Method for manufacturing carbon electrode-based device and carbon electrode-based device manufactured thereby

Abstract

The present invention relates to a method for manufacturing a carbon electrode-based device and a carbon electrode-based device manufactured by the method. According to the present invention, introducing a solvent treatment process using a fluorosolvent induces densification of a carbon electrode without damaging a hole transport layer or perovskite, and thus an effective interface can be formed between the carbon electrode and the hole transport layer. Accordingly, reduction in porosity results in improved conductivity of the carbon electrode, and interface optimization leads to enhanced device performance. In addition, the present invention is suitable for large-area applications at low cost and is compatible with various processes, such as lamination and hot pressing, which can be applied to carbon electrodes.

Description

Method for manufacturing a carbon electrode-based device and a carbon electrode-based device manufactured by the method

[0001] The present invention relates to a method for manufacturing a carbon electrode-based device and a carbon electrode-based device manufactured by the method.

[0002]

[0003] A solar cell is a device that converts sunlight into electrical energy to generate electricity. Typically, a photoactive layer is located between an anode and a cathode, and it generates electrical energy by utilizing the photovoltaic effect, which absorbs solar energy and generates electrons and holes. When the light-absorbing layer absorbs sunlight, electrons in the light-absorbing layer are excited from their ground state, generating electron-hole pairs called excitons. The electrons and holes are separated from the excitons, move to the electrodes, and are collected, generating current.

[0004] The top electrodes of solar cells are made of metals like gold and silver. While these metal electrodes offer high conductivity and can be used thinly and uniformly, they are also expensive and require significant processing costs. Furthermore, they corrode rapidly in high-humidity environments, drastically reducing the "photoelectric conversion efficiency," the rate at which light is converted to electricity.

[0005] Meanwhile, carbon electrodes based on carbon nanoparticles possess high conductivity, making them suitable for use as high-conductivity electrodes. Their hydrophobic nature prevents them from readily binding to water molecules, enabling effective moisture blocking. Furthermore, they are lightweight and flexible, making them easy to attach to solar cells.

[0006] However, carbon electrodes exhibit some porosity immediately after fabrication, as the carbon nanoparticles are not evenly distributed. Consequently, introducing conventional solvents to densify the carbon electrode poses the problem of the solvent dissolving the underlying layer (hole transport layer or perovskite), damaging the device and reducing stability.

[0007]

[0008] The present invention provides a method for manufacturing a carbon electrode-based device by introducing a solvent treatment process that induces densification of a carbon electrode while not damaging the lower layer, and a carbon electrode-based device manufactured by the method.

[0009]

[0010] The method for manufacturing a carbon electrode-based device of the present invention may include the steps of S1) forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on a substrate having a transparent electrode layer formed thereon; S2) forming a two-dimensional perovskite layer by coating a two-dimensional perovskite precursor on the three-dimensional perovskite layer; S3) forming a hole transport layer by coating a hole transport material on the two-dimensional perovskite layer; S4) forming a carbon electrode layer by stacking carbon nanotubes as an electrode material on the hole transport layer; and S5) densifying the carbon electrode layer by treating the carbon electrode layer with an organic solvent.

[0011] The above step S1) may include a step S1-1) of forming a transparent electrode layer by laminating a conductive material on a substrate; a step S1-2) of forming an electron transport layer by coating an electron transport material on the transparent electrode layer; and a step S1-3) of forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on the electron transport layer.

[0012] The conductive material may include at least one selected from transparent conductive oxides including indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO).

[0013] The above electron transport material may include at least one selected from n-type oxides having a conduction band minimum formed at 3.9 to 4.3 eV and a valence band maximum of 6.5 eV or less.

[0014] The above three-dimensional perovskite precursor is FA x MA y Cs a PbI 3-b Br b It may include one or more selected from perovskites having the composition of .

[0015] The above step S1-3) may include the step S1-3-1) of coating the three-dimensional perovskite precursor on the electron transport layer; and the step S1-3-2) of heat-treating the substrate coated with the three-dimensional perovskite precursor to form a three-dimensional perovskite layer.

[0016] In the above step S1-3-1), the three-dimensional perovskite precursor can be dissolved in a solution in which dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) are mixed in a volume ratio of 1 to 2:5 to 10.

[0017] In the above step S1-3-2), the substrate 2.5×2.5 cm 2 After dropping 0.1 to 1 mL of diethyl ether or ethyl acetate on the substrate coated with the three-dimensional perovskite precursor, heat treatment can be performed at 100 to 150°C.

[0018] The above two-dimensional perovskite precursor may include at least one selected from two-dimensional layered perovskites containing an alkylammonium ion or a phenethylammonium ion having 4 to 12 carbon atoms.

[0019] The above step S2) can form a two-dimensional perovskite layer by dissolving the two-dimensional perovskite precursor in isopropyl alcohol at a concentration of 10 to 20 mM and coating it on the three-dimensional perovskite layer.

[0020] The hole transport material is spiro-OMeTAD (2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), DM(N2,N2',N7,N7'-tetrakis(9,9-dimethyl-9H-fluoren-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), EC(N2,N2',N7,N7'-tetrakis(9-ethyl-9H-carbazol-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), It may include one or more hole transport materials selected from PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) and CuPC (copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine).

[0021] In the above step S3), the hole transport material and cobalt salt mixture can be mixed in a weight ratio of 1800 to 2000:1, dissolved in chlorobenzene, and coated on the two-dimensional perovskite layer to form a hole transport layer.

[0022] The above cobalt salt mixture may include 20 to 30 wt% of bis(trifluoromethane) sulfonimide lithium salt (Li-TFSI), 65 to 75 wt% of tri-butyl phosphate (tBP), and 5 to 10 wt% of cobalt salt (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tri[bis(trifluoromethane)sulfonimide]).

[0023] The thickness of the above carbon nanotube may be 30 to 5000 nm.

[0024] In step S5), the organic solvent is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,3,3-hexafluoro-3-methoxy-2-(trifluoromethyl)-propane, 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifuoromethyl)propane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-Pentane, It may include one or more fluorosolvents selected from 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane, Methoxy-nonafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, Perfluoro(dibutylmethylamine), and Perfluorotributylamine.

[0025] In the above step S5), the treatment of the organic solvent is performed on the substrate 2.5×2.5 cm 2 After allowing 0.1 to 1 mL of the organic solvent to permeate the carbon electrode layer, the solvent can be evaporated to densify the carbon electrode layer.

[0026] The roughness (R) of the carbon electrode layer densified in the above step S5 RMS ) can be 10 to 30 nm.

[0027] The carbon electrode-based device according to the present invention has a roughness (R) of the carbon electrode layer RMS ) can be 10 to 30 nm.

[0028] The specific surface area of ​​the carbon electrode-based device according to the present invention is 10 to 150 m 2 g -1 It could be.

[0029] The surface resistance of the carbon electrode-based device according to the present invention is 0.5 to 10 ohm sq. -1 It could be.

[0030] The thickness of the carbon electrode-based device according to the present invention may be 50 μm to 10 mm.

[0031]

[0032] According to the present invention, by introducing a solvent treatment process utilizing a fluorosolvent, densification of the carbon electrode is induced without damaging the hole transport layer or perovskite, thereby forming an effective interface between the carbon electrode and the hole transport layer. Accordingly, the conductivity of the carbon electrode is improved due to reduced porosity, and the performance of the device is enhanced due to interface optimization.

[0033] In addition, it is suitable for large-area production at low cost and is compatible with various processes that can be used for carbon electrodes, such as lamination and hot press.

[0034]

[0035] FIG. 1 schematically illustrates a carbon electrode-based device according to one embodiment of the present invention.

[0036] Figure 2 shows the surface roughness of a carbon electrode layer according to the solvent treatment of the present invention.

[0037] Figure 3 shows the results of measuring the specific surface area of ​​a carbon electrode-based device according to the solvent treatment of the present invention.

[0038] Figure 4 shows a cross-section of a carbon electrode-based device according to the solvent treatment of the present invention.

[0039] Figure 5 shows the surface resistance and thickness of a carbon electrode-based device according to the solvent treatment of the present invention.

[0040] Figure 6 shows the current density-voltage measurement results of a carbon electrode-based device according to the solvent treatment of the present invention.

[0041]

[0042] The embodiments described herein may be modified in various different forms, and the technology according to one embodiment is not limited to the embodiments described below. In addition, the embodiments of one embodiment are provided to more completely explain the present disclosure to a person with average knowledge in the relevant technical field. In this case, unless there is a different definition for the technical and scientific terms used, they have the meaning commonly understood by a person with ordinary skill in the technical field to which this invention belongs, and in the following description and the attached drawings, descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted.

[0043] Additionally, the singular forms used in this specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0044] Additionally, in this specification and the appended claims, the terms first, second, etc. are not used in a limiting sense, but are used for the purpose of distinguishing one component from another.

[0045] Additionally, in this specification and the appended claims, when a part such as a film (layer), region or component is said to be located “on,” “above,” “upper,” “below,” “lower,” or “lower” another part, this includes not only cases where one part is in contact with another part, but also cases where another part exists between the two parts.

[0046] In addition, the terms "about," "substantially," and the like used in this specification and the appended claims are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly utilizing the disclosure in which exact or absolute values ​​are stated to aid in the understanding of this specification and the appended claims.

[0047] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes.

[0048] Furthermore, terms such as “include” or “have” in this specification and the appended claims mean that a feature or component described in the specification is present, and unless specifically limited, do not preclude the possibility that one or more other features or components may be added.

[0049] Hereinafter, a method for manufacturing a carbon electrode-based device of the present invention and a carbon electrode-based device manufactured by the method will be described in detail with reference to the attached drawings.

[0050]

[0051] A solar cell is a device that converts sunlight into electrical energy. It typically has a structure with a photoactive layer between an anode and a cathode, and generates electrical energy by utilizing the photovoltaic effect, which absorbs solar energy and generates electrons and holes.

[0052] The top electrodes of solar cells are made of metals like gold and silver. While these metal electrodes offer high conductivity and can be used thinly and uniformly, they are also expensive and require significant processing costs. Furthermore, they corrode rapidly in high-humidity environments, drastically reducing the "photoelectric conversion efficiency," the rate at which light is converted to electricity.

[0053] Meanwhile, carbon electrodes based on carbon nanoparticles possess high conductivity, making them suitable for use as high-conductivity electrodes. Their hydrophobic nature prevents them from readily binding to water molecules, enabling effective moisture blocking. Furthermore, they are lightweight and flexible, making them easy to attach to solar cells.

[0054] However, carbon electrodes have some porosity immediately after production because nanoparticles are not evenly distributed, and when conventional solvents are introduced to densify the carbon electrode, there is a problem that the lower layer (hole transport layer or perovskite) is dissolved, damaging the device and lowering stability.

[0055] Accordingly, the present invention has developed a solvent treatment process that induces densification of a carbon electrode without damaging the lower layer by utilizing a fluorosolvent, rather than a conventional general solvent. Accordingly, the present invention provides a method for manufacturing a carbon electrode-based device by introducing a solvent treatment process that induces densification of the carbon electrode without damaging the lower layer, and a carbon electrode-based device manufactured by the method. In addition, the present invention provides a method for inducing densification of a carbon electrode through solvent treatment and a carbon electrode manufactured by the method.

[0056]

[0057] FIG. 1 schematically illustrates a carbon electrode-based device according to one embodiment of the present invention.

[0058] A method for manufacturing a carbon electrode-based device according to the present invention may include the steps of S1) forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on a substrate having a transparent electrode layer formed thereon; S2) forming a two-dimensional perovskite layer by coating a two-dimensional perovskite precursor on the three-dimensional perovskite layer; S3) forming a hole transport layer by coating a hole transport material on the two-dimensional perovskite layer; S4) forming a carbon electrode layer by stacking carbon nanotubes as an electrode material on the hole transport layer; and S5) densifying the carbon electrode layer by treating the carbon electrode layer with an organic solvent.

[0059] The above step S1) may include a step S1-1) of forming a transparent electrode layer by laminating a conductive material on a substrate; a step S1-2) of forming an electron transport layer by coating an electron transport material on the transparent electrode layer; and a step S1-3) of forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on the electron transport layer.

[0060] The above step S1-1) is a step of forming a transparent electrode layer by laminating a conductive material on a substrate, and the substrate includes at least one selected from a flexible substrate including glass, plastic, or polymer, and may be, for example, a glass substrate 1.1t, a glass substrate 2.2t, or a flexible substrate 0.1t, but is not limited thereto.

[0061] The conductive material includes at least one selected from transparent conductive oxides including indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO). The conductive material may preferably be FTO, but is not limited thereto.

[0062] In the step S1-1), the lamination of the conductive material can be performed using any method that can form a transparent electrode layer by depositing the conductive material on the substrate without limitation. For example, methods such as sputtering, physical vapor deposition (PVD), and chemical vapor deposition (CVD) can be selected, and sputtering is preferred, but is not limited thereto.

[0063] The thickness of the transparent electrode layer may be 50 to 1000 nm, preferably 75 to 800 nm, and more preferably 100 to 700 nm.

[0064] The above step S1-2) is a step of forming an electron transport layer by coating an electron transport material on the transparent electrode layer, wherein the electron transport material includes at least one selected from n-type oxides including TiO2 and SnO2. The n-type oxide is a material that conducts electricity via electrons, and the minimum of the material's conduction band is formed at 3.9 to 4.3 eV, and the maximum of the valence band is formed at 6.5 eV or less. The electron transport material may preferably be SnO2, but is not limited thereto.

[0065] In the above step S1-2), the coating of the electron transport material can be done without limitation by any method that can form an electron transport layer by coating the electron transport material on the transparent electrode layer. For example, methods such as spin coating, spray coating, and dip coating can be selected, and spin coating is preferred, but is not limited thereto.

[0066] As an example, the step S1-2) may form an electron transport layer by coating the electron transport material dissolved in water on the transparent electrode layer washed with alcohol.

[0067] The thickness of the electron transport layer may be 10 to 1000 nm, preferably 20 to 500 nm, and more preferably 30 to 250 nm.

[0068] The above step S1-3) is a step of forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on the electron transport layer, and specifically, it may include the step S1-3-1) of coating the three-dimensional perovskite precursor on the electron transport layer; and the step S1-3-2) of heat-treating a substrate coated with the three-dimensional perovskite precursor to form a three-dimensional perovskite layer.

[0069] The above three-dimensional perovskite precursor is FA x MA y Cs a PbI 3-b Br b It comprises at least one selected from perovskites having a composition of. In the perovskite, FA is formamidinium, MA is methylammonium, x+y is 1, a is 0 to 1, and b is 0 to 3. In one embodiment, the perovskite comprises FA 0.95 MA 0.05 PbI 2.85 Br 0.15 or FAPbI3 / FA 0.975 MA 0.025 PbI 2.925 Br 0.075 It may be, but is not limited to,

[0070] In the above step S1-3), the coating of the three-dimensional perovskite precursor can be performed by any method that can form a three-dimensional perovskite layer by coating the three-dimensional perovskite precursor on the electron transport layer, and is preferably spin coating, but is not limited thereto.

[0071] As an example, the step S1-3) is a method of dissolving the 3D perovskite precursor in a solution of dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) in a volume ratio of 1 to 2:5 to 10, coating the solution on the electron transport layer, and then coating the substrate with a size of 2.5×2.5 cm. 2 Based on this, 0.1 to 1 mL of diethyl ether or ethyl acetate is dropped onto a substrate coated with the three-dimensional perovskite precursor, and then heat treatment is performed at 100 to 150°C to form a three-dimensional perovskite layer having a dark brown color.

[0072] The thickness of the three-dimensional perovskite layer may be 100 to 1000 nm, preferably 300 to 900 nm, and more preferably 450 to 800 nm.

[0073] The above step S2) is a step of forming a two-dimensional perovskite layer by coating a two-dimensional perovskite precursor on the three-dimensional perovskite layer, wherein the two-dimensional perovskite precursor includes at least one selected from two-dimensional layered perovskites containing an alkylammonium ion or a phenethylammonium ion having 4 to 12 carbon atoms.

[0074] In the above step S2), the coating of the two-dimensional perovskite precursor can be done by any method that can form a two-dimensional perovskite layer by coating the two-dimensional perovskite precursor on the three-dimensional perovskite layer, and is preferably spin coating, but is not limited thereto.

[0075] As an example, the step S4) may be performed by dissolving an alkyl ammonium halide or a phenethyl ammonium halide used as the two-dimensional perovskite precursor in isopropyl alcohol at a concentration of 10 to 20 mM and coating the alkyl ammonium halide on the three-dimensional perovskite layer to form a two-dimensional perovskite layer.

[0076] The thickness of the above two-dimensional perovskite layer may be 10 to 200 nm, preferably 20 to 100 nm, and more preferably 20 to 60 nm.

[0077] The above S3) step is a step of forming a hole transport layer by coating a hole transport material on the two-dimensional perovskite layer, wherein the hole transport material is spiro-OMeTAD (2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), DM (N2,N2',N7,N7'-tetrakis(9,9-dimethyl-9H-fluoren-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), It comprises at least one hole transport material selected from EC(N2,N2',N7,N7'-tetrakis(9-ethyl-9H-carbazol-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), PTAA(poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) and CuPC(copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine). The hole transport material may preferably be spiro-OMeTAD, but is not limited thereto.

[0078] In the above step S3), any method that can form a hole transport layer by coating the hole transport material on the two-dimensional perovskite precursor can be used without limitation, and preferably, spin coating is used, but is not limited thereto.

[0079] As an example, the hole transport material and cobalt salt mixture may be mixed in a weight ratio of 1800 to 2000:1, dissolved in chlorobenzene, and coated on the two-dimensional perovskite layer to form a hole transport layer. The cobalt salt mixture may include 20 to 30 wt% of bis(trifluoromethane) sulfonimide lithium salt (Li-TFSI), 65 to 75 wt% of tri-butyl phosphate (tBP), and 5 to 10 wt% of cobalt salt (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tri[bis(trifluoromethane)sulfonimide]).

[0080] The thickness of the hole transport layer may be 10 to 1000 nm, preferably 20 to 500 nm, and more preferably 20 to 300 nm.

[0081] The above step S4) is a step of forming a carbon electrode layer by stacking carbon nanotubes as an electrode material on the hole transport layer, and the thickness of the carbon nanotubes (CNTs) may be 30 to 5000 nm, preferably 100 to 3500 nm, and more preferably 250 to 2500 nm.

[0082] As an example, the carbon nanotube may be a carbon paste in the form of a slurry containing graphite, carbon black, and a polymeric binder, and the carbon paste may be coated on the hole transport layer and then dried to form a carbon electrode layer. The coating of the carbon paste may be done by any method that can form a carbon electrode layer by coating the carbon paste on the hole transport layer, and is preferably spin coating, but is not limited thereto.

[0083] As another example, the carbon nanotubes may be solidified carbon nanotubes (CNTs) through a dry process, and the carbon electrode layer may be formed by stacking them on the hole transport layer and applying a pressure of several MPa through a device at the level of simply pressing them by hand.

[0084] The thickness of the above carbon electrode layer may be 0.1 to 100 μm. In one embodiment, in the case of carbon paste, the thickness may be 2 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm, and in the case of solidified carbon nanotubes, the thickness may be 0.1 to 50 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

[0085] The above step S5) is a step of densifying the carbon electrode layer by treating the carbon electrode layer with an organic solvent, in which the organic solvent is allowed to permeate the carbon electrode layer and then evaporated to induce densification of the carbon electrode layer.

[0086] In the above step S5), the treatment of the organic solvent can be carried out by any method that allows the organic solvent to permeate the carbon electrode layer without limitation. For example, methods such as drop casting, spin coating, spray coating, and dip coating can be selected, and drop casting is preferred, but is not limited thereto.

[0087] The organic solvent is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,3,3-hexafluoro-3-methoxy-2-(trifluoromethyl)-propane, 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifuoromethyl)propane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-Pentane, Contains at least one fluorinated solvent selected from 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane, Methoxy-nonafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, Perfluoro(dibutylmethylamine), and Perfluorotributylamine.

[0088] As an example, the substrate is 2.5×2.5 cm 2 Based on this, 0.1 to 1 mL of the fluorinated solvent is allowed to permeate the carbon electrode layer, and then evaporated until the fluorinated solvent is no longer visible in the carbon electrode layer, thereby densifying the carbon electrode layer. Due to the optimization of the interface between the carbon hole layer and the hole transport layer, the porosity between the carbon nanotubes in the carbon electrode layer is reduced, forming a densely stacked structure, and an effective interface is formed between the carbon hole layer and the hole transport layer.

[0089] As an example, the roughness (R) of the carbon electrode layer densified in the step S5) RMS) may be 10 to 30 nm, preferably 20 to 30 nm, more preferably 24 to 27 nm.

[0090] The thickness of the carbon electrode-based device according to the present invention may be 50 μm to 10 mm, preferably 200 μm to 5 mm, and more preferably 1 mm to 3 mm.

[0091]

[0092] In addition, a carbon electrode-based device according to the present invention includes a transparent electrode layer disposed on a substrate; an electron transport layer disposed on the transparent electrode layer; a three-dimensional perovskite layer disposed on the electron transport layer; a two-dimensional perovskite layer disposed on the three-dimensional perovskite layer; a hole transport layer disposed on the two-dimensional perovskite layer; and a carbon electrode layer disposed on the hole transport layer.

[0093] The substrate includes at least one selected from a flexible substrate including glass, plastic, or polymer, and may be, for example, a glass substrate 1.1t, a glass substrate 2.2t, or a flexible substrate 0.1t, but is not limited thereto.

[0094] A transparent electrode layer is disposed on the substrate. The transparent electrode layer includes at least one selected from transparent conductive oxides including indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO). The transparent conductive oxide may preferably be an FTO electrode, but is not limited thereto.

[0095] The thickness of the transparent electrode layer may be 50 to 1000 nm, preferably 75 to 800 nm, and more preferably 100 to 700 nm.

[0096] An electron transport layer is disposed on the transparent electrode layer. The electron transport layer includes at least one selected from n-type oxides including TiO2 and SnO2. The n-type oxide is a material that conducts electricity via electrons, and the minimum of the material's conduction band is formed at 3.9 to 4.3 eV, and the maximum of the valence band is formed at 6.5 eV or less. The n-type oxide may preferably be SnO2, but is not limited thereto.

[0097] The thickness of the electron transport layer may be 10 to 1000 nm, preferably 20 to 500 nm, and more preferably 30 to 250 nm.

[0098] A three-dimensional perovskite layer is arranged on the electron transport layer. The three-dimensional perovskite layer is FA x MA y Cs a PbI 3-b Br b It comprises at least one selected from perovskites having a composition of. In the perovskite, FA is formamidinium, MA is methylammonium, x+y is 1, a is 0 to 1, and b is 0 to 3. In one embodiment, the perovskite comprises FA 0.95 MA 0.05 PbI 2.85 Br 0.15 or FAPbI3 / FA 0.975 MA 0.025 PbI 2.925 Br 0.075 It may be, but is not limited to,

[0099] The thickness of the three-dimensional perovskite layer may be 100 to 1000 nm, preferably 300 to 900 nm, and more preferably 450 to 800 nm.

[0100] A two-dimensional perovskite layer is disposed on the three-dimensional perovskite layer. The two-dimensional perovskite layer includes at least one selected from two-dimensional layered perovskites containing an alkylammonium ion or a phenethylammonium ion having 4 to 12 carbon atoms.

[0101] The thickness of the above two-dimensional perovskite layer may be 10 to 200 nm, preferably 20 to 100 nm, and more preferably 20 to 60 nm.

[0102] A hole transport layer is arranged on the above two-dimensional perovskite layer. The hole transport layer is spiro-OMeTAD (2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), DM(N2,N2',N7,N7'-tetrakis(9,9-dimethyl-9H-fluoren-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), EC(N2,N2',N7,N7'-tetrakis(9-ethyl-9H-carbazol-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), It comprises at least one hole transport material selected from poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) and copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPC). The hole transport material may preferably be spiro-OMeTAD, but is not limited thereto.

[0103] The thickness of the hole transport layer may be 10 to 1000 nm, preferably 20 to 500 nm, and more preferably 20 to 300 nm.

[0104] A carbon electrode layer is disposed on the hole transport layer. The carbon electrode layer may include carbon nanotubes (CNTs) as an electrode material. The thickness of the carbon nanotubes may be 30 to 5,000 nm, preferably 100 to 3,500 nm, and more preferably 250 to 2,500 nm.

[0105] As an example, the carbon nanotube may be a carbon paste in the form of a slurry containing graphite, carbon black, and a polymeric binder, or may be a carbon nanotube (CNT) solidified through a dry process.

[0106] The thickness of the above carbon electrode layer may be 0.1 to 100 μm. In one embodiment, in the case of carbon paste, the thickness may be 2 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm, and in the case of solidified carbon nanotubes, the thickness may be 0.1 to 50 μm, preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

[0107] The carbon electrode layer has some porosity immediately after production because the carbon nanotubes are not evenly distributed. Accordingly, the carbon electrode layer can be treated with an organic solvent to reduce the porosity and densify the layer.

[0108] The organic solvent is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,3,3-hexafluoro-3-methoxy-2-(trifluoromethyl)-propane, 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifuoromethyl)propane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-Pentane, Contains at least one fluorinated solvent selected from 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane, Methoxy-nonafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, Perfluoro(dibutylmethylamine), and Perfluorotributylamine.

[0109] The carbon electrode-based device according to the present invention has a roughness (R) of the carbon electrode layer RMS ) may be 10 to 30 nm, preferably 20 to 30 nm, more preferably 24 to 27 nm.

[0110] The specific surface area of ​​the carbon electrode-based device according to the present invention is 10 to 150 m 2 g -1 , preferably 20 to 140 m 2 g -1 , more preferably 50 to 135 m 2 g -1 It could be.

[0111] The surface resistance of the carbon electrode-based device according to the present invention is 0.5 to 10 ohm sq.-1 , preferably 0.5 to 8 ohm sq -1 , more preferably 0.5 to 4 ohm sq -1 It could be.

[0112] The thickness of the carbon electrode-based device according to the present invention may be 50 μm to 10 mm, preferably 200 μm to 5 mm, and more preferably 1 mm to 3 mm.

[0113]

[0114] According to the present invention, by introducing a solvent treatment process utilizing a fluorosolvent, densification of the carbon electrode is induced without damaging the hole transport layer or perovskite, thereby forming an effective interface between the carbon electrode and the hole transport layer. Accordingly, the conductivity of the carbon electrode is improved due to reduced porosity, and the performance of the device is enhanced due to interface optimization.

[0115] In addition, it is suitable for large-area production at low cost and is compatible with various processes that can be used for carbon electrodes, such as lamination and hot press.

[0116]

[0117] Hereinafter, specific examples and experimental examples will be described. However, the examples and experimental examples described below are only illustrative, and the technology described in this specification is not limited thereto.

[0118]

[0119] <Example>

[0120] 2.5×2.5 cm 2A transparent electrode layer 800 nm thick was formed by sputtering fluorine-doped tin oxide (FTO) on a plastic substrate. A 30 nm thick electron transport layer was formed by spin-coating SnO2 nanoparticles dissolved in water on the transparent electrode layer, which was washed with ethanol. Perovskite precursor FA 0.95 MA 0.05 PbI 2.85 Br 0.15 was dissolved in a solution of 1 mL of DMSO and 8 mL of DMF and spin-coated on the electron transport layer. 1 mL of diethyl ether was dropped on the rotating substrate coated with the perovskite precursor, and heat treatment was performed at 150°C to form a 700 nm thick 3D perovskite layer with a dark brown color. 4-methoxy-phenethylammonium iodide, dissolved in IPA and having a concentration of 10 mM, was spin-coated on the 3D perovskite layer to form a 40 nm thick 2D perovskite layer. Spiro-OMeTAD 26596 g, bis(trifluoromethane) sulfonimide lithium salt 3.3 g, tri-butyl phosphate 9.6 g, and tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tri[bis(trifluoromethane)sulfonimide] 1 g were mixed and dissolved in chlorobenzene, and then spin-coated on the two-dimensional perovskite layer to form a 200 nm thick hole transport layer. Carbon nanotubes with a thickness of 500 to 2500 nm were spin-coated on the hole transport layer to form a 30 μm thick carbon electrode layer, thereby fabricating a carbon electrode-based device.

[0121] The carbon electrode-based device was treated with a solvent by drop-casting 0.1 mL of Fluorinert FC-40 (a mixture of Perfluoro(dibutylmethylamine) and Perfluorotributylamine), and the solvent was allowed to permeate the carbon electrode layer. After that, the solvent was evaporated to densify the carbon electrode layer.

[0122]

[0123] <Comparative Example 1>

[0124] It was manufactured in the same manner as in the above example, except that solvent treatment was not performed.

[0125]

[0126] <Comparative Example 2>

[0127] It was manufactured in the same manner as in the above example, except that it was treated with HFE7200 (1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifuoromethyl)propane).

[0128]

[0129] Experimental Example 1

[0130] The surface roughness of the carbon electrode layer of the above example (Solvent-treated) and comparative example 1 (Control) and the specific surface area of ​​the carbon electrode-based device were compared. Roughness (R RMS ) represents the square root of the average of the squares of the measurements of the curvature formed on the carbon electrode. In addition, the specific surface area represents the surface area per unit mass of the carbon electrode-based device.

[0131] Figure 2 shows the surface roughness of a carbon electrode layer according to the solvent treatment of the present invention. The roughness of the example (solvent-treated) was measured to be 25.8 nm, and the roughness of comparative example 1 (control) was measured to be 30.6 nm, confirming that the roughness of the carbon electrode was reduced through solvent treatment.

[0132] Figure 3 shows the results of measuring the specific surface area of ​​a carbon electrode-based device according to the solvent treatment of the present invention. The specific surface area of ​​the solvent-treated device is 130 m 2 g -1 , the specific surface area of ​​Comparative Example 1 (Control) is 150 m 2 g -1 It was measured as , and it was confirmed that the pores of the carbon electrode were reduced through solvent treatment, thereby reducing the specific surface area.

[0133]

[0134] Experimental Example 2

[0135] The cross-section, surface resistance, and thickness of the carbon electrode-based devices of the above example (Solvent-treated) and comparative example 1 (Control) were compared.

[0136] Figure 4 illustrates a cross-section of a carbon electrode-based device according to the solvent treatment of the present invention. It was confirmed that the cross-section of the Example (solvent-treated) was more uniformly stacked compared to that of Comparative Example 1 (Control).

[0137] Figure 5 shows the surface resistance and thickness of a carbon electrode-based device according to the solvent treatment of the present invention. The solvent-treated device has a surface resistance of 3.5 ohm sq. -1 , the thickness was measured to be 750 nm, and Comparative Example 1 (Control) had a surface resistance of 4.5 ohm sq. -1 , the thickness was measured to be 800 nm. It was confirmed that the surface resistance and thickness of the carbon electrode-based device were reduced through solvent treatment.

[0138]

[0139] Experimental Example 3

[0140] To verify the performance of Example (FC-40-treated), Comparative Example 1 (Control) and Comparative Example 2 (HFE-7200-treated), the open circuit voltage (V OC ), short-circuit current density (J SC), fill factor (FF), and power conversion efficiency (PCE) were measured. V OC Wow J SC is a value determined by the intrinsic properties of the electron donor and acceptor, and FF is an external variable that depends on the shape of the solar cell and the structure of the device. PCE refers to the ratio of the output energy to the incident energy from the sun.

[0141] Measurement conditions were 100 mWcm using a standard Si solar cell (RC1000-TC-KG5-N, VLSI Standards). -2 Solar simulations were performed with AM 1.5G sunlight generated by an Oriel Sol3A solar simulator calibrated to .

[0142]

[0143] Table 1 and Figure 6 show the results of current density-voltage measurements of a carbon electrode-based device according to the solvent treatment of the present invention.

[0144]

[0145] V OC (V)J SC (mA cm -2 )FF (%)PCE (%)Solvent-treated, forward1.1524.277.621.53Solvent-treated, reverse1.1524.273.920.52Control, forward1.1824.373.921.14Control, reverse1.1524.269.419.30HFE-7200-treated, forward1.1624.077.521.37HFE-7200-treated, reverse1.1424.071.419.58

[0146]

[0147] When the voltage control direction of the example (FC-40-treated) is forward, V OC Ga 1.15 V, J SC 24.2 mA cm-2 , FF was measured at 77.6%, PCE at 21.53%, and in case of reverse, V OC Ga 1.15 V, J SC 24.2 mA cm -2 , FF was measured at 73.9% and PCE at 20.52%.

[0148] Comparative Example 1 (Control) is when the voltage control direction is forward, V OC Ga 1.18 V, J SC 24.3 mA cm -2 , FF was measured at 73.9%, PCE at 21.14%, and in case of reverse, V OC Ga 1.15 V, J SC 24.2 mA cm -2 , FF was measured at 69.4% and PCE at 19.30%.

[0149] Comparative Example 2 (HFE-7200-treated) shows that when the voltage control direction is forward, V OC Ga 1.16 V, J SC 24.0 mA cm -2 , FF was measured as 77.5%, PCE as 21.37%, and in case of reverse, V OC Ga 1.14 V, J SC 24.0 mA cm -2 , FF was measured at 71.4.4% and PCE at 19.58%.

[0150] Compared to Comparative Example 1 (Control), Example (FC-40-treated) showed consistent values ​​even when the voltage control direction was changed during efficiency measurement, confirming improved stability. In addition, Comparative Example 2 (HFE-7200-treated) showed slightly improved PCE compared to Comparative Example 1 (Control), but it is believed that densification by solvent treatment did not occur sufficiently due to high volatility.

[0151]

[0152] Although the present invention has been described in this specification with specific details and limited examples, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on these descriptions. Therefore, the ideas described in this specification should not be limited to the described examples, and all things that are equivalent or equivalent to the claims below, as well as the claims, are considered to fall within the scope of the ideas described in this specification.

[0153]

[0154] [Explanation of symbols]

[0155] 100: Carbon electrode-based device

[0156] 110: Substrate

[0157] 120: Transmissive electrode layer

[0158] 130: Electron transport layer

[0159] 140: 3D perovskite layer

[0160] 150: 2D perovskite layer

[0161] 160: Hole transport layer

[0162] 170: Carbon electrode layer

Claims

1. S1) A step of forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on a substrate on which a transparent electrode layer is formed; S2) A step of forming a two-dimensional perovskite layer by coating a two-dimensional perovskite precursor on the three-dimensional perovskite layer; S3) A step of forming a hole transport layer by coating a hole transport material on the two-dimensional perovskite layer; S4) A step of forming a carbon electrode layer by laminating carbon nanotubes as an electrode material on the hole transport layer; and S5) A step of densifying the carbon electrode layer by treating the carbon electrode layer with an organic solvent; A method for manufacturing a carbon electrode-based device comprising:

2. In paragraph 1, The above step S1) is a step S1-1) of forming a transparent electrode layer by laminating a conductive material on a substrate; S1-2) A step of forming an electron transport layer by coating an electron transport material on the transparent electrode layer; and S1-3) A step of forming a three-dimensional perovskite layer by coating a three-dimensional perovskite precursor on the electron transport layer; A method for manufacturing a carbon electrode-based device comprising:

3. In paragraph 2, A method for manufacturing a carbon electrode-based device, wherein the conductive material comprises at least one selected from transparent conductive oxides including indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO).

4. In paragraph 2, A method for manufacturing a carbon electrode-based device, wherein the electron transport material comprises at least one selected from n-type oxides having a conduction band minimum of 3.9 to 4.3 eV and a valence band maximum of 6.5 eV or less.

5. In paragraph 2, The above three-dimensional perovskite precursor is FA x MA y Cs a PbI 3-b Br b A method for manufacturing a carbon electrode-based device comprising at least one perovskite having a composition of .

6. In paragraph 2, The step S1-3) above is a method for manufacturing a carbon electrode-based device including the steps S1-3-1) coating the three-dimensional perovskite precursor on the electron transport layer; and S1-3-2) heat-treating the substrate coated with the three-dimensional perovskite precursor to form a three-dimensional perovskite layer.

7. In paragraph 6, A method for manufacturing a carbon electrode-based device, wherein the three-dimensional perovskite precursor is dissolved in a solution containing dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) in a volume ratio of 1 to 2:5 to 10 in the step S1-3-1).

8. In paragraph 6, In the above step S1-3-2), the substrate is 2.5×2.5 cm 2 A method for manufacturing a carbon electrode-based device, comprising dropping 0.1 to 1 mL of diethyl ether or ethyl acetate on a substrate coated with the three-dimensional perovskite precursor, and then performing a heat treatment at 100 to 150° C.

9. In paragraph 1, A method for manufacturing a carbon electrode-based device, wherein the two-dimensional perovskite precursor comprises at least one selected from two-dimensional layered perovskites containing alkylammonium ions or phenethylammonium ions having 4 to 12 carbon atoms.

10. In paragraph 1, The above step S2) is a method for manufacturing a carbon electrode-based device, which comprises dissolving the two-dimensional perovskite precursor in isopropyl alcohol at a concentration of 10 to 20 mM and coating it on the three-dimensional perovskite layer to form a two-dimensional perovskite layer.

11. In paragraph 1, The hole transport material is spiro-OMeTAD (2,2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene), DM(N2,N2',N7,N7'-tetrakis(9,9-dimethyl-9H-fluoren-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), EC(N2,N2',N7,N7'-tetrakis(9-ethyl-9H-carbazol-2-yl)-N2,N2',N7,N7'-tetrakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetraamine), A method for manufacturing a carbon electrode-based device comprising at least one hole transport material selected from poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) and copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPC).

12. In paragraph 1, A method for manufacturing a carbon electrode-based device, comprising mixing the hole transport material and the cobalt salt mixture in a weight ratio of 1800 to 2000:1 in step S3), dissolving it in chlorobenzene, and coating it on the two-dimensional perovskite layer to form a hole transport layer.

13. In paragraph 12, A method for manufacturing a carbon electrode-based device, wherein the cobalt salt mixture comprises 20 to 30 wt% of bis(trifluoromethane) sulfonimide lithium salt (Li-TFSI), 65 to 75 wt% of tri-butyl phosphate (tBP), and 5 to 10 wt% of a cobalt salt (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tri[bis(trifluoromethane)sulfonimide]).

14. In paragraph 1, A method for manufacturing a carbon electrode-based device, wherein the thickness of the carbon nanotube is 30 to 5000 nm.

15. In paragraph 1, In step S5), the organic solvent is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,3,3-hexafluoro-3-methoxy-2-(trifluoromethyl)-propane, 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane, 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifuoromethyl)propane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-Pentane, A method for manufacturing a carbon electrode-based device comprising at least one fluorinated solvent selected from 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane, Methoxy-nonafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, Perfluoro(dibutylmethylamine), and Perfluorotributylamine.

16. In paragraph 1, In the above step S5), the treatment of the organic solvent is performed on the substrate 2.5×2.5 cm 2 A method for manufacturing a carbon electrode-based device, comprising: allowing 0.1 to 1 mL of the organic solvent to permeate the carbon electrode layer; and then evaporating the solvent to densify the carbon electrode layer.

17. In paragraph 16, The roughness (R) of the carbon electrode layer densified in the above step S5) RMS ) A method for manufacturing a carbon electrode-based device having a thickness of 10 to 30 nm.

18. A carbon electrode-based device manufactured by any one of the methods of claims 1 to 17.

19. In paragraph 18, The above carbon electrode-based device has a roughness (R) of the carbon electrode layer RMS ) is a carbon electrode-based device having a thickness of 10 to 30 nm.

20. In paragraph 18, The specific surface area of the above carbon electrode-based device is 10 to 150 m 2 g -1 A carbon electrode-based device.

21. In paragraph 18, The surface resistance of the above carbon electrode-based device is 0.5 to 10 ohm sq. -1 A carbon electrode-based device.

22. In paragraph 18, A carbon electrode-based device having a thickness of 50 μm to 10 mm.

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