Member with film

Abstract

To provide a member with a film, capable of maintaining water-repellent properties for a long period of time even when used in an environment irradiated with ultraviolet rays or plasma.SOLUTION: A member with a film according to the present disclosure includes: a substrate made of ceramics; and a film composed of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element provided on a part of at least one surface of the substrate. An exposed portion of the surface of the substrate has hydrophilicity, and a surface of the film has water-repellency. In addition, the member with a film according to the present disclosure includes: a substrate made of quartz; and a film composed of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element provided on a part of at least one surface of the substrate. An exposed portion of the surface of the substrate has hydrophilicity, and a surface of the film has water-repellency.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a membrane-attached member. [Background technology]

[0002] Conventionally, when imparting water repellency to the surface of window glass or the like, a method of forming a film by coating or chemical vapor deposition of low-molecular-weight fluorine compounds, fluororesins, silicones, etc. has been commonly used. However, with this method, while large water droplets can be made to flow off, small water droplets remain and remain, resulting in reduced visibility. For this reason, there is a demand for a component that maintains water repellency while also having the property of allowing adhering water droplets to quickly flow off (water-slip property).

[0003] In order to increase water sliding properties, for example, Patent Document 1 proposes a water-repellent substrate that includes a substrate and a water-repellent film formed on at least one surface thereof, the water-repellent film including a first water-repellent region and a second water-repellent region adjacent to the first water-repellent region, the water contact angle of the first water-repellent region being 40° to 110°, and the water contact angle of the second water-repellent region being 20° or more higher than the water contact angle of the first water-repellent region.

[0004] The document also describes that the first water-repellent region is made of a layer containing at least one selected from a compound having a polyfluoroalkyl group or a polyfluoroetheralkyl group, an oxide containing hafnium, an oxide containing zirconium, and an oxide containing aluminum, and that the second water-repellent region is made of a layer containing a compound having a polyfluoroalkyl group or a polyfluoroetheralkyl group. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-133264 Summary of the Invention

[0006] The film-coated member according to the present disclosure comprises a ceramic substrate and a film of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element on at least a portion of the surface of the substrate, wherein the exposed surface of the substrate is hydrophilic, and the surface of the film is water-repellent.

[0007] The film-coated member according to the present disclosure comprises a substrate made of quartz and a film of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element formed on at least a portion of the surface of the substrate, wherein the exposed surface of the substrate is hydrophilic, and the surface of the film is water-repellent. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 2 is a plan view showing a membrane member according to a non-limiting embodiment of the present disclosure. [Figure 2] FIG. 2 is a plan view showing a membrane member according to a non-limiting embodiment of the present disclosure. [Figure 3] FIG. 1 is a plan view showing a member for a plasma processing apparatus according to a non-limiting embodiment of the present disclosure. [Figure 4] FIG. 2 is a plan view showing a membrane member according to a non-limiting embodiment of the present disclosure. [Figure 5] FIG. 2 is a plan view showing a membrane member according to a non-limiting embodiment of the present disclosure. [Figure 6] FIG. 1 is a schematic diagram showing a sputtering apparatus for obtaining a film-coated member according to a non-limiting embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] As in Patent Document 1, when the first water-repellent region and the second water-repellent region are formed from a layer containing an organic component such as a polyfluoroalkyl group, there is a problem that they deteriorate in a short period of time when used in an environment exposed to ultraviolet rays or plasma.

[0010] The present disclosure provides a film-coated member that can maintain water-sliding properties for a long period of time even when used in an environment where it is irradiated with ultraviolet rays or plasma.

[0011] The film-coated member according to the present disclosure can maintain water-sliding properties for a long period of time even when used in an environment where it is irradiated with ultraviolet rays or plasma.

[0012] <Membrane-coated materials> Hereinafter, a non-limiting embodiment of the film-coated member of the present disclosure will be described in detail with reference to the drawings. However, for the sake of convenience, the figures referred to below show only the main components necessary for explaining the embodiment in a simplified form. Therefore, the film-coated member may include any component not shown in the figures referred to. Furthermore, the dimensions of the components in the figures do not faithfully represent the actual dimensions of the component components or the dimensional ratios of each component.

[0013] 1, the film-coated member 1A comprises a substrate 2A made of ceramic and a film 3 made of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element on at least a portion of the surface of the substrate 2A. An exposed portion 21 on the surface of the substrate 2A is hydrophilic, and the surface of the film 3 is water-repellent. In these cases, because both the substrate 2A and the film 3 are made of inorganic compounds, they can maintain their water-slip properties for a long period of time even when used in an environment where they are irradiated with ultraviolet rays or plasma.

[0014] The ceramic material of the substrate 2A may be mainly composed of aluminum oxide. The main component may refer to the component that accounts for the largest proportion of the total of all components constituting the ceramic, which is 100% by mass. The main component may be, for example, 80% by mass or more. When the main component of the ceramic is aluminum oxide, it may contain at least one of silicon, magnesium, and calcium as an oxide.

[0015] Each component constituting the ceramic can be identified using an X-ray diffractometer using CuKα radiation, and the content of each identified component can be determined using, for example, an ICP (Inductively Coupled Plasma) emission spectrometer or an X-ray fluorescence analyzer.

[0016] Examples of the oxide, fluoride, oxyfluoride, or nitride of a rare earth element that is the material of the film 3 include yttria (yttrium oxide: YO 3-x (0≦x≦1)), yttrium fluoride (YF3), yttrium oxyfluoride (YOF, Y5O4F7, Y5O6F7, Y6O5F8, Y7O6F9, Y 17 O 14 F 23 ), yttrium nitride (YN), and the like.

[0017] The components constituting the film 3 may be identified using a thin film X-ray diffraction device.

[0018] Film 3 does not necessarily contain only compounds of rare earth elements, but depending on the purity of the target used in forming film 3 and the configuration of the apparatus, it may contain fluorine (F), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), sulfur (S), chlorine (Cl), potassium (K), calcium (Ca), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), strontium (Sr), and the like in addition to rare earth elements.

[0019] Hydrophilicity and water repellency may be evaluated by the static contact angle with pure water (hereinafter simply referred to as "contact angle"). "Hydrophilic" may mean a static contact angle with pure water of less than 90°, and "water repellent" may mean a static contact angle with pure water of more than 90°. The static contact angle may be determined, for example, using a surface contact angle measuring device "CA-X model" or its successor (manufactured by Kyowa Interface Science Co., Ltd.) under the following measurement conditions. Solvent: Pure water Droplet amount: 1mm 3 Hold time: 5 seconds Measurement was performed 48 hours after film formation.

[0020] When the ceramic is mainly composed of aluminum oxide, the contact angle of the exposed portion 21 of the surface of the substrate 2A with pure water may be 60° or more and 80° or less. When the material of the film 3 is yttria, the contact angle of the surface of the film 3 with pure water may be 92° or more and 110° or less.

[0021] The surface of the film 3 may have an average value of the root mean square slope (RΔq) in the roughness curve of 0.3 or less. In this case, the contact angle of the surface of the film 3 with pure water becomes large, at 93° or more, and water droplets adhering to the film 3 can be easily repelled. The surface of the film 3 may have an average value of the root mean square slope (RΔq) in the roughness curve of 0.001 or more.

[0022] The surface of the film 3 may have an average value of the cut level difference (Rδc) (hereinafter simply referred to as the "average cut level difference (Rδc)") of 0.17 μm or less, which represents the difference between the cut level at a load length ratio of 25% on the roughness curve and the cut level at a load length ratio of 75% on the roughness curve. In this case, the contact angle of the surface of the film 3 with pure water becomes large, at 98° or more, so that water droplets adhering to the film 3 can be more easily repelled. Note that the surface of the film 3 may have an average value of the cut level difference (Rδc) of 0.01 μm or more.

[0023] The root mean square slope (RΔq) and cut level difference (Rδc) may be measured, for example, in accordance with JIS B 0601:2001, by drawing four lines to be measured at approximately equal intervals within the measurement range, measuring the line roughness, and calculating the average value for each. In this case, a total of 12 lines are measured on each surface. The measurement conditions may be set, for example, as follows: Measuring instrument: Shape analysis laser microscope (Keyence Corporation's "VK-X1100" or its successor model) Lighting: Coaxial epi-illumination Cutoff value λs: None Cutoff value λc: 0.08 mm Cutoff value λf: None End effect correction: Yes Measurement magnification: 480x (20x24) Measurement points: 3 points Measurement range: 710 μm x 533 μm / 1 location Length of wire to be measured: 560 μm / 1 wire

[0024] The exposed portion 21 on the surface of the substrate 2A may have an average root-mean-square slope (RΔq) of 0.001 or more in the roughness curve. In this case, the contact angle of the exposed portion 21 on the surface of the substrate 2A with pure water is small, at 78° or less, allowing water droplets to easily flow away. The exposed portion 21 on the surface of the substrate 2A may have an average root-mean-square slope (RΔq) of 0.284 or less in the roughness curve, and preferably 0.2 or less.

[0025] The exposed portion 21 on the surface of the substrate 2A may have an average cut level difference (Rδc) of 0.01 μm or more. In this case, the contact angle of the exposed portion 21 on the surface of the substrate 2A with pure water becomes small, at 66° or less, allowing water droplets to flow away more easily. The exposed portion 21 on the surface of the substrate 2A may have an average cut level difference (Rδc) of 0.14 μm or less.

[0026] The substrate 2A may be translucent. For example, when the substrate 2A is made of a translucent ceramic, the substrate 2A will be translucent. Furthermore, the substrate 2B made of quartz, which will be described later, also has translucent properties. Note that the translucent ceramic refers to a ceramic having a total light transmittance of 93% or more, such as translucent alumina, translucent yttria, translucent YAG, etc. The total light transmittance may be determined in accordance with JIS K7361-1:1997.

[0027] The average value of the arithmetic mean roughness (Ra) of the exposed portion 21 of the surface of the substrate 2A may be 0.004 μm or more and 0.17 μm or less. The arithmetic mean roughness (Ra) may be a value measured, for example, in accordance with JIS B 0601:2001 under the above-mentioned measurement conditions.

[0028] The surface of the film 3 may be a polished surface. In this case, the contact angle of the surface of the film 3 with pure water can be made larger than that of the film-formed surface (AS-DEPO surface).

[0029] The surface of the film 3 may be larger in area than the exposed portion 21 on the surface of the substrate 2A on which the film 3 is provided. In this case, the risk of a water film being generated is reduced, improving cleaning efficiency. Furthermore, when the substrate 2A is made of a translucent ceramic, visibility is ensured. This also applies to the substrate 2B made of quartz, which will be described later. In other words, visibility is ensured even when the substrate 2B is made of quartz.

[0030] The thickness of the film 3 may be 5 μm or more. In this case, the film 3 can be used for a long period of time even in an environment exposed to plasma. The thickness of the film 3 may be 8 μm or more. The thickness of the film 3 may be 50 μm or less.

[0031] The surface of the film 3 may be flat, or the flatness of the film 3 may be convex with a flatness of 3 μm or more. In this case, water droplets move more easily from the center of the film 3 toward the periphery, improving water sliding properties. The flatness of the film 3 may be 70 μm or less. For example, the flatness can be measured using a three-dimensional measuring device (CRYSTA-Apex S9106 manufactured by Mitutoyo Corporation or a successor model) to measure the heights of the center, inner periphery, and outer periphery of the circle if the film 3 is, for example, circular, and the maximum difference between these heights is regarded as the flatness of the film 3. The tip diameter of the stylus used in this measurement is, for example, 1 mm.

[0032] The number of measurements varies depending on the diameter of the membrane 3. For example, when the diameter of the membrane 3 is 400 mm or more and 600 mm or less, measurements may be taken at, for example, 29 locations radially from the center of the circle. When the diameter of the membrane 3 is 400 mm or more and 600 mm or less and a through-hole is formed in the center, measurements may be taken at, for example, 28 locations radially from the center of the circle.

[0033] The film 3 may be formed by a physical vapor deposition (PVD) method, in other words, the film 3 may be a PVD film.

[0034] As shown in the example of Fig. 1, there may be a plurality of exposed portions 21. In plan view, the plurality of exposed portions 21 may be linear (strip-shaped). The film 3 may be located between adjacent exposed portions 21. That is, the exposed portions 21 and the film 3 may be striped in plan view.

[0035] Next, a non-limiting embodiment of the film-coated member 1B of the present disclosure will be described with reference to the drawings. Below, differences between the film-coated member 1B and the film-coated member 1A will be mainly described, and detailed descriptions of the same configurations as the film-coated member 1A may be omitted.

[0036] 2, the film-coated member 1B comprises a substrate 2B made of quartz and a film 3 made of an oxide, fluoride, oxyfluoride, or nitride of a rare earth element on at least a portion of the surface of the substrate 2B. An exposed portion 21 on the surface of the substrate 2B is hydrophilic, and the surface of the film 3 is water-repellent. In these cases, because both the substrate 2B and the film 3 are made of inorganic compounds, they can maintain their water-slip properties for a long period of time even when used in an environment where they are irradiated with ultraviolet rays or plasma.

[0037] The contact angle of the exposed portion 21 of the surface of the substrate 2B with pure water may be 50° or more and 63° or less.

[0038] The surface of the film 3 in the film-coated member 1B may have an average value of the root-mean-square slope (RΔq) in the roughness curve of 0.009 or less. In this case, the contact angle of the surface of the film 3 with pure water becomes large, at 102° or more, and water droplets adhering to the film 3 can be easily repelled. The surface of the film 3 in the film-coated member 1B may have an average value of the root-mean-square slope (RΔq) in the roughness curve of 0.001 or more.

[0039] The surface of the film 3 in the film-coated member 1B may have an average cutting level difference (Rδc) of 0.01 μm or less. In this case, the contact angle of the surface of the film 3 with pure water becomes large, at 103° or more, so that water droplets adhering to the film 3 can be more easily repelled. Note that the surface of the film 3 in the film-coated member 1B may have an average cutting level difference (Rδc) of 0.006 μm or more.

[0040] The exposed portion 21 on the surface of the substrate 2B may have an average root-mean-square slope (RΔq) of 0.002 or more in the roughness curve. In this case, the contact angle of the exposed portion 21 on the surface of the substrate 2B with pure water is small, at 60° or less, allowing water droplets to easily flow away. The exposed portion 21 on the surface of the substrate 2B may have an average root-mean-square slope (RΔq) of 0.004 or less in the roughness curve.

[0041] The exposed portion 21 on the surface of the substrate 2B may have an average cut level difference (Rδc) of 0.004 μm or more. In this case, the contact angle of the exposed portion 21 on the surface of the substrate 2B with pure water is reduced to 8° or less, allowing water droplets to flow away more easily. The exposed portion 21 on the surface of the substrate 2B may have an average cut level difference (Rδc) of 0.006 μm or less.

[0042] The film-coated member 1A and the film-coated member 1B may have the following configuration. The film 3 may be made of yttrium oxide, and the full width at half maximum (FWHM) of the diffraction peak on the (222) plane of yttrium oxide obtained by X-ray diffraction may be 0.12° or less, and the coefficient of variation of the full width at half maximum may be 0.03 or less. If the full width at half maximum and its coefficient of variation are within this range, the crystallinity is high, residual stress is small, and its variation is also suppressed, reducing the risk of microcracks occurring in the film 3. Note that while only the upper limits of the full width at half maximum and its coefficient of variation are specified, it goes without saying that the full width at half maximum cannot be zero and does not include zero. In particular, the full width at half maximum is preferably 0.06° or more and 0.1° or less.

[0043] The apparatus used for X-ray diffraction is, for example, EmPyrean (manufactured by Spectris Co., Ltd.), and when this apparatus is used, the measurement conditions are as follows. Measurement range 2θ: 20~80° X-ray output settings: 40mA, 45kV Scan step time: 29 seconds Step size: 0.013° Divergence slit type: Fixed Divergence slit size: 0.25° Synchrotron radiation: CuKα1 (Kα2 removed)

[0044] When calculating the coefficient of variation of the half width, the number of measurements of the half width is, for example, 9. When the film 3 has a circular shape, the X-ray irradiation positions are, for example, the center, positions at 90° intervals on an imaginary circumference on the inner side, and positions at 90° intervals on an imaginary circumference on the outer side.

[0045] The geometric mean of the compressive stress σ11 generated within the surface of the film 3 and the compressive stress σ2 generated within the surface in a direction perpendicular to the compressive stress σ11 may be 120 MPa or more, and the coefficient of variation of the geometric mean may be 0.2 or less.

[0046] If the geometric mean is 120 MPa or more, the hardness of the film 3 increases, so that particles are less likely to detach from the film 3 even when impacted by particles floating inside the plasma processing apparatus, reducing the risk of these detached particles floating around and contaminating the inside of the plasma processing apparatus.

[0047] When the coefficient of variation of the geometric mean is 0.2 or less, the film 3 can withstand the tensile stress generated inside the film 3 even when used in an environment where the temperature rises and falls repeatedly, and the risk of the film 3 being damaged can be reduced.

[0048] The values ​​of the compressive stress σ11 and the compressive stress σ22 may be determined by the 2D method using an X-ray diffraction device.

[0049] When calculating the coefficient of variation of the geometric mean, the number of measurements of the compressive stress σ11 and the compressive stress σ22 is, for example, 9. When the film 3 is circular, the X-ray irradiation positions are, for example, the center, positions at 90° intervals on an imaginary circumference on the inner side, and positions at 90° intervals on an imaginary circumference on the outer side.

[0050] <Method of manufacturing film-coated member> Next, a method for producing a film-coated member according to a non-limiting embodiment of the present disclosure will be described using an example in which the film-coated member 1A is produced.

[0051] First, a substrate 2A made of ceramic may be prepared, and then a film 3 may be formed by PVD on at least one part of the surface of the prepared substrate 2A to obtain a film-coated member 1A.

[0052] Specifically, a method for manufacturing a substrate made of ceramics containing aluminum oxide as the main component will be described.

[0053] Aluminum oxide (Al2O3) A powder with an average particle size of 0.4 μm to 0.6 μm and aluminum oxide B powder with an average particle size of approximately 1.2 μm to 1.8 μm are prepared. Silicon oxide (SiO2) powder is prepared as the Si source, and calcium carbonate (CaCO3) powder is prepared as the Ca source. Note that the silicon oxide powder is a fine powder with an average particle size of 0.5 μm or less. Magnesium hydroxide powder is used to obtain alumina ceramics containing Mg. Note that in the following description, powders other than aluminum oxide A powder and aluminum oxide B powder are collectively referred to as the first minor component powder.

[0054] Then, predetermined amounts of the first minor component powders are weighed out. Next, the mass ratio of aluminum oxide A powder to aluminum oxide B powder is set to 40:60 to 60:40, and the aluminum oxide powder is weighed out so that the content of Al, calculated as Al2O3, is 99.4 mass% or more out of 100 mass% of the components constituting the resulting ceramic, to obtain an aluminum oxide blended powder. Furthermore, for the first minor component powder, the amount of Na in the aluminum oxide blended powder is first determined, and the amount of Na in the resulting ceramic is converted to Na2O, and the components (in this example, Si, Ca, etc.) constituting the first minor component powder are weighed out so that the ratio of this converted value to the value converted to oxide is 1.1 or less.

[0055] Then, a total of 100 parts by mass of the aluminum oxide compound powder and the first subcomponent powder are mixed and stirred in a stirring device with 1 to 1.5 parts by mass of a binder such as PVA (polyvinyl alcohol), 100 parts by mass of a solvent, and 0.1 to 0.55 parts by mass of a dispersant to obtain a slurry.

[0056] The slurry is then sprayed and granulated to obtain granules, which are then molded into a predetermined shape using a powder press molding device, an isostatic press molding device, or the like, and, if necessary, subjected to cutting to obtain a substrate-like molded body.

[0057] Next, the sintered body is sintered at a temperature of 1500°C to 1700°C for a holding time of 4 to 6 hours to obtain a sintered body. The surface of the sintered body on which the film is to be formed is then ground to obtain a ground surface, which is then roughly polished using diamond abrasive grains with an average particle size of 4 μm or more and a cast iron polishing disc. Rough polishing may be performed using diamond abrasive grains with a larger average particle size, followed by diamond abrasive grains with a smaller average particle size. Subsequent finish polishing using diamond abrasive grains with an average particle size of 1 μm to 5 μm and a tin polishing disc results in the substrate 2A (2B). After the finish polishing, polishing may be performed using colloidal silica, ceria, or alumina abrasive grains and a polishing pad made of a nonwoven fabric of polyester fiber impregnated with polyurethane. The average particle size of the colloidal abrasive grains is, for example, 20 μm to 50 μm.

[0058] Next, a method for forming the film will be described with reference to FIG. FIG. 6 is a schematic diagram showing a sputtering apparatus 20, which includes a chamber 9, a gas supply source 13 connected to the inside of the chamber 9, an anode 14 and a cathode 12 located within the chamber 9, and a target 11 connected to the cathode 12 side.

[0059] In the film formation method, the substrate 2A (2B) obtained by the above-described method is placed on the anode 14 side in chamber 9. Furthermore, a target 11 containing a rare earth element, in this case metallic yttrium as the main component, is placed on the cathode 12 side on the opposite side of chamber 9. In this state, the pressure inside chamber 9 is reduced by an exhaust pump, and argon and oxygen are supplied as gas G from gas supply source 13. Here, the pressure of the supplied argon gas is 0.1 Pa or more and 2 Pa or less, and the pressure of the supplied oxygen gas is 1 Pa or more and 5 Pa or less.

[0060] Then, an electric field is applied between the anode 14 and the cathode 12 by a power source, generating plasma P1 and performing sputtering to form a metal yttrium film on the surface of the substrate 2A (2B). The thickness of each formation is sub-nanometer. Next, plasma P2 is generated to oxidize the metal yttrium film. Then, by alternately performing metal yttrium film formation and oxidation processes to achieve a total film thickness of 5 μm to 50 μm, a film-coated member 1A (1B) having an yttrium oxide film can be obtained. The symbol P in FIG. 6 represents plasma P1 or plasma P2.

[0061] The plasma P1 has a spectrum in which the first spectrum, which has the highest intensity, is located at wavelengths of 390 nm to 430 nm, and the other spectrums (second spectrum, third spectrum, and fourth spectrum, in descending order of intensity) are located at wavelengths of 300 nm to 700 nm.

[0062] The plasma P2 has a spectrum in which the first spectrum, which has the highest intensity, is located at a wavelength of 500 nm to 550 nm, and the other spectrums (the second spectrum, third spectrum, and fourth spectrum, in descending order of intensity) are located at a wavelength of 380 nm to 820 nm.

[0063] Also, to form a film of yttrium fluoride, the oxidation step may be replaced by a fluorination step.

[0064] Furthermore, to form a film of yttrium oxyfluoride, it is sufficient to alternately perform the formation of a metallic yttrium film, an oxidation step, and a fluorination step in this order to form a laminate.

[0065] Also, to form a film of yttrium nitride, the oxidation step may be replaced with a nitridation step.

[0066] The power supplied from the power source may be either high frequency power or DC power.

[0067] The film-coated member 1B can be produced in the same manner as the film-coated member 1A, except that the substrate 2B made of quartz is prepared instead of the substrate 2A made of ceramic.

[0068] <Anti-fouling materials> Next, an antifouling member according to a non-limiting embodiment of the present disclosure will be described. An antifouling member according to a non-limiting embodiment of the present disclosure includes a film-coated member 1A, which can maintain water-sliding properties for a long period of time even when used in an environment where it is irradiated with ultraviolet rays or plasma.

[0069] The antifouling member may be a member used in a flowing water environment. Examples of the antifouling member include members used in a flowing water environment such as toilet bowls, toilet toilet basins, bathroom basins, kitchen sinks, shower nozzles, tableware, toilet pipes, water pipes, faucets, private cleaning nozzles, laundry tubs, dishwashers, roofs, building exterior walls, and pavements, as well as tableware that use running water for cleaning, bathtubs, bathroom walls, bathroom floors, bathroom fixtures, automobiles, railroad cars, aircraft, and tiles. The antifouling member may include film-coated member 1B instead of film-coated member 1A.

[0070] <Plasma treatment device components> Next, a non-limiting embodiment of a member for a plasma processing apparatus according to the present disclosure will be described with reference to the drawings, taking as an example a case where the member includes the above-described film-coated member 1A.

[0071] 3 is a top plate of a processing vessel in a plasma processing apparatus, and includes a film-coated member 1 A. In this case, even when used in an environment where ultraviolet rays or plasma are irradiated, the water-repellent property can be maintained for a long period of time.

[0072] When the film-coated member 1A is included in the member 10 for a plasma processing apparatus, the substrate 2A may be disk-shaped. The exposed portion 21 may be annular along the peripheral edge of the substrate 2A in a plan view. The surface area of ​​the film 3 may be largest at the center. The member 10 for a plasma processing apparatus may include a film-coated member 1B instead of the film-coated member 1A.

[0073] Since the above-described film-coated members 1A and 1B of the present disclosure can maintain water-slip properties for a long period of time, they may be included in components for plasma processing apparatuses that are prone to adhesion of plasma reaction products and require repeated removal and cleaning, such as a high-frequency transmission window member that transmits high-frequency waves for generating plasma, a susceptor for placing a semiconductor wafer, etc. Furthermore, the components for plasma processing apparatuses may be the top plate, sidewall, etc. of a chamber having an internal space for plasma processing.

[0074] <Plasma processing equipment> Next, a plasma processing apparatus according to a non-limiting embodiment of the present disclosure will be described. A plasma processing apparatus according to a non-limiting embodiment of the present disclosure includes the above-described member for a plasma processing apparatus 10. In this case, even when used in an environment where ultraviolet rays or plasma are irradiated, water slideability can be maintained for a long period of time.

[0075] Although the embodiments of the present disclosure have been exemplified above, it goes without saying that the present disclosure is not limited to the above-described embodiments and can be any embodiment as long as it does not deviate from the gist of the present disclosure.

[0076] For example, the shape of the exposed portion 21 in plan view is not limited to the illustrated shape. Figures 4 and 5 are diagrams showing variations in the shape of the exposed portion 21. As shown in the example of Figure 4, the exposed portion 21 in the film-coated member 1C may be lattice-shaped in plan view. As shown in the example of Figure 5, the exposed portion 21 in the film-coated member 1D may be lattice-shaped in plan view and positioned so as to surround the center. Furthermore, the surface area of ​​the film 3 may be largest at the center. The shape of the film is rectangular in Figures 1 and 2, circular and annular in Figure 3, and square in Figure 5, but it may also be spiral, or a combination of these shapes.

[0077] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to the following examples. [Example]

[0078] [Samples No. 1-4] <Preparation of test specimens> First, the substrates shown in Table 1 were prepared. The substrates were plate-shaped and made of ceramics containing 99.6% by mass of aluminum oxide and quartz. The aluminum oxides (1) and (2) shown in Table 1 are as follows: Aluminum oxide (1): The average arithmetic mean roughness (Ra) is 0.1 μm Aluminum oxide (2): The average arithmetic mean roughness (Ra) is 0.03 μm The arithmetic mean roughness (Ra) is a value measured in accordance with JIS B 0601: 2001. The measuring instrument used was a shape analysis laser microscope ("VK-X1100" manufactured by Keyence Corporation), and the other measurement conditions were as described above.

[0079] Next, a film was formed on one surface of the substrate to obtain a test piece. The film formation method, film material, and film thickness are as follows. Film formation method: above method Membrane material: Yttria Film thickness: 10 μm

[0080] <Evaluation> The static contact angle of the obtained test piece with pure water was measured 48 hours after the film formation. The measurement method is as follows.

[0081] (Static contact angle to pure water) Measurement equipment: Surface contact angle measurement equipment "CA-X type" manufactured by Kyowa Interface Science Co., Ltd. Solvent: Pure water Droplet amount: 1mm 3 Hold time: 5 seconds Other: Measurements were performed with n=5, and the average value and standard deviation were calculated. The results are shown in the "Contact angle" column in Table 1.

[0082] [Table 1]

[0083] In Samples Nos. 1 to 3 of the present disclosure, the exposed surface of the substrate (without a film) was hydrophilic, and the surface of the film (with a film) was water-repellent even after only 48 hours. From these results, it can be said that Samples Nos. 1 to 3 have water-sliding properties. [Explanation of symbols]

[0084] 1A...Membrane-coated material 1B: Film-coated member 2A: Ceramic substrate 2B: Quartz substrate 21...Exposed part 3...membrane 10. Plasma treatment device component

Claims

1. a substrate made of ceramic; A film-coated member comprising a film of an oxide, fluoride, oxyfluoride or nitride of a rare earth element on at least a portion of the surface of the substrate, A film-coated member, wherein the exposed portion of the surface of the substrate is hydrophilic, and the surface of the film is water-repellent.

2. 2. The film-coated member according to claim 1, wherein the surface of the film has an average value of the root mean square slope (RΔq) of a roughness curve of 0.3 or less.

3. 3. The film-coated member according to claim 1, wherein the surface of the film has an average value of a cut level difference (Rδc) of 0.17 μm or less, which represents the difference between the cut level at a load length ratio of 25% on a roughness curve and the cut level at a load length ratio of 75% on the roughness curve.

4. 4. The film-coated member according to claim 1, wherein the exposed portion of the surface of the substrate has an average value of the root mean square slope (RΔq) in a roughness curve of 0.001 or more.

5. The film-coated member according to any one of claims 1 to 4, wherein the exposed portion of the surface of the substrate has an average value of a cut level difference (Rδc) of 0.01 μm or more, which represents the difference between the cut level at a load length ratio of 25% on a roughness curve and the cut level at a load length ratio of 75% on the roughness curve.

6. a substrate made of quartz; A film-coated member comprising a film of an oxide, fluoride, oxyfluoride or nitride of a rare earth element on at least a portion of the surface of the substrate, A film-coated member, wherein the exposed portion of the surface of the substrate is hydrophilic, and the surface of the film is water-repellent.

7. 7. The film-coated member according to claim 6, wherein the surface of the film has an average value of the root mean square slope (RΔq) of a roughness curve of 0.009 or less.

8. 8. The film-coated member according to claim 6, wherein the surface of the film has an average value of a cut level difference (Rδc) of 0.01 μm or less, which represents the difference between the cut level at a load length ratio of 25% on a roughness curve and the cut level at a load length ratio of 75% on the roughness curve.

9. 9. The film-coated member according to claim 6, wherein the exposed portion of the surface of the substrate has an average value of the root mean square slope (RΔq) in a roughness curve of 0.002 or more.

10. The film-coated member according to any one of claims 6 to 9, wherein the exposed portion of the surface of the substrate has an average value of a cut level difference (Rδc) of 0.004 μm or more, which represents the difference between the cut level at a load length ratio of 25% on a roughness curve and the cut level at a load length ratio of 75% on the roughness curve.

11. The film-coated member according to any one of claims 1 to 10, wherein the surface of the film is a polished surface.

12. 12. The film-coated member according to claim 1, wherein the surface of the film is larger in area than the exposed portion of the surface of the substrate provided with the film.

13. The film-coated member according to any one of claims 1 to 12, wherein the film has a thickness of 5 µm or more.

14. 14. The film-coated member according to claim 1, wherein the surface of said film is flat and the film has a convex flatness of 3 μm or more.

15. The film-coated member according to any one of claims 1 to 14, wherein the film is made of yttrium oxide, and the half-width of the diffraction peak in the (222) plane of the yttrium oxide obtained by X-ray diffraction is 0.12° or less, and the coefficient of variation of the half-width is 0.03 or less.

16. A film-coated member according to any one of claims 1 to 15, wherein the geometric mean of the compressive stress σ11 generated within the surface of the film and the compressive stress σ2 generated within the surface in a direction perpendicular to the compressive stress σ11 is 120 MPa or more, and the coefficient of variation of the geometric mean is 0.2 or less.

17. An antifouling member comprising the film-coated member according to any one of claims 1 to 16.

18. A member for a plasma processing apparatus, comprising the film-coated member according to any one of claims 1 to 16.

19. A plasma processing apparatus comprising the member for a plasma processing apparatus according to claim 18.

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