Coating substrate, and method for manufacturing a coating substrate

Abstract

Provided is a new coated base material which is applicable to various fields and from which high functionality can be expected.　A coated base material (1) is obtained by coating a base material (5) with a coating (3). The thickness of the coating (3) is not less than 60 nm but not more than 10 μm. When the coating (3) is measured, the element percentage of C (carbon) is not less than 0.1 atm% but less than 20 atm%, and the total element percentage of metal elements and O (oxygen) is not less than 70 atm%. The coating (3) is amorphous. The relative density of the coating (3) is not less than 90%.

Description

Technical Field

[0001] The present disclosure relates to a coated substrate and a method for manufacturing the coated substrate.

Background Art

[0002] Patent Documents 1-4 disclose coated substrates provided with metal oxide films. In Patent Documents 1-4, a wet film-forming method is adopted. On the other hand, a dry film-forming method (dry process) may be adopted in order to control the thickness in accordance with a complicated substrate shape. Considering the performance when applied to various fields, the conventional coated substrates are not always sufficient, and the development of new coated substrates has been eagerly desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a novel coated substrate applicable to various fields and capable of expecting high functionality. The present disclosure can be realized in the following forms.

Means for Solving the Problems

[0005] [1] A coated substrate in which a substrate is coated with a film, where the thickness of the film is 60 nm or more and 10 μm or less, When the aforementioned film was measured, the elemental percentage of C (carbon) was 0.1 atm% or more and less than 20 atm%, The total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The aforementioned coating is amorphous, The aforementioned film has a relative density of 90% or more. The coating is a coating substrate having a laminated structure in cross-sectional form. [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 thickness of each layer in the laminated structure is 20 nm or more and 500 nm or less. [4] The coating substrate according to [1] or [2], wherein the aforementioned metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Zr (zirconium), Mo (molybdenum), W (tungsten), V (vanadium), Fe (iron), Cr (chromium), Co (cobalt), Mn (manganese), and Mg (magnesium). [5] The coating substrate according to [1] or [2], wherein the coating contains a compound having at least one structure among a CH bond, a C=O bond, and a CO bond. [6] The coated substrate according to [1] or [2], wherein the elemental percentage of halogen elements in the coating is 0.1 atm% or more. [7] A method for manufacturing a coating substrate using a bath solution containing an organic solvent, The aforementioned bath liquid has a water content of less than 5% by mass, contains at least one metal element, and contains at least one halogen element. A forming step in which a film layer containing the metal element is formed on the negative electrode side of the substrate by applying a voltage while the substrate is immersed in the bath liquid, The process includes a drying step for drying the aforementioned film layer, A method for manufacturing a coated substrate, comprising forming a film having a laminated structure by repeating at least two or more sets of the forming step and the drying step. [8] A coated substrate in which a substrate is coated with a film, where the thickness of the film is 60 nm or more and 10 μm or less, when the film is measured, the elemental percentage of C (carbon) is 0.1 atm% or more and less than 20 atm%, the total elemental percentage of metal elements and O (oxygen) is 70 atm% or more, the film is amorphous, the film has a relative density of 90% or more, a coated substrate.

Advantages of the Invention

[0006] According to the present disclosure, a novel coated substrate applicable to various fields and mass-producible is provided. In addition, in the coated substrate of the present disclosure, cracks inside the film are suppressed ru .

Brief Description of the Drawings

[0009] 1. Coated substrate 1 The coated substrate 1 is formed by coating a substrate 5 with a film 3. The thickness of the film 3 is 40 nm or more and 10 μm or less. When measuring the film 3, the elemental percentage of C (carbon) is 0.1 atm% or more and less than 20 atm%, and the total elemental percentage of the metal element and O (oxygen) is 70 atm% or more. The film 3 is amorphous. The film 3 has a relative density of 90% or more. The film 3 may have a laminated structure as a cross-sectional morphology. That is, there are two types: a first embodiment having a laminated structure (see FIG. 1) and a second embodiment not having a laminated structure (see FIG. 3).

[0010] (1) Substrate 5 The substrate 5 is not particularly limited. In order to enhance the adhesion of the film 3 to the substrate 5, at least the portion (region) of the substrate 5 coated with the film 3 is preferably composed of a material having conductivity and capable of becoming a negative electrode 7 (cathode). By having conductivity and becoming a negative electrode 7 at the portion of the substrate 5 coated with the film 3, the film 3 can be easily formed at this portion by applying a voltage. The surface portion of the substrate 5 may be composed of a material having conductivity and capable of becoming a negative electrode 7. The entire substrate 5 may be composed of a material capable of becoming a negative electrode 7. As the material capable of becoming a negative electrode 7, for example, iron-based alloys and carbon are preferably used. The iron-based alloys are preferably exemplified by one or more selected from, for example, Fe-Ni-Cr alloys (austenitic stainless steels), Fe-Cr alloys (ferritic stainless steels), Fe-Ni alloys (permalloy), Fe-Si alloys (silicon iron), Fe-Si-Al alloys (sendust), Fe-Ni-Mo (supermalloy), Fe-Co alloys (permenjule), Fe-Ni-Co alloys (kovar), and Fe-C-B alloys (amorphous).

[0011] (2) Film 3 (2.1) Thickness From the viewpoint of exhibiting functions appropriate to the material of the film 3, the thickness of the film 3 is 40 nm or more, preferably 100 nm or more, and more preferably 200 nm or more. On the other hand, from the viewpoint of withstanding the stress generated in the film 3 and ensuring adhesion to the substrate 5, the thickness is 10 μm or less, preferably 1000 nm or less, and more preferably 800 nm or less. From these viewpoints, the thickness of the film 3 is 40 nm or more and 10 μm or less, preferably 100 nm or more and 1000 nm or less, and more preferably 200 nm or more and 800 nm or less. If the thickness of the film 3 is not constant, the thickness requirement is satisfied if at least a portion of the thickness of the film 3 is within the above range. The thickness of the film 3 can be determined by FIB-SEM observation.

[0012] (2.2) Percentage of element C (carbon) The elemental percentage of carbon (C) in film 3, as 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 film 3 and stabilizing the properties of film 3. On the other hand, from the viewpoint of allowing film 3 to function sufficiently as an inorganic film, 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 film 3 is not constant, the requirement for the elemental percentage of carbon (C) is satisfied if at least a part of the composition of film 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.

[0013] (2.3) 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 80 atm% or higher, preferably 85 atm% or higher, and more preferably 90 atm% or higher, 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.

[0014] (2.4) Amorphous Coating 3 is amorphous. This amorphous nature can be confirmed using TEM imaging. The amorphous nature of coating 3 allows for the expectation of unique functions such as the absence of grain shedding and the smoothing of the outermost surface due to uniform film growth.

[0015] (2.5) Relative density of film 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 )

[0016] (2.6) Laminated structure The coating 3 may have a layered structure in its cross-sectional form. In this embodiment, the layered structure of the coating 3 can be confirmed by observing a cross-section of the coating 3 cut in the direction of film thickness using a FIB-SEM (dual-beam scanning electron microscope). The layered structure of the coating 3 helps to suppress cracks within the coating 3 and delamination between the coating 3 and the substrate 5.

[0017] (2.7) Thickness of each layer in a laminated structure The thickness of each layer in the laminated structure is not particularly limited. From the viewpoint of improving the strength of the coating 3, the thickness of each layer is preferably 20 nm to 500 nm, more preferably 40 nm to 300 nm, and even more preferably 60 nm to 200 nm. The thickness of each layer can be determined by observing a cross-section of the coating 3 cut in the thickness direction using a FIB-SEM (dual-beam scanning electron microscope).

[0018] (2.8) Metallic elements The metal element is not particularly limited. From the viewpoint of easily forming a film 3 as a high-quality protective film with improved strength by the manufacturing method described later, it is preferable that the metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Zr (zirconium), Mo (molybdenum), W (tungsten), V (vanadium), Fe (iron), Cr (chromium), Co (cobalt), Mn (manganese), and Mg (magnesium).

[0019] (2.9) 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] (2.10) 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. The presence of trace amounts of halogen elements in the coating 3 is thought to remove the oxide film present on the surface 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, thereby ensuring good adhesion between the substrate 5 and the coating 3. From the viewpoint of rapidly promoting organic electrochemical reactions and enabling the coating 3 to function as a high-quality protective film for the substrate 5, it is preferable that the halogen element be at least one selected from the group consisting of I (iodine), Cl (chlorine), and Br (bromine).

[0021] 2. Method for manufacturing the coated substrate 1 The method for manufacturing the coated substrate 1 of this disclosure is not particularly limited. The following describes a preferred manufacturing method. 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 5% by mass, contains at least one metal element, and contains at least one halogen element. This manufacturing method includes a forming step in which a film layer containing a metal element is formed on the negative electrode 7 side (cathode side) of the substrate 5 by applying a voltage while the substrate 5 is immersed in the bath solution. This manufacturing method also includes a drying step in which the film layer is dried. In this manufacturing method, a laminated film 3 is formed by repeating the set of the forming step and the drying step at least twice or more. Furthermore, in the manufacturing method disclosed herein, electrodeposition on the negative electrode 7 side suppresses oxidation of the substrate 5 more effectively than electrodeposition on the positive electrode 6 side (anode side).

[0022] (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 5% by mass. A water content of less than 3% 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.

[0023] (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), Zr (zirconium), Mo (molybdenum), W (tungsten), V (vanadium), Fe (iron), Cr (chromium), Co (cobalt), and Mn (manganese). 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.

[0024] (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 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.

[0025] (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.

[0026] (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.

[0027] (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.

[0028] (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.

[0029] (3) Formation process for forming a film layer (voltage application) In this disclosure, a film layer is formed on the negative electrode substrate 5 by applying a voltage while the substrate 5 is immersed in a bath solution. Specifically, the positive electrode 6 and the negative electrode 7 (substrate 5) are immersed in a 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. 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 1000V, more preferably 20V to 500V, and even more preferably 60V to 200V 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.

[0030] (4) Drying process for drying the film 3 The drying temperature is not particularly limited. From the viewpoint of promoting the shrinkage of individual layers (each coating layer) and thereby suppressing the overall shrinkage of the laminated coating 3, a drying temperature of 0°C to 1000°C is preferred, 10°C to 500°C is more preferred, and 80°C to 300°C is even more preferred. The drying time is not particularly limited. From the viewpoint of promoting the dehydration reaction, for example, a drying time of 1 minute to 3 hours is preferred, 5 minutes to 2 hours is more preferred, and 10 minutes to 1 hour is even more preferred.

[0031] (5) Repeating the set of forming process and drying process In the first embodiment having a laminated structure, the laminated film 3 is formed by repeating the formation step and the drying step at least twice. In the second embodiment not having a laminated structure, the formation step and the drying step may be repeated only once.

[0032] 3. Effects of the coating substrate 1 of this embodiment According to this embodiment, a novel coating substrate 1 is provided that can be applied to various fields and is expected to have high functionality. According to this embodiment, cracks within the coating 3 are suppressed. The coating substrate 1 of this embodiment can be mass-produced using a simple process. 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, the film formation mechanism in this embodiment is presumed to be as follows: It is presumed that a condensation reaction occurs at the cathode while incorporating metal elements from the solvent, followed by an oxide film formation process involving condensation and hydrolysis on the surface of the substrate 5 due to the heat of vaporization during drying. However, this film formation mechanism is a presumption, and this disclosure is not constrained by this film formation mechanism. [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. Preparation of coating substrate Experimental examples 1-1, 1-2, 3-1, 3-2, 5-1, and 5-2 are examples of actual cases. Experimental examples 2-1, 2-2, 4-1, 4-2, 6-1, and 6-2 are examples of actual cases. (1) Experimental Example 1-1 A film deposition apparatus 11 shown in Figure 2 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. Acetone was used as the solvent for the bath solution 2. 600 ppm of iodine was dissolved in the bath solution 2 as a halogen. With the positive electrode 6 and negative electrode 7 immersed in bath solution 2, a film layer formation step was performed by applying 80V between the positive electrode 6 and negative electrode 7 for 1 minute, followed by a drying step of drying at 100°C for 10 minutes. This process was repeated twice. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 with a two-layer structure, consisting of two film layers (single layers) with a thickness of 100 nm and a total thickness of 200 nm, was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in coating 3 was 5.8 atm%, and the combined elemental percentage of aluminum and oxygen was 93.9 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming that film 3 is amorphous. Furthermore, when the relative density of coating 3 was determined using the following method, it was found to be 100%. The relative density of film 3 was determined by the following method: Cross-sectional TEM images were obtained by cutting film 3 in the direction of its thickness. The area of ​​pores was measured in a field of view of 300 nm vertically and 1000 nm horizontally. The relative density (%) was calculated 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 )

[0035] (2) Experimental Examples 1-2 A film deposition apparatus 11 shown in Figure 2 was used. A magnesium 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. Acetone was used as the solvent for the bath solution 2. 600 ppm of iodine was dissolved in the bath solution 2 as a halogen. With the positive electrode 6 and negative electrode 7 immersed in bath solution 2, a film layer formation step was performed by applying 80V between the positive electrode 6 and negative electrode 7 for 1 minute, followed by a drying step of drying at 100°C for 10 minutes. This process was repeated twice. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 with a two-layer structure, consisting of two film layers (single layers) with a thickness of 100 nm and a total thickness of 200 nm, was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in coating 3 was 7.6 atm%, and the combined elemental percentage of magnesium and oxygen was 91.6 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 2-1 A film deposition apparatus 11 shown in Figure 2 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. Acetone was used as the solvent for the bath solution 2. 600 ppm of iodine was dissolved in the bath solution 2 as a halogen. With the positive electrode 6 and negative electrode 7 immersed in the bath solution 2, one set of the following steps was performed: a film layer formation step in which 80V was applied between the positive electrode 6 and negative electrode 7 for 2 minutes, and a drying step in which they were dried at 80°C for 10 minutes. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a single layer (monolayer) film 3 with a thickness of 200 nm was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 6 atm%, and the combined elemental percentage of aluminum and oxygen was 90 atm. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 2-2 A film deposition apparatus 11 shown in Figure 2 was used. A magnesium 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. Acetone was used as the solvent for the bath solution 2. 600 ppm of iodine was dissolved in the bath solution 2 as a halogen. With the positive electrode 6 and negative electrode 7 immersed in the bath solution 2, a film layer formation step was performed by applying 80V between the positive electrode 6 and negative electrode 7 for 2 minutes, followed by a drying step of drying at 80°C for 10 minutes. This set was repeated as one set. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 with a two-layer structure, consisting of two film layers (single layers) with a thickness of 100 nm and a total thickness of 200 nm, was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in film 3 was 9.9 atm%, and the combined elemental percentage of magnesium and oxygen was 89.7 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 3-1 The procedure was the same as in Experimental Example 1, except that the film layer formation step, in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 1 minute, and the drying step, in which the film layer was dried at 80°C for 10 minutes, were repeated 5 times. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 with a five-layer laminated structure, each with a thickness of 100 nm and a total thickness of 500 nm, was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 6 atm%, and the combined elemental percentage of aluminum and oxygen was 90 atm. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 3-2 The procedure was the same as in Experimental Example 1-2, except that the film layer formation step, in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 1 minute, and the drying step, in which the film layer was dried at 80°C for 10 minutes, were repeated five times. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 with a layered structure of five layers, each with a thickness of 100 nm and a total thickness of 500 nm, was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.9 atm%, and the combined elemental percentage of magnesium and oxygen was 90 atm%. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 4-1 The procedure was the same as in Experimental Example 2, except that one set of the film layer formation step was performed by applying 80V between the positive electrode 6 and the negative electrode 7 for 5 minutes, and the drying step was performed by drying at 80°C for 10 minutes. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a single layer (monolayer) film 3 with a thickness of 500 nm was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 6 atm%, and the combined elemental percentage of aluminum and oxygen was 90 atm. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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) Experimental Example 4-2 The procedure was the same as in Experimental Example 2-2, except that one set of steps was performed: a film layer formation step in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 5 minutes, and a drying step in which the film was dried at 80°C for 10 minutes. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a single layer (monolayer) film 3 with a thickness of 500 nm was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.9 atm%, and the combined elemental percentage of magnesium and oxygen was 90 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%.

[0042] (9) Experimental Example 5-1 The procedure was the same as in Experimental Example 1, except that the film layer formation step, in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 1 minute, and the drying step, in which the film layer was dried at 80°C for 10 minutes, were repeated 20 times. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (Field Emission Scanning Electron Microscope) revealed that a film 3 was formed on the surface of the substrate 5, consisting of 20 layers with each film layer (single layer) having a thickness of 100 nm and a total thickness of 2000 nm. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 6 atm%, and the combined elemental percentage of aluminum and oxygen was 90 atm. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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] (10) Experimental Example 5-2 The procedure was the same as in Experimental Example 1-2, except that the film layer formation step, in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 1 minute, and the drying step, in which the film layer was dried at 80°C for 10 minutes, were repeated 20 times. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a film 3 was formed on the surface of the substrate 5, consisting of 20 layers with each film layer (single layer) having a thickness of 100 nm and a total thickness of 2000 nm. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.9 atm%, and the combined elemental percentage of magnesium and oxygen was 90 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%.

[0044] (11) Experimental Example 6-1 The procedure was the same as in Experimental Example 2, except that one set of the film layer formation step was performed by applying 80V between the positive electrode 6 and the negative electrode 7 for 20 minutes, and the drying step was performed by drying at 80°C for 10 minutes. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a single layer (monolayer) film 3 with a thickness of 2000 nm was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was aluminum oxide. Furthermore, the elemental percentage of carbon in film 3 was 6 atm%, and the combined elemental percentage of aluminum and oxygen was 90 atm. Furthermore, the elemental percentage of iodine in this coating 3 was 0.1 atm%. Furthermore, cross-sectional TEM electron diffraction of film 3, cut in the direction of film thickness, showed no diffraction pattern, confirming 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] (12) Experimental Example 6-2 The procedure was the same as in Experimental Example 2-2, except that one set of steps was performed: a film layer formation step in which 80V was applied between the positive electrode 6 and the negative electrode 7 for 20 minutes, and a drying step in which the film was dried at 80°C for 10 minutes. Observation of the cross-section of the negative electrode 7 using a FIB-SEM (field emission scanning electron microscope) revealed that a single layer (monolayer) film 3 with a thickness of 2000 nm was formed on the surface of the substrate 5. Analysis after Ar etching by XPS for 30 seconds revealed that this film 3 was magnesium oxide. Furthermore, the elemental percentage of carbon in film 3 was 8.9 atm%, and the combined elemental percentage of magnesium and oxygen was 90 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%.

[0046] (13) XPS analysis of coating 3 The coatings 3 formed in experimental examples 1-1, 1-2, 3-1, 3-2, 5-1, 5-2, 2-1, 2-2, 4-1, 4-2, 6-1, and 6-2 were analyzed by XPS. C=O bonds and CO bonds were detected in all of the coatings 3.

[0047] 2. Evaluation (1) Evaluation method For each experimental example, the coated substrate was observed using an optical microscope (surface observation) and FIB-SEM (fiber-in-the-glass optoelectronic microscope) (cross-sectional observation). This observation investigated the presence or absence of cracks extending from the film surface of coating 3 to the substrate. Furthermore, after vacuum (reduced pressure) drying of the coated substrates for each experimental example at room temperature, surface observation with an optical microscope and cross-sectional observation with FIB-SEM were performed. This observation was used to investigate the presence or absence of cracks extending from the film surface of coating 3 to the substrate. Furthermore, the coated substrates of each experimental example were heat-treated at 500°C in air, and then the surface was observed using an optical microscope and the cross-section was observed using FIB-SEM. This observation investigated whether or not cracks extended from the surface of coating 3 to the substrate.

[0048] (2) Evaluation results The evaluation results are shown in Table 1. In experimental examples 1-1, 1-2, 3-1, 3-2, 5-1, and 5-2, no cracks were observed after film formation, vacuum drying, or heat treatment. In experimental examples 2-1, 2-2, 4-1, and 4-2, no cracks occurred after film formation. In experimental examples 2-1, 2-2, 4-1, and 4-2, cracks were observed after vacuum drying and after heat treatment. In experimental examples 6-1 and 6-2, cracks were observed after film formation, after vacuum drying, and after heat treatment.

[0049] [Table 1]

[0050] 3. Effects of the Examples According to this embodiment, a novel coating substrate 1 is provided that can be applied to various fields and is expected to have high functionality.

[0051] 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.

[0052] (Note) This specification includes the following inventions: [1] A coated substrate having a film covering the substrate, The thickness of the aforementioned film is 60 nm or more and 10 μm or less. When the aforementioned film was measured, the elemental percentage of C (carbon) was 0.1 atm% or more and less than 20 atm%, The total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The aforementioned coating is amorphous, The aforementioned film has a relative density of 90% or more. The coating is a coating substrate having a laminated structure in cross-sectional form. [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 thickness of each layer in the laminated structure is 20 nm or more and 500 nm or less. [4] The coating substrate according to [1] to [3], wherein the aforementioned metal element is at least one selected from the group consisting of Al (aluminum), Ti (titanium), Zr (zirconium), Mo (molybdenum), W (tungsten), V (vanadium), Fe (iron), Cr (chromium), Co (cobalt), Mn (manganese), and Mg (magnesium). [5] The coating substrate according to [1] to [4], wherein the coating contains a compound having at least one of the structures of a CH bond, a C=O bond, and a CO bond. [6] The coated substrate according to [1] to [5], wherein the elemental percentage of halogen elements in the coating is 0.1 atm% or more. [7] A method for manufacturing a coating substrate using a bath solution containing an organic solvent, The aforementioned bath liquid has a water content of less than 5% by mass, contains at least one metal element, and contains at least one halogen element. A forming step in which a film layer containing the metal element is formed on the negative electrode side of the substrate by applying a voltage while the substrate is immersed in the bath liquid, The process includes a drying step for drying the aforementioned film layer, A method for manufacturing a coated substrate, comprising repeating the above forming step and the above drying step set at least two or more times to form a laminated film. [8] A coated substrate having a film covering the substrate, The thickness of the aforementioned film is 60 nm or more and 10 μm or less. When the aforementioned film was measured, the elemental percentage of C (carbon) was 0.1 atm% or more and less than 20 atm%, The total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The aforementioned coating is amorphous, The coating is a substrate having a relative density of 90% or more. [Explanation of symbols]

[0053] 1 ... Coating substrate 2…Bath liquid 3 ... coating 5...Base material 6...Positive electrode 7...Negative electrode 11...Film deposition equipment

Claims

1. A coated substrate having a film covering the substrate, The thickness of the aforementioned film is 60 nm or more and 10 μm or less. When the aforementioned film was measured, the elemental percentage of C (carbon) was 0.1 atm% or more and less than 20 atm%, The total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The aforementioned coating is amorphous, The aforementioned film has a relative density of 90% or more. The aforementioned coating has a layered structure of at least two layers in cross-sectional form, In the aforementioned laminated structure, the thickness of each layer is 20 nm or more and 500 nm or less. The coating substrate is a coating substrate in which the aforementioned metal element is at least one selected from the group consisting of Al (aluminum) and Mg (magnesium).

2. The coated substrate according to claim 1, wherein the portion of the substrate on which the coating is formed is electrically conductive.

3. The coating substrate according to claim 1 or claim 2, wherein the coating contains a compound having at least one structure among a C-H bond, a C=O bond, and a C-O bond.

4. The coated substrate according to claim 1 or claim 2, wherein the elemental percentage of halogen elements in the coating is 0.1 atm% or more.

5. A method for manufacturing a coating substrate using a bath solution containing an organic solvent, The bath solution has a water content of less than 5% by mass, contains at least one metal element selected from the group consisting of Al (aluminum) and Mg (magnesium), and contains at least one halogen element. A forming step of forming a film layer containing the metal element on the negative electrode side of the substrate by applying a voltage of 10V to 1000V for an application time of 10 seconds to 300 seconds while the substrate is immersed in the bath liquid, The process includes a drying step for drying the aforementioned film layer, By repeating the above forming step and the above drying step set at least twice, a laminated film is formed. When the aforementioned film was measured, the elemental percentage of C (carbon) was 0.1 atm% or more and less than 20 atm%, The total elemental percentage of metal elements and O (oxygen) is 70 atm% or more. The aforementioned coating is amorphous, A method for manufacturing a coated substrate, wherein the coating has a relative density of 90% or more.

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