KR101654310B1 - Method for manufacturing of electrode layer using anodization, and method for manufacturing of perovskite solar cell comprising the same - Google Patents
Method for manufacturing of electrode layer using anodization, and method for manufacturing of perovskite solar cell comprising the same Download PDFInfo
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- KR101654310B1 KR101654310B1 KR1020150081168A KR20150081168A KR101654310B1 KR 101654310 B1 KR101654310 B1 KR 101654310B1 KR 1020150081168 A KR1020150081168 A KR 1020150081168A KR 20150081168 A KR20150081168 A KR 20150081168A KR 101654310 B1 KR101654310 B1 KR 101654310B1
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- layer
- electrode
- titanium dioxide
- perovskite
- electron transport
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000002048 anodisation reaction Methods 0.000 title description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 60
- 230000003647 oxidation Effects 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 3
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000231 atomic layer deposition Methods 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 24
- 229910010413 TiO 2 Inorganic materials 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- 239000002071 nanotube Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 238000007743 anodising Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 239000011787 zinc oxide Substances 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 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
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- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
(A) forming a titanium layer on an electrode; (b) oxidizing the titanium layer by anodic oxidation to prepare a titanium dioxide (TiO 2) layer; And (c) subjecting the titanium dioxide layer to heat treatment to produce a crystallized titanium dioxide layer. The present invention also relates to a method of manufacturing an electrode stacked body. Thus, the titanium dioxide electron transport layer crystallized by the anodic oxidation method can be formed to simplify the process, the thickness of the electron transport layer can be uniform, and the light and transmittance can be improved and the electron transport efficiency can be improved. When the method for producing the electrode laminate is used in a perovskite solar cell, the interfacial surface area between the perovskite layer and the electron transport layer is widened to improve the efficiency of collecting electrons from the perovskite layer to the electron transport layer , The light conversion efficiency can be improved.
Description
The present invention relates to a method of manufacturing an electrode stack and a method of manufacturing the same, and more particularly, to a method of manufacturing a perovskite solar cell including a titanium dioxide electron transport layer Which is uniform in thickness and can improve the interface surface area with the perovskite, and a method for producing the perovskite solar cell including the method for producing the electrode laminate.
Since TiO 2 was first discovered in 1791 by William Gregor of the United Kingdom in an attempt to isolate white metal oxides from black sand, the TiO 2 has been used for photocatalysts, paints, plastics, Medical devices, and the like.
TiO 2, which is applied to most fields, has a nanoparticle structure and can be divided into anatase, rutile and brookite structures according to the arrangement of elements in the particle, and anatase type TiO 2 Nanoparticles are the most widely used.
Among various types of TiO 2 nanostructures, such as porous nanosubstrates, nanowires, nanopillars, and nanotubes, TiO 2 nanotubes have an excellent alignment and a large surface area relative to volume
1999 to anodic oxidation using an electrolyte containing fluoride by Zwilling team Ti-foil substrate on the nanotube array by a later published the results that may be generated, structure control and access is easy anodic oxidation a TiO 2 nano-tubes Has attracted attention as a manufacturing method of a semiconductor device.
However, since the TIO 2 nanotubes manufactured according to the conventional anodic oxidation method (Korean Patent Laid-Open Publication No. 2014-0018450) have a thickness of several micrometers, the nanotubes of recent trends with a nanometer level thickness, the inorganic-based perovskite solar There is a problem that it is difficult to apply to a battery.
In order to solve such a problem, attempts have been made to form a titanium dioxide layer by spin coating or the like, but when the spin coating method is used, the thickness of the titanium dioxide layer formed on the electrode is not uniform, The surface area of the interface with the perovskite layer present in the perovskite layer is relatively small and electrons can not be effectively collected from the perovskite layer.
An object of the present invention is to provide a method of manufacturing an electrode laminate in which a titanium dioxide electron transport layer having a crystallized size of nm is formed on an electrode by using an anodic oxidation method, thereby simplifying the process and improving the light transmittance And to improve the electron transfer efficiency.
It is another object of the present invention to provide a method for manufacturing an electrode laminate, which is applied to a perovskite solar cell, thereby increasing the surface area of the interface with the perovskite layer and improving the efficiency of electron transfer from the perovskite layer And to provide perovskite solar cells with greatly improved solar efficiency.
According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) forming a titanium layer on an electrode; (b) preparing a titanium dioxide (TiO 2) layer by oxidizing the titanium layer by anodic oxidation; And (c) heat treating the titanium dioxide layer to produce a crystallized titanium dioxide layer.
The electrode may include at least one selected from the group consisting of fluorine tin oxide (FTO), indium tin oxide (ITO), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , tin oxide, and zinc oxide.
The titanium layer may be formed on the electrode by sputtering coating or atomic layer deposition.
The titanium layer may be formed to a thickness of 10 to 100 nm.
Preferably, the titanium layer may be formed to a thickness of 20 to 80 nm.
The anodic oxidation method may be performed under a voltage condition of 3 to 10 V.
Preferably, the anodic oxidation method can be carried out under a voltage condition of 4 to 6V.
The anodizing method may be performed for 3 to 40 minutes.
Preferably, the anodizing method may be performed for 4 to 6 minutes.
The heat treatment may be performed at 400 to 600 ° C.
Preferably, the heat treatment may be performed at 400 to 500 ° C.
The crystallized titanium dioxide layer may include an anatase crystal.
The anodic oxidation method may be performed in an electrolyte containing ammonium fluoride.
A step of washing with alcohol after step b may be further carried out.
According to another aspect of the present invention, there is provided a method of manufacturing a perovskite solar cell including the method of manufacturing the electrode stacked body.
The method for manufacturing the perovskite solar cell includes the steps of: (a) forming a titanium layer on an electrode; (b) preparing a titanium dioxide (TiO 2) layer by oxidizing the titanium layer by anodic oxidation; And (c) heat treating the titanium dioxide layer to produce an electron transport layer that is a crystallized titanium dioxide layer; (d) coating a perovskite precursor on the electron transport layer; (e) heat treating the perovskite precursor to form a perovskite light absorbing layer; (f) forming a hole transporting layer on the perovskite light absorbing layer; And (g) forming a counter electrode by coating a conductive electrode material on the pore transfer layer.
After step c, a step of coating aluminum oxide (Al 2 O 3 ) on the titanium dioxide electron transport layer may be further included.
The conductive electrode material may include at least one selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C and a conductive polymer.
The process for producing an electrode laminate according to the present invention can simplify the process by forming an electron transport layer of titanium dioxide crystallized at a nanometer level on an electrode using anodizing, And the electron transfer efficiency can be improved. When the method for producing the electrode laminate is used in a perovskite solar cell, the interfacial surface area between the perovskite layer and the electron transport layer is widened to improve the efficiency of collecting electrons from the perovskite layer to the electron transport layer , The light conversion efficiency can be improved.
1 is a flowchart sequentially illustrating a method of manufacturing an electrode laminate according to the present invention.
FIG. 2 is a schematic diagram showing a comparison of charge collection and recombination phenomena in different electron transport layers of a perovskite solar cell of the present invention and a conventional perovskite solar cell. FIG.
3 is a schematic view of the process of the
4 shows an HR-SEM image of the surface and cross-section of the titanium dioxide electron transport layer prepared according to Example 1, Comparative Examples 1 and 2 of the present invention.
Fig. 5 shows the transmittances of the FTO substrates of Examples 1 to 4, Comparative Example 1 and before the formation of the electron transport layer.
6 shows the results of the analysis of the efficiency of the perovskite solar cell according to the device example 1 and the device comparative example 1. Fig.
FIG. 7 shows the photocurrent-light voltage (JV) characteristics of the perovskite solar cell according to the
Figure 8 shows a surface HR-SEM image of a titanium dioxide electron transport layer formed according to Examples 8-12.
FIG. 9 shows photovoltaic-photovoltaic (JV) characteristics of the perovskite solar cell manufactured according to the
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.
However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof is contemplated by one or more other features But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.
Fig. 1 is a flowchart sequentially showing a method for producing an electrode laminate according to the present invention.
Hereinafter, a method of manufacturing the electrode laminate of the present invention will be described with reference to FIG.
First, a titanium layer is formed on the electrode (step a).
The electrode may be formed of fluorine tin oxide (FTO), indium tin oxide (ITO), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , tin oxide, zinc oxide and the like.
The titanium layer may be formed on the electrode by sputtering, atomic layer deposition, or the like.
The thickness of the titanium layer may be preferably 10 to 100 nm, more preferably 20 to 80 nm, still more preferably 30 to 60 nm.
Next, the formation of the titanium layer and the titanium oxide crystallized by oxidation of the anodic oxidation (TiO 2) layer (step b).
Through the anodic oxidation, the opaque titanium layer can be changed to a transparent crystallized titanium dioxide layer. Since the titanium layer is very thin, the titanium dioxide layer of desired physical properties can be obtained by appropriately adjusting the voltage and time conditions of the anodic oxidation.
The anodic oxidation is preferably carried out in an electrolyte comprising ammonium fluoride.
Specifically, the voltage condition of the anodic oxidation may preferably be 3 to 10 V, more preferably 3 to 8 V, even more preferably 4 to 6 V.
In addition, the time during which the anodic oxidation is performed may be preferably 3 to 40 minutes, more preferably 3 to 20 minutes, even more preferably 4 to 6 minutes.
The condition for the anodic oxidation is to effectively oxidize the titanium layer having a thin thickness to uniformly form the titanium dioxide layer of the nanostructure, and the time condition of the anodic oxidation may be varied depending on the voltage condition. The titanium dioxide layer formed by the anodic oxidation may be amorphous titanium dioxide.
When the anodic oxidation is completed, the laminate including the electrode and the titanium dioxide layer can be washed with alcohol.
Next, the titanium dioxide layer is heat-treated to form a titanium dioxide electron transport layer (step c).
The heat treatment may preferably be performed at 400 to 600 占 폚, more preferably at 400 to 470 占 폚, and still more preferably at 400 to 500 占 폚.
By the heat treatment, the amorphous titanium dioxide can be crystallized to form an anatase crystal. Thus, the light transmittance can be further improved.
Hereinafter, a method of manufacturing the perovskite solar cell of the present invention will be described.
The perovskite solar cell of the present invention may include the above-described method of manufacturing the electrode laminate of the present invention. The production method of the specific perovskite solar cell is as follows.
First, a crystallized titanium dioxide layer is formed on the electrode to produce an electrode laminate.
The manufacturing method of the electrode laminate is the same as the manufacturing method of the electrode laminate including the above-mentioned steps (a) to (c), so that details thereof will be referred to.
Aluminum oxide (Al 2 O 3 ) may be coated on the titanium dioxide electron transfer layer of the electrode stacked body. The aluminum oxide may serve as a supporting layer for allowing the perovskite layer to be uniformly deposited on the electron transporting layer.
A perovskite precursor is then coated on the electron transport layer (step d).
The perovskite precursor may be a compound represented by the following general formula (1).
[Chemical Formula 1]
ABX 3
In formula (1)
A is any one of Pb, Sn, Ti, Nb, Zr, and Ce,
B is an alkyl group substituted C1 to C30 alkyl group,
X is a halogen element.
Various methods such as spin coating, screen printing, and spray coating can be used for the coating, but it is more preferable to use a spin coating method.
Thereafter, the perovskite precursor is heat-treated to form a perovskite light absorbing layer (step e).
By the heat treatment, the perovskite precursor crystallizes and a light absorption layer having a perovskite structure can be formed.
The heat treatment is preferably performed at a temperature of preferably 80 to 150 ° C, more preferably 85 to 130 ° C, and still more preferably 90 to 120 ° C.
Next, a hole transporting layer is formed on the perovskite light absorbing layer (step f).
The hole transport layer may be a single molecule or a hole transport material of a polymer.
Finally, a conductive electrode material is coated on the conductive layer to form a counter electrode (step g).
The conductive electrode material may be Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C or a conductive polymer.
Hereinafter, reference will be made to a perovskite solar cell manufactured by using the method of manufacturing an electrode laminate using anodic oxidation of the present invention and a charge collection of a perovskite solar cell manufactured by a conventional spin coating method, And recombination.
FIG. 2 is a graph showing the relationship between charge collection and recombination phenomena in different electron transport layers of a perovskite solar cell according to the present invention and a perovskite solar cell having an electron transport layer formed using a conventional spin coating method Fig. Here, the electrode is exemplified as FTO, but the scope of the present invention is not limited thereto.
2, in the perovskite solar cell of the present invention, it can be seen that the electron transport layer is uniformly formed on the FTO substrate, and the area of the electron transport layer / perovskite layer interface is wide. In contrast, in the conventional perovskite solar cell, the surface of the electron transport layer is formed flat on the FTO substrate and can not be formed in a uniform thickness, and pinholes may be formed, / Perovskite layer interface area is relatively narrow.
Therefore, when the perovskite solar cell is manufactured by the manufacturing method of the present invention, the interface characteristics between the electron transporting layer and the perovskite layer are improved, so that the charge collection and recombination efficiency can be significantly improved. As a result, The light conversion efficiency can be improved.
[Example]
Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.
Example One
The process of Example 1 is schematically shown in Fig. The first embodiment will be described with reference to FIG.
Titanium (Ti) was coated on the FTO substrate by sputtering to form a titanium layer having a thickness of 40 nm. Potentiostatic anodization was performed using a titanium layer as a working electrode and a carbon plate as a counter electrode. The anodic oxidation was performed at room temperature using an ethylene glycol solution containing 0.25 wt% NH 4 F and 0.3 vol% of deionized water as an electrolyte at 5 V for 5 minutes. After the anodic oxidation, it was washed with ethanol to remove acid salts and debris, and was heat-treated at 450 for 2 hours to prepare an electrode laminate in which a crystallized titanium dioxide layer having a thickness of about 40 nm was formed on the FTO substrate.
Example 2
An electrode laminate having a crystallized titanium dioxide layer having a thickness of 60 nm was prepared in the same manner as in Example 1, except that a 60 nm thick titanium layer was formed instead of 40 nm.
Example 3
An electrode laminate having a crystallized titanium dioxide layer with a thickness of 80 nm was prepared in the same manner as in Example 1, except that a titanium layer having a thickness of 80 nm was formed instead of the titanium layer having a thickness of 40 nm.
Example 4
An electrode laminate having a 20 nm thick crystallized titanium dioxide layer was prepared in the same manner as in Example 1, except that a 20 nm thick titanium layer was formed instead of 40 nm.
Example 5
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that the anodic oxidation was performed at a voltage of 3 V instead of 5 V was prepared.
Example 6
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that anodic oxidation was performed at a voltage of 4 V instead of 5 V was prepared.
Example 7
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that anodic oxidation was performed at a voltage of 7 V instead of 5 V was prepared.
Example 8
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that the anodic oxidation was performed at a voltage of 10 V instead of 5 V was prepared.
Example 9
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 was prepared, except that the anodic oxidation was performed for 4 minutes instead of 5 minutes.
Example 10
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that the anodic oxidation was performed for 8 minutes instead of 5 minutes was made.
Example 11
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 except that anodic oxidation was performed for 16 minutes instead of 5 minutes was prepared.
Example 12
An electrode laminate having a titanium dioxide layer crystallized in the same manner as in Example 1 was prepared, except that the anodic oxidation was performed for 32 minutes instead of 5 minutes.
Comparative Example One
An ethanol solution of 0.5 mM TTIP (titanium isopropoxide) and an ethanol solution of 40 mM HCl were slowly mixed, and the mixed solution was dropped on the same FTO substrate as in Example 1, spin-coated at 2000 rpm for 1 minute, And then heat-treated for 30 minutes to prepare an electrode laminate having a crystallized titanium dioxide layer. The crystallized titanium dioxide layer appeared to have a non-uniform thickness ranging from 20 to 150 nm.
Comparative Example 2
In the first anodization process, the titanium foil used as a substrate was immersed in an acetone / alcohol mixed solution, and ultrafine particles were removed therefrom. To obtain a titanium oxide (TiO 2 ) nanotube, a titanium foil was immersed in an ethylene glycol solution containing 0.25% ammonium fluoride (NH 4 F), and a voltage of 60 V was applied to the carbon rod as a counter electrode. Anodic oxidation. Thereafter, the sample was washed with acetone and alcohol to prepare titanium oxide nanotubes.
Then, the titanium oxide nanotubes are thermally treated at 250 ° C for 2 hours. At this time, the heat treatment temperature was not exceeded 250 占 폚.
The following secondary anodization was performed for 10 minutes under the same conditions as the primary anodization. At this time, new nanotubes are formed from the ends of the nanotubes formed in the first anodization, and consequently, two connected nanotube structures can be formed. The secondary anodization process aims to open the closure of the nanotubes formed during the primary anodization.
Next, two connected nanotubes were immersed in 33 wt% hydrogen peroxide (H 2 O 2 ) to separate them from the titanium foil and thin film separation took place in 5 minutes. After 30 minutes, the nanotube layer formed in the secondary anodization dissolved To form titanium oxide nanotubes having open structures at both ends, and the thickness thereof was measured to be about 14 μm.
Table 1 below shows the manufacturing conditions and results of the electrode laminate in which the crystallized titanium dioxide layers of Examples 1 to 12, Comparative Examples 1 and 2 were formed.
(minute)
(Unevenness)
Device Example One: Perovskite Manufacture of solar cells
The sheet resistance 8Ω / □ of fluorine-doped SnO 2 (FTO) conducting glass (Pilkington TEC 8) to prepare and, FTO after some processing with 2M HCl solution containing a zinc powder, washed with detergent, acetone preparing FTO substrate Respectively. A TiO 2 electron transport layer was formed in the same manner as in Example 1 using the prepared FTO substrate.
Then, an Al 2 O 3 solution was added dropwise to the TiO 2 electron transport layer and spin-coated at 2500 rpm for 1 minute. Al 2 O 3 The coated substrate was heat treated at 150 < 0 > C for 1 hour and cooled to room temperature.
In addition, PbCl 2 was mixed with DMF in a molar ratio of 3: 1 to prepare a 40 wt% perovskite precursor solution of CH 3 NH 3 PbI 3 - x Cl x (real number x ? 3 ).
The perovskite precursor solution was mixed with the Al 2 O 3 Spin coating at 2000 rpm for 60 seconds, and crystallization at 100 캜 for 2 hours to form a light absorbing layer having a perovskite structure.
Spiro-MeOTAD (Merck KGaA) chlorobenzene solution (180 mg / 1 ml) was spin coated on the light absorption layer at 2000 rpm for 60 seconds to form a hole transport layer. Silver (Ag) was deposited as a counter electrode on the hole transport layer to produce a perovskite solar cell.
Device Example 2: Perovskite Manufacture of solar cells
A perovskite solar cell was prepared in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 2 instead of the method of Example 1.
Device Example 3: Perovskite Manufacture of solar cells
A perovskite solar cell was produced in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 3 instead of the method of Example 1.
Device Example 4: Perovskite Manufacture of solar cells
A perovskite solar cell was prepared in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 4 instead of the method of Example 1.
Device Example 5: Perovskite Manufacture of solar cells
A perovskite solar cell was produced in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 5 instead of the method of Example 1.
Device Example 6: Perovskite Manufacture of solar cells
A perovskite solar cell was produced in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 6 instead of the method of Example 1.
Device Example 7: Perovskite Manufacture of solar cells
A perovskite solar cell was prepared in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 7 instead of the method of Example 1.
Device Example 8: Perovskite Manufacture of solar cells
A perovskite solar cell was prepared in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Example 8 instead of the method of Example 1.
Device comparison example One: Perovskite Manufacture of solar cells
A perovskite solar cell was produced in the same manner as in Example 1 except that the TiO 2 electron transport layer was formed by the method of Comparative Example 1 instead of the method of Example 1.
[Test Example]
Test Example 1: HR-SEM image analysis
4 shows HR-SEM images of the surface and cross-section of the titanium dioxide electron transport layer prepared according to Example 1, Comparative Example 1 and Comparative Example 2 of the present invention.
According to FIG. 4, it can be seen that the titanium dioxide electron transport layer of Example 1 appeared roughly like the surface of the FTO substrate, and it was judged that the titanium dioxide electron transport layer was formed to have a substantially uniform thickness according to the roughness of the surface of the FTO substrate . On the other hand, the titanium dioxide electron transport layer of Comparative Example 1 showed a smooth surface as compared to Example 1, and it was found that the titanium dioxide electron transport layer was formed with a non-uniform thickness on the surface of the FTO substrate. In addition, in the case of Comparative Example 2, it was found that the electron transport layer was formed in the form of nanotubes. The thickness of the electron transport layer was found to be significantly thicker than that of Example 1. Therefore, when the electron transport layer is formed by the method of Comparative Example 2, it can be applied to a conventional dye-sensitized solar cell, but it is difficult to apply it to a nano-level perovskite solar cell.
Test Example 2: Transmission Analysis
Fig. 5 shows the transmittances of the FTO substrates of Examples 1 to 4, Comparative Example 1 and before the formation of the electron transport layer. Specifically, FIG. 5A compares the transmittances of Example 1, Comparative Example 1 and FTO substrate, and FIG. 5B compares the transmittances according to the thickness of the
5 (a), the transmittance of the laminate of Example 1 was higher than that of Comparative Example 1, and it was found to be almost the same level as that of the FTO substrate. This result is considered to be because the electron transporting layer of Example 1 has a uniform thickness.
Further, according to Fig. 5 (b), the transmittance of the laminate was lower as the thickness of the titanium dioxide was larger in Examples 1 to 3. Therefore, it is most preferable to form an electron transport layer of about 40 nm in order to maintain the transmittance at a high level.
Test Example 3: Efficiency analysis of perovskite solar cell
6 shows the results of the analysis of the efficiency of the perovskite solar cell according to the device example 1 and the device comparative example 1. Fig.
Specifically, FIG. 6A shows the photovoltaic-light voltage (JV) characteristics of the perovskite solar cell according to the device example 1 and the device comparative example 1, wherein the intensity of light was measured at AM 1.5 . 6 (b) shows the incident photon-to-current efficiency (IPCE). The cell size used for the measurement was 0.09 cm < 2 > and the measurement direction was observed while changing from 1.2 V to 0 V. [
6 (a), the photovoltaic-light voltage (J-V) characteristic of the perovskite solar cell of the device example 1 was superior to that of the device comparative example 1. The power conversion efficiency (η) of the comparative example 1 was 10.5% and that of the comparative example 1 was 13.6%.
6B, the perovskite solar cell of the device example 1 is superior to the device comparative example 1 in IPCE.
Therefore, the perovskite solar cell using the titanium dioxide electron transport layer formation method using the anodic oxidation method of the present invention is considered to have superior energy conversion efficiency as compared with the conventional method of forming the titanium dioxide electron transport layer by the spin coating method do.
Test Example 4: Efficiency analysis of perovskite solar cell according to thickness of electron transport layer
FIG. 7 shows the photocurrent-light voltage (J-V) characteristics of the perovskite solar cell according to the
According to Fig. 7 and Table 2, the efficiency of the device example 1 having the electron transporting layer with a thickness of 40 nm is the most excellent in J SC = 22.7 mA / cm 2 , V OC = 0.91 V, FF = 65.8% and eta = 13.6% Respectively.
It can be judged that the electron transport layer is inefficient in extracting electrons, similar to the problem of comparative element example 1, which is low in efficiency of the thick solar cell (element embodiment 3).
Test Example 5: Adjustment of voltage and time of anodic oxidation Electron transport layer And Perovskite Characteristics of Solar Cell
Figure 8 shows a surface HR-SEM image of a titanium dioxide electron transport layer formed according to Examples 8-12.
According to FIG. 8, the surface voltage was changed from 3 V to 10 V in the formation of the titanium dioxide electron transport layer. At this time, in the case of Example 6 in which the anodic oxidation was performed at a voltage of 4 V, the electron transport layer was most uniformly formed on the FTO substrate, and a coral shape was formed. In addition, it was found that the electron transport layer starts to become nonuniform when it is higher than 10V. Therefore, it is found that it is most preferable to carry out the anodic oxidation under the conditions of the voltage of about 4 to 5 V, that is, the conditions of Example 1 and Example 6 of the present invention, in order to form a uniform titanium dioxide electron transport layer have.
9 shows photocurrent-light voltage (J-V) characteristics of the perovskite solar cell manufactured according to the
According to FIG. 9 and Table 3, it can be seen that an appropriate anodizing voltage is a factor determining the efficiency of the perovskite solar cell. The shape of the titanium dioxide was changed according to the voltage condition of anodization as shown.
However, when the anodization is performed under the condition that the voltage is lower than 3V, the titanium dioxide is not formed well, and the surface of the FTO substrate is exposed at a too high voltage.
Therefore, it is considered that anodization at a voltage of about 5 V is the most suitable method for improving the efficiency of a perovskite solar cell in order to form a titanium dioxide electron transport layer.
The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.
Claims (18)
(b) preparing a titanium dioxide (TiO 2) layer by oxidizing the titanium layer by anodic oxidation; And
(c) heat treating the titanium dioxide layer to produce an electron transport layer which is a crystallized titanium dioxide layer;
Including,
The anodic oxidation method is performed for 4 to 6 minutes under a voltage of 4 to 6 V so that the surface shape of the electron transport layer is formed to correspond to the surface shape of the electrode, Which is uniformly formed on the basis of the above-
A method for manufacturing an electrode laminate for a perovskite solar cell.
Characterized in that the electrode comprises at least one selected from the group consisting of fluorine tin oxide (FTO), indium tin oxide (ITO), ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , tin oxide, Wherein the electrode layer is formed on the electrode layer.
Wherein the titanium layer is formed on the electrode by sputtering coating or atomic layer deposition. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the titanium layer is formed to a thickness of 10 to 100 nm. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the titanium layer is formed to a thickness of 20 to 80 nm. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the heat treatment is performed at 400 to 600 占 폚.
Wherein the heat treatment is performed at 400 to 500 占 폚.
Wherein the crystallized titanium dioxide layer comprises an anatase crystal. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the anodic oxidation method is performed in an electrolyte including ammonium fluoride.
(B) washing with alcohol after step (b) is carried out. ≪ RTI ID = 0.0 > 11. < / RTI >
The method for manufacturing the perovskite solar cell includes:
After step c,
(d) coating a perovskite precursor on the electron transport layer;
(e) heat treating the perovskite precursor to form a perovskite light absorbing layer;
(f) forming a hole transporting layer on the perovskite light absorbing layer; And
(g) forming a counter electrode by coating a conductive electrode material on the hole transport layer. < Desc / Clms Page number 20 >
Step c of the method after step d prior to, perovskite solar cell, comprising a step of further comprising the step of coating the aluminum (Al 2 O 3) oxide on the titanium dioxide electron transport layer.
Wherein the conductive electrode material comprises at least one selected from the group consisting of Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C and a conductive polymer. ≪ / RTI >
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| KR102106643B1 (en) | 2019-03-20 | 2020-05-04 | 한국전력공사 | Method for the fabrication of perovskite solar cell and perovskite solar cell using the same |
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| KR102093431B1 (en) * | 2018-09-13 | 2020-03-25 | 경북대학교 산학협력단 | Perovskite solar cell and method of preparing the Perovskite solar cell |
| KR102106643B1 (en) | 2019-03-20 | 2020-05-04 | 한국전력공사 | Method for the fabrication of perovskite solar cell and perovskite solar cell using the same |
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