CN110573649A - Antifouling film - Google Patents

Abstract

An anti-fouling film for extending the useful life of a machine comprises a substrate and a target deposited on the substrate. The manufacturing method of the substrate comprises sputtering, electrolysis, evaporation and laser.

Description

Antifouling film

The application claims priority date corresponding to singapore patent application No. 10201700127P (application date 1/6 of 2017, entitled "thin film deposition system and sputtering process"). The entire contents of the priority application or related subject matter are incorporated by reference into this application, either in their entirety or where appropriate.

Technical Field

The present application relates to an antifouling film for thin film deposition, and also relates to various methods for manufacturing, modifying, installing, assembling, maintaining, disassembling, replacing, recycling and using the antifouling film for thin film deposition.

Background

A film is a sheet with a thickness of from a fraction of a nanometer or monolayer to a few micrometers. The controlled synthesis of thin film materials is a thin film deposition process that is an essential step in many manufacturing processes. Sputtering Deposition is a thin film Deposition process, and belongs to a sputtering type Physical Vapor Deposition (PVD) method, which is used to produce thin films of electrodes and diffusion barrier layers of integrated circuits, magnetic thin films for magnetic recording media, and indium-tin-oxide (ITO) transparent conductive films for liquid crystal display devices.

Existing sputter deposition techniques often suffer from the disadvantage of accumulating coarse particles (often referred to as "grains") on the resulting film. The "particle" is a kind of particle or granule accumulated on the substrate. These particles typically become several microns in diameter, which can accumulate on substrates such as Large-Scale Integration circuits (LSIs) causing interconnect shorts, breaks, or other problems, resulting in an increased proportion of rejected product.

Particles are mainly generated by the thin film deposition apparatus, and most of the particles originate from thin films that are deposited around the substrate and on the inner walls (e.g., chamber walls), baffles, shields, and other parts of the thin film deposition apparatus and then peeled off. The particles are scattered in a broken state and then deposited on the substrate, which constitutes a main contamination source. However, it is very difficult to keep the inner wall of the thin film deposition apparatus clean in practice. It usually takes a long time to completely clean the inside, and a cleaning worker (i.e., a cleaning technician) sometimes cannot access the inner wall of the thin film deposition apparatus and the devices inside at all. To reduce the amount of coarse particles on the inner wall, it is often necessary to first physically roughen the inner wall, which is most susceptible to contamination, by means such as metal spraying, to fix or trap the deposits as a whole. This method requires careful maintenance of the equipment, while the anti-flaking effect on the deposit is still rather weak. To overcome the above difficulties, antifouling materials in the form of disposable foils have been developed. This method is believed to keep the inner walls clean if the disposable foil is attached to the inner walls and removed after the formation (i.e., deposition) of a thin film on the substrate.

However, these disposable foils have a common fatal drawback. The film-forming material deposited on the foil mounted in place is liable to fall off, resulting in the formation of particles of the thin film deposited on the substrate. Experience has shown that the thicker the layer of film-forming substance on the disposable foil, the more frequent the peeling phenomenon. In practice, it has been found that this phenomenon is particularly likely to occur when the film to be deposited is made of a ceramic material such as silicide or indium tin oxide. To eliminate such peeling, frequent replacement of the foil is required, which seriously affects the efficiency of the thin film deposition operation. There is also a problem that a large amount of contaminants floating around the substrate (especially accompanied by the formation of a large amount of particles) causes unstable quality of the formed film on the substrate during the film formation in the vapor phase growth.

Disclosure of Invention

In such a case, it is highly desirable to take effective measures to cover the inner wall of the thin film deposition apparatus to prevent the formation of particles on the inner wall.

The present application is directed to one or more novel and useful foils for thin film deposition. The present application also provides one or more novel and useful particle collectors (also known as "collectors") for thin film deposition with the one or more foils. The present application also provides various novel and useful methods of making, modifying, installing, maintaining, removing, recycling, replacing, and using the one or more foils for thin film deposition. The essential features of the related invention are set forth in one or more of the independent claims, while the advantageous features are set forth in the respective dependent claims. The foil may be a soft, flexible or deformable film, sheet or sheet.

according to a first aspect, the present application provides an anti-fouling film (e.g., a silicide film) for use in a thin film deposition process (i.e., a sputtering process). The antifouling film may be referred to as an antifouling film, an antifouling sheet, an antifouling layer, an antifouling skin or an antifouling means. The anti-fouling film comprises a flexible sheet or sheet for trapping scattering ions, such as positively charged argon ions or particles, in a vacuum chamber. The flexible sheet is operable or configured to substantially maintain its integrity during one or more thin film deposition processes; for example: the temperature is 300 ℃, 360 ℃, 400 ℃, 465 ℃, 500 ℃, 545 ℃, 600 ℃, 668 ℃, 700 ℃, 763 ℃, 800 ℃, 857 ℃, 900 ℃, 963 ℃ or higher in vacuum (e.g., inside a thin film deposition chamber) or air. 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 structure, chemical composition, shape, size, surface texture, color, certain performance characteristics, and other physical or chemical properties. For example: integrity is considered to be maintained if the anti-fouling film does not delaminate, deform, shrink or discolor on the interior wall of the sputtering chamber after one or more sputtering passes. In addition, the anti-fouling film does not release or discharge contaminants (e.g., ions and gas particles) when exposed to high temperatures or electrical charges (e.g., positively charged as an anode) periodically or continuously.

The anti-fouling film may also comprise one or more substrates (e.g., composite materials), base structures (screens), substrates (e.g., sandwich structures) and coatings, coatings (e.g., gold and silver plating), laminates, and adhesives that are not harmful or release harmful particles upon exposure to the thin film vapor deposition process. The anti-fouling film may also comprise one or more iron foils (e.g. electrolytic iron foils) or iron alloy (iron-based alloy) foils. Different or similar materials (substances) may be selectively used as coating materials on the electrolytic nickel foil, provided that the combined or mixed use does not constitute a source of contamination during the manufacturing process (e.g., sputtering process). For example, a nickel foil may be alloyed with one of the metals, or a nickel foil coated with tungsten silicide may be used for the molybdenum silicide deposition.

The flexible sheet may comprise one or more layers of a metal capable of being fully or partially exposed (e.g., a transition metal or post-transition metal; the flexible sheet may also be provided or constructed using an alloy or metal alloy of the metal.

The flexible sheet may comprise a high purity material, an oxide of a material, or a combination of both. Substantially high purity metals (e.g., nickel at 28 atomic weight or Ni <28Ni >), i.e., pure metals having a purity of greater than 90%, 95%, 99%, 99.9%, 99.995%, or more, can be present on the flexible sheet. Pure metals that are substantially free of impurities or contaminants are suitable for use in sputtering processes that are more sensitive to contamination. For example, the metal layer includes a nickel foil having a purity of more than 50%, 85%, or 99.9% that exhibits a metallic luster at room temperature and in the ambient environment, and the silver surface has a gold tone. An embodiment of a related invention provides a nickel foil having a nickel purity of over 99.9% and a surface that has been oxidized. The oxidized nickel comprises nickel oxide (also called as greennickel ore, NiO), nickel sesquioxide (Ni2O3) and nickel dioxide (NiO 2). Other examples of the metal include a pure tin (Sn) foil coil, a pure zirconium (Zr) foil coil, a pure aluminum (Al) foil coil, SUS304 stainless steel foil, a pure copper (Cu) foil coil, tungsten foil, or molybdenum (Mo) foil.

The flexible sheet (i.e., flexible material) also comprises one or more roughened surfaces (e.g., matte, rough or frosted surfaces, uneven surfaces, and corrugated surfaces). The oxidized side of the flexible sheet has a surface roughness Ra of 1.0 to 50 micrometers (1.0 to 50 μm), more preferably 3.0 to 20 micrometers (3.0 to 20 μm), and most preferably 5.0 to 10.0 micrometers (5.0 to 10.0 μm). In other words, the surface roughness Ra of the oxidized surface of the flexible sheet is 1.0 to 5 micrometers (1.0 to 5 μm), and more preferably 2.0 to 4.0 micrometers (2.0 to 4.0 μm).

The one or more roughened surfaces can comprise an electrolytically treated surface (e.g., an electrolytic nickel foil or surface), an oxidized surface, or a combination of both. The one or more roughened surfaces can also comprise a grit blasted surface. The one or more roughened surfaces may further comprise a laser or laser beam treated surface.

The roughened surface finish comprises a non-uniform surface comprising grains, wrinkles, irregularities, embossments, depressions, or combinations of any of the foregoing.

Embodiments of the present application or uneven surfaces comprise raised portions (e.g., embossments or embossments, protrusions), depressed portions, or a combination of raised and depressed portions. For example, the raised portions and lowered portions (i.e., pits, valleys, dimples, and grooves) are adjacent to one another, forming an uneven surface having a grainy feel, whether in a regular or irregular pattern, whether in a straight line alignment, or whether having checkered markings.

The flexible sheet may have a thickness of substantially from 1 micron to 1 millimeter (1 μm to 1 mm). For example, the flexible sheet has a uniform thickness of 10 microns to 750 microns (10 μm to 750 μm), 15 microns to 550 microns (15 μm to 550 μm), 18 microns to 330 microns (18 μm to 300 μm), 30 microns to 200 microns (30 μm to 200 μm), 40 microns to 100 microns (40 μm to 100 μm), or a combination of any of the uniform thickness ranges described above.

The flexible sheet material may be a disposable or recyclable material. For example, the flexible sheet may be disposed of after a predetermined number of sputters (e.g., 10, 50, 100, and 500) in the vacuum chamber. For example, the flexible sheet may be cleaned or treated (refurbished using an electrolytic process) after multiple thin film depositions. The cleaned or treated flexible sheet, cleaned or refurbished, is reused for thin film deposition.

The anti-fouling film may comprise a predetermined characteristic (e.g., shape, size, and boundary) for attachment to the thin film deposition apparatus. For example, the anti-fouling film may be present in a roll form, similar to an aluminum foil (an aluminum foil mistakenly regarded as a tin foil). Of course, the anti-fouling membrane may be rectangular, square, circular, oval or any combination of these shapes.

The present application also provides a thin film deposition apparatus (e.g., a thin film vapor deposition system or apparatus) equipped with a vacuum chamber or a sputtering chamber. The thin film deposition apparatus comprises a casing (anode cone, baffle plate, substrate casing and target casing) having one or more portions of its surface covered with an antifouling film. For example, the inner surface of the vacuum chamber wall or the inner wall surface is partially or completely covered by the anti-fouling film. The thin film deposition apparatus also includes a fixture (also referred to as a "positioner") for securing the thin film growth substrate to one or more sputtering sources (e.g., magnetrons) for confining electrically charged plasma particles to remain near the surface of the sputtering target. The housing comprises a vacuum-tight or hermetically sealed container with a container wall for accommodating the holder and the sputtering source or sources. One or more portions of the inner surface of the container wall are covered by an anti-fouling film.

In other cases, the anti-fouling film is detachably attached to an inner surface of a container of the apparatus. In other cases, one or more portions of the apparatus or the inner surface of the vessel wall comprises a surface that is covered by a first anti-fouling film on a first surface or a first inner surface and a second surface or an inner surface that is covered by a second anti-fouling film. That is, the thin film deposition apparatus components are covered by a plurality of antifouling films, which may have different profiles, product specifications, performance indexes, or other characteristics. The area or surface where greater contaminant absorption capacity is desired is covered or coated with a higher performance anti-fouling film. The less affected area or surface of the contaminant may be reused, recycled, or used too few times in the thin film deposition process.

According to a second aspect, the present application provides a method of fabricating an anti-fouling film for thin film deposition. The method comprises four steps: the first step, providing a soft sheet for trapping scattered ions; a second step of exposing at least a part of the flexible sheet; a third step of roughening the surface of one or more portions of the flexible sheet; and fourthly, detaching at least one part from the soft sheet. Some of the steps described above may be combined, divided, or adjusted in sequence. For example, the second step of exposing one or more portions of the sheet of flexible material and roughening the surface of one or more portions of the sheet of flexible material may be accomplished by subjecting the sheet of flexible material to one or more electrolyzations. Antifouling films help to achieve a high efficiency and quality thin film deposition process because they can effectively absorb or trap stray particles over a longer period of time, even at higher or cycling temperatures.

The step of roughening the surface of one or more portions of the flexible sheet may include the step of treating the surface with an electrolytic process or electrolysis. The electrolysis process or electrolysis can provide a uniformly roughened surface, the surface roughness of which can be accurately or precisely adjusted.

The step of roughening the surface of one or more portions of the flexible sheet may comprise the step of creating one or more surface structures on the surface of one or more portions of the flexible sheet. The one or more surface structures include grooves, pits, embossments, or any other visible or invisible surface texture.

The method may include the step of oxidizing the surface of one or more portions of the flexible sheet. The method may also electrolyze the surface of one or more portions of the flexible sheet to produce an electrolytic surface (e.g., copper, nickel, or iron) or electrolytic material (e.g., electrolytic copper, electrolytic nickel, or electrolytic iron).

The method may also attach a substrate to the flexible sheet. The substrate comprises a base structure, a substrate, a coating (i.e., "coating"), a plating (i.e., "plating"), a laminate, or an adhesive layer that is not harmful or releases harmful particles to the film during the vapor deposition process. The additional structure provided by the substrate supports the anti-fouling film from flaking or cycling heat and cooling.

According to a third aspect, the present application provides a method of using an anti-fouling film for a thin film deposition process. The first step of the method is to provide a soil resistant film or soil resistant film as described above; the second step is to provide a film deposition device; the third step is to detachably attach (e.g., spot welding or precision spot welding) the antifouling film to the apparatus wall of the thin film deposition apparatus. Some of the steps described above may be combined, divided, or adjusted in sequence. The depleted or used anti-fouling film can be removed using the anti-fouling film application method and a new anti-fouling film can be attached to the device walls of the thin film deposition device (e.g., anode cone, collector, or particle collector). The used anti-fouling film can be recycled (e.g., cleaned or refurbished) and then used in a thin film deposition process or other process.

The method may also utilize the anti-fouling film for the steps of a thin film deposition process (e.g., sputtering). After several thin film depositions, the used anti-fouling film is sometimes removed from the walls of the thin film deposition apparatus and may be subsequently discarded. The used anti-fouling membrane may be replaced with a fresh, new (i.e., not previously used) or cleaned or refurbished anti-fouling membrane.

the method may further comprise a treatment (e.g., cleaning) step of the device wall before or after the antifouling film is attached. The walls of the apparatus (e.g., the interior walls or surfaces of the thin film deposition apparatus) may be roughened, oxidized, sandblasted, or polished to improve the adhesion of the antifouling film.

Embodiments of the method further comprise providing a substrate or attaching (i.e., securing) it to the flexible sheet to provide the anti-fouling film. The substrate helps to enhance structural integrity or reduce antifouling film costs. For example, the anti-fouling film comprises a metal sheet (e.g., stainless steel foil) with a nickel layer. The metal sheet and/or nickel layer may also be subjected to other treatments (e.g., oxidation and electrolysis) prior to being attached to the interior walls of the vacuum chamber for film deposition.

according to a fourth aspect, the present application provides an anti-fouling film (i.e., an anti-fouling method) comprising a substrate (e.g., a substrate) supporting a target, and a target on the substrate to produce an irregular surface. The target and the substrate may be the same material (e.g., nickel). One or more surfaces of the substrate (e.g., both surfaces on both sides) may be irregular or non-uniform surfaces. The substrate may be of a flexible or supple material to facilitate attachment to one or more uneven surfaces or locations (e.g., machine or other parts where applicable).

According to a fifth aspect, the present application provides a method for producing a sputtering-based antifouling film. The first step of the method is to fix the substrate to a fixture (i.e., a positioner); the second step is to place the target on one or more ejectors (e.g., magnetrons); the third step is to empty the chamber surrounding the fixed frame; the fourth step is to fill the chamber with process gas or inert gas (such as argon); the fifth step is to energize one or more injectors to produce a magnetic flow. Some of the steps of the above methods may be combined, divided, or adjusted in sequence.

According to a sixth aspect, the present application provides an electrolysis-based antifouling film production method. The first step of the method is to process the surface of a substrate (e.g. a nickel foil); the second part is to immerse the substrate in an electrolyte solution (e.g., nickel sulfate and ammonium sulfate); the third step is to newly form a surface of the substrate in another electrolyte solution (e.g., nickel sulfate, boric acid, and nickel chloride); and fourthly, putting the substrate into an oven for drying. Some of the steps of the above methods may be combined, divided, or adjusted in sequence.

according to a seventh aspect, the present application provides a method for producing an evaporation-based antifouling film. The first step of the method is to attach the substrate to a fixed frame; the second step is to heat the target (e.g., nickel) to its boiling point (i.e., 2730 ℃); the third step is to evaporate the target (e.g. nickel) onto the substrate (e.g. nickel foil) on the holder (i.e. positioner). Some of the steps of the above methods may be combined, divided, or adjusted in sequence.

According to an eighth aspect, the present application provides a method of producing a laser-based antifouling film. The first step of the method is to place a substrate (e.g., nickel foil) on a porous metal on a chuck; the second step is to put the main foil above the substrate; thirdly, putting the polyimide foil above the main foil; the fourth step is vacuum pumping; the fifth step is to project the laser onto the substrate or the primary foil, or both. Some of the steps of the above methods may be combined, divided, or adjusted in sequence. A plurality of substrates may be vertically arranged with a separator (e.g., a non-metallic material such as paper) disposed between each substrate. Some of the steps of the above methods may be combined, divided, or adjusted in sequence. The substrate may be placed on the associated component for storage. The method may also utilize mechanical means (e.g., end effector grasping or vacuum suction) to transport the substrate.

According to a ninth aspect, the present application provides a metal foil for thin film deposition. The foil comprises a ferromagnetic material (e.g., iron, cobalt, nickel, and gadolinium) to adhere to the sputtering apparatus during sputter deposition and to trap particles that escape during vapor growth. The metal foil is about 0.1 mm (or less than 0.1 mm) thick and one surface of the foil is roughened. Ferromagnetic materials include nickel (Ni) materials or nickel alloys, such as: permalloy, nickel-chromium galvannealed steel, invar, nickel-iron, nickel cast iron, nickel brass, nickel bronze, and alloys with copper, chromium, aluminum, lead, cobalt, silver, and gold (e.g., inconel, monel, and nichrome). The rough surface may be subjected to electrolysis. The metal foil may comprise protrusions or bulges on the electrolytic side or surface. The protrusions may contain fine particles (only a mat surface is seen) which cannot be recognized by the naked eye, or the surface roughness Ra ranges from 05 micrometers to 20 micrometers (05 to 20 μm). The partial grains are projections or bulges having a size of not more than 100 micrometers (100 μm). One or more portions of the metal foil may be oxidized. The metal foil may be removed separately (e.g., as an inseparable piece) from the thin film deposition apparatus components (e.g., particle collector); thus, the metal foil may be considered a disposable foil.

According to a tenth aspect, the present application provides a sputter deposition apparatus equipped with one or more particle collectors. At least one particle collector is connected to the power supply anode; the particle collector may be conical or any shape that is convenient to mount to a piece of equipment.

According to a ninth aspect, the present application provides a method of manufacturing a foil for thin film deposition. The first step of the method is to provide a ferromagnetic material (e.g., iron, cobalt, nickel, and gadolinium); the second step is to attach the ferromagnetic material to the thin film deposition apparatus components, trapping scattering particles during the thin film deposition process. The ferromagnetic material may be welded (e.g., precision spot welded) to the thin film deposition apparatus component as it is attached to the thin film deposition apparatus component. The method can also electrolyze the ferromagnetic material prior to attaching the ferromagnetic material to a thin film deposition apparatus (e.g., a sputter deposition apparatus) part. The method may also roughen the ferromagnetic material prior to attaching the ferromagnetic material to the thin film deposition apparatus component. The method may also (emboss the ferromagnetic material prior to attaching the ferromagnetic material to the thin film deposition apparatus component.

The one or more foils can include one or more nickel foils that can be used in copper and non-copper thin film deposition equipment and sputtering processes. The particle collector covered or fabricated with nickel foil during thin film deposition sputtering is easy to capture scattering particles. The nickel foil covers the particle collector, forming a nickel particle collector for non-copper thin film deposition. The nickel particle collector has stronger particle absorption capacity and longer duration in the film deposition process. The one or more nickel foils have rounded ridges thereon to facilitate spreading of the surface area of the one or more nickel foils for use in non-copper thin film deposition processes. The nickel foil surface has a stronger absorption capacity than the copper foil and therefore can trap more particles in the thin film deposition process. The nickel foil is also able to withstand high temperatures. For example, the melting point of nickel is 1455 ℃ which is 370 ℃ higher than the melting point of copper. In addition, the thermal expansion coefficient of nickel material is smaller than that of copper material. The maximum working temperature of nickel foil is typically around 600 c, which is about 200 c higher than that of copper foil.

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

The antifouling film provided by the present application comprises:

1. A treated electrolytic nickel foil;

2. A treated electrolytic nickel foil coated with a material that is the same as or harmless and similar to a material deposited to form a thin film by vapor phase growth on a substrate;

3. A corrugated metal foil, and

4. A metal foil with a plurality of irregularities, i.e., recesses and protrusions.

the present application also provides a vapor growth-based thin film deposition apparatus, characterized in that: preventing the pollution of the internal device of the equipment and the formation of particles in the deposited film by using an antifouling method; the optional method comprises the following steps: (1) electrolytic nickel foil or nickel foil with a thin layer of nickel or/and nickel oxide fine particles formed by mat-plating nickel on the nickel foil; (2) a nickel foil or an electrolytic nickel foil which forms a thin layer of nickel or/and nickel oxide fine particles by mat nickel plating of a foil material, the plating material being the same as or harmless to and similar to a material which forms a thin film by vapor phase growth on a substrate; (3) a corrugated nickel foil; (4) a nickel foil with several irregularities is produced by an embossing process. The present application also provides an antifouling method for a thin film vapor deposition apparatus, which is selected from the ranges (1) to (4) above. The application also provides a method for preventing the pollution of the internal device of the equipment and the generation of particles in the deposited film by using the antifouling film.

According to a twelfth aspect, the present application provides a vapor growth-based thin film deposition system or apparatus. The system employs a suitable anti-fouling method. The anti-fouling method comprises a treated electrolytic nickel foil having fine particles of nickel, nickel oxide or a mixture of nickel and nickel oxide deposited by nickel plating of a large number of raised portions of the matte surface of the electrolytic nickel foil. Contamination of devices within the system and particle formation in the deposited film can be avoided, reduced or mitigated. The matte surface roughness Ra of the electrolytic nickel foil ranges from 5 micrometers to 10 micrometers (5-10 micrometers). The treated electrolytic nickel foil (i.e., foil) may have fines on one side for trapping particles that escape during vapor phase growth. The foil may be a disposable electrolytic nickel foil and the system may be a sputtering system.

system embodiments employ suitable anti-fouling methods. The anti-fouling method comprises a treated electrolytic nickel foil having fine particles of nickel, nickel oxide or a mixture of nickel and nickel oxide deposited by nickel plating of a large number of raised portions of the matte surface of the electrolytic nickel foil. The foil coating material is the same as or harmless to and similar to the material that is deposited to form a thin film by vapor phase growth on a substrate, such as a silicon wafer, thereby preventing contamination of devices inside the system and formation of particles in the deposited thin film. The matte surface roughness Ra of the electrolytic nickel foil ranges from 5 micrometers to 10 micrometers (5-10 micrometers). One side of the foil may have fines to trap particles that escape during vapor phase growth.

The nickel foil may have nickel, nickel oxide or fine particles of nickel and nickel oxide, which are precipitated on the surface of the nickel foil by nickel plating, and may or may not use a plating layer which is the same as or harmless to and similar to a material deposited to form a thin film based on vapor phase growth. The anti-fouling material may be attached to one or more devices inside the system (e.g., sputtering system) by spot welding to cover them.

Drawings

the drawings (figures) illustrate various embodiments and explain the principles of the disclosed embodiments. It is to be noted, however, that the drawings are designed solely for purposes of illustration and not as a definition of the limits of the related application.

FIG. 1 depicts the use of a nickel foil in a sputtering chamber;

FIG. 2 depicts the principle of making an embossing of a nickel foil by electrolysis;

FIG. 3 is a schematic illustration of an embossing of a nickel foil by precipitation;

Fig. 4 depicts a schematic cross-sectional view of a laser embossing arrangement.

Non-limiting embodiments of the present application will now be described with reference to the above-mentioned figures.

Detailed Description

FIG. 1 depicts the use of a nickel foil in a sputtering chamber. The sputtering chamber is referred to as sputtering chamber 100. The sputtering chamber 100 is shown with the hinged hemispherical door removed and with a concentric highly polished thick steel wall. The inner surface of the concentric steel wall is covered by a fouling resistant film 102, as shown in the hatched area. The antifouling film (i.e., antifouling layer) 102 is basically made of nickel having a purity of more than 99.9%, and is therefore also called "nickel foil".

The sputtering chamber 100 is provided with three magnetrons at the base of concentric walls. Each magnetron 104 is supported by a bracket facing toward the mounting bracket 108. The target 106 is placed on the "facing surface". Three magnetrons 104 are positioned laterally equidistant within a triangular configuration. The tilt of the magnetron 104 can be adjusted independently, manually, or remotely by means of a microcontroller.

The mounting bracket 108 is located on the opposite side of the magnetron 104, i.e. near the top region of the concentric wall. The mount 108 is then connected to a rotating spindle 110. The rotating spindle 110 is connected to the concentric wall at the top end. The fixture is suspended within the sputtering chamber 100 in a manner similar to a ceiling fan. The mounting bracket 108 itself is provided with at least two gripping arms 112 on the surface facing the three magnetrons 104. The gripper arms 112 are fastened to the base plate 114.

The sputtering chamber 100 is equipped with three valves at opposite ends, which are aligned horizontally and are slightly angled toward the top. An inlet valve 116 is provided on the left, an outlet valve 118 is provided in the middle, and a treated gas inlet valve 120 is provided on the right.

Fig. 2 depicts a nickel foil 142 electroembossing process 140. The nickel foil 142 is shown as a one millimeter (1mm) thick disc having a diameter of about one hundred millimeters (100 mm). The top left schematic view shows a circular nickel foil 142 from a side view and a three-dimensional view perspective. Thereafter, a 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 a second step: an irregular surface treatment 176 is provided. Thereafter, a third arrow 170 points to a third "cure" step 178. Thereafter, a fourth arrow 172 points to a fourth step "harden or strengthen 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 transferred to a second vessel 150 containing a solution of nickel sulfate and ammonium sulfate 152.

The second vessel 150 also has two metal electrodes 154 inserted into the nickel sulfate (NiSO4) and ammonium sulfate ((NH4)2SO4)152 solution. The two electrodes 154 are connected to a DC (direct current) power supply (not shown). The DC power supply has a positive electrode and a negative electrode. 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 a second electrode 156 on the right side of the second container 150. The two electrodes 154 and 156 are supported by a fixture (not shown) that suspends the two electrodes 154 and 156 in the solution. The nickel foil 142 acquires an irregular surface when a certain potential is applied by the electrodes 154 and 156 immersed in the solution. If an electrical potential is applied to the solution, the cations of the solution will be directed to the cathode (positive electrode) where the number of electrons is rich, while the anions will be directed to the anode (i.e., negative electrode) where the electrons are absent.

nickel sulfate is a highly soluble blue salt that is used primarily for electroplating. The aqueous nickel sulfate solution reacts with sodium carbonate to produce nickel carbonate, a precursor for the nickel-based catalyst and pigment. Adding ammonium sulfate into the concentrated aqueous solution of nickel sulfate to obtain Ni (NH4)2(SO4) 2.6H 2O precipitate, namely, ammonium nickel sulfate. This blue solid is similar to a molle salt, Fe (NH4)2(SO4) 2.6H 2O, also known as ferrous ammonium sulfate. Precipitates 158 form on the surface of the nickel foil 142, resulting in an irregular surface. The surface includes the top surface and perimeter of the nickel foil 142. However, if the nickel foil 142 is suspended in a solution supported by a holder (not shown), the nickel foil 142 will completely cover the precipitate.

The precipitated nickel foil 160 is then transported to a third vessel 162 containing nickel sulfate (NiSO4), boric acid (H3BO3) and nickel chloride (NiCl2) 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 the nickel ammonium sulfate thereon is cured in a third container 162.

The nickel foil plating formulation includes boric acid. One formulation had a ratio of boric acid (H3BO3) to nickel sulfate (NiSO4) of about 1:10, with very little sodium lauryl sulfate and little sulfuric acid (H2SO 4). The nickel chloride solution is used to plate nickel onto other metal objects. A new layer of nickel is plated onto the irregular surface of the nickel foil. The newly nickel plated nickel foil layer is then dried in an oven 182 to achieve hardening or strengthening 180.

Fig. 3 is a schematic diagram 200 based on the embossing of a deposited nickel foil 142. The nickel foil 142 is a substrate 114, which is fixed by suction by a fixing frame (not shown). The stationary frame (i.e., positioner) is connected to the rotating spindle 110. One end of the rotating spindle 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 evaporated water vapor 204 (indicated by the upward three-way thick arrow) rises to the surface of the nickel foil 142. The evaporated moisture 204 condenses on the surface of the nickel foil 142 to form irregularly inclined pillars 210, as shown by the enlarged circular broken lines. The irregularities 210 occur because the evaporated moisture 204 randomly reaches the surface (nickel foil). Adjacent pillars 210 are of unequal size and the latter is subject to a reduced growth due to portions of the pillars 210 blocking contact of the adjacent pillars 210 with the evaporated moisture 204. Nickel is deposited onto substrate 114 in a vacuum chamber (not shown). The vacuum chamber base pressure was approximately 6.7x10-5 Pa. The nickel deposit thickness is approximately one micron (1 μm). The length of time of contact with the evaporation source 202 affects the thickness of the nickel deposition layer.

Fig. 4 depicts a schematic cross-sectional view of an arrangement of laser embossing 250. A one to two millimeter (1-2 mm) thick solid nickel sheet having a diameter of about twenty millimeters (20mm) was used as the workpiece 252. The workpiece 252 fabrication steps include sawing, soft annealing and subsequent surface polishing. A piece of nickel foil with 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 about 100 μm x 100 μm. The gap between adjacent squares is two microns (2 μm).

the solid nickel workpiece 252 is mounted on a vacuum chuck 256. Then, a nickel foil (main foil) 254 is overlaid on the workpiece 252. A twenty-five micron (25 μm) 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 vacuum chuck 256 and the nickel foil 254 and workpiece 252 are then pressed firmly together. The exhausted air is drawn through the vacuum chamber 264 by a vacuum pump 266. The polyimide foil 258 is then irradiated with a krypton fluoride excimer (excited complex) laser 260. The polyimide foil 258 is a synthetic resin having a high heat resistance.

A laser workstation embedded krypton fluoride (KrF) excimer (excited complex) laser 260 for laser irradiation has a pulse length of twenty-five nanoseconds (25ns) and a wavelength of two hundred forty-eight nanometers (248 nm). The workstation also includes beam shaping and homogenizing optics to form a flat top beam profile in the 100 μm x 100 μm laser spot area. The laser beam scans the polyimide surface via a process controlled x-y-z stage. The laser repetition rate is fixed at a frequency level of one hundred hertz (100 Hz).

The size of the micro-embossed pattern area is defined by the laser spot size. The number of pulses applied to a dot to form a mark is estimated to be approximately twenty or more times. This number of pulses does not drill through the polyimide foil 258, and eventually about 1 μm of polyimide layer remains, sufficient to protect the upper nickel foil 254 from thermal shock from the laser pulses. Thus, the polyimide foil 258, along with any contaminants and debris generated by the laser ablation, can be easily removed after embossing is complete, thereby avoiding debris from contaminating the workpiece 252 or the primary nickel foil 254.

The applied laser pulses are absorbed by the polyimide foil 258, and the polyimide foil 258 forms a plasma plume after laser ablation. The momentum created by the expanding plasma and the shock wave created by the thermal process is sufficient to compress the structured primary foil 254 to the lower nickel sheet 252.

The irregular surface of the nickel foil 142 is made and placed on the surface of the sputtering chamber 100 to extend the time of use of the sputtering chamber 100 before the next maintenance. A sputtered nickel foil 142 having an irregular surface is applied to the chamber walls and components in the sputtering chamber 100.

Functionally, the front of the sputtering chamber 100 of FIG. 1 is made of steel and is capable of withstanding the atmospheric pressure applied when the interior chamber is empty of air or evacuated. The cylinder and the two hemispherical end points achieve uniform pressure distribution. Fig. 1 depicts the application of a nickel foil 142 and the process of obtaining the nickel foil 142 by sputtering.

The sputtering chamber 100 is maintained in a controlled environment during the sputtering process, which is effectively a vacuum interior chamber and is therefore also referred to as a "vacuum chamber". The base pressure of the vacuum chamber is about 10-6bar (10-6 bar). The evacuated inner chamber provides a clean environment free of any suspended matter and invisible charged ions and particles. The sputtering chamber is purged of air through a purge valve 118 and then filled with argon through a machined gas inlet 120. Argon is an inert element and is suitable for high-temperature working environments such as sputtering and the like. The argon gas prevents oxidation and burning of the internal parts.

the magnetron 104 contains an electromagnet that operates based on current. The power supply may be from a power supply network. The electromagnet is coated with a water-resistant material to prevent corrosion and electrical shorting. The cavity of the magnetron 104 is filled with water to cool during the sputtering process. The cooling water may be tap water, and thus, the magnetron 104 is connected by a conduit, and water inlet and outlet are realized at different positions of the magnetron 104. The free electrons continue to hit the argon atoms during sputtering, thereby forming argon positive ions. The positively charged argon ions collide with the target at the magnetron 104. The target 106 nickel has negative charges and can attract argon ions. The attractive force causes the argon ions to bombard the nickel ions. The momentum of the bombardment causes the nickel ions to be diverted toward the substrate 114 suspended atop the inner chamber. The substrate 114 is a nickel foil 142, and the surface of the nickel foil 142 can be irregular by coating nickel ions.

The one millimeter (1mm) thick disc-shaped nickel foil 142 of about one hundred millimeters (100mm) in diameter shown in fig. 2 is merely an example. Providing a greater thickness ensures proper strength during embossing or making irregular surfaces. Too small a foil thickness may result in failure to emboss. The substrate 114, i.e., the nickel foil 142 in fig. 1, may also be the same size.

Hydrochloric acid 146(HCl) in the first vessel 144 removes impurities from the surface of the nickel foil 142 (surface treatment 174 stage). The treated nickel foil 148 or activated nickel foil is then immersed in a second vessel 150 containing an electrolyte consisting of nickel sulfate and ammonium sulfate 152. Nickel sulfate is used for nickel plating of the nickel foil 142. The addition of ammonium sulfate produces crystals on the surface of the nickel foil 142. This is the irregular surface treatment stage 176. The roughened nickel foil is then dipped into a third container 162 to strengthen the roughened surface or to effect curing 178. The coating is finally 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, forming pillars 210 above. The nickel foil 142 is continuously rotated to uniformly distribute the evaporated nickel from the lower evaporation source 202.

fig. 4 illustrates one method of embossing the nickel foil 142 by burning through the overlying primary foil 254 with a laser beam. The vacuum chamber 264 causes the nickel foil 142 to be sucked from the bottom side through the porous metal 262.

A method of using the anti-fouling film 102 (i.e., an anti-fouling method or an anti-fouling means) based on the sputtering process is to fix the substrate 114 to the fixing frame 108. The substrate 114 in this example is a nickel foil 142. The fixture 108 (i.e., positioner) is connected to a rotating spindle 110 that is driven by a rotating motor 208. The target 106 is then placed on the at least one magnetron 104. The target 106 is nickel. The vacuum chamber then achieves a clean controlled environment by exhausting air. The vacuum chamber is then refilled with the treated gas (argon). At least one magnetron 104 is then energized to form a magnetic current. The magnetic current ionizes the argon atoms, producing positively charged argon ions. The argon ions bombard the negatively charged target 106 onto the substrate 114. Finally, the nickel foil 142 produces nickel precipitates, forming an irregular surface.

A method for manufacturing the antifouling material based on electrolysis 140 is to treat the surface of a nickel foil 142 with hydrochloric acid 146 to remove impurities (oxides or particles). The hydrochloric acid treated nickel foil 148 is then immersed in a solution of nickel sulfate and ammonium sulfate 152 to produce a precipitate 158 on the surface of the nickel foil 142. The newly formed surface is then cured 178 in a nickel sulfate, boric acid, and nickel chloride 164 solution. The second and third steps energize electrodes 154 and 156 to achieve plating on the surface. Finally, the nickel foil is hardened and strengthened 180 in an oven 182.

A method of manufacturing an anti-fouling material (i.e., anti-fouling film or material) based on evaporation 200 begins by attaching a nickel foil 142 or substrate 114 to a fixture using a rotating spindle 110 driven by a stepper motor 208. A piece of nickel is then heated to a boiling point of 2730 c, causing the nickel to evaporate onto the nickel foil 142 at the mount. This process occurs within a clean and controlled vacuum chamber. Parts and components are capable of withstanding high temperatures.

A method for manufacturing a laser-based anti-fouling material is to first place a nickel foil 142 (also called a workpiece 252) on a porous metal 262 on a vacuum chuck 256. The perforations in the porous metal 262 allow the vacuum chamber to suck the nickel foil 142 to the bottom of the porous metal 262 (i.e., the primary nickel foil or primary foil). The main nickel foil 254 is then placed over the nickel foil 142. The primary nickel foil 254 is perforated. The distance between every two adjacent holes is the same. The primary foil 254 serves as a template for the laser 260 burn-through operation while also protecting the nickel foil 142 from spiking nickel contamination from the nickel foil 142. Next, a polyimide foil 258 is placed over the primary nickel foil 254. Polyimide foil 258 provides a secure under-layer when vacuum pump 266 is activated. The polyimide foil 258 can also withstand high temperatures. Finally, the laser 260 strikes the nickel foil 142 after passing through the polyimide foil 258 and the primary nickel foil 254. The laser 260 impacts the nickel foil 142 at a predetermined intensity 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 comprises the following steps: the substrates 114 are arranged vertically with spacers placed between adjacent substrates 114. The separator should be a non-metallic material such as paper. The paper used is economical and environment-friendly. The base plate 114 may be packaged in 12 pieces per packet in a rigid case made of material such as perspex. In addition, the rigid case may also utilize a lattice structure to hold the substrates 114, avoiding direct contact between adjacent substrates 114. The vertical arrangement ensures that the substrate 114 surface treatment is not damaged during transport.

A method of using nickel foil 142: the substrate is placed on the surface of the relevant component for storage and then spot-welded thereon. The substrate 114 is typically used primarily for surfaces of internal components of the sputtering chamber 100. The processed substrate 114 helps to extend the life of the sputtering chamber 100 before the next maintenance. During spot welding, the different substrates are held together under pressure by electrodes (different from those used for electrolysis). The substrate 114 is approximately 1mm thick. This process uses two shaped copper alloy electrodes to focus the welding current into a small "spot" while clamping the substrates 114 together. A large current is passed through the weld spot to melt the metal (nickel substrate) to form a weld. Spot welding has attractive properties: the energy can be collected at the welding spot position in a very short time (about 10-100 milliseconds); therefore, excessive heating of the remaining substrate 114 during soldering does not occur. The solder joint is not exposed on the top surface of the adjacent substrate 114, thereby avoiding contamination of the copper electrode.

the shape of the substrate is round. The circular substrate may be converted into other polygonal shapes by other operations as needed.

The substrate (i.e. nickel foil) plating 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. Input/output ports and connectors connect the computer to the stepper motor 208, magnetron 104 and access door of the sputtering chamber 100 shown in fig. 1, the evaporation process 200 shown in fig. 3, and the laser apparatus 250 shown in fig. 4. The computer is used for realizing resource management and controlling the connected external equipment. The computer and the external device are separately powered by the power grid. The computer may control a single process or all four deposition processes described above individually. The six-category (CAT6) Ethernet cable can be used for connecting external equipment (a computer needs to be provided with a corresponding network card), or the USB (universal serial bus) is used for realizing serial communication. The network card is an integral part of the communication module. In addition, wireless communication between the computer and external equipment can be realized by utilizing wireless technologies such as Wi-Fi (radio frequency), Bluetooth and infrared. Arduino Uno is a typical communications module that contains wired and wireless connectors and protocols. Other wireless modules may be plugged into the Arduino Uno. The memory device contains an algorithm that controls the rate of rotation of the stepper motor 208, the current to the magnetron 104. A sensor is also provided to detect the thickness of the deposition on the substrate 114. The output information of the sensor is sent to a computer and processed by an algorithm. The algorithm may indicate a maintenance time based on the sensor feedback information.

Taking the sputtering process as an example: if the stepper motor 208 is rotating at fifty rpm and the current input to the magnetron 104 is one amp in one minute, the deposition thickness should be one micron. However, if the sensor feedback indicates a deviation in the deposition thickness, this indicates that the sputtering chamber 100 needs maintenance (cleaning). Thickness variations may mean that more unwanted particles are adhered to the substrate. The maintenance of the sputtering chamber 100 means the replacement of the nickel foil 142 (substrate).

The computer may also control the activation of the current to the electrodes 154 and 156 shown in FIG. 2 during the electrolysis process 140. The computer may control a plurality of motors for raising the substrate 114 or placing the electrodes 154 and 156 in the electrolyte. In mass production, a plurality of substrates 114 can be placed in the basket and then immersed in the electrolyte to improve production efficiency. A plurality of substrates 114 may be placed in the basket by a series of anthropomorphic robotic arms. The anthropomorphic robotic arm is also computer controlled. After each successful processing of the substrate 114, the anthropomorphic robotic arm retrieves the baskets in the programmed sequence and transports them to the next station (a different electrolyte container) or to a packaging station for final packaging. Virtually all of the different processes can use anthropomorphic robotic arms. For example, an anthropomorphic robotic arm may place the substrate 114 onto the fixture 108 before retrieving it for sputtering, evaporation, and laser embossing processes. The use of an anthropomorphic robot arm ensures stability and good control of the output quality of the substrate 114. The end portion of the anthropomorphic robotic arm grasps the substrate 114 with a delicate design similar to a human hand. In addition, the tip portion of the anthropomorphic robot arm is equipped with a plurality of suction cups, and the substrate is sucked onto the suction cups by vacuum. The end portion is also called an "end effector".

In short, the durability of the antifouling film can be effectively improved by forming the irregular surface film. The anti-fouling film is preferably a nickel material because of its good chemical and mechanical stability under the conditions of use, particularly in the sputtering chamber 100. Three methods of making nickel irregular surfaces are described for use in placing in the sputtering chamber 100. The nickel foil 142, substrate 114 and workpiece 252 may be used interchangeably as the case may be.

In practice, the use of the word "comprising" and variations thereof herein is meant to be open ended or "inclusive" that includes not only the recited elements, but also additional, non-explicitly recited elements, unless otherwise specified.

the term "about" as used herein in reference to constituent component concentrations generally means a deviation of no more than +/-5%, or even +/-4%, +/-3%, +/-2%, +/-1%, or +/-0.5% of the stated value.

In this disclosure, some embodiments may employ a range format. The description of ranges is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the recitation of a range encompasses all possible sub-ranges as well as individual values within the range. For example, a range of "1-6" should be understood to encompass both the sub-ranges 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, etc., as well as individual values within the ranges, such as 1, 2, 3, 4, 5, and 6. This rule applies regardless of the range size.

It will be apparent to those skilled in the art having read the foregoing disclosure that various modifications and adaptations to the use can be made without departing from the spirit and scope of the use and these various modifications and adaptations are intended to be covered by the following claims.

Reference numerals

100 sputtering chamber

102 antifouling film

104 magnetron

106 target material

108 fixed mount

110 rotating spindle

112 grab arm

114 substrate

116 air intake valve

118 exhaust valve

120 treated gas inlet valve

140 electrolytic embossing process

142 nickel foil

144 first container

146 hydrochloric acid

148 hydrochloric acid treated nickel foil

150 second container

152 nickel sulfate and ammonium sulfate

154 first electrode

156 second electrode

158 precipitation

160 precipitated nickel foil

162 third container

164 nickel sulfate, boric acid and nickel chloride

166 first arrow

168 second arrow

170 third arrow

172 fourth arrow

174 surface treatment

176 irregular surface treatment

178 curing

180 hardening or strengthening

182 oven

200 deposition-based nickel foil embossing process

202 evaporation source

204 evaporated water vapor

206 circular dotted line

208 stepping motor

210 column

250 laser embossing

252 workpiece

254 main foil

256 vacuum chuck

258 polyimide foil

260 krypton fluoride excimer (excited complex) laser

262 porous metal

264 vacuum chamber

266 vacuum pump.

Claims (21)

1. An anti-fouling film for a thin film deposition process (e.g., a sputtering process), the anti-fouling film comprising

A flexible sheet for trapping scattered ions in a thin film deposition process;

Wherein the flexible sheet is operable to maintain integrity during the thin film deposition process.

2. The antifouling film according to claim 1, wherein

The flexible sheet comprises a layer of metal.

3. The antifouling film according to claim 1 or 2, wherein

The soft sheet at least comprises a ferromagnetic material.

4. The antifouling film according to any preceding claim, wherein

The flexible sheet comprises a substantially pure material, an oxide of the pure material, or a combination of both.

5. The antifouling film according to any preceding claim, wherein

The flexible sheet also includes a roughened surface.

6. The antifouling film according to claim 5, wherein

The roughened surface comprises a non-uniform surface.

7. The antifouling film according to any preceding claim, wherein

The thickness of the flexible sheet is substantially 1 micron to 1 millimeter (1 μm-1 mm).

8. A thin film deposition apparatus, comprising:

An enclosure comprising at least a portion of its surface covered by an anti-fouling film according to any preceding claim.

9. The thin film deposition apparatus of claim 8, further comprising:

A fixing frame for fastening the substrate for film growth; and

At least one sputter source for confining electrically charged plasma particles;

The enclosure includes a container having a container wall for housing the holder and the at least one sputtering source; and also

At least a portion of the container wall is covered by the anti-fouling film of any preceding claim.

10. The thin film deposition apparatus as claimed in claim 9, wherein

At least a portion of the container wall comprises a first inner surface covered by a first anti-fouling film according to any one of claims 1 to 7; and a second inner surface covered by the second antifouling film according to any one of claims 1 to 7.

11. A method of making an anti-fouling film for use in a thin film deposition process, comprising:

Providing a soft sheet for trapping scattered ions;

Exposing at least a portion of the flexible sheet;

Roughening at least a part of the surface of the flexible sheet; and

Detaching the at least one portion from the flexible sheet.

12. The method of claim 10, wherein

The roughening treatment of the surface of at least a portion of the flexible sheet comprises subjecting the surface to an electrolytic process.

13. The method of claim 10 or 11, wherein

The roughening of the surface of at least a portion of the flexible sheet comprises creating a surface structure on the surface of at least a portion of the flexible sheet.

14. The method of any one of claims 10 to 12 further comprising

Oxidizing at least a portion of a surface of the flexible sheet.

15. The method of any one of claims 10 to 13 further comprising

A substrate is attached to the flexible sheet.

16. a method of using an anti-fouling film for a thin film deposition process, the method comprising:

Providing a soil resistant film according to any one of claims 1 to 7;

Providing a film deposition device;

And attaching the antifouling film to the equipment wall of the thin film deposition equipment.

17. The method of claim 15 further comprising

And carrying out a film deposition process.

18. The method of claim 15 or 16 further comprising

Removing the anti-fouling film from the equipment wall.

19. The method of claim 15 or 16 further comprising

And treating the equipment wall for the thin film deposition process.

20. The method of any one of claims 15 to 18 further comprising

and recycling the antifouling film.

21. The method of any one of claims 15 to 19 further comprising

A substrate for the anti-fouling film is provided.