a base material.
- a crystallized ITO thin film is formed by heating the thin film, and a part of the surface of the crystallized ITO thin film on the first carrier transport layer side is removed to form the first electrode layer.
- a perovskite thin film solar cell includes a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer on a base material in this order.
- the first electrode layer is an ITO thin film in which Sn is added to indium oxide, and includes a crystallized ITO thin film, and in the crystallized ITO thin film, the The difference between the ratio of Sn to In in the surface portion up to 3 nm from the surface on the first carrier transport layer side and the ratio of Sn to In in the remaining portion other than the surface portion is 2% or less.
- FIG. 1 is a cross-sectional view showing an example of a solar cell according to the present embodiment. It is a sectional view showing another example of a solar cell concerning this embodiment. It is a figure which shows the 1st electrode layer formation process in the manufacturing method of the solar cell based on this embodiment. It is a figure which shows the 1st electrode layer formation process in the manufacturing method of the solar cell based on this embodiment. It is a figure which shows the 1st carrier transport layer formation process, the perovskite thin film formation process, the 2nd carrier transport layer formation process, and the 2nd electrode layer formation process in the manufacturing method of the solar cell based on this embodiment. It is a measurement result of Sn/In ratio (ratio of Sn to In, depth profile) with respect to the depth from the surface of the 1st electrode layer (ITO) of an Example and a comparative example.
- Sn/In ratio ratio of Sn to In, depth profile
- FIG. 1 is a sectional view showing an example of a solar cell according to this embodiment
- FIG. 2 is a sectional view showing another example of a solar cell according to this embodiment.
- the solar cell 1 shown in FIGS. 1 and 2 is a perovskite thin film solar cell that uses a perovskite thin film as a photoelectric conversion thin film.
- the solar cell 1 includes a base material 10 , a first electrode layer 21 , a first carrier transport layer 31 , a perovskite thin film 40 , a second carrier transport layer 32 , and a second electrode layer 22 .
- the solar cell 1 shown in FIG. 1 and the solar cell 1 shown in FIG. 2 have different polarities.
- the first carrier transport layer 31 and the second carrier transport layer 32 are a hole transfer layer (HTL) and an electron transport layer (ETL), respectively.
- the first electrode layer 21 and the second electrode layer 22 are an anode and a cathode, respectively.
- the first carrier transport layer 31 and the second carrier transport layer 32 are an electron transport layer (ETL) and a hole transport layer (HTL), respectively
- the first electrode layer 21 and the The two electrode layers 22 are a cathode and an anode, respectively.
- the light-receiving surface may be on the base material 10 side, that is, the first electrode layer 21 side, or the light-receiving surface may be on the opposite side to the base material 10, that is, the second electrode layer 22 side. It may be a surface.
- the base material 10 side and both sides opposite to the base material 10, that is, both sides of the first electrode layer 21 side and the second electrode layer 22 side may function as light receiving surfaces.
- the base material 10 may be a transparent substrate that is insulating and light-transmissive, or may be a transparent film that is flexible.
- the transparent substrate include a substrate made of a material such as glass or resin.
- the transparent film include resin films made of materials such as polyimide, polyethylene naphthalate, and polyethylene terephthalate.
- the first electrode layer 21 is formed on the base material 10 and functions as an anode (FIG. 1) or a cathode (FIG. 2).
- the first electrode layer 21 is made of a transparent conductive film (Transparent Conductive Oxides: TCO) that is electrically conductive and optically transparent.
- TCO Transparent Conductive Oxides
- transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof are used.
- indium-based composite oxides containing indium oxide as a main component are preferred. Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency.
- dopants to the indium oxide to ensure reliability or higher conductivity.
- Examples of the dopant include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, and S.
- ITO Indium Tin Oxide
- tin (Sn) is added to indium oxide, is particularly preferred.
- the first electrode layer 21 is composed of an ITO thin film in which tin is added to indium oxide. Furthermore, as will be described later, the first electrode layer 21 includes a crystallized ITO thin film. In the crystallized ITO thin film of the first electrode layer 21, the ratio of Sn to In in the surface part up to 3 nm, preferably up to 2 nm from the surface on the first carrier transport layer 31 side, and the ratio of Sn to In in the remaining part other than the surface part. The difference from the ratio is 2% or less, preferably 1% or less. That is, the ratio of Sn to In in the surface portion of the crystallized ITO thin film of the first electrode layer 21 is approximately equal to the ratio of Sn to In in the remaining portion other than the surface portion.
- the first electrode layer 21 may include a grid-shaped or slit-shaped metal electrode layer.
- the first electrode layer 21 may include, for example, a planar metal electrode layer on the base material 10 side. Examples of the material for the metal electrode layer include Ag, Au, and Cu.
- the first carrier transport layer 31 is formed on the first electrode layer 21 and functions as a hole transport layer (HTL) (FIG. 1) or an electron transport layer (ETL) (FIG. 2).
- the first carrier transport layer 31 is made of a semiconductor material having optical transparency.
- the first carrier transport layer 31 transports holes (first carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the first electrode layer 21.
- the main materials of the first carrier transport layer 31 as a hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu 2 O), and PTAA (Poly(bis(4-phenyl)(2,4, 6-trimethylphenyl)amine) or Spiro-MeOTAD.
- the first carrier transport layer 31 is an electron transport layer (ETL) that transports electrons (first carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the first electrode layer 21.
- the main material of the first carrier transport layer 31 as an electron transport layer (ETL) includes titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), fullerene, and the like.
- fullerenes include C60, C70, their hydrides, oxides, metal complexes, derivatives with added alkyl groups, etc., such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester). It will be done.
- PCBM [6,6]-Phenyl-C61-Butyric Acid Methyl Ester
- the first carrier transport layer 31 is made of, for example, 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid), MeO-2PACz ([2-(3,6-Dimethoxy-9H-carbazol-9 -yl)ethyl]phosphonic Acid), Me-4PACz ([4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid), etc. Self-Assembled Monolayers). Further, the first carrier transport layer 31 may have a multilayer structure.
- the perovskite thin film 40 is formed on the first carrier transport layer 31 and functions as a photoelectric conversion layer.
- the main material of the perovskite thin film 40 includes a compound represented by the following formula containing an organic atom A, a metal atom B, and a halogen atom X.
- A include organic atoms containing at least one of monovalent organic ammonium ions and amidinium ions.
- Examples of B include metal atoms containing divalent metal ions.
- Examples of X include halogen atoms containing at least one of iodide ion I, bromide ion Br, chloride ion Cl, and fluoride ion F.
- methylammonium MA (CH 3 NH 3 ) is preferable as the organic atom A
- lead Pb is preferable as the metal atom B
- iodide I, bromide as the halogen atom
- At least one of the ion Br and the chloride ion Cl is preferred.
- the main material of the perovskite thin film 40 includes methylammonium lead halide MAPbX 3 (CH 3 NH 3 PbX 3 ), such as MAPbI 3 , MAPbBr 3 , MAPbCl 3 , and the like.
- the halogen atom X may include a plurality of types.
- the main material of the perovskite thin film 40 is methylammonium lead iodide MAPbI y X (3-y) (CH 3 NH 3 PbI y X (3-y) ), for example, MAPbI y Br (3-y) , MAPbI y Cl (3-y), etc. (y is any positive integer).
- a methylammonium lead halide MAPbX 3 (CH 3 NH 3 PbX 3 ) thin film is produced by sequentially forming a lead halide PbX 2 material and a methylammonium halide MAX material into a film, and then reacting the thin film of these materials at a reaction temperature. It is formed. Furthermore, the methylammonium lead iodide MAPbI y X (3-y) ( CH 3 NH 3 PbI y However, they are formed by reacting thin films of these materials at reaction temperatures.
- a methylammonium lead iodide MAPbI 3 (CH 3 NH 3 PbI 3 ) thin film is produced by sequentially forming a lead iodide PbI 2 material and a methylammonium iodide MAI material, and It is formed by reacting a thin film at a reaction temperature.
- the second carrier transport layer 32 is formed on the perovskite thin film 40 and functions as an electron transport layer (ETL) (FIG. 1) or a hole transport layer (HTL) (FIG. 2).
- the second carrier transport layer 32 is made of a semiconductor material having optical transparency.
- the second carrier transport layer 32 is an electron transport layer that transports electrons (second carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the second electrode layer 22.
- Main materials for the second carrier transport layer 32 as an electron transport layer (ETL) include titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), fullerene, and the like.
- fullerenes include, for example, C60, C70, their hydrides, oxides, metal complexes, derivatives with added alkyl groups, etc., such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester), etc.
- PCBM [6,6]-Phenyl-C61-Butyric Acid Methyl Ester
- the second carrier transport layer 32 is an electron transport layer (ETL)
- ETL electron transport layer
- a hole blocking layer may be provided.
- the material for the hole blocking layer include bathocuproine (BCP), SnO formed by atomic layer deposition (ALD), which causes relatively little damage to the adhered layer, and the like.
- the second carrier transport layer 32 is an electron transport layer (ETL)
- ETL electron transport layer
- an electron extraction layer may be provided.
- the material for the electron extraction layer include lithium (Li), lithium fluoride (LiF), and the like.
- the second carrier transport layer 32 is a hole transport layer (second carrier) that transports holes (second carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the second electrode layer 22.
- the main materials of the second carrier transport layer 32 as a hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu 2 O), and PTAA (Poly(bis(4-phenyl)(2,4, 6-trimethylphenyl)amine) or Spiro-MeOTAD.
- the second electrode layer 22 is formed on the second carrier transport layer 32 and functions as a cathode (FIG. 1) or an anode (FIG. 2).
- the second electrode layer 22 may include, for example, a planar metal electrode layer on the base material 10 side.
- the second electrode layer 22 includes a transparent conductive oxide (TCO) that is electrically conductive and transparent. Furthermore, it may include a grid-like or slit-like metal electrode layer.
- transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof are used.
- indium-based composite oxides containing indium oxide as a main component are preferred.
- Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency.
- dopants include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, and S.
- ITO Indium Tin Oxide
- tin (Sn) is added to indium oxide
- the material for the metal electrode layer include Ag, Au, and Cu.
- the solar cell 1 generates a current according to light incident from the base material 10 side, that is, the first electrode layer 21 side, or the side opposite to the base material 10, that is, the second electrode layer 22 side. , is output to the first electrode layer 21 and the second electrode layer 22.
- FIGS. 3A to 3C are diagrams showing a first electrode layer forming step in the solar cell manufacturing method according to the present embodiment
- FIG. 3C is a diagram showing the first carrier transport layer in the solar cell manufacturing method according to the present embodiment. It is a figure which shows a formation process, a perovskite thin film formation process, a 2nd carrier transport layer formation process, and a 2nd electrode layer formation process.
- an ITO thin film in which tin is added to indium oxide is formed on the base material 10, and the formed ITO thin film is heated to form a crystallized ITO thin film 21Z.
- first electrode layer forming step The method for forming the transparent conductive film is not particularly limited, but a CVD method (chemical vapor deposition method) using a vacuum chamber, a PVD method (physical vapor deposition method), a sputtering method, or the like can be used.
- the crystallinity of the ITO thin film is increased by high temperature film formation or room temperature film formation + annealing.
- Sn which is a doping component, may segregate on the surface of the crystallized ITO thin film 21Z. Therefore, the surface becomes highly resistive, the interfacial resistance between the first electrode layer and the first carrier transport layer increases, and the effect of reducing electrical resistance (that is, improving the performance of the solar cell) due to crystallization is reduced.
- the first electrode layer 21 is formed by removing part 21S of the surface of the crystallized ITO thin film 21Z on the first carrier transport layer side (first electrode layer forming step). . Specifically, a portion 21S of the surface of the crystallized ITO thin film 21Z is etched by acid treatment. The portion 21S to be removed is up to 3 nm, preferably up to 2 nm from the surface of the crystallized ITO thin film 21Z. Examples of solutions for acid treatment include hydrochloric acid HCl, ferric chloride FeCl3, and the like.
- the first carrier transport layer 31 is formed on the first electrode layer 21 (first carrier transport layer forming step).
- the method for forming the first carrier transport layer 31 is not particularly limited, and includes, for example, a dry process such as a CVD method, a PVD method, or a sputtering method, or a wet process such as a coating method or a printing method. Among these, the sputtering method is preferred from the viewpoint of forming a dense film.
- a perovskite thin film 40 is formed on the first carrier transport layer 31 (perovskite thin film forming step). For example, after forming a lead iodide PbI 2 material film, a methylammonium iodide MAI material film is formed, and by reacting the lead iodide PbI 2 material film and the methylammonium iodide MAI material film, methyl A perovskite thin film made of ammonium lead iodide MAPbI 3 is formed.
- Methods for forming the perovskite thin film 40 include, but are not particularly limited to, dry processes such as vapor deposition, wet processes such as printing, coating, and solution methods.
- the second carrier transport layer 32 is formed on the perovskite thin film 40 (second carrier transport layer forming step).
- the method for forming the second carrier transport layer 32 is not particularly limited, but includes, for example, a CVD method, a PVD method, a sputtering method, a dry process such as a vapor deposition method, or a wet process such as a coating method or a printing method.
- the second electrode layer 22 is formed on the second carrier transport layer 32.
- the method for forming the second electrode layer 22 is not particularly limited, but includes, for example, a CVD method using a vacuum chamber, a PVD method, a sputtering method, a dry process such as a vapor deposition method, or a wet process such as a printing method or a coating method. Can be mentioned. Among these, sputtering method is preferred.
- the perovskite thin film solar cell 1 of this embodiment shown in FIG. 1 or 2 is obtained.
- the formed ITO thin film is heated to form the crystallized ITO thin film 21Z.
- the crystallinity of the ITO thin film can be improved, the electrical resistance of the ITO thin film can be reduced, and the transmittance of the ITO thin film can be improved.
- the performance of the solar cell 1 can be improved.
- a part 21S of the surface of the crystallized ITO thin film 21Z where Sn, which is a doping component, segregates during crystallization of the ITO thin film is removed.
- the present invention is not limited to the embodiments described above, and various changes and modifications can be made.
- the embodiments described above can also be applied to the production of a perovskite thin film solar cell in a so-called tandem solar cell that combines a crystalline silicon solar cell or an amorphous silicon thin film solar cell and a perovskite thin film solar cell. .
- Example 1 In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer after acid treatment shown in FIG. 3B was produced as Example 1.
- the method for forming the first electrode layer of Example 1 is as follows. - First, as shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees). 1 hour), a crystallized ITO thin film 21Z was formed (film thickness: 122 nm). - Next, as shown in FIG. 3B, a part 21S (2 nm from the surface) of the surface of the crystallized ITO thin film 21Z was removed by acid treatment (HCl) to form a first electrode layer.
- HCl acid treatment
- Comparative example 1 In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer before acid treatment shown in FIG. 3A was produced as Comparative Example 1.
- the method for forming the first electrode layer of Comparative Example 1 is as follows. ⁇ As shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees for 1 hour). ), a crystallized ITO thin film 21Z, that is, a crystallized ITO thin film 21Z whose surface part 21S was not removed, was formed as the first electrode layer (film thickness: 120 nm).
- the Sn/In ratio (ratio of Sn to In) with respect to the depth from the surface of the first electrode layer (ITO) (the surface on the first carrier transport layer side) was measured as a depth profile.
- the depth profile from the surface of the first electrode layer (ITO) was measured by combining etching of the surface of ITO using a sputtering method and XPS measurement. Any known sputtering device may be used as the sputtering device, and the sputtering rate is approximately 1.25 nm/min. And so.
- XPS measurement VersaProbeII manufactured by ULVAC-PHI Inc./model PHI5000 was used. The measurement results of this depth profile are shown in FIG.
- the horizontal axis is the sputtering time, that is, the depth from the surface of the first electrode layer (ITO), and the vertical axis is the Sn/In ratio (ratio of Sn to In).
- the solid line is the depth profile of the first electrode layer (ITO) with acid treatment in Example 1
- the broken line is the depth profile of the first electrode layer (ITO) without acid treatment in Comparative Example 1.
- Perovskite thin film solar cell 10
- Base material 21
- Second electrode layer (cathode or anode) 31
- First carrier transport layer (hole transport layer or electron transport layer) 32
- Second carrier transport layer (electron transport layer or hole transport layer) 40 Perovskite thin film
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Abstract
Provided is a method for manufacturing a perovskite thin film-based solar cell with which further improvements in the performance of the perovskite thin film-based solar cell are achieved. According to the method for manufacturing a perovskite thin film-based solar cell, a first electrode layer 21, a first carrier transport layer 31, a perovskite thin film 40, a second carrier transport layer 32, and a second electrode layer 22 are formed in this order on a substrate 10. A first electrode layer forming step involves: forming an ITO thin film, in which Sn is added to indium oxide, on the substrate 10, and heating the ITO thin film to crystallize the ITO thin film; and removing a portion of the surface of the crystalized ITO thin film on the first carrier transport layer side to form the first electrode layer 21.
Description
本発明は、ペロブスカイト薄膜系太陽電池の製造方法およびペロブスカイト薄膜系太陽電池に関する。
The present invention relates to a method for manufacturing a perovskite thin film solar cell and a perovskite thin film solar cell.
太陽電池として、光電変換部に結晶シリコン基板を用いた結晶シリコン系太陽電池、光電変換部にアモルファスシリコン薄膜等の無機系薄膜を用いた薄膜系太陽電池が知られている。また、薄膜系太陽電池として、光電変換部に有機系薄膜（詳細には、有機／無機ハイブリット系薄膜）であるペロブスカイト薄膜を用いたペロブスカイト薄膜系太陽電池が知られている。特許文献１および２には、ペロブスカイト薄膜系太陽電池が開示されている。
As solar cells, crystalline silicon solar cells that use a crystalline silicon substrate for the photoelectric conversion part and thin film solar cells that use an inorganic thin film such as an amorphous silicon thin film for the photoelectric conversion part are known. Further, as a thin film solar cell, a perovskite thin film solar cell is known in which a perovskite thin film, which is an organic thin film (specifically, an organic/inorganic hybrid thin film), is used in the photoelectric conversion portion. Patent Documents 1 and 2 disclose perovskite thin film solar cells.
ペロブスカイト薄膜系太陽電池は、ガラスまたは樹脂等の基材上に順に形成された、透明導電膜である第１電極層（陽極電極または陰極電極）と、第１キャリア輸送層（正孔輸送膜または電子輸送膜）と、ペロブスカイト薄膜と、第２キャリア輸送層（電子輸送膜または正孔輸送膜）と、第２電極層（陰極電極または陽極電極）とを備える。
A perovskite thin film solar cell consists of a first electrode layer (anode electrode or cathode electrode), which is a transparent conductive film, and a first carrier transport layer (hole transport film or cathode electrode), which are sequentially formed on a base material such as glass or resin. An electron transport film), a perovskite thin film, a second carrier transport layer (electron transport film or hole transport film), and a second electrode layer (cathode electrode or anode electrode).
このようなペロブスカイト薄膜系太陽電池において、第１電極層として、透明導電膜（Transparent Conductive Oxide：ＴＣＯ）、例えばインジウム酸化物にスズＳｎが添加されたＩＴＯ（Indium Tin Oxide）薄膜が用いられることがある。この場合、ＩＴＯ薄膜の電気抵抗の低減または透過率の向上（すなわち、太陽電池の性能向上）のために、高温製膜または室温製膜＋アニールにより、ＩＴＯ薄膜の結晶性を高めることがある。
In such a perovskite thin film solar cell, a transparent conductive oxide (TCO) film, for example, an ITO (Indium Tin Oxide) thin film in which tin is added to indium oxide, can be used as the first electrode layer. be. In this case, in order to reduce the electrical resistance or improve the transmittance of the ITO thin film (that is, to improve the performance of the solar cell), the crystallinity of the ITO thin film may be increased by high-temperature film formation or room temperature film formation + annealing.
しかし、この結晶化の際、結晶化ＩＴＯ薄膜の表面に、ドープ成分であるＳｎが偏析してしまうことがある。そのため、表面が高抵抗化し、第１電極層と第１キャリア輸送層との界面抵抗が増加し、結晶化による電気抵抗の低減（すなわち、太陽電池の性能向上）の効果を低下させてしまう。
However, during this crystallization, Sn, which is a doping component, may segregate on the surface of the crystallized ITO thin film. Therefore, the surface becomes highly resistive, the interfacial resistance between the first electrode layer and the first carrier transport layer increases, and the effect of reducing electrical resistance (that is, improving the performance of the solar cell) due to crystallization is reduced.
本発明は、ペロブスカイト薄膜系太陽電池の更なる性能向上を図るペロブスカイト薄膜系太陽電池の製造方法およびペロブスカイト薄膜系太陽電池を提供することを目的とする。
An object of the present invention is to provide a method for manufacturing a perovskite thin film solar cell and a perovskite thin film solar cell that further improves the performance of the perovskite thin film solar cell.
本発明に係るペロブスカイト薄膜系太陽電池の製造方法は、基材上に、第１電極層と、第１キャリア輸送層と、ペロブスカイト薄膜と、第２キャリア輸送層と、第２電極層とをこの順番に形成するペロブスカイト薄膜系太陽電池の製造方法であって、前記第１電極層の形成工程では、前記基材上に、インジウム酸化物にＳｎが添加されたＩＴＯ薄膜を製膜し、前記ＩＴＯ薄膜を加熱することによって、結晶化ＩＴＯ薄膜を形成し、前記結晶化ＩＴＯ薄膜の前記第１キャリア輸送層側の表面の一部を除去することによって、前記第１電極層を形成する。
The method for manufacturing a perovskite thin film solar cell according to the present invention includes forming a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer on a base material. A method of manufacturing a perovskite thin film solar cell in which the first electrode layer is formed in the step of forming an ITO thin film in which Sn is added to indium oxide on the base material; A crystallized ITO thin film is formed by heating the thin film, and a part of the surface of the crystallized ITO thin film on the first carrier transport layer side is removed to form the first electrode layer.
本発明に係るペロブスカイト薄膜系太陽電池は、基材上に、第１電極層と、第１キャリア輸送層と、ペロブスカイト薄膜と、第２キャリア輸送層と、第２電極層とをこの順番に備えるペロブスカイト薄膜系太陽電池であって、前記第１電極層は、インジウム酸化物にＳｎが添加されたＩＴＯ薄膜であって、結晶化された結晶化ＩＴＯ薄膜を含み、前記結晶化ＩＴＯ薄膜において、前記第１キャリア輸送層側の表面から３ｎｍまでの表面部分におけるＩｎに対するＳｎの割合と、前記表面部分以外の残り部分におけるＩｎに対するＳｎの割合との差が、２％以下である。
A perovskite thin film solar cell according to the present invention includes a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer on a base material in this order. In the perovskite thin film solar cell, the first electrode layer is an ITO thin film in which Sn is added to indium oxide, and includes a crystallized ITO thin film, and in the crystallized ITO thin film, the The difference between the ratio of Sn to In in the surface portion up to 3 nm from the surface on the first carrier transport layer side and the ratio of Sn to In in the remaining portion other than the surface portion is 2% or less.
本発明によれば、ペロブスカイト薄膜系太陽電池の更なる性能向上を図ることができる。
According to the present invention, it is possible to further improve the performance of perovskite thin film solar cells.
以下、添付の図面を参照して本発明の実施形態の一例について説明する。なお、各図面において同一または相当の部分に対しては同一の符号を附すこととする。また、便宜上、ハッチングや部材符号等を省略する場合もあるが、かかる場合、他の図面を参照するものとする。
Hereinafter, an example of an embodiment of the present invention will be described with reference to the accompanying drawings. In addition, the same reference numerals are given to the same or corresponding parts in each drawing. Further, for convenience, hatching, member symbols, etc. may be omitted, but in such cases, other drawings shall be referred to.
（太陽電池）
図１は、本実施形態に係る太陽電池の一例を示す断面図であり、図２は、本実施形態に係る太陽電池の他の一例を示す断面図である。図１および図２に示す太陽電池１は、光電変換薄膜としてペロブスカイト薄膜を用いたペロブスカイト薄膜系の太陽電池である。太陽電池１は、基材１０と、第１電極層２１と、第１キャリア輸送層３１と、ペロブスカイト薄膜４０と、第２キャリア輸送層３２と、第２電極層２２とを備える。 (solar cell)
FIG. 1 is a sectional view showing an example of a solar cell according to this embodiment, and FIG. 2 is a sectional view showing another example of a solar cell according to this embodiment. Thesolar cell 1 shown in FIGS. 1 and 2 is a perovskite thin film solar cell that uses a perovskite thin film as a photoelectric conversion thin film. The solar cell 1 includes a base material 10 , a first electrode layer 21 , a first carrier transport layer 31 , a perovskite thin film 40 , a second carrier transport layer 32 , and a second electrode layer 22 .
図１は、本実施形態に係る太陽電池の一例を示す断面図であり、図２は、本実施形態に係る太陽電池の他の一例を示す断面図である。図１および図２に示す太陽電池１は、光電変換薄膜としてペロブスカイト薄膜を用いたペロブスカイト薄膜系の太陽電池である。太陽電池１は、基材１０と、第１電極層２１と、第１キャリア輸送層３１と、ペロブスカイト薄膜４０と、第２キャリア輸送層３２と、第２電極層２２とを備える。 (solar cell)
FIG. 1 is a sectional view showing an example of a solar cell according to this embodiment, and FIG. 2 is a sectional view showing another example of a solar cell according to this embodiment. The
なお、図１に示す太陽電池１と図２に示す太陽電池１とでは、極性が異なる。具体的には、図１に示す太陽電池１では、第１キャリア輸送層３１および第２キャリア輸送層３２がそれぞれ正孔輸送層（Hole Transfer Layer：ＨＴＬ）および電子輸送層（Electron Transport Layer：ＥＴＬ）であり、第１電極層２１および第２電極層２２がそれぞれ陽極および陰極である。一方、図２に示す太陽電池１では、第１キャリア輸送層３１および第２キャリア輸送層３２がそれぞれ電子輸送層（ＥＴＬ）および正孔輸送層（ＨＴＬ）であり、第１電極層２１および第２電極層２２がそれぞれ陰極および陽極である。
Note that the solar cell 1 shown in FIG. 1 and the solar cell 1 shown in FIG. 2 have different polarities. Specifically, in the solar cell 1 shown in FIG. 1, the first carrier transport layer 31 and the second carrier transport layer 32 are a hole transfer layer (HTL) and an electron transport layer (ETL), respectively. ), and the first electrode layer 21 and the second electrode layer 22 are an anode and a cathode, respectively. On the other hand, in the solar cell 1 shown in FIG. 2, the first carrier transport layer 31 and the second carrier transport layer 32 are an electron transport layer (ETL) and a hole transport layer (HTL), respectively, and the first electrode layer 21 and the The two electrode layers 22 are a cathode and an anode, respectively.
また、図１および図２に示す太陽電池１は、基材１０側、すなわち第１電極層２１側が受光面であってもよいし、基材１０と反対側、すなわち第２電極層２２側が受光面であってもよい。或いは、基材１０側および基材１０と反対側の両側、すなわち第１電極層２１側および第２電極層２２側の両側が受光面として機能してもよい。
In the solar cell 1 shown in FIGS. 1 and 2, the light-receiving surface may be on the base material 10 side, that is, the first electrode layer 21 side, or the light-receiving surface may be on the opposite side to the base material 10, that is, the second electrode layer 22 side. It may be a surface. Alternatively, the base material 10 side and both sides opposite to the base material 10, that is, both sides of the first electrode layer 21 side and the second electrode layer 22 side may function as light receiving surfaces.
基材１０は、絶縁性かつ光透過性を有する透明基板であってもよいし、更にフレキシブル性を有する透明フィルムであってもよい。透明基板としては、ガラスまたは樹脂等の材料で構成された基板が挙げられる。透明フィルムとしては、ポリイミド、ポリエチレンナフタレート、ポリエチレンテレフタレート等の材料で構成された樹脂フィルムが挙げられる。
The base material 10 may be a transparent substrate that is insulating and light-transmissive, or may be a transparent film that is flexible. Examples of the transparent substrate include a substrate made of a material such as glass or resin. Examples of the transparent film include resin films made of materials such as polyimide, polyethylene naphthalate, and polyethylene terephthalate.
第１電極層２１は、基材１０上に形成されており、陽極（図１）または陰極（図２）として機能する。第１電極層２１は、導電性かつ光透過性を有する透明導電膜（Transparent Conductive Oxides：ＴＣＯ）からなる。第１電極層２１の材料としては、透明導電性金属酸化物、例えば、酸化インジウム、酸化スズ、酸化亜鉛、酸化チタンおよびそれらの複合酸化物等が用いられる。これらの中でも、酸化インジウムを主成分とするインジウム系複合酸化物が好ましい。高い導電率と透明性の観点からは、インジウム酸化物が特に好ましい。更に、信頼性またはより高い導電率を確保するため、インジウム酸化物にドーパントを添加すると好ましい。ドーパントとしては、例えば、Ｓｎ、Ｗ、Ｚｎ、Ｔｉ、Ｃｅ、Ｚｒ、Ｍｏ、Ａｌ、Ｇａ、Ｇｅ、Ａｓ、Ｓｉ、またはＳ等が挙げられる。これらの中でも、インジウム酸化物にスズ（Ｓｎ）が添加されたＩＴＯ（Indium Tin Oxide）が特に好ましい。
The first electrode layer 21 is formed on the base material 10 and functions as an anode (FIG. 1) or a cathode (FIG. 2). The first electrode layer 21 is made of a transparent conductive film (Transparent Conductive Oxides: TCO) that is electrically conductive and optically transparent. As the material for the first electrode layer 21, transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof are used. Among these, indium-based composite oxides containing indium oxide as a main component are preferred. Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency. Furthermore, it is preferable to add dopants to the indium oxide to ensure reliability or higher conductivity. Examples of the dopant include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, and S. Among these, ITO (Indium Tin Oxide), in which tin (Sn) is added to indium oxide, is particularly preferred.
すなわち、第１電極層２１は、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜で構成される。更に、後述するように、第１電極層２１は、結晶化された結晶化ＩＴＯ薄膜を含む。
第１電極層２１の結晶化ＩＴＯ薄膜において、第１キャリア輸送層３１側の表面から３ｎｍまで、好ましくは２ｎｍまでの表面部分におけるＩｎに対するＳｎの割合と、表面部分以外の残り部分におけるＩｎに対するＳｎの割合との差は、２％以下、好ましくは１％以下である。すなわち、第１電極層２１の結晶化ＩＴＯ薄膜の表面部分におけるＩｎに対するＳｎの割合は、表面部分以外の残り部分におけるＩｎに対するＳｎの割合と略等しい。 That is, thefirst electrode layer 21 is composed of an ITO thin film in which tin is added to indium oxide. Furthermore, as will be described later, the first electrode layer 21 includes a crystallized ITO thin film.
In the crystallized ITO thin film of thefirst electrode layer 21, the ratio of Sn to In in the surface part up to 3 nm, preferably up to 2 nm from the surface on the first carrier transport layer 31 side, and the ratio of Sn to In in the remaining part other than the surface part. The difference from the ratio is 2% or less, preferably 1% or less. That is, the ratio of Sn to In in the surface portion of the crystallized ITO thin film of the first electrode layer 21 is approximately equal to the ratio of Sn to In in the remaining portion other than the surface portion.
第１電極層２１の結晶化ＩＴＯ薄膜において、第１キャリア輸送層３１側の表面から３ｎｍまで、好ましくは２ｎｍまでの表面部分におけるＩｎに対するＳｎの割合と、表面部分以外の残り部分におけるＩｎに対するＳｎの割合との差は、２％以下、好ましくは１％以下である。すなわち、第１電極層２１の結晶化ＩＴＯ薄膜の表面部分におけるＩｎに対するＳｎの割合は、表面部分以外の残り部分におけるＩｎに対するＳｎの割合と略等しい。 That is, the
In the crystallized ITO thin film of the
なお、基材１０側、すなわち第１電極層２１側が受光面である場合、第１電極層２１は、グリッド状またはスリット状の金属電極層を含んでいてもよい。或いは、基材１０と反対側、すなわち第２電極層２２側が受光面である場合、第１電極層２１は、例えば基材１０側に、面状の金属電極層を含んでいてもよい。金属電極層の材料としては、Ａｇ、Ａｕ、Ｃｕ等が挙げられる。
Note that when the base material 10 side, that is, the first electrode layer 21 side is the light-receiving surface, the first electrode layer 21 may include a grid-shaped or slit-shaped metal electrode layer. Alternatively, when the light-receiving surface is on the side opposite to the base material 10, that is, on the second electrode layer 22 side, the first electrode layer 21 may include, for example, a planar metal electrode layer on the base material 10 side. Examples of the material for the metal electrode layer include Ag, Au, and Cu.
第１キャリア輸送層３１は、第１電極層２１上に形成されており、正孔輸送層（ＨＴＬ）（図１）または電子輸送層（ＥＴＬ）（図２）として機能する。第１キャリア輸送層３１は、光透過性を有する半導体材料からなる。
The first carrier transport layer 31 is formed on the first electrode layer 21 and functions as a hole transport layer (HTL) (FIG. 1) or an electron transport layer (ETL) (FIG. 2). The first carrier transport layer 31 is made of a semiconductor material having optical transparency.
具体的には、図１では、第１キャリア輸送層３１は、ペロブスカイト薄膜４０で光電変換されて生成されたキャリアのうちの正孔（第１キャリア）を第１電極層２１に輸送する正孔輸送層（ＨＴＬ）として機能する。正孔輸送層（ＨＴＬ）としての第１キャリア輸送層３１の主材料としては、酸化ニッケル（ＮｉＯ）、酸化銅（Ｃｕ２Ｏ）、ＰＴＡＡ（Poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)）、または、Ｓｐｉｒｏ－ＭｅＯＴＡＤ等が挙げられる。
Specifically, in FIG. 1, the first carrier transport layer 31 transports holes (first carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the first electrode layer 21. Functions as a transport layer (HTL). The main materials of the first carrier transport layer 31 as a hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu 2 O), and PTAA (Poly(bis(4-phenyl)(2,4, 6-trimethylphenyl)amine) or Spiro-MeOTAD.
一方、図２では、第１キャリア輸送層３１は、ペロブスカイト薄膜４０で光電変換されて生成されたキャリアのうちの電子（第１キャリア）を第１電極層２１に輸送する電子輸送層（ＥＴＬ）として機能する。電子輸送層（ＥＴＬ）としての第１キャリア輸送層３１の主材料としては、酸化チタン（ＴｉＯ２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ２）、または、フラーレン等が挙げられる。
On the other hand, in FIG. 2, the first carrier transport layer 31 is an electron transport layer (ETL) that transports electrons (first carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the first electrode layer 21. functions as The main material of the first carrier transport layer 31 as an electron transport layer (ETL) includes titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), fullerene, and the like.
フラーレンとしては、例えばＣ６０、Ｃ７０、これらの水素化物、酸化物、金属錯体、アルキル基等を付加した誘導体、例えば、ＰＣＢＭ（[6,6]-Phenyl-C61-Butyric Acid Methyl Ester）などが挙げられる。第２キャリア輸送層３２をリチウムＬｉを内包させたフラーレンを含む材料から形成することにより、電子の輸送効率を向上することができる。
Examples of fullerenes include C60, C70, their hydrides, oxides, metal complexes, derivatives with added alkyl groups, etc., such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester). It will be done. By forming the second carrier transport layer 32 from a material containing fullerene containing lithium Li, electron transport efficiency can be improved.
また、第１キャリア輸送層３１は、例えば２ＰＡＣｚ([2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid)、ＭｅＯ－２ＰＡＣｚ（[2-(3,6-Dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic Acid）、Ｍｅ－４ＰＡＣｚ（[4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid）等により形成される自己組織化単分子膜（ＳＡＭ：Self-Assembled Monolayers）であってもよい。また、第１キャリア輸送層３１は、多層構造を有してもよい。
Further, the first carrier transport layer 31 is made of, for example, 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid), MeO-2PACz ([2-(3,6-Dimethoxy-9H-carbazol-9 -yl)ethyl]phosphonic Acid), Me-4PACz ([4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid), etc. Self-Assembled Monolayers). Further, the first carrier transport layer 31 may have a multilayer structure.
ペロブスカイト薄膜４０は、第１キャリア輸送層３１上に形成されており、光電変換層として機能する。ペロブスカイト薄膜４０の主材料としては、有機原子Ａ、金属原子Ｂ、およびハロゲン原子Ｘを含む下記式で表される化合物が挙げられる。
ＡＢＸ３
Ａとしては、１価の有機アンモニウムイオンおよびアミジニウム系イオンのうちの少なくとも１種を含む有機原子が挙げられる。Ｂとしては、２価の金属イオンを含む金属原子が挙げられる。Ｘとしては、ヨウ化物イオンＩ、臭化物イオンＢｒ、塩化物イオンＣｌ、およびフッ化物イオンＦのうちの少なくとも１種を含むハロゲン原子が挙げられる。 The perovskitethin film 40 is formed on the first carrier transport layer 31 and functions as a photoelectric conversion layer. The main material of the perovskite thin film 40 includes a compound represented by the following formula containing an organic atom A, a metal atom B, and a halogen atom X.
ABX 3
Examples of A include organic atoms containing at least one of monovalent organic ammonium ions and amidinium ions. Examples of B include metal atoms containing divalent metal ions. Examples of X include halogen atoms containing at least one of iodide ion I, bromide ion Br, chloride ion Cl, and fluoride ion F.
ＡＢＸ３
Ａとしては、１価の有機アンモニウムイオンおよびアミジニウム系イオンのうちの少なくとも１種を含む有機原子が挙げられる。Ｂとしては、２価の金属イオンを含む金属原子が挙げられる。Ｘとしては、ヨウ化物イオンＩ、臭化物イオンＢｒ、塩化物イオンＣｌ、およびフッ化物イオンＦのうちの少なくとも１種を含むハロゲン原子が挙げられる。 The perovskite
ABX 3
Examples of A include organic atoms containing at least one of monovalent organic ammonium ions and amidinium ions. Examples of B include metal atoms containing divalent metal ions. Examples of X include halogen atoms containing at least one of iodide ion I, bromide ion Br, chloride ion Cl, and fluoride ion F.
これらの中でも、蒸着法（ドライプロセス）の場合、有機原子ＡとしてはメチルアンモニウムＭＡ（ＣＨ３ＮＨ３）が好ましく、金属原子Ｂとしては鉛Ｐｂが好ましく、ハロゲン原子Ｘとしてはヨウ化物Ｉ、臭化物イオンＢｒおよび塩化物イオンＣｌのうちの少なくとも１つが好ましい。すなわち、蒸着法等のドライプロセスの場合、ペロブスカイト薄膜４０の主材料としては、メチルアンモニウムハロゲン化鉛ＭＡＰｂＸ３（ＣＨ３ＮＨ３ＰｂＸ３）、例えばＭＡＰｂＩ３、ＭＡＰｂＢｒ３、ＭＡＰｂＣｌ３等が挙げられる。なお、ハロゲン原子Ｘとしては複数種類を含んでもよい。例えばヨウ化物Ｉと他のハロゲン原子Ｘとを含む場合、ペロブスカイト薄膜４０の主材料としては、メチルアンモニウムヨウ化鉛ＭＡＰｂＩｙＸ（３－ｙ）（ＣＨ３ＮＨ３ＰｂＩｙＸ（３－ｙ））、例えばＭＡＰｂＩｙＢｒ（３－ｙ）、ＭＡＰｂＩｙＣｌ（３－ｙ）等が挙げられる（ｙは任意の正の整数）。
Among these, in the case of vapor deposition method (dry process), methylammonium MA (CH 3 NH 3 ) is preferable as the organic atom A, lead Pb is preferable as the metal atom B, and iodide I, bromide as the halogen atom At least one of the ion Br and the chloride ion Cl is preferred. That is, in the case of a dry process such as a vapor deposition method, the main material of the perovskite thin film 40 includes methylammonium lead halide MAPbX 3 (CH 3 NH 3 PbX 3 ), such as MAPbI 3 , MAPbBr 3 , MAPbCl 3 , and the like. Note that the halogen atom X may include a plurality of types. For example, when containing iodide I and other halogen atoms X, the main material of the perovskite thin film 40 is methylammonium lead iodide MAPbI y X (3-y) (CH 3 NH 3 PbI y X (3-y) ), for example, MAPbI y Br (3-y) , MAPbI y Cl (3-y), etc. (y is any positive integer).
メチルアンモニウムハロゲン化鉛ＭＡＰｂＸ３（ＣＨ３ＮＨ３ＰｂＸ３）薄膜は、ハロゲン化鉛ＰｂＸ２材料およびハロゲン化メチルアンモニウムＭＡＸ材料を順に製膜し、これらの材料の薄膜を反応温度で反応させることにより形成される。また、メチルアンモニウムヨウ化鉛ＭＡＰｂＩｙＸ（３－ｙ）（ＣＨ３ＮＨ３ＰｂＩｙＸ（３－ｙ））薄膜は、例えばハロゲン化鉛ＰｂＸ２材料およびヨウ化メチルアンモニウムＭＡＩ材料を順に製膜し、これらの材料の薄膜を反応温度で反応させることにより形成される。更に具体的な一例によれば、メチルアンモニウムヨウ化鉛ＭＡＰｂＩ３（ＣＨ３ＮＨ３ＰｂＩ３）薄膜は、ヨウ化鉛ＰｂＩ２材料およびヨウ化メチルアンモニウムＭＡＩ材料を順に製膜し、これらの材料の薄膜を反応温度で反応させることにより形成される。
A methylammonium lead halide MAPbX 3 (CH 3 NH 3 PbX 3 ) thin film is produced by sequentially forming a lead halide PbX 2 material and a methylammonium halide MAX material into a film, and then reacting the thin film of these materials at a reaction temperature. It is formed. Furthermore, the methylammonium lead iodide MAPbI y X (3-y) ( CH 3 NH 3 PbI y However, they are formed by reacting thin films of these materials at reaction temperatures. According to a more specific example, a methylammonium lead iodide MAPbI 3 (CH 3 NH 3 PbI 3 ) thin film is produced by sequentially forming a lead iodide PbI 2 material and a methylammonium iodide MAI material, and It is formed by reacting a thin film at a reaction temperature.
第２キャリア輸送層３２は、ペロブスカイト薄膜４０上に形成されており、電子輸送層（ＥＴＬ）（図１）または正孔輸送層（ＨＴＬ）（図２）として機能する。第２キャリア輸送層３２は、光透過性を有する半導体材料からなる。
The second carrier transport layer 32 is formed on the perovskite thin film 40 and functions as an electron transport layer (ETL) (FIG. 1) or a hole transport layer (HTL) (FIG. 2). The second carrier transport layer 32 is made of a semiconductor material having optical transparency.
具体的には、図１では、第２キャリア輸送層３２は、ペロブスカイト薄膜４０で光電変換されて生成されたキャリアのうちの電子（第２キャリア）を第２電極層２２に輸送する電子輸送層（ＥＴＬ）として機能する。電子輸送層（ＥＴＬ）としての第２キャリア輸送層３２の主材料としては、酸化チタン（ＴｉＯ２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ２）、または、フラーレン等が挙げられる。
Specifically, in FIG. 1, the second carrier transport layer 32 is an electron transport layer that transports electrons (second carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the second electrode layer 22. (ETL). Main materials for the second carrier transport layer 32 as an electron transport layer (ETL) include titanium oxide (TiO 2 ), zinc oxide (ZnO), tin oxide (SnO 2 ), fullerene, and the like.
上述したように、フラーレンとしては、例えばＣ６０、Ｃ７０、これらの水素化物、酸化物、金属錯体、アルキル基等を付加した誘導体、例えば、ＰＣＢＭ（[6,6]-Phenyl-C61-Butyric Acid Methyl Ester）などが挙げられる。第２キャリア輸送層３２をリチウムＬｉを内包させたフラーレンを含む材料から形成することにより、電子の輸送効率を向上することができる。
As mentioned above, fullerenes include, for example, C60, C70, their hydrides, oxides, metal complexes, derivatives with added alkyl groups, etc., such as PCBM ([6,6]-Phenyl-C61-Butyric Acid Methyl Ester), etc. By forming the second carrier transport layer 32 from a material containing fullerene containing lithium Li, electron transport efficiency can be improved.
なお、第２キャリア輸送層３２が電子輸送層（ＥＴＬ）の場合、第２キャリア輸送層３２と第２電極層２２との間、または、第２キャリア輸送層３２とペロブスカイト薄膜４０との間に、正孔阻止層が設けられていてもよい。正孔阻止層の材料としては、例えば、バソクプロイン（ＢＣＰ）、被着層へのダメージが比較的小さい原子層堆積（ＡＬＤ：Atomic Layer Deposition）により形成されたＳｎＯ等が挙げられる。
Note that when the second carrier transport layer 32 is an electron transport layer (ETL), there is a gap between the second carrier transport layer 32 and the second electrode layer 22 or between the second carrier transport layer 32 and the perovskite thin film 40. , a hole blocking layer may be provided. Examples of the material for the hole blocking layer include bathocuproine (BCP), SnO formed by atomic layer deposition (ALD), which causes relatively little damage to the adhered layer, and the like.
また、第２キャリア輸送層３２が電子輸送層（ＥＴＬ）の場合、第２キャリア輸送層３２と第２電極層２２との間、または、第２キャリア輸送層３２とペロブスカイト薄膜４０との間に、電子抽出層が設けられていてもよい。電子抽出層の材料としては、例えば、リチウム（Ｌｉ）、フッ化リチウム（ＬｉＦ）等が挙げられる。
In addition, when the second carrier transport layer 32 is an electron transport layer (ETL), there may be a gap between the second carrier transport layer 32 and the second electrode layer 22 or between the second carrier transport layer 32 and the perovskite thin film 40. , an electron extraction layer may be provided. Examples of the material for the electron extraction layer include lithium (Li), lithium fluoride (LiF), and the like.
一方、図２では、第２キャリア輸送層３２は、ペロブスカイト薄膜４０で光電変換されて生成されたキャリアのうちの正孔（第２キャリア）を第２電極層２２に輸送する正孔輸送層（ＨＴＬ）として機能する。正孔輸送層（ＨＴＬ）としての第２キャリア輸送層３２の主材料としては、酸化ニッケル（ＮｉＯ）、酸化銅（Ｃｕ２Ｏ）、ＰＴＡＡ（Poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)）、または、Ｓｐｉｒｏ－ＭｅＯＴＡＤ等が挙げられる。
On the other hand, in FIG. 2, the second carrier transport layer 32 is a hole transport layer (second carrier) that transports holes (second carriers) among carriers generated by photoelectric conversion in the perovskite thin film 40 to the second electrode layer 22. HTL). The main materials of the second carrier transport layer 32 as a hole transport layer (HTL) include nickel oxide (NiO), copper oxide (Cu 2 O), and PTAA (Poly(bis(4-phenyl)(2,4, 6-trimethylphenyl)amine) or Spiro-MeOTAD.
第２電極層２２は、第２キャリア輸送層３２上に形成されており、陰極（図１）または陽極（図２）として機能する。基材１０側、すなわち第１電極層２１側が受光面である場合、第２電極層２２は、例えば基材１０側に、面状の金属電極層を含んでいてもよい。或いは、基材１０と反対側、すなわち第２電極層２２側が受光面である場合、第２電極層２２は、導電性かつ光透過性を有する透明導電膜（Transparent Conductive Oxide：ＴＣＯ）を含んでいてもよく、更には、グリッド状またはスリット状の金属電極層を含んでいてもよい。
The second electrode layer 22 is formed on the second carrier transport layer 32 and functions as a cathode (FIG. 1) or an anode (FIG. 2). When the base material 10 side, that is, the first electrode layer 21 side is the light-receiving surface, the second electrode layer 22 may include, for example, a planar metal electrode layer on the base material 10 side. Alternatively, when the side opposite to the base material 10, that is, the second electrode layer 22 side is the light-receiving surface, the second electrode layer 22 includes a transparent conductive oxide (TCO) that is electrically conductive and transparent. Furthermore, it may include a grid-like or slit-like metal electrode layer.
透明導電膜ＴＣＯの材料としては、透明導電性金属酸化物、例えば、酸化インジウム、酸化スズ、酸化亜鉛、酸化チタンおよびそれらの複合酸化物等が用いられる。これらの中でも、酸化インジウムを主成分とするインジウム系複合酸化物が好ましい。高い導電率と透明性の観点からは、インジウム酸化物が特に好ましい。更に、信頼性またはより高い導電率を確保するため、インジウム酸化物にドーパントを添加すると好ましい。ドーパントとしては、例えば、Ｓｎ、Ｗ、Ｚｎ、Ｔｉ、Ｃｅ、Ｚｒ、Ｍｏ、Ａｌ、Ｇａ、Ｇｅ、Ａｓ、Ｓｉ、またはＳ等が挙げられる。これらの中でも、インジウム酸化物にスズ（Ｓｎ）が添加されたＩＴＯ（Indium Tin Oxide）が特に好ましい。
金属電極層の材料としては、Ａｇ、Ａｕ、Ｃｕ等が挙げられる。 As the material for the transparent conductive film TCO, transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof are used. Among these, indium-based composite oxides containing indium oxide as a main component are preferred. Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency. Furthermore, it is preferable to add dopants to the indium oxide to ensure reliability or higher conductivity. Examples of the dopant include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, and S. Among these, ITO (Indium Tin Oxide), in which tin (Sn) is added to indium oxide, is particularly preferred.
Examples of the material for the metal electrode layer include Ag, Au, and Cu.
金属電極層の材料としては、Ａｇ、Ａｕ、Ｃｕ等が挙げられる。 As the material for the transparent conductive film TCO, transparent conductive metal oxides such as indium oxide, tin oxide, zinc oxide, titanium oxide, and composite oxides thereof are used. Among these, indium-based composite oxides containing indium oxide as a main component are preferred. Indium oxide is particularly preferred from the viewpoint of high conductivity and transparency. Furthermore, it is preferable to add dopants to the indium oxide to ensure reliability or higher conductivity. Examples of the dopant include Sn, W, Zn, Ti, Ce, Zr, Mo, Al, Ga, Ge, As, Si, and S. Among these, ITO (Indium Tin Oxide), in which tin (Sn) is added to indium oxide, is particularly preferred.
Examples of the material for the metal electrode layer include Ag, Au, and Cu.
このような構成により、太陽電池１は、基材１０側、すなわち第１電極層２１側、または基材１０と反対側、すなわち第２電極層２２側から入射する光に応じた電流を生成し、第１電極層２１および第２電極層２２に出力する。
With this configuration, the solar cell 1 generates a current according to light incident from the base material 10 side, that is, the first electrode layer 21 side, or the side opposite to the base material 10, that is, the second electrode layer 22 side. , is output to the first electrode layer 21 and the second electrode layer 22.
（太陽電池の製造方法）
次に、図３Ａ～図３Ｃを参照して、本実施形態の太陽電池の製造方法について説明する。図３Ａおよび図３Ｂは、本実施形態に係る太陽電池の製造方法における第１電極層形成工程を示す図であり、図３Ｃは、本実施形態に係る太陽電池の製造方法における第１キャリア輸送層形成工程、ペロブスカイト薄膜形成工程、第２キャリア輸送層形成工程および第２電極層形成工程を示す図である。 (Method for manufacturing solar cells)
Next, a method for manufacturing a solar cell according to this embodiment will be described with reference to FIGS. 3A to 3C. 3A and 3B are diagrams showing a first electrode layer forming step in the solar cell manufacturing method according to the present embodiment, and FIG. 3C is a diagram showing the first carrier transport layer in the solar cell manufacturing method according to the present embodiment. It is a figure which shows a formation process, a perovskite thin film formation process, a 2nd carrier transport layer formation process, and a 2nd electrode layer formation process.
次に、図３Ａ～図３Ｃを参照して、本実施形態の太陽電池の製造方法について説明する。図３Ａおよび図３Ｂは、本実施形態に係る太陽電池の製造方法における第１電極層形成工程を示す図であり、図３Ｃは、本実施形態に係る太陽電池の製造方法における第１キャリア輸送層形成工程、ペロブスカイト薄膜形成工程、第２キャリア輸送層形成工程および第２電極層形成工程を示す図である。 (Method for manufacturing solar cells)
Next, a method for manufacturing a solar cell according to this embodiment will be described with reference to FIGS. 3A to 3C. 3A and 3B are diagrams showing a first electrode layer forming step in the solar cell manufacturing method according to the present embodiment, and FIG. 3C is a diagram showing the first carrier transport layer in the solar cell manufacturing method according to the present embodiment. It is a figure which shows a formation process, a perovskite thin film formation process, a 2nd carrier transport layer formation process, and a 2nd electrode layer formation process.
まず、図３Ａに示すように、基材１０上に、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜を製膜し、製膜したＩＴＯ薄膜を加熱することによって、結晶化ＩＴＯ薄膜２１Ｚを形成する（第１電極層形成工程）。透明導電膜の形成方法としては、特に限定されないが、真空チャンバを用いたＣＶＤ法（化学気相堆積法）、ＰＶＤ法（物理気相堆積法）またはスパッタリング法等が用いられる。
First, as shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10, and the formed ITO thin film is heated to form a crystallized ITO thin film 21Z. (first electrode layer forming step). The method for forming the transparent conductive film is not particularly limited, but a CVD method (chemical vapor deposition method) using a vacuum chamber, a PVD method (physical vapor deposition method), a sputtering method, or the like can be used.
このとき、ＩＴＯ薄膜の電気抵抗の低減または透過率の向上（すなわち、太陽電池の性能向上）のために、高温製膜または室温製膜＋アニールにより、ＩＴＯ薄膜の結晶性を高める。しかし、この結晶化の際、結晶化ＩＴＯ薄膜２１Ｚの表面に、ドープ成分であるＳｎが偏析してしまうことがある。そのため、表面が高抵抗化し、第１電極層と第１キャリア輸送層との界面抵抗が増加し、結晶化による電気抵抗の低減（すなわち、太陽電池の性能向上）の効果を低下させてしまう。
At this time, in order to reduce the electrical resistance or improve the transmittance of the ITO thin film (that is, to improve the performance of the solar cell), the crystallinity of the ITO thin film is increased by high temperature film formation or room temperature film formation + annealing. However, during this crystallization, Sn, which is a doping component, may segregate on the surface of the crystallized ITO thin film 21Z. Therefore, the surface becomes highly resistive, the interfacial resistance between the first electrode layer and the first carrier transport layer increases, and the effect of reducing electrical resistance (that is, improving the performance of the solar cell) due to crystallization is reduced.
次に、図３Ｂに示すように、結晶化ＩＴＯ薄膜２１Ｚの第１キャリア輸送層側の表面の一部２１Ｓを除去することによって、第１電極層２１を形成する（第１電極層形成工程）。具体的には、酸処理によって、結晶化ＩＴＯ薄膜２１Ｚの表面の一部２１Ｓをエッチングする。除去する一部２１Ｓは、結晶化ＩＴＯ薄膜２１Ｚの表面から３ｎｍまで、好ましくは２ｎｍまでの部分である。酸処理の溶液としては、塩酸ＨＣｌ、塩化第二鉄ＦｅＣｌ３等が挙げられる。
Next, as shown in FIG. 3B, the first electrode layer 21 is formed by removing part 21S of the surface of the crystallized ITO thin film 21Z on the first carrier transport layer side (first electrode layer forming step). . Specifically, a portion 21S of the surface of the crystallized ITO thin film 21Z is etched by acid treatment. The portion 21S to be removed is up to 3 nm, preferably up to 2 nm from the surface of the crystallized ITO thin film 21Z. Examples of solutions for acid treatment include hydrochloric acid HCl, ferric chloride FeCl3, and the like.
これにより、結晶化ＩＴＯ薄膜２１Ｚの表面の高抵抗化を抑制し、第１電極層と第１キャリア輸送層との界面抵抗の増加を抑制し、結晶化による電気抵抗の低減効果の低下（すなわち、太陽電池の性能向上）の効果の低下を抑制する。
This suppresses an increase in the surface resistance of the crystallized ITO thin film 21Z, suppresses an increase in the interfacial resistance between the first electrode layer and the first carrier transport layer, and reduces the effect of reducing electrical resistance due to crystallization (i.e. , the performance improvement of solar cells).
次に、図３Ｃに示すように、第１電極層２１上に、第１キャリア輸送層３１を形成する（第１キャリア輸送層形成工程）。第１キャリア輸送層３１の形成方法としては、特に限定されないが、例えばＣＶＤ法、ＰＶＤ法またはスパッタリング法等のドライプロセス、或いは塗布法、印刷法等のウエットプロセスが挙げられる。これらの中でも、緻密な膜の製膜の観点から、スパッタリング法が好ましい。
Next, as shown in FIG. 3C, the first carrier transport layer 31 is formed on the first electrode layer 21 (first carrier transport layer forming step). The method for forming the first carrier transport layer 31 is not particularly limited, and includes, for example, a dry process such as a CVD method, a PVD method, or a sputtering method, or a wet process such as a coating method or a printing method. Among these, the sputtering method is preferred from the viewpoint of forming a dense film.
次に、第１キャリア輸送層３１上に、ペロブスカイト薄膜４０を形成する（ペロブスカイト薄膜形成工程）。例えば、ヨウ化鉛ＰｂＩ２材料膜を製膜した後、ヨウ化メチルアンモニウムＭＡＩ材料膜を製膜し、ヨウ化鉛ＰｂＩ２材料膜とヨウ化メチルアンモニウムＭＡＩ材料膜とを反応させることにより、メチルアンモニウムヨウ化鉛ＭＡＰｂＩ３からなるペロブスカイト薄膜を形成する。ペロブスカイト薄膜４０の形成方法としては、特に限定されないが、蒸着法等のドライプロセス、或いは印刷法、塗布法または溶液法等のウエットプロセスが挙げられる。
Next, a perovskite thin film 40 is formed on the first carrier transport layer 31 (perovskite thin film forming step). For example, after forming a lead iodide PbI 2 material film, a methylammonium iodide MAI material film is formed, and by reacting the lead iodide PbI 2 material film and the methylammonium iodide MAI material film, methyl A perovskite thin film made of ammonium lead iodide MAPbI 3 is formed. Methods for forming the perovskite thin film 40 include, but are not particularly limited to, dry processes such as vapor deposition, wet processes such as printing, coating, and solution methods.
次に、ペロブスカイト薄膜４０上に、第２キャリア輸送層３２を形成する（第２キャリア輸送層形成工程）。第２キャリア輸送層３２の形成方法としては、特に限定されないが、例えばＣＶＤ法、ＰＶＤ法またはスパッタリング法、あるいは蒸着法等のドライプロセス、或いは塗布法、印刷法等のウエットプロセスが挙げられる。
Next, the second carrier transport layer 32 is formed on the perovskite thin film 40 (second carrier transport layer forming step). The method for forming the second carrier transport layer 32 is not particularly limited, but includes, for example, a CVD method, a PVD method, a sputtering method, a dry process such as a vapor deposition method, or a wet process such as a coating method or a printing method.
次に、第２キャリア輸送層３２上に、第２電極層２２を形成する。第２電極層２２の形成方法としては、特に限定されないが、例えば真空チャンバを用いたＣＶＤ法、ＰＶＤ法またはスパッタリング法、あるいは蒸着法等のドライプロセス、或いは印刷法または塗布法等のウエットプロセスが挙げられる。これらの中でも、スパッタリング法が好ましい。
以上により、図１または図２に示す本実施形態のペロブスカイト薄膜系の太陽電池１が得られる。 Next, thesecond electrode layer 22 is formed on the second carrier transport layer 32. The method for forming the second electrode layer 22 is not particularly limited, but includes, for example, a CVD method using a vacuum chamber, a PVD method, a sputtering method, a dry process such as a vapor deposition method, or a wet process such as a printing method or a coating method. Can be mentioned. Among these, sputtering method is preferred.
Through the above steps, the perovskite thin filmsolar cell 1 of this embodiment shown in FIG. 1 or 2 is obtained.
以上により、図１または図２に示す本実施形態のペロブスカイト薄膜系の太陽電池１が得られる。 Next, the
Through the above steps, the perovskite thin film
以上説明したように、本実施形態の太陽電池の製造方法によれば、第１電極層形成工程において、製膜したＩＴＯ薄膜を加熱して結晶化ＩＴＯ薄膜２１Ｚを形成する。これにより、ＩＴＯ薄膜の結晶性を高め、ＩＴＯ薄膜の電気抵抗を低減し、ＩＴＯ薄膜の透過率を向上することができる。その結果、太陽電池１の性能向上を図ることができる。
As explained above, according to the solar cell manufacturing method of this embodiment, in the first electrode layer forming step, the formed ITO thin film is heated to form the crystallized ITO thin film 21Z. Thereby, the crystallinity of the ITO thin film can be improved, the electrical resistance of the ITO thin film can be reduced, and the transmittance of the ITO thin film can be improved. As a result, the performance of the solar cell 1 can be improved.
更に、第１電極層形成工程において、ＩＴＯ薄膜の結晶化の際に、ドープ成分であるＳｎが偏析する結晶化ＩＴＯ薄膜２１Ｚの表面の一部２１Ｓを除去する。これにより、結晶化ＩＴＯ薄膜２１Ｚの表面の高抵抗化を抑制することができ、第１電極層と第１キャリア輸送層との界面抵抗の増加を抑制することができ、結晶化による電気抵抗の低減効果の低下を抑制することができる。その結果、太陽電池１の更なる性能向上を図ることができる。
Furthermore, in the first electrode layer forming step, a part 21S of the surface of the crystallized ITO thin film 21Z where Sn, which is a doping component, segregates during crystallization of the ITO thin film is removed. Thereby, it is possible to suppress an increase in the surface resistance of the crystallized ITO thin film 21Z, and it is possible to suppress an increase in the interfacial resistance between the first electrode layer and the first carrier transport layer, and to reduce the electrical resistance due to crystallization. Deterioration of the reduction effect can be suppressed. As a result, the performance of the solar cell 1 can be further improved.
以上、本発明の実施形態について説明したが、本発明は上述した実施形態に限定されることなく、種々の変更および変形が可能である。例えば、上述した実施形態では、結晶シリコン系太陽電池またはアモルファスシリコン薄膜系太陽電池と、ペロブスカイト薄膜系太陽電池とを組み合わせたいわゆるタンデム型太陽電池におけるペロブスカイト薄膜系太陽電池の製造にも適用可能である。
Although the embodiments of the present invention have been described above, the present invention is not limited to the embodiments described above, and various changes and modifications can be made. For example, the embodiments described above can also be applied to the production of a perovskite thin film solar cell in a so-called tandem solar cell that combines a crystalline silicon solar cell or an amorphous silicon thin film solar cell and a perovskite thin film solar cell. .
以下、実施例に基づいて本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to the following Examples.
（実施例１）
本実施形態のペロブスカイト薄膜系太陽電池の製造方法において、図３Ｂに示す酸処理後の第１電極層を実施例１として作製した。実施例１の第１電極層の形成方法は以下の通りである。
・まず、図３Ａに示すように、基材１０上に、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜を製膜し（スパッタリング法）、製膜したＩＴＯ薄膜を加熱して（１８０度で１時間）、結晶化ＩＴＯ薄膜２１Ｚを形成した（膜厚１２２ｎｍ）。
・次に、図３Ｂに示すように、結晶化ＩＴＯ薄膜２１Ｚの表面の一部２１Ｓ（表面から２ｎｍの部分）を酸処理（ＨＣｌ）によって除去して第１電極層を形成した。 (Example 1)
In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer after acid treatment shown in FIG. 3B was produced as Example 1. The method for forming the first electrode layer of Example 1 is as follows.
- First, as shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees). 1 hour), a crystallized ITO thin film 21Z was formed (film thickness: 122 nm).
- Next, as shown in FIG. 3B, apart 21S (2 nm from the surface) of the surface of the crystallized ITO thin film 21Z was removed by acid treatment (HCl) to form a first electrode layer.
本実施形態のペロブスカイト薄膜系太陽電池の製造方法において、図３Ｂに示す酸処理後の第１電極層を実施例１として作製した。実施例１の第１電極層の形成方法は以下の通りである。
・まず、図３Ａに示すように、基材１０上に、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜を製膜し（スパッタリング法）、製膜したＩＴＯ薄膜を加熱して（１８０度で１時間）、結晶化ＩＴＯ薄膜２１Ｚを形成した（膜厚１２２ｎｍ）。
・次に、図３Ｂに示すように、結晶化ＩＴＯ薄膜２１Ｚの表面の一部２１Ｓ（表面から２ｎｍの部分）を酸処理（ＨＣｌ）によって除去して第１電極層を形成した。 (Example 1)
In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer after acid treatment shown in FIG. 3B was produced as Example 1. The method for forming the first electrode layer of Example 1 is as follows.
- First, as shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees). 1 hour), a crystallized ITO thin film 21Z was formed (film thickness: 122 nm).
- Next, as shown in FIG. 3B, a
（比較例１）
本実施形態のペロブスカイト薄膜系太陽電池の製造方法において、図３Ａに示す酸処理前の第１電極層を比較例１として作製した。比較例１の第１電極層の形成方法は以下の通りである。
・図３Ａに示すように、基材１０上に、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜を製膜し（スパッタリング法）、製膜したＩＴＯ薄膜を加熱して（１８０度で１時間）、結晶化ＩＴＯ薄膜２１Ｚを、すなわち表面の一部２１Ｓを除去しない結晶化ＩＴＯ薄膜２１Ｚを、第１電極層として形成した（膜厚１２０ｎｍ）。 (Comparative example 1)
In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer before acid treatment shown in FIG. 3A was produced as Comparative Example 1. The method for forming the first electrode layer of Comparative Example 1 is as follows.
・As shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees for 1 hour). ), a crystallized ITO thin film 21Z, that is, a crystallized ITO thin film 21Z whosesurface part 21S was not removed, was formed as the first electrode layer (film thickness: 120 nm).
本実施形態のペロブスカイト薄膜系太陽電池の製造方法において、図３Ａに示す酸処理前の第１電極層を比較例１として作製した。比較例１の第１電極層の形成方法は以下の通りである。
・図３Ａに示すように、基材１０上に、インジウム酸化物にスズＳｎが添加されたＩＴＯ薄膜を製膜し（スパッタリング法）、製膜したＩＴＯ薄膜を加熱して（１８０度で１時間）、結晶化ＩＴＯ薄膜２１Ｚを、すなわち表面の一部２１Ｓを除去しない結晶化ＩＴＯ薄膜２１Ｚを、第１電極層として形成した（膜厚１２０ｎｍ）。 (Comparative example 1)
In the method for manufacturing a perovskite thin film solar cell of this embodiment, a first electrode layer before acid treatment shown in FIG. 3A was produced as Comparative Example 1. The method for forming the first electrode layer of Comparative Example 1 is as follows.
・As shown in FIG. 3A, an ITO thin film in which tin is added to indium oxide is formed on the base material 10 (sputtering method), and the formed ITO thin film is heated (at 180 degrees for 1 hour). ), a crystallized ITO thin film 21Z, that is, a crystallized ITO thin film 21Z whose
（評価）
第１電極層（ＩＴＯ）の表面（第１キャリア輸送層側の表面）からの深さに対するＳｎ／Ｉｎ割合（Ｉｎに対するＳｎの割合）を、デプスプロファイルとして測定した。具体的には、スパッタリング法を用いたＩＴＯの表面のエッチングと、ＸＰＳ測定とを組み合わせることにより、第１電極層（ＩＴＯ）の表面からのデプスプロファイルを測定した。スパッタ装置としては公知のスパッタ装置であればよく、スパッタレートは約１．２５ｎｍ／ｍｉｎ．とした。ＸＰＳ測定としては、アルバック・ファイ社製／型格ＰＨＩ５０００ ＶｅｒｓａＰｒｏｂｅIIを使用した。このデプスプロファイルの測定結果を図４に示す。 (evaluation)
The Sn/In ratio (ratio of Sn to In) with respect to the depth from the surface of the first electrode layer (ITO) (the surface on the first carrier transport layer side) was measured as a depth profile. Specifically, the depth profile from the surface of the first electrode layer (ITO) was measured by combining etching of the surface of ITO using a sputtering method and XPS measurement. Any known sputtering device may be used as the sputtering device, and the sputtering rate is approximately 1.25 nm/min. And so. For the XPS measurement, VersaProbeII manufactured by ULVAC-PHI Inc./model PHI5000 was used. The measurement results of this depth profile are shown in FIG.
第１電極層（ＩＴＯ）の表面（第１キャリア輸送層側の表面）からの深さに対するＳｎ／Ｉｎ割合（Ｉｎに対するＳｎの割合）を、デプスプロファイルとして測定した。具体的には、スパッタリング法を用いたＩＴＯの表面のエッチングと、ＸＰＳ測定とを組み合わせることにより、第１電極層（ＩＴＯ）の表面からのデプスプロファイルを測定した。スパッタ装置としては公知のスパッタ装置であればよく、スパッタレートは約１．２５ｎｍ／ｍｉｎ．とした。ＸＰＳ測定としては、アルバック・ファイ社製／型格ＰＨＩ５０００ ＶｅｒｓａＰｒｏｂｅIIを使用した。このデプスプロファイルの測定結果を図４に示す。 (evaluation)
The Sn/In ratio (ratio of Sn to In) with respect to the depth from the surface of the first electrode layer (ITO) (the surface on the first carrier transport layer side) was measured as a depth profile. Specifically, the depth profile from the surface of the first electrode layer (ITO) was measured by combining etching of the surface of ITO using a sputtering method and XPS measurement. Any known sputtering device may be used as the sputtering device, and the sputtering rate is approximately 1.25 nm/min. And so. For the XPS measurement, VersaProbeII manufactured by ULVAC-PHI Inc./model PHI5000 was used. The measurement results of this depth profile are shown in FIG.
図４において、横軸がスパッタ時間、すなわち第１電極層（ＩＴＯ）の表面からの深さであり、縦軸がＳｎ／Ｉｎ割合（Ｉｎに対するＳｎの割合）である。また、実線が実施例１の酸処理有の第１電極層（ＩＴＯ）のデプスプロファイルであり、破線が比較例１の酸処理無の第１電極層（ＩＴＯ）のデプスプロファイルである。
In FIG. 4, the horizontal axis is the sputtering time, that is, the depth from the surface of the first electrode layer (ITO), and the vertical axis is the Sn/In ratio (ratio of Sn to In). Further, the solid line is the depth profile of the first electrode layer (ITO) with acid treatment in Example 1, and the broken line is the depth profile of the first electrode layer (ITO) without acid treatment in Comparative Example 1.
図４に示すように、比較例１、すなわち酸処理無では、第１電極層（ＩＴＯ）の表面から１．２５ｎｍまでの部分において、Ｉｎに対するＳｎの割合が大きい。これに対して、実施例１、すなわち酸処理有では、第１電極層（ＩＴＯ）の表面から、Ｉｎに対するＳｎの割合を低減できた。
As shown in FIG. 4, in Comparative Example 1, that is, without acid treatment, the ratio of Sn to In was large in the portion up to 1.25 nm from the surface of the first electrode layer (ITO). On the other hand, in Example 1, that is, with acid treatment, the ratio of Sn to In could be reduced from the surface of the first electrode layer (ITO).
１ ペロブスカイト薄膜系太陽電池
１０ 基材
２１ 第１電極層（陽極または陰極）
２１Ｓ 結晶化ＩＴＯ薄膜の表面の一部
２１Ｚ 結晶化ＩＴＯ薄膜
２２ 第２電極層（陰極または陽極）
３１ 第１キャリア輸送層（正孔輸送層または電子輸送層）
３２ 第２キャリア輸送層（電子輸送層または正孔輸送層）
４０ ペロブスカイト薄膜 1 Perovskite thin filmsolar cell 10 Base material 21 First electrode layer (anode or cathode)
21S Part of surface of crystallized ITO thin film 21Z Crystallized ITOthin film 22 Second electrode layer (cathode or anode)
31 First carrier transport layer (hole transport layer or electron transport layer)
32 Second carrier transport layer (electron transport layer or hole transport layer)
40 Perovskite thin film
１０ 基材
２１ 第１電極層（陽極または陰極）
２１Ｓ 結晶化ＩＴＯ薄膜の表面の一部
２１Ｚ 結晶化ＩＴＯ薄膜
２２ 第２電極層（陰極または陽極）
３１ 第１キャリア輸送層（正孔輸送層または電子輸送層）
３２ 第２キャリア輸送層（電子輸送層または正孔輸送層）
４０ ペロブスカイト薄膜 1 Perovskite thin film
21S Part of surface of crystallized ITO thin film 21Z Crystallized ITO
31 First carrier transport layer (hole transport layer or electron transport layer)
32 Second carrier transport layer (electron transport layer or hole transport layer)
40 Perovskite thin film
Claims (8)
- 基材上に、第１電極層と、第１キャリア輸送層と、ペロブスカイト薄膜と、第２キャリア輸送層と、第２電極層とをこの順番に形成するペロブスカイト薄膜系太陽電池の製造方法であって、
前記第１電極層の形成工程では、
前記基材上に、インジウム酸化物にＳｎが添加されたＩＴＯ薄膜を製膜し、前記ＩＴＯ薄膜を加熱することによって、結晶化ＩＴＯ薄膜を形成し、
前記結晶化ＩＴＯ薄膜の前記第１キャリア輸送層側の表面の一部を除去することによって、前記第１電極層を形成する、
ペロブスカイト薄膜系太陽電池の製造方法。 A method for manufacturing a perovskite thin film solar cell, comprising forming a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer in this order on a base material. hand,
In the step of forming the first electrode layer,
Forming an ITO thin film in which Sn is added to indium oxide on the base material and heating the ITO thin film to form a crystallized ITO thin film,
forming the first electrode layer by removing a part of the surface of the crystallized ITO thin film on the first carrier transport layer side;
A method for manufacturing perovskite thin film solar cells. - 前記結晶化ＩＴＯ薄膜の表面の一部を除去する工程では、酸処理によって、前記結晶化ＩＴＯ薄膜の表面の一部をエッチングする、請求項１に記載のペロブスカイト薄膜系太陽電池の製造方法。 The method for manufacturing a perovskite thin film solar cell according to claim 1, wherein in the step of removing a part of the surface of the crystallized ITO thin film, a part of the surface of the crystallized ITO thin film is etched by acid treatment.
- 前記結晶化ＩＴＯ薄膜の表面の一部を除去する工程では、前記結晶化ＩＴＯ薄膜の表面から３ｎｍまでの部分を除去する、請求項１または２に記載のペロブスカイト薄膜系太陽電池の製造方法。 The method for manufacturing a perovskite thin film solar cell according to claim 1 or 2, wherein in the step of removing a part of the surface of the crystallized ITO thin film, a portion up to 3 nm from the surface of the crystallized ITO thin film is removed.
- 基材上に、第１電極層と、第１キャリア輸送層と、ペロブスカイト薄膜と、第２キャリア輸送層と、第２電極層とをこの順番に備えるペロブスカイト薄膜系太陽電池であって、
前記第１電極層は、インジウム酸化物にＳｎが添加されたＩＴＯ薄膜であって、結晶化された結晶化ＩＴＯ薄膜を含み、
前記結晶化ＩＴＯ薄膜において、前記第１キャリア輸送層側の表面から３ｎｍまでの表面部分におけるＩｎに対するＳｎの割合と、前記表面部分以外の残り部分におけるＩｎに対するＳｎの割合との差が、２％以下である、
ペロブスカイト薄膜系太陽電池。 A perovskite thin film solar cell comprising a first electrode layer, a first carrier transport layer, a perovskite thin film, a second carrier transport layer, and a second electrode layer in this order on a base material,
The first electrode layer is an ITO thin film in which Sn is added to indium oxide, and includes a crystallized ITO thin film,
In the crystallized ITO thin film, the difference between the ratio of Sn to In in the surface part up to 3 nm from the surface on the first carrier transport layer side and the ratio of Sn to In in the remaining part other than the surface part is 2%. The following is
Perovskite thin film solar cells. - 前記基材側が受光面であり、
前記基材は光透過性を有し、
前記第１電極層は、前記結晶化ＩＴＯ薄膜を含み、または、前記結晶化ＩＴＯ薄膜と、グリッド状またはスリット状の金属電極層を含み、
前記第２電極層は、面状の金属電極層を含む、
請求項４に記載のペロブスカイト薄膜系太陽電池。 The base material side is a light-receiving surface,
The base material has light transmittance,
The first electrode layer includes the crystallized ITO thin film, or includes the crystallized ITO thin film and a grid-shaped or slit-shaped metal electrode layer,
The second electrode layer includes a planar metal electrode layer.
The perovskite thin film solar cell according to claim 4. - 前記第２電極層側が受光面であり、
前記第２電極層は、透明導電膜を含み、または、透明導電膜と、グリッド状またはスリット状の金属電極層を含み、
前記第１電極層は、面状の金属電極層を更に含む、
請求項４に記載のペロブスカイト薄膜系太陽電池。 The second electrode layer side is a light-receiving surface,
The second electrode layer includes a transparent conductive film, or includes a transparent conductive film and a grid-shaped or slit-shaped metal electrode layer,
The first electrode layer further includes a planar metal electrode layer.
The perovskite thin film solar cell according to claim 4. - 前記基材側および前記第２電極層側の両側が受光面であり、
前記基材は光透過性を有し、
前記第１電極層は、前記結晶化ＩＴＯ薄膜を含み、または、前記結晶化ＩＴＯ薄膜と、グリッド状またはスリット状の金属電極層を含み、
前記第２電極層は、透明導電膜を含み、または、透明導電膜と、グリッド状またはスリット状の金属電極層を含む、
請求項４に記載のペロブスカイト薄膜系太陽電池。 Both sides of the base material side and the second electrode layer side are light receiving surfaces,
The base material has light transmittance,
The first electrode layer includes the crystallized ITO thin film, or includes the crystallized ITO thin film and a grid-shaped or slit-shaped metal electrode layer,
The second electrode layer includes a transparent conductive film, or includes a transparent conductive film and a grid-shaped or slit-shaped metal electrode layer.
The perovskite thin film solar cell according to claim 4. - 前記基材はフィルム状の基材である、請求項４～７のいずれか１項に記載のペロブスカイト薄膜系太陽電池。 The perovskite thin film solar cell according to any one of claims 4 to 7, wherein the base material is a film-like base material.
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