Article having a removable coating and related method

Abstract

Some embodiments relate to an article having a removable coating. The article may comprise a substrate and a coating on the substrate. An etching stop layer may be provided between the substrate and the coating to enable the removal of the coating without damaging the substrate. Some embodiments relate to a method for removing a coating from an article. The method may include the steps of obtaining an article comprising an etching stop layer between the substrate and the coating on the substrate, and removing at least a portion of the coating from the article. Additionally, other embodiments provide an article and a related method.

Description

Technology Field

[0001] The present disclosure relates to articles having a generally removable coating and related methods. Background Technology

[0002] Semiconductor fabrication processes utilize coated substrates. To ensure that the coating adheres to the substrate, the coating and the substrate typically have similar chemical compositions. However, a coating that is chemically similar to the substrate cannot be removed without causing damage to the substrate.

[0003] In a first aspect, a method for removing a coating from an article is disclosed, comprising the following steps: obtaining an article, wherein the article comprises: a substrate, wherein the substrate comprises a magnesium-containing metal body, wherein the magnesium-containing metal body comprises a first metal component; a coating, wherein the coating comprises a second metal component; and an etching stop layer, wherein the etching stop layer comprises magnesium fluoride and is located between the magnesium-containing metal body and the coating; and removing at least a portion of the coating from the article.

[0004] In the second aspect according to the first aspect, the substrate comprises at least one of a plenum, a trench, a structure defining a hole, a structure defining a channel, a structure defining a cavity, or any combination thereof.

[0005] In the third aspect according to any one of the above aspects, the substrate is not a wafer substrate.

[0006] In the fourth aspect according to any one of the above aspects, the substrate is not an integrated circuit.

[0007] In the fifth aspect according to any one of the above aspects, the coating is at least one of a coating that has been chemically modified from a previous state, a coating having a surface modified from a previous state, a coating having a thickness modified from a previous state, a coating having a non-uniform thickness, a coating that does not meet specifications for application, a coating having manufacturing defects, or any combination thereof.

[0008] In the sixth aspect according to any of the above aspects, the second metal component and the first metal component both comprise at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, manganese, or any combination thereof.

[0009] In the seventh aspect according to any one of the above aspects, the first metal component comprises aluminum; and the second metal component comprises aluminum.

[0010] In the eighth aspect according to any one of the above aspects, the etching stop layer is an etching stop region located on the surface of the substrate and below it.

[0011] In the ninth aspect according to any one of the above aspects, removal includes bringing the coating into contact with the etchant.

[0012] In the tenth aspect according to any one of the above aspects, the etchant removes at least a portion of the etching stop layer.

[0013] In the eleventh aspect according to any one of the above aspects, the method further comprises the step of exposing the article to a reactive gas to reform at least a portion of the etching stop layer, wherein the reactive gas phase comprises a fluorine component.

[0014] In the 12th aspect according to any one of the above aspects, the fluorine component is CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, C1-C 10 Polymerized perfluoroalkylethylene having perfluoroalkyl groups, polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA), polyhexafluoropropylene, ethylene / tetrafluoroethylene copolymer (ETFE), polytrifluoroethylene, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), or at least one of any combination thereof, or derived therefrom.

[0015] In the 13th aspect according to any one of the above aspects, the fluorine component in the reactive gas phase reacts with magnesium present in the magnesium-containing metal body to reform the etching stop layer.

[0016] In the 14th aspect according to any one of the above aspects, the ratio of the thickness of the removed coating to the thickness of the removed etching stop layer is at least 2:1.

[0017] In the 15th aspect according to any one of the above aspects, the etching stop layer has a uniform thickness.

[0018] In the 16th aspect according to any one of the above aspects, the method further comprises forming an alternative coating on the etching stop layer.

[0019] In the 17th aspect according to any one of the above aspects, the alternative coating is a thermal atomic layer deposition (ALD) coating.

[0020] In the 18th aspect according to any one of the above aspects, the alternative coating comprises at least one of alumina, yttria, titania, zirconia, tantalum oxide, or any combination thereof.

[0021] The 19th aspect disclosed herein is a method for forming an article comprising the following steps: obtaining a substrate, wherein the substrate comprises a magnesium-containing metal body, wherein the magnesium-containing metal body comprises a first metal component; exposing the substrate to a reactive gas to form an etching stop layer on and below the surface of the substrate, wherein the reactive gas phase comprises a fluorine component that reacts with the magnesium of the magnesium-containing metal body to form magnesium fluoride; and forming a coating on the etching stop layer, wherein the coating comprises a second metal component.

[0022] The 20th aspect disclosed herein is an article comprising: a substrate, wherein the substrate comprises a magnesium-containing metal body, wherein the magnesium-containing metal body comprises a first metal component, wherein the substrate is not a wafer substrate, and wherein the substrate is not an integrated circuit; a coating, wherein the coating comprises a second metal component; and an etching stop layer positioned between the substrate and the coating, wherein the etching stop layer comprises magnesium fluoride formed on the surface of the substrate and underneath the etching stop layer. Brief explanation of the drawing

[0023] Refer to the drawings which form part of the present disclosure and illustrate embodiments in which the materials and methods described herein can be implemented. Fig. 1 is a flowchart of a method for forming an article according to some embodiments of the present disclosure. Fig. 2 is a schematic diagram of an article according to some embodiments of the present disclosure. Fig. 3 is a flowchart of a method for removing a coating from an article according to some embodiments of the present disclosure. Fig. 4is a schematic diagram of (A) a method for forming an article, (B) a method for reworking an article, and (C) a method for reprocessing an article, according to some embodiments of the present disclosure. Specific details for implementing the invention

[0024] Some embodiments relate to articles having a removable coating and related methods. The article may include an etching stop layer between the substrate and the coating, said coating may be chemically similar to the substrate. Since the etching stop layer may be resistant to chemicals and other materials used in the coating removal process, the coating can be removed without causing changes to the substrate that would render the article unsuitable for commercial purposes. Examples of such changes to the substrate may include, but are not limited to, altered surface finish, altered visual appearance, changes in chemical composition, changes in surface morphology, etc. The etching stop layer may provide sufficient adhesion between the substrate and the coating. The etching stop layer may be a highly conformal layer that forms a complete surface covering of high aspect ratio features of the substrate. The etching stop layer may exhibit thermal stability at high temperatures.

[0025] Fig. 1 is a flowchart of a method for forming an article comprising a removable coating according to some embodiments of the present disclosure. Fig. 1 As presented in [the document], the method (100) may include one or more of the following steps: obtaining a substrate (102), exposing the substrate to a reactive gas to form an etching stop layer (104), and forming a coating on the etching stop layer (106).

[0026] In step (102), in some embodiments, a substrate may be obtained. In some embodiments, the substrate may be a metal body comprising one or more metal components. In some embodiments, each of the one or more metal components may comprise, consist of, or essentially consist of at least one of an elemental metal, a metal alloy, a metal compound (e.g., a metal oxide compound), or any combination thereof. In some embodiments, each of the one or more metal components may comprise, consist of, or essentially consist of at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, or any combination thereof. In some embodiments, each of the one or more metal components may be selected from the group consisting of at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, manganese, magnesium oxide, or any combination thereof. In some embodiments, the substrate may comprise, be made of, or essentially made of at least one of a magnesium component, an aluminum component, or any combination thereof.

[0027] In some embodiments, the substrate may be a magnesium-containing metal body. In some embodiments, the magnesium-containing metal body may comprise, be made of, or essentially be made of a magnesium-containing metal (e.g., any metal or metal alloy containing any amount of magnesium, such as trace amounts of magnesium). In some embodiments, the magnesium-containing metal may comprise, be made of, or essentially be made of a first metal component, such as a first aluminum component. In some embodiments, the magnesium-containing metal body may comprise a magnesium-containing alloy. In some embodiments, the magnesium-containing alloy may comprise, be made of, or essentially be made of a first metal component, such as a first aluminum component. In some embodiments, the magnesium-containing metal alloy may comprise, consist of, or essentially consist of, or be selected from the group consisting of at least one of the following: iron alloy (e.g., steel or stainless steel), aluminum alloy, vanadium alloy, magnesium alloy (e.g., stainless magnesium, such as an alloy containing magnesium and lithium, or an alloy containing magnesium and aluminum, etc.), nickel alloy, chromium alloy, zinc alloy, titanium alloy, or any combination thereof.

[0028] In some embodiments, the magnesium component may include a mobile form of magnesium. For example, in some embodiments, the magnesium component may include magnesium in a metallic form as a metal alloy, metal ion, metal oxide, elemental magnesium, or any combination thereof. In some embodiments, the magnesium component includes at least one of a magnesium-containing metal alloy, magnesium ion, magnesium-containing metal oxide, elemental magnesium, or any combination thereof.

[0029] In some embodiments, the substrate may contain magnesium in an amount of at least 0.01 weight% to less than 100 weight%, or any range or lower therein, based on the total weight of the substrate. For example, in some embodiments, the substrate comprises, based on the total weight of the substrate, at least 0.01 wt%, at least 0.1 wt%, at least 1 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 99 wt%, 99 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 1 wt% or less, 0.1 wt% or less, 0.01 wt% or less, greater than 0 wt% to 100 wt%, greater than 10 wt% to 100 wt%, greater than 20 wt% to 100 wt%, 30 Exceeding weight% to 100 weight%, exceeding 40 weight% to 100 weight%, exceeding 50 weight% to 100 weight%, exceeding 60 weight% to 100 weight%, exceeding 70 weight% to 100 weight%, exceeding 80 weight% to 100 weight%, exceeding 90 weight% to 100 weight%, exceeding 0 weight% to 90 weight%, exceeding 0 weight% to 80 weight%, exceeding 0 weight% to 70 weight%, exceeding 0 weight% to 60 weight%, exceeding 0 weight% to 50 weight%, exceeding 0 weight% to 40 weight%, exceeding 0 weight% to 30 weight%, exceeding 0 weight% to 20 weight%, exceeding 0 weight% to 10 weight%, exceeding 0 weight% to 5 weight%, exceeding 0 weight% to 1 weight%, exceeding 0.01 weight% to 1 weight%, 0.It may include magnesium in an amount greater than 1 wt% to 1 wt%, 40 wt% to 99 wt%, 40 wt% to 95 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 50 wt% to 99 wt%, 60 wt% to 99 wt%, 70 wt% to 99 wt%, 80 wt% to 99 wt%, 90 wt% to 99 wt%, 95 wt% to 99 wt%, and / or any range or sub-range between these.

[0030] In some embodiments, the substrate may contain 1 weight percent or less of magnesium oxide (MgO) based on the total weight of the substrate. In some embodiments, the substrate may contain 0.5 weight percent or less of magnesium oxide based on the total weight of the substrate. In some embodiments, the substrate may contain 0.1 weight percent or less of magnesium oxide based on the total weight of the substrate. In some embodiments, the substrate may contain 0.05 weight percent or less of magnesium oxide based on the total weight of the substrate.

[0031] In some embodiments, the substrate may contain at least 0.01 weight% to less than 100 weight% of aluminum based on the total weight of the substrate. For example, in some embodiments, the substrate comprises, based on the total weight of the substrate, at least 0.01 wt%, at least 0.1 wt%, at least 1 wt%, at least 10 wt%, at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 99 wt%, 99 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 1 wt% or less, 0.1 wt% or less, 0.01 wt% or less, greater than 0 wt% to less than 100 wt%, greater than 10 wt% to less than 100 wt%, greater than 20 wt% to less than 100 wt%, Exceeding 30 wt% and less than 100 wt%, exceeding 40 wt% and less than 100 wt%, exceeding 50 wt% and less than 100 wt%, exceeding 60 wt% and less than 100 wt%, exceeding 70 wt% and less than 100 wt%, exceeding 80 wt% and less than 100 wt%, exceeding 90 wt% and less than 100 wt%, exceeding 0 wt% and less than 90 wt%, exceeding 0 wt% and more than 90 wt%, exceeding 0 wt% and more than 80 wt%, exceeding 0 wt% and more than 70 wt%, exceeding 0 wt% and more than 60 wt%, exceeding 0 wt% and more than 50 wt%, exceeding 0 wt% and more than 40 wt%, exceeding 0 wt% and more than 30 wt%, exceeding 0 wt% and more than 20 wt%, exceeding 0 wt% and more than 10 wt%, exceeding 0 wt% and more than 5 wt%, exceeding 0 wt% and more than 1 wt%, and / or any range or sub-range in between. It may contain aluminum.

[0032] In some embodiments, the aluminum alloy may comprise at least one of aluminum, magnesium, silicon, iron, copper, chromium, zinc, titanium, manganese, or any combination thereof. In some embodiments, the aluminum alloy comprises, is made of, or is essentially made of at least one of 96 to 98 weight% aluminum based on the total weight of the aluminum alloy, 0.5 to 1.2 weight% magnesium based on the total weight of the aluminum alloy, 0.4 to 0.8 weight% silicon based on the total weight of the aluminum alloy, more than 0 to 0.7 weight% iron based on the total weight of the aluminum alloy, 0.1 to 0.4 weight% copper based on the total weight of the aluminum alloy, more than 0 to 0.4 weight% chromium based on the total weight of the aluminum alloy, more than 0 to 0.3 weight% zinc based on the total weight of the aluminum alloy, more than 0 to 0.3 weight% titanium based on the total weight of the aluminum alloy, more than 0 to 0.2 weight% manganese based on the total weight of the aluminum alloy, or any combination thereof. In some embodiments, the aluminum alloy may further comprise at least one of the following: one or more metals, one or more transition metals, one or more semiconductor materials, or any combination thereof. In some embodiments, one or more semiconductor materials may comprise a compound comprising at least one of gallium, antimony, tellurium, arsenic, polonium, or any combination thereof.

[0033] In some embodiments, the substrate may comprise, be made of, or essentially consist of at least one of the following: 10 wt% to 99 wt% nickel based on the total weight of the substrate, 40 wt% to 99 wt% vanadium based on the total weight of the substrate, 15 wt% to 99 wt% chromium based on the total weight of the substrate, 40 wt% to 99 wt% aluminum based on the total weight of the substrate, 40 wt% to 99 wt% zinc based on the total weight of the substrate, 40 wt% to 99 wt% titanium based on the total weight of the substrate, greater than 0 wt% to less than 100 wt% iron based on the total weight of the substrate, 2 wt% to 3 wt% molybdenum based on the total weight of the substrate, or any combination thereof. In some embodiments, the weight percentages apply to a metal component comprising a metal or metals in elemental form.

[0034] In some embodiments, the substrate may have at least one feature. In some embodiments, the at least one feature may include, be composed of, or essentially composed of, or be selected from the group consisting of a plenum, a trench, a structure defining a hole, a structure defining an opening, a structure defining a pore channel, a structure defining a cavity (e.g., a partially enclosed area defining a cavity), a flat surface, a non-flat surface, or any combination thereof. In some embodiments, the at least one feature may have a predetermined aspect ratio. For example, in some embodiments, the aspect ratio of the feature may represent a ratio of depth to width. In some embodiments, the aspect ratio of the feature may represent a ratio of width to depth. In some embodiments, the aspect ratio of the feature may represent a ratio of two of length, width, or height. In some embodiments, the aspect ratio of the feature may represent a ratio of depth to diameter. In some embodiments, the aspect ratio of the feature may represent a ratio of diameter to depth. In some embodiments, the aspect ratio of the feature may represent at least the following ratios: width, depth, height, diameter, and circumference.

[0035] In some embodiments, at least one feature may have an aspect ratio of 2:1 to 1000:1, or any range or sub-range therein. For example, at least one feature is at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 15:1, at least 20:1, at least 25:1, at least 30:1, at least 35:1, at least 40:1, at least 45:1, at least 50:1, at least 55:1, at least 60:1, at least 65:1, at least 70:1, at least 75:1, at least 80:1, at least 85:1, at least 90:1, at least 95:1, at least 100:1, at least 200:1, at least 300:1, at least 400:1, at least 500:1, at least 600:1, at least 700:1, at least 800:1, It may have an aspect ratio of at least 900:1 to 1000:1, and / or any range or sub-range in between.

[0036] In some embodiments, the substrate may not include a wafer substrate. In some embodiments, the substrate may not include a silicon wafer. In some embodiments, the substrate may not include an integrated circuit.

[0037] In step (104), in some embodiments, the substrate may be exposed to a reactive gas phase to form an etching stop layer. In some embodiments, the exposure may be performed under conditions sufficient to cause the formation of an etching stop layer. In some embodiments, the exposure may be performed in a chamber configured to expose the reactive gas phase to the substrate. In some embodiments, the exposure may be performed in a process chamber. In some embodiments, the exposure may be performed in a reaction vessel. In some embodiments, the exposure may be performed by vaporizing a solid or liquid precursor material to obtain a reactive gas phase and supplying the reactive gas phase to a process chamber or reaction vessel. In some embodiments, the exposure may be performed by supplying the reactive gas phase to a process chamber or reaction vessel (e.g., without involving the vaporization of a solid or liquid precursor material to obtain the reactive gas phase). In some embodiments, the etching stop layer is formed by a plasma-free deposition process. In some embodiments, the etching stop layer is formed by a non-plasma deposition process.

[0038] In some embodiments, the reactive gas phase may comprise a fluorine component. In some embodiments, the reactive gas phase may comprise a molecular fluorine source vapor that may be derived from a liquid or a solid. In some embodiments, the fluorine component may comprise, consist of, or essentially consist of molecular fluorine. In some embodiments, the fluorine component is not ionic, is substantially ionic, is not processed to form a plasma (e.g., by applying energy other than heat), or is not any combination thereof. In some embodiments, the fluorine component may comprise, consist of, or essentially consist of at least one of a fluorinated organic compound, a perfluorinated organic compound, or any combination thereof. In some embodiments, for example, the fluorine component may comprise, consist of, or essentially consist of at least one of a fluorinated alkane, a perfluorinated alkane, a fluorinated alkene, a perfluorinated alkene, or any combination thereof, wherein one or more of these may be linear or branched. In some embodiments, the fluorine component may comprise, consist of, or essentially consist of, or be selected from the group comprising at least one of CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, or any combination thereof. In some embodiments, the reactive gas phase is distinguished from plasma, a plasma generation process, or any combination thereof.

[0039] In some embodiments, the reactive gaseous phase may comprise a gaseous fluorinated polymer derived from a non-gaseous fluorinated polymer (e.g., a solid or liquid phase fluorinated polymer). In some embodiments, the fluorinated polymer may be a homopolymer or a copolymer. In some embodiments, the fluorinated polymer may comprise a copolymer of at least one fluoroolefin monomer and optionally at least one non-fluorinated comonomer. In some embodiments, the fluorinated polymer may be fluorinated (i.e., partially fluorinated) or perfluorinated, or may comprise a non-fluorinated halogen atom, e.g., non-limitingly, chlorine. In some embodiments, the molecular fluorine source may be liquid or solid at room temperature but vaporizes at the process temperature disclosed herein. Non-limiting examples of the fluorinated polymer include at least one of the following: C1-C 10 Polymerized perfluoroalkylethylene having perfluoroalkyl groups; polytetrafluoroethylene (PTFE); tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer (PFA); tetrafluoroethylene / hexafluoropropylene copolymer (FEP); tetrafluoroethylene / perfluoro(alkyl vinyl ether) / hexafluoropropylene copolymer (EPA); polyhexafluoropropylene; ethylene / tetrafluoroethylene copolymer (ETFE); polytrifluoroethylene; polyvinylidene fluoride (PVDF); polyvinyl fluoride (PVF); polychlorotrifluoroethylene (PCTFE); ethylene / chlorotrifluoroethylene copolymer (ECTFE); or any combination thereof.

[0040] In some embodiments, the etching stop layer may comprise magnesium fluoride (MgF2). In some embodiments, the magnesium fluoride of the etching stop layer may be a reaction product of a magnesium component present within the substrate and a fluorine component present in a reactive gas phase. In some embodiments, the magnesium fluoride of the etching stop layer may be formed on the surface of the substrate and below the surface of the substrate. For example, in some embodiments, the fluorine component may react with at least one of magnesium present on the surface of the substrate, magnesium present below the surface of the substrate, magnesium that has diffused or migrated from a bulk portion of the substrate to the surface or a region adjacent to the surface, or any combination thereof. In some embodiments, the etching stop layer may not be a substantially separate layer formed on the surface of the substrate, but a region formed on the surface of the substrate and optionally below it. In some embodiments, the etching stop layer is not a layer applied to the surface of the substrate through a coating process or deposition process (e.g., chemical vapor deposition, atomic layer deposition, physical vapor deposition, etc.) (and is therefore distinguished therefrom).

[0041] In some embodiments, the etching stop region may comprise, consist of, or essentially consist of at least one of a magnesium compound, a fluoride compound, a magnesium fluoride compound, an oxide compound, a metal compound, a metal oxide compound, or any combination thereof. In some embodiments, the etching stop region may comprise, consist of, or essentially consist of at least one of magnesium fluoride (MgF2), a metal oxide compound, or any combination thereof. In some embodiments, the metal oxide compound may be a reaction product. For example, in some embodiments, the metal oxide compound may be formed upon exposure of the substrate to oxygen. In some embodiments, the etching stop layer may comprise, consist of, or essentially consist of an atomic layer deposition (ALD) coating comprising yttria. In some embodiments, the etching stop layer may comprise, consist of, or essentially consist of an ALD coating comprising zirconia. In some embodiments, the etching stop layer may comprise, be made of, or essentially made of an ALD coating containing titania. In some embodiments, the etching stop layer is AlO x N y It may include an ALD coating comprising, where x is 1 to 5 and N is 1 to 5.

[0042] In some embodiments, exposure may be performed under one or more process conditions. In some embodiments, the process conditions may include a temperature of 200°C to 500°C (e.g., 350°C to 500°C, 375°C to 425°C, 375°C to 450°C, 400°C to 425°C, 400°C to 450°C, etc.), a pressure of 100 Torr to 1500 Torr (250 Torr to 1000 Torr, 500 Torr to 1000 Torr, 250 Torr to 1250 Torr, 500 Torr to 1250 Torr, etc.), a duration of 1 hr to 15 hr (e.g., 2 hr to 13 hr, 3 hr to 12 hr, etc.), or at least one of any combination thereof. In some embodiments, the process conditions must be sufficient for the fluorine of the fluorine component to react with magnesium present in the substrate to form magnesium fluoride (MgF2). In some embodiments, the process conditions must be a temperature, pressure, duration, or any combination thereof sufficient to induce the fluorine of the fluorine component to react with magnesium present in the substrate to form MgF2. In some embodiments, the process conditions may be changed or adjusted to obtain a predetermined thickness, a predetermined coverage rate, a predetermined property (e.g., at least one of corrosion resistance, etching resistance, or any combination thereof), or at least one of any combination thereof.

[0043] In some embodiments, the surface coverage may represent a percentage of an unmasked, exposed surface (e.g., a gas-exposed surface) containing magnesium fluoride. In some embodiments, the exposed surface(s) may also be referred to as the unmasked surface(s). In some embodiments, the surface coverage may be at least 80% to 100%, or any range or sub-range therein. For example, in some embodiments, the surface coverage may be at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or 100%. In some embodiments, the surface coverage may be in the range of 80% to 100%, and / or any range or sub-range therein.

[0044] In some embodiments, the etching stop layer is a conformal layer. In some embodiments, the etching stop layer is a layer with substantially uniform thickness or having uniform thickness. In some embodiments, the etching stop layer may be a corrosion-resistant layer or may form a corrosion-resistant substrate surface. In some embodiments, the etching stop layer may be an etch-resistant layer or may form an etch-resistant substrate surface. In some embodiments, the etching stop layer may passivate the surface of the substrate. In some embodiments, the etching stop layer may be a protective layer. In some embodiments, the etching stop layer may impart at least one improved surface property.

[0045] In some embodiments, the etching stop region may have a thickness of 1 nm to 200 nm, or any range or sub-range therein. For example, in some embodiments, the etching stop region may have a thickness of 5 nm to 200 nm, 10 nm to 200 nm, 25 nm to 200 nm, 50 nm to 200 nm, 100 nm to 200 nm, 150 nm to 200 nm, 1 nm to 150 nm, 25 nm to 150 nm, 50 nm to 150 nm, 100 nm to 150 nm, 25 nm to 130 nm, 50 nm to 130 nm, 75 nm to 130 nm, and / or any range or sub-range therein. In some embodiments, the thickness of the etching stop region can be measured by scanning electron microscope (SEM) cross-sections, X-ray photoelectron spectroscopy (XPS) depth profiling, or energy dispersive X-ray microscopy (EDAX), among other techniques.

[0046] In step (106), a coating may be formed on at least one of an etching stop layer, a substrate, or any combination thereof. In some embodiments, the coating may be formed by exposing an article to one or more precursor gases to form a coating on the surface of the etching stop layer, the substrate, or any combination thereof. In some embodiments, the coating may be formed by a deposition process. In some embodiments, the deposition process may include a non-plasma deposition process. In some embodiments, the deposition process may include a plasma-free deposition process. In some embodiments, the deposition process may include at least one of atomic layer deposition (ALD), chemical vapor deposition (CVD), solution deposition, or physical vapor deposition (PVD). In some embodiments, the deposition process may include thermal atomic layer deposition. In some embodiments, the atomic layer deposition may include a cyclic atomic layer deposition process for forming the coating. In some embodiments, the coating is an atomic layer deposition (ALD) coating or a thermal ALD coating. In some embodiments, the deposition process is a process for forming a conformal coating. In some embodiments, the conformal coating may include a coating having a uniform or substantially uniform thickness.

[0047] In some embodiments, forming may include a process sequence for atomic layer deposition. In some embodiments, the process sequence may involve using one or more precursors in a cyclic atomic layer deposition (ALD) process to form an ALD coating or a thermal ALD coating. In some embodiments, exposure may include a process sequence in which a 3D article is brought into contact with at least a first precursor in a reaction chamber, the reaction chamber is purged, the 3D article is brought into contact with at least a second precursor in a reaction chamber, and the reaction chamber is purged to complete the cycle. In some embodiments, forming may include 1 to 5,000 cycles. In some embodiments, forming may include 100 to 5,000 cycles. In some embodiments, forming may include 50 to 1,500 cycles. In some embodiments, forming may include a number of cycles sufficient to achieve a desired thickness, a desired property, or other features.

[0048] In some embodiments, one or more precursor gases may be selected depending on the specific ALD coating to be formed. In some embodiments, one or more precursors comprising trimethylaluminum and ozone may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors comprising trimethylaluminum and water may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors comprising a cyclopentadienyl compound of metal M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process using ozone (O3) or water vapor (H2O). In some embodiments, one or more precursors comprising a beta-diketonate of M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process in which a reactive pulse of the beta-diketonate metal precursor alternates with a pulse of O3.

[0049] For example, in some embodiments, atomic layer deposition may include a process sequence in which trimethylaluminum and ozone are used in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence in which trimethylaluminum and water are used in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence in which a cyclopentadienyl M compound and ozone are used in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence in which a cyclopentadienyl M compound and water are used in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence in which an M beta-diketonate compound and ozone are used in a cyclic ALD process to form an ALD coating. In some embodiments, other metal oxide precursor compounds may be used.

[0050] In some embodiments, one or more precursors comprising trimethylaluminum and ozone may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors comprising trimethylaluminum and water may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors comprising a cyclopentadienyl compound of metal M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process using ozone (O3) or water vapor (H2O). In some embodiments, one or more precursors comprising a beta-diketonate of M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process in which a reactive pulse of the beta-diketonate metal precursor alternates with a pulse of O3.

[0051] In some embodiments, one or more precursor ligands may be used for the deposition of the coating. In some embodiments, one or more precursor ligands may be hydrogen, linear or branched, cyclic or non-cyclic, saturated or unsaturated, C1-C 10 It may include at least one of aryl, heterocyclic, alkoxy, cycloalkyl, silyl, silylalkyl, silylamide, trimethylsilyl silyl-substituted alkyl, trialkylsilyl-substituted alkyne, trialkylsilylamido-substituted alkyne, dialkylamide, ethylene, acetylene, alkyne, substituted alkene, substituted alkyne, diene, cyclopentadienyl allene, amine, alkyl amine, bidentate amine, ammonia, RNH2 (where R is an organic, e.g., hydrocarbyl substituent), amidate, guanidinate, diazadiene cyclopentadienyl, oxime, hydroxyamine, acetate, beta-diketonate, beta-ketoimineate, nitrile, nitrate, sulfate, phosphate, halogen, hydroxyl, substituted hydroxyl, any derivative thereof, or any combination thereof.

[0052] In some embodiments, the formation may be performed at a temperature of 20°C to 400°C, or any range or lower therein. For example, in some embodiments, the formation is at 25°C to 400°C, 50°C to 400°C, 75°C to 400°C, 100°C to 400°C, 125°C to 400°C, 150°C to 400°C, 175°C to 400°C, 200°C to 400°C, 225°C to 400°C, 250°C to 400°C, 275°C to 400°C, 300°C to 400°C, 325°C to 400°C, 350°C to 400°C, 375°C to 400°C, 20°C to 375°C, 20°C to 350°C, 20°C to 325°C, 20°C to 300°C, 20°C to 275°C, 20°C to 250℃, 20℃ to 225℃, 20℃ to 200℃, 20℃ to 175℃, 20℃ to 150℃, 20℃ to 125℃, 20℃ to 100℃, 20℃ to 75℃, 20℃ to 50℃, 125℃ to 375℃, 150℃ to 350℃, 175℃ to 350℃, 175℃ to 325℃, 200℃ to 350℃, 200℃ to 325℃, 225℃ to 350℃, 225℃ to 325℃, 250℃ to 350℃, 250℃ to 325℃, 275℃ to 350℃, 275℃ to 325℃, 300℃ to It can be performed at a temperature of 350℃, 300℃ to 325℃, and / or any range or sub-range therein.

[0053] In some embodiments, the deposition process is a process for forming a conformal coating. In some embodiments, the conformal coating may include a coating having a uniform or substantially uniform thickness.

[0054] In some embodiments, the coating layer may have a thickness of 1 nm to 50 μm, or any range or sub-range in between. For example, in some embodiments, the coating layer may have a thickness of less than 5 μm, less than 1 μm, or less than 250 nm.In some embodiments, the coating layer is 100 nm to 250 nm, 1 nm to 4 μm, 1 nm to 3 μm, 1 nm to 2 μm, 1 nm to 1 μm, 1 nm to 900 nm, 1 nm to 850 nm, 1 nm to 800 nm, 1 nm to 750 nm, 1 nm to 700 nm, 1 nm to 650 nm, 1 nm to 600 nm, 1 nm to 550 nm, 1 nm to 450 nm, 1 nm to 400 nm, 1 nm to 350 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 1 nm to 150 nm, 1 nm to 100 nm, 1 nm to 50 nm, 50 nm to 5 μm, 100 nm to 5 μm, 200 nm to 5 μm, 300 nm to 5 μm, 400 nm to 5 μm, 500 nm to 5 μm, 600 nm to 5 μm, 700 nm to 5 μm, 800 nm to 5 μm, 900 nm to 5 μm, 1 μm to 5 μm, 2 μm to 5 μm, 3 μm to 5 μm, 4 μm to 5 μm, 1 nm to 750 nm, 1 nm to 500 nm, 2 nm to 500 nm, 1 nm to 250 nm, 20 nm to 125 nm, 20 nm to 250 nm, 20 nm to 500 nm, 50 nm to 500 nm, 50 nm to 400 nm, 50 nm to 300 nm, 50 nm to 200 nm, It may have a thickness of 15 nm to 200 nm, 20 nm to 50 nm, 10 nm to 40 nm, 30 nm to 50 nm, 1 nm to 5 μm, 1 μm to 5 μm, 1 μm to 4 μm, 1 μm to 3 μm, 1 μm to 2 μm, 5 nm to 5 μm, 1 nm to 1 μm, and / or any range or sub-range therein.

[0055] In some embodiments, the coating may comprise at least one second metal component. In some embodiments, at least one second metal component may comprise, consist of, or essentially consist of at least one of an elemental metal, a metal alloy, a metal compound (e.g., a metal oxide compound), or any combination thereof. In some embodiments, at least one second metal component may comprise, consist of, or essentially consist of at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, or any combination thereof. In some embodiments, at least one second metal component may be selected from the group consisting of at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, manganese, magnesium oxide, or any combination thereof. In some embodiments, at least one second metal component may include at least one metal identical to the metal included in the first metal component of the substrate. In some embodiments, for example, the first metal component and the second component include one or more of aluminum or other metals.

[0056] In some embodiments, the coating may comprise, consist of, or essentially consist of at least one of alumina, yttria, titania, zirconia, tantalum oxide, or any combination thereof, or may be selected from the group consisting thereof. In some embodiments, the coating comprises Al2O3; an oxide of formula MO (where M is Ca, Mg, or Be); an oxide of formula M'O2 (where M' is a stoichiometrically acceptable metal); an oxide of formula Re2O3 (where Re is a rare earth element, e.g., a lanthanide element); and formula Ta x O yThe oxide of (where x is greater than 0 and y is greater than 0) may comprise, consist of, or essentially consist of, or be selected from the group consisting thereof. In some embodiments, the lanthanide element may comprise, consist of, or essentially consist of La, Sc, or Y. In some embodiments, the coating may comprise, consist of, or essentially consist of, or be selected from the group consisting of alumina, aluminum oxynitride, yttria, yttria-alumina, silicon oxide, silicon oxynitride, transition metal oxide, transition metal oxynitride, rare earth metal oxide, rare earth metal oxynitride, or any combination thereof. In some embodiments, the method further comprises fluorinating the coating layer to form a coating layer comprising at least one of YOF, YF3, or any combination thereof.

[0057] In some embodiments, the article may be a component of a semiconductor manufacturing tool, for example, but not limited to, for example, a process chamber, a sidewall, a flow head (e.g., a showerhead), a shield, a tray, a support, a nozzle, a valve, a conduit, a stage for handling or holding an object, a fixture for handling a wafer, a ceramic wafer carrier, a wafer holder, a susceptor, a spindle, a chuck, a ring, a baffle, a fastener (e.g., a (threaded) screw, a (threaded) nut, a bolt, a clamp, a rivet, etc.), a membrane, a filter, a three-dimensional network, a conduit (e.g., a gas line), a manifold (e.g., a gas manifold), or at least one of any combination thereof.

[0058] In some embodiments, the magnesium fluoride passivation layer may be biocompatible, and thus the article may be useful as an implantable medical device or any component thereof. For example, in other embodiments, the article may be a medical device or a component of a medical device, e.g., non-limitingly e.g., a medical instrument, a medical implant, or at least one of an article having a medical use. Non-limiting examples of a medical device and / or its components include at least one of a prosthesis (e.g., knee, joint, shoulder, hip, etc.), a dental brace, a hearing aid, a screw, a plate, a catheter, a tube, a valve, a suture, a wire, a stent, a connector, or any combination thereof.

[0059] Some embodiments of the present disclosure relate to articles having a removable coating. In some embodiments, the article is subject to the method of the present disclosure, e.g., e.g., Fig. 1 It includes articles formed according to the method. Accordingly, it will be recognized that the article may include any feature disclosed herein, including those disclosed above and elsewhere in this application.

[0060] Fig. 2 is a schematic diagram of an article comprising a removable coating according to some embodiments of the present disclosure. Fig. 2As presented herein, the article may comprise a substrate (202), an etching stop layer (204), and a coating (206). In some embodiments, the etching stop layer (204) may be present on the surface (210) of the substrate (202). For example, in some embodiments, the etching stop layer (204) may be an etching stop region of the substrate (202) extending from the surface (210) of the substrate (202) to a deep portion within the substrate (202). In some of these embodiments, the substrate (202) may further comprise a bulk region (208), wherein the bulk region (208) is a region of the substrate (202) that is not a region defining the etching stop layer (204). In some embodiments, the etching stop layer (204) may be present on the surface (210) of the substrate (202). In some embodiments, the coating (206) may be present on the surface (210) of the etching stop layer (204). In some embodiments, the coating (206) may be present on the surface of the substrate (202). In some embodiments, the coating (206) may be present on the surface of the etching stop layer (204), wherein the etching stop layer (204) is formed on the surface of the substrate (202).

[0061] In some embodiments, an etching stop layer (204) disposed or located between the substrate (202) and the coating (206) may enable the removal of the coating (206) without degrading the substrate (202) to a commercially unusable state or condition or chemically altering it (e.g., by etching, e.g., dry etching, wet etching, or at least one of any combination thereof, without limitation). For example, in some embodiments, the substrate (202) and the coating (206) may be chemically similar, so that the removal of the coating (206) in the absence of the etching stop layer (204) results in the removal of at least a portion of the substrate (202). In some embodiments, the etching stop layer (204) can passivate the surface of the substrate (202) so that the removal of the coating (206) does not result in any perceptible removal of the substrate (202), or at least even if the substrate is removed to some extent, such removal is acceptable for commercial purposes. In this way, the etching stop layer (204) can be effective as a chemical-resistant layer that enables the reprocessing and / or rework of the article.

[0062] Fig. 3 is a flowchart of a method for removing a coating from an article according to some embodiments of the present disclosure. Fig. 3 As presented herein, a method (300) for removing a coating from an article may include one or more of the following steps: obtaining an article, wherein the article comprises a substrate, a first coating, and an etching stop layer between the substrate and the first coating (302); removing at least a portion of the first coating from the article (304); exposing the article to a reactive gas to reform at least a portion of the etching stop layer (306); and forming a second coating on the etching stop layer (308). In some embodiments, the first coating is a consumed coating and the second coating is a replacement coating.

[0063] In step (302), in some embodiments, an article may be obtained. As mentioned above, in some embodiments, the article may comprise a substrate, a first coating, and an etching stop layer between the substrate and the first coating. In some embodiments, the obtained article is an article formed according to the method of the present disclosure (e.g., Fig. 1 Articles formed according to the method of) and articles of the present disclosure (e.g., Fig. 2 It may include one or more of the articles (as illustrated in the schematic diagram of ). In some embodiments, the obtained article may include an article for rework. In some embodiments, the article for rework may be an article having a first coating formed thereon having defects due to manufacturing errors, for example. In some embodiments, the obtained article may include an article for reprocessing. In some embodiments, the article for reprocessing may be an article in which the first coating has deteriorated due to use (e.g., repeated use) in a process (e.g., semiconductor fabrication process, microelectronic fabrication process, etc.). In some embodiments, the first coating may be any coating to be reworked, removed, replaced, reprocessed (e.g., a coating that has been used or processed one or more times and is considered to be in "end-of-life" condition), or any combination thereof. In some embodiments, the first coating may be a worn-out coating, wherein the worn-out coating may be any coating having defects and / or deteriorated (e.g., due to use).

[0064] For example, in some embodiments, the first coating may comprise a coating to be reworked. In some embodiments, the coating to be reworked may be a coating in a state or condition adverse to the structure, material, use, or operation of the article (e.g., making the article unsuitable for commercial purposes). Accordingly, the first coating may be described in relation to a previous state or condition. For example, in some embodiments, the first coating in a previous state or condition is a method of the present disclosure (e.g., Fig. 1 The coating may be manufactured according to step (106)). In some of these embodiments, the first coating is any coating having at least one characteristic, feature, element, feature, or composition different from the coating of the previous state or previous conditions. In some embodiments, the first coating is a coating that has been used at least once in a process (e.g., a semiconductor fabrication process). In some embodiments, the difference may be at least one of a different chemical composition, a different surface morphology, a different thickness, or any combination thereof. In some embodiments, the first coating may include a coating to be reworked. In some embodiments, the coating to be reworked may be any coating that has been poorly manufactured. For example, in some embodiments, the first coating may be a coating that does not meet specifications for application. In some embodiments, the first coating may be a coating having defects, such as defects that occurred during the formation of the coating. In some embodiments, the coating to be reworked is a coating that has not been used in any process.

[0065] In some embodiments, the first coating may be a coating that has been chemically modified from a previous state. In some embodiments, the first coating may be a coating having a surface modified from a previous state. In some embodiments, the first coating may be a coating having a thickness modified from a previous state. In some embodiments, the first coating may be a coating having a non-uniform thickness. In some embodiments, the first coating may be a coating that does not meet specifications for application. In some embodiments, the first coating may be a coating having manufacturing defects.

[0066] In step (304), in some embodiments, at least a portion of the first coating may be removed from the article. In some embodiments, removal may include contacting the first coating with an etchant to remove at least a portion of the first coating from the article. In some embodiments, the etchant may include any etchant that preferentially etches the first coating over the etching stop layer. In some embodiments, removal of the first coating may be carried out by at least one of dry etching, wet etching, or any combination thereof. In some embodiments, the etchant may remove the first coating entirely from the article. In some embodiments, the etchant may remove at least a portion of the first coating from the article. In some embodiments, the etching stop layer prevents or at least reduces the extent to which the substrate is etched during the etching of the first coating. In some embodiments, the etchant may remove at least a portion of the etching stop layer. In some embodiments, the first coating may be removed by a process other than etching. In some embodiments, for example, the first coating may be removed by a mechanical removal process applied alone or in combination (e.g., blasting, polishing, lapping, ion sputtering, etc.) or stress-induced separation (e.g., peeling). In some embodiments, the first coating may be removed without the application of any mechanical removal process (e.g., blasting, polishing, lapping, ion sputtering, etc.) or stress-induced separation (e.g., peeling).

[0067] In some embodiments, the etchant may have selectivity toward the first coating over at least one of the etching stop layer, the substrate, or any combination thereof. In some embodiments, selectivity may be defined as the ratio of the thickness of the removed etching stop layer to the thickness of the removed substrate. In some embodiments, the selectivity of the etchant may be at least 1.01:1 to 20:1, or any range or sub-range therein. For example, in some embodiments, the selectivity of the etchant may be 2:1 to 5:1, 2:1 to 10:1, 5:1 to 10:1, and / or any range or sub-range therein. In some embodiments, the selectivity of the etchant may be at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 11:1, and / or any range or sub-range therein.

[0068] In step (306), in some embodiments, the article may be exposed to a reactive gas to reform at least a portion of the etching stop layer. In some embodiments, step (306) is optional. For example, in some embodiments, step (306) may be performed when at least a portion of the etching stop layer can be removed by an etchant. In some embodiments, step (306) may be performed when at least a portion of the surface of the substrate may not contain magnesium fluoride. In some embodiments, step (306) may be performed when the etching stop layer or at least a portion of the surface of the substrate requires reformation or recovery of the etching stop layer, magnesium fluoride, or any combination thereof. In some embodiments, the step of exposing the article to a reactive gas to reform the etching stop layer may be performed according to the method of the present disclosure. For example, in some embodiments, the forming step Fig. 1 It can be performed similarly or identically to step (104).

[0069] In step (308), in some embodiments, the second coating may be reformed on at least one of a substrate, an etching stop layer, or any combination thereof. In some embodiments, the second coating may be an alternative coating. In some embodiments, the second coating may produce an article suitable for commercial purposes. In some embodiments, reforming the second coating or the alternative coating on at least one of a substrate, an etching stop layer, or any combination thereof produces a reworked or reprocessed article. In some embodiments, the step of reforming the second coating on at least one of a substrate, an etching stop layer, or any combination thereof may be performed according to the method of the present disclosure. For example, in some embodiments, the reforming step Fig. 1 It can be performed similarly or identically to step (106).

[0070] Fig. 4 is a schematic diagram of (A) a method for forming an article comprising a removable coating, (B) a method for reworking the article, and (C) a method for reprocessing the article, according to some embodiments of the present disclosure. Fig. 4As presented in (A), a substrate (402) comprising a metal alloy (e.g., an aluminum alloy) is presented. In some embodiments, the metal alloy is an aluminum alloy comprising at least 90% aluminum. In some embodiments, the aluminum alloy may comprise 95 to 99 weight% aluminum, greater than 0 weight% and less than 1 weight% silicon, greater than 0 weight% and less than 1 weight% copper, greater than 0 weight% and less than 1 weight% chromium, and greater than 0 weight% and 2 weight% magnesium, wherein the weight% is based on the total weight of the substrate (402). In some embodiments, an etching stop layer (404) may be formed on the surface of and / or beneath the substrate (402). In some embodiments, a coating (406) (e.g., an atomic layer deposition (ALD) coating including alumina, or an alumina ALD coating) may be formed on the surface of the substrate (402), the surface of the etching stop layer (404), or both the surface of the substrate (402) and the surface of the etching stop layer (404) to obtain an article comprising a removable coating.

[0071] Fig. 4 As shown in (B) of, in some embodiments, the coating (406) or the method of forming the coating (406) may have defects or errors. In some embodiments, the coating (406) may be reworked. For example, in some embodiments, the coating (406) is an alumina ALD coating having errors or defects. In some embodiments, the alumina ALD coating (406) may be removed by a wet chemical removal process (e.g., wet etching). In some embodiments, by removing the alumina ALD coating (406) having errors or defects, a replacement alumina ALD coating (not shown) may be formed on the surface of the substrate (402) / etch stop layer (404).

[0072] Fig. 4As shown in (C) of, in some embodiments, the article may be used (e.g., as described above, particularly, may have reached the end of life or have a chemically altered composition). In some embodiments, the coating (406) may be reprocessed. For example, in some embodiments, the coating (406) is an alumina ALD coating that has been used in one or more processes. In some embodiments, the alumina ALD coating (406) may be removed by a wet chemical removal process (e.g., wet etching). In some embodiments, by removing the alumina ALD coating (406) that has been deformed from a previous state or condition, a replacement ALD coating (not shown) may be formed on the surface of the substrate (402) / etch stop layer (404).

Claims

Claim 1 A method for removing a coating from an article, comprising the step of obtaining an article, wherein the article is a substrate comprising a magnesium-containing metal body, wherein the magnesium-containing metal body comprises a first metal component; a consumed coating comprising a second metal component, wherein the consumed coating is disposed on the substrate; and an etching stop layer comprising magnesium fluoride and positioned between the magnesium-containing metal body and the coating; the step of removing at least a portion of the consumed coating from the article; the step of exposing the article to a reactive gas to reform at least a portion of the etching stop layer, wherein the reactive gas phase comprises a fluorine component that reacts with magnesium present in the magnesium-containing metal body to reform the etching stop layer; and the step of forming a replacement coating on the etching stop layer. Claim 2 The method according to claim 1, wherein the consumed coating is at least one of a coating that has been chemically modified from a previous state, a coating having a surface modified from a previous state, a coating having a thickness modified from a previous state, a coating having a non-uniform thickness, a coating that does not meet specifications for semiconductor process application, a coating having manufacturing defects, or any combination thereof. Claim 3 The method according to claim 1, wherein both the second metal component and the first metal component comprise at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, manganese, or any combination thereof. Claim 4 The method according to claim 1, wherein the etching stop layer is an etching stop region located on the surface of the substrate and below the surface of the substrate. Claim 5 A method according to claim 1, wherein the removing step includes the step of contacting the coating with an etchant, and the ratio of the thickness of the removed coating to the thickness of the removed etching stop layer is at least 2:

1. Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete

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