KR20230110978A - Manufacturing method of metal oxide thin film and metal oxide thin film manufactured using these, manufacturing method of perovskite optoelectronic device comprising the same and perovskite optoelectronic device manufactured using these - Google Patents

Abstract

The present invention discloses a method for manufacturing a metal oxide thin film, a method for manufacturing a photoelectric device, and a perovskite photoelectric device manufactured through the method. The present invention comprises the steps of preparing a metal oxide precursor solution containing a metal oxide precursor, a fuel, an acid solution and a connector; reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including a metal oxide intermediate bonded to the linking body; and preparing a metal oxide thin film by immersing the substrate in the metal oxide reaction solution.

Description

Manufacturing method of metal oxide thin film and metal oxide thin film manufactured through the same, manufacturing method of perovskite photoelectric device including the same, perovskite photoelectric device ELECTRONIC DEVICE MANUFACTURED USING THESE}

The present invention relates to a method of manufacturing a metal oxide thin film and a method of producing metal oxide thin films, perovskite optical electric front, perovskite optical electric electronics prepared through this, and more particularly, the present invention, the metal oxide thin film considering the properties of the FTO (fluorine doped tin oxide) or Si that can be applied to the photoelectric element. It relates to a manufacturing method and a method of producing metal oxide thin films, perovskite optical electric front, and perovskite optical photosenators.

The chemical solution deposition method is a technique in which a substrate on which a thin film is to be deposited is supported in a precursor solution capable of forming a metal oxide, and an external reaction (eg, heating) is applied to form a metal oxide nucleation that can be deposited on the substrate. Through this, a metal oxide thin film is formed directly on the substrate.

The chemical solution deposition method is a technology known to be able to uniformly form a thin film over a wide area because nucleation formation and thin film formation are performed simultaneously, and is a technique that can be applied to various types of metal oxide thin film deposition.

However, when the chemical bonding strength between the nucleated precursor and the substrate on which the metal oxide thin film is to be deposited is poor, there is a problem of forming a physical defect between the thin film and the substrate or making it difficult to form a uniform thin film on the entire surface of the substrate.

In general, in the case of a chemical solution deposition method, a metal oxide precursor is nucleated without forming a defect (eg, a metal oxide secondary phase with poor characteristics) and a dense thin film is formed, so that the concentration of the precursor solution, temperature, reaction time for deposition, pH of the solution, etc. are adjusted.

As a result, if the conditions most suitable for the above-mentioned precursor solution (ex. concentration, temperature, reaction time, pH, etc.) and the characteristics of the substrate on which the metal oxide thin film is to be deposited (ex. temperature, pH, etc.) do not match, there is a problem that it is difficult to deposit a high-quality metal oxide thin film.

That is, this means that it is necessary to design a precursor solution suitable for the characteristics of a substrate to be used and introduce a chemical solution deposition technology based thereon.

Therefore, it is necessary to develop a tin oxide chemical solution deposition technology suitable for representative substrates (FTO (Fluorine doped tin oxide), ITO (Indium Tin Oxide), silicon, etc.) applied to various photoelectric conversion devices.

Korean Registered Patent No. 1458448, "Method for manufacturing photoelectrode using chemical solution growth method, photoelectrode and dye-sensitized solar cell by the method" Korean Patent Registration No. 1212626, "Metal Oxide Thin Film and Manufacturing Method, Solution for Metal Oxide Thin Film"

Embodiments of the present invention form a metal oxide intermediate that is preferentially bonded to a linker in a metal oxide precursor solution and apply a chemical solution deposition method using the same to increase bonding with a substrate to form a uniform thin film without forming physical defects on the substrate. It is intended to provide a method for manufacturing a metal oxide thin film that can be formed, a metal oxide thin film manufactured through the same, a method for manufacturing a perovskite photoelectric device, and a perovskite photoelectric device.

In addition, an embodiment of the present invention provides a method for manufacturing a metal oxide thin film capable of minimizing light absorption loss that may appear in a perovskite photoelectric device through an anti-reflection effect, that is, an anti-reflection effect through control of the optical path of incident light by controlling the roughness of the surface shape of the metal oxide thin film, and a method for manufacturing a metal oxide thin film, a perovskite photoelectric device, and a perovskite photoelectric device.

An embodiment of the present invention is to react an oxide precursor solution with oxygen to induce selective bonding with a linker and form a metal oxide intermediate in which large crystal nuclei are generated at the same time to form a metal oxide intermediate without formation of physical defects and at the same time to control the roughness of the surface shape. A method for manufacturing a metal oxide thin film with minimized reflection loss, a metal oxide thin film manufactured through the same, a method for manufacturing a perovskite photoelectric device, and a perovskite photoelectric device.

A method for manufacturing a metal oxide thin film according to an embodiment of the present invention includes preparing a metal oxide precursor solution including a metal oxide precursor, a fuel, an acid solution, and a connector; reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including a metal oxide intermediate bonded to the linking body; and preparing a metal oxide thin film by immersing the substrate in the metal oxide reaction solution.

In the step of reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including the metal oxide intermediate bound to the linker, the linker is selectively bonded to the surface of the metal oxide precursor to form the metal oxide intermediate.

The metal oxide intermediate may be a nucleated metal oxide precursor.

The concentration of the metal oxide reaction solution may be 0.002 M to 0.1 M.

The pH of the metal oxide reaction solution may be 0 to 5.

A reaction time of preparing a metal oxide reaction solution including a metal oxide intermediate combined with a linker by reacting the oxide precursor solution with oxygen may be 1 hour to 12 hours.

A reaction temperature in the step of reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including a metal oxide intermediate bonded to a linker may be 10°C to 30°C.

The metal oxide precursor may include a metal halide.

The conjugate may include a carboxylic acid containing a thiol group as a functional group.

The fuel is acetylacetone, CF₃COCH₂COCF₃, CH₃COCHFCOCH₃, CH₃COCH₂C(=NH)CF₃, CH₃C(=NH)CHFC(=NH)CH₃, CH₃COCH₂C(=NCH₃)CF₃, CH₃C(=NCH₃)CHFC(=NCH₃)CH₃, CH₃C(=NH)CHFC(=NCH₃)CH₃, Ph₂POCH₂COCH₃, urea, thiourea, N-methylurea, citric acid, ascorbic acid, stearic acid, nitromethane, hydrazine, carbohydrazide, oxalyl dihydrazide, malonic acid dihydrazide, tetra formal tris azine, hexamethylenetetramine, and malonic anhydride.

The acid solution may include at least one of hydrochloric acid, nitric acid and sulfuric acid.

The substrate may be fluorine-doped tin oxide (FTO).

The substrate may be silicon (Si).

The substrate may include a first electrode on a surface.

A metal oxide thin film according to an embodiment of the present invention is manufactured by a method for manufacturing a metal oxide thin film according to an embodiment of the present invention.

A method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention includes forming a first electrode on a substrate; forming a first charge transport layer on the substrate on which the first electrode is formed; Forming a perovskite light absorption layer on the first charge transport layer; forming a second charge transport layer on the perovskite light absorption layer; and forming a second electrode on the second charge transport layer, wherein the first charge transport layer is manufactured by the method of manufacturing a metal oxide thin film according to an embodiment of the present invention.

The first charge transport layer and the second charge transport layer may be an electron transport layer or a hole transport layer.

A perovskite optoelectronic device according to an embodiment of the present invention is manufactured by a method for manufacturing a perovskite photoelectric device according to an embodiment of the present invention.

According to an embodiment of the present invention, it is possible to provide a method for manufacturing a metal oxide thin film capable of forming a uniform thin film without forming physical defects on a substrate by increasing the bond between the metal oxide precursor preferentially bonded to a connector in a metal oxide precursor solution and a substrate, and a metal oxide thin film manufactured through the method, a method for manufacturing a perovskite photoelectric device, and a perovskite photoelectric device.

In addition, according to an embodiment of the present invention, a method for manufacturing a metal oxide thin film capable of minimizing light absorption loss that may appear in a perovskite optoelectronic device through an anti-reflection effect, that is, through an anti-reflection effect by controlling the roughness of the surface shape of the metal oxide thin film and controlling the optical path of incident light, and a metal oxide thin film manufactured through the method, a method of manufacturing a perovskite photoelectric device, and a perovskite photoelectric device can be provided. .

According to an embodiment of the present invention, an oxide precursor solution is reacted with oxygen to induce selective bonding with a linker and at the same time form a metal oxide intermediate in which large crystal nuclei are generated to form a metal oxide intermediate without formation of physical defects and at the same time, a method for manufacturing a metal oxide thin film with minimized reflection loss by controlling the roughness of the surface shape, a metal oxide thin film manufactured through the method, a method for manufacturing a perovskite photoelectric device, and a perovskite photoelectric device.

1 is a flowchart illustrating a method of manufacturing a metal oxide thin film according to an embodiment of the present invention.
2 is a flowchart illustrating a method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention.
3 is a cross-sectional view showing a perovskite photoelectric device according to an embodiment of the present invention.
4 is an image observed through a scanning electron microscope and a scanning electron transmission microscope of a metal oxide thin film according to Comparative Example 1, and FIG. 5 is an image observed through a scanning electron microscope and a scanning electron transmission microscope of a metal oxide thin film according to Example 1.
6 is a graph (left) showing current-voltage characteristics of a perovskite photoelectric device according to Comparative Example 2 and a perovskite photoelectric device according to Example 2 (left), and external quantum efficiencies of each perovskite photoelectric device (External Quantum Efficiency) is a graph (right).
7 is a graph showing infrared spectrum (IR Spectrum) through FT-IR (Fourier transform infrared spectroscopy) analysis of metal oxide precursor solutions according to Preparation Examples 1 and 2 of the present invention.
8 is an image observed through a scanning electron microscope of a metal oxide thin film according to Comparative Example 3, and FIG. 9 is an image observed through a scanning electron microscope of a metal oxide thin film according to Example 3.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

Terminology used herein is for describing the embodiments and is not intended to limit the present invention. In this specification, singular forms also include plural forms unless specifically stated otherwise in a phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of one or more other elements or steps in a stated component or step.

"Embodiments," "examples," "aspects," "examples," and the like used herein are not to be construed as preferred or advantageous over any aspect or design described.

Also, the term 'or' means 'inclusive or' rather than 'exclusive or'. That is, unless otherwise stated or clear from the context, the expression 'x employs a or b' means any one of the natural inclusive permutations.

Also, the singular expressions “a” or “an” used in this specification and claims should generally be construed to mean “one or more,” unless indicated otherwise or clear from context to refer to the singular form.

The terms used in the description below have been selected as general and universal in the related technical field, but there may be other terms depending on the development and / or change of technology, convention, preference of technicians, etc. Therefore, terms used in the following description should not be understood as limiting technical ideas, but should be understood as exemplary terms for describing the embodiments.

In addition, in certain cases, there are also terms arbitrarily selected by the applicant, and in this case, their meanings will be described in detail in the corresponding description section. Therefore, terms used in the following description should be understood based on the meaning of the term and the contents throughout the specification, not simply the name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used in a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

Meanwhile, in the description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, the terminology used in this specification is a term used to appropriately express the embodiment of the present invention, which may vary according to the intention of a user or operator or customs in the field to which the present invention belongs. Therefore, definitions of these terms will have to be made based on the content throughout this specification.

1 is a flowchart illustrating a method of manufacturing a metal oxide thin film according to an embodiment of the present invention.

The method for manufacturing a metal oxide thin film according to an embodiment of the present invention is a metal oxide thin film deposition method using a chemical solution deposition method capable of directly forming a metal oxide thin film on the surface of a substrate by applying an external reaction while supporting a substrate to be deposited with a metal oxide thin film in a metal oxide precursor solution capable of forming a metal oxide. A metal oxide thin film (e.g., tin oxide thin film taking into consideration the characteristics of the substrate to which the chemical solution deposition method is applied (curvature of the substrate, material characteristics of the substrate (oxide substrate, silicon substrate, etc. material characteristics)), etc. ) is a chemical solution deposition method.

The method for manufacturing a metal oxide thin film according to an embodiment of the present invention includes preparing a metal oxide precursor solution including a metal oxide precursor, a fuel, an acid solution, and a linker (S110), reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including a metal oxide intermediate bound to the linker (S120), and preparing a metal oxide thin film by immersing a substrate in the metal oxide reaction solution (S130).

Therefore, the method for manufacturing a metal oxide thin film according to an embodiment of the present invention reacts an oxide precursor solution with oxygen to induce selective bonding with a linker and at the same time forms a metal oxide intermediate in which large crystal nuclei are generated (nucleation) to form physical defects. It is possible to form a uniform thin film with controlled roughness of the surface shape at the same time.

First, the method of manufacturing a metal oxide thin film according to an embodiment of the present invention includes preparing a metal oxide precursor solution including a metal oxide precursor, a fuel, an acid solution, and a connector (S110).

A metal oxide precursor means a compound in a previous step for forming a metal oxide.

The metal oxide precursor may include an organic compound of a metal, an inorganic compound of a metal (eg, a metal halide), or a combination thereof, but is not limited thereto. For example, the metal oxide precursor may include a compound containing a metal selected from the group consisting of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and combinations thereof, but is not limited thereto.

Preferably, the metal oxide precursor may be a metal halide, more preferably, the metal halide may include at least one tin halide such as SnCl ₂ , SnF _{2 ,} SnCl _{2 ,} SnBr _{2 ,} SnI ₂ , and the like, and even more preferably, the metal oxide precursor may include SnCl ₂ .

The linker is for increasing bonding strength between the substrate and the metal oxide thin film, and may be selectively combined with a metal oxide precursor to form a metal oxide intermediate.

Therefore, in the method for manufacturing a metal oxide thin film according to an embodiment of the present invention, a uniform thin film can be formed without formation of physical defects on the substrate by increasing the bonding between the metal oxide precursor (or metal oxide intermediate) and the substrate by including a linker in the metal oxide precursor solution.

More specifically, in the method for manufacturing a metal oxide thin film according to an embodiment of the present invention, a metal oxide precursor solution is prepared by including a linking body in a metal oxide precursor solution, and the linking body may have a functional group having high bonding strength with a substrate to be applied and a functional group having high bonding strength with the metal oxide precursor. Therefore, the metal oxide intermediate may be formed by reacting the oxide precursor solution with oxygen so that the metal oxide precursor is preferentially bonded to a functional group having a high bonding strength with the metal oxide precursor. The metal oxide intermediate thus formed is a functional group included in the connector and has a high bonding strength with the substrate, and bonding strength with the substrate can be further improved.

The coupling body may include a carboxylic acid containing a thiol group as a functional group, and preferably, thioglycolic acid may be used as the coupling body.

The fuel is acetylacetone, CF.₃COCH₂COCF₃, CH₃COCHFCOCH₃, CH₃COCH₂C(=NH)CF₃, CH₃C(=NH)CHFC(=NH)CH₃, CH₃COCH₂C(=NCH₃)CF₃, CH₃C(=NCH₃)CHFC(=NCH₃)CH₃, CH₃C(=NH)CHFC(=NCH₃)CH₃, Ph₂POCH₂COCH₃, urea, thiourea, N-methylurea, citric acid, ascorbic acid, stearic acid, nitromethane, hydrazine, carbohydrazide, oxalyl dihydrazide, malonic acid dihydrazide, tetraformal tris azine, hexamethylenetetramine, and malonic acid anhydride. Preferably, urea may be used as a fuel.

The fuel can adjust the pH in the metal oxide precursor solution or inhibit aggregation that may occur between the metal oxide precursors.

The acid solution may include at least one of hydrochloric acid, nitric acid and sulfuric acid, and preferably, hydrochloric acid may be used as the acid solution.

The acid solution can adjust the pH in the metal oxide precursor solution or increase the solubility of the metal oxide precursor.

Thereafter, the method of manufacturing a metal oxide thin film according to an embodiment of the present invention includes preparing a metal oxide reaction solution including a metal oxide intermediate combined with a connector by reacting the oxide precursor solution with oxygen (S120).

In the chemical solution deposition method, since the metal oxide precursor in the metal oxide precursor solution is attached to the substrate after crystal nuclei are formed by an external reaction, thinning occurs. When the chemical bonding strength between the substrate and the metal oxide precursor (metal oxide intermediate) is low, there is a problem in that thinning proceeds while forming a physical defect between the metal oxide thin film and the substrate, or a uniform thin film is not formed on the entire surface of the substrate.

However, the method for manufacturing a metal oxide thin film according to an embodiment of the present invention introduces a linker into a metal oxide precursor solution and reacts the oxide precursor solution with oxygen in the air to prepare a metal oxide reaction solution including a metal oxide intermediate bonded to the linker (S120). By proceeding with the reaction so that the linker is well bonded to the metal oxide precursor (or metal oxide intermediate), a high-quality metal oxide thin film can be formed on the substrate without forming a physical defect between the metal oxide thin film and the substrate.

Therefore, in the step of preparing a metal oxide reaction solution including a metal oxide intermediate coupled to a linker by reacting the oxide precursor solution with oxygen (S120), selective bonding between the metal oxide precursor and the linker is induced to form a metal oxide intermediate in which the linker is selectively bonded to the surface of the metal oxide precursor.

The process of this selective coupling reaction can be induced through the following chemical reaction.

The linkage defined above is a substance that has a functional group that binds to the metal ion of a metal oxide (a functional group that is easy to combine with a metal ion) and a functional group that binds to a substrate to be attached to (a functional group that is easy to bind to). In order to take advantage of these characteristics, a linker is added to the oxide precursor solution and then reacted with oxygen to induce a reaction in which the metal ion in the metal oxide precursor is combined with a functional group that binds to the metal ion of the metal oxide that the linker has (a functional group that is easy to combine with the metal ion).

Accordingly, in the step of preparing a metal oxide reaction solution including a metal oxide intermediate bonded to a linker by reacting the oxide precursor solution with oxygen (S120), a selective coupling reaction to form the metal oxide intermediate may proceed.

The metal oxide intermediate may be bonded to the surface of the metal oxide precursor.

The metal oxide intermediate through the above-mentioned selective bonding reaction is a combination of a metal ion-binding functional group of a metal oxide (a functional group that is easy to combine with a metal ion) and a metal ion in a metal oxide precursor. An example is as follows.

It is a form in which a Sn-S bond is formed by the reaction of sulfur ions formed when hydrogen ions are released from the thiol group of thioglycolic acid, which can function as a linker, and tin ions included in metal oxide precursors.

Therefore, in the method for manufacturing a metal oxide thin film according to an embodiment of the present invention, a linker is bonded to the surface of a metal oxide precursor through a reaction step of reacting with oxygen to form a metal oxide thin film in which surface roughness is secured without physical defects on a substrate (eg, an FTO substrate or a Si substrate) including curves (eg, patterns, etc.).

That is, in the method for manufacturing a metal oxide thin film according to an embodiment of the present invention, an oxide precursor solution reacts with oxygen to induce selective bonding with a linker, and at the same time, a metal oxide intermediate having large crystal nuclei is formed to control the surface roughness of the metal oxide thin film, thereby minimizing reflection loss. Therefore, it is possible to minimize light absorption loss that may occur in a perovskite optoelectronic device through a reflection loss reduction effect through control of an optical path of incident light, that is, an anti-reflection effect.

The metal oxide intermediate may be a nucleated metal oxide precursor.

More specifically, the oxide reaction solution reacts the metal oxide precursor solution with oxygen in the air, so that the metal oxide precursor is poly-condensed and the nuclei of the precursor grow, thereby forming a metal oxide intermediate in which nuclei of the metal oxide precursor are formed.

Thus, the size of the metal oxide intermediate may be several nanometers to several micrometers.

The concentration of the metal oxide reaction solution may be 0.002 M or more, and preferably, the concentration of the metal oxide reaction solution may be 0.002 M to 0.1 M.

If the concentration of the metal oxide reaction solution is less than 0.002 M, a problem may arise as the concentration is too small to form crystals. However, the reaction does not occur even if the concentration is less than this concentration, and depending on the purpose of inducing the reaction and the type of metal oxide thin film to be implemented, the reaction can be induced even at a lower concentration to realize a dense metal oxide thin film.

If the concentration of the metal oxide reaction solution is 0.1 M or more, excessive formation of crystal nuclei in the solution may cause problems in realizing a rather dense thin film. However, higher than this concentration does not mean that the reaction does not occur, and depending on the purpose of inducing this reaction and the type of metal oxide thin film to be implemented, the reaction can be induced even at a higher concentration to realize a dense metal oxide thin film.

The pH of the metal oxide reaction solution may be 0 to 5. However, the above pH does not mean that the reaction is not induced, and depending on the type of metal of the metal oxide to be formed, a dense metal oxide thin film can be realized through the above reaction even at a higher pH.

The reaction time (first reaction time) of the step (S120) of preparing a metal oxide reaction solution including a metal oxide intermediate bonded to a linker by reacting the oxide precursor solution with oxygen may be 1 hour or more, preferably. The reaction time (first reaction time) may be 1 hour to 12 hours, more preferably, the reaction time (first reaction time) may be 3 hours.

However, the fact that the reaction time (first reaction time) is 3 hours or less does not mean that the reaction is not induced, and depending on the metal type of the metal oxide to be formed, the metal oxide reaction solution including the metal oxide intermediate bound to the linker can be implemented through the reaction even in less time.

In addition, the reaction time (first reaction time) in the step of preparing a metal oxide reaction solution containing a metal oxide intermediate bound to a linker by reacting the oxide precursor solution with oxygen (S120) may be within 12 hours, but the reaction dioxidation is 12 hours or more This does not mean that the reaction is not induced, and depending on the metal type of the metal oxide to be formed, a metal oxide reaction solution containing a metal oxide intermediate bound to a linker can be implemented even for a longer time depending on the metal type of the metal oxide to be formed.

The reaction temperature in the step (S120) of preparing a metal oxide reaction solution including a metal oxide intermediate combined with a linker by reacting the oxide precursor solution with oxygen may be 10 °C to 30 °C.

This is a condition for preparing a metal oxide reaction solution containing a metal oxide intermediate in an environment close to room temperature, and this reaction is not induced even if the temperature is outside the above-mentioned temperature range. Depending on the type of metal of the metal oxide to be formed, a metal oxide reaction solution containing a metal oxide intermediate bound to a linker can be prepared through the above reaction at a higher or lower temperature.

Finally, the method of manufacturing a metal oxide thin film according to an embodiment of the present invention includes a step of preparing a metal oxide thin film by immersing a substrate in a metal oxide reaction solution (S130).

In the step of preparing a metal oxide thin film by immersing the substrate in a metal oxide reaction solution (S130), poly-condensing of the metal oxide precursor increases the nuclei of the metal oxide precursor, thereby thinning the metal oxide intermediate in which the nuclei of the metal oxide precursor having large particles are formed. A secured metal oxide thin film can be formed.

The substrate may include at least one of glass, fluorine-doped tin oxide (FTO), quartz, Si, Al ₂ O ₃ , SiC, GaAs, and InP, and preferably, the substrate may include at least one of fluorine-doped tin oxide (FTO) and silicon (Si).

According to the embodiment, an organic substrate may be used as the substrate, and the organic substrate may include kapton foil, polyimide (PI), polyethersulfone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polyphenylene sulfide ( It may include at least one of polyphenylene sulfide (PPS), polyarylate, polycarbonate (PC), cellulose triacetate (CTA), and cellulose acetate propionate (CAP), but is not limited thereto.

Preferably, the substrate may include fluorine doped tin oxide (FTO). In the case of FTO, since it generally has a surface shape with curves, when trying to implement a metal oxide thin film based on a solution process on the substrate, there is a problem in that the thin film is formed while forming physical defects between the curves.

In addition, in the case of the solution process, in the case of the chemical solution deposition method to be used in the present invention, when the properties of the substrate and the metal oxide to be applied are different from each other, a uniform thin film cannot be formed on the entire surface and physical defects are formed. There is a problem in that the thin film is formed.

According to an embodiment, the substrate may include a first electrode on a surface thereof, and the first electrode may be formed on the substrate in a curved pattern.

The first electrode may include at least one of fluorine doped tin oxide (FTO), indium doped tin oxide (ITO), aluminum doped zinc oxide (AZO), and indium doped zinc oxide (IZO), but is not limited thereto.

The reaction time (second reaction time) of preparing a metal oxide thin film by immersing the substrate in a metal oxide reaction solution (S130) may be 2 hours or more, preferably, the reaction time (second reaction time) may be 2 hours to 24 hours, more preferably, when a silicon substrate is used as a substrate, the reaction time (second reaction time) may be 4 hours, and when an FTO substrate is used, the reaction time (second reaction time) may be 12 hours. .

However, even if the reaction time (second reaction time) is outside the corresponding range, this does not mean that the reaction is not induced, and depending on the purpose of inducing the reaction (the purpose of controlling the thickness of the thin film to be implemented), the reaction can be induced even for a longer time to implement a dense metal oxide thin film.

The reaction temperature in the step of preparing a metal oxide thin film by immersing the substrate in the metal oxide reaction solution (S130) may be 70 ° C. or higher, but the reaction is not induced if the temperature is lower than the above temperature.

Preferably, the reaction temperature may be 50 °C to 200 °C, more preferably, the reaction temperature may be 70 °C.

According to an embodiment, preparing a metal oxide thin film by immersing the substrate in a metal oxide reaction solution (S130) may further include heat-treating the metal oxide thin film formed on the substrate.

In the method for manufacturing a metal oxide thin film according to an embodiment of the present invention, a highly crystalline metal oxide thin film may be formed by heat-treating the metal oxide thin film. Additional heat treatment of the formed metal oxide thin film is a process for removing impurities that may be included in the metal oxide thin film and increasing the crystallinity of the metal oxide thin film in step S130.

The heat treatment time may be 1 hour or more, but the effect of the heat treatment reaction does not appear if the time is less than the above, and a high-quality metal oxide thin film can be obtained through the heat treatment reaction even in a shorter time depending on the metal type of the metal oxide to be formed. Preferably, the heat treatment time may be 1 hour to 3 hours, more preferably, the heat treatment time may be 1 hour.

The heat treatment temperature may be 150 ° C. or higher, but the effect of the heat treatment reaction does not appear if the temperature is lower than the above temperature, and a high-quality metal oxide thin film can be obtained through the heat treatment reaction even in less time depending on the metal type of the metal oxide to be formed. Preferably, the heat treatment temperature may be 100 °C to 500 °C, more preferably, the heat treatment temperature may be 150 °C.

A metal oxide thin film according to an embodiment of the present invention may be manufactured through the method for manufacturing a metal oxide thin film according to an embodiment of the present invention.

In the metal oxide thin film according to an embodiment of the present invention, the diameter of the metal oxide crystal particles included in the metal oxide thin film may be increased by a process of selective bonding of the connecting body and the connecting body.

Therefore, the metal oxide thin film according to an embodiment of the present invention has surface roughness increased by large metal oxide crystal particles, thereby improving carrier collection ability, and reducing reflection loss through control of the optical path of incident light.

The metal oxide thin film according to an embodiment of the present invention may be used as a charge transport layer of a perovskite optoelectronic device. In the embodiment of the present invention, the electron transport layer is exemplified among the charge transport layers, but the method of the present invention is not limited to the electron transport layer, and may also be used as a metal oxide-based hole transport layer.

Hereinafter, with reference to FIGS. 2 and 3, a method for manufacturing a perovskite photoelectric device according to an embodiment of the present invention and a perovskite photoelectric device manufactured through the method according to an embodiment of the present invention will be described.

2 is a flowchart illustrating a method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention.

The method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention includes forming a first electrode on a substrate (S210), forming a first charge transport layer on the substrate on which the first electrode is formed (S220), forming a perovskite light absorption layer on the first charge transport layer (S230), forming a second charge transport layer on the perovskite light absorption layer (S240), and a second charge transport layer. and forming a second electrode thereon (S250).

The first charge transport layer and the second charge transport layer may function as an electron transport layer or a hole transport layer, and at this time, the first charge transport layer positioned below the perovskite light absorption layer may be manufactured through the method of manufacturing a metal oxide thin film according to an embodiment of the present invention.

In the method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention, the first charge transport layer and the second charge transport layer may be an electron transport layer or a hole transport layer, and when an electron transport layer is used as the first charge transport layer, a hole transport layer may be used as the second charge transport layer. Also, when a hole transport layer is used as the first charge transport layer, an electron transport layer may be used as the second charge transport layer.

In addition, in the method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention, the first charge transport layer positioned below the perovskite light absorption layer may be manufactured through the method of manufacturing a metal oxide thin film according to an embodiment of the present invention. The first charge transport layer may be positioned on the substrate on which the first electrode is formed or on the substrate.

For example, a metal oxide thin film may be formed on an FTO substrate, and a metal oxide thin film may also be formed on Si where only the substrate exists.

If the first charge transport layer is manufactured through the method of manufacturing a metal oxide thin film according to an embodiment of the present invention, the second charge transport layer that is not manufactured through the method of manufacturing a metal oxide thin film according to an embodiment of the present invention may be an electron transport layer or a hole transport layer used in the art.

First, the method of manufacturing a perovskite photoelectric device according to an embodiment of the present invention includes forming a first electrode on a substrate (S210) and forming a first charge transport layer on the substrate on which the first electrode is formed (S220) through the method of manufacturing a metal oxide thin film according to an embodiment of the present invention.

The first electrode may be formed of the following materials or methods.

The first electrode is aluminum (Al), silver (Ag), gold (Au), copper (Cu), palladium (Pd), platinum (Pt), indium tin oxide (ITO, indium zinc oxide), indium zinc oxide (IZO, aluminum zinc oxide), aluminum zinc oxide (AZO, aluminum zinc oxide), fluorine-containing tin oxide (FTO, fluorine tin oxide), carbon nanotube (CNT, Carbon Nano Tube), graphene, and may include at least one of, but is not limited thereto.

The first electrode may be formed through a solution coating method or a deposition method.

The solution coating method may include any one of spin coating, spray coating, ultra spray coating, electrospinning coating, slot die coating, gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing, and nozzle printing.

The deposition method may include any one of sputtering, atomic layer deposition, chemical vapor deposition, thermal deposition, co-evaporation, and plasma-enhanced chemical vapor deposition under reduced pressure, normal pressure, or pressurized conditions.

The first charge transport layer may be a metal oxide thin film according to an embodiment of the present invention manufactured through a method for manufacturing a metal oxide thin film according to an embodiment of the present invention. The first charge transport layer may be an electron transport layer or a hole transport layer, and the electron transport layer may allow electrons generated in the perovskite light absorption layer to be easily transferred to the electrode. In addition, the hole transport layer may allow holes generated in the perovskite light absorption layer to be easily transferred to the electrode.

Thereafter, a step of forming a perovskite light absorption layer on the first charge transport layer (S230) is performed.

The perovskite light absorption layer is formed on the first charge transport layer, and the perovskite light absorption layer separates electrons (e) and holes (h) formed by absorbing photons of sunlight to generate current. It can serve as a photoelectric conversion layer.

The perovskite light absorption layer included in the perovskite photoelectric device according to an embodiment of the present invention may include a perovskite compound represented by Formula 1 below.

[Formula 1]

ABX ₃

(In Formula 1, A is a monovalent cation, M is a divalent metal cation, and X is a monovalent halide anion.)

Specifically, A may be a monovalent organic ligand, a monovalent inorganic cation, or a combination thereof.

The perovskite compound may be an organic/inorganic hybrid perovskite compound or an inorganic metal halide perovskite compound, depending on the type of A in Formula 1.

More specifically, when A in Formula 1 is a monovalent organic ligand, the perovskite compound may be an organic-inorganic hybrid perovskite compound composed of organic A, inorganic materials B and X, and a combination of organic and inorganic materials.

On the other hand, when A in Formula 1 is a monovalent inorganic cation, the perovskite compound may be an inorganic metal halide perovskite compound composed of inorganic materials A, B, and X, and composed entirely of inorganic materials.

For example, when A is an organic ligand, it may be a C _1-24 straight or branched alkyl, an amine group (-NH ₃ ), a hydroxyl group (-OH), a cyano group (-CN), a halogen group, a nitro group (-NO), a methoxy group (-OCH ₃ ) or a C _1-24 straight or branched chain alkyl substituted with an imidazolium group, or a combination thereof.

Alternatively, when A is an inorganic cation, it may be Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Fr ⁺ , Cu(I) ⁺ , Ag(I) ⁺ , Au(I) ⁺ or a combination thereof.

B may include at least one of Pb ²⁺ , Sn ²⁺ , Ge ²⁺ , Cu ²⁺ , Co ²⁺ , Ni ²⁺ , Ti ²⁺ , Zr ²⁺ , Hf ²⁺ and Rf ²⁺ .

X may include any one of F ^- , Cl ^- , Br ^- and I ^- , and is not limited to the above materials unless the size of the ion is excessively large.

According to embodiments, the perovskite compound may have a single structure, a double structure, a triple structure, or a Ruddlesden-Popper structure.

The perovskite compound of formula 1 has a three-dimensional single phase, and the perovskite compound of the double structure is (A1) _a (B1) _b (X1) _c and (A2) _a (B2) _b (X2) _c is alternately stacked to form a light absorption layer.

In this case, A1 and A2 in (A1) _a (B1) _b (X1) _c and (A2) _a (B2) _b (X2) _c are the same or different monovalent cations, B1 and B2 are the same or different divalent metal cations, and X1 and X2 mean the same or different monovalent anions. Here, A1, B1, and X1 may differ from A2, B2, and X2 in at least one or more ways.

In the perovskite compound having a triple structure, (A1) _a (B1) _b (X1) _c and (A2) _a (B2) _b (X2) _c and (A3) _a (B3) _b (X3) _c are alternately stacked to form the light absorption layer 130, wherein A1, A2, and A3 are the same or different monovalent cations, and B1, B2, and B3 are the same or different divalent metal cations or It is a trivalent metal cation, and X1, X2, and X3 mean the same or different monovalent anions. Here, A1, B1, X1 and A2, B2, X2 and A3, B3, X3 may differ by at least one or more from each other.

The Ludlesten-Popper structure is (A1) _a (B1) _b (X1) _c {(A2) _a (B2) _b (X2) _c } _n (A1) _a (B1) _b (X1) _c , where n is a natural number.

The perovskite light absorption layer may be formed through a solution coating method, and the solution coating method may include any one of spin coating, spray coating, ultra spray coating, electrospinning coating, slot die coating, gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing, and nozzle printing.

Thereafter, a step of forming a second charge transport layer on the perovskite light absorption layer (S240) is performed.

The second charge transport layer may be an electron transport layer or a hole transport layer, and the electron transport layer may allow electrons generated in the perovskite light absorption layer to be easily transferred to the electrode. In addition, the hole transport layer may allow holes generated in the perovskite light absorption layer to be easily transferred to the electrode.

In the case of the second charge transport layer in which the metal oxide thin film manufactured by the method of manufacturing a metal oxide thin film according to an embodiment of the present invention is not used, an electron transport layer or a hole transport layer known in the art may be used.

The electron transport layer is fullerene (C60), a fullerene derivative, TPBi (2,2′,2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)), PBI (polybenzimidazole) and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), NDI (naphthalene diimide) and their derivatives, TiO₂, SnO₂, ZnO, ZnSnO₃, 2,4,6-Tris(3-(pyrimidin-5-yl)phenyl)-1,3,5-triazine, 8-Hydroxyquinolinolato-lithium, 1,3,5-Tris(1-phenyl-1Hbenzimidazol-2-yl)benzene, 6,6'-Bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2'- bipyridyl, 4,4'-Bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl(BTB), Rb₂CO₃(Rubidium carbonate), ReO₃(Rhenium(VI) oxide), and the fullerene derivative may be PCBM ((6,6)-phenyl-C61-butyric acid-methylester) or PCBCR ((6,6)-phenyl-C61-butyric acid cholesteryl ester), but is not limited thereto.

The electron transport layer may be formed through a solution coating method, and the solution coating method may include any one of spin coating, spray coating, ultra spray coating, electrospinning coating, slot die coating, gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing, and nozzle printing.

The hole transport layer is P3HT (poly[3-hexylthiophene]), MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV (poly[2-methoxy-5-(2''-ethylhexyloxy)-p-phenylene vinylene]), P3OT (poly(3-octyl thiophene)), POT (poly(octyl thiophene)), P3DT (poly(3-decyl thiophene)), P3DDT (poly(3-dodecyl thiophene), PPV (poly(p-phenylene vinylene)), TFB (poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenyl amine), Polyaniline, Spiro-MeOTAD ([2,22′,7,77′-tetrki s (N,N-dipmethoxyphenylamine)-9,9,9′-spirobi fluorine]), CuSCN, CuI, MoO_x, V.O._x, NiO_x, CuO_x, PCPDTBT (Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl-4H- cyclopenta [2,1-b:3,4-b']dithiophene-2,6-diyl]], Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole )-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD (poly((4,8-diethylhexyloxyl) benzo([1,2-b:4,5-b']dithiophene)-2,6-diyl)-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl )), PFDTBT (poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene)-alt-5,5-(4', 7,-di-2-thienyl-2',1', 3'-benzothiadiazole)]), PFO-DBT (poly[2,7-.9,9-(dioctyl-fluorene)-alt-5,5-(4',7'-di-2-. thienyl-2', 1', 3'-benzothiadiazole)]), PSiFDTBT (poly[(2,7-dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]), PSBTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2- b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PCDTBT (Poly [[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]), P FB (poly(9,9′′-dioctylfluorene-co-bis(N,N′′-(4,butylphenyl))bis(N,N′′-phenyl-1,4-phenylene)diamine), F8BT (poly(9,9′′-dioctylfluorene-cobenzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS, poly(3,4-ethylenedioxythiophene) poly(styrenesulfo nate), PTAA (poly(triarylamine)), poly(4-butylphenyldiphenyl-amine), 4,4'-bis[N-(1-naphtyl)-N-phenylamino]-biphenyl (NPD), bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthalen-1-yl)-N,N'-diphenyl-benzidine (NPB), N,N'- Diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine (TPD), copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenylamino)phenoxybenzene (m-MTDAPB), starburst amines 4,4 ', 4 "-tri (N-carbazolyl) triphenylamine (TCTA), 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA), and at least one or more copolymers thereof may be selected, but is not limited to the above materials.

The hole transport layer may be formed through a solution coating method, and the solution coating method may include any one of spin coating, spray coating, ultra spray coating, electrospinning coating, slot die coating, gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing, and nozzle printing.

Finally, a step of forming a second electrode on the second charge transport layer (S250) proceeds.

The second electrode may be formed of a conductive material having excellent electrical characteristics. The second electrode may include at least one of aluminum (Al), silver (Ag), gold (Au), copper (Cu), palladium (Pd), platinum (Pt), indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), fluorine-containing tin oxide (FTO), carbon nanotube (CNT), and graphene.

The second electrode may be formed through a solution coating method or a deposition method.

The solution coating method may include any one of spin coating, spray coating, ultra spray coating, electrospinning coating, slot die coating, gravure coating, bar coating, roll coating, dip coating, shear coating, screen printing, inkjet printing, and nozzle printing, and the deposition method may include any one of sputtering, atomic layer deposition, chemical vapor deposition, thermal deposition, simultaneous evaporation, and plasma enhanced chemical vapor deposition under reduced pressure, normal pressure, or pressurized conditions. can

3 is a cross-sectional view showing a perovskite photoelectric device according to an embodiment of the present invention.

Since the perovskite photoelectric device according to the embodiment of the present invention is manufactured by the method of manufacturing the perovskite photoelectric device according to the embodiment of the present invention, description of overlapping components will be omitted.

A perovskite photoelectric device according to an embodiment of the present invention includes a first electrode 120 formed on a substrate 110, a first charge transport layer 130 formed on the first electrode, a perovskite light absorption layer 140 formed on the first charge transport layer 130, a second charge transport layer 150 formed on the perovskite light absorption layer 140, and a second charge transport layer 15 0) may include a second electrode 160 formed on it.

In the perovskite optoelectronic device according to an embodiment of the present invention, a metal oxide thin film manufactured by the method of manufacturing a metal oxide thin film according to an embodiment of the present invention may be used as the first charge transport layer.

In the perovskite optoelectronic device according to an embodiment of the present invention, since the first charge transport layer 130 includes a metal oxide thin film manufactured by the method of manufacturing a metal oxide thin film according to an embodiment of the present invention, it is possible to improve uniformity by forming an electron transport layer or a hole transport layer having surface roughness secured without formation of physical defects on the FTO substrate or Si substrate.

In addition, in the perovskite photoelectric device according to an embodiment of the present invention, since the first charge transport layer 130 includes a metal oxide thin film manufactured by the method of manufacturing a metal oxide thin film according to an embodiment of the present invention, a perovskite solar cell having an excellent photoelectric conversion efficiency of 25.21%, which is the world's highest efficiency level, can be implemented.

Preparation Example 1: Metal Oxide Precursor Solution

l의 티오글리콜 산( Thioglycolic acid)를 용액에 첨가하여 금속 산화물 전구체 용액을 제조한다.After dissolving 5 g of urea and 3-5 ml of HCl in 400 ml of 0.012 M SnCl ₂ aqueous solution,

A metal oxide precursor solution is prepared by adding l of Thioglycolic acid to the solution.

Preparation Example 2: Metal oxide reaction solution

l의 티오글리콜 산( Thioglycolic acid)를 용액에 첨가하여 금속 산화물 전구체 용액을 제조한 다음, 금속 산화물 전구체 용액을 대기 중 산소와 반응할 수 있도록 3시간 이상 상온 반응을 하여 금속 산화물 반응 용액을 제조한다.After dissolving 3-5 ml of urea and HCl in 400 ml of 0.012 M SnCl ₂ aqueous solution,

A metal oxide precursor solution is prepared by adding l of thioglycolic acid to the solution, and then the metal oxide reaction solution is prepared by reacting the metal oxide precursor solution at room temperature for 3 hours or more to react with oxygen in the air.

Preparation Example 3: [CH ₃ NH ₃ PbBr ₃ ] _0.05 -[HC(NH ₂ ) ₂ PbI ₃ ] _0.95 solution

[CH ₃ NH ₃ PbBr ₃ ] _0.05 -[HC(NH ₂ ) ₂ PbI ₃ ] _0.95 solution of 1.4M concentration was dissolved in a mixed solvent (a mixed solvent in which dimethyl sulfoxide and dimethylformamide were mixed in a ratio of 1:8 was used as the solvent) HC(NH ₂ ) ₂ I and PbI ₂ in a 1::1 molar ratio to match the molar concentration, and CH ₃ NH It was prepared by dissolving ₃ Br and PbBr ₂ in a 1:1 molar ratio according to the molar concentration.

Comparative Example 1

A glass substrate (FTO; F-doped SnO ₂ , hereinafter referred to as FTO substrate) coated with fluorine-containing tin oxide having a size of 1 in * 1 in is washed in the order of surfactant distilled water, ethanol, and acetone. The cleaned FTO substrate is cleaned using a UV ozone clearner for 30 minutes. The cleaned FTO substrate is inserted into a substrate tray, placed vertically, and the substrate tray is immersed in the reaction solution prepared in Preparation Example 1.

Store the above solution bowl containing the substrate tray in an oven set at 70 °C for at least 4 hours. During the above-mentioned immersion time, the immersed substrate tray was taken out of the reaction solution, washed with distilled water, and subjected to a heat treatment process for 1 hour on a hot plate maintained at a temperature of 150 ° C. and atmospheric pressure to form a SnO ₂ thin film.

Example 1: FTO/metal oxide thin film

A glass substrate (FTO; F-doped SnO ₂ , hereinafter referred to as FTO substrate) coated with fluorine-containing tin oxide having a size of 1 in * 1 in is washed in the order of surfactant distilled water, ethanol, and acetone. The cleaned FTO substrate is cleaned using a UV ozone clearner for 30 minutes. The cleaned FTO substrate is inserted into a substrate tray, placed vertically, and the substrate tray is immersed in the reaction solution prepared in Preparation Example 2.

Store the above solution bowl containing the substrate tray in an oven set at 70 °C for at least 4 hours. During the above-mentioned immersion time, the immersed substrate tray was taken out of the reaction solution, washed with distilled water, and subjected to a heat treatment process for 1 hour on a hot plate maintained at a temperature of 150 ° C. and atmospheric pressure to form a SnO ₂ thin film.

Comparative Example 2

The solution prepared in Preparation Example 3 was collectively applied (injected) to the center of rotation on the SnO ₂ thin film prepared in Comparative Example 1, and spin coating was started at 5000 rpm. When the spin coating time reached 25 seconds, diethyl ether, a non-solvent, was collectively applied (injected) to the center of rotation of the substrate being spun, and then spin coating was further performed for 5 seconds.

After spin coating was performed, a halide perovskite film was formed by treatment on a hot plate at 150° C. and atmospheric pressure for 10 minutes. A 90 g/L concentration of Spiro-MeOTAD solution (prepared by dissolving Spiro-MeOTAD in chlorobenzene according to the concentration) was collectively applied (injected) to the center of rotation of the prepared halide perovskite film, and spin coating was performed at 2000 rpm for 34 seconds.

After masking the fabricated film, a 100 nm gold electrode was deposited using a vacuum evaporator (a vacuum evaporator maintained at 5 Х 10 ^-6 torr).

Example 2: Perovskite Solar Cell

The solution prepared in Preparation Example 3 was collectively applied (injected) to the center of rotation on the SnO ₂ thin film prepared in Example 1, and spin coating was started at 5000 rpm. When the spin coating time reached 25 seconds, diethyl ether, a non-solvent, was collectively applied (injected) to the center of rotation of the substrate being spun, and then spin coating was further performed for 5 seconds. After spin coating was performed, a halide perovskite film was formed by treatment on a hot plate at 150° C. and atmospheric pressure for 10 minutes.

A 90 g/L concentration of Spiro-MeOTAD solution (prepared by dissolving Spiro-MeOTAD in chlorobenzene according to the concentration) was collectively applied (injected) to the center of rotation of the prepared halide perovskite film, and spin coating was performed at 2000 rpm for 34 seconds.

After masking the fabricated film, a 100 nm gold electrode was deposited using a vacuum evaporator (a vacuum evaporator maintained at 5 Х 10 ^-6 torr).

Comparative Example 3

A 1 in * 1 in size silicon substrate (Silicon, hereinafter Si substrate) is washed in the order of surfactant distilled water, ethanol, and acetone. The cleaned Si substrate is inserted into a substrate tray and placed in a vertical direction to immerse the substrate tray in the reaction solution prepared in Preparation Example 1.

Store the above solution bowl containing the substrate tray in an oven set at 70 °C for at least 4 hours. During the above-mentioned immersion time, the immersed substrate tray was taken out of the reaction solution, washed with distilled water, and subjected to a heat treatment process on a hot plate maintained at a temperature of 150 ° C. and atmospheric pressure for 1 hour to form a SnO ₂ thin film.

Example 3: Si/metal oxide thin film

A 1 in * 1 in size silicon substrate (Silicon, hereinafter Si substrate) is washed in the order of surfactant distilled water, ethanol, and acetone. The cleaned Si substrate is inserted into a substrate tray and placed in a vertical direction to immerse the substrate tray in the reaction solution prepared in Preparation Example 2.

Store the above solution bowl containing the substrate tray in an oven set at 70 °C for at least 4 hours. During the above-mentioned immersion time, the immersed substrate tray was taken out of the reaction solution, washed with distilled water, and subjected to a heat treatment process on a hot plate maintained at a temperature of 150 ° C. and atmospheric pressure for 1 hour to form a SnO ₂ thin film.

4 is an image observed through a scanning electron microscope and a scanning transmission electron microscope of a metal oxide thin film according to Comparative Example 1, and FIG. 5 is an image observed through a scanning electron microscope and a scanning transmission electron microscope of a metal oxide thin film according to Example 1.

4 and 5, in the metal oxide thin film according to Comparative Example 1 prepared on the FTO substrate through a chemical solution deposition method using a metal oxide precursor solution according to Preparation Example 1, physical defects are formed on the concave surface of the FTO. It can be seen that.

On the other hand, since the metal oxide thin film according to Example 1 was prepared through a chemical solution deposition method using a metal oxide reaction solution according to Preparation Example 2 that induces selective bonding with a linker (thioglycolic acid), physical defects are not formed in the FTO. It can be seen that a tin oxide thin film is formed.

This can be seen as a result of the chemical solution deposition method through a metal oxide reaction solution in which selective bonding with a linker has occurred in order to enhance the chemical bonding between the FTO and the tin oxide precursor.

In addition, it can be seen that, unlike the metal oxide thin film according to Comparative Example 1, the surface shape of the tin oxide thin film according to Example 1 is more rough.

This can be seen as a result of thinning after the formation of precursor nuclei (metal oxide intermediate).

6 is a graph (left) showing current-voltage characteristics of a perovskite photoelectric device according to Comparative Example 2 and a perovskite photoelectric device according to Example 2 (External Quantum Efficiency) of each graph (right).

Table 1 is a table showing the photoelectric conversion efficiency through the results according to FIG. 6 .

의 항온 조건으로 측정하였다. 또한 도 6의 외부양자효율은 QE Measurement 장치(Newport, model QUANTX-300)로 측정하였다.6 and Table 1 show that an artificial solar device (ORIEL class A solar simulator, Newport, model 91195A) and a source-meter (source-meter, Kethley, model 2420) were used, and standard test conditions of 1,000 W/m2 of sunlight intensity and 25

was measured under constant temperature conditions. In addition, the external quantum efficiency of FIG. 6 was measured with a QE Measurement device (Newport, model QUANTX-300).

[Table 1]

Referring to FIG. 6 and Table 1, it can be seen that the perovskite photoelectric device according to Example 2 exhibits higher photoelectric conversion efficiency than the perovskite photoelectric device according to Comparative Example 2. In particular, it can be seen that the perovskite photoelectric device according to Example 2 has a higher current density (Jsc).

This can be seen as a result of the metal oxide thin film according to Example 1 used in the perovskite optoelectronic device according to Example 2 having no physical defects.

In addition, looking at the photoelectric conversion efficiency and external quantum efficiency evaluation results of FIG. 6, the metal oxide thin film according to Example 1 has a more rough control of the surface shape than the metal oxide thin film according to Comparative Example 1. Due to the effect (increase in the collecting ability of carriers generated in the light absorption layer due to the increase in the contact area with the perovskite layer according to the rough surface and reduction in light loss due to the reflection reduction effect due to the optical path control effect by the rough surface), the perovskite photoelectric device is implemented. It can be confirmed that it is possible to obtain a high current density.

In addition, as a result of evaluating the external quantum efficiency, it can be seen that the perovskite solar cell to which the metal oxide thin film according to Example 1 is applied has a higher external quantum efficiency. This can also be seen as a result of proving the light loss reduction caused by rough control of the surface shape. What the external quantum efficiency means is that the higher the external quantum efficiency, the smaller the reflection when the same light is absorbed, so it can be proven that more photons are incident to the light absorption layer and more electrons/holes are produced and converted into power.

7 is a graph showing infrared spectrum (IR Spectrum) through FT-IR (Fourier transform infrared spectroscopy) analysis of metal oxide precursor solutions according to Preparation Examples 1 and 2 of the present invention.

Referring to FIG. 7 , it can be seen that the bond between the connector and the precursor (Sn—S bond) appears only when the oxide precursor solution reacts with oxygen for 3 hours.

That is, when a high-temperature reaction of 70 ° C. is performed without performing the step of preparing a metal oxide reaction solution containing a metal oxide intermediate bonded to a linker by reacting the oxide precursor solution with oxygen at room temperature, the high-temperature reaction at 70 ° C. is performed. Since the high-temperature reaction proceeds in a state where the linker is not bonded to the metal oxide precursor (or metal oxide intermediate), it is disadvantageous for bonding with the substrate, and physical defects may be formed as shown in FIG. 4.

8 is an image observed through a scanning electron microscope of a metal oxide thin film according to Comparative Example 3, and FIG. 9 is an image observed through a scanning electron microscope of a metal oxide thin film according to Example 3.

Referring to FIGS. 8 and 9, in the metal oxide thin film according to Comparative Example 3 prepared on a silicon substrate through a chemical solution deposition method using a metal oxide precursor solution according to Preparation Example 1, tin oxide is not deposited on the entire surface of the silicon substrate. It can be seen that a non-uniform thin film is formed.

On the other hand, in the case of the metal oxide thin film according to Example 3, since it was prepared through a chemical solution deposition method using the metal oxide precursor solution according to Preparation Example 2, which induces selective bonding with the connector (thioglycolic acid), it can be seen that a tin oxide thin film can be formed uniformly on the entire surface of the silicon substrate.

This can be seen as a result of the chemical solution deposition method through a metal oxide reaction solution in which selective bonding with a linker has occurred in order to enhance the chemical bonding between the silicon substrate and the tin oxide precursor.

As described above, although the present invention has been described by the limited embodiments and drawings, the present invention is not limited to the above embodiments, and those skilled in the art can make various modifications and variations from these descriptions. Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

110: substrate 120: first electrode
130: first charge transport layer 140: perovskite light absorption layer
150: second charge transport layer 160: second electrode

Claims (18)

preparing a metal oxide precursor solution including a metal oxide precursor, a fuel, an acid solution, and a connector;
reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution including a metal oxide intermediate bonded to the linking body; and
preparing a metal oxide thin film by immersing a substrate in the metal oxide reaction solution;
Method for producing a metal oxide thin film comprising a.
According to claim 1,
In the step of reacting the oxide precursor solution with oxygen to prepare a metal oxide reaction solution containing a metal oxide intermediate bound to the linker,
Method for producing a metal oxide thin film in which the linker is selectively bonded to the surface of the metal oxide precursor to form the metal oxide intermediate.
According to claim 1,
The method of manufacturing a metal oxide thin film, characterized in that the metal oxide intermediate is a metal oxide precursor in which crystal nuclei are generated (nucleation).
According to claim 1,
The method for producing a metal oxide thin film, characterized in that the concentration of the metal oxide reaction solution is 0.002 M to 0.1 M.
According to claim 1,
Method for producing a metal oxide thin film, characterized in that the pH of the metal oxide reaction solution is 0 to 5.
According to claim 1,
A method for producing a metal oxide thin film, characterized in that the reaction time of preparing a metal oxide reaction solution containing a metal oxide intermediate bonded to a linker by reacting the oxide precursor solution with oxygen is 1 hour to 12 hours.
According to claim 1,
A method for producing a metal oxide thin film, characterized in that the reaction temperature in the step of preparing a metal oxide reaction solution containing a metal oxide intermediate combined with a linker by reacting the oxide precursor solution with oxygen is 10 ℃ to 30 ℃.
According to claim 1,
The method of manufacturing a metal oxide thin film, characterized in that the metal oxide precursor comprises a metal halide.
According to claim 1,
The method of producing a metal oxide thin film, characterized in that the linkage comprises a carboxylic acid containing a thiol group as a functional group.
According to claim 1,
상기 연료는 아세틸아세톤, CF ₃ COCH ₂ COCF ₃ , CH ₃ COCHFCOCH ₃ , CH ₃ COCH ₂ C(=NH)CF ₃ , CH ₃ C(=NH)CHFC(=NH)CH ₃ , CH ₃ COCH ₂ C(=NCH ₃ )CF ₃ , CH ₃ C(=NCH ₃ )CHFC(=NCH ₃ )CH ₃ , CH ₃ C(=NH)CHFC(=NCH ₃ )CH ₃ , Ph ₂ POCH ₂ COCH ₃ , 우레아, 싸이오우레아, N-메틸우레아, 시트르산, 아스코르브산, 스테아르산, 나이트로메테인, 하이드라진, 카보하이드라자이드, 옥살릴 다이하이드라자이드, 말론산 다이하이드라자이드, 테트라 폼알 트리스 아진, 헥사메틸렌테트라민 및 말론산 무수물 중 적어도 어느 하나를 포함하는 것을 특징으로 하는 금속 산화물 박막의 제조방법.
According to claim 1,
The method of producing a metal oxide thin film, characterized in that the acid solution contains at least one of hydrochloric acid, nitric acid and sulfuric acid.
According to claim 1,
The method of manufacturing a metal oxide thin film, characterized in that the substrate comprises fluorine doped tin oxide (FTO).
According to claim 1,
The method of manufacturing a metal oxide thin film, characterized in that the substrate comprises silicon (Si).
According to claim 1,
The method of manufacturing a metal oxide thin film, characterized in that the substrate comprises a first electrode on the surface.
A metal oxide thin film manufactured by the method of manufacturing a metal oxide thin film according to claim 1.
forming a first electrode on the substrate;
forming a first charge transport layer on the substrate on which the first electrode is formed;
Forming a perovskite light absorption layer on the first charge transport layer;
forming a second charge transport layer on the perovskite light absorption layer; and
forming a second electrode on the second charge transport layer;
including,
The method of manufacturing a perovskite optoelectronic device, characterized in that the first charge transport layer is manufactured by the method of manufacturing a metal oxide thin film according to claim 1.
According to claim 16,
The method of manufacturing a perovskite photoelectric device, characterized in that the first charge transport layer and the second charge transport layer is an electron transport layer or a hole transport layer.
A perovskite optoelectronic device manufactured by the method of manufacturing a perovskite photoelectric device according to claim 16.