KR102796955B1 - Manufacturing method for perovskite solar cell and perovskite solar cell manufactured by the same method - Google Patents

Abstract

The present invention relates to a method for manufacturing a perovskite solar cell and a perovskite solar cell manufactured thereby, and more specifically, to a method for manufacturing a perovskite solar cell and a perovskite solar cell manufactured thereby, comprising the steps of: (S10) forming a hole transport layer (HTL) on a perovskite layer of a laminate in which a substrate layer, a first electrode layer, an electron transport layer, and a perovskite layer are sequentially laminated, by applying and drying a dispersion solution containing a surface-modified metal oxide and a dispersion solvent; and (S20) laminating a second electrode layer on the hole transport layer.

Description

{MANUFACTURING METHOD FOR PEROVSKITE SOLAR CELL AND PEROVSKITE SOLAR CELL MANUFACTURED BY THE SAME METHOD}

The present invention relates to a method for manufacturing a perovskite solar cell and a perovskite solar cell manufactured therefrom, and more specifically, to a method for manufacturing a perovskite solar cell capable of forming a hole transport layer with improved interaction at the interface between a perovskite layer and an electrode layer while minimizing damage to the perovskite layer, and a perovskite solar cell manufactured therefrom.

Solar cells are the core elements of solar power generation that directly convert sunlight into electricity, and are currently being used widely for power supply in homes and even in space. Recently, they have been used in the fields of aviation, meteorology, and communications, and solar cars and solar air conditioners are also attracting attention.

These solar cells mainly use silicon semiconductors, but there is a problem that the unit cost of generation is high due to the raw material price of high-purity silicon semiconductors and the complexity of the solar cell manufacturing process using them. In other words, since the unit cost of generation using conventional fossil fuels is 3 to 10 times higher, there is a limitation that the market is growing due to subsidies from each country's government. For this reason, research and development of solar cells that do not use silicon has been active, and since the 1990s, dye-sensitized solar cells (DSSCs) using dyes, which are organic semiconductor materials, and polymer solar cells (Polymer Solar Cells) using conductive polymers have been studied in earnest. Despite many efforts from academia and industry, organic semiconductor-based solar cells such as DSSCs and polymer solar cells have not reached the commercialization stage. However, with the recent advent of perovskite solar cells (PSCs) that combine the advantages of DSSCs and polymer solar cells, expectations for the next-generation solar cells are growing even higher.

Perovskite solar cells are a hybrid solar cell of conventional DSSCs and polymer solar cells. Unlike DSSCs, they do not use liquid electrolytes, which improves reliability. They are solar cells that can achieve high efficiency due to the optical superiority of perovskite. Their efficiency has been continuously improving through recent process improvements, material improvements, and structural improvements.

FIG. 1 is a drawing showing a perovskite solar cell having an n-i-p (forward) structure. Referring to FIG. 1, a perovskite solar cell (100) is composed of a substrate layer (10), a first electrode layer (20), an electron transport layer (30), a perovskite layer (40), a hole transport layer (50), and a second electrode layer (60). In the case of the perovskite solar cell (100) having the n-i-p structure, a hole transport layer (50) is coated on the perovskite layer (40). When coating the hole transport layer (50), since the perovskite layer (40) should not be damaged, the solvent used for coating the hole transport layer (50) is very limited. Due to this problem, most devices are manufactured by applying an organic hole transport layer.

However, when applying an organic hole transport layer, there are problems with low hole conductivity and stability, so research is actively being conducted to replace it with an inorganic hole transport layer. In particular, metal oxides such as nickel oxide are very stable and most of them also have high hole conductivity, so they can be good replacement candidates.

In order to form a metal oxide film using a solution process, the degree of dispersion of the metal oxide in the dispersion solution is important. However, since most dispersion solvents are polar solvents that affect the perovskite material, there is a problem that it is difficult to apply to a perovskite solar cell with an n-i-p structure. To solve this problem, a method can be used to form a metal oxide film (i.e., a hole transport layer) on the perovskite layer by improving the degree of dispersion in a nonpolar solvent by attaching a substance with a long alkyl chain to the surface of the metal oxide.

However, due to the hydrophobic alkyl chain, the metal oxide film has difficulty in adhering to the relatively hydrophilic perovskite layer (40). This causes a defect site to be generated at the interface between the surface of the perovskite layer (40) and the metal oxide film, which acts as a recombination site where electrons and holes recombine, which has a problem of adversely affecting the characteristics of the solar cell device.

Therefore, the problem to be solved by the present invention is to provide a method for manufacturing a perovskite solar cell that does not deteriorate the device characteristics of the solar cell by minimizing damage to the perovskite layer and improving the adhesive strength at the interface between the perovskite layer and the hole transport layer and at the interface between the hole transport layer and the electrode layer.

And, the problem that the present invention seeks to solve is to provide a perovskite solar cell manufactured by the method for manufacturing the perovskite solar cell.

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 description below.

In order to achieve the above object, a method for manufacturing a perovskite solar cell according to one aspect of the present invention comprises the steps of (S10) forming a hole transport layer (HTL) by applying and drying a dispersion solution containing a surface-modified metal oxide and a dispersion solvent on the perovskite layer of a laminate in which a substrate layer, a first electrode layer, an electron transport layer, and a perovskite layer are sequentially laminated; and (S20) laminating a second electrode layer on the hole transport layer.

Here, the dispersion solvent may be a nonpolar solvent.

At this time, the nonpolar solvent may be one selected from the group consisting of chlorobenzene, toluene, benzene, hexane, dimethyl ether, chloroform, ethyl acetate, and dichloromethane, or a mixture of two or more thereof.

And, the metal oxide may be nickel oxide (NiO _x ).

Meanwhile, the surface-modified metal oxide may be a compound that includes a) a binding portion that binds to the metal oxide, b) an alkyl chain portion connected to the binding portion, and c) a terminal portion formed at a terminal of the alkyl chain portion and enhancing adhesion to the perovskite layer or the second electrode layer, and is attached to the surface of the metal oxide.

At this time, the binding portion may include one or two or more selected from the group consisting of -COOH, -CONHOH, -NH ₂ , -CSSH, -PO ₃ H ₂ and -SO ₃ H.

And, the alkyl chain portion may be an alkyl chain containing 3 to 20 carbons.

Additionally, the terminal portion may include one or two or more selected from the group consisting of -NH ₂ , -Cl, -Br, -I, and -S.

Meanwhile, the concentration of the surface-modified metal oxide in the dispersion may be 5 to 30 mg/ml.

And, the surface-modified metal oxide may be manufactured by a method including: (S11) a step of dispersing a metal oxide in deionized water (DI water) or chlorobenzene to manufacture a metal oxide dispersion; (S12) a step of dropping a modifier into the metal oxide dispersion and stirring for 30 minutes to 24 hours; and (S13) a step of drying the resultant of step (S12) at a temperature of 60° C. or higher.

At this time, a step of removing residues of the modifying agent by washing with ethanol may be further included between the step (S12) and the step (S13).

Meanwhile, a perovskite solar cell according to another aspect of the present invention is characterized in that a substrate layer, a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer (HTL), and a second electrode layer are sequentially laminated, the hole transport layer including a surface-modified metal oxide, and the surface-modified metal oxide includes a compound including a) a binding portion that binds to the metal oxide, b) an alkyl chain portion connected to the binding portion, and c) a terminal portion formed at a terminal of the alkyl chain portion and enhancing adhesion with the perovskite layer or the second electrode layer, wherein the compound is attached to the surface of the metal oxide.

Here, the substrate layer may include one or two or more selected from the group consisting of silicon oxide, aluminum oxide, indium tin oxide (ITO), fluorine tin oxide (FTO), glass, quartz, polyimide, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS).

In addition, the first electrode layer and the second electrode layer may independently include one or two or more 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.

In addition, the electron transport layer may include one or two or more 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.

And, 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 , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI ₃ , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Cl _3-x , (CH It may include _{one or two or more} selected from the group consisting of ( ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Br _3-x and (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) 1-y PbCl _x Br 3-x .

According to the present invention, it is possible to prevent performance degradation of a perovskite solar cell by minimizing damage to the perovskite layer and improving adhesion at the interface between the perovskite layer and the hole transport layer including the metal oxide and at the interface between the hole transport layer and the electrode layer.

In addition, by preventing the occurrence of defect sites at the interface between the hole transport layer and the perovskite layer, the recombination of electrons and holes can be prevented, ultimately improving the photoelectric conversion efficiency.

The following drawings attached to this specification illustrate preferred embodiments of the present invention and, together with the detailed description of the invention described below, serve to further understand the technical idea of the present invention; therefore, the present invention should not be interpreted as being limited to matters described in such drawings.
Figure 1 is a side view showing a perovskite solar cell with a nip structure.
FIG. 2 is a side view showing a laminate in which a substrate layer, a first electrode layer, an electron transport layer, and a perovskite layer are laminated according to the present invention.
FIG. 3 is a conceptual diagram showing a surface-modified metal oxide according to one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

The embodiments of the present invention described below are provided to more clearly explain the present invention to those skilled in the art, and the scope of the present invention is not limited by the following embodiments, and the following embodiments may be modified in various other forms.

The terminology used herein is used to describe particular embodiments only and is not intended to be limiting of the present invention. The singular forms used herein include the plural forms unless the context clearly dictates otherwise. In addition, the terms "comprise" and/or "comprising" as used herein specify the presence of stated features, steps, numbers, operations, elements, elements and/or groups thereof, but do not exclude the presence or addition of one or more other features, steps, numbers, operations, elements, elements and/or groups thereof. In addition, the term "connected" as used herein not only means that certain elements are directly connected, but also includes a concept that even indirectly connects elements by interposing other elements between them.

In addition, when it is said in this specification that a certain element is located "on" another element, this includes not only cases where a certain element is in contact with the other element, but also cases where another element exists between the two elements. The term "and/or" as used in this specification includes any and all combinations of one or more of the listed items. In addition, the terms "about," "substantially," and the like as used in this specification are used to mean a range of or close to the numerical value or degree, taking into account inherent manufacturing and material tolerances, and are used to prevent infringers from unfairly utilizing the disclosure that mentions exact or absolute numbers provided to aid the understanding of this specification.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. The sizes and thicknesses of areas or parts illustrated in the attached drawings may be somewhat exaggerated for the clarity of the specification and convenience of explanation. Like reference numerals represent like components throughout the detailed description.

FIG. 2 is a side view showing a laminate in which a substrate layer, a first electrode layer, an electron transport layer, and a perovskite layer are laminated according to the present invention.

Referring to FIGS. 1 and 2, a method for manufacturing a perovskite solar cell (100) according to the present invention includes a step (S10) of forming a hole transport layer (50, HTL) by applying and drying a dispersion solution containing a surface-modified metal oxide and a dispersion solvent on the perovskite layer (40) of a laminate in which a substrate layer (10), a first electrode layer (20), an electron transport layer (30), and a perovskite layer (40) are sequentially laminated; and a step (S20) of laminating a second electrode layer (60) on the hole transport layer (50).

According to the present invention, by applying a metal oxide thin film as a hole transport layer (50) instead of a conventional organic hole transport layer, the hole conductivity can be further improved, and while minimizing damage to the perovskite layer (40), the adhesion at the interface between the perovskite layer (40) and the hole transport layer (50) including the metal oxide and at the interface between the hole transport layer (50) and the second electrode layer (60) can be improved, thereby preventing a decrease in the performance of the perovskite solar cell (100).

In addition, by preventing the occurrence of defect sites at the interface between the hole transport layer (50) and the perovskite layer (40), the recombination of electrons and holes can be prevented, ultimately improving the photoelectric conversion efficiency.

At this time, the dispersion solvent may be a non-polar solvent, and non-limiting examples of such non-polar solvents include one selected from the group consisting of chlorobenzene, toluene, benzene, hexane, dimethyl ether, chloroform, ethyl acetate, and dichloromethane, or a mixture of two or more thereof.

Since most of the conventional dispersion solvents of metal oxides are polar solvents that adversely affect the perovskite layer, there were problems in applying them to perovskite solar cells with an n-i-p (forward) structure. Therefore, in order to reduce the damage to the perovskite layer, a nonpolar solvent had to be used instead of a polar solvent. However, when a nonpolar solvent was used, there was a problem that the dispersion of the metal oxide was reduced. In the present invention, by applying a surface-modified metal oxide in which the surface of the metal oxide is modified, the dispersion of the metal oxide in a nonpolar solvent can be improved.

Here, the metal oxide is preferably nickel oxide (NiO _x ), which has the advantage of having high hole mobility within the material compared to other organic hole transporters or other metal oxides.

FIG. 3 is a conceptual diagram showing a surface-modified metal oxide according to one embodiment of the present invention.

Referring to FIG. 3, the surface-modified metal oxide may be a compound that includes a) a binding portion (52) that binds to the metal oxide (51), b) an alkyl chain portion (53) connected to the binding portion (52), and c) a terminal portion (54) that is formed at the terminal of the alkyl chain portion (53) and enhances adhesion to the perovskite layer (40) or the second electrode layer (60), and is attached to the surface of the metal oxide (51).

At this time, the binding portion (52) is not limited to a functional group that binds to the metal oxide (51), but specifically, it may include one or two or more selected from the group consisting of -COOH, -CONHOH, -NH ₂ , -CSSH, -PO ₃ H ₂ and -SO ₃ H.

And, the alkyl chain portion (53) may be an alkyl chain containing 3 to 20 carbons, and when such an alkyl chain portion (53) is included, the degree of dispersion of the metal oxide (51) in a non-polar solvent can be further improved. When the number of carbons included in the alkyl chain portion (53) is less than 3, a problem of not improving the degree of dispersion in a non-polar solvent may occur, and when the number of carbons exceeds 20, a problem in charge transfer (limitation of hole mobility in a hole transport layer or limitation of charge extraction at the interface) may occur due to the long alkyl chain when applied to a solar cell.

In addition, the terminal portion (54) is not limited to a functional group that improves adhesion to the perovskite layer (40) or the second electrode layer (60), but specifically, for adhesion to the perovskite layer (40), -NH ₂ , -Cl, -Br, -I, etc. are possible, and for adhesion to the second electrode layer (60), -S, etc. are possible.

Meanwhile, in the dispersion, the concentration of the surface-modified metal oxide may be 5 to 30 mg/ml, and when the above numerical range is satisfied, the perovskite layer (40) can be completely coated with an appropriate thickness. When it is less than the above numerical range, a problem may occur in which the surface-modified metal oxide cannot completely coat the perovskite layer (40), and when it exceeds the above numerical range, the surface-modified metal oxide is coated too thickly on the perovskite layer (40), so that the hole movement distance becomes too long, and thus a problem in which the performance of the solar cell element deteriorates may occur.

At this time, the dispersion may be manufactured by introducing and dispersing a mixture of a surface-modified metal oxide and a non-polar solvent into an ultrasonicator.

Meanwhile, the surface-modified metal oxide may be manufactured by a method including: (S11) a step of dispersing a metal oxide in deionized water (DI water) or chlorobenzene to manufacture a metal oxide dispersion; (S12) a step of dropping a modifier into the metal oxide dispersion and stirring for 30 minutes to 24 hours; and (S13) a step of drying the resultant of step (S12) at a temperature of 60° C. or higher.

The surface-modified metal oxide manufactured by this method further improves the adhesion between the perovskite layer (40) and the second electrode layer (60) by appropriately disposing the above-described compound on the surface of the metal oxide.

In addition, by further including a step of removing residues of the modifier by washing with ethanol, which is performed between the above step (S12) and the above step (S13), impurities are removed by removing the modifier that did not participate in the reaction.

Meanwhile, a perovskite solar cell (100) according to another aspect of the present invention is characterized in that a substrate layer (10), a first electrode layer (20), an electron transport layer (30), a perovskite layer (40), a hole transport layer (50, HTL, Hole Transport Layer), and a second electrode layer (60) are sequentially laminated, and the hole transport layer (50) includes a surface-modified metal oxide, and the surface-modified metal oxide includes a compound that is attached to the surface of the metal oxide (51), including a) a binding portion (52) that binds to the metal oxide (51), b) an alkyl chain portion (53) connected to the binding portion (52), and c) a terminal portion (54) that is formed at a terminal of the alkyl chain portion (53) and enhances adhesion to the perovskite layer (40) or the second electrode layer (60).

Since the above hole transport layer (50) includes a surface-modified metal oxide, the adhesion between the perovskite layer (40) and the hole transport layer (50) including the metal oxide and the interface between the hole transport layer (50) and the second electrode layer (60) can be improved, thereby preventing a decrease in the performance of the perovskite solar cell (100).

Here, the substrate layer (10) may include a transparent material that transmits light. In addition, the substrate layer (10) may include a material that selectively transmits light of a desired wavelength. The substrate layer (10) may 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, and for example, the polymer may include at least one of polyimide, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS).

The above substrate layer (10) may have a thickness ranging from, for example, 100 μm to 150 μm, and may have a thickness of, for example, 125 μm. However, the material and thickness of the substrate layer (10) are not limited to those described above, and may be appropriately selected according to the technical idea of the present invention.

And, the first electrode layer (20) can be formed of a conductive material having light transmittance. The conductive material having light transmittance can include, for example, a transparent conductive oxide, a carbonaceous conductive material, a metallic material, etc. As the transparent conductive oxide, for example, 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. can be used. As the carbonaceous conductive material, for example, graphene or carbon nanotubes can be used, and as the metallic material, for example, metal (Ag) nanowires, and multilayer metal thin films such as Au/Ag/Cu/Mg/Mo/Ti can be used. The term “transparent” in this specification refers to being able to transmit light to a certain degree or more, and is not necessarily interpreted to mean complete transparency. The materials described above are not necessarily limited to the embodiments described above, and can be formed of various materials, and the structures thereof can also be variously modified, such as being single-layered or multi-layered.

At this time, the first electrode layer (20) may be formed by being laminated on the substrate layer (10) or may be formed as an integral part with the substrate layer (10).

And, the electron transport layer (30) is positioned on the first electrode layer (20) and can function to allow electrons generated in the perovskite layer (40) to be easily transferred to the first electrode layer (20). The electron transport layer (30) can include a metal oxide, and for example, 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, SrTi oxide, etc. can be used. The electron transport layer (30) according to the present invention can also include TiO ₂ , SnO ₂ , WO ₃ or TiSrO ₃ having a compact structure. This electron transport layer (30) can further include an n-type or p-type dopant as needed.

Meanwhile, the perovskite layer (40) includes a perovskite compound.

In the perovskite solar cell (100) according to the present invention, a perovskite compound is adopted as a photoactive material that absorbs sunlight to generate photoelectron-photohole pairs. Perovskite has the advantages of having a direct band gap, a high light absorption coefficient of about 1.5×10 ⁴ cm ^-1 at 550 nm, excellent charge transfer characteristics, and excellent tolerance to defects.

In addition, perovskite compounds have the advantage of being able to form a light absorber that forms a photoactive layer through an extremely simple, easy, and inexpensive process of applying and drying a solution, and the light absorber can be formed of coarse crystal grains by spontaneous crystallization through drying of the applied solution, and in particular, it has excellent conductivity for both electrons and holes.

These perovskite compounds can be represented by the following chemical formula 1.

[Chemical Formula 1]

ABX ₃

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

Perovskite compounds include, for example, 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 , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI ₃ , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Cl _3-x , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Br _3-x , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbCl _x Br _3-x , etc. can be used (0≤x, y≤1). In addition, compounds in which A of ABX ₃ is partially doped with Cs can also be used.

Meanwhile, the hole transport layer (50) may further include a doping material, and the doping material may be a dopant selected from the group consisting of Li series dopants, Co series dopants, Cu series dopants, Cs series dopants, and combinations thereof, but is not limited thereto. The thickness of the hole transport layer (50) may be 10 to 500 nm, but is not limited thereto.

At this time, it is preferable that the metal oxide of the hole transport layer (50) is nickel oxide (NiO _x ), which has the advantage of having high hole mobility within the material compared to other organic hole transporters or other metal oxides.

In addition, the surface-modified metal oxide is as described above in the specification of the present invention.

In addition, the second electrode layer (60) may be formed of a conductive material having light transmittance. The conductive material having light transmittance may include, for example, a transparent conductive oxide, a carbonaceous conductive material, a metallic material, etc. As the transparent conductive oxide, for example, 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. may be used. As the carbonaceous conductive material, for example, graphene or carbon nanotubes can be used, and as the metallic material, for example, metal (Ag) nanowires, and multilayer metal thin films such as Au/Ag/Cu/Mg/Mo/Ti can be used. The term “transparent” in this specification refers to being able to transmit light to a certain degree or more, and is not necessarily interpreted to mean complete transparency. The materials described above are not necessarily limited to the embodiments described above, and can be formed of various materials, and the structures thereof can also be variously modified, such as being single-layered or multi-layered.

Meanwhile, although not shown, a bus electrode (not shown) may be further arranged on the second electrode layer (60) to lower the resistance of the second electrode layer (60) and to facilitate charge transfer. The bus electrode may be formed of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, and/or compounds thereof.

In addition to the above-described layer structures and/or materials, various layer structures and materials that constitute the perovskite solar cell (100) can be applied to the electron transport layer (30)/perovskite layer (40)/hole transport layer (50).

In this specification, preferred embodiments of the present invention have been disclosed, and although specific terms have been used, they have been used only in a general sense to easily explain the technical contents of the present invention and to help the understanding of the invention, and are not intended to limit the scope of the present invention. In addition to the embodiments disclosed herein, it will be apparent to those skilled in the art that other modified examples based on the technical idea of the present invention can be implemented. For example, those skilled in the art will recognize that the method for manufacturing a perovskite solar cell according to the embodiments described with reference to FIGS. 1 to 3 and the perovskite solar cell manufactured thereby can be variously modified. Therefore, the scope of the invention should not be defined by the described embodiments, but should be defined by the technical idea described in the claims.

10: Substrate layer
20: 1st electrode layer
30: Electron transport layer
40: Perovskite layer
50: Hole transport layer
51: Metal oxide
52: Binding part
53: Alkyl chain
54: The terminal part
60: Second electrode layer
100: Perovskite solar cells

Claims (20)

(S10) A step of forming a hole transport layer (HTL) by applying and drying a dispersion solution containing a surface-modified metal oxide and a dispersion solvent on the perovskite layer of a laminate in which a substrate layer, a first electrode layer, an electron transport layer, and a perovskite layer are sequentially laminated; and
(S20) comprising a step of laminating a second electrode layer on the hole transport layer,
A method for manufacturing a perovskite solar cell, wherein the above dispersion solvent is a non-polar solvent. delete In the first paragraph,
A method for manufacturing a perovskite solar cell, wherein the nonpolar solvent is one selected from the group consisting of chlorobenzene, toluene, benzene, hexane, dimethyl ether, chloroform, ethyl acetate, and dichloromethane, or a mixture of two or more thereof. In the first paragraph,
A method for manufacturing a perovskite solar cell, wherein the metal oxide is nickel oxide (NiO _x ). In the first paragraph,
A method for manufacturing a perovskite solar cell, wherein the surface-modified metal oxide comprises a compound attached to the surface of the metal oxide, wherein the compound comprises: a) a binding portion that binds to the metal oxide, b) an alkyl chain portion connected to the binding portion, and c) a terminal portion formed at a terminal of the alkyl chain portion and enhancing adhesion to the perovskite layer or the second electrode layer. In paragraph 5,
A method for manufacturing a perovskite solar cell, wherein the binding portion comprises one or more selected from the group consisting of -COOH, -CONHOH, -NH ₂ , -CSSH, -PO ₃ H ₂ and -SO ₃ H. In paragraph 5,
A method for manufacturing a perovskite solar cell, wherein the above alkyl chain portion is an alkyl chain containing 3 to 20 carbons. In paragraph 5,
A method for manufacturing a perovskite solar cell, wherein the terminal portion comprises one or two or more selected from the group consisting of -NH ₂ , -Cl, -Br, -I, and -S. In the first paragraph,
A method for manufacturing a perovskite solar cell, wherein the concentration of the surface-modified metal oxide in the above dispersion is 5 to 30 mg/ml. In the first paragraph,
The above surface-modified metal oxide is,
(S11) A step of preparing a metal oxide dispersion by dispersing a metal oxide in chlorobenzene;
(S12) A step of dropping a modifier into the metal oxide dispersion and stirring for 30 minutes to 24 hours; and
(S13) A method for manufacturing a perovskite solar cell, the method comprising a step of drying the resultant of step (S12) at a temperature of 60° C. or higher. In Article 10,
is performed between the above steps (S12) and (S13),
A method for manufacturing a perovskite solar cell, further comprising a step of removing residues of the above modifier by washing with ethanol. A substrate layer, a first electrode layer, an electron transport layer, a perovskite layer, a hole transport layer (HTL), and a second electrode layer are laminated in sequence.
The above hole transport layer comprises a surface-modified metal oxide,
The surface-modified metal oxide is a compound that includes a) a binding portion that binds to the metal oxide, b) an alkyl chain portion connected to the binding portion, and c) a terminal portion formed at the terminal of the alkyl chain portion and enhancing adhesion to the perovskite layer or the second electrode layer, and is attached to the surface of the metal oxide.
A perovskite solar cell, wherein a dispersion containing a metal oxide is applied to a dispersion solution containing a nonpolar solvent, thereby preventing damage to the perovskite layer. In Article 12,
A perovskite solar cell in which the above metal oxide is nickel oxide (NiO _x ). In Article 12,
A perovskite solar cell wherein the binding portion comprises one or more selected from the group consisting of -COOH, -CONHOH, -NH ₂ , -CSSH, -PO ₃ H ₂ and -SO ₃ H. In Article 12,
A perovskite solar cell, wherein the above alkyl chain portion is an alkyl chain containing 3 to 20 carbons. In Article 12,
A perovskite solar cell wherein the terminal portion comprises one or two or more selected from the group consisting of -NH ₂ , -Cl, -Br, -I, and -S. In Article 12,
A perovskite solar cell comprising one or more of the following: the substrate layer is selected from the group consisting of silicon oxide, aluminum oxide, indium tin oxide (ITO), fluorine tin oxide (FTO), glass, quartz, polyimide, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS). In Article 12,
A perovskite solar cell, wherein the first electrode layer and the second electrode layer independently include one or two or more 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. In Article 12,
A perovskite solar cell, wherein the electron transport layer comprises one or two or more 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. In Article 12,
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 , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI ₃ , (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Cl _3-x , (CH ₃ NH A perovskite _solar cell comprising one or more selected from the group consisting of ₃ )(HC(NH ₂ ) ₂ ) _1-y PbI _x Br _3-x and (CH ₃ NH ₃ )(HC(NH ₂ ) ₂ ) _1- y PbCl x Br 3- _x .