Coated base and method for producing coated base

Abstract

Provided is a novel coated substrate (1) which can be used in various fields and which is expected to have high functionality. A coated base material (1) is obtained by coating a base material (5) with a coating film (3). The thickness of the coating film (3) is 60 nm to 10 [mu] m, when the coating film (3) is measured, the elemental percentage of C (carbon) is 0.1 atm% to less than 10 atm%, the total elemental percentage of metal elements and O (oxygen) is 80 atm% or more, the relative density of the coating film (3) is 90% or more, and gamma-Al2O3 is contained in the coating film (3).

Description

Technical Field

[0001] This invention relates to a coated substrate and a method for manufacturing the coated substrate. Background Technology

[0002] Patent documents 1-4 disclose coated substrates with metal oxide coatings. Patent documents 1-4 employ a wet film-forming method. On the other hand, a dry film-forming method (dry process) is sometimes used to control the thickness to conform to complex substrate shapes.

[0003] If performance is considered when applied to various fields, existing coating substrates may not be sufficient, and there is an urgent need to develop new coating substrates.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2011-32521

[0007] Patent Document 2: Japanese Patent Application Publication No. 2009-147192

[0008] Patent Document 3: Japanese Patent Application Publication No. 2015-93821

[0009] Patent Document 4: Japanese Patent Application Publication No. 9-202606 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] This invention was made in view of the above-mentioned circumstances, and its object is to provide a novel coated substrate that can be applied to various fields and is expected to have high functionality. This invention can be implemented in the following ways.

[0012] Methods for solving problems [1]

[0014] A coated substrate, wherein, is a coated substrate formed by coating a substrate with a film, wherein, The thickness of the aforementioned coating is greater than 60 nm and less than 10 μm. When the above coating was tested, the elemental percentage of C (carbon) was ≥0.1 atm% and <10 atm%. The combined elemental percentage of metallic elements and oxygen (O) is over 80 atm. The relative density of the aforementioned coating is over 90%. The above coating contains γ-Al2O3. [2]

[0016] According to the coating substrate described in [1], the coating has a laminated structure as a cross-sectional shape. [3]

[0018] According to the coating substrate described in [1] or [2], the portion on which the coating is formed is conductive. [4]

[0020] According to the coating substrate described in [2], the thickness of each layer in the above-mentioned laminated structure is 30 nm or more and 500 nm or less. [5]

[0022] According to the coating substrate described in [1] or [2], wherein, There is no oxide coating originating from the oxidation of the substrate between the aforementioned coating and the aforementioned substrate, or The thickness of the oxide coating, which originates from the oxidation of the substrate, between the coating and the substrate is less than 100 nm. [6]

[0024] A method for manufacturing a coated substrate, wherein the coated substrate is manufactured using a bath solution with an organic solvent as the solvent, wherein... The above-mentioned bath liquid contains less than 5% by mass of water, contains at least one metallic element, and contains at least one halogen element. With the substrate immersed in the aforementioned bath solution, a coating containing the aforementioned metal element is formed on the substrate on the negative electrode side by applying a voltage. Then, γ-Al2O3 is formed by heat treatment in a non-oxidizing atmosphere.

[0025] Invention Effects

[0026] According to the present invention, a novel coating substrate is provided that can be applied to various fields and can be mass-produced.

[0027] In addition, in the coated substrate of the present invention, the coating has high conformity to the deformation of the substrate.

[0028] In addition, the coating substrate of the present invention has high adhesion between the coating and the substrate. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the cross-section of the coated substrate.

[0030] Figure 2 This is a schematic diagram of a film-forming device.

[0031] Figure 3 This is a graph showing the XRD measurement results (X-ray diffraction peaks) of Experiment Example 1. Detailed Implementation

[0032] The present invention will now be described in detail. It should be noted that, unless otherwise specified, in this specification, references to numerical ranges using "-" include both a lower limit and an upper limit. For example, a reference such as "10-20" includes either "10" as the lower limit or "20" as the upper limit. That is, "10-20" has the same meaning as "more than 10 and less than 20". Furthermore, in this specification, the upper and lower limits of each numerical range can be arbitrarily combined.

[0033] 1.Coated substrate 1

[0034] The substrate 1 is formed by coating the substrate 5 with the coating film 3. The thickness of the coating film 3 is greater than 60 nm and less than 10 μm.

[0035] When the coating 3 was measured, the elemental percentage of C (carbon) was ≥0.1 atm% and <10 atm%, and the combined elemental percentage of metal elements and O (oxygen) was ≥80 atm%. The relative density of coating 3 was ≥90%. Coating 3 contained γ-Al₂O₃.

[0036] (1) Substrate 5

[0037] The substrate 5 is not particularly limited. In order to improve the adhesion of the coating 3 to the substrate 5, it is preferable that at least the portion (area) of the substrate 5 covered by the coating 3 is made of a material that is conductive and can serve as a negative electrode 7 (cathode). By making the portion of the substrate 5 covered by the coating 3 conductive and serving as a negative electrode 7 (cathode), the coating 3 can be easily formed at that portion by applying a voltage.

[0038] The surface portion of the substrate 5 can be made of a material that is conductive and can serve as the negative electrode 7. The entire substrate 5 can be made of a material that can serve as the negative electrode 7. As a material that can serve as the negative electrode 7, iron-based alloys and carbon are preferred. Examples of iron-based alloys preferably include one or more selected from Fe-Ni-Cr alloys (austenitic stainless steel), Fe-Cr alloys (ferritic stainless steel), Fe-Ni alloys (permalloy), Fe-Si alloys (ferrosilicon), Fe-Si-Al alloys (ferrosilicon-aluminum alloy), Fe-Ni-Mo (super-permeable magnetic alloy), Fe-Co alloys (permalloy), Fe-Ni-Co alloys (Kova alloy), and Fe-CB alloys (amorphous alloy).

[0039] (2) Covering 3

[0040] (2.1) Thickness

[0041] From the viewpoint of exhibiting a function corresponding to the material of the coating 3, the thickness of the coating 3 is 60 nm or more, preferably 200 nm or more, and more preferably 300 nm or more. On the other hand, from the viewpoint of being able to withstand the stress generated in the coating 3 and ensure adhesion to the substrate 5, the thickness of the coating 3 is 10 μm or less, preferably 1000 nm or less, and more preferably 800 nm or less. From these viewpoints, the thickness of the coating 3 is 60 nm or more and 10 μm or less, preferably 200 nm or more and 1000 nm or less, and more preferably 300 nm or more and 800 nm or less. It should be noted that when the thickness of the coating 3 is not fixed, the thickness requirement is satisfied as long as at least a portion of the coating 3 has a thickness within the above range. The thickness of the coating 3 can be determined by observation using FIB-SEM (dual-beam scanning electron microscopy).

[0042] (2.2) Elemental percentage of C (carbon)

[0043] From the viewpoint of suppressing grain growth in the coating 3 and stabilizing the properties of the coating 3, the elemental percentage of carbon (C) when the coating 3 is measured by X-ray photoelectron spectroscopy (XPS) is 0.1 atm% or more, preferably 0.5 atm% or more, and more preferably 1 atm% or more. On the other hand, from the viewpoint of enabling the coating 3 to fully function as an inorganic coating, the elemental percentage of carbon (C) is less than 10 atm%, preferably 8 atm% or less, and more preferably 5 atm% or less. From these viewpoints, the elemental percentage of carbon (C) is 0.1 atm% or more and less than 10 atm%, preferably 0.5 atm% or more and 8 atm% or less, and more preferably 1 atm% or more and 5 atm% or less. It should be noted that when the composition of the coating 3 is not fixed, the requirement for the elemental percentage of carbon (C) is satisfied as long as at least a portion of the composition of the coating 3 is within the above range.

[0044] Compositional analysis based on X-ray photoelectron spectroscopy can be performed using an X-ray photoelectron spectroscopy analyzer. As measurement conditions, the X-ray source can be set to Kα rays from aluminum, the beam diameter to be 100 μm, the X-ray incident angle relative to the surface to be analyzed to be 45°, and the cross-section can be scanned.

[0045] (2.3) The total elemental percentage of metallic elements and O (oxygen).

[0046] From the viewpoint of enabling the coating 3 to fully function as an inorganic coating, the total elemental percentage of metal elements and O (oxygen) when measuring the coating 3 using X-ray photoelectron spectroscopy (XPS) is 80 atm% or more, preferably 85 atm% or more, and more preferably 90 atm% or more. It should be noted that 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%. Even when the composition of the coating 3 is not fixed, the requirement for the total elemental percentage of metal elements and O (oxygen) is satisfied as long as at least a portion of the composition of the coating 3 falls within the above range.

[0047] (2.4) Relative density of coating 3

[0048] From the viewpoint of fully utilizing the function of the coating 3, the relative density of the coating 3 is 90% or more, preferably 95% or more, and more preferably 98% or more. The relative density of the coating 3 can be 100%.

[0049] The relative density of the coating 3 can be determined by the following method. Obtain a cross-sectional TEM image cut along the thickness direction of the coating 3. Measure the area of ​​the pores within a field of view of 300 nm vertically and 1000 nm horizontally. Calculate the relative density (%) according to the following formula (1). The average of the relative densities of the 10 locations is the relative density of the coating 3. It should be noted that when the thickness of the coating 3 is less than 300 nm vertically, the measurement is performed within a field of view corresponding to the thickness of the coating 3.

[0050] Relative density (%) = {(S1-S2) / S1} × 100 (1)

[0051] (In the formula, S1 is the area of ​​the field of view (nm) of 300nm (vertical) × 1000nm (horizontal). 2 S2 is the total area (nm) of pores within a field of view of 300nm x 1000nm. 2 ))

[0052] (2.5)γ-Al2O3

[0053] The coating 3 contains γ-Al2O3. If the coating 3 contains γ-Al2O3 (γ-Al2O3 phase), it exhibits the following effects: Compared to α-Al2O3, γ-Al2O3 has lower strength but higher flexibility. If the coating contains γ-Al2O3, the coating 3's conformability to the substrate 5 increases under mechanical or thermal expansion deformation.

[0054] (2.6) Layered structure

[0055] The coating 3 preferably has a layered structure as its cross-sectional shape. The layered structure of the coating 3 can be confirmed by observing the cross-section cut along the thickness direction of the coating 3 using FIB-SEM (dual-beam scanning electron microscopy).

[0056] By having a layered structure, the coating 3 can suppress internal cracks and peeling between the coating 3 and the substrate 5.

[0057] (2.7) Thickness of each layer in the stacked structure

[0058] There is no particular limitation on the thickness of each layer in a stacked structure.

[0059] From the viewpoint of ensuring the strength of the coating 3, the thickness of each layer is preferably 30 nm or more and 500 nm or less, more preferably 60 nm or more and 200 nm or less, and even more preferably 80 nm or more and 150 nm or less. The thickness of each layer can be determined by observing the cross-section of the coating 3 cut along the thickness direction using FIB-SEM (dual-beam scanning electron microscopy).

[0060] (2.8) Oxidation coating

[0061] Preferably, there is no oxide coating originating from the oxidation of the substrate 5 between the coating 3 and the substrate 5, or the thickness of the oxide coating originating from the oxidation of the substrate 5 between the coating 3 and the substrate 5 is less than 100 nm. If this requirement is met, the adhesion of the coating 3 to the substrate 5 is improved, and the following of the coating 3 to the substrate 5 becomes higher when the substrate 5 is deformed mechanically or thermally. The presence and thickness of the oxide coating can be determined by observing the cross-section of the coating 3 cut along the film thickness direction using FIB-SEM (dual-beam scanning electron microscopy).

[0062] (2.9) Halogen elements

[0063] When measuring the coating 3 using X-ray photoelectron spectroscopy, the elemental percentage of halogens 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 halogens is 3 atm% or less.

[0064] It is believed that by including trace amounts of halogen elements in the coating 3, the oxide coating present on the surface of the substrate 5 is removed by the action of the halogen elements, resulting in a structure where the coating 3 is in direct contact with the substrate 5, thus ensuring the tightness of the adhesion between the substrate 5 and the coating 3. From the viewpoint of enabling the organic electrochemical reaction to proceed rapidly and enabling the coating 3 to function as a high-quality protective film for the substrate 5, the halogen element is preferably at least one selected from the group consisting of I (iodine), Cl (chlorine), and Br (bromine).

[0065] (2.10) Metallic elements

[0066] There is no particular limitation on the metal element. From the viewpoint that a coating 3 with improved strength can be easily formed by the manufacturing method described later, the metal element is preferably 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).

[0067] 2. Method for manufacturing the coated substrate 1

[0068] The manufacturing method of the coated substrate 1 of the present invention is not particularly limited.

[0069] The preferred manufacturing method will now be described. The preferred manufacturing method is a method for manufacturing a coating 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 formation step in which a coating film 3 containing metal elements is formed on the substrate 5 on the negative electrode 7 side (cathode side) by applying a voltage while the substrate 5 is immersed in the bath solution. Furthermore, this manufacturing method forms γ-Al₂O₃ by heat treatment in a non-oxidizing atmosphere after the formation step (heat treatment step).

[0070] It should be noted that in the manufacturing method of the present invention, electrodeposition on the negative electrode 7 side is more effective in suppressing the oxidation of the substrate 5 compared to electrodeposition on the positive electrode 6 side (anode side).

[0071] (1) Bath liquid 2

[0072] Bath solution 2 uses an organic solvent as the solvent.

[0073] (1.1) Moisture content

[0074] From the viewpoint of ensuring the homogeneity of the coating 3 and inhibiting the oxidation of the substrate 5, the moisture content of the bath liquid 2 is less than 5% by mass. Preferably, the moisture content is less than 3% by mass, more preferably less than 0.1% by mass. The moisture content can be 0% by mass. The moisture content of the bath liquid 2 can be determined by GC-MS analysis.

[0075] (1.2) Metallic elements

[0076] The bath liquid 2 contains at least one metallic element. The metallic element is not particularly limited. From the viewpoint of enabling the coating 3 to function as a high-quality protective film for the substrate 5, the metallic element is preferably 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 the present invention, an oxide film is formed as the coating 3, which depends on the metallic element in the bath liquid 2.

[0077] Metal elements contained in bath 2 can be supplied to bath 2 through dissolution from positive electrode 6 (anode). When metal elements dissolve from positive electrode 6 into bath 2, not only is film formation rate management easier, but continuous and stable film formation on multiple substrates 5 is also possible. When supplying metal elements to bath 2 through dissolution from positive electrode 6, positive electrode 6 preferably uses at least one electrode selected from Al, Ti, and Mo.

[0078] The metal elements in bath solution 2 can be supplied by metal alkoxides and / or inorganic metal compounds. When metal elements are supplied through the dissolution of metal alkoxides and / or inorganic metal compounds, elements that are difficult to dissolve and supply from the positive electrode 6 (anode) can also be addressed. Furthermore, in this case, two or more metal elements can be combined to form a coating with controlled composition ratios.

[0079] Examples of metal alkoxides include aluminum alkoxides, titanium alkoxides, and molybdenum alkoxides.

[0080] Examples of aluminum alkoxides include aluminum trioxides. Examples of aluminum trioxides include aluminum tripropoxide (e.g., aluminum triisopropoxide, aluminum tri-n-propoxide), aluminum triethanolamine, aluminum tributoxide (e.g., aluminum trisec-butoxide, aluminum tri-n-butoxide), etc.

[0081] Examples of titanium alkoxides include titanium triols and titanium tetraols, with titanium tetraols being preferred. Examples of titanium tetraols include titanium tetrapropoxide (e.g., titanium tetraisopropoxide, titanium tetran-propoxide, etc.), titanium tetramethanol, titanium tetraethanol, titanium tetrabutoxide (e.g., titanium tetraisobutoxide, titanium tetran-butoxide, etc.), titanium tetrapentoxide, titanium tetrahexyl alcohol, and titanium tetra(2-ethylhexyl alcohol).

[0082] Examples of inorganic metal compounds include aluminum chloride, aluminum bromide, aluminum iodide, and titanium iodide.

[0083] When the metal element in bath 2 is supplied by metal alkoxides and / or inorganic metal compounds, the concentration of the metal element in bath 2 is not particularly limited. In this case, from the viewpoint of forming a good coating 3, the concentration of the metal element in bath 2 is preferably 1 ppm or more and 100 ppm or less, more preferably 3 ppm or more and 10 ppm or less, and even more preferably 4 ppm or more and 6 ppm or less. It should be noted that "ppm" means "parts per million" and is "mg / L". In addition, when bath 2 contains two or more metal elements, the above-mentioned concentration of metal elements refers to the total concentration of the two or more metal elements. The concentration of the metal element in bath 2 can be determined by ICP-MS analysis.

[0084] (1.3) Halogens

[0085] The bath solution 2 contains at least one halogen element. By containing a halogen element in the bath solution 2, coating formation is achieved at a practical speed, and the coating 3 easily becomes homogeneous. The halogen element is not particularly limited. From the viewpoint of enabling rapid organic electrochemical reactions and allowing the coating 3 to function as a high-quality protective film for the substrate 5, the halogen element is preferably at least one selected from the group consisting of Cl (chlorine), Br (bromine), and I (iodine).

[0086] The concentration of halogens in bath solution 2 is not particularly limited. From the viewpoint of moderately suppressing the reaction rate and benefiting the homogeneity and thickness control of the coating 3, as well as suppressing the peeling of the coating 3, the concentration of halogens is preferably 1 ppm or more and 20,000 ppm or less, more preferably 5 ppm or more and 2,000 ppm or less, and even more preferably 10 ppm or more and 100 ppm or less. It should be noted that "ppm" refers to "parts per million" (mg / L). The concentration of halogens in bath solution 2 can be determined by the amount of halogens added during bath solution preparation or by ICP-MS analysis of the bath solution.

[0087] (1.4) Organic solvents

[0088] By using an organic solvent as the solvent for bath 2, the generation of gas during coating formation and the oxidation of the substrate 5 itself are suppressed. From the viewpoint of good coating formation 3, the solvent preferably contains at least one selected from the group consisting of ketones and nitriles. It is speculated that by containing ketones and nitriles in the solvent, a condensation reaction occurs at the electrode surface (cathode surface), making electrodeposition possible. In addition, by containing ketones in the solvent, a ketone-enol tautomerism is generated in the presence of halogens, thereby increasing the reactivity of bath 2.

[0089] (1.4.1) Ketones

[0090] There are no particular restrictions on the use of ketones as long as they are organic solvents containing a carbonyl group (-C(=O)-) other than an ester bond.

[0091] Examples of ketones include acetone, methyl ethyl ketone (MEK), 1-hexanone, 2-hexanone, 4-heptanone, 2-heptanone (methyl pentyl ketone), 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, diisobutyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, phenylacetone, acetophenone, methyl naphthyl ketone, cyclohexanone (CHN), and methyl cyclohexanone. Among these, acetone and methyl ethyl ketone are preferred from the viewpoint of forming a particularly good coating 3.

[0092] (1.4.2) Nitriles

[0093] Nitriles are organic solvents containing a nitrile group (-CN) in their structure. Examples of nitrile include acetonitrile, propionitrile, valerate, and butyronitrile. Among these, acetonitrile is preferred from the viewpoint of forming a particularly good coating 3.

[0094] (2) Substrate 5

[0095] Regarding “substrate 5”, the description in “(1) Substrate 5” in “1. Coated Substrate 1” above can be directly applied.

[0096] (3) Forming process of coating 3 (voltage application)

[0097] In this invention, while the substrate 5 is immersed in a bath solution, a coating 3 is formed on the substrate 5 on the negative electrode side by applying a voltage. 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.

[0098] As the positive electrode 6, any of the known conductive substrates can be used. When the metal element in the bath 2 is supplied through the dissolution of the positive electrode 6, the positive electrode 6 is preferably at least one electrode selected from Al, Ti, and Mo. The shape, thickness, size, etc., of the positive electrode 6 are not particularly limited. The positive electrode 6 can be, for example, in the form of foil, plate, foam, nonwoven fabric, mesh, felt, or expanded metal mesh.

[0099] Positive electrode 6 and negative electrode 7 are preferably configured relative to each other.

[0100] Positive terminal 6 and negative terminal 7 are connected to a DC power supply, which can generate a potential gradient between positive terminal 6 and negative terminal 7.

[0101] In order to generate a potential gradient between the positive electrode 6 and the negative electrode 7, while the positive electrode 6 and the negative electrode 7 are immersed in the bath liquid 2, a voltage (e.g., a constant voltage) is applied to the two electrodes through a power source connected to the positive electrode 6 and the negative electrode 7.

[0102] Regarding the potential gradient generated between the two electrodes, from the viewpoint of forming a coating at a practical speed, under constant voltage conditions, it is preferably 10V or more and 300V or less, more preferably 20V or more and 100V or less, and even more preferably 60V or more and 80V or less.

[0103] There is no particular limitation on the application time of the applied voltage. The application time 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.

[0104] It should be noted that the voltage does not have to be constant; rather, its magnitude can vary.

[0105] The forming process can be performed once or more than twice. By repeatedly performing the forming process twice or more, the coating 3 can be thickened. By repeatedly performing the forming process twice or more, a laminated structure (laminated cross-ribbed structure) of the coating 3 can be constructed.

[0106] (4) Heat treatment process

[0107] γ-Al2O3 can be selectively generated in the coating 3 by heat treatment under a non-oxidizing atmosphere.

[0108] The non-oxidizing atmosphere can be any of the following: reducing atmosphere, inactive atmosphere, or vacuum atmosphere. The oxygen concentration in the non-oxidizing atmosphere is preferably less than 100 ppm.

[0109] There is no particular limitation on the heat treatment temperature. From the viewpoint of selectively generating γ-Al2O3, the heat treatment temperature is preferably 800°C or higher and 1300°C or lower, more preferably 900°C or higher and 1200°C or lower, and even more preferably 950°C or higher and 1050°C or lower.

[0110] There is no particular limitation on the heat treatment time. From the viewpoint of selectively generating γ-Al2O3, the heat treatment time is preferably 0.25 hours or more and 3 hours or less, more preferably 0.5 hours or more and 2 hours or less, and even more preferably 0.75 hours or more and 1 hour or less.

[0111] (5) Relationship between the forming process and the heat treatment process

[0112] If the coating 3 is formed in two or more steps, a heat treatment step can be performed after the final forming step.

[0113] Furthermore, if the coating 3 is formed in two or more steps, a heat treatment step may be performed between the forming steps. In this case, a heat treatment step may be performed between all the forming steps. Alternatively, a mixture of heat treatment steps and non-heat treatment steps may exist between the forming steps. It should be noted that even if the coating 3 is formed in two or more steps and a heat treatment step is performed between the forming steps, a heat treatment step may be performed after the final forming step.

[0114] 3. Effects of this implementation method

[0115] According to this embodiment, a novel coated substrate 1 is provided that can be applied to various fields and is expected to have high functionality.

[0116] According to this embodiment, a coating 3 with excellent adhesion to the substrate 5 can be formed. Furthermore, the coating 3 can be made thicker than before.

[0117] In this embodiment, the coated substrate 1 is protected by a dense γ-Al2O3 crystalline phase protective film, so the coating 3 has a high degree of conformity to the substrate 5 when the substrate 5 is mechanically or thermally deformed.

[0118] The coating substrate 1 of this embodiment can be mass-produced using a simple process.

[0119] The coating substrate 1 of this embodiment can be formed without using expensive raw materials, or with the amount of expensive raw materials used being extremely small, thus being cost-effective.

[0120] It should be noted that the film-forming mechanism in this embodiment is hypothesized as follows. It is hypothesized that while absorbing metal elements from the solvent, a condensation reaction occurs at the cathode, followed by condensation and hydrolysis on the surface of the substrate 5 caused by the heat of vaporization during drying—a process of oxide film formation. However, this film-forming mechanism is hypothetical, and the present invention is not constrained by it.

[0121] Example

[0122] The invention will be described in more detail through examples.

[0123] It should be noted that the measurement conditions for XPS (X-ray photoelectron spectroscopy) are as follows.

[0124] [Measurement Conditions]

[0125] X-ray beam diameter: 100μmΦ

[0126] Signal reception angle: 45.0°

[0127] Pulse energy: 140eV

[0128] Measurements were taken after 30 seconds of Ar etching (etching rate: 10 nm / min converted to SiO2).

[0129] 1. Experimental Example (Solvent: Acetone, Positive Electrode 6: Aluminum)

[0130] (1) Fabrication of the coating substrate 1

[0131] use Figure 2 The film-forming apparatus 11 shown uses aluminum wire as the positive electrode 6 and a Kovar alloy plate as the negative electrode 7. The negative electrode 7 is a substrate 5 on which the coating 3 is formed. The solvent for the bath 2 is acetone. The bath 2 contains 50 ppm of iodine as a halogen.

[0132] The formation process of applying 80V for 1 minute between the positive electrode 6 and the negative electrode 7 while the positive electrode 6 and the negative electrode 7 are immersed in the bath liquid 2 is repeated 9 times.

[0133] Then, a heat treatment was performed at 1000°C for 45 minutes under a non-oxidizing atmosphere (based on a hydrogen-based reducing atmosphere).

[0134] (2) Results of various measurements

[0135] The cross-section of the negative electrode 7 was observed using FIB-SEM (Field Emission Scanning Electron Microscopy). The results showed that a film 3 with a total thickness of 600 nm and a multilayered structure was formed on the surface of the substrate 5. Furthermore, the thickness of each layer was between 50 nm and 100 nm. This observation also confirmed that there was no oxide coating originating from the oxidation of the substrate 5 between the film 3 and the substrate 5.

[0136] Analysis using XPS after 30 seconds of Ar etching revealed that the coating 3 was aluminum oxide.

[0137] In addition, the carbon element percentage in the coating 3 is 5.8 atm, and the combined element percentage of aluminum and oxygen is 93.9 atm.

[0138] In addition, the iodine element percentage in the coating 3 is 0.1 atm.

[0139] In addition, the coating 3 was analyzed using XRD (X-ray crystal structure analysis) before and after heat treatment, and the results are as follows: Figure 3 The black dots observed after heat treatment are peaks originating from γ-Al2O3, which were not present before heat treatment. Based on this result, it can be concluded that γ-Al2O3 was generated in the coating 3 through heat treatment.

[0140] In addition, the relative density of the coating 3 was determined by the following method, and the result was a relative density of 100%.

[0141] The relative density of the coating 3 was determined by the following method. A cross-sectional TEM image was obtained by cutting along the thickness direction of the coating 3. The area of ​​the pores was measured in a field of view of 300 nm in length and 1000 nm in width. The relative density (%) was calculated according to the following formula (1). The average of the relative densities of the 10 locations was taken as the relative density of the coating 3. It should be noted that when the thickness of the coating 3 is less than 300 nm in length, the measurement was performed in a field of view corresponding to the thickness of the coating 3.

[0142] Relative density (%) = {(S1-S2) / S1} × 100 (1)

[0143] (In the formula, S1 is the area of ​​the field of view (nm) of 300nm (vertical) × 1000nm (horizontal).2 S2 is the total area (nm) of pores within a field of view of 300nm x 1000nm. 2 ))

[0144] 2. Effects of the Implementation Example

[0145] According to this embodiment, a novel coated substrate 1 is provided that can be applied to various fields and is expected to have high functionality.

[0146] The present invention is not limited to the embodiments described in the detailed description above, and various modifications or alterations can be made within the scope of the claims of the present invention.

[0147] (Postscript)

[0148] The following inventions are included in this specification. [1]

[0150] A coated substrate, wherein, is a coated substrate formed by coating a substrate with a film, wherein, The thickness of the aforementioned coating is greater than 60 nm and less than 10 μm. When the above coating was tested, the elemental percentage of C (carbon) was ≥0.1 atm% and <10 atm%. The combined elemental percentage of metallic elements and oxygen (O) is over 80 atm. The relative density of the aforementioned coating is over 90%. The above coating contains γ-Al2O3. [2]

[0152] According to the coating substrate described in [1], the coating has a laminated structure as a cross-sectional shape. [3]

[0154] According to the coating substrate described in [1] or [2], the portion on which the coating is formed is conductive. [4]

[0156] According to the coating substrate described in [2] or [3], the thickness of each layer in the above-described laminated structure is 30 nm or more and 500 nm or less. [5]

[0158] The coating substrate according to any one of [1] to [4], wherein, There is no oxide coating originating from the oxidation of the substrate between the aforementioned coating and the aforementioned substrate, or The thickness of the oxide coating, which originates from the oxidation of the substrate, between the coating and the substrate is less than 100 nm. [6]

[0160] A method for manufacturing a coated substrate, wherein the coated substrate is manufactured using a bath solution with an organic solvent as the solvent, wherein... The above-mentioned bath liquid contains less than 5% by mass of water, contains at least one metallic element, and contains at least one halogen element. With the substrate immersed in the aforementioned bath solution, a coating containing the aforementioned metal element is formed on the substrate on the negative electrode side by applying a voltage. Then, γ-Al2O3 is formed by heat treatment in a non-oxidizing atmosphere.

[0161] Symbol Explanation

[0162] 1…Coated substrate

[0163] 2 …bath liquid

[0164] 3 …Laminating

[0165] 5 …substrate

[0166] 6 …positive electrode

[0167] 7 … Negative electrode

[0168] 11…film forming apparatus

Claims

1. A coated substrate, which is a coated substrate formed by coating a substrate with a film, wherein, The thickness of the coating is greater than 60 nm and less than 10 μm. When the coating is measured, the elemental percentage of C (carbon) is greater than 0.1 atm% and less than 10 atm%. The combined elemental percentage of metallic elements and oxygen (O) is over 80 atm. The relative density of the coating is above 90%. The coating contains γ-Al2O3.

2. The coated substrate according to claim 1, wherein, The coating has a layered structure as its cross-sectional shape.

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

4. The coated substrate according to claim 2, wherein, The thickness of each layer in the stacked structure is greater than 30 nm and less than 500 nm.

5. The coated substrate according to claim 1 or claim 2, wherein, There is no oxide coating originating from the oxidation of the substrate between the coating and the substrate, or The thickness of the oxide coating, which originates from the oxidation of the substrate, is less than 100 nm between the coating and the substrate.

6. A method for manufacturing a coated substrate, wherein the method uses a bath solution with an organic solvent as the solvent, wherein... The bath liquid contains less than 5% by mass of water, contains at least one metallic element, and contains at least one halogen element. With the substrate immersed in the bath liquid, a coating containing the metal element is formed on the substrate on the negative electrode side by applying a voltage. Then, γ-Al2O3 is formed by heat treatment in a non-oxidizing atmosphere.

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