WO2018124459A1 - Perovskite compound and preparation method therefor, and solar cell comprising perovskite compound and manufacturing method therefor - Google Patents
Perovskite compound and preparation method therefor, and solar cell comprising perovskite compound and manufacturing method therefor Download PDFInfo
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- WO2018124459A1 WO2018124459A1 PCT/KR2017/012676 KR2017012676W WO2018124459A1 WO 2018124459 A1 WO2018124459 A1 WO 2018124459A1 KR 2017012676 W KR2017012676 W KR 2017012676W WO 2018124459 A1 WO2018124459 A1 WO 2018124459A1
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Images
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- C—CHEMISTRY; METALLURGY
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- C01G29/00—Compounds of bismuth
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/90—Antimony compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/94—Bismuth compounds
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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
- H01L31/0216—Coatings
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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
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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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- 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
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a perovskite compound, a method for producing the same, a solar cell including the perovskite compound and a method for producing the same.
- Solar cells are a technology field that is attracting attention at the present time when there is an urgent need for alternative energy as a means for converting solar energy into electrical energy.
- silicon-based solar cells include polycrystalline silicon, monocrystalline silicon, and thin-film silicon solar cells, among which polycrystalline silicon is mainly commercialized.
- the silicon crystals have to be heated and melted to a high temperature to form a predetermined thickness or more, and then the crystals must be gradually grown.
- Perovskite materials are attracting attention as a substitute for silicon materials because they have an ideal band gap and high light absorption for converting light into electricity.
- the solar cell using the perovskite material can be implemented in a relatively simple and less expensive than using a silicon crystal, it can compensate for the disadvantages of the silicon-based solar cell in terms of manufacturing process.
- the efficiency of the solar cell is higher than the initial development stage, and thus it is recognized as an advantageous material in terms of efficiency improvement.
- the perovskite material is vulnerable to moisture tends to decrease the efficiency rapidly over time, there is a problem that the durability is weak at high temperatures.
- the perovskite material has a problem in terms of toxicity because heavy metals such as Pb is used, there is a certain restriction in using as a solar cell material.
- an object of the present invention is to provide a high efficiency solar cell and a method of manufacturing the same using the perovskite compound and a method for producing the same according to an embodiment of the present invention.
- an object of the present invention is to provide a highly stable perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
- an object of the present invention is to provide a perovskite compound, a method for producing the same, a solar cell, and a method for manufacturing the same, which are easy and economical to manufacture.
- an object of the present invention is to provide an environmentally friendly perovskite compound and a method for manufacturing the same, a solar cell comprising the perovskite compound and a method for producing the same.
- a perovskite compound represented by the following formula is provided.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Z is one of F, I, Br, and Cl
- the perovskite compound has a triclinic crystal structure.
- the first electrode A light absorbing layer formed on the first electrode; And a second electrode formed on the light absorbing layer, wherein the light absorbing layer is provided with a solar cell including a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Z is one of F, I, Br, and Cl
- the perovskite compound has a triclinic crystal structure.
- the first electrode may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And a TiO 2 layer formed on the first substrate.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the flexible transparent electrode substrate is polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), ethylene vinyl Acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate (PCTG), modified triacetylcellulose (TAC), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydimethylsilone It may be formed of a polymer substrate selected from the group consisting of phosphine (PDMS), silicone resin, fluorine resin and modified epoxy resin
- the TiO 2 layer is a blocking TiO 2 layer; And a mesoporous TiO 2 layer formed on the blocking TiO 2 layer.
- the first electrode may further include a ZrO 2 layer formed on the TiO 2 layer.
- the second electrode may include carbon.
- the step of preparing a XZ compound powder and YZ 3 compound powder comprising the step of preparing a compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Z is one of F, I, Br, and Cl
- the compound represented by the above formula may have a triclinic crystal structure.
- the concentration of the XZ compound may be 1 mol, and the concentration of the YZ 3 compound may be 3 mol.
- forming a first electrode Forming a light absorbing layer on the first electrode; And forming a second electrode on the light absorbing layer, wherein the light absorbing layer is provided with a solar cell manufacturing method including a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Z is one of F, I, Br, and Cl
- the perovskite compound has a triclinic crystal structure.
- the forming of the first electrode may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And forming a TiO 2 layer on the first substrate.
- a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
- the forming of the first electrode may further include forming a ZrO 2 layer on the TiO 2 layer.
- the forming of the light absorbing layer may include forming a X a Y b Z c solution; And dropping, spin coating, or screen printing the X a Y b Z c solution on the first electrode.
- the forming of the X a Y b Z c solution may include preparing an XZ compound powder and a YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; Heat-treating the mixed powder to prepare a compound represented by the following formula; And dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent.
- DMF dimethyl formamide
- DMSO dimethyl sulfoxide
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Z is one of F, I, Br, and Cl
- the compound represented by the above formula may have a triclinic crystal structure.
- the forming of the light absorbing layer may further include drying the X a Y b Z c solution.
- the forming of the second electrode may include preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; Preparing a carbon powder; Coating the carbon powder on the second substrate; And heat treating the second substrate coated with the carbon powder.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the forming of the second electrode may include applying a paste containing carbon on the light absorbing layer.
- the present invention can provide a highly efficient perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
- the present invention can provide a highly stable perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
- the present invention can provide a perovskite compound, a method for producing the same, a solar cell, and a method for manufacturing the same, which are easy and economical to manufacture.
- the present invention can provide an environmentally friendly perovskite compound, a method for producing the same, a solar cell including the perovskite compound and a method for producing the same.
- FIG. 1 is a view showing a perovskite compound according to an embodiment of the present invention.
- FIG. 2 is a photograph of the coating of the perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
- 3 is a bandgap graph of a perovskite compound according to an embodiment of the present invention.
- FIG. 6 is a view schematically showing a solar cell according to an embodiment of the present invention.
- FIG. 7 is a photograph of a solar cell according to an embodiment of the present invention.
- FIG. 8 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- FIG. 11 is a graph comparing the efficiency of the solar cell according to the embodiment of the present invention and the solar cell of the prior art.
- FIG. 12 is a graph comparing the efficiency change of the solar cell according to the prior art (comparative example) and the solar cell according to the embodiment of the present invention over time.
- FIG. 13 is a view showing a perovskite compound according to an embodiment of the present invention.
- FIG. 14 is a photograph of a perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
- FIG. 15 is a view schematically showing a solar cell according to an embodiment of the present invention.
- FIG. 16 is a photograph of a solar cell according to an embodiment of the present invention.
- FIG. 17 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- 19 to 21 is a graph comparing the efficiency according to the thickness change of TiO 2 according to the experimental example of the present invention.
- FIG. 22 is an AFM photograph of a perovskite compound according to an embodiment of the present invention.
- Figure 23 is a XRD measurement result showing the structural change before and after heat treatment in the perovskite compound production method according to an embodiment of the present invention.
- 24 is a view showing the change in light absorbency before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
- 25 is a schematic view of a solar cell according to an embodiment of the present invention.
- 26 is a view showing the efficiency of the solar cell according to an embodiment of the present invention.
- FIG. 27 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- FIG. 28 is a view showing a crystal structure of a perovskite compound according to the embodiment of the present invention.
- 29 shows the theoretical bandgap of a perovskite compound in accordance with an embodiment of the present invention.
- FIG. 30 is a XRD measurement result diagram showing the structural change before and after heat treatment in the perovskite compound production method according to an embodiment of the present invention.
- FIG. 31 is a SEM photograph showing structural changes before and after heat treatment in a method of preparing perovskite compound according to an embodiment of the present invention.
- 32 is a view showing the change in light absorbency before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
- FIG 33 is a view showing a band gap change before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
- FIG. 34 is a schematic view of a solar cell according to an embodiment of the present invention.
- 35 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- the coupling does not only mean the case where the physical contact is directly between the components in the contact relationship between the components, other components are interposed between the components, the components in the other components Use it as a comprehensive concept until each contact.
- the perovskite compound according to the embodiment of the present invention follows the formula below.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the first perovskite compound follows the formula:
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Such a first perovskite compound may be referred to as 3-2-9 perovskite compound for convenience.
- Perovskite compound (X 3 Bi 2 Z 9 ) according to an embodiment of the present invention can improve the problem that the structure of the perovskite compound of the prior art vulnerable to moisture, low durability at high temperatures.
- the perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi, and thus may replace a highly toxic substance such as lead (Pb).
- the perovskite compound according to the embodiment of the present invention is excellent in terms of stability.
- Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
- the method for producing a perovskite compound according to an embodiment of the present invention comprises the steps of preparing an XZ compound powder, BiZ 3
- the method may include preparing a compound powder, mixing the XZ compound powder and the BiZ 3 compound powder to form a mixed powder, and heat treating the mixed powder to prepare a compound represented by the following formula. .
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the formula in the heat treatment of the mixed powder may be X 3 Bi 2 Z 9 .
- the heat treatment may include heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may be carried out in the range of 140 or more and 200 or less.
- the concentration of the XZ compound may be 1.5 mmol, and the concentration of the BiZ 3 compound may be 1 mmol.
- the heat treatment may be performed in 50 minutes or more and 70 minutes or less.
- FIG. 2 is a photograph of the coating of the perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
- FIG 3 is a bandgap graph of the perovskite compound according to an embodiment of the present invention
- Figure 4 is an XRD graph of the perovskite compound according to an embodiment of the present invention
- Figure 5 is an embodiment of the present invention TGA analysis graph of the perovskite compound according.
- the perovskite compound produced according to the perovskite compound manufacturing method according to an embodiment of the present invention can be seen that the bandgap energy is represented as 2.2eV high, X 3 Bi 2 It can be seen that the Y 9 crystal structure was formed.
- FIG. 6 is a view schematically showing a solar cell 1000 according to an embodiment of the present invention.
- 7 is a photograph showing a cross section of the solar cell 1000 according to an embodiment of the present invention.
- a solar cell may include a first electrode 100, a light absorbing layer 200 formed on the first electrode, and a light absorbing layer 200 formed on the first electrode 100.
- Including a second electrode 300, the first electrode 100, the second electrode 300 may be formed by being bonded to the light absorbing layer by the adhesive force of the light absorbing layer 200.
- the light absorbing layer 200 includes a perovskite compound
- the perovskite compound may be represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the formula may be X 3 Bi 2 Z 9 .
- the first electrode 100 may include a TiO 2 layer 120 selected from an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, or a flexible transparent electrode substrate, and is formed on the selected substrate. Can be.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the flexible transparent electrode substrate includes a polymer substrate on which a metal wiring layer is formed, and the polymer substrate includes polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), and polymethylmethacrylate ( PMMA), polyimide (PI), ethylene vinyl acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate ( PCTG), modified triacetylcellulose (TAC), cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), It may be a substrate selected from the group consisting of polyetherimide (PEI), polydimethylsilonce
- the substrate included in the first electrode of the present invention is not limited to the examples presented above.
- the TiO 2 layer 120 may include a blocking TiO 2 layer 122 and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 layer 122.
- the TiO 2 layer 120 may function as an electron transport layer.
- the first electrode 100 may further include a ZrO 2 layer 130, as with the TiO 2 layer 120, and performs a ZrO 2 layer 130 functioning as an electron transport layer.
- the second electrode 300 may be a carbon electrode.
- Carbon electrode can maintain a high efficiency of the solar cell over time because a reaction such as oxidation does not occur by the perovskite compound.
- a carbon electrode may be bonded by an adhesive force of a perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
- FIG. 8 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- the first electrode 100 and the second electrode 300 is characterized in that the adhesive is formed by the light absorbing layer 200.
- forming the light absorbing layer 200 (S200) includes the step of forming a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the chemical formula in the step (S200) of forming the light absorbing layer 200 may be X 3 Bi 2 Z 9 .
- a first electrode preparing a substrate of any one of a flexible transparent electrode substrate, an indium tin oxide (ITO) substrate or a Fluorine Doped Tin Oxide (FTO) substrate (S110) and a flexible transparent electrode substrate, ITO
- the method may include forming a TiO 2 layer on any one of a substrate and a Fluorine Doped Tin Oxide (FTO) substrate (S120).
- Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer.
- FTO Fluorine Doped Tin Oxide
- the etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI.
- the cleaned Fluorine Doped Tin Oxide (FTO) substrate can be dried at 100 and treated for 600 seconds in a UV Ozone cleaner.
- Forming the TiO 2 layer (S120) may include forming a blocking TiO 2 layer and forming a Mesoporous TiO 2 layer on the blocking TiO 2 layer.
- Blocking forming a TiO 2 layer may include the step, step, drying the coated film to form the TiO 2 TiO 2 coating on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
- Titanium diisopropoxide bis (acetylacetonate) 75 wt The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
- TiO 2 coating film can be formed by spin coating at 2000rpm for 20s seconds.
- TiO 2 TiO 2 coating film may be dried by heat treatment at 125 or more for 5 minutes.
- the forming of the Mesoporous TiO 2 layer on the Blocking TiO 2 layer may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
- Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
- the TiO 2 coating film may be dried by heat treatment at 450 or more for 30 minutes.
- the forming of the first electrode (S100) may further include forming roughness on the mesoporous TiO 2 layer (S140).
- TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer.
- the first heat treatment step may be performed at a temperature range of 70 to 100, and the second heat treatment step may be performed at 450 or more 30 minutes.
- the adhesion between the light absorbing layer and the TiO 2 layer may be further improved.
- Forming the light absorbing layer (S200) may include forming an X 3 Bi 2 Z 9 solution.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the formula may be X 3 Bi 2 Z 9 .
- an X 3 Bi 2 Z 9 solution may be disposed between the first electrode 100 and the second electrode 300.
- Dropping (S260) or by spin coating the X 3 Bi 2 Z 9 solution on the first electrode or the second electrode may be formed by selectively performing.
- forming the light absorbing layer (S200) may include drying the X 3 Bi 2 Z 9 solution (S270).
- the drying of the X 3 Bi 2 Y 9 solution may be performed at a temperature range of 0 to 200.
- the forming of the second electrode (S300) may include preparing a substrate of any one of a glass substrate, a glass substrate on which Fluorine Doped Tin Oxide (FTO) or an Indium Tin Oxide (ITO) is deposited, and a flexible transparent electrode substrate ( S310), preparing a carbon powder (S320), by using the carbon powder, any one of the glass substrate, FTO (Fluorine Doped Tin Oxide) or ITO (Indium Tin Oxide) is deposited and a flexible transparent electrode substrate It may include the step of coating the carbon powder on one substrate (S330) and the step of heat-treating the carbon powder-coated substrate (S340).
- FTO Fluorine Doped Tin Oxide
- ITO Indium Tin Oxide
- the heat treatment of the substrate coated with carbon powder (S340) may be performed at a temperature range of 300 or more.
- Heat treatment of the substrate coated with carbon powder (S340) may be performed for 25 to 35 minutes.
- the method may further include forming an adhesive layer on side surfaces of the light absorbing layer, the first electrode layer, the light absorbing layer, and the second electrode layer (S400).
- the adhesive layer may be formed of an epoxy resin.
- the light absorbance of the perovskite compound increased as the heat treatment temperature was increased in the range of 200 at room temperature, but it was confirmed that it rapidly decreased in 300 (Experimental Example 6).
- the experimental results show that the perovskite compound has a different light absorbency according to the heat treatment temperature, and it can be confirmed that there is an appropriate heat treatment temperature.
- the light absorbance of the perovskite compound increased with increasing concentration in the range of 0.1M (Experimental Example 7) to 1.0M (Experimental Example 11), but 0.5 at 2.0M (Experimental Example 12). It can be seen that it was lower than M (Experimental Example 9) and decreased.
- the perovskite compound shows a result of different light absorbance according to the concentration, it can be confirmed that there is a proper concentration.
- the heat treatment temperature and concentration of the perovskite compound act as a factor influencing the light absorption. Specifically, the light absorption was the highest when the heat treatment temperature is 200 and the concentration is 1.0M.
- 11 is a graph comparing the efficiency of the solar cell according to the embodiment of the present invention and the solar cell of the prior art.
- 12 is a graph comparing the efficiency change of the solar cell according to the prior art (comparative example) and the solar cell according to the embodiment of the present invention over time.
- a solar cell comprising a first electrode, a light absorbing layer formed on the first electrode, and a second electrode formed on the light absorbing layer.
- Each component is deposited in a vacuum over 10 -5 torr using spin coating, vacuum evaporator
- FA 3 bi 2 I 9 powder was formed by heat treatment using the synthesized FAI powder and biI3 powder.
- It is formed by bonding the light absorbing layer and the first electrode, the light absorbing layer and the second electrode by using the adhesive force of the light absorbing layer.
- a junction solar cell according to an exemplary embodiment of the present invention is manufactured in that a process of Ag and Au in a vacuum state of 10 ⁇ 5 torr or more is performed to form a second electrode on a light absorbing layer. There is a difference in process.
- the solar cell (experimental example) according to the embodiment of the present invention is different in terms of structure from the laminated solar cell (comparative example) in that carbon material is used instead of metal.
- the junction type solar cell according to an exemplary embodiment of the present invention has been shown to have excellent durability in terms of its initial efficiency even after elapse of time.
- the carbon electrode is stable to the perovskite crystal structure and can maintain the light absorption of the perovskite compound even by mutual bonding.
- junction solar cell according to the embodiment of the present invention is implemented by performing a heat treatment process in a relatively low temperature range, not a deposition such as vacuum deposition process, it is easier than the stacked solar cell in terms of manufacturing process.
- the bonded solar cell according to the embodiment of the present invention is economical in terms of cost by using a carbon material other than a metal such as Ag and Au.
- FIG. 13 is a view showing a crystal structure of a perovskite compound according to an embodiment of the present invention.
- Perovskite compound (X 3 Sb 2 Y 9 ) according to an embodiment of the present invention can improve the problem that the perovskite compound structure of the prior art is vulnerable to moisture, low durability at high temperatures.
- the perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Sb, and thus may replace a highly toxic substance such as lead (Pb).
- the perovskite compound according to the embodiment of the present invention is excellent in terms of stability.
- FIG. 14 is a photograph of a perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
- Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
- the method for producing a perovskite compound according to an embodiment of the present invention comprises the steps of preparing a XZ compound powder, SbZ 3
- the method may include preparing a compound powder, mixing the XZ compound powder and the SbZ 3 compound powder to form a mixed powder, and heat treating the mixed powder to prepare a compound represented by the following formula. .
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
- the heat treatment may include heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may be carried out in the range of 140 °C 200 °C.
- the concentration of the XZ compound may be 1.5 mmol, and the concentration of the SbZ 3 compound may be 1 mmol.
- the heat treatment may be performed in 50 minutes or more and 70 minutes or less.
- 15 is a view schematically showing a solar cell 1000 according to an embodiment of the present invention.
- 16 is a photograph showing a cross section of a solar cell 1000 according to an embodiment of the present invention.
- a solar cell 1000 according to an embodiment of the present invention is disposed on a first electrode 100, a light absorbing layer 200, and a light absorbing layer 200 formed on the first electrode.
- a second electrode 300 is formed, the first electrode 100, the second electrode 300 may be formed by being bonded to the light absorbing layer by the adhesive force of the light absorbing layer 200.
- the light absorbing layer 200 may include a perovskite compound, and the perovskite compound may be represented by a chemical formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
- the first electrode 100 may include a TiO 2 layer 120 selected from an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, or a flexible transparent electrode substrate, and is formed on the selected substrate. Can be.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the flexible transparent electrode substrate includes a polymer substrate on which a metal wiring layer is formed, and the polymer substrate includes polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), and polymethylmethacrylate ( PMMA), polyimide (PI), ethylene vinyl acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate ( PCTG), modified triacetylcellulose (TAC), cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), It may be a substrate selected from the group consisting of polyetherimide (PEI), polydimethylsilonce
- the substrate included in the first electrode of the present invention is not limited to the examples presented above.
- the TiO 2 layer 120 may include a blocking TiO 2 layer 122 and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 layer 122.
- the TiO 2 layer 120 may function as an electron transport layer.
- the first electrode 100 may further include a ZrO 2 layer 130, as with the TiO 2 layer 120, and performs a ZrO 2 layer 130 functioning as an electron transport layer.
- the thickness of the TiO 2 layer may be formed in the range of 300 nm or more and 6 ⁇ m or less, and the thickness of the ZrO 2 layer may be formed in the range of 300 nm or more and 2 ⁇ m or less.
- the second electrode 300 may be a carbon electrode.
- Carbon electrode can maintain a high efficiency of the solar cell over time because a reaction such as oxidation does not occur by the perovskite compound.
- a carbon electrode may be bonded by an adhesive force of a perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
- FIG. 17 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
- forming the light absorbing layer 200 (S200) includes the step of forming a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the step of forming the light absorbing layer 200 (S200) the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
- Forming the first electrode (S100) comprises preparing a substrate of any one of a flexible transparent electrode substrate, an indium tin oxide (ITO) substrate or a Fluorine Doped Tin Oxide (FTO) substrate (S110) and a flexible transparent electrode substrate,
- the method may include forming a TiO 2 layer on one of an ITO substrate and a Fluorine Doped Tin Oxide (FTO) substrate (S120).
- Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer.
- FTO Fluorine Doped Tin Oxide
- the etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI.
- the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
- Forming the TiO 2 layer (S120) may include forming a blocking TiO 2 layer and forming a Mesoporous TiO 2 layer on the blocking TiO 2 layer.
- Blocking forming a TiO 2 layer may include the step, step, drying the coated film to form the TiO 2 TiO 2 coating on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
- Titanium diisopropoxide Sbs acetylacetonate 75 wt .
- The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
- TiO 2 coating film can be formed by spin coating at 2000rpm for 20s seconds.
- TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 °C 5 minutes.
- the forming of the Mesoporous TiO 2 layer on the Blocking TiO 2 layer may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
- Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
- the TiO 2 coating film may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
- the forming of the first electrode (S100) may further include forming roughness on the mesoporous TiO 2 layer (S140).
- TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer.
- the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C.
- the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
- the adhesion between the light absorbing layer and the TiO 2 layer may be further improved.
- Forming the light absorbing layer (S200) may include forming a X 3 Sb 2 Y 9 solution.
- Forming the X 3 Sb 2 Y 9 solution preparing a XZ compound powder (S210), preparing a SbZ 3 compound powder (S220), the XZ compound powder and the SbZ 3 compound powder mixed and mixed Forming a powder (S230), by heat-treating the mixed powder, to produce a compound represented by the following formula (S240) and the step of dissolving the heat-treated mixed powder in a DMF solvent (S250) may be included. .
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the formula in the step of heat-treating the mixed powder may be X 3 Sb 2 Z 9 .
- forming the light absorbing layer (S200) may include drying the X 3 Sb 2 Z 9 solution (S270).
- Drying the X 3 Sb 2 Z 9 solution may be carried out at a temperature range of 0 °C to 200 °C.
- the forming of the second electrode (S300) may include preparing a substrate of any one of a glass substrate, a glass substrate on which Fluorine Doped Tin Oxide (FTO) or an Indium Tin Oxide (ITO) is deposited, and a flexible transparent electrode substrate ( S310), preparing a carbon powder (S320), by using the carbon powder, any one of the glass substrate, FTO (Fluorine Doped Tin Oxide) or ITO (Indium Tin Oxide) is deposited and a flexible transparent electrode substrate It may include the step of coating the carbon powder on one substrate (S330) and the step of heat-treating the carbon powder coated substrate (S340).
- FTO Fluorine Doped Tin Oxide
- ITO Indium Tin Oxide
- the heat treatment of the substrate coated with carbon powder (S340) may be performed at a temperature range of 300 ° C. or higher.
- Heat treatment of the substrate coated with carbon powder (S340) may be performed for 25 to 35 minutes.
- the method may further include forming an adhesive layer on side surfaces of the light absorbing layer, the first electrode layer, the light absorbing layer, and the second electrode layer (S400).
- the adhesive layer may be formed of an epoxy resin.
- a solar cell comprising a first electrode, a light absorbing layer formed on the first electrode, and a second electrode formed on the light absorbing layer.
- Each component is deposited in a vacuum over 10 -5 torr using spin coating, vacuum evaporator
- a junction solar cell according to an exemplary embodiment of the present invention is manufactured in that a process of Ag and Au in a vacuum state of 10 ⁇ 5 torr or more is performed to form a second electrode on a light absorbing layer. There is a difference in process.
- the solar cell (experimental example) according to the embodiment of the present invention is different in terms of structure from the laminated solar cell (comparative example) in that carbon material is used instead of metal.
- the junction type solar cell according to the embodiment of the present invention has been shown to be excellent in terms of durability since the initial efficiency is maintained over time.
- the carbon electrode is stable to the perovskite crystal structure and can maintain the light absorption of the perovskite compound even by mutual bonding.
- TiO 2 according to the experimental example of the present invention
- the thickness change of each concentration is compared, and the efficiency of the solar cell at each thickness will be compared.
- TiO 2 concentration 500mg / ml
- TiO 2 thickness 1.5 ⁇ m
- TiO 2 thickness 500 nm
- 19 to 21 are TiO 2 according to the experimental example of the present invention. This is a graph comparing the efficiency according to the change in thickness.
- the efficiency of the solar cell according to the concentration of ZrO 2 formed on the TiO 2 is compared.
- the concentration of TiO 2 in Experimental Examples 4 and 5 was the same at 2 g / ml.
- the solar cell efficiency is 0.0002%.
- the efficiency of the solar cell is 4.57%, which is 500mg / ml. In, high efficiency was shown.
- the efficiency of the solar cell increased from 2.9% when ZrO 2 was not used to 4.57% when used.
- the bonded solar cell according to the exemplary embodiment of the present invention is implemented by performing a heat treatment process in a relatively low temperature range rather than a deposition process such as vacuum deposition, thereby making it easier than a stacked solar cell in terms of a manufacturing process.
- the bonded solar cell according to the embodiment of the present invention is economical in terms of cost by using a carbon material other than a metal such as Ag and Au.
- Perovskite compound according to an embodiment of the present invention may be represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- Such a second perovskite compound may be referred to as a perovskite compound having a 1-2-7 structure for convenience.
- the X 1 Y 2 Z 7 perovskite compound will be mainly described, but the description is 1.6 ⁇ b ⁇ 2.4, 5.6 ⁇ The same applies to all X a Y b Z c perovskite compounds that satisfy c ⁇ 8.4.
- the perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi and Sb, and thus may replace a highly toxic substance such as lead (Pb).
- the perovskite compound according to an embodiment of the present invention is not easily oxidized in the air is excellent in terms of stability.
- Figure 22 is an AFM picture of the perovskite compound according to an embodiment of the present invention.
- (A) is a partially enlarged view of FIG. 22 (b). 22 shows the flatness of RbBi 2 I 7 .
- Specific roughness of RbBi 2 I 7 of FIG. 22 is the same as that in Table 5 below.
- Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
- the method for producing a perovskite compound includes the steps of preparing an XZ compound powder and YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And heat treating the mixed powder to prepare a compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the formula in the heat treatment of the mixed powder may be X 1 Y 2 Z 7 .
- the heat treatment may include heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may be carried out in the range of 100 °C to 200 °C.
- the X 1 Y 2 Z 7 material may be finally formed. That is, the concentration of the XZ compound may be 1 mmol, and the concentration of the YZ 3 compound may be 2 mmol.
- the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
- Figure 23 and 24 are views showing the effect of the heat treatment step.
- Figure 23 is a XRD measurement results showing the structural change before and after the heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention
- Figure 24 is a perovskite compound preparation according to an embodiment of the present invention
- RbBi 2 I 7 was used, (a) before the heat treatment, and (b) after the heat treatment.
- Figure 24 shows the absorbance of the material when using UV-visible spectroscopy. Before the heat treatment, the absorption region was extended to approximately 600 nm, but after the heat treatment, the absorption region was expanded to 7000 nm (see shading).
- the absorption region of the material is enlarged by the heat treatment, and when such a material is used in the solar cell, the solar cell efficiency may increase.
- FIG 25 is a view schematically showing a solar cell according to an embodiment of the present invention
- Figure 26 is a view showing the efficiency of the solar cell according to an embodiment of the present invention.
- the solar cell according to the exemplary embodiment of the present invention is formed on the first electrode 100, the light absorbing layer 200 formed on the first electrode 100, and the light absorbing layer 200. It includes a second electrode 300, the light absorbing layer 200 includes a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the above formula may be X 1 Y 2 Z 7 .
- the first electrode 100 and the second electrode 300 may be attached to the light absorbing layer 200 by the adhesive force of the perovskite compound of the light absorbing layer 200.
- the first electrode 100 may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate, and a TiO 2 formed on the first substrate. It may include layer 120.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- TiO 2 formed on the first substrate. It may include layer 120.
- An ITO substrate is a glass substrate on which ITO is deposited
- an FTO substrate is a glass substrate on which FTO is deposited.
- the flexible transparent electrode substrate polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), Ethylene Vinyl Acetate (EVA), Amorphous Polyethylene Terephthalate (APET), Polypropylene Terephthalate (PPT), Polyethylene Terephthalate Glycerol (PETG), Polycyclohexylenedimethylene Terephthalate (PCTG), Modified Triacetyl Cellulose (TAC) ), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydie It may be formed of a polymer substrate selected from the group consisting of methylsilone silane (PDMS), silicone resin, fluorine resin and modified epoxy resin
- the flexible transparent electrode substrate is not limited to the examples presented above.
- the TiO 2 layer 120 may function as an electron transport layer.
- the TiO 2 layer 120 may include a blocking TiO 2 122 layer and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 122 layer.
- the first electrode 100 may further include a ZrO 2 layer 130.
- ZrO 2 layer 130 is formed on the TiO 2 layer 120, and performs a function as an electron transport layer, like TiO 2 layer 120.
- the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
- the second electrode 300 may include carbon. That is, the second electrode 300 may be a layer formed of carbon. In addition, the second electrode 300 may be coated with carbon powder on the second substrate.
- the second substrate may be a substrate selected from any one of a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the second electrode 300 may be formed on the light absorbing layer 200 in the air, and thus the second electrode 300 may be removed in a vacuum state. There is no need to form.
- the carbon electrode may be bonded by the adhesive force of the perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
- FIG. 26 illustrates that the first electrode 100 includes FTO, blocking TiO 2 122, a mesoporous TiO 2 layer 124, and a ZrO 2 layer 130, and the light absorbing layer 200 includes RbBi 2 I 7 .
- the second electrode 300 represents the efficiency of the solar cell using carbon formed in the FTO. Specific efficiency of the solar cell is shown in the following [Table 6].
- FF fill factor
- PCE power conversion efficiency
- FIG. 27 is a flowchart schematically illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
- the light absorbing layer 200 includes a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the above formula in the step of forming the light absorbing layer 200 may be X 1 Y 2 Z 7 .
- Forming the first electrode 100 may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
- the method may include forming a TiO 2 layer 120 on the S110 and the first substrate (S120).
- first substrate is implemented using the FTO substrate.
- FTO substrate the type of first substrate is not limited.
- Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer 120.
- FTO Fluorine Doped Tin Oxide
- the etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
- Forming the TiO 2 layer 120 may include forming a blocking TiO 2 layer 122 and forming a mesoporous TiO 2 layer 124 on the blocking TiO 2 122 layer. have.
- forming a blocking TiO 2 layer 122 may include the step, step, drying the TiO 2 coating to form the TiO 2 coating layer on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
- Titanium diisopropoxide bis (acetylacetonate) 75 wt The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
- TiO 2 coating film can be formed by spin-coating (spin coating) at 2000rpm for 20 seconds.
- TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 °C 5 minutes.
- Forming the mesoporous TiO 2 layer 124 on the blocking TiO 2 layer 122 may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
- Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
- the TiO 2 coating layer may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
- forming the first electrode 100 may further include forming roughness on the mesoporous TiO 2 layer 124.
- TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer 124.
- Forming the roughness may include preparing a mixed solution of 1 ml of 20 mM TiCl 4 solution and 99 ml of distilled water, impregnating the substrate on which the mesoporous TiO 2 layer 124 is formed, the first heat treatment step, A washing step, a drying step and a second heat treatment step may be performed.
- the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C.
- the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
- the adhesion between the light absorbing layer 200 and the TiO 2 layer 120 to be formed on the first electrode 100 is further improved. Can be.
- the forming of the first electrode 100 may further include forming a ZrO 2 layer 130 on the TiO 2 layer 120 (S130).
- the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 layer 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
- Forming a light absorbing layer (200) (S200) is A 1 B 2 C 7 to form a solution, and A 1 B 2 C 7 solution the second dropping (dropping) on the first electrode 100, spin coating It may include a step (S250) for (spin coating) or screen printing (screen printing).
- Forming the X 1 Y 2 Z 7 solution preparing a XZ compound powder and YZ 3 compound powder (S210), mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder (S220) ), Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) and dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent (S240) It may include.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the above formula in the heat treatment of the mixed powder may be X 1 Y 2 Z 7 .
- Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) may include the step of heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may be carried out in the range of 100 °C to 200 °C.
- the concentration of the XZ compound may be 1 mmol
- the concentration of the YZ 3 compound may be 2 mmol
- the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
- the X 1 Y 2 Z 7 solution is formed and then applied on the first electrode 100, wherein the X 1 Y 2 Z 7 solution application may be selectively performed during dropping, spin coating or screen printing.
- Forming the light absorbing layer 200 (S200) may further include the step (S250) of drying the X 1 Y 2 Z 7 solution. That is, a step of drying the X 1 Y 2 Z 7 solution applied on the first electrode 100 may be added. Drying the X 1 Y 2 Z 7 solution (S250) may be carried out at a temperature range of 0 °C to 200 °C.
- the forming of the second electrode 300 includes preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. (S310), preparing a carbon powder (S320), coating the carbon powder on the second substrate (S330), and heat treating the carbon substrate coated with the second substrate (S340). can do.
- the step (S340) of heat treating the second substrate coated with the carbon powder may be performed for 25 minutes to 35 minutes at a temperature of 300 ° C. or higher and 600 ° C. or lower.
- the forming of the second electrode 300 may include applying a paste including carbon powder on the light absorbing layer 200 and drying the paste.
- the third Perovskite Compound (1-3-10 Perovskite compound)
- the perovskite compound according to an embodiment of the present invention may be represented by the following formula.
- the largest atomic model is X
- the hidden atomic model is Y
- the small atomic model is Z.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- a: b: c 1: 3: 10.
- such a third perovskite compound may be referred to as a perovskite compound having a 1-3-10 structure for convenience.
- the X 1 Y 2 Z 7 perovskite compound will be mainly described, but the description is about 2.4 ⁇ b ⁇ 3.6, 8 ⁇ The same applies to all X a Y b Z c perovskite compounds that satisfy c ⁇ 12.
- the third perovskite compound may form a triclinic crystal structure.
- Solid materials may be classified into crystalline structures and non-crystalline or amorphous structures according to the order of atomic arrangements.
- the perovskite compound has a triclinic crystal structure in the crystalline structure.
- Figure 29 shows the theoretical bandgap of the perovskite compound, in particular CsBi 3 I 10 according to an embodiment of the present invention.
- the theoretical bandgap of the perovskite compound according to an embodiment of the present invention is 1.25 eV.
- the perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi and Sb, and thus may replace a highly toxic substance such as lead (Pb).
- the perovskite compound according to an embodiment of the present invention is not easily oxidized in the air is excellent in terms of stability.
- the theoretical band gap of the perovskite compound according to the embodiment of the present invention is 1.25 eV.
- the ideal bandgap of the light absorbing layer for the high efficiency solar cell is 1.4 eV and is similar to the band gap of the perovskite compound according to the embodiment of the present invention.
- the perovskite compound according to the embodiment of the present invention may contribute to the improvement of solar cell efficiency when used in a solar cell.
- Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
- the method for producing a perovskite compound includes the steps of preparing an XZ compound powder and YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And heat treating the mixed powder to prepare a compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the formula in the heat treatment of the mixed powder may be X 1 Y 3 Z 10 .
- the compound in the heat treatment step, may have a triclinic crystal structure.
- the perovskite compound When A is substituted and bonded to the empty space of XZ 3 of trigonal or rhombohedral crystal structure through heat treatment, when the chemical formula of X 1 Y 3 Z 10 is satisfied, the perovskite compound has a tetragonal crystal structure. Can be.
- Cs is substituted into the empty space of BiI 3 having a trigonal (rhombohedral) crystal structure through heat treatment. The structure is broken and finally CsBi 3 I 10 of the triclinic crystal structure is formed.
- the heat treatment may include heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may be 100 ° C or more and 200 ° C or less.
- the concentration of the XZ compound may be 1 mol
- the concentration of the YZ 3 compound may be 3 mol.
- the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
- Figure 30 to 33 are views showing the effect of the heat treatment step.
- Figure 30 is a XRD measurement results showing the structural change before and after the heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention
- Figure 31 is a perovskite compound preparation according to an embodiment of the present invention SEM picture showing the structural change before and after the heat treatment in the method
- Figure 32 is a view showing the change in light absorbance before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention
- Figure 33 is an embodiment of the present invention Figure showing the bandgap change before and after heat treatment in the perovskite compound manufacturing method according to the example.
- the material has a more dense structure after the heat treatment.
- the grain size of the thin film is increased, and as the grain size increases, solar cell efficiency may increase.
- Figure 32 shows the absorbance of the material when using UV-visible spectroscopy. Before the heat treatment, the absorption region was expanded to approximately 570 nm, but after the heat treatment, the absorption region was enlarged to 730 nm (see shading). In the actual picture, the orange film was changed to black, which is easy to absorb light.
- bandgap values obtained through the results of FIG. 32 The bandgap value was 2.3 eV before the heat treatment, but dropped to 1.8 eV after the heat treatment. 32 and 33, it can be interpreted that the band gap is lowered due to the heat treatment to increase the wavelength for absorbing light. As a result, the band gap of the perovskite compound is lowered to 1.25 to 1.8 eV due to the heat treatment, thereby approaching 1.4 eV. Thus, when the perovskite compound is used in a solar cell, the solar cell efficiency may increase.
- FIG. 34 is a view schematically showing a solar cell according to an embodiment of the present invention.
- the solar cell according to the embodiment of the present invention is formed on the first electrode 100, the light absorbing layer 200 formed on the first electrode 100, and the light absorbing layer 200. It includes a second electrode 300, the light absorbing layer 200 includes a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the above formula may be X 1 Y 3 Z 10 .
- the compound may have a triclinic crystal structure.
- the first electrode 100 and the second electrode 300 may be attached to the light absorbing layer 200 by the adhesive force of the perovskite compound of the light absorbing layer 200.
- the first electrode 100 may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate, and a TiO 2 formed on the first substrate. It may include layer 120.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- TiO 2 formed on the first substrate. It may include layer 120.
- An ITO substrate is a glass substrate on which ITO is deposited
- an FTO substrate is a glass substrate on which FTO is deposited.
- the flexible transparent electrode substrate polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), Ethylene Vinyl Acetate (EVA), Amorphous Polyethylene Terephthalate (APET), Polypropylene Terephthalate (PPT), Polyethylene Terephthalate Glycerol (PETG), Polycyclohexylenedimethylene Terephthalate (PCTG), Modified Triacetyl Cellulose (TAC) ), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydie It may be formed of a polymer substrate selected from the group consisting of methylsilone silane (PDMS), silicone resin, fluorine resin and modified epoxy resin
- the flexible transparent electrode substrate is not limited to the examples presented above.
- the TiO 2 layer 120 may function as an electron transport layer.
- the TiO 2 layer 120 may include a blocking TiO 2 122 layer and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 122 layer.
- the first electrode 100 may further include a ZrO 2 layer 130.
- ZrO 2 layer 130 is formed on the TiO 2 layer 120, and performs a function as an electron transport layer, like TiO 2 layer 120.
- the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
- the second electrode 300 may include carbon. That is, the second electrode 300 may be a layer formed of carbon. In addition, the second electrode 300 may be coated with carbon powder on the second substrate.
- the second substrate may be a substrate selected from any one of a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
- ITO indium tin oxide
- FTO fluorine doped tin oxide
- the second electrode 300 may be formed on the light absorbing layer 200 in the air, and thus the second electrode 300 may be removed in a vacuum state. There is no need to form.
- the carbon electrode may be bonded by the adhesive force of the perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
- 35 is a flowchart schematically illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
- the light absorbing layer 200 includes a perovskite compound represented by the following formula.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the perovskite compound represented by the above formula may be X 1 Y 3 Z 10 .
- the perovskite compound may form a triclinic crystal structure.
- Forming the first electrode 100 may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
- the method may include forming a TiO 2 layer 120 on the S110 and the first substrate (S120).
- first substrate is implemented using the FTO substrate.
- FTO substrate the type of first substrate is not limited.
- Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer 120.
- FTO Fluorine Doped Tin Oxide
- the etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
- Forming the TiO 2 layer 120 may include forming a blocking TiO 2 layer 122 and forming a mesoporous TiO 2 layer 124 on the blocking TiO 2 122 layer. have.
- forming a blocking TiO 2 layer 122 may include the step, step, drying the TiO 2 coating to form the TiO 2 coating layer on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
- Titanium diisopropoxide bis (acetylacetonate) 75 wt The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
- TiO 2 coating film can be formed by spin-coating (spin coating) at 2000rpm for 20 seconds.
- TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 °C 5 minutes.
- Forming the mesoporous TiO 2 layer 124 on the blocking TiO 2 layer 122 may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
- Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
- the TiO 2 coating layer may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
- forming the first electrode 100 may further include forming roughness on the mesoporous TiO 2 layer 124.
- TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer 124.
- Forming the roughness may include preparing a mixed solution of 1 ml of 20 mM TiCl 4 solution and 99 ml of distilled water, impregnating the substrate on which the mesoporous TiO 2 layer 124 is formed, the first heat treatment step, A washing step, a drying step and a second heat treatment step may be performed.
- the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C.
- the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
- the adhesion between the light absorbing layer 200 and the TiO 2 layer 120 to be formed on the first electrode 100 is further improved. Can be.
- the forming of the first electrode 100 may further include forming a ZrO 2 layer 130 on the TiO 2 layer 120 (S130).
- the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 layer 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
- Forming a light absorbing layer (200) (S200) is A 1 B 3 C 10 to form a solution, and A 1 B 3 C 10 solution to the first electrode 100 is dropping (dropping), spin-coated on the (Spin coating) or screen printing (screen printing) may include the step (S250).
- Forming the X 1 Y 3 Z 10 solution preparing a XZ compound powder and YZ 3 compound powder (S210), mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder (S220) ), Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) and dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent (S240) It may include.
- X FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
- the compound represented by the above formula may be X 1 Y 3 Z 10 .
- the heat treatment of the mixed powder to prepare a compound represented by the chemical formula (S230) may include heating the mixed powder in a heating furnace.
- the temperature in the heating furnace may range from 100 ° C. to 200 ° C.
- the compound may have a triclinic crystal structure.
- X is substituted and bonded to the empty space of XZ 3 of trigonal or rhombohedral crystal structure, and when the chemical formula of X 1 Y 3 Z 10 is satisfied, the perovskite compound has a tetragonal crystal structure. Can be.
- Cs is substituted into the empty space of BiI 3 having a trigonal (rhombohedral) crystal structure through heat treatment. The structure is broken and finally CsBi 3 I 10 of the triclinic crystal structure is formed.
- the concentration of the XZ compound may be 1 mol
- the concentration of the YZ 3 compound may be 3 mol.
- the step of the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
- the application of the X 1 Y 3 Z 10 solution may be selectively performed during dropping, spin coating, screen printing.
- Forming the light absorbing layer 200 (S200) may further include the step (S250) of drying the X 1 Y 3 Z 10 solution. That is, a step of drying the X 1 Y 3 Z 10 solution applied on the first electrode 100 may be added. Drying the X 1 Y 3 Z 10 solution (S250) may be carried out at a temperature range of 0 °C to 200 °C.
- the forming of the second electrode 300 includes preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. (S310), preparing a carbon powder (S320), coating the carbon powder on the second substrate (S330), and heat treating the carbon substrate coated with the second substrate (S340). can do.
- the step (S340) of heat treating the second substrate coated with the carbon powder may be performed for 20 minutes to 40 minutes at a temperature of 300 ° C. or higher and 600 ° C. or lower.
- the forming of the second electrode 300 may include applying a carbon-containing paste on the light absorbing layer 200, and may further include drying the paste.
Abstract
A perovskite compound of the present invention is represented by the following chemical formula. [Chemical formula] XaYbZc, X = one of FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, and Li; Y = one of Bi and Sb; Z = one of F, I, Br, and C1; 0.5<b<0.7 and 2.5<c<3.5, 1.6<b<2.4 and 5.6<c<8.4, or 2.4<b<3.6 and 8<c<12 is satisfied when a = 1; and the perovskite compound has a triclinic crystalline structure when a=1, 2.4<b<3.6, and 8<c<12.
Description
본 발명은 페로브스카이트 화합물 및 그 제조방법, 페로브스카이트 화합물을 포함하는 태양전지 및 그 제조방법에 관한 것이다.The present invention relates to a perovskite compound, a method for producing the same, a solar cell including the perovskite compound and a method for producing the same.
태양 전지는 태양광 에너지를 전기에너지로 변환할 수 있는 수단으로 대체 에너지에 대한 요구가 시급한 현 시점에서 주목 받고 있는 기술 분야이다. Solar cells are a technology field that is attracting attention at the present time when there is an urgent need for alternative energy as a means for converting solar energy into electrical energy.
현재 상용화되고 있는 태양 전지는 실리콘 계열의 태양전지가 주류를 이루고 있다. Currently commercially available solar cells include silicon-based solar cells.
구체적으로 실리콘 계열의 태양전지는 다결정 실리콘, 단결정 실리콘, 박막 실리콘 태양전지가 있으며, 그 중에서도 다결정 실리콘이 주로 상용화 되고 있다. Specifically, silicon-based solar cells include polycrystalline silicon, monocrystalline silicon, and thin-film silicon solar cells, among which polycrystalline silicon is mainly commercialized.
한편, 단결정 실리콘 태양전지는 신뢰성이 높아 가장 오래 사용되었으며, 실리콘을 이용하는 태양 전지 중에서는 가장 변환 효율이 좋다.On the other hand, single crystal silicon solar cells have long been used because of their high reliability, and among the solar cells using silicon, the conversion efficiency is the best.
다만, 고온에서는 오히려 비결정 실리콘 태양전지 보다 변환 효율이 낮아지는 문제점이 있다. However, there is a problem that the conversion efficiency is lower than the amorphous silicon solar cell at a high temperature.
또한, 실리콘 결정을 이용한 태양전지는 실리콘 결정이 일정 두께 이상 형성하기 위해 모래를 고온으로 가열해 녹인 후 서서히 결정을 성장시켜야 된다. In addition, in the solar cell using silicon crystals, the silicon crystals have to be heated and melted to a high temperature to form a predetermined thickness or more, and then the crystals must be gradually grown.
따라서, 실리콘 결정을 일정 두께 이상 형성하기 위해서는 많은 전력이 소모된다. Therefore, a large amount of power is consumed to form the silicon crystal more than a certain thickness.
더 나아가, 실리콘 결정을 이용한 태양전지는 효율 측면에서 개선되지 않고 일정 수준에서 머물고 있어 보다 나은 재료의 개발을 통한 효율 개선 요구가 증가되고 있는 상황이다. Furthermore, solar cells using silicon crystals do not improve in terms of efficiency, but remain at a certain level, and demand for efficiency improvement through the development of better materials is increasing.
페로브스카이트 소재는 광을 전기로 변환하는데 이상적인 밴드 갭과 높은 광 흡수도를 가져 실리콘 소재를 대체할 소재로서 주목 받고 있다. Perovskite materials are attracting attention as a substitute for silicon materials because they have an ideal band gap and high light absorption for converting light into electricity.
또한, 페로브스카이트 소재를 이용한 태양전지는 실리콘 결정을 이용하는 경우 보다 비용이 적게 들고 비교적 간단하게 구현될 수 있어, 제조 공정 측면에서도 실리콘 기반의 태양 전지의 단점을 보완할 수 있다. In addition, the solar cell using the perovskite material can be implemented in a relatively simple and less expensive than using a silicon crystal, it can compensate for the disadvantages of the silicon-based solar cell in terms of manufacturing process.
더 나아가, 페로브스카이트 소재를 이용한 경우 태양 전지의 효율이 초기 개발 단계보다 높은 상승세를 보여 효율 개선 측면에서도 유리한 소재로 인정받고 있다. Furthermore, when the perovskite material is used, the efficiency of the solar cell is higher than the initial development stage, and thus it is recognized as an advantageous material in terms of efficiency improvement.
다만, 페로브스카이트 소재는 습기에 취약해 시간 경과에 따라 효율이 급격히 감소하는 경향이 있으며, 고온에서 내구성이 취약한 문제점이 있다. However, the perovskite material is vulnerable to moisture tends to decrease the efficiency rapidly over time, there is a problem that the durability is weak at high temperatures.
또한, 페로브스카이트 소재는 Pb와 같은 중금속이 이용되어 유독성 측면에서도 문제점이 있어, 태양전지의 소재로 이용함에 있어 일정한 제약이 따른다. In addition, the perovskite material has a problem in terms of toxicity because heavy metals such as Pb is used, there is a certain restriction in using as a solar cell material.
본 발명의 배경기술은 한국등록특허 제10-1688222호에 개시되어 있다.Background art of the present invention is disclosed in Korea Patent Registration No. 10-1688222.
본 발명의 일측면에 따르면, 본 발명의 목적은 본 발명의 실시예에 따른 페로브스카이트 화합물 및 그 제조방법을 이용하여, 고효율의 태양전지 및 그 제조방법을 제공하기 위한 것이다.According to an aspect of the present invention, an object of the present invention is to provide a high efficiency solar cell and a method of manufacturing the same using the perovskite compound and a method for producing the same according to an embodiment of the present invention.
본 발명의 다른 측면에 따르면, 본 발명의 목적은 안정성이 높은 페로브스카이트 화합물 및 그 제조방법, 태양전지 및 그 제조방법을 제공하기 위한 것이다.According to another aspect of the present invention, an object of the present invention is to provide a highly stable perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
본 발명의 또 다른 측면에 따르면, 본 발명의 목적은 제조 공정이 용이하고 경제적인 페로브스카이트 화합물 및 그 제조방법, 태양전지 및 그 제조방법을 제공하기 위한 것이다. According to still another aspect of the present invention, an object of the present invention is to provide a perovskite compound, a method for producing the same, a solar cell, and a method for manufacturing the same, which are easy and economical to manufacture.
본 발명의 또 다른 측면에 따르면, 본 발명의 목적은 친환경적인 페로브스카이트 화합물 및 그 제조방법, 페로브스카이트 화합물을 포함하는 태양전지 및 그 제조방법을 제공하기 위한 것이다.According to another aspect of the present invention, an object of the present invention is to provide an environmentally friendly perovskite compound and a method for manufacturing the same, a solar cell comprising the perovskite compound and a method for producing the same.
본 발명의 일 측면에 따르면, 하기의 화학식으로 표시되는 페로브스카이트 화합물이 제공된다.According to one aspect of the present invention, a perovskite compound represented by the following formula is provided.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,
a=1에 대하여, for a = 1,
0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12
을 만족하고, Satisfying,
a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐.When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
본 발명의 일 측면에 따르면, 제1 전극; 상기 제1 전극 상에 형성되는 광 흡수층; 및 상기 광 흡수층 상에 형성되는 제2 전극을 포함하고, 상기 광 흡수층은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함하는 태양전지가 제공된다.According to an aspect of the invention, the first electrode; A light absorbing layer formed on the first electrode; And a second electrode formed on the light absorbing layer, wherein the light absorbing layer is provided with a solar cell including a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,
a=1에 대하여, for a = 1,
0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12
을 만족하고, Satisfying,
a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐.When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
상기 제1 전극은 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판; 및 상기 제1 기판 상에 형성되는 TiO2층을 포함할 수 있다.The first electrode may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And a TiO 2 layer formed on the first substrate.
상기 유연 투명 전극 기판은, 폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성 에폭시수지로 이루어지는 군으로부터 선택되는 폴리머 기판으로 형성될 수 있다.The flexible transparent electrode substrate is polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), ethylene vinyl Acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate (PCTG), modified triacetylcellulose (TAC), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydimethylsilone It may be formed of a polymer substrate selected from the group consisting of phosphine (PDMS), silicone resin, fluorine resin and modified epoxy resin.
상기 TiO2층은, blocking TiO2층; 및 상기 blocking TiO2층 상에 형성되는 mesoporous TiO2층을 포함할 수 있다.The TiO 2 layer is a blocking TiO 2 layer; And a mesoporous TiO 2 layer formed on the blocking TiO 2 layer.
상기 제1 전극은 상기 TiO2층 상에 형성되는 ZrO2층을 더 포함할 수 있다.The first electrode may further include a ZrO 2 layer formed on the TiO 2 layer.
상기 제2 전극은 카본을 포함할 수 있다.The second electrode may include carbon.
본 발명의 일 측면에 따르면, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; 상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; 및 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함하는, 페로브스카이트 화합물 제조방법이 제공된다.According to one aspect of the invention, the step of preparing a XZ compound powder and YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And by heat-treating the mixed powder, there is provided a method for producing a perovskite compound comprising the step of preparing a compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,
a=1에 대하여, for a = 1,
0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12
을 만족하고, Satisfying,
상기 혼합 분말을 열처리하는 단계에서, In the step of heat-treating the mixed powder,
a=1, 2.4<b<3.6, 8<c<12인 경우, 상기의 화학식으로 표시되는 화합물은 삼사정계(triclinic)의 결정 구조를 가질 수 있다.When a = 1, 2.4 <b <3.6, and 8 <c <12, the compound represented by the above formula may have a triclinic crystal structure.
상기 XZ 화합물의 농도는 1mol이고, 상기 YZ3화합물의 농도는 3mol일 수 있다.The concentration of the XZ compound may be 1 mol, and the concentration of the YZ 3 compound may be 3 mol.
본 발명의 일 측면에 따르면, 제1 전극을 형성하는 단계; 상기 제1 전극 상에 광 흡수층을 형성하는 단계; 및 상기 광 흡수층 상에 제2 전극을 형성하는 단계를 포함하고, 상기 광 흡수층은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함하는 태양전지 제조방법이 제공된다.According to an aspect of the invention, forming a first electrode; Forming a light absorbing layer on the first electrode; And forming a second electrode on the light absorbing layer, wherein the light absorbing layer is provided with a solar cell manufacturing method including a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,
a=1에 대하여, for a = 1,
0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12
을 만족하고, Satisfying,
a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐.When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
상기 제1 전극을 형성하는 단계는, 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판을 준비하는 단계; 및 상기 제1 기판 상에 TiO2층을 형성하는 단계를 포함할 수 있다.The forming of the first electrode may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And forming a TiO 2 layer on the first substrate.
상기 제1 전극을 형성하는 단계는, 상기 TiO2층 상에 ZrO2층을 형성하는 단계를 더 포함할 수 있다.The forming of the first electrode may further include forming a ZrO 2 layer on the TiO 2 layer.
상기 광 흡수층을 형성하는 단계는, XaYbZc 용액을 형성하는 단계; 및 XaYbZc 용액을 상기 제1 전극 상에 드롭핑(dropping), 스핀 코팅(spin coating) 또는 스크린 프린팅(screen printing)하는 단계를 포함할 수 있다.The forming of the light absorbing layer may include forming a X a Y b Z c solution; And dropping, spin coating, or screen printing the X a Y b Z c solution on the first electrode.
상기 XaYbZc 용액을 형성하는 단계는, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; 상기 XZ 화합물 분말 및 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계; 및 상기 열처리 된 혼합 분말을 DMF(dimethyl formamide) 또는 DMSO(Dimethyl sulfoxide) 용매에 용해시키는 단계를 포함할 수 있다. The forming of the X a Y b Z c solution may include preparing an XZ compound powder and a YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; Heat-treating the mixed powder to prepare a compound represented by the following formula; And dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,
a=1에 대하여, for a = 1,
0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12
을 만족함.Satisfied.
상기 혼합 분말을 열처리 하는 단계에서, In the step of heat-treating the mixed powder,
a=1, 2.4<b<3.6, 8<c<12인 경우, 상기의 화학식으로 표시되는 화합물은 삼사정계(triclinic)의 결정 구조를 가질 수 있다.When a = 1, 2.4 <b <3.6, and 8 <c <12, the compound represented by the above formula may have a triclinic crystal structure.
상기 광 흡수층을 형성하는 단계는, 상기 XaYbZc 용액을 건조하는 단계를 더 포함할 수 있다.The forming of the light absorbing layer may further include drying the X a Y b Z c solution.
상기 제2 전극을 형성하는 단계는, 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제2 기판을 준비하는 단계; 탄소 분말을 준비하는 단계; 상기 제2 기판 상에 상기 탄소 분말을 코팅하는 단계; 및 상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계를 포함할 수 있다.The forming of the second electrode may include preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; Preparing a carbon powder; Coating the carbon powder on the second substrate; And heat treating the second substrate coated with the carbon powder.
상기 제2 전극을 형성하는 단계는, 탄소를 함유하는 페이스트를 상기 광 흡수층 상에 도포하는 단계를 포함할 수 있다. The forming of the second electrode may include applying a paste containing carbon on the light absorbing layer.
본 발명의 일측면에 따르면, 본 발명은 고효율의 페로브스카이트 화합물 및 그 제조방법, 태양전지 및 그 제조방법을 제공할 수 있다.According to one aspect of the invention, the present invention can provide a highly efficient perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
본 발명의 다른 측면에 따르면, 본 발명은 안정성이 높은 페로브스카이트 화합물 및 그 제조방법, 태양전지 및 그 제조방법을 제공할 수 있다.According to another aspect of the present invention, the present invention can provide a highly stable perovskite compound, a method for producing the same, a solar cell and a method for producing the same.
본 발명의 또 다른 측면에 따르면, 본 발명은 제조 공정이 용이하고 경제적인 페로브스카이트 화합물 및 그 제조방법, 태양전지 및 그 제조방법을 제공할 수 있다.According to still another aspect of the present invention, the present invention can provide a perovskite compound, a method for producing the same, a solar cell, and a method for manufacturing the same, which are easy and economical to manufacture.
본 발명의 또 다른 측면에 따르면, 본 발명은 친환경적인 페로브스카이트 화합물 및 그 제조방법, 페로브스카이트 화합물을 포함하는 태양전지 및 그 제조방법을 제공할 수 있다. According to another aspect of the present invention, the present invention can provide an environmentally friendly perovskite compound, a method for producing the same, a solar cell including the perovskite compound and a method for producing the same.
도 1은 본 발명의 실시예에 따른 페로브스카이트 화합물을 나타낸 도면이다.1 is a view showing a perovskite compound according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법으로 형성된 페로브스카이트 화합물의 코팅 사진이다. 2 is a photograph of the coating of the perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
도 3은 본 발명의 실시예에 따른 페로브스카이트 화합물의 밴드갭 그래프이다.3 is a bandgap graph of a perovskite compound according to an embodiment of the present invention.
도 4는 본 발명의 실시예에 따른 페로브스카이트 화합물의 XRD 그래프이다.4 is an XRD graph of a perovskite compound according to an embodiment of the present invention.
도 5는 본 발명의 실시예에 따른 페로브스카이트 화합물의 TGA 분석 그래프이다. 5 is a TGA analysis graph of the perovskite compound according to the embodiment of the present invention.
도 6은 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면이다.6 is a view schematically showing a solar cell according to an embodiment of the present invention.
도 7은 본 발명의 실시예에 따른 태양전지의 사진이다. 7 is a photograph of a solar cell according to an embodiment of the present invention.
도 8은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다. 8 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
도 9는 페로브스카이트 화합물의 열처리 온도에 따른 광 흡수도를 나타낸 그래프이다.9 is a graph showing the light absorption according to the heat treatment temperature of the perovskite compound.
도 10은 페로브스카이트 화합물의 농도 변화에 따른 광 흡수도를 나타낸 그래프이다.10 is a graph showing the light absorbance according to the concentration change of the perovskite compound.
도 11은 종래기술의 태양전지와 본 발명의 실시예에 따른 태양전지의 효율을 비교한 그래프이다. 11 is a graph comparing the efficiency of the solar cell according to the embodiment of the present invention and the solar cell of the prior art.
도 12는 종래기술에 따른 태양전지(비교예)와 본 발명의 실시예에 따른 태양전지의 시간 경과에 따른 효율 변화를 비교한 그래프이다. 12 is a graph comparing the efficiency change of the solar cell according to the prior art (comparative example) and the solar cell according to the embodiment of the present invention over time.
도 13은 본 발명의 실시예에 따른 페로브스카이트 화합물을 나타낸 도면이다.13 is a view showing a perovskite compound according to an embodiment of the present invention.
도 14는 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법에 의해 형성된 페로브스카이트 화합물의 사진이다. 14 is a photograph of a perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
도 15는 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면이다.15 is a view schematically showing a solar cell according to an embodiment of the present invention.
도 16은 본 발명의 실시예에 따른 태양전지의 사진이다. 16 is a photograph of a solar cell according to an embodiment of the present invention.
도 17은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다. 17 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
도 18은 종래기술에 따른 태양전지(비교예)와 본 발명의 실시예에 따른 태양전지의 시간 경과에 따른 효율 변화를 비교한 그래프이다. 18 is a graph comparing the change of efficiency over time of the solar cell according to the prior art (comparative example) and the solar cell according to the embodiment of the present invention.
도 19 내지 도 21은 본 발명의 실험예에 따른 TiO2 의 두께 변화에 따른 효율을 비교한 그래프이다.19 to 21 is a graph comparing the efficiency according to the thickness change of TiO 2 according to the experimental example of the present invention.
도 22는 본 발명의 실시예에 따른 페로브스카이트 화합물의 AFM 사진.22 is an AFM photograph of a perovskite compound according to an embodiment of the present invention.
도 23은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 XRD 측정 결과 도면.Figure 23 is a XRD measurement result showing the structural change before and after heat treatment in the perovskite compound production method according to an embodiment of the present invention.
도 24는 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 광흡수도 변화를 나타낸 도면.24 is a view showing the change in light absorbency before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
도 25는 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면.25 is a schematic view of a solar cell according to an embodiment of the present invention.
도 26은 본 발명의 실시예에 따른 태양전지의 효율을 나타낸 도면.26 is a view showing the efficiency of the solar cell according to an embodiment of the present invention.
도 27은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도. 27 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
도 28은 본 발명의 실시예에 따른 페로브스카이트 화합물의 결정 구조를 나타낸 도면.28 is a view showing a crystal structure of a perovskite compound according to the embodiment of the present invention.
도 29는 본 발명의 실시예에 따른 페로브스카이트 화합물의 이론적 밴드갭을 나타낸 도면.29 shows the theoretical bandgap of a perovskite compound in accordance with an embodiment of the present invention.
도 30은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 XRD 측정 결과 도면.30 is a XRD measurement result diagram showing the structural change before and after heat treatment in the perovskite compound production method according to an embodiment of the present invention.
도 31은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 SEM 사진.FIG. 31 is a SEM photograph showing structural changes before and after heat treatment in a method of preparing perovskite compound according to an embodiment of the present invention. FIG.
도 32는 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 광흡수도 변화를 나타낸 도면.32 is a view showing the change in light absorbency before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
도 33은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 밴드갭 변화를 나타낸 도면.33 is a view showing a band gap change before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention.
도 34는 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면.34 is a schematic view of a solar cell according to an embodiment of the present invention.
도 35는 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도.35 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 그리고, 명세서 전체에서, "상에"라 함은 대상 부분의 위 또는 아래에 위치함을 의미하는 것이며, 반드시 중력 방향을 기준으로 상 측에 위치하는 것을 의미하는 것이 아니다.The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof. In addition, in the specification, "on" means to be located above or below the target portion, and does not necessarily mean to be located above the gravity direction.
또한, 결합이라 함은, 각 구성 요소 간의 접촉 관계에 있어, 각 구성 요소 간에 물리적으로 직접 접촉되는 경우만을 뜻하는 것이 아니라, 다른 구성이 각 구성 요소 사이에 개재되어, 그 다른 구성에 구성 요소가 각각 접촉되어 있는 경우까지 포괄하는 개념으로 사용하도록 한다.In addition, the coupling does not only mean the case where the physical contact is directly between the components in the contact relationship between the components, other components are interposed between the components, the components in the other components Use it as a comprehensive concept until each contact.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention.
본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.
이하, 본 발명의 실시예를 첨부한 도면들을 참조하여 상세히 설명하기로 한다. 본 발명을 설명함에 있어 전체적인 이해를 용이하게 하기 위하여 도면 번호에 상관없이 동일한 수단에 대해서는 동일한 참조 번호를 사용하기로 한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, the same reference numerals will be used for the same means regardless of the reference numerals in order to facilitate the overall understanding.
도면에서 나타난 각 구성의 크기 및 두께는 설명의 편의를 위해 임의로 나타내었으므로, 본 발명이 반드시 도시된 바에 한정되지 않는다.Since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, the present invention is not necessarily limited to the illustrated.
첨부 도면을 참조하여 설명함에 있어, 동일하거나 대응하는 구성 요소는 동일한 도면번호를 부여하고 이에 대한 중복되는 설명은 생략하기로 한다.In the description with reference to the accompanying drawings, the same or corresponding components will be given the same reference numerals and redundant description thereof will be omitted.
본 발명의 실시예에 따른 페로브스카이트 화합물은 하기의 화학식을 따른다.The perovskite compound according to the embodiment of the present invention follows the formula below.
[화학식][Formula]
XaYbZc
X a Y b Z c
여기서, here,
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
한편, 제1 페로브스카이트 화합물은 a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5을 만족하고, 제2 페로브스카이트 화합물은 a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4를 만족하고, 제3 페로브스카이트 화합물은 a=1에 대하여, 2.4<b<3.6, 8<c<12을 만족하고, 제3 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가진다.On the other hand, the first perovskite compound satisfies 0.5 <b <0.7, 2.5 <c <3.5 for a = 1, and the second perovskite compound is 1.6 <b <2.4 for a = 1. , 5.6 <c <8.4, and the third perovskite compound satisfies 2.4 <b <3.6, 8 <c <12 for a = 1, and the third perovskite compound is triclinic system ( triclinic) crystal structure.
제1 First
페로브스카이트Perovskite
화합물(3-2-9 Compound (3-2-9
페로브스카이트Perovskite
화합물) compound)
제1 페로브스카이트 화합물은 하기의 화학식을 따른다.The first perovskite compound follows the formula:
[화학식][Formula]
XaYbZc
X a Y b Z c
여기서, here,
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5을 만족하고, 바람직하게는 a:b:c=3:2:9 이다. 이러한 제1 페로브스카이트 화합물을 편의 상 3-2-9 페로브스카이트 화합물이라 부를 수 있다.For a = 1, 0.5 <b <0.7, 2.5 <c <3.5 are satisfied, and a: b: c = 3: 2: 9 is preferable. Such a first perovskite compound may be referred to as 3-2-9 perovskite compound for convenience.
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5을 만족한다는 것은 페로브스카이트 화합물의 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1일 때, 0.5<b<0.7, 2.5<c<3.5 인 것을 의미한다. 상기의 범위 내에서는 후술하는 발명의 효과가 발휘될 수 있다.For a = 1, satisfying 0.5 <b <0.7, 2.5 <c <3.5 means that 0.5 <b when the total moles of monovalent organic / inorganic cations contained in the X position of the perovskite compound a = 1 It means that <0.7, 2.5 <c <3.5. Within the above range, the effects of the invention described later can be exerted.
이하, Y=Bi인 경우와 Y=Sb인 경우를 나누어 설명하도록 하며, 먼저 Y=Bi인 경우에 대해 설명한다.Hereinafter, the case of Y = Bi and the case of Y = Sb will be described separately. First, the case of Y = Bi will be described.
도 1은 본 발명의 실시예에 따른 페로브스카이트 화합물의 결정구조를 나타낸 도면으로. XaYbZc 에서, X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나, Y=Bi, Z=F, I, Br, Cl 중 하나이며, a:b:c=3:2:9 이다. 1 is a view showing a crystal structure of a perovskite compound according to an embodiment of the present invention. In X a Y b Z c , one of X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li, Y = Bi, Z = F, I, One of Br, Cl, and a: b: c = 3: 2: 9.
이하, X3Bi2Z9 페로브스카이트 화합물에 대해 주로 설명하지만, 해당 설명은 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5을 만족하는 모든 XaBibZc 페로브스카이트 화합물에 대해서도 동일하게 적용될 수 있다.Hereinafter, the X 3 Bi 2 Z 9 perovskite compound will be mainly described, but the description is 0.5 <b <0.7, 2.5 <with respect to the total mole number a = 1 of the monovalent organic / inorganic cation contained in the X position. The same applies to all X a Bi b Z c perovskite compounds that satisfy c <3.5.
본 발명의 실시예에 따른 페로브스카이트 화합물(X3Bi2Z9)은 종래기술의 페로브스카이트 화합물 구조가 습기에 취약하고, 고온에서 내구성이 낮은 문제점을 개선할 수 있다. Perovskite compound (X 3 Bi 2 Z 9 ) according to an embodiment of the present invention can improve the problem that the structure of the perovskite compound of the prior art vulnerable to moisture, low durability at high temperatures.
본 발명의 실시예에 따른 페로브스카이트 화합물은 Bi를 이용하여 페로브스카이트 결정구조를 형성하므로 납(Pb)과 같은 높은 독성의 물질을 대체할 수 있다. The perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi, and thus may replace a highly toxic substance such as lead (Pb).
따라서, 본 발명의 실시예에 따른 페로브스카이트 화합물은 안정성 측면에서 우수하다.Therefore, the perovskite compound according to the embodiment of the present invention is excellent in terms of stability.
본 발명의 실시예에 따른 페로브스카이트 화합물의 광 흡수도, 태양 전지에 적용됨에 따른 효율의 개선 등에 관한 효과에 대해서는 후술하기로 한다. Effects of the light absorption of the perovskite compound according to the embodiment of the present invention, the improvement of the efficiency according to the application to the solar cell, and the like will be described later.
본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 화합물의 전구체 분말을 혼합한 후 열처리하여 형성되는 것에 특징이 있다. Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
구체적으로, 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 XZ 화합물 분말을 준비하는 단계, BiZ3
화합물 분말을 준비하는 단계, 상기 XZ 화합물 분말 및 상기 BiZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계 및 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함할 수 있다. Specifically, the method for producing a perovskite compound according to an embodiment of the present invention comprises the steps of preparing an XZ compound powder, BiZ 3 The method may include preparing a compound powder, mixing the XZ compound powder and the BiZ 3 compound powder to form a mixed powder, and heat treating the mixed powder to prepare a compound represented by the following formula. .
[화학식] [Formula]
XaBibZc
X a Bi b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
혼합 분말을 열처리하는 단계에서, 바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 혼합 분말을 열처리하는 단계에서 상기 화학식으로 표시되는 화합물은 X3Bi2Z9일 수 있다.In the step of heat treating the mixed powder, preferably a: b: c = 3: 2: 9. For example, the compound represented by the formula in the heat treatment of the mixed powder may be X 3 Bi 2 Z 9 .
상기 열처리 하는 단계는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 한편, 상기 가열노 내의 온도는 140 이상 200 이하의 범위에서 수행될 수 있다. The heat treatment may include heating the mixed powder in a heating furnace. On the other hand, the temperature in the heating furnace may be carried out in the range of 140 or more and 200 or less.
한편, XZ 화합물의 농도는 1.5mmol 이고, BiZ3화합물의 농도는 1mmol 일 수 있다. Meanwhile, the concentration of the XZ compound may be 1.5 mmol, and the concentration of the BiZ 3 compound may be 1 mmol.
상기 열처리하는 단계는 50분 이상 70분 이하로 수행될 수 있다. The heat treatment may be performed in 50 minutes or more and 70 minutes or less.
도 2는 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법으로 형성된 페로브스카이트 화합물의 코팅 사진이다. 2 is a photograph of the coating of the perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
또한, 본 발명의 실시예에 따른 제조방법에 의해 형성된 페로브스카이트 화합물의 분석 그래프는 도 3 내지 도 5에 나타내었다. In addition, an analysis graph of the perovskite compound formed by the preparation method according to an embodiment of the present invention is shown in Figs.
도 3은 본 발명의 실시예에 따른 페로브스카이트 화합물의 밴드갭 그래프이고, 도 4는 본 발명의 실시예에 따른 페로브스카이트 화합물의 XRD 그래프이며, 도 5는 본 발명의 실시예에 따른 페로브스카이트 화합물의 TGA 분석 그래프이다. 3 is a bandgap graph of the perovskite compound according to an embodiment of the present invention, Figure 4 is an XRD graph of the perovskite compound according to an embodiment of the present invention, Figure 5 is an embodiment of the present invention TGA analysis graph of the perovskite compound according.
도 3 내지 5를 참조하면, 본 발명의 실시예에 따른 페로브스카이트 화합물 제조 방법에 따라 생성된 페로브스카이트 화합물은 밴드갭 에너지가 2.2eV 로 높게 나타낸 것을 확인할 수 있으며, X3Bi2Y9 결정 구조가 형성되었음을 확인할 수 있다. 3 to 5, the perovskite compound produced according to the perovskite compound manufacturing method according to an embodiment of the present invention can be seen that the bandgap energy is represented as 2.2eV high, X 3 Bi 2 It can be seen that the Y 9 crystal structure was formed.
이하에서는, 본 발명의 실시예에 따른 페로브스카이트 화합물을 포함하는 태양전지에 대하여 설명한다.Hereinafter, a solar cell including a perovskite compound according to an embodiment of the present invention will be described.
도 6은 본 발명의 실시예에 따른 태양전지(1000)를 개략적으로 나타낸 도면이다. 도 7은 본 발명의 실시예에 따른 태양전지(1000)의 단면을 나타낸 사진이다.6 is a view schematically showing a solar cell 1000 according to an embodiment of the present invention. 7 is a photograph showing a cross section of the solar cell 1000 according to an embodiment of the present invention.
도 6 및 도 7을 참조하면, 본 발명의 실시예에 따른 태양전지는 제1 전극(100), 상기 제1 전극 상에 형성되는 광 흡수층(200) 및 광 흡수층(200) 상에 형성되는 제2 전극(300)을 포함하되, 제1 전극(100), 제2 전극(300)은 광 흡수층(200)의 접착력에 의해 상기 광 흡수층과 접착되어 형성될 수 있다. 6 and 7, a solar cell according to an embodiment of the present invention may include a first electrode 100, a light absorbing layer 200 formed on the first electrode, and a light absorbing layer 200 formed on the first electrode 100. Including a second electrode 300, the first electrode 100, the second electrode 300 may be formed by being bonded to the light absorbing layer by the adhesive force of the light absorbing layer 200.
한편, 본 발명의 실시예에 따른 광 흡수층(200)은 페로브스카이트 화합물을 포함하고, 페로브스카이트 화합물은 하기의 화학식으로 표시될 수 있다. On the other hand, the light absorbing layer 200 according to the embodiment of the present invention includes a perovskite compound, the perovskite compound may be represented by the following formula.
[화학식] [Formula]
XaBibZc
X a Bi b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 상기 화학식으로 표시되는 페로브스카이트 화합물은 X3Bi2Z9일 수 있다.Preferably a: b: c = 3: 2: 9. For example, the perovskite compound represented by the formula may be X 3 Bi 2 Z 9 .
제1 전극(100)은 ITO (indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 또는 유연 투명 전극 기판 중 어느 하나가 선택되고, 선택된 기판 상에 형성되는 TiO2층(120)을 포함할 수 있다. The first electrode 100 may include a TiO 2 layer 120 selected from an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, or a flexible transparent electrode substrate, and is formed on the selected substrate. Can be.
유연 투명 전극 기판은 금속 배선층이 형성된 폴리머 기판을 포함하여, 폴리머 기판은 폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성에폭시수지로 이루어지는 군으로부터 선택되는 기판일 수 있다. The flexible transparent electrode substrate includes a polymer substrate on which a metal wiring layer is formed, and the polymer substrate includes polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), and polymethylmethacrylate ( PMMA), polyimide (PI), ethylene vinyl acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate ( PCTG), modified triacetylcellulose (TAC), cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), It may be a substrate selected from the group consisting of polyetherimide (PEI), polydimethylsiloncene (PDMS), silicone resin, fluorine resin and modified epoxy resin.
다만, 본 발명의 제1 전극에 포함되는 기판은 상기의 제시된 예로 제한되지 않는다. However, the substrate included in the first electrode of the present invention is not limited to the examples presented above.
TiO2층(120)은 blocking TiO2층 (122) 및 blocking TiO2층(122) 상에 형성되는 mesoporous TiO2층(124)을 포함할 수 있다. The TiO 2 layer 120 may include a blocking TiO 2 layer 122 and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 layer 122.
TiO2층(120)은 전자수송층으로서의 기능을 수행할 수 있다The TiO 2 layer 120 may function as an electron transport layer.
제1 전극(100)은 ZrO2층(130)을 더 포함할 수 있으며, TiO2층(120)과 마찬가지로, ZrO2층(130) 전자수송층으로서의 기능을 수행한다. The first electrode 100 may further include a ZrO 2 layer 130, as with the TiO 2 layer 120, and performs a ZrO 2 layer 130 functioning as an electron transport layer.
제2 전극(300)은 카본 전극(Carbon)일 수 있다. The second electrode 300 may be a carbon electrode.
카본(Carbon) 전극은 페로브스카이트 화합물에 의해 산화 등과 같은 반응이 일어나지 않아 시간 경과에 따른 태양 전지의 효율을 높게 유지시켜 줄 수 있다. Carbon electrode can maintain a high efficiency of the solar cell over time because a reaction such as oxidation does not occur by the perovskite compound.
한편, 카본(Carbon) 전극은 금속 전극과 달리 진공 증착 방식을 이용하지 않고, 페로브스카이트 화합물의 접착력에 의해 접착될 수 있어, 페로브스카이트 화합물과 용이하게 결합될 수 있다.Meanwhile, unlike a metal electrode, a carbon electrode may be bonded by an adhesive force of a perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
이하에서는, 태양전지 제조방법을 도면을 참조하여 설명하기로 한다. Hereinafter, a solar cell manufacturing method will be described with reference to the drawings.
도 8은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다. 8 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
도 8을 참조하면, 본 발명의 실시예에 따른 태양전지의 제조방법은 제1 전극(100)을 형성하는 단계(S100), 제1 전극(100) 상에 광 흡수층(200)을 형성하는 단계(S200) 및 광 흡수층(200) 상에 제2 전극(300)을 형성하는 단계(S300)를 포함하되, Referring to FIG. 8, in the method of manufacturing a solar cell according to an exemplary embodiment of the present invention, forming a first electrode 100 (S100) and forming a light absorbing layer 200 on the first electrode 100. (S200) and forming a second electrode 300 on the light absorbing layer 200 (S300),
제1 전극(100) 및 제2 전극(300)은 광 흡수층(200)에 의해 접착되어 형성되는 것을 특징으로 한다. The first electrode 100 and the second electrode 300 is characterized in that the adhesive is formed by the light absorbing layer 200.
한편, 광 흡수층(200)을 형성하는 단계(S200)는 하기의 화학식으로 표시되는 페로브스카이트 화합물을 형성하는 단계를 포함한다. On the other hand, forming the light absorbing layer 200 (S200) includes the step of forming a perovskite compound represented by the following formula.
[화학식] [Formula]
XaBibZc
X a Bi b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 광 흡수층(200)을 형성하는 단계(S200)에서 상기 화학식으로 표시되는 페로브스카이트 화합물은 X3Bi2Z9일 수 있다.Preferably a: b: c = 3: 2: 9. For example, the perovskite compound represented by the chemical formula in the step (S200) of forming the light absorbing layer 200 may be X 3 Bi 2 Z 9 .
제1 전극을 형성하는 단계(S100) 유연 투명 전극 기판, ITO (indium tin oxide) 기판 또는 FTO(Fluorine Doped Tin Oxide) 기판 중 어느 하나의 기판을 준비하는 단계(S110) 및 유연 투명 전극 기판, ITO 기판 및 FTO(Fluorine Doped Tin Oxide) 기판 중 어느 하나의 기판 상에 TiO2층을 형성하는 단계(S120)를 포함할 수 있다. Forming a first electrode (S100) preparing a substrate of any one of a flexible transparent electrode substrate, an indium tin oxide (ITO) substrate or a Fluorine Doped Tin Oxide (FTO) substrate (S110) and a flexible transparent electrode substrate, ITO The method may include forming a TiO 2 layer on any one of a substrate and a Fluorine Doped Tin Oxide (FTO) substrate (S120).
(이하에서는, FTO기판을 이용하여 실시하는 예만 설명하기로 한다. 다만, 본 발명의 실시예 들은 상기 언급한 바와 같이 유연성과 투명성이 있는 기판을 모두 포함하는 것이며, 이하에서 설명하는 예로 제한하는 것은 아니다.)(Hereinafter, only the example performed using the FTO substrate will be described. However, the embodiments of the present invention include both flexible and transparent substrates as mentioned above. no.)
FTO 기판을 준비하는 단계(S110)는 FTO 기판과 TiO2층 간 접착력을 향상시키기 위해 FTO(Fluorine Doped Tin Oxide) 기판을 가공하는 단계를 포함할 수 있다. Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer.
예를 들면, FTO(Fluorine Doped Tin Oxide) 기판에 에칭할 부분을 제외한 나머지 부분에 Zn 분말을 고르게 도포시킨 후 HCl을 DI water 에 1:1 에서 1:3 비율로 희석 시킨 용액을 균일하게 도포할 수 있다. For example, evenly apply Zn powder to the remaining portions other than the portions to be etched on a Fluorine Doped Tin Oxide (FTO) substrate, and then uniformly apply a solution in which HCl is diluted 1: 1 to 1: 3 in DI water. Can be.
에칭된 상기 FTO(Fluorine Doped Tin Oxide) 기판을 아세톤, IPA, DI 순으로 초음파 세척기를 이용하여 세척할 수 있다. The etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI.
다음으로, 세척된 FTO(Fluorine Doped Tin Oxide) 기판은 100에서 건조하고, UV Ozone cleaner에서 600 초간 처리할 수 있다. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate can be dried at 100 and treated for 600 seconds in a UV Ozone cleaner.
따라서, 상기와 같은 FTO 기판의 표면 처리를 통해 TiO2층과의 접착력을 향상시킬 수 있다. Therefore, it is possible to improve the adhesion with the TiO 2 layer through the surface treatment of the FTO substrate as described above.
TiO2층을 형성하는 단계(S120)는 Blocking TiO2층을 형성하는 단계 및 Blocking TiO2층 상에 Mesoporous TiO2층을 형성하는 단계를 포함할 수 있다. Forming the TiO 2 layer (S120) may include forming a blocking TiO 2 layer and forming a Mesoporous TiO 2 layer on the blocking TiO 2 layer.
Blocking TiO2층을 형성하는 단계는 TiO2 용액을 제조하는 단계, TiO2 용액을 이용하여 FTO 기판에 TiO2 코팅막을 형성하는 단계, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Blocking forming a TiO 2 layer may include the step, step, drying the coated film to form the TiO 2 TiO 2 coating on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
TiO2 용액을 제조하는 단계에서 TiO2 용액은 Titanium diisopropoxide bis(acetylacetonate) 75 wt. % in isopropanol 용액을 1-butanol 용액에 희석시켜 0.15M의 농도로 제조될 수 있다. In preparing a solution of TiO 2 TiO 2 solution Titanium diisopropoxide bis (acetylacetonate) 75 wt . The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
TiO2 코팅막을 형성하는 단계에서 TiO2 코팅막은 20s초동안 2000rpm에서 스핀 코팅함으로 형성될 수 있다.In the step of forming the TiO 2 coating TiO 2 coating film can be formed by spin coating at 2000rpm for 20s seconds.
TiO2 코팅막을 건조하는 단계에서 TiO2 코팅막은 125 이상에서 5분간 열처리함으로써 건조될 수 있다. In the step of drying the coating layer TiO 2 TiO 2 coating film may be dried by heat treatment at 125 or more for 5 minutes.
다음으로, Blocking TiO2층 상에 Mesoporous TiO2층을 형성하는 단계는 mesoporous TiO2 용액을 제조하고, TiO2 코팅막을 형성한 후, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Next, the forming of the Mesoporous TiO 2 layer on the Blocking TiO 2 layer may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
mesoporous TiO2 용액은 mesoporous TiO2를 무수 에탄올(hydrous ethanol)에 용해하여 제조될 수 있으며, 필요에 따라 농도를 조절하여 사용할 수 있다.Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
mesoporous TiO2층에서, TiO2 코팅막은 450 이상에서 30분간 열처리함으로써 건조될 수 있다. In the mesoporous TiO 2 layer, the TiO 2 coating film may be dried by heat treatment at 450 or more for 30 minutes.
한편, 제1 전극을 형성하는 단계(S100)는 상기 mesoporous TiO2층에 조도를 형성하는 단계(S140)를 더 포함할 수 있다. Meanwhile, the forming of the first electrode (S100) may further include forming roughness on the mesoporous TiO 2 layer (S140).
상기 mesoporous TiO2 층에 조도를 형성하기 위해 TiCl4 용액을 이용할 수 있다. TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer.
예를 들면, 20 mM의 TiCl4
용액 1ml와 증류수 99ml를 섞은 혼합 용액을 준비하는 단계, 상기 혼합 용액에 mesoporous TiO2 층이 형성된 기판을 함침하는 단계, 다음으로, 제1차 열처리 단계, 세정하는 단계, 건조하는 단계 및 2차 열처리 단계를 수행할 수 있다. For example, 20 mM TiCl 4 Preparing a mixed solution of 1 ml of solution and 99 ml of distilled water, impregnating the substrate with the mesoporous TiO 2 layer formed therein, followed by a first heat treatment step, a cleaning step, a drying step, and a second heat treatment. The steps can be performed.
조도를 형성하는 단계에서 1차 열처리 단계는 70 내지 100의 온도범위에서 진행될 수 있으며, 2차 열처리 단계는 450 이상 30분 진행될 수 있다.In the step of forming the roughness, the first heat treatment step may be performed at a temperature range of 70 to 100, and the second heat treatment step may be performed at 450 or more 30 minutes.
상기와 같이 일련의 제조 공정에 의해 mesoporous TiO2층 상에 조도가 형성됨으로써, 광 흡수층과 TiO2층 간의 접착력이 보다 향상될 수 있다. As the roughness is formed on the mesoporous TiO 2 layer by a series of manufacturing processes as described above, the adhesion between the light absorbing layer and the TiO 2 layer may be further improved.
광 흡수층을 형성하는 단계(S200)는 X3Bi2Z9 용액을 형성하는 단계를 포함할 수 있다. Forming the light absorbing layer (S200) may include forming an X 3 Bi 2 Z 9 solution.
X3Bi2Z9 용액을 형성하는 단계는, XZ 화합물 분말을 준비하는 단계(S210), Bi Z9 화합물 분말을 준비하는 단계(S220), 상기 XZ 화합물 분말 및 상기 BiZ9 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계(S230), 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계(S240) 및 상기 열처리 된 혼합 분말을 DMF 용매에 용해시키는 단계(S250)를 포함할 수 있다. Forming the X 3 Bi 2 Z 9 solution, preparing a XZ compound powder (S210), preparing a Bi Z 9 compound powder (S220), by mixing the XZ compound powder and the BiZ 9 compound powder Forming a mixed powder (S230), heat-treating the mixed powder to produce a compound represented by the following formula (S240) and the step of dissolving the heat-treated mixed powder in a DMF solvent (S250) have.
[화학식] [Formula]
XaBibZc
X a Bi b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
혼합 분말을 열처리하는 단계에서, 바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 혼합 분말을 열처리하는 단계에서, 상기 화학식으로 표시되는 화합물은 X3Bi2Z9일 수 있다.In the step of heat treating the mixed powder, preferably a: b: c = 3: 2: 9. For example, in the heat treatment of the mixed powder, the compound represented by the formula may be X 3 Bi 2 Z 9 .
S210 내지 S240의 일련의 과정은 페로브스카이트 화합물의 제조 공정과 동일하므로 생략하기로 한다. Since a series of processes of S210 to S240 are the same as the process of producing the perovskite compound, it will be omitted.
광 흡수층을 형성하는 단계(S200)는 제1 전극(100) 및 제2 전극(300)을 준비한 후, X3Bi2Z9 용액을 제1 전극(100)과 제2 전극(300) 사이에 드롭핑(dropping) 하는 단계(S260) 또는 X3Bi2Z9 용액을 상기 제1 전극 또는 제2 전극 상에 스핀 코팅하는 단계를 선택적으로 수행하여 형성할 수 있다. In the forming of the light absorbing layer (S200), after preparing the first electrode 100 and the second electrode 300, an X 3 Bi 2 Z 9 solution may be disposed between the first electrode 100 and the second electrode 300. Dropping (S260) or by spin coating the X 3 Bi 2 Z 9 solution on the first electrode or the second electrode may be formed by selectively performing.
다음으로 광 흡수층을 형성하는 단계(S200)는 X3Bi2Z9 용액을 건조하는 단계(S270)를 포함할 수 있다.Next, forming the light absorbing layer (S200) may include drying the X 3 Bi 2 Z 9 solution (S270).
상기 X3Bi2Y9 용액을 건조하는 단계는 0 이상 200 이하의 온도 범위에서 수행될 수 있다. The drying of the X 3 Bi 2 Y 9 solution may be performed at a temperature range of 0 to 200.
한편, 제2 전극을 형성하는 단계(S300)는 유리 기판, FTO(Fluorine Doped Tin Oxide) 또는 ITO (Indium Tin Oxide)가 증착된 유리 기판 및 유연 투명 전극 기판 중 어느 하나의 기판을 준비하는 단계(S310), 탄소 분말을 준비하는 단계(S320), 상기 탄소 분말을 이용하여, 상기 유리 기판, FTO(Fluorine Doped Tin Oxide) 또는 ITO (Indium Tin Oxide)가 증착된 유리 기판 및 유연 투명 전극 기판 중 어느 하나의 기판상에 탄소 분말을 코팅하는 단계(S330) 및 상기 탄소 분말이 코팅된 기판을 열처리하는 단계(S340)를 포함할 수 있다.The forming of the second electrode (S300) may include preparing a substrate of any one of a glass substrate, a glass substrate on which Fluorine Doped Tin Oxide (FTO) or an Indium Tin Oxide (ITO) is deposited, and a flexible transparent electrode substrate ( S310), preparing a carbon powder (S320), by using the carbon powder, any one of the glass substrate, FTO (Fluorine Doped Tin Oxide) or ITO (Indium Tin Oxide) is deposited and a flexible transparent electrode substrate It may include the step of coating the carbon powder on one substrate (S330) and the step of heat-treating the carbon powder-coated substrate (S340).
상기 탄소 분말이 코팅된 기판을 열처리하는 단계(S340)는 300 이상의 온도 범위에서 수행될 수 있다. The heat treatment of the substrate coated with carbon powder (S340) may be performed at a temperature range of 300 or more.
탄소 분말이 코팅된 기판을 열처리하는 단계(S340)는 25분 내지 35분 동안 수행될 수 있다.Heat treatment of the substrate coated with carbon powder (S340) may be performed for 25 to 35 minutes.
다음으로, 광 흡수층과 상기 제1 전극층, 상기 광 흡수층과 상기 제2 전극층의 측면에 접착층을 형성하는 단계(S400)를 더 포함할 수 있다. 상기 접착층은 에폭시 수지로 형성될 수 있다.Next, the method may further include forming an adhesive layer on side surfaces of the light absorbing layer, the first electrode layer, the light absorbing layer, and the second electrode layer (S400). The adhesive layer may be formed of an epoxy resin.
광 흡수도 및 태양전지의 효율Light Absorption and Solar Cell Efficiency
도 9는 페로브스카이트 화합물의 열처리 온도에 따른 광 흡수도를 나타낸 그래프이다.9 is a graph showing the light absorption according to the heat treatment temperature of the perovskite compound.
도 9를 참조하면, 실온(RT, 실험예 1), 50(실험예 2), 100(실험예 3), 150(실험예 4), 200(실험예 5), 300(실험예 6)의 온도 범위에 열처리된 페로프스카이트 화합물의 광 흡수도을 측정 결과를 확인할 수 있다. 9, the room temperature (RT, Experimental Example 1), 50 (Experimental Example 2), 100 (Experimental Example 3), 150 (Experimental Example 4), 200 (Experimental Example 5), 300 (Experimental Example 6) The result of measuring the light absorbance of the perovskite compound heat-treated in the temperature range can be confirmed.
도 9에 도시된 바와 같이 페로브스카이트 화합물의 광 흡수도은 실온에서 200 범위에서는 열처리 온도가 증가할수록 증가했으나, 300(실험예 6)에서는 급격히 감소한 것을 확인할 수 있다. As shown in FIG. 9, the light absorbance of the perovskite compound increased as the heat treatment temperature was increased in the range of 200 at room temperature, but it was confirmed that it rapidly decreased in 300 (Experimental Example 6).
따라서, 상기 실험결과를 통해 페로브스카이트 화합물은 열처리 온도에 따라 광 흡수도이 상이한 결과를 나타내고, 적정의 열처리 온도가 있음을 확인할 수 있다. Therefore, the experimental results show that the perovskite compound has a different light absorbency according to the heat treatment temperature, and it can be confirmed that there is an appropriate heat treatment temperature.
열처리 온도가 200(실험예 5) 일 때, 광 흡수도가 가장 높게 나타남을 확인할 수 있다. When the heat treatment temperature is 200 (Experimental Example 5), it can be seen that the light absorption is the highest.
도 10은 페로브스카이트 화합물의 농도 변화에 따른 광 흡수도를 나타낸 그래프이다. 10 is a graph showing the light absorbance according to the concentration change of the perovskite compound.
도 10을 참조하면, 0.1M(실험예 7), 0.3M(실험예 8), 0.5M(실험예 9), 0.7M(실험예 10), 1.0M(실험예 11), 2.0M(실험예 12) 각각의 페로프스카이트 화합물 농도에서의 광 흡수도을 측정 결과를 확인할 수 있다.Referring to FIG. 10, 0.1M (Experimental Example 7), 0.3M (Experimental Example 8), 0.5M (Experimental Example 9), 0.7M (Experimental Example 10), 1.0M (Experimental Example 11), 2.0M (Experimental) Example 12) The result of measuring the light absorbency at each concentration of perovskite compound can be confirmed.
도 10에 도시된 바와 같이, 페로브스카이트 화합물의 광 흡수도은 0.1M(실험예 7) 내지 1.0M(실험예 11) 구간에서는 농도가 증가할수록 증가하였으나, 2.0M(실험예 12)에서는 0.5M(실험예 9) 보다 낮게 나타나 감소한 것을 확인할 수 있다.As shown in FIG. 10, the light absorbance of the perovskite compound increased with increasing concentration in the range of 0.1M (Experimental Example 7) to 1.0M (Experimental Example 11), but 0.5 at 2.0M (Experimental Example 12). It can be seen that it was lower than M (Experimental Example 9) and decreased.
따라서, 상기 실험결과를 통해 페로브스카이트 화합물은 농도에 따라 광 흡수도이 상이한 결과를 나타내고, 적정의 농도가 있음을 확인할 수 있다.Therefore, through the experimental results, the perovskite compound shows a result of different light absorbance according to the concentration, it can be confirmed that there is a proper concentration.
농도가 1.0M(실험예 11) 일 때, 광 흡수도가 가장 높게 나타남을 확인할 수 있다. When the concentration is 1.0M (Experimental Example 11), it can be seen that the light absorption is the highest.
페로브스카이트 화합물의 열처리 온도 및 농도는 광 흡수도에 영향을 미치는 요인으로 작용하며, 구체적으로, 열처리 온도는 200, 농도는 1.0M일 때 광 흡수도가 가장 높게 나타났다. The heat treatment temperature and concentration of the perovskite compound act as a factor influencing the light absorption. Specifically, the light absorption was the highest when the heat treatment temperature is 200 and the concentration is 1.0M.
한편, 상기의 실험 결과를 통해 최적의 광 흡수도를 갖는 페로브스카이트 화합물을 제조함으로써, 태양전지의 효율도 보다 개선될 수 있다. On the other hand, by producing a perovskite compound having an optimal light absorption through the above experimental results, the efficiency of the solar cell can be further improved.
이하에서는, 도면을 참조하여 종래기술의 태양전지와 본 발명의 실시예에 따른 태양전지의 효율을 비교하여 설명하기로 한다. Hereinafter, with reference to the drawings will be described by comparing the efficiency of the solar cell of the prior art and the solar cell according to the embodiment of the present invention.
도 11은 종래기술의 태양전지와 본 발명의 실시예에 따른 태양전지의 효율을 비교한 그래프이다. 도 12는 종래기술에 따른 태양전지(비교예)와 본 발명의 실시예에 따른 태양전지의 시간 경과에 따른 효율 변화를 비교한 그래프이다. 11 is a graph comparing the efficiency of the solar cell according to the embodiment of the present invention and the solar cell of the prior art. 12 is a graph comparing the efficiency change of the solar cell according to the prior art (comparative example) and the solar cell according to the embodiment of the present invention over time.
[비교예] [Comparative Example]
제1 전극, 제1 전극상에 형성된 광 흡수층, 광 흡수층 상에 형성된 제2 전극을 포함하는 태양전지 A solar cell comprising a first electrode, a light absorbing layer formed on the first electrode, and a second electrode formed on the light absorbing layer.
(1) 광 흡수층의 제조방법 (1) Manufacturing Method of Light Absorption Layer
합성한 FAI 분말과 biI3 분말을 DMF 용매에 녹인 다음 필터 후 사용Synthesized FAI powder and biI 3 powder in DMF solvent and then used after filter
스핀코팅 방법을 이용하여 4000 rpm, 25s 의 조건으로 코팅 후 RT~200 에서 10분간 후 열처리After spin coating at 4000 rpm and 25 s for 10 minutes at RT ~ 200
HTL (Spiro, P3HT 등)HTL (Spiro, P3HT, etc.)
Spiro 또는 P3HT 분말을 toluene 또는 chlorobenzene 에 녹인 후 필터. Dissolve Spiro or P3HT powder in toluene or chlorobenzene and filter.
스핀코팅 방법을 이용하여 3000 rpm, 30s 의 조건으로 코팅.Coating at 3000 rpm, 30 s using spin coating method.
(2) 제2 전극(2) second electrode
진공 증발기 (evaporator)를 이용하여 10-5 torr 이상의 진공에서 Ag, Au 등의 금속 전극을 증착Deposition of metal electrodes, such as Ag and Au, at a vacuum of 10 -5 torr or more using a vacuum evaporator
(3) 적층방법(3) Lamination Method
각각의 구성은 스핀 코팅, 진공 증발기를 이용하여 10-5 torr 이상의 진공상태에서 증착됨Each component is deposited in a vacuum over 10 -5 torr using spin coating, vacuum evaporator
[실험예]Experimental Example
(1) 광 흡수층의 제조방법 (1) Manufacturing Method of Light Absorption Layer
합성한 FAI 분말과 biI3 분말을 이용하여 열처리하여 FA3bi2I9 분말을 형성FA 3 bi 2 I 9 powder was formed by heat treatment using the synthesized FAI powder and biI3 powder.
(2) 제2 전극(2) second electrode
Carbon 전극을 형성Form Carbon Electrode
(3) 적층방법(3) Lamination Method
광 흡수층의 접착력을 이용하여 광 흡수층과 제1 전극, 광 흡수층과 제2 전극이 접착되어 형성.It is formed by bonding the light absorbing layer and the first electrode, the light absorbing layer and the second electrode by using the adhesive force of the light absorbing layer.
적층형 태양전지(비교예)는 광 흡수층 상에 제2 전극이 형성되기 위해 Ag 및 Au를 10-5 torr 이상의 진공 상태에서 공정이 진행되는 점에서 본 발명의 실시예에 따른 접합형 태양전지의 제조공정 측면에서 차이점이 있다. In the stacked solar cell (comparative example), a junction solar cell according to an exemplary embodiment of the present invention is manufactured in that a process of Ag and Au in a vacuum state of 10 −5 torr or more is performed to form a second electrode on a light absorbing layer. There is a difference in process.
또한, 본 발명의 실시예에 따른 태양전지(실험예)는 금속이 아닌 카본 재료가 이용되는 점에서 적층형 태양전지(비교예)와 구조적 측면에서 차이가 있다. In addition, the solar cell (experimental example) according to the embodiment of the present invention is different in terms of structure from the laminated solar cell (comparative example) in that carbon material is used instead of metal.
상기와 같은 적층형 태양전지(비교예)와 접합형 태양전지(실시예)의 효율을 각각 측정한 결과 하기에 [표 1]에 나타났다. As a result of measuring the efficiency of the laminated solar cell (comparative example) and the junction type solar cell (example) as described above, it is shown in Table 1 below.
[표 1]에 나타난 것과 같이 0.025 %, 3.47 %로 나타났으며, 접합형 태양전지(실시예)의 효율이 140 배 정도 높게 나타난 것을 확인할 수 있다. As shown in Table 1, it was found that 0.025%, 3.47%, and the efficiency of the bonded solar cell (example) were about 140 times higher.
| Voc(V)Voc (V) | Jsc(mA/cm2)Jsc (mA / cm 2 ) | FF(%)FF (%) | PCE(%)PCE (%) | |
| 적층형(비교예)Stacked type (comparative example) | 0.490.49 | 0.130.13 | 3737 | 0.0250.025 |
| 접합형(실시예)Bonding type (Example) | 0.600.60 | 16.1716.17 | 35.735.7 | 3.473.47 |
[표1] 태양전지의 효율[Table 1] Efficiency of Solar Cell
[식] 효율 (%) = 개방전압(V) * 단락전류밀도(mA/cm2) * 충전률(%)Efficiency (%) = Open Voltage (V) * Short Circuit Current Density (mA / cm 2 ) * Charge Rate (%)
한편, 도 12를 참조하면, 본 발명의 실시예에 따른 접합형 태양전지(실시예)는 시간 경과이 경과하여도 초기 효율이 유지됨으로써, 내구성 측면에서도 우수한 것으로 나타났다. Meanwhile, referring to FIG. 12, the junction type solar cell according to an exemplary embodiment of the present invention has been shown to have excellent durability in terms of its initial efficiency even after elapse of time.
반면, 비교에 따른 적층형 태양전지(비교예)는 5일 이내 효율이 0에 근접하여, 내구성이 매우 낮을 것을 확인할 수 있다. On the other hand, compared to the stacked solar cell according to the comparison (comparative example) within 5 days efficiency is close to 0, it can be confirmed that the durability is very low.
이는 본 발명의 실시예에 따른 접합형 태양전지는 카본 전극이 페로브스카이트 결정구조에 대해 안정하여, 상호 접합에 의해서도 페로브스카이트 화합물의 광 흡수율을 유지시켜 줄 수 있기 때문이다. This is because in the junction type solar cell according to the embodiment of the present invention, the carbon electrode is stable to the perovskite crystal structure and can maintain the light absorption of the perovskite compound even by mutual bonding.
또한, 본 발명의 실시예에 따른 접합형 태양전지는 진공 증착과 같은 증착이 공정이 아닌 비교적 낮은 온도 범위의 열처리 공정을 수행하여 구현함으로써, 제조공정 측면에서도 적층형 태양전지 보다 용이하다. In addition, the junction solar cell according to the embodiment of the present invention is implemented by performing a heat treatment process in a relatively low temperature range, not a deposition such as vacuum deposition process, it is easier than the stacked solar cell in terms of manufacturing process.
더 나아가, 본 발명의 실시예에 따른 접합형 태양전지는 Ag, Au 과 같은 금속이 아닌 Carbon 재료를 이용하여 비용 측면에서도 경제적이다.Furthermore, the bonded solar cell according to the embodiment of the present invention is economical in terms of cost by using a carbon material other than a metal such as Ag and Au.
이하, XaYbZc 의 화학식을 따르는 제1 페로브스카이트 화합물에서, Y=Sb인 경우에 대해 설명한다.Hereinafter, the case where Y = Sb in the 1st perovskite compound which follows the chemical formula of X a Y b Z c will be described.
도 13은 본 발명의 실시예에 따른 페로브스카이트 화합물의 결정구조를 나타낸 도면으로. XaYbZc 에서, X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나, Y=Bi, Z=F, I, Br, Cl 중 하나이며, a:b:c=3:2:9 이다. 13 is a view showing a crystal structure of a perovskite compound according to an embodiment of the present invention. In X a Y b Z c , one of X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li, Y = Bi, Z = F, I, One of Br, Cl, and a: b: c = 3: 2: 9.
이하, X3Sb2Z9 페로브스카이트 화합물에 대해 주로 설명하지만, 해당 설명은 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5을 만족하는 모든 XaSbbZc 페로브스카이트 화합물에 대해서도 동일하게 적용될 수 있다.Hereinafter, the X 3 Sb 2 Z 9 perovskite compound will be mainly described, but the description is 0.5 <b <0.7, 2.5 <with respect to the total mole number a = 1 of the monovalent organic / inorganic cation contained in the X position. The same applies to all X a Sb b Z c perovskite compounds that satisfy c <3.5.
본 발명의 실시예에 따른 페로브스카이트 화합물(X3Sb2Y9)은 종래기술의 페로브스카이트 화합물 구조가 습기에 취약하고, 고온에서 내구성이 낮은 문제점을 개선할 수 있다. Perovskite compound (X 3 Sb 2 Y 9 ) according to an embodiment of the present invention can improve the problem that the perovskite compound structure of the prior art is vulnerable to moisture, low durability at high temperatures.
본 발명의 실시예에 따른 페로브스카이트 화합물은 Sb를 이용하여 페로브스카이트 결정구조를 형성하므로 납(Pb)과 같은 높은 독성의 물질을 대체할 수 있다. The perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Sb, and thus may replace a highly toxic substance such as lead (Pb).
따라서, 본 발명의 실시예에 따른 페로브스카이트 화합물은 안정성 측면에서 우수하다. Therefore, the perovskite compound according to the embodiment of the present invention is excellent in terms of stability.
본 발명의 실시예에 따른 페로브스카이트 화합물의 광 흡수도, 태양 전지에 적용됨에 따른 효율의 개선 등에 관해서는 후술하기로 한다. Light absorbance of the perovskite compound according to the embodiment of the present invention, improvement of efficiency according to application to a solar cell, etc. will be described later.
도 14는 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법에 의해 형성된 페로브스카이트 화합물의 사진이다. 14 is a photograph of a perovskite compound formed by the method for producing a perovskite compound according to an embodiment of the present invention.
본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 화합물의 전구체 분말을 혼합한 후 열처리하여 형성되는 것에 특징이 있다. Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
구체적으로, 본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 XZ 화합물 분말을 준비하는 단계, SbZ3
화합물 분말을 준비하는 단계, 상기 XZ 화합물 분말 및 상기 SbZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계 및 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함할 수 있다. Specifically, the method for producing a perovskite compound according to an embodiment of the present invention comprises the steps of preparing a XZ compound powder, SbZ 3 The method may include preparing a compound powder, mixing the XZ compound powder and the SbZ 3 compound powder to form a mixed powder, and heat treating the mixed powder to prepare a compound represented by the following formula. .
[화학식] [Formula]
XaSbbZc
X a Sb b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 상기 화학식으로 표시되는 페로브스카이트 화합물은 X3Sb2Z9일 수 있다.Preferably a: b: c = 3: 2: 9. For example, the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
상기 열처리 하는 단계는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 한편, 상기 가열노 내의 온도는 140℃ 이상 200℃ 이하의 범위에서 수행될 수 있다. The heat treatment may include heating the mixed powder in a heating furnace. On the other hand, the temperature in the heating furnace may be carried out in the range of 140 ℃ 200 ℃.
한편, XZ 화합물의 농도는 1.5mmol이고, SbZ3화합물의 농도는 1mmol일 수 있다. Meanwhile, the concentration of the XZ compound may be 1.5 mmol, and the concentration of the SbZ 3 compound may be 1 mmol.
상기 열처리하는 단계는 50분 이상 70분 이하로 수행될 수 있다. The heat treatment may be performed in 50 minutes or more and 70 minutes or less.
상기와 같은 제조 공정에 의해 도 14에 나타난 사진과 같은 페로브스카이트 화합물을 얻을 수 있다. By the above manufacturing process it is possible to obtain a perovskite compound as shown in the photograph shown in FIG.
이하에서는, 본 발명의 실시예에 따른 태양전지에 대하여 설명하기로 한다. Hereinafter, a solar cell according to an embodiment of the present invention will be described.
도 15는 본 발명의 실시예에 따른 태양전지(1000)를 개략적으로 나타낸 도면이다. 도 16은 본 발명의 실시예에 따른 태양전지(1000)의 단면을 나타낸 사진이다.15 is a view schematically showing a solar cell 1000 according to an embodiment of the present invention. 16 is a photograph showing a cross section of a solar cell 1000 according to an embodiment of the present invention.
도 15 및 도 16을 참조하면, 본 발명의 실시예에 따른 태양전지(1000)는 제1 전극(100), 상기 제1 전극 상에 형성되는 광 흡수층(200) 및 광 흡수층(200) 상에 형성되는 제2 전극(300)을 포함하되, 제1 전극(100), 제2 전극(300)은 광 흡수층(200)의 접착력에 의해 상기 광 흡수층과 접착되어 형성될 수 있다. 15 and 16, a solar cell 1000 according to an embodiment of the present invention is disposed on a first electrode 100, a light absorbing layer 200, and a light absorbing layer 200 formed on the first electrode. Including a second electrode 300 is formed, the first electrode 100, the second electrode 300 may be formed by being bonded to the light absorbing layer by the adhesive force of the light absorbing layer 200.
한편, 본 발명의 실시예에 따른 광 흡수층(200)은 페로브스카이트 화합물을 포함하고, 페로브스카이트 화합물은 화학식으로 표시될 수 있다. Meanwhile, the light absorbing layer 200 according to the embodiment of the present invention may include a perovskite compound, and the perovskite compound may be represented by a chemical formula.
[화학식] [Formula]
XaSbbZc
X a Sb b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 상기 화학식으로 표시되는 페로브스카이트 화합물은 X3Sb2Z9일 수 있다.Preferably a: b: c = 3: 2: 9. For example, the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
제1 전극(100)은 ITO (indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 또는 유연 투명 전극 기판 중 어느 하나가 선택되고, 상기 선택된 기판 상에 형성되는TiO2층 (120)을 포함할 수 있다. The first electrode 100 may include a TiO 2 layer 120 selected from an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, or a flexible transparent electrode substrate, and is formed on the selected substrate. Can be.
유연 투명 전극 기판은 금속 배선층이 형성된 폴리머 기판을 포함하여, 폴리머 기판은 폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성에폭시수지로 이루어지는 군으로부터 선택되는 기판일 수 있다. The flexible transparent electrode substrate includes a polymer substrate on which a metal wiring layer is formed, and the polymer substrate includes polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), and polymethylmethacrylate ( PMMA), polyimide (PI), ethylene vinyl acetate (EVA), amorphous polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate ( PCTG), modified triacetylcellulose (TAC), cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), It may be a substrate selected from the group consisting of polyetherimide (PEI), polydimethylsiloncene (PDMS), silicone resin, fluorine resin and modified epoxy resin.
다만, 본 발명의 제1 전극에 포함되는 기판은 상기의 제시된 예로 제한되지 않는다. However, the substrate included in the first electrode of the present invention is not limited to the examples presented above.
TiO2층(120)은 blocking TiO2층(122) 및 blocking TiO2층(122) 상에 형성되는 mesoporous TiO2층(124)을 포함할 수 있다. The TiO 2 layer 120 may include a blocking TiO 2 layer 122 and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 layer 122.
TiO2층(120)은 전자수송층으로서의 기능을 수행할 수 있다The TiO 2 layer 120 may function as an electron transport layer.
제1 전극(100)은 ZrO2층(130)을 더 포함할 수 있으며, TiO2층(120)과 마찬가지로, ZrO2층(130) 전자수송층으로서의 기능을 수행한다. The first electrode 100 may further include a ZrO 2 layer 130, as with the TiO 2 layer 120, and performs a ZrO 2 layer 130 functioning as an electron transport layer.
한편, 상기 TiO2층의 두께는, 300nm 이상 6um 이하의 범위에서 형성될 수 있으며, ZrO2층의 두께는 300nm 이상 2um 이하의 범위에서 형성될 수 있다.Meanwhile, the thickness of the TiO 2 layer may be formed in the range of 300 nm or more and 6 μm or less, and the thickness of the ZrO 2 layer may be formed in the range of 300 nm or more and 2 μm or less.
제2 전극(300)은 카본 전극(Carbon)일 수 있다. The second electrode 300 may be a carbon electrode.
카본(Carbon) 전극은 페로브스카이트 화합물에 의해 산화 등과 같은 반응이 일어나지 않아 시간 경과에 따른 태양 전지의 효율을 높게 유지시켜 줄 수 있다. Carbon electrode can maintain a high efficiency of the solar cell over time because a reaction such as oxidation does not occur by the perovskite compound.
한편, 카본(Carbon) 전극은 금속 전극과 달리 진공 증착 방식을 이용하지 않고, 페로브스카이트 화합물의 접착력에 의해 접착될 수 있어, 페로브스카이트 화합물과 용이하게 결합될 수 있다.Meanwhile, unlike a metal electrode, a carbon electrode may be bonded by an adhesive force of a perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
이하에서는, 태양전지 제조방법을 도면을 참조하여 설명하기로 한다. Hereinafter, a solar cell manufacturing method will be described with reference to the drawings.
도 17은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다. 17 is a flowchart schematically showing a method of manufacturing a solar cell according to an embodiment of the present invention.
도 17을 참조하면, 본 발명의 실시예에 따른 태양전지의 제조방법은 제1 전극(100)을 형성하는 단계(S100), 제1 전극(100) 상에 광 흡수층(200)을 형성하는 단계(S200) 및 광 흡수층(200) 상에 제2 전극(300)을 형성하는 단계(S300)를 포함하되, 제1 전극(100) 및 제2 전극(300)은 광 흡수층(200)에 의해 접착되어 형성되는 것을 특징으로 한다. Referring to FIG. 17, in the method of manufacturing a solar cell according to an exemplary embodiment of the present invention, forming a first electrode 100 (S100) and forming a light absorbing layer 200 on the first electrode 100. (S200) and forming the second electrode 300 on the light absorbing layer 200 (S300), wherein the first electrode 100 and the second electrode 300 are bonded by the light absorbing layer 200. It is characterized in that the formed.
한편, 광 흡수층(200)을 형성하는 단계(S200)는 하기의 화학식으로 표시되는 페로브스카이트 화합물을 형성하는 단계를 포함한다. On the other hand, forming the light absorbing layer 200 (S200) includes the step of forming a perovskite compound represented by the following formula.
[화학식] [Formula]
XaSbbZc
X a Sb b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
광 흡수층(200)을 형성하는 단계(S200)에서 바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 광 흡수층(200)을 형성하는 단계(S200) 상기 화학식으로 표시되는 페로브스카이트 화합물은 X3Sb2Z9일 수 있다.In the step S200 of forming the light absorbing layer 200, preferably, a: b: c = 3: 2: 9. For example, the step of forming the light absorbing layer 200 (S200) the perovskite compound represented by the formula may be X 3 Sb 2 Z 9 .
제1 전극을 형성하는 단계(S100)는 유연 투명 전극 기판, ITO (indium tin oxide) 기판 또는 FTO(Fluorine Doped Tin Oxide) 기판 중 어느 하나의 기판을 준비하는 단계(S110) 및 유연 투명 전극 기판, ITO 기판 및 FTO(Fluorine Doped Tin Oxide) 기판 중 어느 하나의 기판 상에 TiO2층을 형성하는 단계(S120)를 포함할 수 있다 Forming the first electrode (S100) comprises preparing a substrate of any one of a flexible transparent electrode substrate, an indium tin oxide (ITO) substrate or a Fluorine Doped Tin Oxide (FTO) substrate (S110) and a flexible transparent electrode substrate, The method may include forming a TiO 2 layer on one of an ITO substrate and a Fluorine Doped Tin Oxide (FTO) substrate (S120).
(이하에서는, FTO기판을 이용하여 실시하는 예만 설명하기로 한다. 다만, 본 발명의 실시예 들은 상기 언급한 바와 같이 유연성과 투명성이 있는 기판을 모두 포함하는 것이며, 이하에서 설명하는 예로 제한하는 것은 아니다.)(Hereinafter, only the example performed using the FTO substrate will be described. However, the embodiments of the present invention include both flexible and transparent substrates as mentioned above. no.)
FTO 기판을 준비하는 단계(S110)는 FTO 기판과 TiO2층 간 접착력을 향상시키기 위해 FTO(Fluorine Doped Tin Oxide) 기판을 가공하는 단계를 포함할 수 있다. Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer.
예를 들면, FTO(Fluorine Doped Tin Oxide) 기판에 에칭할 부분을 제외한 나머지 부분에 Zn 분말을 고르게 도포시킨 후 HCl을 DI water 에 1:1 에서 1:3 비율로 희석 시킨 용액을 균일하게 도포할 수 있다. For example, evenly apply Zn powder to the remaining portions other than the portions to be etched on a Fluorine Doped Tin Oxide (FTO) substrate, and then uniformly apply a solution in which HCl is diluted 1: 1 to 1: 3 in DI water. Can be.
에칭된 상기 FTO(Fluorine Doped Tin Oxide) 기판을 아세톤, IPA, DI 순으로 초음파 세척기를 이용하여 세척할 수 있다. The etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI.
다음으로, 세척된 FTO(Fluorine Doped Tin Oxide) 기판은 100℃에서 건조하고, UV Ozone cleaner에서 600 초간 처리할 수 있다. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
따라서, 상기와 같은 FTO 기판의 표면 처리를 통해 TiO2층과의 접착력을 향상시킬 수 있다. Therefore, it is possible to improve the adhesion with the TiO 2 layer through the surface treatment of the FTO substrate as described above.
TiO2층을 형성하는 단계(S120)는 Blocking TiO2층을 형성하는 단계 및 Blocking TiO2층 상에 Mesoporous TiO2층을 형성하는 단계를 포함할 수 있다. Forming the TiO 2 layer (S120) may include forming a blocking TiO 2 layer and forming a Mesoporous TiO 2 layer on the blocking TiO 2 layer.
Blocking TiO2층을 형성하는 단계는 TiO2 용액을 제조하는 단계, TiO2 용액을 이용하여 FTO 기판에 TiO2 코팅막을 형성하는 단계, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Blocking forming a TiO 2 layer may include the step, step, drying the coated film to form the TiO 2 TiO 2 coating on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
TiO2 용액을 제조하는 단계에서 TiO2 용액은 Titanium diisopropoxide Sbs(acetylacetonate) 75 wt. % in isopropanol 용액을 1-butanol 용액에 희석시켜 0.15M의 농도로 제조될 수 있다. In preparing a solution of TiO 2 TiO 2 solution Titanium diisopropoxide Sbs (acetylacetonate) 75 wt . The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
TiO2 코팅막을 형성하는 단계에서 TiO2 코팅막은 20s초동안 2000rpm에서 스핀 코팅함으로 형성될 수 있다.In the step of forming the TiO 2 coating TiO 2 coating film can be formed by spin coating at 2000rpm for 20s seconds.
TiO2 코팅막을 건조하는 단계에서 TiO2 코팅막은 125℃ 이상에서 5분간 열처리함으로써 건조될 수 있다. In the step of drying the coating layer TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 ℃ 5 minutes.
다음으로, Blocking TiO2층 상에 Mesoporous TiO2층을 형성하는 단계는 mesoporous TiO2 용액을 제조하고, TiO2 코팅막을 형성한 후, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Next, the forming of the Mesoporous TiO 2 layer on the Blocking TiO 2 layer may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
mesoporous TiO2 용액은 mesoporous TiO2를 무수 에탄올(hydrous ethanol)에 용해하여 제조될 수 있으며, 필요에 따라 농도를 조절하여 사용할 수 있다.Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
mesoporous TiO2층에서, TiO2 코팅막은 450℃ 이상에서 30분간 열처리함으로써 건조될 수 있다. In the mesoporous TiO 2 layer, the TiO 2 coating film may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
한편, 제1 전극을 형성하는 단계(S100)는 상기 mesoporous TiO2층에 조도를 형성하는 단계(S140)를 더 포함할 수 있다. Meanwhile, the forming of the first electrode (S100) may further include forming roughness on the mesoporous TiO 2 layer (S140).
상기 mesoporous TiO2 층에 조도를 형성하기 위해 TiCl4 용액을 이용할 수 있다. TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer.
예를 들면, 20 mM의 TiCl4
용액 1ml와 증류수 99ml를 섞은 혼합 용액을 준비하는 단계, 상기 혼합 용액에 mesoporous TiO2 층이 형성된 기판을 함침하는 단계, 다음으로, 제1차 열처리 단계, 세정하는 단계, 건조하는 단계 및 2차 열처리 단계를 수행할 수 있다. For example, 20 mM TiCl 4 Preparing a mixed solution of 1 ml of solution and 99 ml of distilled water, impregnating the substrate with the mesoporous TiO 2 layer formed therein, followed by a first heat treatment step, a cleaning step, a drying step, and a second heat treatment. The steps can be performed.
조도를 형성하는 단계에서 1차 열처리 단계는 70℃ 내지 100℃의 온도범위에서 진행될 수 있으며, 2차 열처리 단계는 450℃ 이상 30분 진행될 수 있다.In the step of forming the roughness, the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C., and the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
상기와 같이 일련의 제조 공정에 의해 mesoporous TiO2층 상에 조도가 형성됨으로써, 광 흡수층과 TiO2층 간의 접착력이 보다 향상될 수 있다. As the roughness is formed on the mesoporous TiO 2 layer by a series of manufacturing processes as described above, the adhesion between the light absorbing layer and the TiO 2 layer may be further improved.
광 흡수층을 형성하는 단계(S200)는 X3Sb2Y9 용액을 형성하는 단계를 포함할 수 있다. Forming the light absorbing layer (S200) may include forming a X 3 Sb 2 Y 9 solution.
X3Sb2Y9 용액을 형성하는 단계는, XZ 화합물 분말을 준비하는 단계(S210), SbZ3 화합물 분말을 준비하는 단계(S220), 상기 XZ 화합물 분말 및 상기 SbZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계(S230), 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계(S240) 및 상기 열처리 된 혼합 분말을 DMF 용매에 용해시키는 단계(S250)를 포함할 수 있다.Forming the X 3 Sb 2 Y 9 solution, preparing a XZ compound powder (S210), preparing a SbZ 3 compound powder (S220), the XZ compound powder and the SbZ 3 compound powder mixed and mixed Forming a powder (S230), by heat-treating the mixed powder, to produce a compound represented by the following formula (S240) and the step of dissolving the heat-treated mixed powder in a DMF solvent (S250) may be included. .
[화학식] [Formula]
XaSbbZc
X a Sb b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Z=F, I, Br, Cl 중 하나 Z = F, I, Br, Cl
a=1에 대하여, 0.5<b<0.7, 2.5<c<3.5 for a = 1, 0.5 <b <0.7, 2.5 <c <3.5
혼합 분말을 열처리는 단계에서, 바람직하게는 a:b:c=3:2:9 일 수 있다. 예를 들어, 혼합 분말을 열처리는 단계에서 상기 화학식으로 표시되는 화합물은 X3Sb2Z9일 수 있다.The heat treatment of the mixed powder may be carried out in a step, preferably a: b: c = 3: 2: 9. For example, the compound represented by the formula in the step of heat-treating the mixed powder may be X 3 Sb 2 Z 9 .
S210 내지 S240의 일련의 과정은 페로브스카이트 화합물의 제조 공정과 동일하므로 생략하기로 한다. Since a series of processes of S210 to S240 are the same as the process of producing the perovskite compound, it will be omitted.
광 흡수층을 형성하는 단계(S200)는 제1 전극(100) 및 제2 전극(300)을 준비한 후, X3Sb2Z9
용액을 제1 전극(100)과 제2 전극(300) 사이에 dropping 하는 단계(S260) 또는 X3Sb2Z9 용액을 상기 제1 전극 또는 제2 전극 상에 스핀 코팅하는 단계를 선택적으로 수행하여 형성할 수 있다. Forming the light absorbing layer (S200) after preparing the first electrode 100 and the second electrode 300, X 3 Sb 2 Z 9 Selectively dropping the solution between the first electrode 100 and the second electrode 300 (S260) or spin coating the X 3 Sb 2 Z 9 solution on the first electrode or the second electrode. Can be formed.
다음으로 광 흡수층을 형성하는 단계(S200)는 X3Sb2Z9 용액을 건조하는 단계(S270)를 포함할 수 있다.Next, forming the light absorbing layer (S200) may include drying the X 3 Sb 2 Z 9 solution (S270).
상기 X3Sb2Z9 용액을 건조하는 단계는 0 ℃ 이상 200 ℃ 이하의 온도 범위에서 수행될 수 있다. Drying the X 3 Sb 2 Z 9 solution may be carried out at a temperature range of 0 ℃ to 200 ℃.
한편, 제2 전극을 형성하는 단계(S300)는 유리 기판, FTO(Fluorine Doped Tin Oxide) 또는 ITO (Indium Tin Oxide)가 증착된 유리 기판 및 유연 투명 전극 기판 중 어느 하나의 기판을 준비하는 단계(S310), 탄소 분말을 준비하는 단계(S320), 상기 탄소 분말을 이용하여, 상기 유리 기판, FTO(Fluorine Doped Tin Oxide) 또는 ITO (Indium Tin Oxide)가 증착된 유리 기판 및 유연 투명 전극 기판 중 어느 하나의 기판 상에 탄소 분말을 코팅하는 단계(S330) 및 상기 탄소 분말이 코팅된 기판을 열처리하는 단계(S340)를 포함할 수 있다.The forming of the second electrode (S300) may include preparing a substrate of any one of a glass substrate, a glass substrate on which Fluorine Doped Tin Oxide (FTO) or an Indium Tin Oxide (ITO) is deposited, and a flexible transparent electrode substrate ( S310), preparing a carbon powder (S320), by using the carbon powder, any one of the glass substrate, FTO (Fluorine Doped Tin Oxide) or ITO (Indium Tin Oxide) is deposited and a flexible transparent electrode substrate It may include the step of coating the carbon powder on one substrate (S330) and the step of heat-treating the carbon powder coated substrate (S340).
상기 탄소 분말이 코팅된 기판을 열처리하는 단계(S340)는 300℃ 이상의 온도 범위에서 수행될 수 있다. The heat treatment of the substrate coated with carbon powder (S340) may be performed at a temperature range of 300 ° C. or higher.
탄소 분말이 코팅된 기판을 열처리하는 단계(S340)는 25분 내지 35분 동안 수행될 수 있다.Heat treatment of the substrate coated with carbon powder (S340) may be performed for 25 to 35 minutes.
다음으로, 광 흡수층과 상기 제1 전극층, 상기 광 흡수층과 상기 제2 전극층의 측면에 접착층을 형성하는 단계(S400)를 더 포함할 수 있다. 상기 접착층은 에폭시 수지로 형성될 수 있다.Next, the method may further include forming an adhesive layer on side surfaces of the light absorbing layer, the first electrode layer, the light absorbing layer, and the second electrode layer (S400). The adhesive layer may be formed of an epoxy resin.
태양전지의 효율Solar cell efficiency
이하에서는, 종래기술에 따라 제조된 태양전지(비교예)와 본 발명의 실시예에 따라 제조된 태양전지(실험예)의 효율 차이를 실험을 통하여 증명하기로 한다. Hereinafter, the difference in efficiency between the solar cell manufactured according to the prior art (comparative example) and the solar cell manufactured according to the embodiment of the present invention (experimental example) will be demonstrated through experiments.
[비교예] [Comparative Example]
제1 전극, 제1 전극상에 형성된 광 흡수층, 광 흡수층 상에 형성된 제2 전극을 포함하는 태양전지 A solar cell comprising a first electrode, a light absorbing layer formed on the first electrode, and a second electrode formed on the light absorbing layer.
(1) 광 흡수층의 제조방법 (1) Manufacturing Method of Light Absorption Layer
합성한 FAI 분말과 SbI3 분말을 DMF 용매에 녹인 다음 필터 후 사용Synthesized FAI powder and SbI 3 powder in DMF solvent and then used after filter
스핀코팅 방법을 이용하여 4000 rpm, 25s 의 조건으로 코팅 후 RT~200 ℃ 에서 10분간 후 열처리After spin coating at 4000 rpm and 25 s for 10 minutes at RT ~ 200 ℃
HTL (Spiro, P3HT 등)HTL (Spiro, P3HT, etc.)
Spiro 또는 P3HT 분말을 toluene 또는 chlorobenzene 에 녹인 후 필터. Dissolve Spiro or P3HT powder in toluene or chlorobenzene and filter.
스핀코팅 방법을 이용하여 3000 rpm, 30s 의 조건으로 코팅.Coating at 3000 rpm, 30 s using spin coating method.
(2) 제2 전극(2) second electrode
진공 증발기 (evaporator)를 이용하여 10-5 torr 이상의 진공에서 Ag, Au 등의 금속 전극을 증착Deposition of metal electrodes, such as Ag and Au, at a vacuum of 10 -5 torr or more using a vacuum evaporator
(3) 적층방법(3) Lamination Method
각각의 구성은 스핀 코팅, 진공 증발기를 이용하여 10-5 torr 이상의 진공상태에서 증착됨Each component is deposited in a vacuum over 10 -5 torr using spin coating, vacuum evaporator
[실험예]Experimental Example
(1) 광 흡수층의 제조방법 (1) Manufacturing Method of Light Absorption Layer
합성한 FAI 분말과 SbI3
분말을 이용하여 열처리하여 FA3Sb2I9 분말을 형성Synthesized FAI Powder and SbI 3 Heat treatment with powder to form FA 3 Sb 2 I 9 powder
(2) 제2 전극(2) second electrode
Carbon 전극을 형성Form Carbon Electrode
(3) 적층방법(3) Lamination Method
광 흡수층의 접착력을 이용하여 광 흡수층과 제1 전극, 광 흡수층과 제2 전극이 접착되어 형성Formed by bonding the light absorbing layer and the first electrode, the light absorbing layer and the second electrode using the adhesive force of the light absorbing layer
적층형 태양전지(비교예)는 광 흡수층 상에 제2 전극이 형성되기 위해 Ag 및 Au를 10-5 torr 이상의 진공 상태에서 공정이 진행되는 점에서 본 발명의 실시예에 따른 접합형 태양전지의 제조공정 측면에서 차이점이 있다. In the stacked solar cell (comparative example), a junction solar cell according to an exemplary embodiment of the present invention is manufactured in that a process of Ag and Au in a vacuum state of 10 −5 torr or more is performed to form a second electrode on a light absorbing layer. There is a difference in process.
또한, 본 발명의 실시예에 따른 태양전지(실험예)는 금속이 아닌 카본 재료가 이용되는 점에서 적층형 태양전지(비교예)와 구조적 측면에서 차이가 있다. In addition, the solar cell (experimental example) according to the embodiment of the present invention is different in terms of structure from the laminated solar cell (comparative example) in that carbon material is used instead of metal.
상기와 같은 적층형 태양전지(비교예)와 접합형 태양전지(실시예)의 효율을 각각 측정한 결과 하기에 [표 2]에 나타났다. As a result of measuring the efficiency of the stacked solar cell (comparative example) and the bonded solar cell (example) as described above, it is shown in Table 2 below.
[표 2]에 나타난 것과 같이 0.025 %, 3.47 %로 나타났으며, 접합형 태양전지(실시예)의 효율이 140 배 정도 높게 나타난 것을 확인할 수 있다. As shown in [Table 2], 0.025% and 3.47% were found, and the efficiency of the junction type solar cell (example) was about 140 times higher.
| Voc(V)Voc (V) | Jsc(mA/cm2)Jsc (mA / cm 2 ) | FF(%)FF (%) | PCE(%)PCE (%) | |
| 적층형(비교예)Stacked type (comparative example) | 0.490.49 | 0.130.13 | 3737 | 0.0250.025 |
| 접합형(실시예)Bonding type (Example) | 0.600.60 | 16.1716.17 | 35.735.7 | 3.473.47 |
[표 2] 태양전지의 효율[Table 2] Efficiency of Solar Cell
[식] 효율 (%) = 개방전압(V) * 단락전류밀도(mA/cm2) * 충전률(%)Efficiency (%) = Open Voltage (V) * Short Circuit Current Density (mA / cm 2 ) * Charge Rate (%)
한편, 도 18을 참조하면, 본 발명의 실시예에 따른 접합형 태양전지(실시예)는 시간이 경과하여도 초기 효율이 유지됨으로써, 내구성 측면에서도 우수한 것으로 나타났다. Meanwhile, referring to FIG. 18, the junction type solar cell according to the embodiment of the present invention has been shown to be excellent in terms of durability since the initial efficiency is maintained over time.
반면, 비교에 따른 적층형 태양전지(비교예)는 5일 이내 효율이 0에 근접하여, 내구성이 매우 낮을 것을 확인할 수 있다. On the other hand, compared to the stacked solar cell according to the comparison (comparative example) within 5 days efficiency is close to 0, it can be confirmed that the durability is very low.
이는 본 발명의 실시예에 따른 접합형 태양전지는 카본 전극이 페로브스카이트 결정구조에 대해 안정하여, 상호 접합에 의해서도 페로브스카이트 화합물의 광 흡수율을 유지시켜 줄 수 있기 때문이다. This is because in the junction type solar cell according to the embodiment of the present invention, the carbon electrode is stable to the perovskite crystal structure and can maintain the light absorption of the perovskite compound even by mutual bonding.
이하에서는, 본 발명의 실험예에 따른 TiO2
의 농도별 두께 변화를 비교하고, 각각의 두께에서의 태양전지의 효율을 비교하기로 한다. Hereinafter, TiO 2 according to the experimental example of the present invention The thickness change of each concentration is compared, and the efficiency of the solar cell at each thickness will be compared.
[실험예 1]Experimental Example 1
TiO2의 농도 : 2g/ml, Concentration of TiO 2 : 2 g / ml,
TiO2의 두께 : 5 μmTiO 2 thickness: 5 μm
[실험예 2]Experimental Example 2
TiO2의 농도 : 500mg/mlTiO 2 concentration: 500mg / ml
TiO2의 두께 : 1.5 μmTiO 2 thickness: 1.5 μm
[실험예 3]Experimental Example 3
TiO2의 농도 : 300mg/mlTiO 2 concentration: 300mg / ml
TiO2의 두께 : 500 nmTiO 2 thickness: 500 nm
도 19 내지 도 21은 본 발명의 실험예에 따른 TiO2
의 두께 변화에 따른 효율을 비교한 그래프이다.
19 to 21 are TiO 2 according to the experimental example of the present invention. This is a graph comparing the efficiency according to the change in thickness.
| Voc(V)Voc (V) | Jsc(mA/cm2)Jsc (mA / cm 2 ) | FF(%)FF (%) | PCE(%)PCE (%) | |
| 실험예 1(5 μm)Experimental Example 1 (5 μm) | 0.570.57 | 12.6512.65 | 39.6339.63 | 2.902.90 |
| 실험예 2(1.5 μm)Experimental Example 2 (1.5 μm) | 0.390.39 | 0.580.58 | 27.7927.79 | 0.060.06 |
| 실험예 3(500 nm)Experimental Example 3 (500 nm) | 0.380.38 | 14.614.6 | 21.8321.83 | 1.231.23 |
[표 3] TiO2
의 두께에 따른 효율 비교표Table 3 TiO 2 Comparison table for the thickness of
도 19 내지 도 21 및 [표 3]을 참조하면, TiO2 의 두께가 두꺼울수록 태양전지의 효율은 높게 나타났으며, 본 발명의 실험예에서는 5 μm 일 때, 2.90 % 로 500nm 일 때 보다 2 배 이상 높게 나타났다. 19 to 21 and Table 3, the thicker the thickness of TiO 2, the higher the efficiency of the solar cell was. In the experimental example of the present invention, when 5 μm, 2.90%, and when compared to 500 nm 2 It was more than twice as high.
이하에서는, TiO2 상에 형성되는 ZrO2 농도에 따른 태양전지의 효율을 비교한다. Hereinafter, the efficiency of the solar cell according to the concentration of ZrO 2 formed on the TiO 2 is compared.
실험예 4 및 5 에서 TiO2의 농도 : 2g/ml 으로 동일하다. The concentration of TiO 2 in Experimental Examples 4 and 5 was the same at 2 g / ml.
그 외 실험 조건: 0~1V Dwell time : 200ms Mask size : 0.16mmOther test conditions: 0 ~ 1V Dwell time: 200ms Mask size: 0.16mm
[실험예 4]Experimental Example 4
ZrO2 농도 : 2mg/mlZrO 2 concentration: 2mg / ml
[실험예 5]Experimental Example 5
ZrO2 농도 : 500mg/mlZrO 2 concentration: 500mg / ml
| Voc(V)Voc (V) | Jsc(mA/cm2)Jsc (mA / cm 2 ) | FF(%)FF (%) | PCE(%)PCE (%) | |
| 실험예 4ZrO2 농도: 3g/mlExperimental Example 4 ZrO 2 Concentration: 3 g / ml | 0.1090.109 | 0.0060.006 | 23.9223.92 | 0.00020.0002 |
| 실험예 5ZrO2 농도: 500mg/mlExperimental Example 5 ZrO 2 Concentration: 500 mg / ml | 0.470.47 | 15.9615.96 | 60.1760.17 | 4.574.57 |
[표 4] ZrO2 농도에 따른 효율 비교표 [Table 4] Efficiency comparison table according to ZrO2 concentration
[표 4]를 참조하면, ZrO2 농도에 따라 태양전지의 효율이 상이하게 나타남을 확인할 수 있다. Referring to [Table 4], it can be seen that the efficiency of the solar cell is different depending on the ZrO 2 concentration.
예를 들면, ZrO2 농도가 2g/ml 일 때, 태양전지의 효율은 0.0002 % 로 나타났으며, ZrO2 농도가 500mg/ml 일 때, 태양전지의 효율은 4.57%로 나타나 500mg/ml의 농도에서, 높은 효율 나타냈다. For example, when the ZrO 2 concentration is 2g / ml, the solar cell efficiency is 0.0002%. When the ZrO 2 concentration is 500mg / ml, the efficiency of the solar cell is 4.57%, which is 500mg / ml. In, high efficiency was shown.
또한, 태양전지의 효율은 ZrO2을 사용하지 않았을 때 2.9% 에서 사용했을 때 4.57%로 효율이 상승되었다. In addition, the efficiency of the solar cell increased from 2.9% when ZrO 2 was not used to 4.57% when used.
상기의 실험 결과로부터 ZrO2 농도를 조절하여 태양전지의 효율이 개선할 수 있음을 확인할 수 있다. From the above experimental results, it can be seen that the efficiency of the solar cell can be improved by adjusting the ZrO 2 concentration.
상기 검토한 바와 같이 본 발명의 실시예에 따른 접합형 태양전지는 진공 증착과 같은 증착이 공정이 아닌 비교적 낮은 온도 범위의 열처리 공정을 수행하여 구현함으로써, 제조공정 측면에서도 적층형 태양전지 보다 용이하다. As discussed above, the bonded solar cell according to the exemplary embodiment of the present invention is implemented by performing a heat treatment process in a relatively low temperature range rather than a deposition process such as vacuum deposition, thereby making it easier than a stacked solar cell in terms of a manufacturing process.
더 나아가, 본 발명의 실시예에 따른 접합형 태양전지는 Ag, Au 과 같은 금속이 아닌 Carbon 재료를 이용하여 비용 측면에서도 경제적이다. Furthermore, the bonded solar cell according to the embodiment of the present invention is economical in terms of cost by using a carbon material other than a metal such as Ag and Au.
제2 2nd
페로브스카이트Perovskite
화합물(1-2-7 Compound (1-2-7
페로브스카이트Perovskite
화합물) compound)
본 발명의 실시예에 따른 페로브스카이트 화합물은 하기의 화학식으로 표시될 수 있다. Perovskite compound according to an embodiment of the present invention may be represented by the following formula.
[화학식][Formula]
XaYbZcX a Y b Zc
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족하고, 바람직하게는 a:b:c=1:2:7 이다. 이러한 제2 페로브스카이트 화합물을 편의 상 1-2-7 구조의 페로브스카이트 화합물이라고 부를 수 있다.For a = 1, 1.6 <b <2.4, 5.6 <c <8.4 are satisfied, and a: b: c = 1: 2: 7 is preferable. Such a second perovskite compound may be referred to as a perovskite compound having a 1-2-7 structure for convenience.
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족한다는 것은 페로브스카이트 화합물의 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1일 때, 1.6<b<2.4, 5.6<c<8.4 인 것을 의미한다. 상기의 범위 내에서는 후술하는 발명의 효과가 발휘될 수 있다. For a = 1, satisfying 1.6 <b <2.4, 5.6 <c <8.4 means 1.6 <b when the total moles of monovalent organic / inorganic cations contained in the X position of the perovskite compound a = 1 It means that <2.4, 5.6 <c <8.4. Within the above range, the effects of the invention described later can be exerted.
이하, X1Y2Z7 페로브스카이트 화합물에 대해 주로 설명하지만, 해당 설명은 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족하는 모든 XaYbZc 페로브스카이트 화합물에 대해서도 동일하게 적용될 수 있다.Hereinafter, the X 1 Y 2 Z 7 perovskite compound will be mainly described, but the description is 1.6 <b <2.4, 5.6 < The same applies to all X a Y b Z c perovskite compounds that satisfy c <8.4.
본 발명의 실시예에 따른 페로브스카이트 화합물은 Bi, Sb 을 이용하여 페로브스카이트 결정구조를 형성하므로 납(Pb)과 같은 높은 독성의 물질을 대체할 수 있다. 또한, 본 발명의 실시예에 따른 페로브스카이트 화합물은 공기 중에서 쉽게 산화되지 않아 안정성 측면에서 우수하다. The perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi and Sb, and thus may replace a highly toxic substance such as lead (Pb). In addition, the perovskite compound according to an embodiment of the present invention is not easily oxidized in the air is excellent in terms of stability.
한편, 도 22에는 본 발명의 실시예에 따른 페로브스카이트 화합물의 AFM 사진이 도시되어 있다. 도 22(a)는 도 22(b)의 부분확대도이다. 도 22는 RbBi2I7의 평탄도를 보여준다. 도 22의 RbBi2I7의 구체적인 조도는 다음의 [표 5]의 수치와 같다.On the other hand, Figure 22 is an AFM picture of the perovskite compound according to an embodiment of the present invention. (A) is a partially enlarged view of FIG. 22 (b). 22 shows the flatness of RbBi 2 I 7 . Specific roughness of RbBi 2 I 7 of FIG. 22 is the same as that in Table 5 below.
| Ra (nm)Ra (nm) | Rq (nm)Rq (nm) | Rz (nm)Rz (nm) |
| 71.771.7 | 94.794.7 | 671671 |
본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 화합물의 전구체 분말을 혼합한 후 열처리하여 형성되는 것에 특징이 있다.Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
구체적으로 페로브스카이트 화합물의 제조방법은, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; 상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; 및 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함한다.Specifically, the method for producing a perovskite compound includes the steps of preparing an XZ compound powder and YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And heat treating the mixed powder to prepare a compound represented by the following formula.
[화학식][Formula]
XaYbZcX a Y b Zc
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족For a = 1, 1.6 <b <2.4, 5.6 <c <8.4 are satisfied
상기 혼합 분말을 열처리하는 단계에서, 바람직하게는 a:b:c=1:2:7 이다. 즉, 상기 혼합 분말을 열처리하는 단계에서 상기의 화학식으로 표시되는 화합물은 X1Y2Z7 일 수 있다.In the step of heat-treating the mixed powder, preferably a: b: c = 1: 2: 7. That is, the compound represented by the formula in the heat treatment of the mixed powder may be X 1 Y 2 Z 7 .
상기 열처리 하는 단계는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 상기 가열노 내의 온도는 100℃ 이상 200℃ 이하의 범위에서 수행될 수 있다. The heat treatment may include heating the mixed powder in a heating furnace. The temperature in the heating furnace may be carried out in the range of 100 ℃ to 200 ℃.
한편, XZ 화합물 분말과 YZ3 화합물 분말을 1:2 의 농도 비율로 혼합하면 최종적으로 X1Y2Z7 물질이 만들어질 수 있다. 즉, XZ 화합물의 농도는 1mmol 이고, YZ3화합물의 농도는 2mmol 일 수 있다. 또한, 상기 열처리하는 단계는 5분 이상 20분 이하로 수행될 수 있다.Meanwhile, when the XZ compound powder and the YZ 3 compound powder are mixed at a concentration ratio of 1: 2, the X 1 Y 2 Z 7 material may be finally formed. That is, the concentration of the XZ compound may be 1 mmol, and the concentration of the YZ 3 compound may be 2 mmol. In addition, the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
도 23 및 도 24는 상기 열처리 하는 단계에 따른 효과를 나타내는 도면이다. 구체적으로, 도 23은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 XRD 측정 결과 도면이고, 도 24는 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 광흡수도 변화를 나타낸 도면이다.23 and 24 are views showing the effect of the heat treatment step. Specifically, Figure 23 is a XRD measurement results showing the structural change before and after the heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention, Figure 24 is a perovskite compound preparation according to an embodiment of the present invention A diagram showing the change in light absorbency before and after heat treatment in the method.
도 23 및 도 24에서, RbBi2I7가 사용되었고, (a)는 열처리 전을, (b)는 열처리 후를 나타낸다.In FIGS. 23 and 24, RbBi 2 I 7 was used, (a) before the heat treatment, and (b) after the heat treatment.
도 23을 참조하면, 열처리 후에 결정성이 향상되는 것을 알 수 있다. Referring to FIG. 23, it can be seen that the crystallinity is improved after the heat treatment.
도 24는 UV-visible spectroscopy을 이용하였을 때 물질의 흡수도를 나타내고 있다. 열처리 전에는 흡수영역이 대략 600nm까지이나, 열처리 후에는 7000nm까지로 확대(음영 참고)되었다. Figure 24 shows the absorbance of the material when using UV-visible spectroscopy. Before the heat treatment, the absorption region was extended to approximately 600 nm, but after the heat treatment, the absorption region was expanded to 7000 nm (see shading).
열처리에 의하여 물질의 흡수 영역이 확대되었음을 알 수 있으며, 이러한 물질이 태양전지에 사용되면 태양전지 효율이 증가할 수 있다.It can be seen that the absorption region of the material is enlarged by the heat treatment, and when such a material is used in the solar cell, the solar cell efficiency may increase.
도 25는 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면이고, 도 26은 본 발명의 실시예에 따른 태양전지의 효율을 나타낸 도면이다.25 is a view schematically showing a solar cell according to an embodiment of the present invention, Figure 26 is a view showing the efficiency of the solar cell according to an embodiment of the present invention.
도 25를 참조하면, 본 발명의 실시예에 따른 태양전지는 제1 전극(100), 상기 제1 전극(100) 상에 형성되는 광 흡수층(200) 및 상기 광 흡수층(200) 상에 형성되는 제2 전극(300)을 포함하고, 상기 광 흡수층(200)은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함한다.Referring to FIG. 25, the solar cell according to the exemplary embodiment of the present invention is formed on the first electrode 100, the light absorbing layer 200 formed on the first electrode 100, and the light absorbing layer 200. It includes a second electrode 300, the light absorbing layer 200 includes a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZcX a Y b Zc
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족For a = 1, 1.6 <b <2.4, 5.6 <c <8.4 are satisfied
바람직하게는 a:b:c=1:2:7 일 수 있다. 즉, 상기의 화학식으로 표시되는 페로브스카이트 화합물은 X1Y2Z7 일 수 있다.Preferably a: b: c = 1: 2: 7. That is, the perovskite compound represented by the above formula may be X 1 Y 2 Z 7 .
제1 전극(100)과 제2 전극(300)은 광 흡수층(200)의 페로브스카이트 화합물의 접착력에 의하여 광 흡수층(200)에 접착될 수 있다.The first electrode 100 and the second electrode 300 may be attached to the light absorbing layer 200 by the adhesive force of the perovskite compound of the light absorbing layer 200.
제1 전극(100)은 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판 및 상기 제1 기판 상에 형성되는 TiO2층(120)을 포함할 수 있다.The first electrode 100 may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate, and a TiO 2 formed on the first substrate. It may include layer 120.
ITO(indium tin oxide) 기판은 ITO가 증착된 유리 기판, FTO 기판은 FTO가 증착된 유리 기판이다. An ITO substrate is a glass substrate on which ITO is deposited, and an FTO substrate is a glass substrate on which FTO is deposited.
또한, 상기 유연 투명 전극 기판은, 폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성 에폭시수지로 이루어지는 군으로부터 선택되는 폴리머 기판으로 형성될 수 있다.In addition, the flexible transparent electrode substrate, polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), Ethylene Vinyl Acetate (EVA), Amorphous Polyethylene Terephthalate (APET), Polypropylene Terephthalate (PPT), Polyethylene Terephthalate Glycerol (PETG), Polycyclohexylenedimethylene Terephthalate (PCTG), Modified Triacetyl Cellulose (TAC) ), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydie It may be formed of a polymer substrate selected from the group consisting of methylsilone silane (PDMS), silicone resin, fluorine resin and modified epoxy resin.
다만, 유연 투명 전극 기판은 상기의 제시된 예로 제한되지 않는다.However, the flexible transparent electrode substrate is not limited to the examples presented above.
TiO2층(120)은 전자수송층으로서의 기능을 수행할 수 있다. TiO2층(120)은, blocking TiO2(122)층 및 상기 blocking TiO2(122)층 상에 형성되는 mesoporous TiO2층(124)을 포함할 수 있다The TiO 2 layer 120 may function as an electron transport layer. The TiO 2 layer 120 may include a blocking TiO 2 122 layer and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 122 layer.
상기 제1 전극(100)은 ZrO2층(130)을 더 포함할 수 있다. ZrO2층(130)은 TiO2층(120) 상에 형성되며, TiO2층(120)과 마찬가지로 전자수송층으로서의 기능을 수행한다.The first electrode 100 may further include a ZrO 2 layer 130. ZrO 2 layer 130 is formed on the TiO 2 layer 120, and performs a function as an electron transport layer, like TiO 2 layer 120.
이 경우, 제1 전극(100)은 제1 기판, blocking TiO2(122), mesoporous TiO2층(124), ZrO2층(130) 순으로 적층되어 형성된다.In this case, the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
제2 전극(300)은 카본(carbon)을 포함할 수 있다. 즉, 제2 전극(300)은 카본으로 형성된 층일 수 있다. 또한, 제2 전극(300)은 제2 기판에 탄소 분말이 코팅된 것일 수 있다.The second electrode 300 may include carbon. That is, the second electrode 300 may be a layer formed of carbon. In addition, the second electrode 300 may be coated with carbon powder on the second substrate.
여기서, 제2 기판은 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 기판일 수 있다.Here, the second substrate may be a substrate selected from any one of a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
본 발명의 실시예에 따른 페로브스카이트 화합물은 공기 중에서 쉽게 산화되지 않으므로 공기 중에서 제2 전극(300)이 광 흡수층(200) 상에 형성될 수 있으므로, 진공 상태에서 제2 전극(300)을 형성할 필요가 없다. Since the perovskite compound according to the embodiment of the present invention is not easily oxidized in the air, the second electrode 300 may be formed on the light absorbing layer 200 in the air, and thus the second electrode 300 may be removed in a vacuum state. There is no need to form.
한편, 카본 전극은 금속 전극과 달리 진공 증착 방식을 이용하지 않고, 페로브스카이트 화합물의 접착력에 의해 접착될 수 있어, 페로브스카이트 화합물과 용이하게 결합될 수 있다.Meanwhile, unlike the metal electrode, the carbon electrode may be bonded by the adhesive force of the perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
도 26은 제1 전극(100)은 FTO, blocking TiO2(122), mesoporous TiO2층(124), ZrO2층(130)을 포함하고, 광 흡수층(200)은 RbBi2I7을 포함하며, 제2 전극(300)은 FTO에 카본이 형성된 것을 이용한 태양전지의 효율을 나타낸 것이다. 구체적인 태양전지의 효율은 다음의 [표 6]와 같다.FIG. 26 illustrates that the first electrode 100 includes FTO, blocking TiO 2 122, a mesoporous TiO 2 layer 124, and a ZrO 2 layer 130, and the light absorbing layer 200 includes RbBi 2 I 7 . The second electrode 300 represents the efficiency of the solar cell using carbon formed in the FTO. Specific efficiency of the solar cell is shown in the following [Table 6].
| Voc (V)Voc (V) | Jsc (mA/cm2)Jsc (mA / cm2) | FF (%)FF (%) | PCE (%)PCE (%) |
| 0.330.33 | 10.1210.12 | 46.5746.57 | 1.551.55 |
상기 [표 6]에서 FF는 fill factor, PCE는 power conversion efficiency를 의미한다. In Table 6, FF means fill factor and PCE means power conversion efficiency.
도 27은 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다.27 is a flowchart schematically illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
도 27을 참조하면, 본 발명의 실시예에 따른 태양전지의 제조방법은, 제1 전극(100)을 형성하는 단계(S100), 광 흡수층(200)을 형성하는 단계(S200), 제2 전극(300)을 형성하는 단계(S300)를 포함하고, 광 흡수층(200)은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함한다.Referring to FIG. 27, in the method of manufacturing the solar cell according to the exemplary embodiment of the present invention, forming the first electrode 100 (S100), forming the light absorbing layer 200 (S200), and the second electrode Forming step 300 (S300), the light absorbing layer 200 includes a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZcX a Y b Zc
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족For a = 1, 1.6 <b <2.4, 5.6 <c <8.4 are satisfied
광 흡수층(200)을 형성하는 단계(S200)에서, 바람직하게는 a:b:c=1:2:7 이다. 즉, 광 흡수층(200)을 형성하는 단계(S200)에서 상기의 화학식으로 표시되는 페로브스카이트 화합물은 X1Y2Z7 일 수 있다.In the step (S200) of forming the light absorbing layer 200, preferably a: b: c = 1: 2: 7. That is, the perovskite compound represented by the above formula in the step of forming the light absorbing layer 200 may be X 1 Y 2 Z 7 .
제1 전극(100)을 형성하는 단계(S100)는 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판을 준비하는 단계(S110) 및 제1 기판 상에 TiO2층(120)을 형성하는 단계(S120)를 포함할 수 있다. Forming the first electrode 100 (S100) may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. The method may include forming a TiO 2 layer 120 on the S110 and the first substrate (S120).
(이하에서는, 제1 기판을 FTO기판을 이용하여 실시하는 예를 설명하기로 한다. 다만, 하기의 설명이 다른 종류의 제1 기판에도 적용될 수 있으며, 제1 기판의 종류를 제한하는 것은 아니다.)(Hereinafter, an example in which the first substrate is implemented using the FTO substrate will be described. However, the following description may be applied to other types of first substrates, but the type of the first substrate is not limited. )
FTO 기판을 준비하는 단계(S110)는 FTO 기판과 TiO2층(120) 간 접착력을 향상시키기 위해 FTO(Fluorine Doped Tin Oxide) 기판을 가공하는 단계를 포함할 수 있다. Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer 120.
예를 들면, FTO(Fluorine Doped Tin Oxide) 기판에 에칭할 부분을 제외한 나머지 부분에 Zn 분말을 고르게 도포시킨 후 HCl을 DI water 에 1:1 에서 1:3 비율로 희석 시킨 용액을 균일하게 도포할 수 있다. For example, evenly apply Zn powder to the remaining portions other than the portions to be etched on a Fluorine Doped Tin Oxide (FTO) substrate, and then uniformly apply a solution in which HCl is diluted 1: 1 to 1: 3 in DI water. Can be.
에칭된 상기 FTO(Fluorine Doped Tin Oxide) 기판을 아세톤, IPA, DI 순으로 초음파 세척기를 이용하여 세척할 수 있다. 다음으로, 세척된 FTO(Fluorine Doped Tin Oxide) 기판은 100℃에서 건조하고, UV Ozone cleaner에서 600 초간 처리할 수 있다. The etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
상기와 같은 FTO 기판의 표면 처리를 통해 TiO2층(120)과의 접착력을 향상시킬 수 있다.Through the surface treatment of the FTO substrate as described above it is possible to improve the adhesion to the TiO 2 layer 120.
TiO2층(120)을 형성하는 단계(S120)는 Blocking TiO2층(122)을 형성하는 단계 및 blocking TiO2(122)층 상에 mesoporous TiO2층(124)을 형성하는 단계를 포함할 수 있다. Forming the TiO 2 layer 120 (S120) may include forming a blocking TiO 2 layer 122 and forming a mesoporous TiO 2 layer 124 on the blocking TiO 2 122 layer. have.
blocking TiO2층(122)을 형성하는 단계는 TiO2 용액을 제조하는 단계, TiO2 용액을 이용하여 FTO 기판에 TiO2 코팅막을 형성하는 단계, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. forming a blocking TiO 2 layer 122 may include the step, step, drying the TiO 2 coating to form the TiO 2 coating layer on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
TiO2 용액을 제조하는 단계에서 TiO2 용액은 Titanium diisopropoxide bis(acetylacetonate) 75 wt. % in isopropanol 용액을 1-butanol 용액에 희석시켜 0.15M의 농도로 제조될 수 있다. In preparing a solution of TiO 2 TiO 2 solution Titanium diisopropoxide bis (acetylacetonate) 75 wt . The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
TiO2 코팅막을 형성하는 단계에서 TiO2 코팅막은 20초동안 2000rpm에서 스핀 코팅(spin coating)함으로 형성될 수 있다.In the step of forming the TiO 2 coating TiO 2 coating film can be formed by spin-coating (spin coating) at 2000rpm for 20 seconds.
TiO2 코팅막을 건조하는 단계에서 TiO2 코팅막은 125℃ 이상에서 5분간 열처리함으로써 건조될 수 있다. In the step of drying the coating layer TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 ℃ 5 minutes.
blocking TiO2층(122) 상에 mesoporous TiO2층(124)을 형성하는 단계는 mesoporous TiO2 용액을 제조하고, TiO2 코팅막을 형성한 후, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Forming the mesoporous TiO 2 layer 124 on the blocking TiO 2 layer 122 may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
mesoporous TiO2 용액은 mesoporous TiO2를 무수 에탄올(hydrous ethanol)에 용해하여 제조될 수 있으며, 필요에 따라 농도를 조절하여 사용할 수 있다.Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
mesoporous TiO2층(124)에서, TiO2 코팅막은 450℃ 이상에서 30분간 열처리함으로써 건조될 수 있다. In the mesoporous TiO 2 layer 124, the TiO 2 coating layer may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
한편, 제1 전극(100)을 형성하는 단계(S100)는 상기 mesoporous TiO2층(124)에 조도를 형성하는 단계를 더 포함할 수 있다. 상기 mesoporous TiO2층(124)에 조도를 형성하기 위해 TiCl4 용액을 이용할 수 있다. Meanwhile, forming the first electrode 100 (S100) may further include forming roughness on the mesoporous TiO 2 layer 124. TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer 124.
조도를 형성하는 단계는, 20 mM의 TiCl4 용액 1ml와 증류수 99ml를 섞은 혼합 용액을 준비하는 단계, 상기 혼합 용액에 mesoporous TiO2층(124)이 형성된 기판을 함침하는 단계, 1차 열처리 단계, 세정하는 단계, 건조하는 단계 및 2차 열처리 단계를 수행할 수 있다. Forming the roughness may include preparing a mixed solution of 1 ml of 20 mM TiCl 4 solution and 99 ml of distilled water, impregnating the substrate on which the mesoporous TiO 2 layer 124 is formed, the first heat treatment step, A washing step, a drying step and a second heat treatment step may be performed.
조도를 형성하는 단계에서 1차 열처리 단계는 70℃ 내지 100℃의 온도범위에서 진행될 수 있으며, 2차 열처리 단계는 450℃ 이상 30분 진행될 수 있다.In the step of forming the roughness, the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C., and the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
상기와 같이 일련의 제조 공정에 의해 mesoporous TiO2층(124) 상에 조도가 형성됨으로써, 제1 전극(100) 상에 형성될 광 흡수층(200)과 TiO2층(120) 간의 접착력이 보다 향상될 수 있다.As the roughness is formed on the mesoporous TiO 2 layer 124 by a series of manufacturing processes as described above, the adhesion between the light absorbing layer 200 and the TiO 2 layer 120 to be formed on the first electrode 100 is further improved. Can be.
한편, 제1 전극(100)을 형성하는 단계(S100)는 TiO2층(120) 상에 ZrO2층(130)을 형성하는 단계(S130)를 더 포함할 수 있다. 이 경우, 제1 전극(100)은 제1 기판, blocking TiO2층(122), mesoporous TiO2층(124), ZrO2층(130) 순으로 적층되어 형성된다.Meanwhile, the forming of the first electrode 100 (S100) may further include forming a ZrO 2 layer 130 on the TiO 2 layer 120 (S130). In this case, the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 layer 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
광 흡수층(200)을 형성하는 단계(S200)는 A1B2C7 용액을 형성하는 단계 및 A1B2C7 용액을 상기 제1 전극(100) 상에 드롭핑(dropping), 스핀 코팅(spin coating) 또는 스크린 프린팅(screen printing)하는 단계(S250)를 포함할 수 있다.Forming a light absorbing layer (200) (S200) is A 1 B 2 C 7 to form a solution, and A 1 B 2 C 7 solution the second dropping (dropping) on the first electrode 100, spin coating It may include a step (S250) for (spin coating) or screen printing (screen printing).
X1Y2Z7 용액을 형성하는 단계는, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계(S210), 상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계(S220), 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계(S230) 및 상기 열처리 된 혼합 분말을 DMF(dimethyl formamide) 또는 DMSO(Dimethyl sulfoxide) 용매에 용해시키는 단계(S240)를 포함할 수 있다.Forming the X 1 Y 2 Z 7 solution, preparing a XZ compound powder and YZ 3 compound powder (S210), mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder (S220) ), Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) and dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent (S240) It may include.
[화학식][Formula]
XaYbZcX a Y b Zc
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 1.6<b<2.4, 5.6<c<8.4을 만족For a = 1, 1.6 <b <2.4, 5.6 <c <8.4 are satisfied
혼합 분말을 열처리하는 단계에서, 바람직하게는 a:b:c=1:2:7 이다. 즉, 혼합 분말을 열처리하는 단계에서 상기의 화학식으로 표시되는 화합물은 X1Y2Z7 일 수 있다.In the step of heat-treating the mixed powder, preferably a: b: c = 1: 2: 7. That is, the compound represented by the above formula in the heat treatment of the mixed powder may be X 1 Y 2 Z 7 .
상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계(S230)는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 상기 가열노 내의 온도는 100℃ 이상 200℃ 이하의 범위에서 수행될 수 있다. Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) may include the step of heating the mixed powder in a heating furnace. The temperature in the heating furnace may be carried out in the range of 100 ℃ to 200 ℃.
한편, XZ 화합물의 농도는 1mmol 이고, YZ3화합물의 농도는 2mmol 일 수 있다. 또한, 상기 열처리하는 단계는 5분 이상 20분 이하로 수행될 수 있다.Meanwhile, the concentration of the XZ compound may be 1 mmol, and the concentration of the YZ 3 compound may be 2 mmol. In addition, the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
X1Y2Z7 용액이 형성된 후 제1 전극(100) 상에 도포되며, 이 때, X1Y2Z7 용액 도포는 드롭핑, 스핀 코팅 또는 스크린 프린팅 중 선택적으로 수행될 수 있다.The X 1 Y 2 Z 7 solution is formed and then applied on the first electrode 100, wherein the X 1 Y 2 Z 7 solution application may be selectively performed during dropping, spin coating or screen printing.
광 흡수층(200)을 형성하는 단계(S200)는 상기 X1Y2Z7 용액을 건조하는 단계(S250)를 더 포함할 수 있다. 즉, 제1 전극(100) 상에 도포된 X1Y2Z7 용액을 건조하는 단계가 추가될 수 있다. X1Y2Z7 용액을 건조하는 단계(S250)는 0 ℃ 이상 200 ℃ 이하의 온도 범위에서 수행될 수 있다.Forming the light absorbing layer 200 (S200) may further include the step (S250) of drying the X 1 Y 2 Z 7 solution. That is, a step of drying the X 1 Y 2 Z 7 solution applied on the first electrode 100 may be added. Drying the X 1 Y 2 Z 7 solution (S250) may be carried out at a temperature range of 0 ℃ to 200 ℃.
제2 전극(300)을 형성하는 단계(S300)는 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제2 기판을 준비하는 단계(S310), 탄소 분말을 준비하는 단계(S320), 상기 제2 기판 상에 상기 탄소 분말을 코팅하는 단계(S330) 및 상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계(S340)를 포함할 수 있다. The forming of the second electrode 300 (S300) includes preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. (S310), preparing a carbon powder (S320), coating the carbon powder on the second substrate (S330), and heat treating the carbon substrate coated with the second substrate (S340). can do.
여기서, 상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계(S340)는 300℃ 이상 600℃ 이하 온도에서 25분 내지 35분 동안 수행될 수 있다.Here, the step (S340) of heat treating the second substrate coated with the carbon powder may be performed for 25 minutes to 35 minutes at a temperature of 300 ° C. or higher and 600 ° C. or lower.
한편, 제2 전극(300)을 형성하는 단계는 탄소 분말을 포함하는 페이스트(paste)를 광 흡수층(200) 상에 도포하고 건조하는 단계로 이루어질 수도 있다.Meanwhile, the forming of the second electrode 300 may include applying a paste including carbon powder on the light absorbing layer 200 and drying the paste.
제3 The third
페로브스카이트Perovskite
화합물(1-3-10 Compound (1-3-10
페로브스카이트Perovskite
화합물) compound)
도 28을 참조하면, 본 발명의 실시예에 따른 페로브스카이트 화합물은 하기의 화학식으로 표시될 수 있다. 도 28에서 가장 큰 원자모형은 X, 숨어있는 원자모형은 Y, 작은 원자모형이 Z이다. Referring to Figure 28, the perovskite compound according to an embodiment of the present invention may be represented by the following formula. In Fig. 28, the largest atomic model is X, the hidden atomic model is Y, and the small atomic model is Z.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 2.4<b<3.6, 8<c<12for a = 1, 2.4 <b <3.6, 8 <c <12
바람직하게 a:b:c=1:3:10일 수 있다.Preferably a: b: c = 1: 3: 10.
본 명세서에서 이러한 제3 페로브스카이트 화합물을 편의 상 1-3-10 구조의 페로브스카이트 화합물이라고 부를 수 있다.In the present specification, such a third perovskite compound may be referred to as a perovskite compound having a 1-3-10 structure for convenience.
a=1에 대하여, 2.4<b<3.6, 8<c<12을 만족한다는 것은 페로브스카이트 화합물의 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1일 때, 2.4<b<3.6, 8<c<12 인 것을 의미한다. 상기의 범위 내에서는 후술하는 발명의 효과가 발휘될 수 있다.For a = 1, satisfying 2.4 <b <3.6, 8 <c <12 means 2.4 <b when the total moles of monovalent organic / inorganic cations contained in the X position of the perovskite compound are a = 1. It means that <3.6, 8 <c <12. Within the above range, the effects of the invention described later can be exerted.
이하, X1Y2Z7 페로브스카이트 화합물에 대해 주로 설명하지만, 해당 설명은 X 위치에 함유되는 1가 유/무기 양이온의 총 몰수 a=1에 대하여, 2.4<b<3.6, 8<c<12을 만족하는 모든 XaYbZc 페로브스카이트 화합물에 대해서도 동일하게 적용될 수 있다.Hereinafter, the X 1 Y 2 Z 7 perovskite compound will be mainly described, but the description is about 2.4 <b <3.6, 8 < The same applies to all X a Y b Z c perovskite compounds that satisfy c <12.
제3 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 이룰 수 있다. 고체 물질은 원자 배열의 규칙성 여부에 따라서 결정질(crystalline structure)과 비결정질(non-crystalline 또는 amorphous structure)로 구분될 수 있다. 상기 페로브스카이트 화합물은 결정질 구조 중에서 삼사정계(triclinic) 결정 구조를 가진다.The third perovskite compound may form a triclinic crystal structure. Solid materials may be classified into crystalline structures and non-crystalline or amorphous structures according to the order of atomic arrangements. The perovskite compound has a triclinic crystal structure in the crystalline structure.
한편, 도 29에는 본 발명의 실시예에 따른 페로브스카이트 화합물, 특히 CsBi3I10의 이론적 밴드갭이 나타나있다. 본 발명의 실시예에 따른 페로브스카이트 화합물의 이론적 밴드갭은 1.25eV이다.On the other hand, Figure 29 shows the theoretical bandgap of the perovskite compound, in particular CsBi 3 I 10 according to an embodiment of the present invention. The theoretical bandgap of the perovskite compound according to an embodiment of the present invention is 1.25 eV.
본 발명의 실시예에 따른 페로브스카이트 화합물은 Bi, Sb 을 이용하여 페로브스카이트 결정구조를 형성하므로 납(Pb)과 같은 높은 독성의 물질을 대체할 수 있다. 또한, 본 발명의 실시예에 따른 페로브스카이트 화합물은 공기 중에서 쉽게 산화되지 않아 안정성 측면에서 우수하다. The perovskite compound according to the embodiment of the present invention may form a perovskite crystal structure using Bi and Sb, and thus may replace a highly toxic substance such as lead (Pb). In addition, the perovskite compound according to an embodiment of the present invention is not easily oxidized in the air is excellent in terms of stability.
또한, 상술한 바와 같이, 본 발명의 실시예에 따른 페로브스카이트 화합물의 이론적 밴드갭은 1.25eV이다. 고효율 태양전지를 위한 광 흡수층의 이상적인 밴드갭은 1.4eV 이며 본 발명의 실시예에 따른 페로브스카이트 화합물의 밴드갭과 유사하다. In addition, as described above, the theoretical band gap of the perovskite compound according to the embodiment of the present invention is 1.25 eV. The ideal bandgap of the light absorbing layer for the high efficiency solar cell is 1.4 eV and is similar to the band gap of the perovskite compound according to the embodiment of the present invention.
따라서, 본 발명의 실시예에 따른 페로브스카이트 화합물은 태양전지에 사용되는 경우 태양전지 효율 개선에 기여할 수 있다.Therefore, the perovskite compound according to the embodiment of the present invention may contribute to the improvement of solar cell efficiency when used in a solar cell.
본 발명의 실시예에 따른 페로브스카이트 화합물의 제조방법은 화합물의 전구체 분말을 혼합한 후 열처리하여 형성되는 것에 특징이 있다.Method for producing a perovskite compound according to an embodiment of the present invention is characterized by being formed by mixing the precursor powder of the compound and then heat treatment.
구체적으로 페로브스카이트 화합물의 제조방법은, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; 상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; 및 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함한다.Specifically, the method for producing a perovskite compound includes the steps of preparing an XZ compound powder and YZ 3 compound powder; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And heat treating the mixed powder to prepare a compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 2.4<b<3.6, 8<c<12for a = 1, 2.4 <b <3.6, 8 <c <12
상기 혼합 분말을 열처리하는 단계에서, 바람직하게 a:b:c=1:3:10일 수 있다. 즉, 상기 혼합 분말을 열처리하는 단계에서 상기의 화학식으로 표시되는 화합물은 X1Y3Z10일 수 있다.In the step of heat-treating the mixed powder, it may be preferably a: b: c = 1: 3: 10. That is, the compound represented by the formula in the heat treatment of the mixed powder may be X 1 Y 3 Z 10 .
또한, 상기 열처리 하는 단계에서, 상기 화합물은 삼사정계(triclinic)의 결정 구조를 가질 수 있다.In addition, in the heat treatment step, the compound may have a triclinic crystal structure.
열처리를 통하여 삼방정계(trigonal 또는 rhombohedral) 결정구조의 XZ3의 빈 공간에 A가 치환 결합되는데 X1Y3Z10의 화학식을 만족하는 경우에 페로브스카이트 화합물은 삼사정계의 결정 구조를 가질 수 있다.When A is substituted and bonded to the empty space of XZ 3 of trigonal or rhombohedral crystal structure through heat treatment, when the chemical formula of X 1 Y 3 Z 10 is satisfied, the perovskite compound has a tetragonal crystal structure. Can be.
예를 들어, X=Cs, Y=Bi, Z=I인 경우, 열처리를 통하여 삼방정계(능면체) 결정구조를 가지는 BiI3의 빈 공간에 Cs가 치환되어 들어가는데 Cs 양이 증가하면서 삼방정계 결정 구조가 깨지고 최종적으로 삼사정계 결정 구조의 CsBi3I10가 형성된다.For example, in the case of X = Cs, Y = Bi, Z = I, Cs is substituted into the empty space of BiI 3 having a trigonal (rhombohedral) crystal structure through heat treatment. The structure is broken and finally CsBi 3 I 10 of the triclinic crystal structure is formed.
상기 열처리는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 상기 가열노 내의 온도는 100℃ 이상 200℃ 이하일 수 있다. The heat treatment may include heating the mixed powder in a heating furnace. The temperature in the heating furnace may be 100 ° C or more and 200 ° C or less.
한편, XZ 화합물 분말과 YZ3 화합물 분말을 1:3 의 농도 비율로 혼합하면 최종적으로 X1Y3Z10
물질이 만들어질 수 있다. 즉, XZ 화합물의 농도는 1 mol이고, YZ3화합물의 농도는 3 mol 일 수 있다. 또한, 상기 열처리하는 단계는 5분 이상 20분 이하로 수행될 수 있다.Meanwhile, when the XZ compound powder and the YZ 3 compound powder are mixed at a concentration ratio of 1: 3, finally X 1 Y 3 Z 10 Material can be made. That is, the concentration of the XZ compound may be 1 mol, and the concentration of the YZ 3 compound may be 3 mol. In addition, the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
도 30 내지 도 33은 상기 열처리 하는 단계에 따른 효과를 나타내는 도면이다. 구체적으로, 도 30은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 XRD 측정 결과 도면이고, 도 31은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 구조 변화를 나타낸 SEM 사진이고, 도 32는 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 광흡수도 변화를 나타낸 도면이고, 도 33은 본 발명의 실시예에 따른 페로브스카이트 화합물 제조방법에서 열처리 전후의 밴드갭 변화를 나타낸 도면이다.30 to 33 are views showing the effect of the heat treatment step. Specifically, Figure 30 is a XRD measurement results showing the structural change before and after the heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention, Figure 31 is a perovskite compound preparation according to an embodiment of the present invention SEM picture showing the structural change before and after the heat treatment in the method, Figure 32 is a view showing the change in light absorbance before and after heat treatment in the perovskite compound manufacturing method according to an embodiment of the present invention, Figure 33 is an embodiment of the present invention Figure showing the bandgap change before and after heat treatment in the perovskite compound manufacturing method according to the example.
도 30 내지 도 33에서, 본 발명의 실시예에 따른 페로브스카이트 화합물로 형성된 박막이 실험에 사용되었고, (a)는 열처리 전을, (b)는 열처리 후를 나타낸다.30 to 33, a thin film formed of the perovskite compound according to an embodiment of the present invention was used in the experiment, (a) before the heat treatment, (b) after the heat treatment.
도 30을 참조하면, 열처리 후에 26도 부근에서 새로운 피크(peak)가 나타났음을 알 수 있다. 즉, 물질의 구조가 변하였다. 여기서 물질의 구조가 변하였다는 것은 화합물이 삼사정계 결정 구조를 가지게 되었음을 의미한다.Referring to FIG. 30, it can be seen that a new peak appeared near 26 degrees after the heat treatment. That is, the structure of the material has changed. Here, the change in the structure of the material means that the compound has a triclinic crystal structure.
도 31을 참조하면, 열처리 후에 물질이 더욱 조밀한 구조를 이루게 됨을 알 수 있다. 특히, CsBi3I10의 경우 박막의 그레인(grain)의 크기가 커지는데, 그레인의 크기가 커지면 태양전지 효율이 증가될 수 있다.Referring to FIG. 31, it can be seen that the material has a more dense structure after the heat treatment. Particularly, in the case of CsBi 3 I 10 , the grain size of the thin film is increased, and as the grain size increases, solar cell efficiency may increase.
도 32는 UV-visible spectroscopy을 이용하였을 때 물질의 흡수도를 나타내고 있다. 열처리 전에는 흡수영역이 대략 570nm까지이나, 열처리 후에는 730nm까지로 확대(음영 참고)되었다. 실제 사진에서도 주황색이던 박막이 빛을 흡수하기 용이한 검은색으로 변화하였다.Figure 32 shows the absorbance of the material when using UV-visible spectroscopy. Before the heat treatment, the absorption region was expanded to approximately 570 nm, but after the heat treatment, the absorption region was enlarged to 730 nm (see shading). In the actual picture, the orange film was changed to black, which is easy to absorb light.
도 33에는 도 32의 결과를 통해 구한 밴드갭 값이 도시되어 있다. 밴드갭 값은 열처리 전에는 2.3eV 이지만, 열처리 후에는 1.8eV 로 낮아졌다. 도 32와 도 33 을 종합해보면, 열처리로 인해 밴드갭이 낮아지면서 빛의 흡수할 수 있는 파장이 늘어난 것으로 해석될 수 있다. 결국, 열처리로 인하여 페로브스카이트 화합물의 밴드갭이 1.25 ~ 1.8 eV로 낮아져 1.4eV에 가까워지므로 상기 페로브스카이트 화합물이 태양전지에 사용되면 태양전지 효율이 증가할 수 있다.33 shows bandgap values obtained through the results of FIG. 32. The bandgap value was 2.3 eV before the heat treatment, but dropped to 1.8 eV after the heat treatment. 32 and 33, it can be interpreted that the band gap is lowered due to the heat treatment to increase the wavelength for absorbing light. As a result, the band gap of the perovskite compound is lowered to 1.25 to 1.8 eV due to the heat treatment, thereby approaching 1.4 eV. Thus, when the perovskite compound is used in a solar cell, the solar cell efficiency may increase.
도 34는 본 발명의 실시예에 따른 태양전지를 개략적으로 나타낸 도면이다. 34 is a view schematically showing a solar cell according to an embodiment of the present invention.
도 34를 참조하면, 본 발명의 실시예에 따른 태양전지는 제1 전극(100), 상기 제1 전극(100) 상에 형성되는 광 흡수층(200) 및 상기 광 흡수층(200) 상에 형성되는 제2 전극(300)을 포함하고, 상기 광 흡수층(200)은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함한다.Referring to FIG. 34, the solar cell according to the embodiment of the present invention is formed on the first electrode 100, the light absorbing layer 200 formed on the first electrode 100, and the light absorbing layer 200. It includes a second electrode 300, the light absorbing layer 200 includes a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 2.4<b<3.6, 8<c<12for a = 1, 2.4 <b <3.6, 8 <c <12
바람직하게 a:b:c=1:3:10일 수 있다. 즉, 상기의 화학식으로 표시되는 페로브스카이트 화합물은 X1Y3Z10일 수 있다.Preferably a: b: c = 1: 3: 10. That is, the perovskite compound represented by the above formula may be X 1 Y 3 Z 10 .
또한, 상기 화합물은 삼사정계(triclinic)의 결정 구조를 가질 수 있다.In addition, the compound may have a triclinic crystal structure.
제1 전극(100)과 제2 전극(300)은 광 흡수층(200)의 페로브스카이트 화합물의 접착력에 의하여 광 흡수층(200)에 접착될 수 있다.The first electrode 100 and the second electrode 300 may be attached to the light absorbing layer 200 by the adhesive force of the perovskite compound of the light absorbing layer 200.
제1 전극(100)은 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판 및 상기 제1 기판 상에 형성되는 TiO2층(120)을 포함할 수 있다.The first electrode 100 may include a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate, and a TiO 2 formed on the first substrate. It may include layer 120.
ITO(indium tin oxide) 기판은 ITO가 증착된 유리 기판, FTO 기판은 FTO가 증착된 유리 기판이다. An ITO substrate is a glass substrate on which ITO is deposited, and an FTO substrate is a glass substrate on which FTO is deposited.
또한, 상기 유연 투명 전극 기판은, 폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성 에폭시수지로 이루어지는 군으로부터 선택되는 폴리머 기판으로 형성될 수 있다.In addition, the flexible transparent electrode substrate, polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), Ethylene Vinyl Acetate (EVA), Amorphous Polyethylene Terephthalate (APET), Polypropylene Terephthalate (PPT), Polyethylene Terephthalate Glycerol (PETG), Polycyclohexylenedimethylene Terephthalate (PCTG), Modified Triacetyl Cellulose (TAC) ), Cycloolefin polymer (COP), cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydie It may be formed of a polymer substrate selected from the group consisting of methylsilone silane (PDMS), silicone resin, fluorine resin and modified epoxy resin.
다만, 유연 투명 전극 기판은 상기의 제시된 예로 제한되지 않는다.However, the flexible transparent electrode substrate is not limited to the examples presented above.
TiO2층(120)은 전자수송층으로서의 기능을 수행할 수 있다. TiO2층(120)은, blocking TiO2(122)층 및 상기 blocking TiO2(122)층 상에 형성되는 mesoporous TiO2층(124)을 포함할 수 있다The TiO 2 layer 120 may function as an electron transport layer. The TiO 2 layer 120 may include a blocking TiO 2 122 layer and a mesoporous TiO 2 layer 124 formed on the blocking TiO 2 122 layer.
상기 제1 전극(100)은 ZrO2층(130)을 더 포함할 수 있다. ZrO2층(130)은 TiO2층(120) 상에 형성되며, TiO2층(120)과 마찬가지로 전자수송층으로서의 기능을 수행한다.The first electrode 100 may further include a ZrO 2 layer 130. ZrO 2 layer 130 is formed on the TiO 2 layer 120, and performs a function as an electron transport layer, like TiO 2 layer 120.
이 경우, 제1 전극(100)은 제1 기판, blocking TiO2(122), mesoporous TiO2층(124), ZrO2층(130) 순으로 적층되어 형성된다.In this case, the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
제2 전극(300)은 카본(carbon)을 포함할 수 있다. 즉, 제2 전극(300)은 카본으로 형성된 층일 수 있다. 또한, 제2 전극(300)은 제2 기판에 탄소 분말이 코팅된 것일 수 있다.The second electrode 300 may include carbon. That is, the second electrode 300 may be a layer formed of carbon. In addition, the second electrode 300 may be coated with carbon powder on the second substrate.
여기서, 제2 기판은 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 기판일 수 있다.Here, the second substrate may be a substrate selected from any one of a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate.
본 발명의 실시예에 따른 페로브스카이트 화합물은 공기 중에서 쉽게 산화되지 않으므로 공기 중에서 제2 전극(300)이 광 흡수층(200) 상에 형성될 수 있으므로, 진공 상태에서 제2 전극(300)을 형성할 필요가 없다. Since the perovskite compound according to the embodiment of the present invention is not easily oxidized in the air, the second electrode 300 may be formed on the light absorbing layer 200 in the air, and thus the second electrode 300 may be removed in a vacuum state. There is no need to form.
한편, 카본 전극은 금속 전극과 달리 진공 증착 방식을 이용하지 않고, 페로브스카이트 화합물의 접착력에 의해 접착될 수 있어, 페로브스카이트 화합물과 용이하게 결합될 수 있다.Meanwhile, unlike the metal electrode, the carbon electrode may be bonded by the adhesive force of the perovskite compound without using a vacuum deposition method, and thus may be easily combined with the perovskite compound.
도 35는 본 발명의 실시예에 따른 태양전지의 제조방법을 개략적으로 나타낸 순서도이다.35 is a flowchart schematically illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
도 35를 참조하면, 본 발명의 실시예에 따른 태양전지의 제조방법은, 제1 전극(100)을 형성하는 단계(S100), 광 흡수층(200)을 형성하는 단계(S200), 제2 전극(300)을 형성하는 단계(S300)를 포함하고, 광 흡수층(200)은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함한다.Referring to FIG. 35, in the method of manufacturing a solar cell according to an embodiment of the present invention, forming the first electrode 100 (S100), forming the light absorbing layer 200 (S200), and the second electrode Forming step 300 (S300), the light absorbing layer 200 includes a perovskite compound represented by the following formula.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 2.4<b<3.6, 8<c<12for a = 1, 2.4 <b <3.6, 8 <c <12
바람직하게 a:b:c=1:3:10일 수 있다. 즉, 상기의 화학식으로 표시되는 페로브스카이트 화합물은 X1Y3Z10일 수 있다.Preferably a: b: c = 1: 3: 10. That is, the perovskite compound represented by the above formula may be X 1 Y 3 Z 10 .
상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 이룰 수 있다. The perovskite compound may form a triclinic crystal structure.
제1 전극(100)을 형성하는 단계(S100)는 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판을 준비하는 단계(S110) 및 제1 기판 상에 TiO2층(120)을 형성하는 단계(S120)를 포함할 수 있다. Forming the first electrode 100 (S100) may include preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. The method may include forming a TiO 2 layer 120 on the S110 and the first substrate (S120).
(이하에서는, 제1 기판을 FTO기판을 이용하여 실시하는 예를 설명하기로 한다. 다만, 하기의 설명이 다른 종류의 제1 기판에도 적용될 수 있으며, 제1 기판의 종류를 제한하는 것은 아니다.)(Hereinafter, an example in which the first substrate is implemented using the FTO substrate will be described. However, the following description may be applied to other types of first substrates, but the type of the first substrate is not limited. )
FTO 기판을 준비하는 단계(S110)는 FTO 기판과 TiO2층(120) 간 접착력을 향상시키기 위해 FTO(Fluorine Doped Tin Oxide) 기판을 가공하는 단계를 포함할 수 있다. Preparing the FTO substrate (S110) may include processing a Fluorine Doped Tin Oxide (FTO) substrate to improve adhesion between the FTO substrate and the TiO 2 layer 120.
예를 들면, FTO(Fluorine Doped Tin Oxide) 기판에 에칭할 부분을 제외한 나머지 부분에 Zn 분말을 고르게 도포시킨 후 HCl을 DI water 에 1:1 에서 1:3 비율로 희석 시킨 용액을 균일하게 도포할 수 있다. For example, evenly apply Zn powder to the remaining portions other than the portions to be etched on a Fluorine Doped Tin Oxide (FTO) substrate, and then uniformly apply a solution in which HCl is diluted 1: 1 to 1: 3 in DI water. Can be.
에칭된 상기 FTO(Fluorine Doped Tin Oxide) 기판을 아세톤, IPA, DI 순으로 초음파 세척기를 이용하여 세척할 수 있다. 다음으로, 세척된 FTO(Fluorine Doped Tin Oxide) 기판은 100℃에서 건조하고, UV Ozone cleaner에서 600 초간 처리할 수 있다. The etched Fluorine Doped Tin Oxide (FTO) substrate may be cleaned using an ultrasonic cleaner in the order of acetone, IPA, and DI. Next, the cleaned Fluorine Doped Tin Oxide (FTO) substrate may be dried at 100 ° C. and treated for 600 seconds in a UV Ozone cleaner.
상기와 같은 FTO 기판의 표면 처리를 통해 TiO2층(120)과의 접착력을 향상시킬 수 있다.Through the surface treatment of the FTO substrate as described above it is possible to improve the adhesion to the TiO 2 layer 120.
TiO2층(120)을 형성하는 단계(S120)는 Blocking TiO2층(122)을 형성하는 단계 및 blocking TiO2(122)층 상에 mesoporous TiO2층(124)을 형성하는 단계를 포함할 수 있다. Forming the TiO 2 layer 120 (S120) may include forming a blocking TiO 2 layer 122 and forming a mesoporous TiO 2 layer 124 on the blocking TiO 2 122 layer. have.
blocking TiO2층(122)을 형성하는 단계는 TiO2 용액을 제조하는 단계, TiO2 용액을 이용하여 FTO 기판에 TiO2 코팅막을 형성하는 단계, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. forming a blocking TiO 2 layer 122 may include the step, step, drying the TiO 2 coating to form the TiO 2 coating layer on the FTO substrate using a TiO 2 solution for preparing a TiO 2 solution.
TiO2 용액을 제조하는 단계에서 TiO2 용액은 Titanium diisopropoxide bis(acetylacetonate) 75 wt. % in isopropanol 용액을 1-butanol 용액에 희석시켜 0.15M의 농도로 제조될 수 있다. In preparing a solution of TiO 2 TiO 2 solution Titanium diisopropoxide bis (acetylacetonate) 75 wt . The% in isopropanol solution may be prepared in a concentration of 0.15 M by diluting in 1-butanol solution.
TiO2 코팅막을 형성하는 단계에서 TiO2 코팅막은 20초동안 2000rpm에서 스핀 코팅(spin coating)함으로 형성될 수 있다.In the step of forming the TiO 2 coating TiO 2 coating film can be formed by spin-coating (spin coating) at 2000rpm for 20 seconds.
TiO2 코팅막을 건조하는 단계에서 TiO2 코팅막은 125℃ 이상에서 5분간 열처리함으로써 건조될 수 있다. In the step of drying the coating layer TiO 2 TiO 2 coating film may be dried by heat treatment at more than 125 ℃ 5 minutes.
blocking TiO2층(122) 상에 mesoporous TiO2층(124)을 형성하는 단계는 mesoporous TiO2 용액을 제조하고, TiO2 코팅막을 형성한 후, TiO2 코팅막을 건조하는 단계를 포함할 수 있다. Forming the mesoporous TiO 2 layer 124 on the blocking TiO 2 layer 122 may include preparing a mesoporous TiO 2 solution, forming a TiO 2 coating layer, and then drying the TiO 2 coating layer.
mesoporous TiO2 용액은 mesoporous TiO2를 무수 에탄올(hydrous ethanol)에 용해하여 제조될 수 있으며, 필요에 따라 농도를 조절하여 사용할 수 있다.Mesoporous TiO 2 solution can be prepared by dissolving mesoporous TiO 2 in anhydrous ethanol (hydrous ethanol), it can be used by adjusting the concentration as needed.
mesoporous TiO2층(124)에서, TiO2 코팅막은 450℃ 이상에서 30분간 열처리함으로써 건조될 수 있다. In the mesoporous TiO 2 layer 124, the TiO 2 coating layer may be dried by heat treatment at 450 ° C. or higher for 30 minutes.
한편, 제1 전극(100)을 형성하는 단계(S100)는 상기 mesoporous TiO2층(124)에 조도를 형성하는 단계를 더 포함할 수 있다. 상기 mesoporous TiO2층(124)에 조도를 형성하기 위해 TiCl4 용액을 이용할 수 있다. Meanwhile, forming the first electrode 100 (S100) may further include forming roughness on the mesoporous TiO 2 layer 124. TiCl 4 solution may be used to form roughness in the mesoporous TiO 2 layer 124.
조도를 형성하는 단계는, 20 mM의 TiCl4 용액 1ml와 증류수 99ml를 섞은 혼합 용액을 준비하는 단계, 상기 혼합 용액에 mesoporous TiO2층(124)이 형성된 기판을 함침하는 단계, 1차 열처리 단계, 세정하는 단계, 건조하는 단계 및 2차 열처리 단계를 수행할 수 있다. Forming the roughness may include preparing a mixed solution of 1 ml of 20 mM TiCl 4 solution and 99 ml of distilled water, impregnating the substrate on which the mesoporous TiO 2 layer 124 is formed, the first heat treatment step, A washing step, a drying step and a second heat treatment step may be performed.
조도를 형성하는 단계에서 1차 열처리 단계는 70℃ 내지 100℃의 온도범위에서 진행될 수 있으며, 2차 열처리 단계는 450℃ 이상 30분 진행될 수 있다.In the step of forming the roughness, the first heat treatment step may be performed at a temperature range of 70 ° C. to 100 ° C., and the second heat treatment step may be performed at 450 ° C. or more for 30 minutes.
상기와 같이 일련의 제조 공정에 의해 mesoporous TiO2층(124) 상에 조도가 형성됨으로써, 제1 전극(100) 상에 형성될 광 흡수층(200)과 TiO2층(120) 간의 접착력이 보다 향상될 수 있다.As the roughness is formed on the mesoporous TiO 2 layer 124 by a series of manufacturing processes as described above, the adhesion between the light absorbing layer 200 and the TiO 2 layer 120 to be formed on the first electrode 100 is further improved. Can be.
한편, 제1 전극(100)을 형성하는 단계(S100)는 TiO2층(120) 상에 ZrO2층(130)을 형성하는 단계(S130)를 더 포함할 수 있다. 이 경우, 제1 전극(100)은 제1 기판, blocking TiO2층(122), mesoporous TiO2층(124), ZrO2층(130) 순으로 적층되어 형성된다.Meanwhile, the forming of the first electrode 100 (S100) may further include forming a ZrO 2 layer 130 on the TiO 2 layer 120 (S130). In this case, the first electrode 100 is formed by stacking the first substrate, the blocking TiO 2 layer 122, the mesoporous TiO 2 layer 124, and the ZrO 2 layer 130.
광 흡수층(200)을 형성하는 단계(S200)는 A1B3C10 용액을 형성하는 단계 및 A1B3C10 용액을 상기 제1 전극(100) 상에 드롭핑(dropping), 스핀 코팅(spin coating)또는 스크린 프린팅(screen printing)하는 단계(S250)를 포함할 수 있다.Forming a light absorbing layer (200) (S200) is A 1 B 3 C 10 to form a solution, and A 1 B 3 C 10 solution to the first electrode 100 is dropping (dropping), spin-coated on the (Spin coating) or screen printing (screen printing) may include the step (S250).
X1Y3Z10 용액을 형성하는 단계는, XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계(S210), 상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계(S220), 상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계(S230) 및 상기 열처리 된 혼합 분말을 DMF(dimethyl formamide) 또는 DMSO(Dimethyl sulfoxide) 용매에 용해시키는 단계(S240)를 포함할 수 있다.Forming the X 1 Y 3 Z 10 solution, preparing a XZ compound powder and YZ 3 compound powder (S210), mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder (S220) ), Heat-treating the mixed powder to prepare a compound represented by the following formula (S230) and dissolving the heat-treated mixed powder in DMF (dimethyl formamide) or DMSO (dimethyl sulfoxide) solvent (S240) It may include.
[화학식][Formula]
XaYbZc
X a Y b Z c
X=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, Li
Y=Bi, Sb 중 하나One of Y = Bi, Sb
Z=F, I, Br, Cl 중 하나Z = F, I, Br, Cl
a=1에 대하여, 2.4<b<3.6, 8<c<12for a = 1, 2.4 <b <3.6, 8 <c <12
혼합 분말을 열처리하는 단계에서, 바람직하게 a:b:c=1:3:10일 수 있다. 즉, 혼합 분말을 열처리하는 단계에서, 상기의 화학식으로 표시되는 화합물은 X1Y3Z10일 수 있다.In the step of heat-treating the mixed powder, preferably a: b: c = 1: 3: 10. That is, in the heat treatment of the mixed powder, the compound represented by the above formula may be X 1 Y 3 Z 10 .
상기 혼합 분말을 열처리하여, 상기의 화학식으로 표시되는 화합물을 제조하는 단계(S230)는 가열노 내에 상기 혼합 분말을 가열하는 단계를 포함할 수 있다. 상기 가열노 내의 온도가 100℃ 이상 200℃ 이하의 범위일 수 있다.The heat treatment of the mixed powder to prepare a compound represented by the chemical formula (S230) may include heating the mixed powder in a heating furnace. The temperature in the heating furnace may range from 100 ° C. to 200 ° C.
상기 열처리 하는 단계에서, 상기 화합물은 삼사정계(triclinic)의 결정 구조를 가질 수 있다.In the heat treatment step, the compound may have a triclinic crystal structure.
열처리를 통하여 삼방정계(trigonal 또는 rhombohedral) 결정구조의 XZ3의 빈 공간에 X가 치환 결합되는데 X1Y3Z10의 화학식을 만족하는 경우에 페로브스카이트 화합물은 삼사정계의 결정 구조를 가질 수 있다.Through heat treatment, X is substituted and bonded to the empty space of XZ 3 of trigonal or rhombohedral crystal structure, and when the chemical formula of X 1 Y 3 Z 10 is satisfied, the perovskite compound has a tetragonal crystal structure. Can be.
예를 들어, X=Cs, Y=Bi, Z=I인 경우, 열처리를 통하여 삼방정계(능면체) 결정구조를 가지는 BiI3의 빈 공간에 Cs가 치환되어 들어가는데 Cs 양이 증가하면서 삼방정계 결정 구조가 깨지고 최종적으로 삼사정계 결정 구조의 CsBi3I10가 형성된다.For example, in the case of X = Cs, Y = Bi, Z = I, Cs is substituted into the empty space of BiI 3 having a trigonal (rhombohedral) crystal structure through heat treatment. The structure is broken and finally CsBi 3 I 10 of the triclinic crystal structure is formed.
한편, XZ 화합물의 농도는 1 mol이고, YZ3화합물의 농도는 3 mol일 수 있다. 또한, 상기 열처리하는 단계는 단계는 5분 이상 20분 이하로 수행될 수 있다.Meanwhile, the concentration of the XZ compound may be 1 mol, and the concentration of the YZ 3 compound may be 3 mol. In addition, the step of the heat treatment may be performed for 5 minutes or more and 20 minutes or less.
X1Y3Z10 용액이 형성된 후 제1 전극(100) 상에 도포되며, 이 때, X1Y3Z10 용액 도포는 드롭핑, 스핀 코팅, 스크린 프린팅 중 선택적으로 수행될 수 있다.After forming the X 1 Y 3 Z 10 solution is applied on the first electrode 100, at this time, the application of the X 1 Y 3 Z 10 solution may be selectively performed during dropping, spin coating, screen printing.
광 흡수층(200)을 형성하는 단계(S200)는 상기 X1Y3Z10 용액을 건조하는 단계(S250)를 더 포함할 수 있다. 즉, 제1 전극(100) 상에 도포된 X1Y3Z10 용액을 건조하는 단계가 추가될 수 있다. X1Y3Z10 용액을 건조하는 단계(S250)는 0 ℃ 이상 200 ℃ 이하의 온도 범위에서 수행될 수 있다.Forming the light absorbing layer 200 (S200) may further include the step (S250) of drying the X 1 Y 3 Z 10 solution. That is, a step of drying the X 1 Y 3 Z 10 solution applied on the first electrode 100 may be added. Drying the X 1 Y 3 Z 10 solution (S250) may be carried out at a temperature range of 0 ℃ to 200 ℃.
제2 전극(300)을 형성하는 단계(S300)는 유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제2 기판을 준비하는 단계(S310), 탄소 분말을 준비하는 단계(S320), 상기 제2 기판 상에 상기 탄소 분말을 코팅하는 단계(S330) 및 상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계(S340)를 포함할 수 있다. The forming of the second electrode 300 (S300) includes preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate. (S310), preparing a carbon powder (S320), coating the carbon powder on the second substrate (S330), and heat treating the carbon substrate coated with the second substrate (S340). can do.
여기서, 상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계(S340)는 300℃ 이상 600℃ 이하 온도에서 20분 내지 40분 동안 수행될 수 있다.Here, the step (S340) of heat treating the second substrate coated with the carbon powder may be performed for 20 minutes to 40 minutes at a temperature of 300 ° C. or higher and 600 ° C. or lower.
한편, 제2 전극(300)을 형성하는 단계는 탄소를 함유하는 페이스트(paste)를 광 흡수층(200) 상에 도포하는 단계를 포함하고, 상기 페이스트를 건조하는 단계를 더 포함할 수 있다.Meanwhile, the forming of the second electrode 300 may include applying a carbon-containing paste on the light absorbing layer 200, and may further include drying the paste.
이상, 본 발명의 실시예에 대하여 설명하였으나, 해당 기술 분야에서 통상의 지식을 가진 자라면 특허청구범위에 기재된 본 발명의 사상으로부터 벗어나지 않는 범위 내에서, 구성 요소의 부가, 변경, 삭제 또는 추가 등에 의해 본 발명을 다양하게 수정 및 변경시킬 수 있을 것이며, 이 또한 본 발명의 권리범위 내에 포함된다고 할 것이다.As mentioned above, although embodiment of this invention was described, the person of ordinary skill in the art should add, change, delete, add, etc. the component within the range which does not deviate from the idea of this invention described in the claim. The present invention may be modified and changed in various ways, which will also be included within the scope of the present invention.
<부호의 설명><Description of the code>
100: 제1 전극100: first electrode
200: 광 흡수층200: light absorbing layer
300: 제2 전극300: second electrode
Claims (19)
- 다음의 화학식으로 표시되는 페로브스카이트 화합물.Perovskite compound represented by the following formula.[화학식][Formula]XaYbZc X a Y b Z cX=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, LiY=Bi, Sb 중 하나One of Y = Bi, SbZ=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,a=1에 대하여, for a = 1,0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12을 만족하고, Satisfying,a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
- 제1 전극;A first electrode;상기 제1 전극 상에 형성되는 광 흡수층; 및A light absorbing layer formed on the first electrode; And상기 광 흡수층 상에 형성되는 제2 전극을 포함하고,A second electrode formed on the light absorbing layer,상기 광 흡수층은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함하는 태양전지.The light absorbing layer is a solar cell comprising a perovskite compound represented by the following formula.[화학식][Formula]XaYbZc X a Y b Z cX=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, LiY=Bi, Sb 중 하나One of Y = Bi, SbZ=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,a=1에 대하여, for a = 1,0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12을 만족하고, Satisfying,a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
- 제2항에 있어서, The method of claim 2,상기 제1 전극은The first electrode is유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판; 및A first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And상기 제1 기판 상에 형성되는 TiO2층을 포함하는 태양전지.A solar cell comprising a TiO 2 layer formed on the first substrate.
- 제3항에 있어서, The method of claim 3,상기 유연 투명 전극 기판은, The flexible transparent electrode substrate,폴리에틸렌 테레프탈레이트 (PET), 폴리에틸렌 설폰(PES), 폴리에틸렌 나프탈레이트(PEN), 폴리카보네이트(PC), 폴리메틸메타크릴레이트(PMMA), 폴리이미드 (PI), 에틸렌비닐아세테이트(EVA), 아몰포스폴리에틸렌테레프탈레이트(APET), 폴리프로필렌테레프탈레이트(PPT), 폴리에틸렌테레프탈레이트글리세롤(PETG), 폴리사이클로헥실렌디메틸렌테레프탈레이트(PCTG), 변성트리아세틸셀룰로스(TAC), 사이클로올레핀폴리머(COP), 사이클로올레핀코폴리머(COC), 디시클로펜타디엔폴리머(DCPD), 시클로펜타디엔폴리머(CPD), 폴리아릴레이트(PAR), 폴리에테르이미드(PEI), 폴리다이메틸실론세인(PDMS), 실리콘수지, 불소수지 및 변성 에폭시수지로 이루어지는 군으로부터 선택되는 폴리머 기판으로 형성되는 태양전지.Polyethylene terephthalate (PET), polyethylene sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), ethylene vinyl acetate (EVA), amorphous Polyethylene terephthalate (APET), polypropylene terephthalate (PPT), polyethylene terephthalate glycerol (PETG), polycyclohexylenedimethylene terephthalate (PCTG), modified triacetylcellulose (TAC), cycloolefin polymer (COP), Cycloolefin copolymer (COC), dicyclopentadiene polymer (DCPD), cyclopentadiene polymer (CPD), polyarylate (PAR), polyetherimide (PEI), polydimethylsiloncene (PDMS), silicone resin And a polymer substrate selected from the group consisting of fluorine resins and modified epoxy resins.
- 제3항에 있어서,The method of claim 3,상기 TiO2층은,The TiO 2 layer is,blocking TiO2층; 및 blocking TiO 2 layer; And상기 blocking TiO2층 상에 형성되는 mesoporous TiO2층을 포함하는 태양전지.A solar cell comprising a mesoporous TiO 2 layer formed on the blocking TiO 2 layer.
- 제2항에 있어서,The method of claim 2,상기 제1 전극은 상기 TiO2층 상에 형성되는 ZrO2층을 더 포함하는 태양전지.The first electrode further comprises a ZrO 2 layer formed on the TiO 2 layer.
- 제2항에 있어서,The method of claim 2,상기 제2 전극은 카본을 포함하는 태양전지.The second electrode is a solar cell containing carbon.
- XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; Preparing an XZ compound powder and a YZ 3 compound powder;상기 XZ 화합물 분말 및 상기 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; 및Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder; And상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계를 포함하는, 페로브스카이트 화합물 제조방법.Heat-treating the mixed powder to produce a compound represented by the following formula, perovskite compound manufacturing method.[화학식][Formula]XaYbZc X a Y b Z cX=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, LiY=Bi, Sb 중 하나One of Y = Bi, SbZ=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,a=1에 대하여, for a = 1,0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12을 만족함Satisfied
- 제8항에 있어서,The method of claim 8,상기 혼합 분말을 열처리하는 단계에서, In the step of heat-treating the mixed powder,a=1, 2.4<b<3.6, 8<c<12인 경우, 상기의 화학식으로 표시되는 화합물은 삼사정계(triclinic)의 결정 구조를 가지는, 페로브스카이트 화합물 제조방법.When a = 1, 2.4 <b <3.6, 8 <c <12, the compound represented by the said formula has a triclinic crystal structure, The perovskite compound manufacturing method.
- 제8항에 있어서,The method of claim 8,상기 XZ 화합물의 농도는 1mol이고, 상기 YZ3화합물의 농도는 3mol인 페로브스카이트 화합물 제조방법.The concentration of the XZ compound is 1 mol, the concentration of the YZ 3 compound is 3 mol perovskite compound manufacturing method.
- 제1 전극을 형성하는 단계;Forming a first electrode;상기 제1 전극 상에 광 흡수층을 형성하는 단계; 및 Forming a light absorbing layer on the first electrode; And상기 광 흡수층 상에 제2 전극을 형성하는 단계를 포함하고,Forming a second electrode on the light absorbing layer;상기 광 흡수층은 하기의 화학식으로 표시되는 페로브스카이트 화합물을 포함하는 태양전지 제조방법.The light absorbing layer is a solar cell manufacturing method comprising a perovskite compound represented by the following formula.[화학식][Formula]XaYbZc X a Y b Z cX=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, LiY=Bi, Sb 중 하나One of Y = Bi, SbZ=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,a=1에 대하여, for a = 1,0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12을 만족하고, Satisfying,a=1, 2.4<b<3.6, 8<c<12인 경우, 상기 페로브스카이트 화합물은 삼사정계(triclinic)의 결정 구조를 가짐When a = 1, 2.4 <b <3.6, 8 <c <12, the perovskite compound has a triclinic crystal structure.
- 제11항에 있어서, The method of claim 11,상기 제1 전극을 형성하는 단계는,Forming the first electrode,유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제1 기판을 준비하는 단계; 및Preparing a first substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate; And상기 제1 기판 상에 TiO2층을 형성하는 단계를 포함하는 태양전지 제조방법.Forming a TiO 2 layer on the first substrate.
- 제12항에 있어서,The method of claim 12,상기 제1 전극을 형성하는 단계는,Forming the first electrode,상기 TiO2층 상에 ZrO2층을 형성하는 단계를 더 포함하는 태양전지 제조방법.Forming a ZrO 2 layer on the TiO 2 layer further comprises a solar cell manufacturing method.
- 제11항에 있어서,The method of claim 11,상기 광 흡수층을 형성하는 단계는Forming the light absorbing layer isXaYbZc 용액을 형성하는 단계; 및Forming a X a Y b Z c solution; AndXaYbZc 용액을 상기 제1 전극 상에 드롭핑(dropping), 스핀 코팅(spin coating) 또는 스크린 프린팅(screen printing)하는 단계를 포함하는 태양전지 제조방법. A method of manufacturing a solar cell comprising dropping, spin coating, or screen printing a X a Y b Z c solution on the first electrode.
- 제14항에 있어서,The method of claim 14,상기 XaYbZc 용액을 형성하는 단계는,Forming the X a Y b Z c solution,XZ 화합물 분말 및 YZ3 화합물 분말을 준비하는 단계; Preparing an XZ compound powder and a YZ 3 compound powder;상기 XZ 화합물 분말 및 YZ3 화합물 분말을 혼합하여 혼합 분말을 형성하는 단계; Mixing the XZ compound powder and the YZ 3 compound powder to form a mixed powder;상기 혼합 분말을 열처리하여, 하기의 화학식으로 표시되는 화합물을 제조하는 단계; 및 Heat-treating the mixed powder to prepare a compound represented by the following formula; And상기 열처리 된 혼합 분말을 DMF(dimethyl formamide) 또는 DMSO(Dimethyl sulfoxide) 용매에 용해시키는 단계를 포함하는 태양전지 제조방법.Dissolving the heat-treated mixed powder in a dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) solvent.[화학식][Formula]XaYbZc X a Y b Z cX=FA(CH(NH2)2), MA(CH3NH2), Cs, Rb, Na, K, Li 중 하나X = FA (CH (NH 2 ) 2 ), MA (CH 3 NH 2 ), Cs, Rb, Na, K, LiY=Bi, Sb 중 하나One of Y = Bi, SbZ=F, I, Br, Cl 중 하나이고,Z is one of F, I, Br, and Cl,a=1에 대하여, for a = 1,0.5<b<0.7, 2.5<c<3.5 또는 1.6<b<2.4, 5.6<c<8.4 또는 2.4<b<3.6, 8<c<120.5 <b <0.7, 2.5 <c <3.5 or 1.6 <b <2.4, 5.6 <c <8.4 or 2.4 <b <3.6, 8 <c <12을 만족함.Satisfied.
- 제15항에 있어서,The method of claim 15,상기 혼합 분말을 열처리 하는 단계에서, In the step of heat-treating the mixed powder,a=1, 2.4<b<3.6, 8<c<12인 경우, 상기의 화학식으로 표시되는 화합물은 삼사정계(triclinic)의 결정 구조를 가지는, 태양전지 제조방법.When a = 1, 2.4 <b <3.6, 8 <c <12, the compound represented by the said formula has a triclinic crystal structure, The solar cell manufacturing method.
- 제14항에 있어서, The method of claim 14,상기 광 흡수층을 형성하는 단계는,Forming the light absorbing layer,상기 XaYbZc 용액을 건조하는 단계를 더 포함하는 태양전지 제조방법.The method of manufacturing a solar cell further comprising the step of drying the X a Y b Z c solution.
- 제11항에 있어서, The method of claim 11,상기 제2 전극을 형성하는 단계는,Forming the second electrode,유리 기판, ITO(indium tin oxide) 기판, FTO(Fluorine Doped Tin Oxide) 기판 및 유연 투명 전극 기판 중 어느 하나로 선택되는 제2 기판을 준비하는 단계;Preparing a second substrate selected from a glass substrate, an indium tin oxide (ITO) substrate, a fluorine doped tin oxide (FTO) substrate, and a flexible transparent electrode substrate;탄소 분말을 준비하는 단계;Preparing a carbon powder;상기 제2 기판 상에 상기 탄소 분말을 코팅하는 단계; 및 Coating the carbon powder on the second substrate; And상기 탄소 분말이 코팅된 상기 제2 기판을 열처리하는 단계를 포함하는 태양전기 제조방법.The solar cell manufacturing method comprising the step of heat-treating the second substrate coated with the carbon powder.
- 제11항에 있어서,The method of claim 11,상기 제2 전극을 형성하는 단계는, 탄소를 함유하는 페이스트를 상기 광 흡수층 상에 도포하는 단계를 포함하는 태양전지 제조방법.The forming of the second electrode may include applying a carbon-containing paste onto the light absorbing layer.
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| KR1020160181477A KR20180077402A (en) | 2016-12-28 | 2016-12-28 | Perovskite compound and fabrication therof, solar cell comprising perovskite compound and fabrication therof |
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| KR1020170085536A KR102223890B1 (en) | 2017-07-05 | 2017-07-05 | PEROVSKITE COMPOUND of 1-2-7 STRUCTURE AND FABRICATION THEROF, SOLAR CELL COMPRISING PEROVSKITE COMPOUND of 1-2-7 STRUCTURE AND FABRICATION THEROF |
| KR1020170085520A KR101963252B1 (en) | 2017-07-05 | 2017-07-05 | PEROVSKITE COMPOUND of 1-3-10 STRUCTURE AND FABRICATION THEROF, SOLAR CELL COMPRISING PEROVSKITE COMPOUND of 1-3-10 STRUCTURE AND FABRICATION THEROF |
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