TW201825567A - Antifouling film capable of extending the service life of a machine by trapping scattering ions or particles during the film deposition - Google Patents

Abstract

The present invention relates to an antifouling film for extending the service life of a machine, comprising a substrate and a target material deposited on the substrate. The method for fabricating the substrate comprises sputtering, electrolysis, evaporation, and laser. A method for fabricating an antifouling film for film deposition, comprising the following steps: providing a soft sheet for trapping scattering ions; exposing at least a portion of the soft sheet; roughening at least a portion of the soft sheet; and stripping the at least one portion of the soft sheet, wherein the treatment of roughening the at least one portion of the soft sheet comprises a surface treatment by electrolysis.

Description

Antifouling film

The present invention relates to the field of an antifouling film for film deposition (also referred to as an antifouling film, an antifouling foil, an antifouling film, or an antifouling foil), and also relates to the production and modification of antifouling films for film deposition. , Installation, assembly, maintenance, removal, replacement, recycling and use.

The film is usually a sheet with a thickness of a few nanometers or a single layer to a few microns. Controlled thin film material synthesis is a thin film deposition process that forms the basic step of many production processes. Sputter deposition is a thin film deposition process as a sputtering-type physical vapor deposition (PVD) method for producing integrated circuit electrodes and diffusion barrier films, magnetic films for magnetic recording media, and indium tin for liquid crystal display devices Oxide (ITO) transparent conductive film.

Existing sputter deposition techniques often result in the accumulation of coarse-grained particles (commonly referred to as "particles") on the produced film, which is a significant disadvantage. The "particle" is a kind of extremely fine or fine particles that are accumulated on a substrate. The final particle diameter can reach several micrometers, and its accumulation on substrates such as LSI (Large Integrated Circuit) causes short circuit, disconnection or other problems that cause the proportion of defective products to increase.

Particles are mainly produced by thin film deposition equipment, and most of them come from thin films deposited on substrates and inner walls (such as chamber walls), louvers, shields, and other parts of thin film deposition equipment and then peeled off. Particles accumulate on the substrate in a broken state and constitute a major source of pollution. However, the inner walls of thin film deposition equipment are actually very difficult to keep clean. It often takes a long time to completely clean the interior, and sometimes the cleaners (ie, cleaning technicians) do not have access at all to the inner walls of the thin film deposition equipment and the internal devices. In order to reduce the number of coarse particles on the inner wall, it is usually necessary to first use a metal to physically roughen the inner wall that is most affected by pollution such as spraying, so as to fix or trap the precipitate as a whole. This method requires careful maintenance of the equipment, and the anti-stripping effect on the sediment is still quite weak. To overcome these difficulties, antifouling materials in the form of disposable foils have been developed. According to this method, if the disposable foil is attached to the inner wall and is removed after forming (ie, depositing) a film on the substrate, the inner wall can be kept clean.

However, these disposable foils have one and the same fatal flaw. The film-forming substance deposited on the foil in place is easy to fall off, causing the film deposited on the substrate to still form particles. Experience has shown that the thicker the film-forming substance layer on the disposable foil, the more frequent the peeling phenomenon. It has also been found in practice that this phenomenon is particularly prone to occur when ceramic products such as silicide or indium tin oxide are used for the film to be deposited. In order to eliminate this peeling phenomenon, frequent replacement of the foil is required, which will seriously affect the efficiency of the film deposition operation. Another problem is that during the film formation process based on vapor growth, the large amount of pollutants floating around the substrate (especially the formation of a large number of particles) causes the quality of the film formed on the substrate to be unstable. In this case, it is very necessary to take effective measures to cover the inner wall of the film deposition equipment to prevent particles from forming on the inner wall.

This application requires the priority date corresponding to Singapore Patent Application No. 10201700127P (the submission date is January 6, 2017, and its name is "Thin Film Deposition System and Sputtering Process"). This application contains the entire contents of the priority application or related subject matter or, where appropriate, the contents of the priority application or related subject matter by reference.

This application aims to provide one or more new practical foils for thin film deposition. This application will also provide one or more new practical particle collectors (also known as "collectors") with the one or more foils for thin film deposition. This application also provides various new and practical methods for making, modifying, installing, maintaining, removing, recycling, replacing, and using the foil for one or more thin film depositions. The basic characteristics of the related invention are described by one or more independent items of the patent application scope, while the advantageous characteristics are described by the corresponding patent application scope subsidiary items. The foil can be a soft, flexible or deformable film, sheet or sheet.

According to the first case, the present application provides an antifouling film (such as a silicide film) for a thin film deposition process (ie, a sputtering process). Antifouling film can also be called antifouling film, antifouling film, antifouling sheet, antifouling layer, antifouling skin, antifouling skin or antifouling means. Antifouling film contains a soft sheet or sheet material (also known as flexible sheet, bendable sheet, soft material or flexible film, such as aluminum foil, nickel foil and other alloy foils) for capturing the tape in a vacuum chamber Positively charged argon ions or particles. After being properly handled or configured, the soft sheet can basically maintain its integrity during one or more thin film deposition processes; for example: 300 ° C, 360 ° C, 400 ° C in a vacuum (such as inside a thin film deposition chamber) or air , 465 ° C, 500 ° C, 545 ° C, 600 ° C, 668 ° C, 700 ° C, 763 ° C, 800 ° C, 857 ° C, 900 ° C, 963 ° C or higher. The "integrity" includes structure, chemical composition, shape, size, surface texture, color, certain performance characteristics, and other physical or chemical properties. For example, the "integrity" includes one or more of indicators such as structure, chemical composition, shape, size, surface texture, color, certain performance characteristics, and other physical or chemical properties. For example, if the anti-fouling film is not peeled, deformed, shrunk, or discolored on the inner wall of the sputtering chamber after one or more sputterings, it is considered to maintain good integrity. In addition, the antifouling film does not release or discharge pollutants (such as ions and gas particles) when it is exposed to high temperature or electric charges (such as positively charged as an anode) periodically or continuously.

The antifouling film may also include one or more substrates (such as composite materials), base structures (screens), substrates (such as sandwich structures), and coatings, coatings that are harmless or do not release harmful particles during thin film vapor deposition (Such as gold and silver), laminates, and adhesives. The antifouling film may also include one or more layers of iron foil (such as electrolytic iron foil) or iron alloy (iron-based alloy) foil. Electrolytic nickel foil also uses different or similar materials (substances) as coating materials, provided that the combined use or mixed use does not constitute a source of pollution during the manufacturing process (such as the sputtering process). For example, nickel foil can be plated with one of the metals that make up the alloy, or nickel foil coated with tungsten silicide can be used for molybdenum silicide deposition.

The soft sheet may include one or more layers of metal (such as a transition metal or a post-transition metal) that can be fully or partially exposed. Soft sheets can also be provided or constructed using alloys of metals or metal alloys. It is particularly worth noting that the metal contains one or more ferromagnetic materials (also known as "ferromagnets") that can be substantially close to 100% pure or in alloy form. Nickel (either pure nickel or alloy) is a ferromagnetic material.

The soft sheet material may comprise a pure metal material, an oxide of the material, or a combination of the two. Pure metals (such as nickel or Ni < ₂₈ Ni> with an atomic weight of 28) may be present on the soft sheet, that is, pure metals having a purity of more than 90%, 95%, 99%, 99.9%, 99.995% or higher. Pure metals that are essentially free of impurities or contaminants are suitable for use in sputtering processes that are more sensitive to contamination. For example, the metal layer contains nickel foil with a purity of more than 50%, 85%, or 99.9%. It exhibits a metallic luster at room temperature and in the surrounding environment, and the silver surface has a gold hue. An embodiment of a related invention provides a nickel foil having a nickel purity of more than 99.9%, the surface of which has been oxidized. Nickel oxide includes NiO (green nickel oxide), Ni ₂ O ₃ and NiO ₂ . Examples of other metals include pure tin (Sn) foil coil, pure zirconium (Zr) foil coil, pure aluminum (Al) foil coil, SUS304 stainless steel foil, pure copper (Cu) foil coil, tungsten foil, and molybdenum (Mo) Foil.

Soft sheets (i.e., flexible materials) also include one or more roughened surfaces (such as matte, rough or matte surfaces, uneven surfaces, and wrinkled surfaces). The surface roughness Ra of the oxidized surface of the soft sheet is 1.0 μm to 50 μm. The better or better case is 3.0 μm to 20 μm, and the best case is 5.0 μm to 10.0 μm. In other words, the surface roughness Ra of the oxidized surface of the soft sheet is 1.0 μm to 5 μm, and the optimized case is 2.0 μm to 4.0 μm.

The one or more roughened surfaces may include an electrolytically treated surface (such as an electrolytic nickel foil or surface), an oxidized surface, or a combination of the two. The one or more roughened surfaces may also include a sandblasted surface. The one or more roughened surfaces may further include a laser or laser beam treatment surface.

The roughened surface includes an uneven surface including fine grains, wrinkles, irregularities, embossing, concave portions, or a combination of any of the foregoing.

The embodiments of the present application or the uneven surface include convex portions (such as embossed or embossed, convex), concave portions or a combination of convex portions and concave portions. For example, the convex and concave portions (ie, pits, depressions, dimples, and grooves) are adjacent to each other to form a grainy uneven surface, whether in a regular or irregular form, whether it is aligned linearly, With checkered markings.

Soft sheet thicknesses range from 1µm to 1mm. For example, the average thickness of a soft sheet is 10µm ~ 750µm, 15µm ~ 550µm, 18µm ~ 300µm, 30µm ~ 200µm, 40µm ~ 100µm or a combination of any of the above thickness ranges.

Soft sheets can be disposable or recyclable materials. For example, a soft sheet can be disposed of after being sputtered in a vacuum chamber for a predetermined number of times (for example, 10 times, 50 times, 100 times, and 500 times). For example, soft sheets can be cleaned or treated (using the recommended electrolytic process) after multiple film depositions. The cleaned or treated soft sheet is cleaned or reconditioned for reuse in film deposition.

The antifouling film may include a predetermined characteristic (such as shape, size, and boundary) for attachment to a thin film deposition apparatus. For example, antifouling films can come in the form of a roll, similar to aluminum foil (aluminum foil that is mistaken for tin foil). Of course, the antifouling film can be rectangular, square, circular, circular oval, or any combination of these shapes.

The present application also provides a set of thin film deposition equipment (such as a thin film vapor growth system or device) equipped with a vacuum chamber or a sputtering chamber. The thin film deposition equipment includes a cover (anode cone, louver, substrate cover, and target cover), and one or more parts of the cover surface are covered by an antifouling film. For example, the inner surface of the vacuum chamber wall or the inner wall surface is partially or completely covered with an antifouling film. The thin film deposition equipment also includes a fixed frame (also known as a "positioning frame") for fastening the thin film growth substrate and one or more sputtering sources (such as magnetrons) so that charged plasma particles are always located on the sputtering target Near the surface. The enclosure contains a vacuum-tight or hermetically sealed container with a side wall surrounding a holder or more sources of sputtering. One or more parts of the inner surface of the container wall are covered by an antifouling film.

In some cases, the antifouling film is detachably attached to the inner surface of the container. In other cases, one or more parts or the inner surface of the wall of the device includes a surface covered by a first antifouling film or a first inner surface, and a second surface or inner surface is covered by a second antifouling film . Thin film deposition equipment parts are covered by multiple antifouling films, which can have different profiles, product specifications, performance indicators or other characteristics. The parts or surfaces that require a stronger pollutant absorption capacity are covered or covered by a higher performance antifouling film. Sites or surfaces less affected by contaminants can be reused, recycled, or used fewer times during film deposition.

According to a second aspect, this application provides a method for making an antifouling film for thin film deposition. The method includes four steps: the first step is to provide a soft sheet for capturing scattered ions; the second step is to expose at least a part of the soft sheet; the third step is to perform the surface of one or more parts of the soft sheet Roughening treatment; in the fourth step, the soft sheet is detached at least in part. Some of these steps can be combined, split, or reordered. For example, the second step of exposing one or more portions of the soft sheet and roughening the surface of the one or more portions of the soft sheet can be achieved by performing one or more electrolytic cycles on the soft sheet. The antifouling film helps to achieve a high-efficiency and high-quality film deposition process, because it can effectively absorb or trap loose particles during longer processes, even at higher or loop temperature conditions.

The surface roughening of one or more portions of the soft sheet may include surface treatment using an electrolytic process or electrolysis. The electrolytic process or electrolysis can provide a uniform rough surface, and its surface roughness can be adjusted accurately or precisely.

Surface roughening of one or more portions of the soft sheet may include forming one or more surface structures on the surface of one or more portions of the soft sheet. One or more surface structures include grooves, pits, embossing, or any other visible or invisible surface texture.

The method may include oxidizing one or more partial surfaces of the soft sheet. This method can also electrolyze one or more partial surfaces of the soft sheet, thereby producing an electrolytic surface (such as copper, nickel, or iron) or an electrolytic material (such as electrolytic copper, electrolytic nickel, or electrolytic iron).

This method can also attach a substrate to a soft sheet. A substrate contains a base structure, a substrate, a coating (ie, "coating"), a plating layer (ie, "plating"), a layer of laminate, or a harmless or harmful substance that is not released to the film during vapor deposition An adhesive layer of particles. The additional structural support provided by the substrate prevents the antifouling film from peeling or being heated and cooled in the loop.

According to a third aspect, the present application provides a method for using an antifouling film for a thin film deposition process. The first step of the method is to provide an antifouling film or the antifouling film described above; the second step is to provide a thin film deposition equipment; the third step is to detach the antifouling film to (such as spot welding (Or precision spot welding) on the walls of thin film deposition equipment. Some of these steps can be combined, split, or reordered. Use the antifouling film method to remove a spent or used antifouling film and attach a new antifouling film to the wall of a thin film deposition device such as an anode cone, collector, or particle collector. Used antifouling films can be recycled (eg, cleaned or refurbished) and then used for film deposition or other processes.

This method can also be used for thin film deposition (eg, sputtering) using an antifouling film. After several thin film depositions, the used antifouling film is sometimes removed from the wall of the thin film deposition equipment and can be subsequently treated. Used antifouling films can be replaced with new, new (ie, unused) antifouling films that have been cleaned or reworked.

The method may further include treating (eg, cleaning) the device wall before or after the antifouling film is attached. Equipment walls (such as the inner walls or surfaces of thin film deposition equipment) can be roughened, oxidized, sandblasted, or polished to improve the adhesion of antifouling films.

Method embodiments also include using a substrate or attaching (ie, fixing) it to a soft sheet to provide an antifouling film. Substrates help to enhance structural integrity or reduce the cost of antifouling films. For example, the antifouling film includes a metal plate with a nickel layer (such as stainless steel foil). The metal plate and / or nickel layer may be subjected to other treatments (such as oxidation and electrolysis) before being attached to the interior of the vacuum chamber for thin film deposition.

According to a fourth aspect, the antifouling film (that is, an antifouling method) provided by the present application supports a target through a substrate (such as a substrate), and the target (or target) on the substrate generates an irregular surface. The target and substrate can be made of the same material (for example, nickel). One or more surfaces of the substrate (eg, two surfaces on both sides) may be irregular or uneven surfaces. The substrate can be made of a flexible or soft material for attachment to one or more uneven surfaces or parts (such as a machine or other applicable part).

According to a fifth aspect, the present application provides a method for producing an antifouling film based on sputtering. The first step of the method is to fix the substrate to a fixed frame (ie, a positioner); the second step is to place the target on one or more ejectors (such as a magnetron); the third step is to empty the surrounding fixation The fourth step is to fill the chamber with a process gas or an inert gas (such as argon); the fifth step is to energize one or more ejectors to generate a magnetic current. Some steps in the above method can be combined, divided, or adjusted.

According to a sixth aspect, the present application provides a method for producing an antifouling film based on electrolysis. The first step of this method is to treat the surface of a substrate (such as nickel foil); the second step is to immerse the substrate in an electrolyte solution (such as nickel sulfate and ammonium sulfate); the third step is to immerse another electrolyte solution (such as nickel sulfate, boric acid and chlorine The new surface of the substrate is processed in nickel); the fourth step is to put the substrate in an oven to dry. Some steps in the above method can be combined, divided, or adjusted.

According to a seventh aspect, the present application provides a method for producing an antifouling film based on evaporation. The first step of this method is to attach the substrate to the holder; the second step is to heat the target (such as nickel) to its boiling point (ie 2730 ° C); the third step is to evaporate the target (such as nickel) to the fixed On the base plate on the rack (ie the positioner). Some steps in the above method can be combined, divided, or adjusted.

According to an eighth aspect, the present application provides a laser-based antifouling film production method. The first step of the method is to place the substrate (such as nickel foil) on the porous metal on the chuck; the second step is to place the main foil on the substrate; the third step is to place the polyimide foil on the main plate Above the foil; the fourth step is to evacuate; the fifth step is to project the laser onto the substrate or the main foil, or both. Some steps in the above method can be combined, divided, or adjusted. Multiple substrates can be arranged vertically with a partition (such as non-metal materials such as paper) between each substrate. Some steps in the above method can be combined, divided, or adjusted. The substrate can be stored on related parts. This method can also use mechanical means (such as end effector gripping or vacuum suctioning) to transport the substrate.

According to a ninth aspect, the present application provides a metal foil for thin film deposition. The foil includes a ferromagnetic material (such as iron, cobalt, nickel, and thallium) to attach to the sputtering equipment during the sputter deposition process and to capture particles that escape during gas phase growth. The thickness of the metal foil is about 0.1 mm, and one surface of the foil is roughened. Ferromagnetic materials include nickel (Ni) or nickel alloys, such as permalloy, nickel chromium constant elastic steel, invar, nickel iron, nickel cast iron, nickel brass, nickel bronze, and copper, chromium, aluminum, lead, and cobalt , Silver and gold alloys (e.g. Inconel, Inconel stainless steel, Monel and Inconel titanium). Rough surfaces can be electrolyzed. The metal foil may include protrusions or projections on the electrolytic side or surface. The protrusions may include fine particles that cannot be recognized by the naked eye (only a matte surface is seen), or the surface roughness Ra ranges from 5 to 20 μm. Part of the fine particles are bumps or protrusions with a size not exceeding 100 µm. One or more portions of the metal foil may be oxidized. Metal foil can be disposed of separately from thin film deposition equipment components such as particle collectors, such as indivisible sheets; therefore, metal foil is a disposable foil.

According to a tenth aspect, the present application provides a sputtering deposition apparatus equipped with one or more particle collectors. At least one particle collector is connected to the power anode; the particle collector can be conical or any shape that facilitates the installation of equipment parts.

According to an eleventh aspect, the present application provides a method for manufacturing a foil for thin film deposition. The first step of the method is to provide a ferromagnetic material (such as iron, cobalt, nickel, and thallium); the second step is to attach the ferromagnetic material to a thin film deposition equipment part to capture scattering particles during the thin film deposition process. When ferromagnetic materials are attached to thin film deposition equipment components, ferromagnetic materials can be welded (such as precision spot welding) to thin film deposition equipment components. This method can also electrolyze ferromagnetic materials before attaching them to parts of thin film deposition equipment, such as sputtering deposition equipment. This method can also roughen the ferromagnetic material before attaching it to a thin film deposition equipment component. This method can also emboss the ferromagnetic material before attaching it to a thin film deposition equipment part.

The one or more foils may include one or more nickel foils that can be used in copper and non-copper thin film deposition equipment and sputtering processes. Scattered particles are easily captured by a particle collector covered or made with nickel foil during the thin film deposition sputtering process. The nickel foil covers the particle collector to form a nickel particle collector for non-copper thin film deposition. Nickel particle collectors have greater particle absorption and last longer during film deposition. The one or more nickel foils have circular convex patterns, which facilitates the expansion of the surface area of the one or more nickel foils and can be used in non-copper thin film deposition processes. Nickel foil has a stronger absorption capacity than copper foil, so it can trap more particles during film deposition. Nickel foil can also withstand high temperatures. For example, the melting point of nickel is 1455 ° C, which is 370 ° C higher than the melting point of copper. In addition, the thermal expansion rate of the nickel material is also lower than that of the copper material. The maximum working temperature of nickel foil is usually around 600 ° C, which is 200 ° C higher than copper foil.

Nickel foil for film deposition has stronger particle absorption capacity, is more durable, and has a longer life during film deposition. Nickel foil is particularly suitable for non-copper thin film deposition processes. Due to the excellent properties of nickel foil, the use of nickel foil for film deposition enables the development of advanced semiconductor manufacturing processes.

The antifouling film provided by the present application includes: 1. a treated electrolytic nickel foil; 2. a treated electrolytic nickel foil coated with and deposited as a thin film by vapor phase growth on a substrate The same or harmless and similar material; 3. a wrinkled metal foil; and 4. a metal foil with many irregularities (ie pits and embossing).

The present application also provides a thin film deposition device based on vapor phase growth, which is characterized by: using an antifouling method to prevent contamination of internal devices of the device and forming particles in the deposited film; optional methods include: (1) electrolytic nickel foil or through nickel foil Nickel foil with matte surface nickel plating to form a thin layer of nickel or / and nickel oxide fine particles; (2) A nickel foil or electrolytic nickel foil that is formed by nickel plating of the foil matte surface to form nickel or / and nickel oxide fine particles. Layer, the material of the plating layer is the same as the material of the precipitation film to be made by the substrate vapor phase growth or harmless and similar to it; (3) a wrinkled nickel foil; (4) a number of irregularities of nickel produced by embossing Foil. This application also provides an antifouling method for thin film vapor deposition equipment, which is selected from the above range (1) to (4). This application also uses the antifouling film to prevent the device from contaminating and forming particles in the deposited film inside the device.

According to a twelfth aspect, the present application provides a thin film deposition system or device based on vapor phase growth. The system uses appropriate antifouling methods. The antifouling method includes a treated electrolytic nickel foil with fine particles of nickel, nickel oxide, or a mixture of nickel and nickel oxide, and precipitation is achieved by nickel plating on a large number of raised areas on the matte side of the electrolytic nickel foil. Contamination of devices in the system and formation of particles in deposited films can be avoided, reduced or mitigated. The surface roughness Ra of the matte surface of the electrolytic nickel foil ranges from 5 to 10 μm. The treated electrolytic nickel foil (namely, the foil) may have fine particles on one side, which are used to capture the particles scattered during the gas phase growth process. The foil can be a treatable electrolytic nickel foil and the system can be a sputtering system.

The system embodiment employs an appropriate antifouling method. The antifouling method includes a treated electrolytic nickel foil with fine particles of nickel, nickel oxide, or a mixture of nickel and nickel oxide, and precipitation is achieved by nickel plating on a large number of raised areas on the matte side of the electrolytic nickel foil. The material of the foil coating is the same as or non-harmful and similar to the material of the precipitation film that is to be produced by vapor growth of a substrate (such as a silicon wafer), thereby preventing contamination of internal devices of the system and formation of particles in the deposited film. The surface roughness Ra of the matte surface of the electrolytic nickel foil ranges from 5 to 10 μm. One side of the foil can have fine particles, which are used to capture the particles that escape during the gas phase growth process.

Nickel foil can have fine particles of nickel, nickel oxide, or nickel and nickel oxide, which are precipitated on the surface of nickel foil by nickel plating. The material based on vapor phase growth or substrate can be the same or A harmless and similar coating. The antifouling material can be covered by spot welding to one or more devices inside the system (such as a sputtering system).

The non-limiting exemplary embodiment of this application will now be described with reference to the above drawings.

Figure 1 illustrates the application of a nickel foil in a sputtering chamber. The sputtering chamber refers to the sputtering chamber 100. The sputtering chamber 100 shown in the figure has been removed with a hinged hemispherical door and uses concentric high-polished thick steel walls. The inner surface of the concentric steel wall is covered by an antifouling film 102, as shown in the shaded part in the figure. The antifouling film (ie, the antifouling layer) 102 is basically made of nickel having a purity of more than 99.9%, so it is also called "nickel foil".

Three magnetrons are provided at the base of the concentric wall of the sputtering chamber 100. Each magnetron 104 is supported by a bracket, and the opposite side faces the fixed frame 108. The target 106 is placed on the "opposite side". Three magnetrons 104 are placed in a triangular structure at equal distances laterally. The inclination of the magnetron 104 can be adjusted manually and independently, or remotely by means of a microcontroller.

The fixing frame 108 is located on the opposite side of the magnetron 104, that is, near the top region of the concentric wall. The fixed frame 108 is then connected to the rotating main shaft 110. The rotating main shaft 110 is connected to a concentric wall at the top end. The fixing frame is suspended in the sputtering chamber 100 like a ceiling fan to some extent. The fixing frame 108 is provided with at least two grasping arms 112 on the surface facing the three magnetrons 104. The grasping arm 112 is fastened to the base plate 114.

There are three valves at the opposite end of the 100 door of the sputtering chamber. The valves are aligned straight and slightly inclined to the top. An intake valve 116 is provided on the left, an exhaust valve 118 is provided in the middle, and a processed gas intake valve 120 is provided on the right.

FIG. 2 illustrates the embossing principle of the electrolytic foil 140 of the nickel foil 142. The nickel foil 142 shown in the figure is a disc that is one millimeter (1 mm) thick and has a diameter of about one hundred millimeters (100 mm). The upper left schematic diagram shows the round nickel foil 142 from a side view and a three-dimensional view. After that, the first arrow 166 points to the first step. The first step is a surface treatment 174 of the nickel foil 142. Thereafter, a second arrow 168 points to the second step: providing an irregular surface treatment 176. Thereafter, the third arrow 170 points to the third step "curing" 178. Thereafter, the fourth arrow 172 points to the fourth step "hardening or strengthening 180".

Specifically, the nickel foil 142 is immersed in a first container 144 containing hydrochloric acid 146 (HCl). The hydrochloric acid-treated nickel foil 148 is then transported to a second container 150 containing a solution of nickel sulfate and ammonium sulfate 152.

The second container 150 also has two metal electrodes 154 inserted into a solution of nickel sulfate (NiSO ₄ ) and ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) 152. The two electrodes 154 are connected to a DC (direct current) power source (not shown). DC power supplies have positive and negative poles. The positive electrode is connected to the first electrode 154 on the left side of the second container 150. The negative electrode is connected to the second electrode 156 on the right side of the second container 150. The two electrodes 154 and 156 are supported by a holder (not shown) which suspends the two electrodes 154 and 146 in the solution. When a certain potential is applied to the electrodes 154 and 156 immersed in the solution, the nickel foil 142 obtains an irregular surface. A solution is an electrolyte that produces a conductive solution when dissolved in a polar solvent such as water (H ₂ O) mixed with nickel sulfate and ammonium sulfate 152 solutions. The dissolved electrolyte is separated into cations and anions. The solution is electrically neutral. The solution is electrically neutral. If a potential is applied to the solution, the cations in the solution will be directed to the cathode (positive electrode) with a greater number of electrons, and the anions will be directed to the anode lacking electrons (that is, negative (Electrode). Anions and cations move in opposition to each other in solution to generate a current.

Nickel sulfate is a highly soluble blue salt that is mainly used in electroplating. The nickel sulfate aqueous solution reacts with sodium carbonate to produce nickel-based catalyst and pigment precursor nickel carbonate. Ni (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O precipitated by adding ammonium sulfate to a concentrated aqueous solution of nickel sulfate, namely nickel ammonium sulfate. This blue solid is similar to the Mohr salt, and Fe (NH ₄ ) ₂ (SO ₄ ) ₂ .6H ₂ O is also called ferrous ammonium sulfate. A precipitate 158 forms on the surface of the nickel foil 142, resulting in an irregular surface. The surface includes a top surface and a periphery of the nickel foil 142. However, if the nickel foil 142 is suspended in the solution and supported by a holder (not shown), the nickel foil 142 will completely cover the precipitate.

Then, the precipitated nickel foil 160 is transported to a third container 162 containing nickel sulfate (NiSO ₄ ), boric acid (H ₃ BO ₃ ), and nickel chloride (NiCl ₂ ) 164. The third container 162 has another set of electrodes 154 and 156 connected to a DC power source. The irregular surface of the nickel foil 160 with nickel ammonium sulfate is cured in a third container 162.

Boric acid is included in the nickel foil plating formulation. In one of the formulations, the ratio of boric acid (H ₃ BO ₃ ) to nickel sulfate (NiSO ₄ ) is about 1:10, and there is a very small amount of sodium lauryl sulfate and a small amount of sulfuric acid (H ₂ SO ₄ ). Nickel chloride solution is used to electroplate nickel onto other metal items. A new nickel layer is plated on the irregular surface of the nickel foil. Then, the newly nickel-plated nickel foil layer is dried in an oven 182 to achieve hardening or strengthening 180.

FIG. 3 is a schematic diagram of embossing the nickel foil 142 by the precipitation 200. The nickel foil 142 is a base plate 114 which is fixed by suction by a fixing frame (not shown). The fixed frame (ie, the positioner) is connected to the rotating main shaft 110. One end of the rotating main shaft 110 is connected to a stepping motor 208. The evaporation source 202 is disposed below the substrate 114. The nickel foil 142 is inclined toward the evaporation source 202. The evaporation source 202 contains nickel, and the evaporation water vapor 204 (shown by the upward three-directional thick arrow) rises to the surface of the nickel foil 142. The evaporated water vapor 204 condenses on the surface of the nickel foil 142 to form an irregular inclined column 210, as shown by the circled line in the enlarged view. The reason for the irregular body 210 is that the evaporated water vapor 204 randomly arrives on the surface (nickel foil). The sizes of the adjacent columns 210 are different, and because some of the columns 210 block the contact between the adjacent columns 210 and the evaporated water vapor 204, the growth of the latter is reduced. Nickel is deposited on a substrate 114 in a vacuum chamber (not shown). The vacuum chamber base pressure is approximately 6.7x10 ^-5 Pa. The nickel deposit is approximately one micron (1µm) thick. The length of the contact time with the evaporation source 202 affects the thickness of the nickel deposition layer.

Figure 4 depicts a schematic cross-sectional view of a laser engraving 250 arrangement. A piece of one to two millimeter (1 to 2 mm) thick solid nickel sheet having a diameter of about twenty millimeters (20 mm) was used as the workpiece 252. The workpiece 252 manufacturing steps include sawing, soft annealing, and subsequent surface polishing. A nickel foil having a thickness of about three micrometers (3 μm) was used as the main foil 254 as a template. The main foil 254 grid perforation size is approximately 100µm x 100µm. The gap between adjacent squares is two micrometers (2µm).

A solid nickel workpiece 252 is mounted on the vacuum chuck 256. After that, a nickel foil (main foil) 254 covers the workpiece 252. A 25 micron (25µm) thick polyimide foil 258 covers the vacuum chuck 256, the main foil 254, and the workpiece 252. After the vacuum pump 266 is turned on, the polyimide foil 258 seals the chuck 256, and then the nickel foil 254 and the workpiece 252 are firmly pressed together. The exhausted air passes through the vacuum chamber 264 under the suction of the vacuum pump 266. Then, the polyfluorene imide foil 258 is irradiated with a fluorinated excimer (excitation complex) laser 260. Polyimide foil 258 is a synthetic resin with high heat resistance.

The pulse length of the built-in KrF excimer (excitation complex) laser 260 for laser irradiation is 25 nanoseconds (25ns) and the wavelength is 248 nanometers ( 248nm). The workstation also includes a beam-shaping and homogenizing optics to form a flat top beam pattern within a 100µm x 100µm laser spot. The laser beam scans the surface of the polyimide by means of a programmed x-y-z stage. The laser repetition rate is fixed at a frequency level of one hundred hertz (100Hz).

The size of the micro-embossed drawing area is limited by the size of the laser spot. The number of pulses applied to form a mark at one point is estimated to be about twenty or more. This number of pulses cannot drill through the polyimide foil 258, and finally a polyimide layer of about 1 μm will remain, which is enough to protect the upper nickel foil 254 from the thermal shock of the laser pulse. Therefore, the polyimide foil 258 together with all the pollutants and debris generated by laser ablation can be easily removed after the embossing is completed, thereby preventing the debris from contaminating the workpiece 252 or the main nickel foil 254.

The applied laser pulse is absorbed by the polyimide foil 258, and the polyimide foil 258 is laser ablated to form a plasma plume. The momentum generated by the expanding plasma and the shock wave caused by the thermal process is sufficient to press the structured main foil 254 into a lower nickel sheet 252.

The purpose of making the irregular surface of the nickel foil 142 and placing it on the surface of the sputtering chamber 100 is to extend the service time of the sputtering chamber 100 before the next maintenance. Sputtered nickel foil 142 with an irregular surface is applied to the chamber walls and components in the sputtering chamber 100.

From a functional perspective, the front part of the sputtering chamber 100 shown in FIG. 1 is made of steel, and can withstand the atmospheric pressure applied when the inner chamber lacks air or is evacuated. The cylinder and the two hemisphere endpoints achieve a uniform pressure distribution. FIG. 1 illustrates the application of the nickel foil 142 and the process of obtaining the nickel foil 142 by sputtering.

The sputtering chamber 100 needs to maintain a controlled environment during the sputtering process. This environment is actually a vacuum inner chamber, so it is also called a "vacuum chamber". The base pressure of the vacuum inner chamber is approximately 10 ^-6 bar. The vacuum inner chamber provides a clean environment without any suspended matter and invisible charged ions and particles. The sputtering chamber is exhausted through the exhaust valve 118 and filled with argon gas through the processed gas inlet 120. Argon is an inert element suitable for high temperature working environments such as sputtering. Argon prevents oxidation and combustion of internal parts.

The magnetron 104 contains an electromagnet that operates based on current. Power can come from the power grid. The electromagnet is coated with a waterproof material to prevent corrosion and electrical shorts. The inner cavity of the magnetron 104 cools the sputtering process with water. The cooling water may be tap water, so the magnetron 104 needs to be connected by a conduit, and water inflow and outlet water are realized at different positions of the magnetron 104. Free electrons continue to hit argon atoms during sputtering, thereby forming positive argon ions. The positively charged argon ions collide with the target on the magnetron 104. The target 106 nickel is negatively charged and can attract argon mobiles. Attraction causes argon ions to bombard nickel ions. The bombardment momentum caused the nickel ions to turn toward the substrate 114 suspended on top of the inner chamber. The substrate 114 is a type of nickel foil 142, and the surface of the nickel foil 142 can be made irregular by coating nickel ions.

The disc-shaped nickel foil 142 having a thickness of about one millimeter (1 mm) and a diameter of about one hundred millimeters (100 mm) is only an example. Setting a larger thickness ensures proper strength during embossing or making irregular surfaces. Too small foil thickness makes embossing impossible. The substrate 114 is a nickel foil 142 shown in FIG. 1 and may be the same size.

Hydrochloric acid 146 (HCl) in the first container 144 removes impurities from the surface of the nickel foil 142 (surface treatment step 174). Then, the treated nickel foil 148 is immersed in a second container 150 containing an electrolytic solution (composed of nickel sulfate and ammonium sulfate 152). Nickel sulfate is used for nickel plating on the nickel foil 142. Adding ammonium sulfate produces crystals on the surface of the nickel foil 142. This is the irregular surface treatment stage 176. Then, the roughened nickel foil is immersed in the third container 162 to strengthen the rough surface or achieve curing 178. Finally, the coating is hardened or strengthened 180 by baking in an oven 182.

Figure 3 depicts the evaporation process of nickel. The evaporated nickel condenses on the lower temperature surface of the nickel foil 142, and a column 210 is formed above it. The nickel foil 142 is continuously rotated to uniformly distribute the evaporated nickel from the evaporation source 202 below.

FIG. 4 illustrates a method of embossing a nickel foil 142, that is, using a laser beam to burn through the main foil 254 covered thereon. The vacuum chamber 264 causes the nickel foil 142 to be sucked up from the bottom side by the porous metal 262.

In a method for using the antifouling film 102 based on a sputtering process (that is, an antifouling method or an antifouling method), firstly, the substrate 114 is fixed to the fixing frame 108. This example refers to the substrate 114 in the nickel foil 142. The fixed frame 108 (ie, the positioner) is connected to a rotary main shaft 110 driven by a rotary motor 208. Then, the target 106 is placed on at least one magnetron 104. The target 106 is nickel. The vacuum chamber then achieves a clean, controlled environment by removing air. Then, the processed gas (argon) was refilled into the vacuum chamber. Next, at least one magnetron 104 is energized to form a magnetic current. The magnetic current ionizes the argon atoms, generating positively charged argon ions. Argon ions bombard the negatively-charged target material 106 onto the substrate 114. Finally, nickel foil 142 generates nickel precipitation, forming an irregular surface.

An antifouling method based on electrolysis 140, the first is to remove impurities (oxides or particles) by treating the surface of the nickel foil with hydrochloric acid 146. Then, the nickel foil 148 treated with hydrochloric acid was immersed in a solution of nickel sulfate and ammonium sulfate 152, and a precipitate 158 was generated on the surface of the nickel foil 142. The newly formed surface is then cured 178 in a solution of nickel sulfate, boric acid, and nickel chloride 164. In the second and third steps, the electrodes 154 and 156 are energized to achieve over-plating on the surface. Finally, the nickel foil is hardened and strengthened 180 in an oven 182.

An antifouling method (ie, an antifouling film or an antifouling method) based on evaporation 200, firstly, a nickel foil 142 or a substrate 114 is connected to a fixed frame by a rotating main shaft 110 driven by a stepping motor 208. Then, a piece of nickel is heated to a boiling point of 2730 ° C, so that the nickel is evaporated onto the nickel foil 142 at the fixed frame. The process takes place in a clean and controlled vacuum chamber. Parts and components can withstand high temperatures.

A laser-based antifouling method is to first place a nickel foil 142 (also known as a workpiece 252) on a porous metal 262 on a vacuum chuck 256. The perforations on the porous metal 262 enable the vacuum chamber to suck the nickel foil 142 to the bottom of the porous metal 262 (ie, the main nickel foil or the main foil). Then, the main nickel foil 254 is placed over the nickel foil 142. The main nickel foil 254 is perforated. The spacing between adjacent holes is the same. The main foil 254 serves as a template for the laser 260 burn-through operation, and also prevents the nickel foil 142 from being contaminated with nickel from the nickel foil 142. Next, a polyimide foil 258 is placed over the main nickel foil 254. When the vacuum pump 266 is activated, the polyimide foil 258 can provide a safe underlying structure. Polyimide foil 258 can also withstand high temperatures. Finally, the laser 260 passes through the polyimide foil 258 and the main nickel foil 254 and impacts the nickel foil 142. The laser 260 impacts the nickel foil 142 with a predetermined strength without causing perforation. The impact point of the laser 260 forms a notch. The impacted points contrast with the unimpacted surface, creating an irregular surface.

A nickel foil packaging method: substrates 114 are arranged vertically, and a partition is placed between adjacent substrates 114. The separator should be a non-metallic material such as paper. Using paper is both economical and environmentally friendly. The base plate 114 can be packed in a hard case made of Perspex plexiglass or the like in packages of 12 pieces each. In addition, the hard box can also use a slot structure to receive the substrate 114 to avoid direct contact between adjacent substrates 114. The vertical arrangement can ensure that the surface treatment of the substrate 114 is not damaged during transportation.

A method of using nickel foil 142: the substrate is stored on the surface of the relevant component, and then spot welding is performed on it. The substrate 114 is generally mainly used for the surface of the internal parts of the sputtering chamber 100. The processed substrate 114 helps to extend the use time of the sputtering chamber 100 before the next maintenance. During the spot welding process, different substrates are bonded together under the pressure of electrodes (different from those used in electrolysis). The thickness of the substrate 114 is about 1 mm. This process uses two shaped copper alloy electrodes to pool the welding current onto a small "dot" while sandwiching the substrate 114 together. When a large current passes through the solder joint, the metal (nickel substrate) is melted to form a weld. The attractive feature of spot welding is that energy can be collected at the position of the solder joint in a very short time (about 10-100 milliseconds); therefore, the remaining substrate 114 will not be excessively heated during soldering. The welding seam is not exposed on the top surface of the adjacent substrate 114 to avoid contamination of the copper electrode.

The shapes of the substrates are all circular. If necessary, the circular substrate can be converted into other polygons through other operations.

The substrate (ie, nickel foil) coating or deposition process is controlled by a control system. The control system includes a computer, a storage device, a series of input and output (I / O) ports and connectors, and a communication module. The input / output ports and connectors connect the computer to the stepper motor 208, the magnetron 104 and the access door of the sputtering chamber 100 shown in FIG. 1, the evaporation process 200 shown in FIG. 3, and the laser device 250 shown in FIG. The computer is used to implement resource management and control the above-mentioned external equipment connected. Computers and external devices are powered by the grid separately. The computer can control a single process or all four deposition processes described above individually. You can use Category 6 (CAT6) Ethernet cables to connect external devices (computers need to have corresponding network cards installed), or use USB (Universal Serial Bus) to implement serial communication. The network card is part of the communication module. In addition, wireless technology such as Wi-Fi (radio frequency), Bluetooth, and infrared can be used to achieve wireless communication between the computer and external devices. Arduino Uno is a typical communication module containing wired and wireless connectors and protocols. Other wireless modules can be plugged into Arduino Uno. The storage device contains an algorithm that controls the rotation rate of the stepper motor 208 and the current flowing to the magnetron 104. A sensor is also provided to detect the deposition thickness on the substrate 114. The sensor output information is sent to a computer and processed by an algorithm. The algorithm can indicate maintenance time based on sensor feedback information.

Take the sputtering process as an example: if the speed of the stepping motor 208 is fifty revolutions per minute, and the current input to the magnetron within one minute is one ampere, the deposition thickness should be one micron. However, if the sensor feedback information shows a deviation in the thickness of the deposition, it indicates that the sputtering chamber 100 needs maintenance (cleaning). The thickness deviation means that more unwanted particles are adhered to the substrate. The nickel foil 142 (substrate) needs to be replaced during the maintenance of the sputtering chamber 100.

The computer can also control the activation of the currents of the electrodes 154 and 156 shown in FIG. 2 during the electrolysis 140 process. The computer can control multiple motors for raising the substrate 114 or the electrodes 154 and 156 or placing them into the electrolyte. During mass production, multiple substrates 114 can be placed in a hanging basket and immersed in electrolyte to improve production efficiency. The plurality of substrates 114 can be placed in a gondola by means of a series of anthropomorphic robotic arms. Anthropomorphic manipulators are also controlled by computers. After each successful processing of the substrate 114, the anthropomorphic robotic arm retrieves the gondola and transfers it to the next station (different electrolyte container) according to the programmed formula or sends it to the packaging station for final packaging. In fact, anthropomorphic robots can be used for all different processes. For example, the anthropomorphic robotic arm can place the substrate 114 on the fixed frame 108 and then retrieve it, which is suitable for sputtering, evaporation, and laser marking processes. The use of anthropomorphic robotic arm can ensure the stability and good control of the output quality of the substrate 114. The end portion of the anthropomorphic robot arm grasps the substrate 114 with a delicate design similar to a human hand. In addition, the end of the anthropomorphic robot arm is equipped with a plurality of suction cups, and the substrate is sucked onto the suction cups by using a vacuum. The end part is also called "end effector".

In short, the durability of antifouling films can be effectively improved by making irregular surface films. Antifouling film is recommended to use nickel material, because it has good chemical and mechanical stability under the application conditions (especially the sputtering chamber 100). This application describes three methods for making an irregular surface of nickel for use in the sputtering chamber 100. The nickel foil 142, the substrate 114, and the workpiece 252 can be used interchangeably according to specific situations.

In practice, the word “comprising or comprise” and its grammatical changes mean “open” or “inclusive” language, which includes not only the statement elements but also additional non-explicit statement elements, unless otherwise stated Regulations.

The term "approximately" as used herein when referring to the concentration of constituent components generally means that the deviation does not exceed +/- 5% of the stated value, or even +/- 4%, +/- 3%, +/- 2% , +/- 1%, or +/- 0.5%.

In this disclosure, some embodiments may adopt a range format. The scope description is only for convenience and brevity of description, and should not be regarded as a hard limit on the scope of disclosure. Accordingly, a range expression encompasses all possible subranges as well as a single numerical value within a range. For example, the range "1 ~ 6" should be understood to cover both the subranges 1 ~ 3, 1 ~ 4, 1 ~ 5, 2 ~ 4, 2 ~ 6, 3 ~ 6, etc., as well as a single numerical value within the range, such as 1 , 2, 3, 4, 5 and 6. This rule applies regardless of the size of the range.

Obviously, after reading the above disclosure, a person skilled in the art can understand various modifications and adjustments of the application without departing from the spirit and scope of the application, and the various modifications and adjustments must not exceed the scope of the appended claims.

100‧‧‧Sputtering Room

102‧‧‧Antifouling film

104‧‧‧Magnetron

106‧‧‧Target

108‧‧‧ fixed frame

110‧‧‧rotating spindle

112‧‧‧Grab arm

114‧‧‧ substrate

116‧‧‧Air inlet valve

118‧‧‧ exhaust valve

120‧‧‧ Treated gas inlet valve

140‧‧‧ electrolytic embossing

142‧‧‧nickel foil

144‧‧‧First container

146‧‧‧ hydrochloric acid

148‧‧‧ nickel foil treated with hydrochloric acid

150‧‧‧ second container

152‧‧‧ Nickel sulfate and ammonium sulfate

154‧‧‧First electrode

156‧‧‧Second electrode

158‧‧‧precipitate

160‧‧‧ precipitated nickel foil

162‧‧‧The third container

164‧‧‧ Nickel sulfate, boric acid and nickel chloride

166‧‧‧first arrow

168‧‧‧second arrow

170‧‧‧ the third arrow

172‧‧‧the fourth arrow

174‧‧‧Surface treatment

176‧‧‧Irregular surface treatment

178‧‧‧cured

180‧‧‧ Hardened or strengthened

182‧‧‧Oven

200‧‧‧ Based on deposited nickel foil embossing

202‧‧‧ evaporation source

204‧‧‧Evaporated water vapor

206‧‧‧Circle Polyline

208‧‧‧Stepper motor

210‧‧‧columns

250‧‧‧laser marking

252‧‧‧Workpiece

254‧‧‧Main foil

256‧‧‧Vacuum Chuck

258‧‧‧Polyimide foil

260‧‧‧Hr fluoride excimer (excitation complex) laser

262‧‧‧Porous metal

264‧‧‧vacuum chamber

266‧‧‧Vacuum pump

The drawings illustrate various embodiments and explain the principles of the disclosed embodiments. It should be noted, however, that these drawings are for illustration purposes only and are not intended to define the limits of the relevant application.

Figure 1 describes the application of a nickel foil in a sputtering chamber; Figure 2 describes the principle of nickel foil embossing by electrolysis; Figure 3 is a schematic diagram of nickel foil embossing by precipitation; Figure 4 describes the laser engraving setup Schematic cross-section.

no

Claims (20)

An antifouling film for a thin film deposition process includes: a soft sheet that captures scattered ions during the thin film deposition process; wherein the soft sheet can maintain its integrity during the thin film deposition process during the thin film deposition process Sex. The antifouling film according to item 1 of the patent application scope, wherein the soft sheet comprises a layer of metal. The antifouling film according to item 1 of the patent application scope, wherein the soft sheet comprises at least one ferromagnetic material. The antifouling film according to item 1 of the patent application scope, wherein the soft sheet comprises a high-purity material, an oxide of the high-purity material, or a combination of the high-purity material and the high-purity material oxide object. The antifouling film according to item 1 of the patent application scope, wherein the soft sheet further includes a rough surface. The antifouling film according to item 1 of the scope of patent application, wherein the thickness of the soft sheet ranges from 1 μm to 1 mm. A thin film deposition device includes: a cover or a container, at least a part of a surface of which is covered with an antifouling film as described in item 1 of the scope of patent application. According to claim 7 of the patent application scope, the thin film deposition apparatus further includes: a fixing frame for fastening the substrate for thin film growth; and at least one sputtering source capable of generating charged plasma or particles; a container, which can be used for The fixed frame and the at least one sputtering source are received; and at least a part of the inner wall of the container is covered with the antifouling film described in the first item of the patent application scope. The thin film deposition apparatus according to item 8 of the scope of patent application, wherein the first surface of the inner wall of the container is covered by the first antifouling film described in item 1 of the scope of patent application; and the second surface of the inner wall of the container is covered by Cover the second antifouling film as described in the first patent application. A method for manufacturing an antifouling film for thin film deposition, comprising: providing a soft sheet for capturing scattered ions; exposing at least a part of the soft sheet; roughening at least a part of the soft sheet; and peeling off Said at least a part of the soft sheet. The method as set forth in claim 10, wherein the roughening treatment of at least a part of the soft sheet includes surface treatment by electrolysis. The method according to item 11 of the scope of patent application, wherein roughening at least a part of the soft sheet includes manufacturing a surface structure. The method according to item 10 of the patent application scope further comprises subjecting the at least a part of the soft sheet to an oxidation treatment. The method according to item 10 of the patent application scope further includes attaching a substrate to the soft sheet. A method for using an antifouling film for thin film deposition, comprising: providing an antifouling film according to item 10 of the scope of the applied patent; providing a thin film deposition device; covering the container wall of the thin film deposition device with the antifouling film on. The method according to item 15 of the patent application scope further includes performing a thin film deposition production process. The method according to item 15 of the patent application scope further comprises at least partially removing the antifouling film from the container wall. The method according to item 15 of the patent application scope further includes surface-treating the container wall used in the thin film deposition process. The method according to item 15 of the patent application scope further comprises recycling the antifouling film. The method according to item 15 of the patent application scope further comprises providing a substrate for the antifouling film.