Articles Having Removable Coatings and Related Methods - Patent application

Abstract

Some embodiments relate to an article having a removable coating. The article may include a substrate and a coating on the substrate. An etch stop layer may be provided between the substrate and the coating to allow removal of the coating without damaging the substrate. Some embodiments relate to a method of removing a coating from an article. The method may include obtaining an article including an etch stop layer between the substrate and the coating on the substrate, and removing at least a portion of the coating from the article. Other embodiments further provide articles and associated methods.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates generally to articles having removable coatings and related methods. [Background technology]

[0002] Semiconductor manufacturing processes utilize coated substrates. The coating and substrate typically have similar chemical compositions to ensure that the coating adheres to the substrate. However, due to its chemical similarity to the substrate, the coating cannot be removed without causing damage to the substrate. Summary of the Invention

[0003] In a first aspect, there is provided a method for removing a coating from an article, the method comprising: obtaining an article, the article comprising: a substrate including a magnesium-containing metal body including a first metal component; a coating including a second metal component; and an etch stop layer including magnesium fluoride, the etch stop layer being located between the magnesium-containing metal body and the coating; removing at least a portion of the coating from the article; A method is disclosed that includes:

[0004] The second aspect of the first aspect, wherein the substrate includes 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] A third embodiment of any of the previous embodiments, wherein the substrate is not a wafer substrate.

[0006] The fourth embodiment of any of the previous embodiments, wherein the substrate is not an integrated circuit.

[0007] The fifth embodiment of any of the previous embodiments, wherein the coating is at least one of a coating that is chemically altered from a previous state, a coating having a surface that is altered from a previous state, a coating that has a thickness that is altered from a previous state, a coating that has a non-uniform thickness, a coating that does not meet application specifications, a coating that has manufacturing defects, or any combination thereof.

[0008] The sixth embodiment of any of the previous embodiments, 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.

[0009] The seventh embodiment of any of the previous embodiments, wherein the first metal component comprises aluminum and the second metal component comprises aluminum.

[0010] An eighth embodiment of any of the previous embodiments, wherein the etch stop layer is an etch stop region located at and below the surface of the substrate.

[0011] The ninth embodiment of any of the previous embodiments, wherein the removing comprises contacting the coating with an etching agent.

[0012] The tenth embodiment of any of the previous embodiments, wherein the etchant removes at least a portion of the etch stop layer.

[0013] An eleventh embodiment of any of the previous embodiments, wherein the method further comprises exposing the article to a reactive gas phase to reorganize at least a portion of the etch stop layer, the reactive gas phase comprising a fluorine component.

[0014] Fluorine components are CF4, C2F4, C3F6, C4F8, CHF3, C2H2F2, C2F6, HF, CH3F, C1-C 1012. The twelfth aspect of any of the preceding aspects, comprising or derived from at least one of polymerized perfluoroalkylethylene having a perfluoroalkyl group, 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.

[0015] The thirteenth embodiment of any of the previous embodiments, wherein the fluorine component of the reactive gas phase reacts with magnesium present within the magnesium-containing metal body to reorganize the etch stop layer.

[0016] A fourteenth embodiment of any of the previous embodiments, wherein a ratio of a thickness of the coating that is removed to a thickness of the etch stop layer that is removed is at least 2:1.

[0017] A fifteenth embodiment of any of the previous embodiments, wherein the etch stop layer has a uniform thickness.

[0018] A sixteenth embodiment of any of the previous embodiments, wherein the method further comprises forming a replacement coating on the etch stop layer.

[0019] A seventeenth embodiment of any of the previous embodiments, wherein the alternative coating is a thermal atomic layer deposition (ALD) coating.

[0020] The eighteenth embodiment of any of the previous embodiments, wherein the alternative coating comprises at least one of alumina, yttria, titania, zirconia, tantalum oxide, or any combination thereof.

[0021] A nineteenth aspect disclosed herein is a method for forming an article, the method comprising: obtaining a substrate, the substrate comprising a magnesium-containing metal body that includes a first metal component; exposing the substrate to a reactive gas phase to form an etch stop layer on and beneath the substrate, the reactive gas phase including a fluorine component that reacts with magnesium of the magnesium-containing metal body to form magnesium fluoride; forming a coating on the etch stop layer, the coating comprising a second metallic component; The method includes:

[0022] A twentieth aspect disclosed herein is an article, comprising: a substrate including a magnesium-containing metal body including a first metal component, the substrate being not a wafer substrate and not an integrated circuit; a coating comprising a second metal component; and an etch stop layer located between the substrate and the coating, the etch stop layer comprising magnesium fluoride formed on and beneath the surface of the substrate; The article includes:

[0023] Reference is made to the drawings which form a part of this disclosure and which illustrate embodiments in which the materials and methods described herein may be practiced. [Brief description of the drawings]

[0024] [Figure 1] 1 is a flowchart of a method for forming an article according to some embodiments of the present disclosure. [Diagram 2] 1 is a schematic diagram of an article according to some embodiments of the present disclosure. [Diagram 3] 1 is a flowchart of a method for removing a coating from an article according to some embodiments of the present disclosure. [Figure 4] 1A-1C are schematic diagrams of methods for (A) forming an article, (B) reworking an article, and (C) modifying an article, according to some embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Some embodiments relate to articles having removable coatings and related methods. The article may include an etch stop layer between the substrate and the coating, which may be chemically similar to the substrate. The etch stop layer may be resistant to chemicals and other substances used in the coating removal process, such that the coating may 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, an altered surface finish, an altered visual appearance, a change in chemical composition, a change in surface morphology, and the like. The etch stop layer may provide sufficient adhesion between the substrate and the coating. The etch stop layer may be a highly conformal layer with complete surface coverage of high aspect ratio features of the substrate. The etch stop layer may exhibit thermal stability at high temperatures.

[0026] 1 is a flow chart of a method for forming an article including a removable coating according to some embodiments of the present disclosure. As shown in FIG. 1, the method 100 may include one or more of the following steps: obtaining a substrate 102, exposing the substrate to a reactive gas phase to form an etch stop layer 104, and forming a coating on the etch stop layer 106.

[0027] In step 102, in some embodiments, a substrate may be obtained. In some embodiments, the substrate may be a metal body including one or more metal components. In some embodiments, each of the one or more metal components may include, consist of, or consist essentially 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 include, consist of, or consist essentially 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 include, consist of, or consist essentially of at least one of a magnesium component, an aluminum component, or any combination thereof.

[0028] In some embodiments, the substrate may be a magnesium-containing metal body. In some embodiments, the magnesium-containing metal body may comprise, consist of, or consist essentially of a magnesium-containing metal (e.g., any metal or metal alloy containing any amount of magnesium, including trace amounts of magnesium). In some embodiments, the magnesium-containing metal may comprise, consist of, or consist essentially 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, consist of, or consist essentially of a first metal component, such as a first aluminum component. In some embodiments, the magnesium-containing metal alloy may comprise, consist of, or consist essentially of at least one of, or be selected from the group consisting of, an iron alloy (e.g., steel or stainless steel), an aluminum alloy, a vanadium alloy, a magnesium alloy (e.g., stainless magnesium, such as an alloy containing magnesium and lithium, or an alloy containing magnesium and aluminum), a nickel alloy, a chromium alloy, a zinc alloy, a titanium alloy, or any combination thereof.

[0029] In some embodiments, the magnesium component can include magnesium in a mobile form. For example, in some embodiments, the magnesium component can include magnesium in metallic form as a metal alloy, a metal ion, a 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 ions, a magnesium-containing metal oxide, elemental magnesium, or any combination thereof.

[0030] In some embodiments, the substrate can include at least 0.01% to less than 100% by weight magnesium based on the total weight of the substrate, or any range or subrange therebetween. For example, in some embodiments, the substrate can include at least 0.01%, at least 0.1%, at least 1%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 99%, 99% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 1% or less, 0.1% or less, 0.01% or less, 0% to 100%, 10% to 100%, 20% to 100%, 30% to 100%, 40% to 100%, or any range or subrange therebetween. 0%, over 50% ~ 100%, over 60% ~ 100%, over 70% ~ 100%, over 80% ~ 100%, over 90% ~ 100%, over 0% ~ 90%, over 0% ~ 80%, 0% More than 70%, More than 0% ~ 60%, More than 0% ~ 50%, More than 0% ~ 40%, More than 0% ~ 30%, More than 0% ~ 20%, More than 0% ~ 10%, More than 0% ~ 5%, More than 0% ~ 1%, 0.01 % to 1%, greater than 0.1% to 1%, 40% to 99%, 40% to 95%, 40% to 90%, 40% to 80%, 40% to 70%, 40% to 60%, 50% to 99%, 60% to 99%, 70% to 99%, 80% to 99%, 90% to 99%, 95% to 99%, and / or any range or subrange therebetween.

[0031] In some embodiments, the substrate may comprise 1% or less by weight magnesium oxide (MgO) based on the total weight of the substrate. In some embodiments, the substrate may comprise 0.5% or less by weight magnesium oxide based on the total weight of the substrate. In some embodiments, the substrate may comprise 0.1% or less by weight magnesium oxide based on the total weight of the substrate. In some embodiments, the substrate may comprise 0.05% or less by weight magnesium oxide based on the total weight of the substrate.

[0032] In some embodiments, the substrate may comprise at least 0.01% to less than 100% by weight aluminum based on the total weight of the substrate. For example, in some embodiments, the substrate may comprise at least 0.01%, at least 0.1%, at least 1%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 99%, 99% or less, 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 1% or less, 0.1% or less, 0.01% or less by weight aluminum based on the total weight of the substrate. The following may include more than 0% to less than 100%, more than 10% to less than 100%, more than 20% to less than 100%, more than 30% to less than 100%, more than 40% to less than 100%, more than 50% to less than 100%, more than 60% to less than 100%, more than 70% to less than 100%, more than 80% to less than 100%, more than 90% to less than 100%, more than 0% to 90%, more than 0% to 80%, more than 0% to 70%, more than 0% to 60%, more than 0% to 50%, more than 0% to 40%, more than 0% to 30%, more than 0% to 20%, more than 0% to 10%, more than 0% to 5%, more than 0% to 1%, and / or any range or subrange therebetween.

[0033] In some embodiments, the aluminum alloy may include at least one of aluminum, magnesium, silicon, iron, copper, chromium, zinc, titanium, manganese, or any combination thereof. In some embodiments, the aluminum alloy includes, consists of, or consists essentially of at least one of 96% to 98% aluminum by weight based on the total weight of the aluminum alloy, 0.5% to 1.2% magnesium by weight based on the total weight of the aluminum alloy, 0.4% to 0.8% silicon by weight based on the total weight of the aluminum alloy, greater than 0% to 0.7% iron by weight based on the total weight of the aluminum alloy, 0.1% to 0.4% copper by weight based on the total weight of the aluminum alloy, greater than 0% to 0.4% chromium by weight based on the total weight of the aluminum alloy, greater than 0% to 0.3% zinc by weight based on the total weight of the aluminum alloy, greater than 0% to 0.3% titanium by weight based on the total weight of the aluminum alloy, greater than 0% to 0.2% manganese by weight based on the total weight of the aluminum alloy, or any combination thereof. In some embodiments, the aluminum alloy may further include at least one of one or more metals, one or more transition metals, one or more semiconductor materials, or any combination thereof. In some embodiments, the one or more semiconductor materials may include a compound including at least one of gallium, antimony, tellurium, arsenic, polonium, or any combination thereof.

[0034] In some embodiments, the substrate may comprise, consist of, or consist essentially of at least one of: 10%-99% nickel by weight based on the total weight of the substrate; 40%-99% vanadium by weight based on the total weight of the substrate; 15%-99% chromium by weight based on the total weight of the substrate; 40%-99% aluminum by weight based on the total weight of the substrate; 40%-99% zinc by weight based on the total weight of the substrate; 40%-99% titanium by weight based on the total weight of the substrate; greater than 0% and less than 100% iron by weight based on the total weight of the substrate; 2%-3% molybdenum by weight based on the total weight of the substrate; or any combination thereof. In some embodiments, the weight percentages above refer to metal components, including metals or metals in elemental form.

[0035] In some embodiments, the substrate may have at least one feature. In some embodiments, the at least one feature may include, consist of, consist essentially 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 region defining a cavity), a planar surface, a non-planar surface, or any combination thereof. In some embodiments, the at least one feature may have an aspect ratio. For example, in some embodiments, the aspect ratio of a feature may refer to the ratio of depth to width. In some embodiments, the aspect ratio of a feature may refer to the ratio of width to depth. In some embodiments, the aspect ratio of a feature may refer to the ratio of two of length, width, or height. In some embodiments, the aspect ratio of a feature may refer to the ratio of depth to diameter. In some embodiments, the aspect ratio of a feature may refer to the ratio of diameter to depth. In some embodiments, the aspect ratio of a feature may refer to the ratio of at least one of the following: width, depth, height, diameter, and circumference.

[0036] In some embodiments, at least one feature may have an aspect ratio of 2:1 to 1000:1, or any range or subrange therebetween. For example, at least one feature may have an aspect ratio of 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, at least 900:1, up to 1000:1, and / or any range or subrange therebetween.

[0037] 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.

[0038] In step 104, in some embodiments, the substrate may be exposed to a reactive gas phase to form an etch stop layer. In some embodiments, the exposure may occur under conditions sufficient to result in the formation of an etch stop layer. In some embodiments, the exposure may occur in a chamber configured to expose the reactive gas phase to the substrate. In some embodiments, the exposure may occur in a process chamber. In some embodiments, the exposure may occur in a reactor. In some embodiments, the exposure may occur by vaporizing a solid or liquid precursor material to obtain a reactive gas phase and delivering the reactive gas phase to a process chamber or reactor. In some embodiments, the exposure may occur by delivering the reactive gas phase to a process chamber or reactor (e.g., without vaporizing a solid or liquid precursor material to obtain a reactive gas phase). In some embodiments, the etch stop layer is formed by a plasma-free deposition process. In some embodiments, the etch stop layer is formed by a non-plasma deposition process.

[0039] In some embodiments, the reactive gas phase may include a fluorine component. In some embodiments, the reactive gas phase may include a molecular fluorine source vapor, which may be derived from a liquid or a solid. In some embodiments, the fluorine component may include, consist of, or consist essentially of molecular fluorine. In some embodiments, the fluorine component is not ionic, is not substantially ionic, has not been treated (e.g., by applying energy other than heat) to form a plasma, or any combination thereof. In some embodiments, the fluorine component may include, consist of, or consist essentially 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 include, consist of, or consist essentially of at least one of a fluorinated alkane, a perfluorinated alkane, a fluorinated alkene, a perfluorinated alkene, or any combination thereof, any one or more of which may be linear or branched. In some embodiments, the fluorine component may comprise, consist of, consist essentially of, or be selected from the group consisting of 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 different from the plasma, the process that generates the plasma, or any combination thereof.

[0040] In some embodiments, the reactive gas phase may include 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 include 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), perfluorinated, or may contain non-fluorine halogen atoms, such as, but not limited to, chlorine. In some embodiments, the molecular fluorine source may be a liquid or solid at room temperature, but vaporizes at the process temperatures disclosed herein. Non-limiting examples of fluoropolymers include, but are not limited to, C1-C 10 The polymeric perfluoroalkyl ethylene having a perfluoroalkyl group may include at least one of: polymerized perfluoroalkyl ethylene having a perfluoroalkyl group; 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.

[0041] In some embodiments, the etch stop layer may include magnesium fluoride (MgF2). In some embodiments, the magnesium fluoride of the etch stop layer may be a reaction product of a magnesium component present in the substrate and a fluorine component present in the reactive gas phase. In some embodiments, the magnesium fluoride of the etch 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 at the surface of the substrate, magnesium present below the surface of the substrate, magnesium diffusing or migrating 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 etch stop layer may not be a substantially separate layer formed on the surface of the substrate, but rather may be a region formed on the surface of the substrate and possibly below. In some embodiments, the etch stop layer is not (and thus is distinct from) a layer applied to the substrate surface via a coating or deposition process (e.g., chemical vapor deposition, atomic layer deposition, physical vapor deposition, etc.).

[0042] In some embodiments, the etch stop region may include, consist of, or consist essentially of at least one of magnesium compounds, fluoride compounds, magnesium fluoride compounds, oxide compounds, metal compounds, metal oxide compounds, or any combination thereof. In some embodiments, the etch stop region may include, consist of, or consist essentially of at least one of magnesium fluoride (MgF2), metal oxide compounds, or any combination thereof. In some embodiments, the metal oxide compounds may be reaction products. For example, in some embodiments, the metal oxide compounds may be formed upon exposure of the substrate to oxygen. In some embodiments, the etch stop layer may include, consist of, or consist essentially of an atomic layer deposition (ALD) coating comprising yttria. In some embodiments, the etch stop layer may include, consist of, or consist essentially of an ALD coating comprising zirconia. In some embodiments, the etch stop layer may include, consist of, or consist essentially of an ALD coating comprising titania. In some embodiments, the etch stop layer may include, consist of, or consist essentially of an ALD coating comprising titania. In some embodiments, the etch stop layer may include, consist of, or consist essentially of an ALD coating comprising AlO x N y wherein x is 1-5 and N is 1-5.

[0043] In some embodiments, the exposure may be at one or more process conditions. In some embodiments, the process conditions may include at least one of a temperature between 200° C. and 500° C. (e.g., between 350° C. and 500° C., between 375° C. and 425° C., between 375° C. and 450° C., between 400° C. and 425° C., between 400° C. and 450° C., etc.), a pressure between 100 Torr and 1500 Torr (e.g., between 250 Torr and 1000 Torr, between 500 Torr and 1000 Torr, between 250 Torr and 1250 Torr, between 500 Torr and 1250 Torr, etc.), a duration between 1 hour and 15 hours (e.g., between 2 hours and 13 hours, between 3 hours and 12 hours, etc.), or any combination thereof. In some embodiments, the process conditions should 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 should be at a temperature, pressure, duration, or any combination thereof sufficient to cause the fluorine of the fluorine component to react with the magnesium present in the substrate to form MgF2. In some embodiments, the process conditions can be altered or adjusted to obtain at least one of a predetermined thickness, a predetermined coverage, a predetermined property (e.g., at least one of corrosion resistance, etch resistance, or any combination thereof), or any combination thereof.

[0044] In some embodiments, surface coverage may refer to the percentage of the exposed, unmasked surface (e.g., gas-exposed surface) that comprises magnesium fluoride. In some embodiments, exposed surface may refer to the unmasked surface. In some embodiments, surface coverage may be at least 80%-100%, or any range or subrange therebetween. For example, in some embodiments, 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, surface coverage may be in the range of 80%-100%, and / or any range or subrange therebetween.

[0045] In some embodiments, the etch stop layer is a conformal layer. In some embodiments, the etch stop layer is a layer having a substantially uniform or uniform thickness. In some embodiments, the etch stop layer may be a corrosion resistant layer or may form a corrosion resistant substrate surface. In some embodiments, the etch stop layer may be an etch resistant layer or may form an etch resistant substrate surface. In some embodiments, the etch stop layer may passivate the surface of the substrate. In some embodiments, the etch stop layer may be a protective layer. In some embodiments, the etch stop layer may impart at least one improved surface property.

[0046] In some embodiments, the etch stop region may have a thickness of 1 nm to 200 nm, or any range or subrange therebetween. For example, in some embodiments, the etch 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 subrange therebetween. In some embodiments, the thickness of the etch stop region may be measured by scanning electron microscope (SEM) cross section, X-ray photoelectron spectroscopy (XPS) depth profiling, or energy disruptive x-ray microscopy (EDAX), among other techniques.

[0047] In step 106, a coating may be formed on at least one of the etch stop layer, the substrate, or any combination thereof. In some embodiments, the coating may be formed by exposing the article to one or more precursor gases to form a coating on a surface of the etch 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 to form 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 to form a conformal coating. In some embodiments, the conformal coating may include a coating having a uniform or substantially uniform thickness.

[0048] In some embodiments, the forming may include a process sequence for atomic layer deposition. In some embodiments, the process sequence may utilize 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, the exposing may include a process sequence of contacting the 3D article with at least a first precursor in a reaction chamber, purging the reaction chamber, contacting the 3D article with at least a second precursor in the reaction chamber, and purging the reaction chamber to complete a cycle. In some embodiments, the forming may include 1 to 5000 cycles. In some embodiments, the forming may include 100 to 5000 cycles. In some embodiments, the forming may include 50 to 1500 cycles. In some embodiments, the forming may include a sufficient number of cycles to achieve a desired thickness, desired properties, or other attributes.

[0049] In some embodiments, the precursor gas or gases may be selected based on the particular ALD coating to be formed. In some embodiments, one or more precursors including trimethylaluminum and ozone may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors including trimethylaluminum and water may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors including a cyclopentadienyl compound of a metal M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process utilizing ozone (O3) or water vapor (H2O). In some embodiments, one or more precursors including a beta-diketonate of M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process in which reactive pulses of a beta-diketonate metal precursor alternate with pulses of O3.

[0050] For example, in some embodiments, atomic layer deposition may include a process sequence that utilizes trimethylaluminum and ozone in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence that utilizes trimethylaluminum and water in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence that utilizes a cyclopentadienyl M compound and ozone in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence that utilizes a cyclopentadienyl M compound and water in a cyclic ALD process to form an ALD coating. In some embodiments, atomic layer deposition may include a process sequence that utilizes an M beta diketonate compound and ozone in a cyclic ALD process to form an ALD coating. In some embodiments, other metal oxide precursor compounds may be used.

[0051] In some embodiments, one or more precursors including trimethylaluminum and ozone may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors including trimethylaluminum and water may be useful precursor compositions for depositing Al2O3. In some embodiments, one or more precursors including a cyclopentadienyl compound of a metal M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process utilizing ozone (O3) or water vapor (H2O). In some embodiments, one or more precursors including a beta-diketonate of M or Ln may be useful precursor compositions for depositing MO or Ln2O3 in a cyclic ALD process in which reactive pulses of a beta-diketonate metal precursor alternate with pulses of O3.

[0052] In some embodiments, one or more precursor ligands may be used to deposit the coating. In some embodiments, the one or more precursor ligands may be hydrogen, C1-C 10 The alkyl group may include at least one of: alkyl (which may be linear or branched, cyclic or acyclic, saturated or unsaturated); aryl, heterocycle, alkoxy, cycloalkyl, silyl, silylalkyl, silylamide, trimethylsilylsilyl-substituted alkyl, trialkylsilyl-substituted alkyne, trialkylsilylamide-substituted alkyne, dialkylamide, ethylene, acetylene, alkyne, substituted alkene, substituted alkyne, diene, cyclopentadienyl arene, amine, alkylamine, bidentate amine, ammonia, RNH2 (wherein R is an organic group, e.g., a hydrocarbyl substituent), amidinate, guanidinate, diazadiene cyclopentadienyl, oxime, hydroxyamine, acetate, β-diketonate, β-ketoiminate, nitrile, nitrate, sulfate, phosphate, halogen, hydroxyl, substituted hydroxyl, any derivative thereof, or any combination thereof.

[0053] In some embodiments, the forming can occur at a temperature between 20° C. and 400° C., or any range or subrange therebetween. For example, in some embodiments, the formation may be performed at temperatures between 25°C and 400°C, 50°C and 400°C, 75°C and 400°C, 100°C and 400°C, 125°C and 400°C, 150°C and 400°C, 175°C and 400°C, 200°C and 400°C, 225°C and 400°C, 250°C and 400°C, 275°C and 400°C, 300°C and 400°C, 325°C and 400°C, 350°C and 400°C, 375°C and 400°C, 20°C and 375°C, 20°C and 350°C, 20°C and 325°C, 20°C and 300°C, 20°C and 275°C, 20°C and 250°C, 20°C and 225°C, 20°C and ... The reaction may be performed at a temperature of from 0°C to 200°C, 20°C to 175°C, 20°C to 150°C, 20°C to 125°C, 20°C to 100°C, 20°C to 75°C, 20°C to 50°C, 125°C to 375°C, 150°C to 350°C, 175°C to 350°C, 175°C to 325°C, 200°C to 350°C, 200°C to 325°C, 225°C to 350°C, 225°C to 325°C, 250°C to 350°C, 250°C to 325°C, 275°C to 350°C, 275°C to 325°C, 300°C to 350°C, 300°C to 325°C, and / or any range or subrange therebetween.

[0054] In some embodiments, the deposition process is a process that forms a conformal coating. In some embodiments, the conformal coating may include a coating having a uniform or substantially uniform thickness.

[0055] In some embodiments, the coating layer may have a thickness of 1 nm to 50 μm, or any range or subrange therebetween. 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 has a thickness of 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 800 nm, 850 nm to 900 nm, 900 nm to 1000 nm, 100 nm to 15 ... nm~5μm, 800nm~5μm, 900nm~5μm, 1μm~5μm, 2μm~5μm, 3μm~5μm, 4μm~5μm, 1nm~750nm, 1nm~500 nm, 2nm~500nm, 1nm~250nm, 20nm~125nm, 20nm~250nm, 20nm~500nm, 50nm~500nm, 50nm~400nm , 50 nm to 300 nm, 50 nm to 200 nm, 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 subrange therebetween.

[0056] In some embodiments, the coating may include at least one second metal component. In some embodiments, the at least one second metal component may include, consist of, or consist essentially 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, the at least one second metal component may include, consist of, or consist essentially of at least one of magnesium, aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, or any combination thereof. In some embodiments, the 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, the at least one second metal component may include at least one metal that is the same as the metal included in the first metal component of the substrate. In some embodiments, for example, in some embodiments, the first metal component and the second component include one or more of aluminum, or other metals.

[0057] In some embodiments, the coating may comprise, consist of, consist essentially of, or be selected from the group consisting of at least one of alumina, yttria, titania, zirconia, tantalum oxide, or any combination thereof. In some embodiments, the coating may comprise at least one of Al2O3; oxides of the formula MO, where M is Ca, Mg, or Be; oxides of the formula M'O2, where M' is a stoichiometrically allowed metal; oxides of the formula Re2O3, where Re is a rare earth element, e.g., a lanthanide element; and oxides of the formula Ta x O ywhere x is greater than 0 and y is greater than 0. In some embodiments, the lanthanide element may comprise, consist of, or consist essentially of, one or more of the oxides of La, Sc, or Y. In some embodiments, the coating may comprise, consist of, or consist essentially of, or may be selected from the group consisting of at least one 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.

[0058] In some embodiments, the article may be a component of a semiconductor manufacturing tool, such as, for example, but not limited to, at least one of 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 wafer handling fixture, 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 any combination thereof.

[0059] In some embodiments, the magnesium fluoride passivation layer may be biocompatible such that 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, such as, for example, but not limited to, at least one of a medical instrument, a medical implant, or an article having a medical application. Non-limiting examples of medical devices and / or components thereof 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, an enclosure, a wire, a stent, a connector, or any combination thereof.

[0060] Some embodiments of the present disclosure relate to articles having removable coatings. In some embodiments, the article includes an article formed according to a method of the present disclosure, such as the method of FIG. 1. It will be understood that the article can thus include any of the features disclosed herein, including those disclosed above and elsewhere herein.

[0061] FIG. 2 is a schematic diagram of an article including a removable coating according to some embodiments of the present disclosure. As shown in FIG. 2, the article may include a substrate 202, an etch stop layer 204, and a coating 206. In some embodiments, the etch stop layer 204 may be on a surface 210 of the substrate 202. For example, in some embodiments, the etch stop layer 204 may be an etch stop region of the substrate 202 that extends from the surface 210 of the substrate 202 to a depth within the substrate 202. In some of these embodiments, the substrate 202 may further comprise a bulk region 208, which is a region of the substrate 202 that is not a region that defines the etch stop layer 204. In some embodiments, the etch stop layer 204 may be on the surface 210 of the substrate 202. In some embodiments, the coating 206 may be on the surface 210 of the etch stop layer 204. In some embodiments, the coating 206 may be on the surface of the substrate 202. In some embodiments, the coating 206 may be on a surface of the etch stop layer 204 , which is formed on the surface of the substrate 202 .

[0062] In some embodiments, the etch stop layer 204 may be disposed or located between the substrate 202 and the coating 206 and allow for removal of the coating 206 (e.g., by etching, such as, but not limited to, at least one of a dry etch, a wet etch, or any combination thereof) without degrading or chemically altering the substrate 202 to a state or condition that is not commercially useful. For example, in some embodiments, the substrate 202 and the coating 206 may be chemically similar such that removal of the coating 206 in the absence of the etch stop layer 204 removes at least a portion of the substrate 202. In some embodiments, the etch stop layer 204 may passivate the surface of the substrate 202 such that removal of the coating 206 does not result in any appreciable removal of the substrate 202, or if at least some removal of the substrate occurs, the degree of removal is acceptable for commercial purposes. In this manner, the etch stop layer 204 may be effective as a chemically resistant layer that allows for refurbishment and / or reworking of the article.

[0063] 3 is a flow chart of a method for removing a coating from an article according to some embodiments of the present disclosure. As shown in FIG. 3, the method 300 for removing a coating from an article may include one or more of the following steps: obtaining an article 302, the article including a substrate, a first coating, and an etch stop layer between the substrate and the first coating; removing at least a portion of the first coating from the article 304; exposing the article to a reactive gas phase to reorganize at least a portion of the etch stop layer 306; forming a second coating on the etch stop layer 308, where in some embodiments the first coating is a used coating and the second coating is a replacement coating.

[0064] In step 302, in some embodiments, an article may be obtained. As mentioned above, in some embodiments, the article may include a substrate, a first coating, and an etch stop layer between the substrate and the first coating. In some embodiments, the obtained article may include any one or more of an article formed according to the method of the present disclosure (e.g., an article formed according to the method of FIG. 1) and an article of the present disclosure (e.g., an article shown in the schematic diagram of FIG. 2). In some embodiments, the obtained article may include an article for rework. In some embodiments, the article for rework may be an article in which the first coating is formed with defects, for example due to manufacturing errors. In some embodiments, the obtained article may include an article for refurbishment. In some embodiments, the article for refurbishment may be an article in which the first coating has deteriorated due to use (e.g., repeated use) in a process (e.g., a semiconductor manufacturing process, a microelectronic manufacturing process, etc.). In some embodiments, the first coating may be any coating that has been at least one of reworked, removed, replaced, refurbished (e.g., a coating that has been used or processed one or more times and is considered to be in an "end of life" condition), or any combination thereof. In some embodiments, the first coating may be a used coating, which may be any coating that has defects and / or has deteriorated (e.g., due to use).

[0065] For example, in some embodiments, the first coating may include a coating to be refurbished. In some embodiments, the coating to be refurbished may be a coating in a state or condition that is detrimental to the structure, material, use, or operation of the article (e.g., rendering the article unsuitable for commercial purposes). Thus, the first coating may be described with reference to a previous state or condition. For example, in some embodiments, the previous state or condition of the first coating may be a coating prepared according to the method of the present disclosure (e.g., step 106 of FIG. 1). In some of these embodiments, the first coating is any coating that has at least one property, characteristic, element, attribute, or composition that differs from the coating in the previous state or condition. In some embodiments, the first coating is a coating that has been used at least once in a process (e.g., a semiconductor manufacturing process, etc.). 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 is poorly manufactured. For example, in some embodiments, the first coating may be a coating that does not meet the specifications of the application. In some embodiments, the first coating may be a coating that has defects, such as defects created 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.

[0066] In some embodiments, the first coating may be a coating that is chemically altered from a previous state. In some embodiments, the first coating may be a coating that has a surface that is altered from a previous state. In some embodiments, the first coating may be a coating that has a thickness that is altered from a previous state. In some embodiments, the first coating may be a coating that has a non-uniform thickness. In some embodiments, the first coating may be a coating that does not meet the specifications of the application. In some embodiments, the first coating may be a coating that has a manufacturing defect.

[0067] In step 304, in some embodiments, at least a portion of the first coating may be removed from the article. In some embodiments, removing 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 etch stop layer. In some embodiments, removal of the first coating may proceed by at least one of a dry etch, a wet etch, or any combination thereof. In some embodiments, the etchant may remove the first coating in its entirety 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 etch stop layer prevents or at least reduces the extent to which the substrate is etched during etching of the first coating. In some embodiments, the etchant may remove at least a portion of the etch 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 applying a mechanical removal process (e.g., blasting, abrading, lapping, ion sputtering, etc.) or stress-induced separation (e.g., delamination), alone or in combination with the application of a mechanical removal process (e.g., blasting, abrading, lapping, ion sputtering, etc.) or stress-induced separation (e.g., delamination). In some embodiments, the first coating may be removed without applying a mechanical removal process (e.g., blasting, abrading, lapping, ion sputtering, etc.) or stress-induced separation (e.g., delamination).

[0068] In some embodiments, the etchant may have selectivity for the first coating over at least one of the etch stop layer, the substrate, or any combination thereof. In some embodiments, the selectivity may be defined as the ratio of the thickness of the etch stop layer removed to the thickness of the substrate removed. In some embodiments, the selectivity of the etchant may be at least 1.01:1 to 20:1, or any range or subrange therebetween. 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 subrange therebetween. 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 subrange therebetween.

[0069] In step 306, in some embodiments, the article may be exposed to a reactive gas phase to reorganize at least a portion of the etch stop layer. In some embodiments, step 306 is an optional step. For example, in some embodiments, step 306 may be performed when at least a portion of the etch stop layer may 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 be free of magnesium fluoride. In some embodiments, step 306 may be performed when at least a portion of the etch stop layer or the surface of the substrate requires reorganization or repair of the etch stop layer, magnesium fluoride, or any combination thereof. In some embodiments, exposing the article to a reactive gas phase to reorganize the etch stop layer may be performed according to the methods of the present disclosure. For example, in some embodiments, the forming step may be performed similarly or identically to step 104 of FIG. 1.

[0070] In step 308, in some embodiments, the second coating may be reorganized on at least one of the substrate, the etch stop layer, or any combination thereof. In some embodiments, the second coating may be a replacement coating. In some embodiments, the second coating may produce an article suitable for commercial purposes. In some embodiments, reorganizing the second coating or replacement coating on at least one of the substrate, the etch stop layer, or any combination thereof produces a reworked or refurbished article. In some embodiments, the reorganizing of the second coating on at least one of the substrate, the etch stop layer, or any combination thereof may be performed according to the method of the present disclosure. For example, in some embodiments, the reorganizing may be performed similarly or identically to step 106 of FIG. 1.

[0071] FIG. 4 is a schematic diagram of a process for (A) forming an article including a removable coating, (B) reworking an article, and (C) refurbishing an article, according to some embodiments of the present disclosure. As shown in FIG. 4A, a substrate 402 including a metal alloy (e.g., an aluminum alloy) is shown. In some embodiments, the metal alloy is an aluminum alloy including at least 90% aluminum. In some embodiments, the aluminum alloy may include 95%-99% aluminum by weight, more than 0% and less than 1% silicon by weight, more than 0% and less than 1% copper by weight, more than 0% and less than 1% chromium by weight, and more than 0% and less than 2% magnesium by weight, the % weights being based on the total weight of the substrate 402. In some embodiments, an etch stop layer 404 may be formed on and / or below the surface of 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 etch stop layer 404, or both the surface of the substrate 402 and the surface of the etch stop layer 404 to obtain an article including a removable coating.

[0072] 4B, in some embodiments, coating 406 or the process forming coating 406 may have defects or errors. In some embodiments, coating 406 may be reworked. For example, in some embodiments, coating 406 is an alumina ALD coating having errors or defects. In some embodiments, alumina ALD coating 406 may be removed by a wet chemical removal process (e.g., wet etching). In some embodiments, by removing alumina ALD coating 406 having errors or defects, a replacement alumina ALD coating (not shown) may be formed on the surface of substrate 402 / etch stop layer 404.

[0073] As shown in FIG. 4C, in some embodiments, the article may be in use (e.g., may have reached end of life or may have a chemically altered composition, among other things, as described above). In some embodiments, coating 406 may be refurbished. For example, in some embodiments, coating 406 is an alumina ALD coating that was used in one or more processes. In some embodiments, alumina ALD coating 406 may be removed by a wet chemical removal process (e.g., wet etching). In some embodiments, a replacement ALD coating (not shown) may be formed on the surface of substrate 402 / etch stop layer 404 by removing alumina ALD coating 406 having an alteration from a previous state or condition.

Claims

1. A method for removing a coating from an article, This involves acquiring articles for reprocessing or refurbishment, and the articles are A substrate containing a magnesium-containing metal body containing a first metal component, A coating comprising 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, or YOF, YF3, or any combination thereof, which is placed on a substrate and requires rework or modification, An etching stop layer containing magnesium fluoride, wherein the etching stop layer is located between the magnesium-containing metal body and the coating. Acquiring goods, including, Removing at least a portion of the coating from an article, comprising contacting the coating with an etching agent that removes at least a portion of the etching stop layer, Exposing the article to a reactive gas phase to reform at least a portion of the etching stop layer, Forming an alternative coating on the etching stop layer and Methods that include...

2. The coating A coating that has been chemically modified from its previous state. A coating having a surface that has been modified from its previous state. A coating having a modified thickness from its previous state. A coating with an uneven thickness, Coatings that do not meet the specifications for their intended use. A coating with a manufacturing defect, or Any combination of these The method according to claim 1, wherein at least one of the following is the method according to claim 1.

3. The method according to claim 1, wherein the first metallic component comprises at least one of aluminum, vanadium, iron, nickel, chromium, zinc, molybdenum, titanium, lithium, copper, manganese, silicon, copper, manganese, or any combination thereof.

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 it.

5. The method according to claim 1, wherein the first metallic component comprises aluminum, and the coating is selected from alumina, aluminum oxynitride, yttria-alumina, or any combination thereof.

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