Method for manufacturing a solar cell and a solar cell manufactured therefrom

Abstract

The present invention relates to a method for manufacturing a solar cell and a solar cell manufactured therefrom, and more particularly, to a method for manufacturing a solar cell, the method including the step of manufacturing a laminate in which a first electrode layer, a hole transport layer (HTL), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially stacked, the hole transport layer or the electron transport layer being formed by coating and drying a dispersion liquid including a metal oxide surface-modified with a carboxylic acid (R-COOH), a dispersion solvent, and a hydroxide, and a solar cell manufactured therefrom.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a solar cell and a solar cell manufactured therefrom, and more particularly, to a method for manufacturing a perovskite solar cell capable of forming a uniform metal oxide thin film layer and a perovskite solar cell manufactured therefrom.

Background Art

[0002] A solar cell is a core element of solar power generation that directly converts sunlight into electricity, and currently, it is widely used for power supply not only in households but also in space. In recent years, solar cells have been used in fields such as aviation, meteorology, and communication, and solar-powered vehicles and solar air conditioners have also attracted attention.

[0003] Such solar cells mainly use silicon semiconductors, but due to the price of raw materials for high-purity silicon semiconductors and the complexity of the solar cell manufacturing process using them, they have the problem of high power generation costs. That is, since solar cells have a unit price that is 3 to 10 times higher than that of conventional fossil fuel power generation, there is a limit to the growth of the market through government subsidies in various countries. For this reason, research and development of solar cells that do not use silicon have been activated, and since the 1990s, dye-sensitized solar cells (DSSCs) using dyes, which are organic semiconductor materials, and polymer solar cells using conductive polymers have begun to be seriously studied. Although such organic semiconductor-based solar cells such as DSSCs and polymer solar cells have not reached the commercialization stage despite many efforts in the academic and industrial fields, in recent years, with the emergence of perovskite solar cells (PSCs) that integrate the advantages of DSSCs and polymer solar cells, the expectation for next-generation solar cells has been further heightened.

[0004] The perovskite solar cell is a hybrid solar cell that combines a conventional DSSC and a polymer solar cell. Since it does not use a liquid electrolyte like a DSSC, its reliability is improved, and it is a solar cell capable of high efficiency due to the excellent optical properties of perovskite. In recent years, its efficiency has been continuously improved through process improvements, material improvements, and structural improvements.

[0005] FIG. 1 is a diagram showing a solar cell. Referring to FIG. 1, the solar cell 100 is composed of a substrate layer 10, a first electrode layer 20, a hole transport layer 30, a photoactive layer 40, an electron transport layer 50, and a second electrode layer 60.

[0006] The hole transport layer 30 or the electron transport layer 50 of the solar cell 100 may contain a metal oxide thin film. When a metal oxide thin film is applied as the hole transport layer 30, the metal oxide is very stable and has the advantage of high hole conductivity.

[0007] In order to uniformly form the metal oxide thin film, the surface of the metal oxide is modified using an acid functional group such as acetic acid (AA) or trifluoroacetic acid (TFA) to facilitate the dispersion of the metal oxide in the dispersion solvent.

[0008] However, even when the surface of the metal oxide is modified as described above, the dispersibility is only improved in a non-polar solvent such as isopropyl alcohol (IPA), and the dispersibility is still low in a polar solvent such as deionized water (DI water) or ethanol. Eventually, there was a problem that it was difficult to form a metal oxide thin film when using a dispersion liquid containing a metal oxide dispersed in a polar solvent.

Summary of the Invention

Problems to be Solved by the Invention

[0009] Accordingly, the problem to be solved by the present invention is to provide a method for manufacturing a solar cell that can successfully disperse metal oxides surface-modified not only in non-polar solvents but also in polar solvents, and can form a uniform metal oxide thin film.

[0010] And the problem to be solved by the present invention is to provide a solar cell manufactured by the method for manufacturing a solar cell.

[0011] The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0012] To achieve the above object, a method for manufacturing a solar cell according to one aspect of the present invention includes a step of manufacturing a laminate in which a first electrode layer, a hole transport layer (HTL, Hole Transport Layer), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially laminated, and the hole transport layer or the electron transport layer is formed by applying and drying a dispersion liquid containing a metal oxide surface-modified with a carboxylic acid (R-COOH), a dispersion solvent, and a hydroxide.

[0013] Here, the hydrogen ion concentration of the dispersion liquid may be from pH 8 to pH 13.

[0014] On the other hand, the hydroxide may be any one selected from the group consisting of NH4OH, LiOH, NaOH, KOH, RbOH, CsOH, TMAH (Tetramethylammonium hydroxide), and TBMH (Tetrabutylammonium hydroxide), or a mixture of two or more of these.

[0015] And the metal oxide may be tin oxide, and the tin oxide may be SnO2.

[0016] Also, the carboxylic acid may be acetic acid or trifluoroacetic acid.

[0017] And the dispersion solvent may be any one selected from the group consisting of isopropyl alcohol (IPA), deionized water (DI water), and ethanol, or may be two or more of these.

[0018] Further, the laminate may further include a substrate layer on the lower surface of the first electrode layer.

[0019] And the photoactive layer may be a perovskite layer.

[0020] On the other hand, a solar cell according to another aspect of the present invention is one in which a substrate layer, a first electrode layer, a hole transport layer (HTL, Hole Transport Layer), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially laminated, and the hole transport layer or the electron transport layer includes a metal oxide layer, and the metal oxide layer is characterized in that a compound containing a carboxy group (-COOH) adheres to the surface, and a surface-modified metal oxide is uniformly formed in a thin film.

[0021] Here, the first electrode layer and the second electrode layer may each independently include any one selected from the group consisting of ITO (Indium Tin Oxide), ICO (Indium Cerium Oxide), IWO (Indium Tungsten Oxide), ZITO (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide), GITO (Gallium Indium Tin Oxide), GIO (Gallium Indium Oxide), GZO (Gallium Zinc Oxide), AZO (Aluminum doped Zinc Oxide), FTO (Fluorine Tin Oxide), and ZnO, or may include two or more of these.

[0022] And the electron transport layer may be any one selected from the group consisting of titanium oxide, zinc oxide, indium oxide, tin oxide, tungsten oxide, niobium oxide, molybdenum oxide, magnesium oxide, zirconium oxide, strontium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, aluminum oxide, yttrium oxide, scandium oxide, samarium oxide, gallium oxide, and strontium titanate, or may contain any two or more thereof.

[0023] Also, the hole transport layer may be any one selected from the group consisting of tungsten oxide (WO x ), molybdenum oxide (MoO x ), vanadium oxide (V2O5), and nickel oxide (NiO x ), or may contain any two or more thereof.

[0024] And the substrate layer may be any one selected from the group consisting of silicon oxide, aluminum oxide, ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide), glass, quartz, polyimide, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS), or may contain any two or more thereof.

[0025] On the other hand, the photoactive layer may be a perovskite layer. At this time, the perovskite layer may be CH3NH3PbI3, CH3NH3PbI x Cl 3-x , MAPbI3, CH3NH3PbI x Br 3-x , CH3NH3PbCl x Br 3-x , HC(NH2)2PbI3, HC(NH2)2PbI x Cl 3-x , HC(NH2)2PbI x Br 3-x , HC(NH2)2PbCl x Br3-x , (CH3NH3)(HC(NH2)2) 1-y PbI3, (CH3NH3)(HC(NH2)2) 1-y PbI x Cl 3-x , (CH3NH3)(HC(NH2)2) 1-y PbI x Br 3-x and (CH3NH3)(HC(NH2)2) 1-y PbCl x Br 3-x It may be any one selected from the group consisting of or include two or more of these.

[0026] And the solar cell may have a perovskite-perovskite tandem structure in which the perovskite layer includes a first perovskite layer and a second perovskite layer laminated on the first perovskite layer.

[0027] Also, the solar cell may have a silicon-perovskite tandem structure in which the substrate layer includes a silicon solar cell.

Advantages of the Invention

[0028] According to the present invention, a hydroxide is further added to a dispersion containing a surface-modified metal oxide so that the surface-modified metal oxide is well dispersed even in a polar solvent, and as a result, a hole transport layer or an electron transport layer including a uniform metal oxide thin film can be formed.

[0029] Thus, when the hole transport layer or the electron transport layer comes to include a uniformly formed metal oxide thin film, it can ultimately greatly contribute to the improvement of the performance of the solar cell.

Brief Description of the Drawings

[0030] The following drawings attached to this specification illustrate preferred embodiments of the present invention and, together with the detailed description of the invention to be described later, serve to further understand the technical idea of the present invention. Therefore, the present invention should not be construed as being limited only to the matters described in such drawings.

[0031]

Figure 1

[0032]

Figure 2

Mode for Carrying Out the Invention

[0033] Hereinafter, each embodiment of the present invention will be described in detail with reference to the attached drawings.

[0034] Each embodiment of the present invention described below is provided to more clearly explain the present invention to those having ordinary knowledge in the technical field. The scope of the present invention is not limited by the following embodiments, and the following embodiments can be modified into many other forms.

[0035] The terms used in this specification are for explaining specific embodiments and are not for limiting the present invention. The terms in the singular form used in this specification may include plural forms unless the context clearly indicates otherwise. Also, the terms "comprise" and / or "comprising" used in this specification specify the presence of the recited shape, step, number, operation, member, element, and / or group thereof, and do not exclude the presence or addition of one or more other shapes, steps, numbers, operations, members, elements, and / or groups thereof. Further, the term "connected" used in this specification is a concept that includes not only that each member is directly connected, but also that other members are further interposed between the members and indirectly connected.

[0036] In addition, when it is stated in this specification that one member is located "above" another member, this includes not only the case where one member is in contact with the other member, but also the case where there is still another member between the two members. The term "and / or" used in this specification includes any one and all combinations of one or more of the listed items. Further, in this specification, terms of degree such as "about" and "substantially" are used in the sense of the numerical value or range of degree or close thereto, taking into account inherent manufacturing and material tolerances, and are used to prevent an infringer from improperly using the disclosed content that mentions an exact or absolute numerical value provided to facilitate the understanding of the present application.

[0037] Hereinafter, each embodiment of the present invention will be described in detail. The areas, sizes, and thicknesses of the parts shown in the attached drawings may be somewhat exaggerated for the clarity of the specification and the convenience of explanation. The same reference numerals throughout the detailed description denote the same components.

[0038] The method for manufacturing a solar cell according to the present invention includes a step of manufacturing a laminate in which a first electrode layer, a hole transport layer (HTL), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially laminated, and the hole transport layer or the electron transport layer is formed by applying and drying a dispersion liquid containing a metal oxide surface-modified with a carboxylic acid (R-COOH), a dispersion solvent, and a hydroxide.

[0039] Conventionally, even when the surface of a metal oxide was modified, only the dispersibility was improved with a non-polar solvent such as isopropyl alcohol (IPA), and the dispersibility was low with a polar solvent such as deionized water (DI water) or ethanol. Eventually, there was a problem that it was difficult to form a metal oxide thin film when using a dispersion liquid containing a metal oxide dispersed in a polar solvent.

[0040] However, according to the present invention, by further adding a hydroxide to the dispersion containing the surface-modified metal oxide and appropriately adjusting the pH of the dispersion, the surface-modified metal oxide can be well dispersed even in a polar solvent, and a hole transport layer or an electron transport layer including a uniform metal oxide thin film can be formed.

[0041] Therefore, when such a hole transport layer or electron transport layer is included, the performance of the solar cell is finally improved.

[0042] At this time, the dispersion can exhibit basicity, and the hydrogen ion concentration of the dispersion may be pH 8 to pH 13. By satisfying such conditions, the surface-modified metal oxide can be dispersed as uniformly as possible in the dispersion.

[0043] On the other hand, the hydroxide is not greatly limited as long as it contains a hydroxyl group (-OH group), and more specifically, it may be any one selected from the group consisting of NH4OH, LiOH, NaOH, KOH, RbOH, CsOH, etc. or a mixture of two or more of these.

[0044] Furthermore, the hydroxide may contain an amine group, and specific examples thereof include TMAH (Tetramethylammonium hydroxide), TBMH (Tetrabutylammonium hydroxide), etc., but it is not limited thereto.

[0045] And the metal oxide may be tin oxide, and more specifically, the tin oxide may be SnO2.

[0046] Also, the carboxylic acid may be acetic acid or trifluoroacetic acid, but it is not limited thereto.

[0047] The dispersion solvent may be a non-polar solvent such as isopropyl alcohol (IPA), or a polar solvent such as deionized water (DI water) and ethanol, but is not limited thereto. Any one selected from the group consisting of these solvents or two or more thereof may be used, and various solvents within the range capable of achieving the object of the present invention may be used.

[0048] Further, the laminate may further include a substrate layer on the lower surface of the first electrode layer, and it is more preferable that the photoactive layer is a perovskite layer. Each component of the solar cell will be described in detail later.

[0049] On the other hand, referring to FIG. 1, the solar cell according to another aspect of the present invention is one in which a substrate layer 10, a first electrode layer 20, a hole transport layer (HTL, Hole Transport Layer) 30, a photoactive layer 40, an electron transport layer 50, and a second electrode layer 60 are sequentially laminated, and the hole transport layer 30 or the electron transport layer 50 includes a metal oxide layer, and the metal oxide layer is characterized in that a compound containing a carboxy group (-COOH) adheres to the surface and a surface-modified metal oxide is uniformly formed as a thin film.

[0050] As in the present invention, the solar cell 100 including the hole transport layer 30 or the electron transport layer 50 in which the surface-modified metal oxide is uniformly formed as a thin film can greatly improve its device performance.

[0051] At this time, the metal oxide may be tin oxide, and more specifically, the tin oxide may be SnO2.

[0052] On the one hand, the substrate layer 10 can include a transparent substance that allows light to pass through. Further, the substrate layer 10 can include a substance that selectively allows light of a desired wavelength to pass through. The substrate layer 10 can include, for example, a TCO (Transparent Conductive Oxide) such as silicon oxide, aluminum oxide, ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide), glass, quartz, or a polymer. For example, the polymer can include at least one of polyimide, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS).

[0053] The substrate layer 10 can have a thickness in the range of, for example, 100 μm to 150 μm, and can have a thickness of, for example, 125 μm. However, the material and thickness of the substrate layer 10 are not limited to the above description and can be appropriately selected according to the technical idea of the present invention.

[0054] In addition, as the substrate layer 10, in addition to those described above, the silicon solar cell itself may be used, which will be described in detail later.

[0055] And the first electrode layer 20 may be formed of a conductive material having translucency. The conductive material having translucency may include, for example, transparent conductive oxides, carbonaceous conductive materials, and metallic materials. Examples of the transparent conductive oxide may include ITO (Indium Tin Oxide), ICO (Indium Cerium Oxide), IWO (Indium Tungsten Oxide), ZITO (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide), GITO (Gallium Indium Tin Oxide), GIO (Gallium Indium Oxide), GZO (Gallium Zinc Oxide), AZO (Aluminum doped Zinc Oxide), FTO (Fluorine Tin Oxide), ZnO, etc. Examples of the carbonaceous conductive material may include graphene or carbon nanotubes, etc., and examples of the metallic material may include metal (Ag) nanowires, metallic thin films having a multilayer structure such as Au / Ag / Cu / Mg / Mo / Ti, etc. In this specification, the term "transparent" means that light can be transmitted to a certain degree or more, and is not necessarily interpreted to mean complete transparency. Each of the substances described above is not necessarily limited to each of the embodiments described above, and can be formed of various materials, and its structure can also be variously deformed such as a single layer or a multilayer.

[0056] At this time, the first electrode layer 20 may be formed by being laminated on the substrate layer 10, or may be formed integrally with the substrate layer 10.

[0057] And a hole transport layer 30 may be laminated on the first electrode layer 20, which serves to transmit holes generated in the photoactive layer 40 to the first electrode layer 20.

[0058] As described above, the hole transport layer 30 may include a metal oxide layer formed by uniformly forming a surface-modified metal oxide in a thin film, or tungsten oxide (WOx ), molybdenum oxide (MoO x ), vanadium oxide (V2O5), nickel oxide (NiO x ), and at least one of the metal oxides selected from the mixtures thereof. Further, it may contain at least one selected from the group consisting of monomolecular hole transport materials and polymer hole transport materials, but is not limited thereto, and any material used in the industry can be used without limitation. For example, spiro-MeOTAD [2,2’,7,7’-tetrakis(N,N-p-dimethoxyphenylamino)-9,9’-spirobifluorene] can be used as the monomolecular hole transport material, and P3HT [poly(3-hexylthiophene)], PTAA (polytriarylamine), or poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS) can be used as the polymer hole transport material, but is not limited thereto.

[0059] In addition, the hole transport layer 30 may further contain a doping substance, and as the doping substance, a dopant selected from the group consisting of Li series dopants, Co series dopants, Cu series dopants, Cs series dopants, and combinations thereof can be used, but is not limited thereto.

[0060] The hole transport layer 30 may be formed by applying a hole transport layer precursor solution on the first electrode layer 20 and drying it. Before applying the precursor solution, the work function of the first electrode layer 20 can be reduced, surface impurities can be removed, and hydrophilic treatment can be performed by performing UV-ozone treatment on the first electrode layer 20. When applying the precursor solution, methods such as spin coating can be used, but are not limited thereto. The thickness of the formed hole transport layer 30 may be 10 nm to 500 nm.

[0061] On the other hand, the photoactive layer 40 may preferably be a perovskite layer containing a perovskite compound.

[0062] In the solar cell 100 according to the present invention, a perovskite compound can be adopted as a photoactive material that absorbs sunlight and generates photoexcited electron-hole pairs. Although the perovskite has a direct band gap, its light absorption coefficient is about 1.5×10 4 cm -1 at 550 nm, which is relatively high, and it has advantages of excellent charge transfer characteristics and excellent resistance to defects.

[0063] In addition, the perovskite compound has the advantage that it is extremely simple and easy, such as solution coating and drying, and a light absorber forming a photoactive layer can be formed through a simple process at low cost. Crystallization occurs spontaneously by drying the applied solution, and a light absorber with large crystal grains can be formed. In particular, it has excellent conductivity for all electrons and holes.

[0064] Such a perovskite compound can be represented by the structure of Chemical Formula 1 below.

[0065]

Chemical formula

[0066] (Here, A represents a monovalent organic ammonium cation or a metal cation, B represents a divalent metal cation, and X represents a halogen anion.)

[0067] Examples of the perovskite compound include CH3NH3PbI3, CH3NH3PbI x Cl 3-x , MAPbI3, CH3NH3PbI x Br 3-x , CH3NH3PbCl x Br 3-x , HC(NH2)2PbI3, HC(NH2)2PbI x Cl 3-x , HC(NH2)2PbI x Br 3-x , HC(NH2)2PbCl x Br3-x 、(CH3NH3)(HC(NH2)2) 1-y PbI3, (CH3NH3)(HC(NH2)2) 1-y PbI x Cl 3-x 、(CH3NH3)(HC(NH2)2) 1-y PbI x Br 3-x 、(CH3NH3)(HC(NH2)2) 1-y PbCl x Br 3-x etc. may be used (0 ≤ x, y ≤ 1). Also, a compound in which A of ABX3 is partially doped with Cs may be used.

[0068] And the electron transport layer 50 is located on the photoactive layer 40 and can function so that electrons generated in the photoactive layer 40 can be easily transmitted to the second electrode layer 60.

[0069] As described above, the electron transport layer 50 can include a metal oxide layer in which a surface-modified metal oxide is uniformly formed as a thin film, or can also include a general metal oxide. As the electron transport layer 50, for example, titanium oxide, zinc oxide, indium oxide, tin oxide, tungsten oxide, niobium oxide, molybdenum oxide, magnesium oxide, zirconium oxide, strontium oxide, yttrium oxide, lanthanum oxide, vanadium oxide, aluminum oxide, yttrium oxide, scandium oxide, samarium oxide, gallium oxide, strontium titanate, etc. may be used. The electron transport layer 50 according to the present invention can also include TiO2, SnO2, WO3, or TiSrO3 having a compact structure. Such an electron transport layer 50 can further include an n-type or p-type dopant if necessary.

[0070] In addition to the above-described hole transport layer 30 / photoactive layer 40 / electron transport layer 50, various layer structures and substances constituting the solar cell 100 can be applied to the layer structure and / or substances described above, and the hole transport layer 30 and the electron transport layer 50 may be formed with their positions changed from each other.

[0071] And the second electrode layer 60 may be formed of a conductive material having translucency. The conductive material having translucency may include, for example, transparent conductive oxides, carbonaceous conductive materials, and metallic materials. Examples of the transparent conductive oxide may include ITO (Indium Tin Oxide), ICO (Indium Cerium Oxide), IWO (Indium Tungsten Oxide), ZITO (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide), GITO (Gallium Indium Tin Oxide), GIO (Gallium Indium Oxide), GZO (Gallium Zinc Oxide), AZO (Aluminum doped Zinc Oxide), FTO (Fluorine Tin Oxide), ZnO, etc. Examples of the carbonaceous conductive material may include graphene or carbon nanotubes, etc., and examples of the metallic material may include metal (Ag) nanowires, metallic thin films having a multilayer structure such as Au / Ag / Cu / Mg / Mo / Ti, etc. In this specification, the term "transparent" means that light can be transmitted to a certain extent or more, and is not necessarily interpreted to mean complete transparency. Each of the substances described above is not necessarily limited to each of the embodiments described above, and can be formed of various materials, and its structure can also be variously deformed such as a single layer or a multilayer.

[0072] On the other hand, although not shown in the figure, a bus electrode (not shown) may be further disposed on the second electrode layer 60 in order to reduce the resistance of the second electrode layer 60 and further facilitate the transfer of charges. The bus electrode may be formed of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, and / or their compounds, etc.

[0073] FIG. 2 is a side view showing a perovskite solar cell according to another embodiment of the present invention.

[0074] Referring to FIG. 2, the solar cell 100 according to the present invention may be a solar cell having a perovskite-perovskite tandem structure in which the perovskite layer includes a first perovskite layer 40a and a second perovskite layer 40b laminated on the first perovskite layer 40a.

[0075] At this time, the first perovskite layer 40a and the second perovskite layer 40b can have different energy band gaps from each other. By using each material having such various energy band gaps, light energy in a wide spectral region can be effectively used.

[0076] As an example, in a tandem-structured solar cell, a single-junction solar cell including an absorption layer having a relatively large band gap is located on the light-receiving surface, and a single-junction solar cell including an absorption layer having a relatively small band gap can be located on the opposite surface of the light-receiving surface. Thereby, the tandem-structured solar cell can move the threshold wavelength to the longer wavelength side by absorbing light in the short wavelength region at the front surface and absorbing light in the long wavelength region at the rear surface. As a result, the tandem-structured solar cell has the advantage that the entire absorption wavelength region can be widely utilized.

[0077] Further, the solar cell 100 may be a solar cell having a silicon-perovskite tandem structure.

[0078] At this time, the substrate layer 10 may be a silicon solar cell itself or may include a silicon solar cell.

[0079] Here, the silicon solar cell may be a general known silicon solar cell, and its structure and form are not limited, and it can be freely applied as long as the object of the present invention can be achieved.

[0080] On the other hand, in addition to the above-described hole transport layer 30 / photoactive layer 40 / electron transport layer 50, various layer structures and substances constituting the solar cell 100 can be applied to the layer structure and / or substance.

[0081] In this specification, preferred embodiments of the present invention are disclosed and specific terms are used, but these are used only in a general sense for easily explaining the technical content of the present invention and facilitating the understanding of the invention, and are not intended to limit the scope of the present invention. It is obvious to those having ordinary knowledge in the technical field to which the present invention pertains that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein. For example, those having ordinary knowledge in the relevant technical field can understand that the manufacturing method of the solar cell according to the embodiment described with reference to FIG. 1 and the solar cell manufactured therefrom can be variously modified. Therefore, the scope of the invention should not be determined by the described embodiments, but by the technical idea described in the claims.

Industrial Applicability

[0082] The present invention can be used in the field of manufacturing perovskite solar cells.

Claims

1. A method for manufacturing a laminate in which a first electrode layer, a hole transport layer (HTL, Hole Transport Layer), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially laminated, wherein the hole transport layer or the electron transport layer is formed by applying and drying a dispersion liquid containing a metal oxide surface-modified with a carboxylic acid (R-COOH), a dispersion solvent, and a hydroxide, and each of the metal oxides has a compound containing a carboxylic acid (R-COOH) attached to its surface, wherein the hydrogen ion concentration of the dispersion liquid is pH 8 to 13, wherein the hydroxide is any one selected from the group consisting of TMAH (Tetramethylammonium hydroxide) and TBMH (Tetrabutylammonium hydroxide) or a mixture of two or more thereof, wherein the carboxylic acid includes acetic acid or trifluoroacetic acid, a method for manufacturing a solar cell.

2. The method for manufacturing a solar cell according to claim 1, wherein the metal oxide is tin oxide.

3. The tin oxide is SnO ２ The method for manufacturing a solar cell according to claim 2, wherein the tin oxide is SnO

4. The method for manufacturing a solar cell according to claim 1, wherein the dispersion solvent is any one selected from the group consisting of isopropyl alcohol (IPA), deionized water (DI water), and ethanol, or two or more thereof.

5. The method for manufacturing a solar cell according to claim 1, wherein the laminate further includes a substrate layer on the lower surface of the first electrode layer.

6. The method for manufacturing a solar cell according to claim 1, wherein the photoactive layer is a perovskite layer.

7. A substrate layer, a first electrode layer, a hole transport layer (HTL, Hole Transport Layer), a photoactive layer, an electron transport layer, and a second electrode layer are sequentially laminated, wherein the hole transport layer or the electron transport layer includes a metal oxide layer, wherein the metal oxide layer is formed of a thin film of a surface-modified metal oxide having a compound containing a carboxy group (-COOH) attached to its surface, and each of the metal oxides has a compound containing a carboxylic acid (R-COOH) attached to its surface, and the carboxylic acid includes acetic acid or trifluoroacetic acid, The hole transport layer or the electron transport layer contains any one selected from the group consisting of TMAH (Tetramethylammonium hydroxide) and TBMAH (Tetrabutylammonium hydroxide), or two or more thereof, a solar cell.

8. The solar cell according to claim 7, wherein the metal oxide is tin oxide.

9. The tin oxide is SnO ２ The solar cell according to claim 8, wherein the tin oxide is SnO

10. The first electrode layer and the second electrode layer are independently of each other ITO (Indium Tin Oxide), ICO (Indium Cerium Oxide), IWO (Indium Tungsten Oxide), ZITO (Zinc Indium Tin Oxide), ZIO (Zinc Indium Oxide), ZTO (Zinc Tin Oxide), GITO (Gallium Indium Tin Oxide), GIO (Gallium Indium Oxide), GZO (Gallium Zinc Oxide), AZO (Aluminum doped Zinc Oxide), FTO (Fluorine Tin Oxide), and ZnO, or two or more thereof, the solar cell according to claim 7.

11. The electron transport layer contains any one selected from the group consisting of Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, and SrTi oxide, or two or more thereof, the solar cell according to claim 7.

12. The hole transport layer is any one selected from the group consisting of tungsten oxide (WO ｘ ), molybdenum oxide (MoO ｘ ), vanadium oxide (V ２ O ５ ), and nickel oxide (NiO ｘ ), or contains two or more of these, the solar cell according to claim 7.

13. The substrate layer contains any one selected from the group consisting of silicon oxide, aluminum oxide, ITO (Indium Tin Oxide), FTO (Fluorine Tin Oxide), glass, quartz, polyimide, polyethylene naphthalate (polyethylene naphthalate, PEN), polyethylene terephthalate (polyethylene terephthalate, PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS), or two or more thereof, the solar cell according to claim 7.

14. The solar cell according to claim 7, wherein the photoactive layer is a perovskite layer.

15. The perovskite layer is CH ３ NH ３ PbI ３ 、CH ３ NH ３ PbI ｘ Cl ３－ｘ 、MAPbI ３ 、CH ３ NH ３ PbI ｘ Br ３－ｘ 、CH ３ NH ３ PbCl ｘ Br ３－ｘ 、HC(NH ２ ) ２ PbI ３ 、HC(NH ２ ) ２ PbI ｘ Cl ３－ｘ 、HC(NH ２ ) ２ PbI ｘ Br ３－ｘ 、HC(NH ２ ) ２ PbCl ｘ Br ３－ｘ The solar cell according to claim 14, comprising any one selected from the group consisting of these or two or more thereof.

16. The solar cell according to claim 14, wherein the solar cell has a perovskite-perovskite tandem structure including a first perovskite layer and a second perovskite layer laminated on the first perovskite layer.

17. The solar cell according to claim 14, wherein the solar cell has a silicon-perovskite tandem structure in which the substrate layer includes a silicon solar cell.

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