Coating substrate, and method for manufacturing a coating substrate
A coated substrate with controlled film thickness and composition addresses the limitations of conventional substrates, offering enhanced functionality and durability for diverse applications through a dry film deposition method.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- NITERRA CO LTD
- Filing Date
- 2023-07-20
- Publication Date
- 2026-06-01
AI Technical Summary
Conventional coated substrates are inadequate for various applications and mass production due to limitations in controlling film thickness on complex shapes and substrate compatibility.
A coated substrate with a film thickness of 1 nm to 800 nm, having a total elemental percentage of metal elements and oxygen of 70 atm% or more, and a relative density of 90% or more, with specific thickness variations on edge and convex regions, and amorphous structure, formed using a dry film deposition method.
The coated substrate provides enhanced functionality and durability, is cost-effective, and suitable for mass production, with improved adhesion and stress mitigation on complex shapes.
Smart Images
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Abstract
Description
[Technical Field]
[0001] This disclosure relates to a coated substrate. [Background technology]
[0002] Patent documents 1-4 disclose coated substrates equipped with a metal oxide film. Patent documents 1-4 employ a wet film deposition method. On the other hand, dry film deposition methods (dry processes) are sometimes used to control the thickness to match complex substrate shapes. Considering applicability to various fields and mass production capabilities, conventional coating substrates are not always sufficient, and the development of new coating substrates was urgently needed. [Prior art documents] [Patent Documents]
[0003] [Patent Document 1] Japanese Patent Publication No. 2011-32521 [Patent Document 2] Japanese Patent Publication No. 2009-147192 [Patent Document 3] Japanese Patent Publication No. 2015-93821 [Patent Document 4] Japanese Patent Application Publication No. 9-202606 [Overview of the project] [Problems that the invention aims to solve]
[0004] This disclosure is made in view of the above circumstances and aims to provide a novel coating substrate that is applicable to various fields and can be mass-produced. This disclosure can be realized in the following forms. [Means for solving the problem]
[0005] [1] The substrate is covered with a film, The thickness of the aforementioned film is 1 nm or more and less than 800 nm. When the aforementioned film was measured by X-ray photoelectron spectroscopy, the total elemental percentage of metal elements and O (oxygen) was 70 atm% or more. The relative density of the aforementioned film is 90% or more. A coating substrate that satisfies at least one of the following conditions (1) and (2). Condition (1): The maximum thickness of the film formed on the edge region of the surface of the substrate is greater than the thickness of the film formed on the inner region of the surface that is inside the edge region. Condition (2): The maximum thickness of the film formed on the region of the surface of the substrate where the convex portion exists is greater than the thickness of the film formed on the region of the surface where the convex portion does not exist. [2] The coated substrate according to [1], wherein the portion of the substrate on which the coating is formed has conductivity. [3] The coated substrate according to [1] or [2], wherein the elemental percentage of C (carbon) is 0.1 atm% or more and less than 20 atm% when the coating is measured by X-ray photoelectron spectroscopy. [4] The coating is amorphous, as described in [1] or [2]. [5] The coated substrate according to [1] or [2], wherein, in the condition (1) above, the maximum thickness of the film formed on the edge region is 10% or more greater than the thickness of the film formed on the inner region. [6] The coated substrate according to [1] or [2], wherein, in the above condition (2), the maximum thickness of the film formed on the region where the convex portion exists is 10% or more greater than the thickness of the film formed on the region where the convex portion does not exist. [7] In the above condition (1), the thickness of the coating decreases from the area of maximum thickness of the coating formed on the edge region toward the inner region, as described in [1] or [2]. [8] In the above condition (2), the thickness of the film decreases from the site with the maximum thickness of the film formed on the convex portion existing area toward the convex portion non-existing area. The coated substrate according to [1] or [2]. [9] The metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). The coated substrate according to [1] or [2].
Advantages of the Invention
[0006] According to the present disclosure, a novel coated substrate applicable to various fields and mass-producible is provided.
Brief Description of the Drawings
[0007] [Figure 1] It is a schematic diagram of the cross section of the coated substrate. [Figure 2] It is a schematic diagram of the cross section of the coated substrate. [Figure 3] It is a schematic diagram of the film forming apparatus. [Figure 4] It is a graph showing the relationship between the electrolysis time and the deposition weight (deposition mass). [Figure 5] It is a graph showing the relationship between the number of trial productions of the sample and the concentration of the aluminum element in the bath solution.
Embodiments for Carrying Out the Invention
[0008] The following provides a detailed explanation of this disclosure. In this specification, when numerical ranges are described using "-", unless otherwise specified, both the lower and upper limits are included. For example, the description "10-20" includes both the lower limit "10" and the upper limit "20". In other words, "10-20" has the same meaning as "10 or more and 20 or less". Furthermore, in this specification, the upper and lower limits of each numerical range can be combined in any way.
[0009] 1. Coating substrate 1 The coated substrate 1 is formed by coating the substrate 5 with a film 3. The thickness T of the film 3 is 1 nm or more and less than 800 nm. When the film 3 is measured by X-ray photoelectron spectroscopy, the total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The relative density of the film 3 is 90% or more. The coated substrate 1 satisfies at least one of the following conditions (1) and (2). The functionality of the coated substrate 1 is enhanced by satisfying at least one of conditions (1) and (2). Condition (1): The maximum thickness T1max of the film 3 formed on the edge region S1 of the surface S of the substrate 5 is greater than the thickness T2 of the film 3 formed on the inner region S2 which is inside the edge region S1 of the surface S. Condition (2): The maximum thickness T3max of the film 3 formed on the convex portion region S3 of the surface S of the substrate 5 is greater than the thickness T4 of the film 3 formed on the non-convex portion region S4 of the surface S.
[0010] Figure 1 shows a schematic cross-section of an example of a coated substrate 1. In Figure 1, an example is shown in which the coating 3 is formed on one side of the substrate 5, but the coating 3 may also be formed on both sides. Figure 2 shows a schematic cross-section of another example of the coated substrate 1. In Figure 2, an example is shown in which the coating 3 is formed on one side of the substrate 5, but the coating 3 may also be formed on both sides.
[0011] (1) Base material 5 The base material 5 is not particularly limited. In order to improve the adhesion of the coating 3 to the base material 5, it is preferable that at least the portion (region) of the base material 5 covered by the coating 3 is made of a material that is conductive and can act as a negative electrode 7 (cathode). By having the portion of the base material 5 covered by the coating 3 be conductive and act as a negative electrode 7 (cathode), the coating 3 can be easily formed on this portion by the manufacturing method described later. The surface of the base material 5 may be made of a material that is conductive and can become the negative electrode 7. The entire base material 5 may be made of a material that can become the negative electrode 7. Suitable materials that can become the negative electrode 7 include, for example, iron-based alloys and carbon. Suitable examples of iron-based alloys include one or more selected from Fe-Ni-Cr alloys (stainless steel), Fe-Ni alloys (permalloy), Fe-Si alloys (silicon-iron), Fe-Si-Al alloys (Sendust), Fe-Ni-Mo (supermalloy), Fe-Co alloys (permendur), and Fe-CB alloys (amorphous).
[0012] (2) Coating 3 (2.1) Thickness T The thickness T of the film 3 is the shortest distance from a point on the surface of the film 3 to the surface S of the substrate 5. From the viewpoint of exhibiting functions according to the material of the film 3, the thickness T of the film 3 is 1 nm or more, preferably 10 nm or more, and more preferably 50 nm or more. On the other hand, from the viewpoint of withstanding the stress generated in the film 3 and ensuring adhesion with the substrate 5, it is less than 800 nm, preferably 500 nm or less, and more preferably 200 nm or less. From these viewpoints, the thickness T of the film 3 is 1 nm or more and less than 800 nm, preferably 10 nm or more and 500 nm or less, and more preferably 50 nm or more and 200 nm or less. If the thickness T of the film 3 is not constant, the requirement for thickness T is satisfied if at least a part of the thickness T of the film 3 is within the above range. The thickness of the film 3 can be determined by FIB-SEM observation.
[0013] (2.2) Conditions regarding the thickness T of the coating 3 (1) Condition (1) is that the maximum thickness T1max of the film 3 formed on the edge region S1 of the surface S of the substrate 5 is greater than the thickness T2 of the film 3 formed on the inner region S2 which is inside the edge region S1 of the surface S. The maximum thickness T1max of the film 3 formed on the edge region S1 is the maximum value of the thickness T1 of the film 3 formed on the edge region S1. The edge region S1 is not particularly limited as long as it is the edge of the surface S. For example, in a cross-sectional view, the edge region S1 is the area within a radius of 5 mm centered on the edge SE of the surface S of the base material 5. In the example in Figure 1, the edge region S1 is the area enclosed by the dashed line. In the example in Figure 1, the maximum thickness T1max is the thickness T1 at the edge SE. The maximum thickness T1max is not particularly limited. The maximum thickness T1max is preferably, for example, 10 nm to 1000 nm, more preferably 50 nm to 800 nm, and even more preferably 100 nm to 500 nm. The thickness T2 is not particularly limited as long as it is less than the maximum thickness T1max. For example, the thickness T2 is preferably 1 nm to 800 nm, more preferably 10 nm to 500 nm, and even more preferably 50 nm to 200 nm. In condition (1), the maximum thickness T1max of the coating 3 formed on the edge region S1 is preferably 10% or more greater than the thickness T2 of the coating 3 formed on the inner region S2, more preferably 20% or more greater, and even more preferably 30% or more greater, from the viewpoint of improving the functionality of the coated substrate 1. If the thickness T2 is not uniform, this relationship is satisfied if the maximum thickness T1max is greater than the thickness T2 by a predetermined percentage or more, using the thickness T2 value in at least a part of the inner region S2. There is no upper limit to the ratio of the maximum thickness T1max to the thickness T2, but in condition (1), the maximum thickness T1max is preferably 400% or less of the thickness T2. In condition (1), it is preferable that the thickness T of the coating 3 decreases from the area with the maximum thickness T1max of the coating 3 formed on the edge region S1 toward the inner region S2. Irregularities of 10% or less of the maximum thickness T1max are not considered. This structure allows for the widespread mitigation of the effects of residual stress generated at the interface of the substrate 5. Furthermore, condition (1) regarding the thickness T of the coating 3 is determined by observing a cross-section of the coated substrate 1 perpendicular to the surface S of the substrate 5 using FIB-SEM.
[0014] (2.3) Conditions regarding the thickness T of the coating 3 (2) Condition (2) is that the maximum thickness T3max of the film 3 formed on the convex portion-existing region S3 of the surface S of the substrate 5 is greater than the thickness T4 of the film 3 formed on the convex portion-non-existing region S4 of the surface S. The maximum thickness T3max of the film 3 formed on the convex portion-existing region S3 is the maximum value of the thickness T3 of the film 3 formed on the convex portion-existing region S3. The shape, size, and number of convex portions 12 are not particularly limited. If there are multiple convex portions 12, condition (2) is satisfied in the film 3 formed on the convex portion-existing region S3 related to one convex portion 12 and in the film 3 formed on the adjacent convex portion-non-existing region S4, then condition (2) regarding the thickness T of the film 3 is satisfied. The convex portions 12 may be, for example, mountain-shaped, protruding, needle-shaped, or columnar. The maximum height h of the convex portion 12 is not particularly limited, but is preferably 100 nm to 10 mm, more preferably 500 nm to 5 mm, and even more preferably 1000 nm to 2 mm. The maximum height h of the convex portion 12 refers to the height relative to the surface S of the substrate 5 in the region S4 where the convex portion is not present. The area occupied by the convex portion 12 when viewed from vertically above the substrate 5 is not particularly limited, but is preferably 10 μm. 2 100mm or more 2 The following is preferred: 100 μm 2 10mm or more 2 The following is more preferable: 500 μm 2 1mm or more 2 The following is even more preferable. The maximum thickness T3max is not particularly limited. The maximum thickness T3max is preferably 10 nm to 1000 nm, more preferably 50 nm to 800 nm, and even more preferably 100 nm to 500 nm. The thickness T4 is not particularly limited as long as it is less than the maximum thickness T3max. For example, the thickness T4 is preferably 1 nm to 800 nm, more preferably 10 nm to 500 nm, and even more preferably 50 nm to 200 nm. In condition (2), the maximum thickness T3max of the coating 3 formed on the convex portion-existing region S3 is preferably 10% or more greater than the thickness T4 of the coating 3 formed on the convex portion-non-existing region S4, more preferably 20% or more greater, and even more preferably 30% or more greater, from the viewpoint of enhancing the functionality of the coated substrate 1. If the thickness T4 is not uniform, this relationship is satisfied if the maximum thickness T3max is greater than the thickness T4 by a predetermined percentage or more, using the thickness T4 value in at least a part of the convex portion-non-existing region S4. There is no upper limit to the ratio of the maximum thickness T3max to the thickness T4, but in condition (2), the maximum thickness T3max is preferably 400% or less of the thickness T4. In condition (2), it is preferable that the thickness T of the coating 3 decreases from the area where the maximum thickness T3max of the coating 3 is formed on the convex portion present region S3 toward the area S4 where the convex portion does not exist. Note that irregularities of 10% or less of the maximum thickness T3max are not considered. This structure allows for the widespread mitigation of the effects of residual stress generated at the interface of the substrate 5. Furthermore, condition (2) regarding the thickness T of the coating 3 is determined by observing a cross-section of the coated substrate 1 perpendicular to the surface S of the substrate 5 using FIB-SEM.
[0015] (2.4) Percentage of the element C (carbon) The elemental percentage of carbon (C) when the coating 3 is measured by X-ray photoelectron spectroscopy (XPS) is preferably 0.1 atm% or more, more preferably 0.5 atm% or more, and more preferably 1 atm% or more, from the viewpoint of suppressing grain growth in the coating 3 and stabilizing the properties of the coating 3. On the other hand, from the viewpoint of allowing the coating 3 to function sufficiently as an inorganic coating, it is preferably less than 20 atm%, more preferably 15 atm% or less, and more preferably 10 atm% or less. From these viewpoints, the elemental percentage of carbon (C) is preferably 0.1 atm% or more and less than 20 atm%, more preferably 0.5 atm% or more and 15 atm% or less, and more preferably 1 atm% or more and 10 atm% or less. If the composition of the coating 3 is not constant, the requirement for the elemental percentage of carbon (C) is satisfied if at least a part of the composition of the coating 3 is within the above range. Compositional analysis by X-ray photoelectron spectroscopy can be performed using an X-ray photoelectron spectrometer. The measurement conditions involve using an aluminum metal K-alpha X-ray source, a beam diameter of 100 μm, and an X-ray incidence angle of 45° relative to the surface to be analyzed. The measurement is performed by scanning the cross-section.
[0016] (2.5) Total elemental percentage of metallic elements and O (oxygen) When the coating 3 is measured by X-ray photoelectron spectroscopy (XPS), the total elemental percentage of metal elements and O (oxygen) is 70 atm% or more, preferably 80 atm% or more, and more preferably 90 atm% or more, from the viewpoint of ensuring that the coating 3 functions sufficiently as an inorganic coating. The upper limit of the total elemental percentage of metal elements and O (oxygen) is the value obtained by subtracting the elemental percentage of C (carbon) (atm%) from 100 atm%. If the composition of the coating 3 is not constant, the requirement for the total elemental percentage of metal elements and O (oxygen) is satisfied if at least a part of the composition of the coating 3 is within the above range.
[0017] (2.6) Relative density of coating 3 The relative density of the coating 3 is 90% or more, preferably 95% or more, and more preferably 98% or more, from the viewpoint of fully exhibiting the function of the coating 3. The relative density of the coating 3 may also be 100%. The relative density of film 3 is determined by the following method: Obtain a cross-sectional TEM image of film 3 cut in the direction of film thickness. Measure the pore area in a field of view of 300 nm vertically and 1000 nm horizontally. Calculate the relative density (%) from equation (1) below. The average of the relative densities of 10 fields of view is the relative density of film 3. If the thickness of film 3 is less than 300 nm vertically, the measurement should be performed in a field of view that matches the thickness of film 3. Relative density (%) = {(S1-S2) / S1} × 100 (1) (In the formula, S1 is the area of the field of view, which is 300 nm vertically and 1000 nm horizontally (nm) 2 ) and S2 is the total area of pores (nm) within a field of view of 300 nm vertically × 1000 nm horizontally. 2 )
[0018] (2.7) Amorphous The coating 3 is preferably amorphous. Amorphous properties can be confirmed using TEM imaging. The amorphous nature of the coating 3 allows for the expectation of unique functionalities, such as the absence of grain shedding and smoothing of the outermost surface due to uniform film growth.
[0019] (2.8) Compounds having at least one of the following structures: CH bond, C=O bond, CO bond It is preferable that the coating 3 contains a compound having at least one of the following structures: CH bond, C=O bond, or CO bond. Compounds having at least one of the CH, C=O, or CO bond structures volatilize at lower temperatures than elemental carbon, inducing shrinkage of the coating 3, which is presumed to improve the density of the coating 3. Furthermore, it is presumed that the presence of compounds having at least one of the following structures—CH bond, C=O bond, or CO bond—in the film 3 helps maintain the flexibility of the film 3 and improves its adhesion to the substrate 5.
[0020] (2.9) Halogen elements When the coating 3 is measured by X-ray photoelectron spectroscopy, the elemental percentage of halogen elements is preferably 0.1 atm% or more, more preferably 0.3 atm% or more, and even more preferably 0.5 atm% or more. The upper limit of the elemental percentage of halogen elements is 3 atm% or less. It is believed that the presence of trace amounts of halogen elements in the coating 3 removes the oxide film present on the surface S of the substrate 5 through the action of the halogen elements, resulting in a structure where the coating 3 and the substrate 5 are in direct contact, and consequently ensuring good adhesion between the substrate 5 and the coating 3.
[0021] (2.10) Metal elements The metal element is not particularly limited. From the viewpoint of enabling the coating 3 to function as a good protective film for the substrate 5, it is preferable that the metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin).
[0022] 2. Method for manufacturing the coated substrate 1 The method for manufacturing the coated substrate 1 of this disclosure is not particularly limited. A preferred manufacturing method is described below (see Figure 3). The preferred manufacturing method is a method for manufacturing a coated substrate 1 using a bath solution 2 with an organic solvent as the solvent. The bath solution 2 has a water content of less than 1% by mass, contains at least one metal element, and contains at least one halogen element. With the substrate 5 immersed in the bath solution 2, a voltage is applied to form a film 3 on the substrate 5 on the negative electrode 7 side (cathode side). In the manufacturing method of this disclosure, electrodeposition on the negative electrode 7 side can suppress oxidation of the substrate 5 more than electrodeposition on the positive electrode 6 side (anode side).
[0023] (1) Bath liquid 2 Bath solution 2 uses an organic solvent as its solvent. (1.1) Moisture content To ensure the homogeneity of the coating 3 and suppress oxidation of the substrate 5, the water content of the bath solution 2 is set to less than 1% by mass. A water content of less than 0.5% by mass is preferable, and less than 0.1% by mass is more preferable. A water content of 0% by mass is also acceptable. The water content of the bath solution 2 can be determined by GC-MS analysis.
[0024] (1.2) Metallic elements The bath solution 2 contains at least one metal element. The metal element is not particularly limited. From the viewpoint of enabling the film 3 to function as a good protective film for the substrate 5, it is preferable that the metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). In the manufacturing method of this disclosure, an oxide film, which is a film 3, is formed depending on the metal element in the bath solution 2. The metal elements contained in the bath solution 2 may be supplied into the bath solution 2 by the dissolution of the positive electrode 6 (anode). When the metal elements dissolve from the positive electrode 6 into the bath solution 2, it becomes easier to control the film deposition rate and enables continuous and stable film deposition on multiple substrates 5. When the metal elements are supplied to the bath solution 2 by the dissolution of the positive electrode 6, it is preferable that the positive electrode 6 is at least one electrode selected from Al electrodes, Ti electrodes, and Mo electrodes. The metal elements in the bath solution 2 may be supplied from metal alkoxides and / or inorganic metal compounds. When the metal elements are supplied by dissolving metal alkoxides and / or inorganic metal compounds, it is possible to accommodate elements that are difficult to supply by dissolving the positive electrode 6 (anode). In this case, it is also possible to form a film with a controlled composition ratio by combining multiple metal elements. Examples of metal alkoxides include aluminum alkoxide, titanium alkoxide, and molybdenum alkoxide. Examples of aluminum alkoxides include aluminum trialkoxide. Examples of aluminum trialkoxides include aluminum trippropoxide (e.g., aluminum triisopropoxide, aluminum tri-n-propoxide), aluminum triethoxide, and aluminum tributoxide (e.g., aluminum trisec-butoxide, aluminum tri-n-butoxide). Examples of titanium alkoxides include titanium trialkoxide and titanium tetraalkoxide, with titanium tetraalkoxide being preferred. Examples of titanium tetraalkoxides include titanium tetrapropoxide (e.g., titanium tetraisopropoxide, titanium tetra n-propoxide, etc.), titanium tetramethoxide, titanium tetraethoxide, titanium tetrabutoxide (e.g., titanium tetraisobutoxide, titanium tetra n-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexoxide, and titanium tetra(2-ethylhexoxide). Examples of inorganic metal compounds include aluminum chloride, aluminum bromide, aluminum iodide, and titanium iodide. When the metal elements in the bath solution 2 are supplied from metal alkoxides and / or inorganic metal compounds, the concentration of the metal elements in the bath solution 2 is not particularly limited. In this case, from the viewpoint of forming a good film 3, the concentration of the metal elements in the bath solution 2 is preferably 1 ppm to 100 ppm, more preferably 3 ppm to 10 ppm, and even more preferably 4 ppm to 6 ppm. Note that "ppm" means "parts per million" and is "mg / L". Also, when the bath solution 2 contains multiple metal elements, the above concentration of metal elements refers to the total concentration of multiple metal elements. The concentration of metal elements in the bath solution 2 can be measured by ICP-MS analysis.
[0025] (1.3) Halogen elements Bath solution 2 contains at least one halogen element. The inclusion of a halogen element in bath solution 2 allows for film formation at a practical speed and facilitates the homogeneity of the film 3. The halogen element is not particularly limited. From the viewpoint of rapidly advancing the organic electrochemical reaction and allowing the film 3 to function as a good protective film for the substrate 5, it is preferable that the halogen element is at least one selected from the group consisting of Cl (chlorine), Br (bromine), and I (iodine). The concentration of halogen elements in bath solution 2 is not particularly limited. From the viewpoint of moderately suppressing the reaction rate, controlling the homogeneity and thickness T of the film 3, and suppressing the peeling of the film 3, the concentration of halogen elements is preferably 1 ppm to 20,000 ppm, more preferably 5 ppm to 2,000 ppm, and even more preferably 10 ppm to 100 ppm. Note that "ppm" means "parts per million" and is "mg / L". The concentration of halogen elements in bath solution 2 can be determined by the amount of halogen elements added during bath preparation or by ICP-MS analysis of the bath solution.
[0026] (1.4) Organic solvents By using an organic solvent in bath solution 2, the generation of gases during film formation and the oxidation of the substrate 5 itself are suppressed. From the viewpoint of good film formation 3, it is preferable that the solvent contains at least one selected from the group consisting of ketones and nitriles. It is presumed that the inclusion of ketones and nitriles in the solvent causes a condensation reaction to occur on the electrode surface (cathode surface), enabling electrodeposition. Furthermore, it is thought that the inclusion of ketones in the solvent causes ketoenol tautomerism in the presence of halogens, improving the reactivity of bath solution 2.
[0027] (1.4.1) Ketones The ketone is not particularly limited as long as it is an organic solvent having a carbonyl group (-C(=O)-) other than an ester bond. Examples of ketones include acetone, methyl ethyl ketone (MEK), 1-hexanone, 2-hexanone, 4-heptanone, 2-heptanone (methyl amyl ketone), 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, diisobutyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, phenylacetone, acetophenone, methyl naphthyl ketone, cyclohexanone (CHN), and methylcyclohexanone. Among these, acetone and methyl ethyl ketone are preferred as ketones from the viewpoint of particularly good film formation 3.
[0028] (1.4.2) Nitriles Nitriles are organic solvents that contain a nitrile group (-CN) in their structure. Examples of nitriles include acetonitrile, propionitol, valeronitrile, and butyronitrile. Among these, acetonitrile is preferred as the nitrile because it allows for particularly good film formation 3.
[0029] (2) Base material 5 For "Base Material 5," the explanation in the "(1) Base Material 5" section of "1. Covering Base Material 1" above applies as is.
[0030] (3) Voltage application With the substrate 5 immersed in the bath solution 2, a voltage is applied to form a film 3 on the substrate 5 on the negative electrode 7 side. Specifically, the positive electrode 6 and the negative electrode 7 (substrate 5) are immersed in the bath solution 2 to generate a potential gradient between the two electrodes. Any known conductive substrate can be used as the positive electrode 6. When the metal elements in the bath liquid 2 are supplied by the dissolution of the positive electrode 6, the positive electrode 6 is preferably at least one electrode selected from Al electrodes, Ti electrodes, and Mo electrodes. The shape, thickness, size, etc., of the positive electrode 6 are not particularly limited. The positive electrode 6 may be, for example, foil-shaped, plate-shaped, foam-shaped, non-woven fabric-shaped, mesh-shaped, felt-shaped, or expanded. It is preferable that the positive electrode 6 and the negative electrode 7 are arranged facing each other. The positive electrode 6 and the negative electrode 7 are connected to a DC power supply, and the DC power supply can generate a potential gradient between the positive electrode 6 and the negative electrode 7. In order to generate a potential gradient between the positive electrode 6 and the negative electrode 7, the positive electrode 6 and the negative electrode 7 are immersed in the bath liquid 2, and a voltage (e.g., a constant voltage) is applied to both electrodes by a power supply connected to the positive electrode 6 and the negative electrode 7. From the viewpoint of enabling film formation at a practical speed, the potential gradient generated between the two electrodes is preferably 10V to 300V, more preferably 20V to 100V, and even more preferably 60V to 80V in the case of a constant voltage. The duration for which voltage is applied is not particularly limited. For example, the application duration is preferably 10 seconds or more and 300 seconds or less, more preferably 30 seconds or more and 240 seconds or less, and even more preferably 60 seconds or more and 180 seconds or less. Furthermore, the voltage does not have to be constant; its magnitude may be varied.
[0031] (4) Post-film formation processing steps After the formation of film 3, the amount of carbon in film 3 may be reduced by heat treatment and / or light irradiation. By reducing the amount of carbon in film 3 by heat treatment and / or light irradiation, the purity of the inorganic oxide film can be controlled. The heat treatment temperature is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, a temperature of 100°C to 1000°C is preferred, 300°C to 800°C is more preferred, and 500°C to 600°C is even more preferred. The heat treatment processing time is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, it is preferably 1 minute or more and 60 minutes or less, more preferably 5 minutes or more and 45 minutes or less, and even more preferably 10 minutes or more and 30 minutes or less. The wavelength of light used in light irradiation is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, the wavelength of light is preferably 250 nm to 1100 nm, more preferably 300 nm to 800 nm, and even more preferably 400 nm to 500 nm. The light irradiation time is not particularly limited. From the viewpoint of efficiently reducing the amount of carbon, it is preferably 3 seconds to 120 seconds, more preferably 5 seconds to 60 seconds, and even more preferably 10 seconds to 30 seconds. Furthermore, the decrease in the amount of carbon in film 3 can be confirmed by XPS analysis.
[0032] 3. Effects of the coating substrate 1 of this embodiment The coated substrate 1 of this embodiment offers excellent functionality and / or durability by selectively forming a thicker coating 3 on the edge region S1 and the convex region S3, which are particularly prone to contact with the surrounding environment, when using the coated substrate 1. According to this embodiment, a novel coating substrate 1 is provided that is applicable to various fields and can be mass-produced. The coating substrate 1 of this embodiment is cost-effective because it can be formed without using expensive raw materials, or with only a very small amount of expensive raw materials. Furthermore, since the coating 3 is formed on the coated substrate 1 of this embodiment without necessarily requiring post-treatment such as heat treatment or light irradiation, the options for the material and shape of the substrate 5 can be expanded. [Examples]
[0033] The present disclosure will be further described by examples. Furthermore, the measurement conditions for XPS (X-ray photoelectron spectroscopy) in the following explanation are as follows: [Measurement conditions] X-ray beam diameter: 100 μmΦ Signal acquisition angle: 45.0° Pass energy: 140 eV Ar etching in 30 seconds (etching rate: 10 nm / min in terms of SiO2 equivalent)
[0034] 1. An example in which a metal element is supplied to the bath solution 2 by the dissolution of the positive electrode 6. (1) Example 1 (Solvent: MEK, Cathode 6: Aluminum) The film forming apparatus 11 shown in FIG. 3 was used. An aluminum wire was used as the positive electrode 6. A stainless steel plate was used as the negative electrode 7. The negative electrode 7 is a base material 5 on which a film 3 is formed on the surface. Methyl ethyl ketone (MEK) was used as the solvent of the bath solution 2. 600 ppm of iodine as a halogen was dissolved in the bath solution 2. With the positive electrode 6 and the negative electrode 7 immersed in the bath solution 2, 80 V was applied between the positive electrode 6 and the negative electrode 7 for 3 minutes. When the cross-section of the negative electrode 7 was observed with a FIB-SEM (field emission scanning electron microscope), as shown in FIG. 2, a 700-nm film 3 was formed on the surface of the base material 5. After performing Ar etching with XPS for 30 seconds and then analyzing, it was found that this film 3 was aluminum oxide. Also, the elemental percentage of carbon element in the film 3 was 5.8 atm%, and the total elemental percentage of aluminum element and oxygen element was 93.9 atm%. Also, the elemental percentage of iodine element in this film 3 was less than 0.1 atm% (measurement lower limit). Also, in the cross-sectional TEM image obtained by cutting the film 3 in the film thickness direction, no crystal grains were observed, so it was confirmed that the film 3 was amorphous. Also, when the relative density of the film 3 was determined by the following method, the relative density was 100%. The relative density of the film 3 was determined by the following method. A cross-sectional TEM image obtained by cutting the film 3 in the film thickness direction was acquired. The area of pores was measured in a field of view of 300 nm in length and 1000 nm in width. The relative density (%) was determined from the following formula (1). The average value of the relative densities of 10 fields of view is the relative density of the film 3. When the thickness of the film 3 is smaller than 300 nm in length, the measurement shall be performed in a field of view adjusted to the thickness of the film 3. Relative density (%) = {(S1 - S2) / S1} × 100 (1) (In the formula, S1 is the area (nm 2 ) of a field of view of 300 nm in length and 1000 nm in width, and S2 is the total area (nm 2 ) of pores in a field of view of 300 nm in length and 1000 nm in width)
[0035] (2) Example 2 (solvent: acetone, positive electrode 6: aluminum) Acetone was used as the solvent for bath solution 2. 14 ppm of iodine was dissolved in bath solution 2 as a halogen. The experiment was conducted in the same manner as in Example 1. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a 130 nm thick film 3 was found to have formed on the surface of the substrate 5. XPS analysis revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in coating 3 was 6.5 atm%, and the combined elemental percentage of aluminum and oxygen was 93.3 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0036] (3) Example 3 (Solvent: MEK, Cathode 6: Titanium) A titanium wire was used as the positive electrode 6. The experiment was conducted in the same manner as in Example 1. Observation of the cross-section of the negative electrode 7 using FIB-SEM revealed that a 90 nm thick film 3 was formed on the surface of the substrate 5. XPS analysis confirmed that this film 3 was titanium oxide. Furthermore, the elemental percentage of carbon in coating 3 was 24.6 atm%, and the combined elemental percentage of titanium and oxygen was 78.7 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.3 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0037] (4) Example 4 (Solvent: Acetone, Cathode 6: Titanium) Acetone was used as the solvent for bath solution 2. 2400 ppm of iodine was dissolved in bath solution 2 as a halogen. The experiment was conducted in the same manner as in Example 3. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a 500 nm thick film 3 was found to be formed on the surface of the substrate 5. XPS analysis revealed that this film 3 was titanium oxide. Furthermore, the elemental percentage of carbon in coating 3 was 9.2 atm%, and the combined elemental percentage of titanium and oxygen was 83.7 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.4 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0038] (5) Example 5 (Solvent: MEK, Positive electrode 6: Molybdenum) A molybdenum wire was used as the positive electrode 6. The experiment was conducted in the same manner as in Example 1. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a 160 nm thick film 3 was found to be formed on the surface of the substrate 5. XPS analysis revealed that this film 3 was molybdenum oxide. Furthermore, the elemental percentage of carbon in film 3 was 14.8 atm%, and the combined elemental percentage of molybdenum and oxygen was 78.7 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was less than 0.1 atm% (below the detection limit). Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0039] (6) Example 6 (Solvent: Acetone, Positive electrode 6: Molybdenum) Acetone was used as the solvent for bath solution 2. 2400 ppm of iodine was dissolved in bath solution 2 as a halogen. The experiment was conducted in the same manner as in Example 5. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a 480 nm thick film 3 was found to have formed on the surface of the substrate 5. XPS analysis revealed that this film 3 was molybdenum oxide. Furthermore, the elemental percentage of carbon in film 3 was 12.7 atm%, and the combined elemental percentage of molybdenum and oxygen was 78.0 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was less than 0.1 atm% (below the detection limit). Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0040] (7) Example 7 (Solvent: Acetonitrile, Positive electrode 6: Aluminum) Acetonitrile was used as the solvent for bath solution 2. 2400 ppm of iodine, as a halogen, was dissolved in bath solution 2. The experiment was conducted in the same manner as in Example 1. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a 140 nm thick film 3 was found to have formed on the surface of the substrate 5. XPS analysis revealed that this film 3 was aluminum oxide. Oxygen was present in film 3, which was not present in bath solution 2. This oxygen is presumed to have originated from water contained in bath solution 2 or from water absorbed from the atmosphere. Furthermore, the elemental percentage of carbon in coating 3 was 9.8 atm%, and the combined elemental percentage of aluminum and oxygen was 90.1 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0041] (8) FIB-SEM observation of coating 3 in Examples 1-7 The cross-sections of the coating 3 in Examples 1-7 were observed using FIB-SEM. In all of Examples 1-7, the maximum thickness T1max of the coating 3 formed on the edge region S1 of the surface S of the substrate 5 was greater than the thickness T2 of the coating 3 formed on the inner region S2, which is inside the edge region S1 of the surface S. Furthermore, in all of Examples 1-7, the maximum thickness T1max of the film 3 formed on the edge region S1 was 10% or more greater than the thickness T2 of the film 3 formed on the inner region S2. Furthermore, in all of Examples 1-7, the thickness T of the coating 3 decreased from the area with the maximum thickness T1max of the coating 3 formed on the edge region S1 toward the inner region S2.
[0042] 2. Example in which a metal element is supplied to the bath from a metal alkoxide. (1) Example 8 (Solvent: Acetone, Metal alkoxide: Aluminum triisopropoxide) A film deposition apparatus 11 shown in Figure 3 was used. A carbon electrode was used as the positive electrode 6. A stainless steel plate was used as the negative electrode 7. The negative electrode 7 is the substrate 5 on which the film 3 is formed on the surface S. Acetone was used as the solvent for the bath solution 2. In bath solution 2, aluminum triisopropoxide was dissolved at a concentration of 16 mg / L (16 ppm), and iodine as a halogen was dissolved at a concentration of 2400 mg / L (2400 ppm). With the positive electrode 6 and negative electrode 7 immersed in bath solution 2, 80V was applied between the positive electrode 6 and negative electrode 7 for 3 minutes. Observation of the cross-section of the negative electrode 7 using FIB-SEM (Field Emission Scanning Electron Microscope) revealed that a 140 nm thick film 3 had formed on the surface of the substrate 5. XPS (X-ray Photoelectron Spectroscopy) analysis showed that this film 3 was made of aluminum oxide. Furthermore, the elemental percentage of carbon in coating 3 was 8.4 atm%, and the combined elemental percentage of aluminum and oxygen was 84.3 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was less than 0.1 atm% (below the detection limit). Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0043] (2) Example 9 (Solvent: MEK, Metal alkoxide: Aluminum triisopropoxide) Methyl ethyl ketone (MEK) was used as the solvent for bath solution 2. Otherwise, the experiment was conducted in the same manner as in Example 8. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a film 3 was found to have formed on the surface S of the substrate 5. XPS analysis revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.6 atm%, and the combined elemental percentage of aluminum and oxygen was 83.6 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was less than 0.1 atm% (below the detection limit). Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0044] (3) Example 10 (Solvent: Acetone, Metal alkoxide: Titanium tetraisopropoxide) Titanium tetraisopropoxide was used instead of aluminum triisopropoxide. Otherwise, the experiment was conducted in the same manner as in Example 8. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a film 3 was found to have formed on the surface S of the substrate 5. XPS analysis revealed that this film 3 was titanium oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.8 atm%, and the combined elemental percentage of titanium and oxygen was 86.1 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 1.3 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0045] (4) Example 11 (Solvent: Acetone, Metal alkoxide: Titanium tetra-n-propoxide) Titanium tetra-n-propoxide was used instead of aluminum triisopropoxide. Otherwise, the experiment was conducted in the same manner as in Example 8. When the cross-section of the negative electrode 7 was observed using FIB-SEM, a film 3 was found to have formed on the surface S of the substrate 5. XPS analysis revealed that this film 3 was titanium oxide. Furthermore, the elemental percentage of carbon in coating 3 was 9.5 atm%, and the combined elemental percentage of titanium and oxygen was 85.9 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.9 atm%. Furthermore, since no crystal grains were observed in the cross-sectional TEM image of film 3 cut in the direction of film thickness, it was confirmed that film 3 is amorphous. Furthermore, when the relative density of film 3 was determined using the method described above, the relative density was found to be 100%.
[0046] (5) FIB-SEM observation of coating 3 in Example 8-11 The cross-sections of the coating 3 in Examples 8-11 were observed using FIB-SEM. In all of Examples 8-11, the maximum thickness T1max of the coating 3 formed on the edge region S1 of the surface S of the substrate 5 was greater than the thickness T2 of the coating 3 formed on the inner region S2, which is inside the edge region S1 of the surface S. Furthermore, in all of Examples 8-11, the maximum thickness T1max of the film 3 formed on the edge region S1 was 10% or more greater than the thickness T2 of the film 3 formed on the inner region S2. Furthermore, in all of Examples 8-11, the thickness T of the coating 3 decreased from the area with the maximum thickness T1max of the coating 3 formed on the edge region S1 toward the inner region S2.
[0047] 3. Analysis of coating 3 by FT-IR The coatings 3 formed in Examples 1, 2, 3, and 7 were analyzed by FT-IR. The measurement conditions were as follows. Measurement method: Single reflection ATR method Total number of times: 64 Resolution: 4cm -1 Aperture: 150 μm
[0048] In all coatings 3, 3000 cm -1 -2800cm -1 A peak, presumably related to CH stretching vibration, was detected.
[0049] 4. XPS analysis of coating 3 The films 3 formed in Examples 1, 2, and 3 were analyzed by XPS. C=O bonds and CO bonds were detected in all of the films 3.
[0050] 5. Differences in film formation rate depending on the type of solvent. The relationship between electrodeposition time and precipitated weight was investigated for various solvents. A film deposition apparatus 11 shown in Figure 1 was used. An aluminum wire was used as the positive electrode 6. A stainless steel plate was used as the negative electrode 7. The negative electrode 7 is a substrate 5 on which a film 3 is formed on its surface S. Various solvents were used for the bath solution 2: acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and diisobutyl ketone. Iodine was dissolved in each of the bath solutions 2 at a concentration of 2100 mg / L (2100 ppm) as a halogen. With the positive electrode 6 and negative electrode 7 immersed in bath solution 2, 80V was applied between the positive electrode 6 and negative electrode 7 for 1 minute to 3 minutes. Figure 4 shows the relationship between the application time (electrodeposition time) and the precipitated weight (deposited mass) for each solvent used. The precipitated weight is the weight of the formed film. The graph in Figure 4 shows that the precipitated weight tends to increase with increasing electrodeposition time. Furthermore, the graph in Figure 4 shows that the deposition rate is faster when the number of carbon atoms in the hydrocarbon groups of the solvent is smaller.
[0051] 6. Relationship between the concentration of metal elements in bath solution 2 and the adhesion of the coating. The first sample (coated substrate 1) was prepared in the same manner as in Example 1. The first sample was removed from the bath solution 2, and a new stainless steel plate was placed in the bath solution 2 and applied in the same manner as in Example 1 to prepare the second sample. The third and fourth samples were prepared in the same manner. When removing each sample from the bath solution 2, a portion of the bath solution 2 was taken out and the concentration of aluminum element was measured by ICP-MS. Figure 5 shows the relationship between the number of sample prototypes and the concentration of aluminum element in bath solution 2. From the graph in Figure 5, it can be seen that the concentration of aluminum element tends to increase as the number of prototypes increases. Also, in the fourth sample, the coating 3 was slightly peeling off from the substrate 5. Therefore, it was found that in order to continuously produce samples, the concentration of aluminum element should be between 1 ppm and 6 ppm.
[0052] 7. Relationship between the concentration of halogen elements in bath solution 2 and the adhesion of the coating. A film deposition apparatus 11 shown in Figure 3 was used. An aluminum wire was used as the positive electrode 6. A stainless steel plate was used as the negative electrode 7. The negative electrode 7 is the substrate 5 on which a film 3 is formed on its surface S. Various solvents such as acetone and methyl ethyl ketone (MEK) were used as the solvent for the bath solution 2. Iodine as a halogen was dissolved in each bath solution 2 in the amounts shown in Table 1. With the positive electrode 6 and negative electrode 7 immersed in each bath solution 2, 80V was applied between the positive electrode 6 and negative electrode 7 for 3 minutes to prepare the first sample (coating substrate 1). The first sample was removed from the bath solution 2, and a new stainless steel plate was placed in the bath solution 2 and the same procedure was followed to prepare the second sample. Subsequent samples were prepared in the same manner. The results are shown in Table 1. The evaluations in Table 1 are as follows: A: Film 3 was formed. The adhesion between film 3 and substrate 5 was good. B: Film 3 was formed. The adhesion between film 3 and substrate 5 was somewhat poor, and film 3 was peeling off.
[0053] From the results in Table 1, it was possible to form film 3 regardless of the iodine concentration. From the viewpoint of suppressing the peeling of film 3, it was confirmed that the iodine concentration should preferably be between 0.001 g / L and 0.10 g / L (between 1 mg / L and 100 mg / L = between 1 ppm and 100 ppm).
[0054] [Table 1]
[0055] 8. Examination of the types of base material 5 We attempted to form the coating 3 using various substrates 5. Instead of the stainless steel plate which was the negative electrode 7 in Example 1, we used a permalloy plate, a titanium plate, a copper plate, and a carbon plate, respectively. Otherwise, the experiment was conducted in the same manner as in Example 1. A stable film 3 was formed on all substrates 5. Therefore, it was confirmed that a stable film 3 can be formed regardless of the type of substrate 5.
[0056] 9. Effects of the Examples According to this embodiment, a novel coating substrate 1 that is applicable to various fields and can be mass-produced is provided.
[0057] The present invention is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of the claims of the present invention.
[0058] (Note) This specification includes the following inventions: [1] The substrate is covered with a film, The thickness of the aforementioned film is 1 nm or more and less than 800 nm. When the aforementioned film was measured by X-ray photoelectron spectroscopy, the total elemental percentage of metal elements and O (oxygen) was 70 atm% or more. The relative density of the aforementioned film is 90% or more. A coating substrate that satisfies at least one of the following conditions (1) and (2). Condition (1): The maximum thickness of the film formed on the edge region of the surface of the substrate is greater than the thickness of the film formed on the inner region of the surface that is inside the edge region. Condition (2): The maximum thickness of the film formed on the region of the surface of the substrate where the convex portion exists is greater than the thickness of the film formed on the region of the surface where the convex portion does not exist. [2] The coated substrate according to [1], wherein the portion of the substrate on which the coating is formed has conductivity. [3] The coated substrate according to [1] or [2], wherein the elemental percentage of C (carbon) is 0.1 atm% or more and less than 20 atm% when the coating is measured by X-ray photoelectron spectroscopy. [4] The coating is amorphous, as described in any one of the claims [1] to [3]. [5] The coated substrate according to any one of [1] to [4], wherein, in the condition (1) above, the maximum thickness of the film formed on the edge region is 10% or more greater than the thickness of the film formed on the inner region. [6] The coated substrate according to any one of [1] to [5], wherein, in the above condition (2), the maximum thickness of the film formed on the region where the convex portion exists is 10% or more greater than the thickness of the film formed on the region where the convex portion does not exist. [7] The coated substrate according to any one of [1] to [6], wherein, in condition (1) above, the thickness of the coating decreases from the area of maximum thickness of the coating formed on the edge region toward the inner region. [8] In the above condition (2), the thickness of the coating decreases from the area with the maximum thickness of the coating formed on the area where the convex portion exists toward the area where the convex portion does not exist, as described in any one of [1] to [7]. [9] The coating substrate according to any one of [1] to [8], wherein the aforementioned metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin). [Explanation of Symbols]
[0059] 1 ... Coating substrate 2…Bath liquid 3 ... coating 5...Base material 6...Positive electrode 7...Negative electrode 11...Film deposition equipment 12 ...convex part S…Surface S1...Edge area S2…inner area S3...Convex region S4...Convex non-existence area SE...end T...thickness T1 ... thickness T1max…Maximum thickness T2 ... thickness T3 ... thickness T3max…Maximum thickness T4 ... thickness h...maximum height
Claims
1. The substrate is covered with a film, The thickness of the aforementioned film is 1 nm or more and less than 800 nm. When the aforementioned film was measured by X-ray photoelectron spectroscopy, the total elemental percentage of metal elements and O (oxygen) was 70 atm% or more. The relative density of the aforementioned film is 98% or more. When the aforementioned film was measured by X-ray photoelectron spectroscopy, the elemental percentage of C (carbon) was 0.1 atm% to 15 atm%, and the elemental percentage of halogen elements was 0.1 atm% to 3 atm%, The following conditions (1) and (2) must be met: In the cross-sectional TEM image taken in the direction of the film thickness, no crystal grains were observed. The aforementioned coating is a coating substrate that does not contain Si. Condition (1): The maximum thickness of the film formed on the edge region of the surface of the substrate is greater than the thickness of the film formed on the inner region of the surface that is inside the edge region. Condition (2): The maximum thickness of the film formed on the region of the surface of the substrate where the convex portion exists is greater than the thickness of the film formed on the region of the surface where the convex portion does not exist.
2. The coated substrate according to claim 1, wherein the portion of the substrate on which the film is formed is electrically conductive.
3. The coating is amorphous, as described in claim 1 or claim 2.
4. The coated substrate according to claim 1 or claim 2, wherein, in the condition (1) above, the maximum thickness of the film formed on the edge region is 10% or more greater than the thickness of the film formed on the inner region.
5. The coated substrate according to claim 1 or claim 2, wherein, in the condition (2) above, the maximum thickness of the film formed on the region where the convex portion exists is 10% or more greater than the thickness of the film formed on the region where the convex portion does not exist.
6. The coated substrate according to claim 1 or claim 2, wherein, in the condition (1) above, the thickness of the coating decreases from the portion with the maximum thickness of the coating formed on the edge region toward the inner region.
7. The coated substrate according to claim 1 or claim 2, wherein, in the condition (2) above, the thickness of the coating decreases from the area with the maximum thickness of the coating formed on the area where the convex portion exists toward the area where the convex portion does not exist.
8. The coating substrate according to claim 1 or claim 2, wherein the aforementioned metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Mo (molybdenum), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Zr (zirconium), V (vanadium), W (tungsten), Ta (tantalum), Nb (niobium), and Sn (tin).
9. A method for producing a coated substrate according to claim 1, A method for manufacturing a coated substrate, comprising immersing the substrate in a bath solution having a water content of less than 1% by mass, containing at least one metal element and at least one halogen element, and applying a voltage to form the coating on the substrate on the negative electrode side.