Mask frame for photocatalytic electrolytic deposition, and method for manufacturing large-area patterned photocatalytic film by using same

Abstract

The present invention relates to a mask frame for forming a uniform pattern on a large-area substrate in a photocatalytic electrolytic deposition process. The mask frame comprises: a main insulating holder supporting a deposition substrate; an insulating mask and a metal mask stacked on the main holder; and a metal edge frame and a fastening means fixing same. According to the present invention, each mask and the frame are tightly fastened in a precisely aligned state, thereby securing uniform pattern precision even in a large area. In addition, the present invention relates to a method for manufacturing a large-area patterned photocatalyst film by using the mask frame and a photocatalyst film manufactured thereby.

Description

Mask frame for photocatalytic electrolytic deposition, and a method for manufacturing a large-area patterned photocatalytic film using the same.

[0001] The present invention relates to a technology for maximizing light absorption and catalytic reactions through a large-area patterned copper-iron composite photocatalytic film, and in particular, to a method for efficiently forming a photocatalytic pattern on a large-area film surface using a mask frame for photocatalytic electrolytic deposition.

[0002] Photocatalytic technology utilizes materials that absorb light to catalyze chemical reactions, and is primarily used in fields such as solar-powered water splitting, air and water purification, organic pollutant decomposition, and carbon dioxide fuel conversion. The greatest advantage of photocatalysts is that they can accelerate chemical reactions using natural light, such as sunlight, making them a 주목받는 (highly regarded) renewable and eco-friendly technology. In particular, technologies that use photocatalysts to split water to generate hydrogen or convert carbon dioxide into fuel have the potential to simultaneously achieve clean energy production and environmental protection.

[0003] The fields where photocatalysts are most widely used are water and air purification. The potential for hydrogen fuel cells, which produce hydrogen through solar-powered water splitting, is increasing significantly and is considered an important alternative to conventional fossil fuels. Furthermore, eco-friendly fuels can be produced through the reduction of carbon dioxide using photocatalysts, establishing this as a crucial technology for addressing climate change.

[0004] These photocatalytic technologies yield even greater effects in large-area applications. Using large-area photocatalytic films allows the photocatalytic material to be distributed over a wide surface area, absorbing more light and thereby inducing chemical reactions with higher efficiency. In particular, the technology of maximizing reaction efficiency by patterning photocatalysts on the surface of large-area films plays a crucial role in photoelectrochemical systems. Photocatalytic patterning allows the photocatalyst to be placed only in specific regions of the film surface, thereby further increasing light absorption and optimizing the space where reactions can occur.

[0005] While photocatalytic electrolytic deposition can be used to pattern photocatalysts, existing photocatalyst patterning technologies face several challenges. Conventional processes are complex, leading to high production costs that make it difficult to mass-produce large-area films. Furthermore, existing patterning methods struggle to form uniform patterns on large-area films, limiting their commercial application.

[0006] In addition, the poor adhesion between the mask and the deposition substrate causes bubbles to form between the masks, which hinders the uniform deposition essential for the patterning process and inevitably has a negative impact on the performance of the photocatalytic film.

[0007] Accordingly, the present invention presents a technology that improves the patterning process of large-area photocatalytic films in a simple and economical manner to solve the problems of existing technologies. Furthermore, to increase the efficiency of the photocatalytic patterning process, the present invention proposes a method for efficiently patterning a photocatalyst on the surface of a large-area film using a mask frame for photocatalytic electrolytic deposition, thereby simplifying the process and reducing production costs to create conditions favorable for commercial mass production.

[0008] One objective of the present invention is to provide a mask frame for photocatalytic electrolytic deposition that enables the efficient performance of a photocatalytic electrolytic deposition process.

[0009] Another objective of the present invention is to provide a method for manufacturing a large-area patterned photocatalytic film using the mask frame for photocatalytic electrolytic deposition described above.

[0010] Another objective of the present invention is to provide a film having a patterned photocatalyst to maximize light absorption and catalytic reaction.

[0011] In one aspect, the present invention comprises a main holder made of an insulating material having a plane on which a surface of a deposition substrate is placed, a bezel ledge on the edge of the plane having a height equal to or smaller than the thickness of the deposition substrate, and a plurality of first fastening holes formed along the edge on the surface of the bezel ledge; an insulating mask made of an insulating material having a height on the bezel ledge of the main holder, wherein the insulating mask includes a second fastening hole corresponding to the first fastening hole on the edge of the insulating mask and includes a first pattern hole in an area corresponding to the plane; a metal mask made of a metal material having a third fastening hole and a second pattern hole corresponding to the insulating mask; a first metal ledge frame made of a metal material corresponding to the bezel ledge, wherein the first metal ledge frame is placed on the metal mask and includes a fourth fastening hole corresponding to the third fastening hole; a second metal ledge frame made of a metal material corresponding to the bezel ledge, wherein the second metal ledge frame is placed on the back surface of the main holder and includes a fifth fastening hole corresponding to the third fastening hole; and the first, second, third, fourth, and fifth A mask frame for photocatalytic electrolytic deposition is provided, comprising a fastening means for fastening a laminate in which the first metal rim frame, the metal mask, the insulating mask, the main holder, and the second metal rim are stacked by penetrating a fastening hole and firmly compressing and fastening it.

[0012] The mask frame for photocatalytic electrolytic deposition used in the present invention plays a crucial role in maximizing the precision and efficiency of the deposition process by organically combining various components. By examining the roles and interactions of each component, one can understand how parts such as the main holder, insulating mask, metal mask, first and second metal frame rims, and fastening means cooperate to enable stable and precise photocatalytic deposition.

[0013] In the present invention, the main holder is a key component that supports a deposition substrate and is configured to provide a space on which the deposition substrate is placed. In the present invention, the bezel ledge refers to a portion of the main holder's edge that is formed to be raised one step higher in order to accurately fix or position the deposition substrate. At this time, in order to fully accommodate the deposition substrate, the height of the deposition substrate must not be higher than the height of the bezel ledge; therefore, the height of the bezel ledge must be higher than or at least equal to the height of the deposition substrate. A plurality of first fastening holes are formed along the edge of the bezel ledge surface, and these fastening holes are holes through which a fastening means can pass, thereby assisting in firmly joining each component using the fastening means.

[0014] Furthermore, the main holder must be manufactured from an insulating material that provides electrical insulation. This is to block unnecessary electrical connections between the substrate and the mask and to prevent electrical interference during the electrolytic deposition process. This enables stable deposition and allows for efficient photocatalytic patterning by preventing electrical contact between the substrate and the mask. In other words, the main holder is an essential component that supports the substrate to ensure the stability of the overall structure and plays a role in maintaining precision during the deposition process when combined with other parts.

[0015] The insulating mask provides electrical insulation between the substrate and the mask and plays a key role in defining the deposition area. A first pattern hole is formed on the surface of the insulating mask; here, a pattern hole refers to a hole formed on the mask surface to define the deposition area of ​​the material and enable accurate deposition according to a target pattern.

[0016] The lower portion of the insulating mask can come into contact with the main holder through the bezel edge of the main holder, and the upper portion of the insulating mask can be combined with a metal mask to facilitate precise patterning. When the insulating mask is accurately fixed to the main holder, a desired pattern can be accurately formed, and it can subsequently play a key role in controlling the deposition process together with the metal mask.

[0017] The metal mask serves to form a pattern of the material to be actually deposited and to complement the durability of the insulating mask. The metal mask provides heat resistance, durability, and physical stability, and can play an important role in forming the pattern during the deposition process. A second pattern hole is formed in the metal mask, and the second pattern hole can be formed with the same shape and size as the first pattern hole and positioned to correspond to it. Due to this arrangement, the first pattern hole and the second pattern hole do not overlap or interfere with each other, and deposition can be performed without interference between the pattern holes during the deposition process, allowing the deposition material to be deposited at an accurate location.

[0018] The metal rim frame serves a structural role in fixing the mask and the main holder. The first metal rim frame is positioned at the top, and the second metal rim frame is positioned at the bottom, thereby stably fixing the mask and the main holder located between them. The mask frame according to the present invention is secured by the two metal rim frames while stably fixing the deposition substrate so that it does not lift in the bezel space, thereby ensuring perfect contact between the mask and the substrate. As a result, no bubbles are generated; if bubbles are not generated, structural stability is maintained during the deposition process, enabling uniform and accurate deposition. This can contribute to improving the overall deposition quality.

[0019] Finally, the fastening means firmly joins each component to ensure perfect adhesion between the deposition substrate and the mask. Through the first, second, third, fourth, and fifth fastening holes, all components are compressed and joined, thereby preventing the formation of air layers or bubbles between the mask and the substrate, which enables uniform deposition. The fastening means ensures that all components are precisely fixed and remain in place without deformation during the deposition process.

[0020] In the present invention, each component is organically combined to solve the problem of poor adhesion between the mask and the substrate, and in particular, prevents the problem of bubble formation. In conventional technology, there was a problem where the uniformity of deposition decreased if bubbles formed between masks or if the adhesion between the mask and the deposition substrate became incomplete; however, the present invention solves these problems through fastening means and a metal frame, enabling the uniform deposition of the deposition material. In addition, the metal mask and the insulating mask are accurately positioned to control patterned deposition, thereby enabling precise patterning and maximizing deposition efficiency and reaction efficiency. Through such precise adhesion and patterning, the present invention can dramatically improve the precision and efficiency of photocatalytic deposition, which was a limitation of conventional technology.

[0021] In one embodiment, the deposition substrate may include an FTO substrate. The FTO substrate is a substrate comprising fluorine-doped tin oxide, and as a material with excellent conductivity, heat resistance, flexibility, and light transmittance, it can be an ideal choice for precise patterning in an electrolytic deposition process.

[0022] In one embodiment, the first pattern hole and the second pattern hole may be characterized by a plurality of holes forming a checkerboard pattern. When the first pattern hole and the second pattern hole are formed such that a plurality of square-shaped holes are arranged orthogonally, the pattern may be formed in a checkerboard pattern. A person skilled in the art may form a pattern of a desired shape by appropriately changing the size and shape of the holes of the pattern hole as needed.

[0023] In one embodiment, the fastening means may include a screw, a rivet, a bolt-nut, or a clamp. The fastening means may serve to accurately secure each component and ensure close contact between the mask and the deposition substrate.

[0024] In one embodiment, a method for manufacturing a large-area patterned photocatalytic film using an electrolytic deposition method is provided, comprising: a first step of preparing a precursor solution containing a photocatalytic precursor material and a deposition substrate; a second step of receiving the deposition substrate in a space formed by a bezel ledge in the main holder of the photocatalytic electrolytic deposition mask frame and electrically connecting it to the outside; and a third step of applying voltage to the deposition substrate to deposit a photocatalyst on the deposition substrate by an oxidation-reduction reaction.

[0025] The first step corresponds to a step of preparing a precursor solution containing a photocatalytic precursor material and a deposition substrate to manufacture a large-area patterned photocatalytic film according to the present invention. Here, the photocatalytic precursor material refers to a compound capable of being converted into a photocatalyst, and means a material to be deposited on a substrate through electrolytic deposition. For example, the photocatalyst may be a copper-iron composite oxide photocatalyst. The precursor solution refers to a liquid solution containing the photocatalytic precursor material. The deposition substrate refers to a substrate made of a conductive material that serves as the surface on which the photocatalyst is deposited in the electrolytic deposition process.

[0026] The second step refers to the step of receiving the deposition substrate into a mask frame for photocatalytic electrolytic deposition immediately before voltage application. The deposition substrate is inserted into the bezel space formed by the bezel jaw in the main holder, and then the deposition substrate is connected to an external electrical circuit using an ultra-fine flame-retardant wire (e.g., AWG 30) to complete the preparation for voltage application. At this time, the deposition substrate is stably coupled to the main holder by the bezel jaw, and then a current supply device is connected to prepare for the electrolytic deposition process to proceed in the third step.

[0027] The third step is to apply voltage to the deposition substrate. When voltage is applied to the deposition substrate, the photocatalytic precursor material is oxidized, and through this, the photocatalyst is deposited on the deposition substrate. The deposition substrate acts as a working electrode, and when current flows, the photocatalytic precursor material can be converted into a photocatalyst through an electrochemical reaction.

[0028] In one embodiment, the photocatalyst may be characterized by being deposited in a large-area patterned manner according to the shapes of the first pattern hole and the second pattern hole of the mask frame for photocatalytic electrolytic deposition. The pattern holes formed in the insulating mask and the metal mask may serve to define the patterned shape. A person skilled in the art may form a deposition pattern of a desired shape by appropriately changing the size and shape of the holes of the pattern holes as needed.

[0029] In one embodiment, the photocatalytic precursor material comprises copper (Cu), iron (Fe), and an oxidizing agent to produce a copper-iron oxide composite photocatalyst. Copper and iron metals are the basic materials of the copper-iron oxide composite photocatalyst, and when they are oxidized, copper ions (Cu 2+ ) and iron ions (Fe 3+ It becomes capable of combining with oxygen to form a copper-iron complex oxide. An oxidizing agent is a substance that can oxidize copper and iron while being reduced itself, and is added to convert a photocatalytic precursor material into an active state.

[0030] In one embodiment, the oxidizing agent may include KClO4. KClO4 is a powerful oxidizing agent that can play an important role in oxidizing copper (Cu) and iron (Fe), which are photocatalytic precursor materials, to convert them into photocatalytic materials. This oxidizing agent promotes the transfer of electrons in an oxidation-reduction reaction, thereby helping to form photocatalytic materials, such as copper-iron composite oxides, on a deposition substrate.

[0031] In one embodiment, the deposition substrate may include an FTO substrate. The FTO substrate (Fluorine-doped Tin Oxide) has electrical conductivity and high transmittance and may be a substrate suitable for precisely depositing a photocatalytic film. The FTO substrate simultaneously performs the role of a working electrode in the electrolytic deposition process and can help to uniformly deposit the photocatalytic material by effectively transmitting current. In addition, the FTO substrate may provide characteristics advantageous for increasing photocatalytic efficiency in photoelectrochemical applications.

[0032] In one embodiment, the voltage application process may be characterized by using a potentiostat to apply voltage conditions of -0.30V to -0.40V to the deposition substrate. Preferably, the voltage conditions may be -0.35V to -0.38V, and most preferably -0.36V. The voltage conditions play an important role in efficiently oxidizing the photocatalytic precursor material and enabling uniform deposition. If the voltage is too low, the photocatalytic precursor material may not be sufficiently oxidized, resulting in incomplete deposition; if the voltage is too high, problems such as non-uniform deposition due to substrate damage or unnecessary side reactions may occur. Therefore, it is important to apply voltage within an appropriate voltage range.

[0033] In another aspect, the present invention provides a large-area patterned photocatalytic film comprising a deposition substrate including a conductive material, a copper-iron composite oxide photocatalyst formed on the deposition substrate, and a transparent conductive layer formed on the photocatalyst, wherein the copper-iron composite oxide photocatalyst is formed in a specific pattern on the deposition substrate.

[0034] The deposition substrate must be composed of a conductive material to effectively transmit current, and since current can flow through the substrate, it becomes possible to oxidize the photocatalytic precursor material and deposit the photocatalytic material. The copper-iron composite oxide photocatalyst is a patterned photocatalyst formed on the aforementioned deposition substrate, and it is a material with excellent photocatalytic properties capable of absorbing light, promoting electron transfer, and efficiently inducing redox reactions. Copper has excellent ability to absorb light in the visible light region, while iron has excellent ability to promote electron transfer and redox reactions. The composite oxide combining these two materials provides high efficiency and stability in photocatalytic reactions, thereby promoting chemical reactions and demonstrating excellent performance in photoelectrochemical applications.

[0035] In one embodiment, the copper-iron composite oxide photocatalyst may be characterized by being formed in a checkerboard pattern on the deposition substrate. The patterned structure can significantly improve the efficiency of the photocatalyst. In the checkerboard pattern, the copper-iron composite oxide is precisely distributed, and since each pattern hole expands the reaction surface area of ​​the photocatalytic material, the light absorption rate is increased and light scattering and reflection are reduced, thereby maximizing the efficiency of the photocatalytic reaction. In addition, the patterned structure can increase the reaction rate and promote efficient electron transfer by expanding the surface area where the catalytic reaction occurs.

[0036] In one embodiment, the deposition substrate may be a double-sided conductive substrate in which a metal conductive layer is formed on one side and a non-conductive layer is formed on the other side. Such a double-sided conductive substrate can provide a structure that allows current to flow only on a specific side while maintaining electrical conductivity. The side with the metal conductive layer acts as an electrode for supplying current, and the side with the non-conductive layer provides electrical insulation, which can help control the precise flow of current during the electrolytic deposition process.

[0037] In one embodiment, the metal conductive layer may comprise one or more metals from the group consisting of Au, Ag, Ti, Cr, Ni, and Pt, and the non-conductive layer may comprise one or more metals from the group consisting of Ni, Ti, and Pt. The metal conductive layer plays an important role in current transmission, and the non-conductive layer provides electrical insulation, thereby enabling efficient electrolytic deposition. By composing the material of each layer with the metal materials, a double-sided conductive substrate can be manufactured.

[0038] In one embodiment, the metal conductive layer may have a thickness of 5 to 100 nm. If the thickness of the metal conductive layer is too thin, sufficient electrical conductivity may not be provided, and if it is too thick, the distance between the substrate and the photocatalytic material may become too far, which may reduce the efficiency of photocatalytic deposition. Therefore, it may be important to simultaneously optimize the conductivity and photocatalytic performance of a large-area patterned photocatalytic film by setting an appropriate thickness of the metal conductive layer.

[0039] The mask frame for photocatalytic electrolytic deposition according to the present invention can solve the problems of deposition uniformity and stability of the patterning process that occurred in conventional photocatalytic electrolytic deposition processes, thereby helping to form a photocatalytic pattern on a film surface at low cost through a simple process.

[0040] The method for manufacturing a large-area patterned photocatalytic film using an electrolytic deposition method according to the present invention utilizes a mask frame for photocatalytic electrolytic deposition to increase the electrolytic deposition efficiency and improve the precision of the photocatalytic pattern, thereby enabling uniform patterning even in large-area films.

[0041] The large-area patterned photocatalytic film according to the present invention can maximize light absorption and catalytic reaction efficiency through a photocatalytic material formed on the film surface, and as a result, can be utilized in various photocatalytic applications, including the field of solar carbon dioxide conversion fuel production.

[0042] Figure 1 is a diagram showing the problems of the patterning process that occurred in the first and second generation mask frames and the process of solving them in the third generation reactor.

[0043] Figure 2 shows a photograph (left) showing the individual components of a mask frame for photocatalytic electrolytic deposition and a schematic diagram (right) showing the combined state of the components.

[0044] FIG. 3 is a photograph showing the process of manufacturing a large-area patterned photocatalyst film using a mask frame and an electrolytic deposition method according to one embodiment of the present invention, and the appearance of the large-area patterned photocatalyst film manufactured thereby.

[0045] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. As the present invention is susceptible to various modifications and may take various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention. Similar reference numerals have been used for similar components in the description of each drawing.

[0046] The terms used in this application are used merely to describe specific embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, terms such as "comprising" or "having" are intended to indicate the presence of the features, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, steps, actions, components, parts, or combinations thereof.

[0047] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0048]

[0049] In this invention, a large-area patterned film utilizing a copper-iron composite photocatalyst is developed, which can be produced using a simpler and more economical method instead of the complex existing processes. This technology is expected to maximize the efficiency required to produce solar carbon dioxide conversion fuels and provide a more cost-effective method than existing technologies, thereby enhancing the commercialization potential of photocatalyst technology and making a significant contribution to the clean energy sector.

[0050] In the present invention, the process of manufacturing a large-area patterned film utilizes an electrolytic deposition method, which refers to a method of depositing a desired metal or compound by passing an electric current through an electrolyte solution. The process using the electrolytic deposition method operates in such a way that metal ions dissolved in the electrolyte bind to the deposition substrate by the electric current, and can be used to precisely deposit metal thin films or composites onto a substrate. Since the electrolytic deposition method can be performed at a relatively low temperature while providing high accuracy and uniformity, it can be efficient for photocatalytic deposition.

[0051] A mask frame can be used in the photocatalyst manufacturing process, and it serves to facilitate the selective deposition of photocatalytic material in a desired shape during the deposition process. This allows for the formation of precise patterns on large-area films and enables the free adjustment of pattern sizes. In this process, the mask frame is appropriately positioned, and electrolytic deposition is utilized to ensure that the photocatalytic material is deposited only in specific areas.

[0052] Furthermore, the mask allows for size diversification and can be manufactured in various sizes and shapes to match the desired pattern size. Since patterns of different sizes can be formed within the same process, experimental adjustments are facilitated, and uniform patterning is possible even on large-area films. This can be advantageous for increasing cost efficiency during mass production and optimizing photocatalytic films for diverse applications.

[0053] Figure 1 shows photographs of the first and second generations of conventional photocatalytic mask frame patterning mask frames and the third generation of photocatalytic electrolytic deposition mask frames according to the present invention.

[0054] In order to pattern a photocatalyst by selectively depositing it only on specific parts, the main holder that accommodates the deposition substrate must be made of an insulating material. If the main holder is made of a conductive material rather than an insulating material, the current flow may be abnormal, causing deposition to occur on unintended areas, and a short circuit may occur at the point where the main holder and the substrate come into contact, thereby degrading the quality of the deposited film. In one embodiment, the main holder may be made of an insulating material such as acrylic. Since acrylic has no electrical conductivity and thus does not allow current to flow, using an acrylic main holder can be advantageous for controlling the current flow to only the deposition substrate area during the electrolytic deposition process.

[0055] Here, it can be seen that the conventional mask frames of the first and second generations shown in Fig. 1 consist simply of a mask and a main holder. Since the acrylic main holder does not have high strength, it can deform when subjected to mechanical force. In this case, when the components are joined by fastening means, a problem arises where the deposition substrate accommodated in the main holder lifts up, making it difficult to place the deposition substrate flat. Consequently, the adhesion rate between the mask and the deposition substrate becomes poor. When the adhesion rate between the mask and the deposition substrate is poor, bubbles form in the space between the mask and the deposition substrate. These bubbles form an air layer between the mask and the deposition substrate, which can cause the area to not be deposited or to be deposited unevenly. As a result, the conventional mask frames of the first and second generations suffer from reduced patterning accuracy and degraded photocatalytic performance due to bubbles; in severe cases, this can lead to substrate damage and process instability, which can adversely affect the overall deposition quality.

[0056] To solve these problems, the present invention aims to increase the adhesion rate between the substrate and the mask and minimize bubble generation by introducing an additional configuration. Each configuration of the mask frame for photocatalytic electrolytic deposition according to the present invention, such as the third generation, will be explained through Figure 2 below.

[0057] On the left side of FIG. 2, the five components of the mask frame for photocatalytic electrolytic deposition according to the present invention can be seen disassembled. The numbers in the photograph are numberings to distinguish each component, where 1 represents the main holder, 3 represents the insulating mask, 4 represents the metal mask, 5 represents the first metal border frame, and 6 represents the second metal border frame.

[0058] Referring to the right side of FIG. 2, a mask frame for photocatalytic electrolytic deposition according to the present invention is shown in a combined state. Based on the bottom surface, the second metal frame (6), main holder (1), insulating mask (3), metal mask (4), and first metal frame (5) are arranged in that order, and then the fastening holes of each component are arranged to correspond to each other, and can be firmly joined together through fastening means such as screws or rivets.

[0059] A bezel ledge may be formed along the edge of the main holder (1) to accommodate a deposition substrate such as FTO. A bezel space is formed by the bezel ledge formed along the edge, and a deposition substrate can be accommodated in this bezel space. At this time, in order to fully accommodate the deposition substrate, the height of the deposition substrate must not be higher than the height of the bezel ledge, so the height of the bezel ledge must be higher than or at least equal to the height of the deposition substrate.

[0060] In this invention, by combining high-strength metal rim frames vertically, the insulating mask and the metal mask are designed to be stably and completely joined, thereby preventing deformation of the substrate while it remains fixed, even when secured by fastening means. This helps to keep the FTO electrode stable and prevent it from lifting during the deposition process. Since the close contact between the mask and the substrate is continuously maintained, bubbles do not form during the deposition process, enabling precise patterning.

[0061] Hereinafter, the method and principle of electrolytic deposition of a photocatalyst using a mask frame for electrolytic deposition of a photocatalyst according to the present invention will be explained.

[0062] The photocatalytic electrodeposition method used in the present invention utilizes the principle of depositing metal ions onto a substrate using an oxidation-reduction reaction by passing an electric current through an electrolyte solution. Through this method, large-area patterned photocatalytic films can be fabricated, and it is based on a three-electrode electrodeposition synthesis method. A three-electrode electrodeposition synthesis method is a method of performing electrodeposition using three electrodes: a working electrode, a counter electrode, and a reference electrode. In the present invention, the working electrode refers to the electrode used to induce the desired reaction and signifies the deposition substrate itself connected by wires; in the embodiments of the present invention, an FTO electrode was used. The counter electrode is the electrode that completes the flow of current, and in the embodiments of the present invention, a platinum mesh (Pt mesh) was used. Finally, the reference electrode is the electrode that provides a reference point for potential measurement, and an Ag / AgCl electrode was used.

[0063] According to one embodiment of the present invention, the photocatalyst to be prepared is a copper-iron composite oxide photocatalyst, and an electrolyte solution containing copper ions and iron ions must be prepared. Accordingly, the electrolytic deposition process in the embodiment according to the present invention was carried out by preparing a solution containing 4 mM copper metal (Cu), 12 mM iron metal (Fe), and 50 mM oxidizing agent in the electrolyte solution, and then applying a potential of -0.36 V to the FTO substrate. Here, the oxidizing agent is a substance that induces oxidation of the deposition material while being reduced itself in an oxidation-reduction reaction, and KClO4 was used in the embodiment of the present invention.

[0064] Subsequently, a desired voltage was applied to the working electrode using a potentiostat; in the embodiment of the present invention, electricity was applied under conditions of a voltage of -0.36 V and a current of -2 mA. When voltage is applied to the working electrode, electron transfer occurs due to an oxidation-reduction reaction on the surface of the working electrode, and as a result, copper and iron metals are oxidized on the surface of the working electrode, forming copper ions (Cu 2+ ) and iron ions (Fe3+ It becomes a copper-iron composite oxide by combining with oxygen, and by depositing this copper-iron composite oxide photocatalyst on the surface of the working electrode, the photocatalyst can be formed on the surface of the working electrode.

[0065] A copper-iron composite oxide photocatalyst can be formed into a specific pattern by a mask of a mask frame for photocatalytic electrolytic deposition. The shape of the pattern is determined by the shape of the pattern holes in the mask, and according to one embodiment of the present invention, the pattern holes of the mask are formed in a checkerboard format with orthogonal arrangements in a square shape. As a result, the shape of the copper-iron composite oxide formed on the deposition substrate is also patterned in a checkerboard format with orthogonal arrangements in a square shape. This enables the fabrication of a photocatalyst patterned on a large-area film. Furthermore, when using the photocatalytic electrolytic deposition mask frame according to the present invention, bubbles are not formed during the deposition process, thereby enabling precise patterning.

[0066] The photograph on the right in Fig. 3 shows a large-area patterned photocatalytic film, through which it can be confirmed that a copper-iron composite photocatalytic pattern is precisely formed on an FTO substrate. This patterning was controlled by a mask of an electrolytic deposition mask frame according to the present invention, thereby allowing the surface of the film to be evenly patterned and covered with the deposited photocatalyst.

[0067] The film used in the present invention serves as a deposition substrate and is a film composed of a conductive material that has electrical conductivity and can be manufactured over a large area. In one embodiment, it may be preferable for the film to include FTO. To improve conductivity, the film may be a double-sided conductive substrate in which a metal conductive layer is formed on one side and a non-conductive layer is formed on the other side. Here, the metal deposited on the metal conductive layer may include Au, Ag, Ti, Cr, Ni, Pt, etc., and these metals are used by controlling their thickness within a range of 5 to 100 nm. The non-conductive layer is a layer deposited on the back side of the conductive film to control the current flow between the conductive material and the photocatalytic material to facilitate an efficient reaction, and may be selected and deposited from a group of candidates such as Ni, Ti, and Pt.

[0068] The present invention involves patterning and depositing a photocatalytic material onto a deposition substrate film and then forming a transparent conductive layer thereon. The transparent conductive layer controls the movement of electrons when a photoelectrochemical reaction occurs due to the photocatalyst and can prevent corrosion of the photocatalytic material, which is advantageous for ensuring the stability of the device.

[0069] Patterned photocatalytic films exhibit superior light absorption and catalytic reaction efficiency compared to non-patterned films. Patterned structures absorb light more efficiently and can increase the reaction rate by expanding the surface area of ​​the catalytic reaction. Patterned structures can be designed to efficiently absorb light in regions divided into uniform, fine sizes and shapes. This reduces light scattering and reflection, thereby enabling more efficient light absorption. Furthermore, patterned structures can enhance reaction rates by increasing the surface area of ​​the catalytic reaction. As the surface area of ​​each pattern expands, the reaction area of ​​the photocatalytic material is broadened, which can lead to a significant improvement in reaction efficiency.

[0070]

[0071] The mask frame for photocatalytic electrolytic deposition presented in this invention can contribute to precise patterning and improved reaction efficiency by resolving the problems of bubble formation and non-uniform deposition that may occur in existing technologies. Furthermore, it can contribute to improving reaction rates through the stable deposition of photocatalytic materials and expanding the potential for application to various photochemical reactions.

[0072] The present invention presents a novel approach for efficiently enhancing photocatalytic performance in a method for manufacturing a large-area patterned photocatalytic film using a mask frame for photocatalytic electrolytic deposition. The photocatalytic electrolytic deposition method according to the present invention enables precise patterning and large-area application through a process utilizing a mask frame for photocatalytic electrolytic deposition and an electrolytic deposition method, thereby maximizing light absorption and catalytic reaction efficiency. Furthermore, the deposition of the photocatalytic material is carried out uniformly and efficiently, enabling excellent performance in various application fields.

[0073] The technical advantages of the present invention significantly enhance the commercialization potential of photocatalytic technology for clean energy production and will establish itself as a core technology for environmental protection and sustainable energy production. Furthermore, the present invention possesses characteristics advantageous for large-area application and is expected to serve as an innovative method for manufacturing photocatalytic films in an efficient and economical manner.

[0074]

[0075] Although the present invention has been described above with reference to preferred embodiments, those skilled in the art will understand that various modifications and changes can be made to the invention without departing from the spirit and scope of the invention as set forth in the following claims.

Claims

A main holder made of insulating material having a plane on which a surface of a deposition substrate is placed, a bezel ledge on the edge of the plane having a height equal to or smaller than the thickness of the deposition substrate, and a plurality of first fastening holes formed along the edge on the surface of the bezel ledge; An insulating mask having an insulating material with a height on the bezel ledge of the main holder, wherein the insulating mask includes a second fastening hole corresponding to the first fastening hole on the edge of the insulating mask and includes a first pattern hole in the area corresponding to the plane; A metal mask made of a metal material having a third fastening hole and a second pattern hole corresponding to the insulating mask above; A first metal frame made of a metal material corresponding to the bezel ledge, comprising a fourth fastening hole corresponding to the third fastening hole and placed on the metal mask; A second metal frame made of a metal material corresponding to the bezel ledge, comprising a fifth fastening hole corresponding to the third fastening hole and positioned on the back surface of the mail holder; and A fastening means comprising a first metal rim frame, a metal mask, an insulating mask, a main holder, and a second metal rim that penetrates the first, second, third, fourth, and fifth fastening holes and firmly compresses and fastens a laminate in which the first metal rim frame, the metal mask, the insulating mask, the main holder, and the second metal rim are stacked. Mask frame for photocatalytic electrolytic deposition. In paragraph 1, The above-mentioned deposition substrate includes an FTO substrate. Mask frame for photocatalytic electrolytic deposition. In paragraph 1, The first pattern hole and the second pattern hole are characterized by a plurality of holes forming a checkerboard pattern. Mask frame for photocatalytic electrolytic deposition. In paragraph 1, The above fastening means includes screws, rivets, bolt-nuts, or clamps. Mask frame for photocatalytic electrolytic deposition. A first step of preparing a precursor solution containing a photocatalytic precursor material and a deposition substrate; A second step of accommodating the deposition substrate in a space formed by a bezel edge in the main holder of a mask frame for photocatalytic electrolytic deposition according to any one of claims 1 to 4, and electrically connecting it to the outside; A third step comprising applying voltage to the deposition substrate to deposit a photocatalyst on the deposition substrate by means of an oxidation-reduction reaction. Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. In paragraph 5, Characterized by the photocatalyst being deposited in a large-area patterned manner according to the shape of the first pattern hole and the second pattern hole of the mask frame for the photocatalyst electrolytic deposition. Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. In paragraph 5, The above photocatalytic precursor material comprises copper (Cu), iron (Fe), and an oxidizing agent, Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. In Paragraph 7, The above oxidizing agent includes KClO4, Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. In paragraph 5, The above-mentioned deposition substrate includes an FTO substrate, Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. In paragraph 5, The process of applying the above voltage is characterized by using a potentiostat to perform the process on the deposition substrate under voltage conditions of -0.30 to -0.40 V. Method for manufacturing a large-area patterned photocatalytic film using electrolytic deposition. A deposition substrate comprising a conductive material; A copper-iron composite oxide photocatalyst formed on the above-deposited substrate; and It includes a transparent conductive layer formed on the above photocatalyst, and The copper-iron composite oxide photocatalyst is formed in a specific pattern on the deposition substrate, Large-area patterned photocatalytic film. In Paragraph 11, The copper-iron composite oxide photocatalyst is formed in a checkerboard pattern on the deposition substrate. Large-area patterned photocatalytic film. In Paragraph 11, A double-sided conductive substrate having a metal conductive layer formed on one side of the deposition substrate and a non-conductive layer formed on the other side. Large-area patterned photocatalytic film. In Paragraph 13, The above metal conductive layer comprises one or more metals from the group consisting of Au, Ag, Ti, Cr, Ni, and Pt, Large-area patterned photocatalytic film. In Paragraph 14, The metal conductive layer has a thickness of 5 to 100 nm, Large-area patterned photocatalytic film.

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