Erosion resistant metal fluoride coatings deposited by atomic layer deposition

Abstract

Embodiments of this disclosure relate to articles, coated articles, and methods of coating such articles with a fluoride coating containing rare earth metals. The coating may comprise at least a first metal (e.g., a rare earth metal, tantalum, zirconium, etc.) and a second metal that have been co-deposited onto the surface of the article. The coating may comprise a homogeneous mixture of the first and second metals and does not involve mechanical separation between layers within the coating.

Description

[Technical Field]

[0001] Embodiments of this disclosure relate to corrosion-resistant metal fluoride coatings, coated articles, and methods of forming such coatings using atomic layer deposition. [Previous Technology]

[0002] In the semiconductor industry, devices are manufactured through several manufacturing processes that produce structures with ever-decreasing dimensions. Some manufacturing processes, such as plasma etching and plasma cleaning processes, expose a substrate to a high-speed flow of plasma to etch or clean it. Plasma can be highly corrosive and can corrode the processing chambers and other surfaces exposed to it. This corrosion can generate particles that often contaminate the substrate being processed, thus contributing to device defects. Fluorinated plasmas (which may include fluoride ions and free radicals) can be particularly harsh, resulting in particles generated by the interaction of the plasma with the materials within the processing chamber. Plasma can damage the protective coating and underlying materials of chamber components; it can cause surface damage to the protective coating and increase the risk of cracking and delamination. Drift in the rate of free radical recombination caused by slow fluorination on the chamber surfaces can also cause wafer process drift.

[0003] As device geometry shrinks, sensitivity to defects increases and requirements for particulate contaminants (i.e., wafer-level performance) become more stringent. To minimize particulate contamination introduced by plasma etching and / or plasma cleaning processes, plasma-resistant chamber materials have been developed. Examples of such plasma-resistant materials include ceramics composed of Al2O3, AlN, SiC, Y2O3, quartz, and ZrO2. Different ceramics offer different material properties, such as plasma resistance, rigidity, flexural strength, thermal shock resistance, etc. Moreover, different ceramics have different material costs. Accordingly, some ceramics have excellent plasma resistance, others have lower costs, and still others have excellent flexural strength and / or thermal shock resistance.

[0004] Plasma spray coatings formed from Al2O3, AlN, SiC, Y2O3, quartz, and ZrO2 can reduce particle generation from chamber components; however, such plasma spray coatings cannot penetrate and coat high aspect ratio features such as nozzle orifices. Although some deposition techniques can coat high aspect ratio features, the resulting coatings may erode and form particles in certain plasma environments (e.g., fluorinated plasmas), or suffer from mechanical separation of the layer due to insufficient interdiffusion within the coating. [Summary of the Invention]

[0005] The embodiments described herein relate to an article comprising: a body; and a rare earth metal-containing fluoride coating on the surface of the body, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, wherein the first metal and the second metal are independently selected from the group consisting of: rare earth metals, zirconium, hafnium, aluminum and tantalum, wherein the first metal is different from the second metal, and wherein the rare earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal and the second metal.

[0006] A further embodiment relates to a method comprising: co-depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition, wherein co-depositing the rare earth metal-containing fluoride coating comprises: contacting the surface with a first precursor for a first duration to form a partial metal adsorption layer comprising a first metal (M1), wherein the first precursor is selected from the group consisting of rare earth metal-containing precursors, zirconium-containing precursors, hafnium-containing precursors, aluminum-containing precursors, and tantalum-containing precursors; and contacting the partial metal adsorption layer with a second precursor different from the first precursor for a second duration to form a first metal (M1) comprising a first metal (M1). 1) A co-adsorption layer of a second metal (M2), wherein the second metal precursor is selected from the group consisting of rare earth metal precursors, zirconium precursors, hafnium precursors, aluminum precursors and tantalum precursors, wherein the first metal is different from the second metal; and contacting the co-adsorption layer with reactants to form the rare earth metal fluoride coating, wherein the rare earth metal fluoride coating comprises about 1 mol% to about 40 mol% of the first metal and about 1 mol% to about 40 mol% of the second metal; wherein the rare earth metal fluoride coating comprises a homogeneous mixture of the first metal and the second metal.

[0007] According to an embodiment, a method is also described, comprising: co-depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition, wherein co-depositing the rare earth metal-containing fluoride coating comprises: performing at least one co-doping cycle, comprising: contacting the surface with a mixture of a first precursor and a second precursor for a first duration to form a co-adsorption layer, wherein the first precursor and the second precursor are each selected from the group consisting of: rare earth metal-containing precursors, zirconium-containing precursors, hafnium-containing precursors, aluminum-containing precursors, and tantalum-containing precursors. A precursor; and contacting the co-adsorption layer with a fluorine-containing reactant to form the rare-earth metal-containing fluoride coating, wherein the rare-earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, wherein the first metal and the second metal are independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum and tantalum, wherein the first metal is different from the second metal, and wherein the rare-earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal and the second metal.

[0008] According to an embodiment, a method is also described herein, comprising: depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition, wherein depositing the rare earth metal-containing fluoride coating comprises: contacting the surface with a first precursor for a first duration to form a first metal adsorption layer; contacting the first metal adsorption layer with a fluorine-containing reactant to form a first metal fluoride layer; contacting the first metal fluoride layer with a second precursor for a second duration to form a second metal adsorption layer; contacting the second metal adsorption layer with the fluorine-containing reactant or additional fluorine-containing reactant to form a second metal fluoride layer; and forming the rare earth metal-containing fluoride coating from the first metal fluoride layer and the second metal fluoride layer, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, wherein the first metal and the second metal are independently selected from the group consisting of rare earth metals, zirconium, hafnium, and tantalum, wherein the first metal is different from the second metal.

Implementation Method

[0019] The embodiments described herein relate to fluoride coatings containing composite metals, comprising mixtures of multiple metals. The embodiments also relate to coated articles and methods for forming such fluoride coatings containing composite metals using atomic layer deposition. A fluoride coating containing composite metals may include a first metal (M1) and a second metal (M2), wherein the first metal and the second metal are independently selected from rare earth metals (RE), zirconium, tantalum, hafnium, and aluminum, and wherein the first metal is different from the second metal. In some embodiments, a fluoride coating containing rare earth metals may include more than two metals, such as M1, M2, M3, M4, etc., each independently selected from rare earth metals, zirconium, tantalum, hafnium, and aluminum. For example, rare-earth metal-containing fluoride coatings can be in the form of M1xM2yFz (e.g., YxZryFz, YxEryFz, YxTayFz, etc.), M1wM2xM3yFz (e.g., YwErxFz, YwZrxHfyFz, etc.), M1vM2wM3xM4yFz (e.g., YvErwZrxHfyFz), and / or more complex metal fluoride coatings containing a large amount of mixed metals. As will be discussed in more detail below, multiple different metals (e.g., a first metal, a second metal, etc.) can be co-deposited onto the article using non-line-of-sight techniques such as atomic layer deposition (ALD). Alternatively, multiple different metal fluorides can be sequentially deposited and then interdiffused to form a composite metal fluoride coating. Such coatings are resistant to plasma chemicals used in semiconductor processing (e.g., brominated plasmas with bromide ions and bromine radicals). Without being bound by any particular theory, it is believed that incorporating a second metal (M2) or a third, fourth metal, etc. (i.e., M3, M4, etc.) into the coating reduces vacancies in the material, thereby reducing the diffusion of fluorine (e.g., from CF4 plasma) into the coating.

[0020] According to the embodiments described herein, the coating may be formed from multiple metals (e.g., REwMyFz, YxZryFz, or REwYxZryFz) co-deposited in a single adsorption layer. In some embodiments, at least one of the metals is a rare earth metal. The at least one rare earth metal may be selected from yttrium, erbium, lanthanum, diurethane, scandium, thiocyanate, samarium, or dysprosium. In some embodiments, the coating may be formed from tantalum and at least one additional metal. In embodiments, the at least one additional metal may be selected from rare earth metals (RE), zirconium (Zr), aluminum (Al), hafnium (Hf), silicon (Si), and hafnium (Hf). According to an embodiment, the fluoride coating containing the composite metal may contain about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, or about 10 mol% to about 20 mol% of a first rare earth metal and about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, or about 10 mol% to about 20 mol% of a second metal.

[0021] In some embodiments, the coating may be formed by co-deposition of at least one rare earth metal (e.g., as a first metal) and at least one additional (e.g., a second) metal (e.g., REwMyFz, YxZryFz, or REwYxZryFz) on a single adsorption layer. The at least one rare earth metal may be selected from yttrium, erbium, lanthanum, diurethane, scandium, thiosulfate, samarium, or dysprosium. Alternatively, the coating may be formed from tantalum and at least one additional metal. In embodiments, the at least one additional metal may be selected from rare earth metals (RE), zirconium (Zr), aluminum (Al), hafnium (Hf), and silicon (Si). According to an embodiment, the rare earth metal-containing fluoride coating may contain at least one rare earth metal of about 5 mol% to about 30 mol%, or about 10 mol% to about 25 mol%, or about 15 mol% to about 20 mol%, and at least one additional metal of about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, or about 10 mol% to about 20 mol%.

[0022] The coating provides resistance to erosion by plasmas (e.g., fluorinated plasmas) used for semiconductor processing and chamber cleaning. Therefore, the coating provides good particle performance and process stability performance during such processing and cleaning processes. As used herein, the terms "erosion-resistant coating" or "plasma-resistant coating" refer to a coating that exhibits a particularly low erosion rate when exposed to specific plasmas, chemicals, and free radicals (e.g., fluorine-based plasmas, chemicals, and / or free radicals, chlorine-based plasmas, chemicals, and / or free radicals, etc.). Co-deposition schemes result in coatings that reduce surface fluorination that can lead to wafer process drift, achieve much more uniform coatings on the angstrom scale, and improve phase control (e.g., lack of interdiffusion, thus leaving YF3 and other metallic phases in the coating). According to embodiments, co-deposition schemes result in coatings with a uniform metallic mixture and are believed, without being bound by any particular theory, to reduce vacancies within the co-deposited coating (compared to oxide coatings), thereby preventing fluorine diffusion into the coating. For example, coatings comprising a mixture of Y₂O₃ and ZrO₂ deposited using deposition techniques other than ALD, or deposited via ALD using sequential deposition techniques, may include one or more separated phases at some locations. This can result in some vacancies in the Y₂O₃ phase, potentially increasing susceptibility to fluorination. In contrast, ALD deposition of YxZryFz (e.g., YF-ZrF solid solutions) using co-deposition and / or co-doping techniques can reduce or mitigate phase separation and result in a homogeneous mixture of Y and Zr. Co-deposition schemes also offer the flexibility to adjust the proportions of the deposited metals, for example, by adjusting the number and / or pulse duration, temperature, pressure, etc. This flexibility enables the formation of coatings with specific molar ratios of two or more metals.

[0023] In embodiments, the composite metal fluoride coating may include a two-metal composition (M1xM2yFz), a three-metal composition (M1wM2xM3yFz), a four-metal composition (M1vM2wM3xM4yFz), a five-metal composition (M1uM2vM3wM4xM5yFz), a six-metal composition (M1tM2uM3vM4wM5xM6yFz), etc. In each composite metal fluoride coating, the variables t, u, v, w, x, y, z can be positive integers or decimal values. Some example values ​​of t, u, v, w, x, y, z can be in the range of about 0.1 to about 10. In some embodiments, the composite metal fluoride coating is a fluoride coating containing rare earth metals. In the embodiments, a rare-earth metal-containing fluoride coating is selected from YxZryFz, ErxZryFz, YwErxZryFz, YwErxHfyFz, YwZrxHfyFz, ErwZrxHfyFz, YvErwZrxHfyFz, YxHfyFz, ErxHfyFz, YxTayFz, ErxTayFz, YwErxTayFz, YwTaxZryFz, YwTaxHfyFz, ErwTaxZryFz, ErwTaxHfyFz, and YvErwTaxHfyFz. In one embodiment, the rare-earth metal-containing fluoride coating comprises YZrF having an atomic ratio of yttrium to zirconium of 3. In another embodiment, the rare-earth metal-containing fluoride coating comprises YZrOF and has an atomic ratio of yttrium to zirconium of 4.6. In a further embodiment, the rare-earth metal-containing fluoride coating may comprise a composition selected from LawYxZryFz, LuwYxZryFz, ScwYxZryFz, GdwYxZryFz, SmwYxZryFz, DywYxZryFz, LawYxZryFz, LuwYxTayFz, ScwYxTayFz, GdwYxTayFz, SmwYxTayFz, DywYxTayFz, ErwYxHfyFz, LawYxHfyFz, LuwYxHfyFz, ScwYxHfyFz, GdwYxHfyFz, SmwYxHfyFz, and DywYxHfyFz. In some embodiments, the coating may comprise REwZrxAlyFz, for example, YwZrxAlyFz. Other composite fluorides may also be used.

[0024] Examples of yttrium fluoride compounds that can form anti-plasma coatings include YF, YxAlyFz, YxZryFz, YxHfyFz, YaZrxAlyFz, YaZrxHfyFz, YaHfxAlyFz, YvZrwHfxAlyFz, or YxEryFz. The yttrium content in the coating can range from about 0.1 mol% to close to 100 mol%. For yttrium fluorides, the yttrium content can range from about 0.1 mol% to close to 100 mol%, and the fluorine content can range from about 0.1 mol% to close to 100 mol%.

[0025] Examples of erbium-containing fluoride compounds that can form anti-plasma coatings include Er₂O₃, ErxAlyFz (e.g., Er₃Al₅F₁₂), ErxZryFz, ErxHfyFz, EraZrxAlyFz, EraZrxHfyFz, EraHfxAlyFz, YxEryFz, and EraYxZryFz (e.g., single-phase solid solutions of Y₂O₃, ZrO₂, and Er₂O₃). The erbium content in the anti-plasma coating can range from about 0.1 mol% to close to 100 mol%. For erbium-containing fluorides, the erbium content can range from about 0.1 mol% to close to 100 mol%, and the fluorine content can range from about 0.1 mol% to close to 100 mol%.

[0026] Advantageously, Y₂O₃ and Er₂O₃ are miscible. A single-phase solid solution can be formed for any combination of Y₂O₃ and Er₂O₃. For example, a mixture of just over 0 mol% Er₂O₃ and slightly less than 100 mol% Y₂O₃ can be combined and co-deposited to form an anti-plasma coating as a single-phase solid solution. Alternatively, a mixture of just over 0 mol% Er₂O₃ and slightly less than 100 mol% Y₂O₃ can be combined to form an anti-plasma coating as a single-phase solid solution. The anti-plasma coating of Y₂EryF₂ can contain more than 0 mol% to less than 100 mol% YF₃ and more than 0 mol% to less than 100 mol% Er₂F₃. Some notable examples include 90-99 mol% YF3 and 1-10 mol% ErF3, 80-89 mol% YF3 and 11-20 mol% ErF3, 70-79 mol% YF3 and 21-30 mol% ErF3, 60-69 mol% YF3 and 31-40 mol% ErF3, and 50-59 mol% YF3 and 41-50 mol% ErF3. The single-phase solid solutions of YxEryFz can possess a monoclinic cubic state at temperatures below approximately 2330 ºC. The solutions are: 40-49 mol% YF3 and 51-60 mol% ErF3, 30-39 mol% YF3 and 61-70 mol% ErF3, 20-29 mol% YF3 and 71-80 mol% ErF3, 10-19 mol% YF3 and 81-90 mol% ErF3, and 1-10 mol% YF3 and 90-99 mol% ErF3.

[0027] Advantageously, ZrO2 can be combined with YF3 and ErF3 to form a single-phase solid solution (e.g., EraYxZryFz) containing a mixture of zirconium, YF3, and ErF3. The solid solution of YaErxZryFz can have a cubic, hexagonal, tetragonal, and / or cubic fluorite structure. The solid solution of YaErxZryFz can contain more than 0 mol% to 60 mol% Zr, more than 0 mol% to 99 mol% ErF3, and more than 0 mol% to 99 mol% YF3. Some notable amounts of ZrO2 that can be used include 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 30 mol%, 50 mol%, and 60 mol%. Some notable amounts of ErF3 and / or YF3 that can be used include 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, and 90 mol.

[0028] The anti-plasma coating of YaZrxAlyFz may contain more than 0 mol% to 60 mol% Zr, more than 0 mol% to 99 mol% YF3, and more than 0 mol% to 60 mol% Al. Some notable amounts of ZrO2 that can be used include 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 30 mol%, 50 mol%, and 60 mol%. Some notable amounts of YF3 that can be used include 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, and 90 mol%. Some notable amounts of Al2O3 that can be used include 2 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, and 60 mol%. In one example, the anti-plasma coating of YaZrxAlyFz contains 42 mol% YF3, 40 mol% Zr, and 18 mol% Al and has a layered structure. In another example, the anti-plasma coating of YaZrxAlyFz contains 63 mol% YF3, 10 mol% Zr, and 27 mol% ErF3 and has a layered structure.

[0029] In an embodiment, the rare earth metal-containing fluoride coating contains about 1 mol% to about 40 mol% of a first metal (e.g., a rare earth metal, such as Y, Er, or tantalum) and about 1 mol% to about 40 mol% of a second metal (e.g., a rare earth metal, Zr, Hf, Ta, Al, Si). In a further embodiment, the composite metal fluoride coating contains about 1 mol% to about 40 mol% or about 5 mol% to about 30 mol% of Ta and about 1 mol% to about 40 mol% or about 1 mol% to about 20 mol% of a second metal (e.g., RE, Zr, Hf, Al, Si). In embodiments, the composite metal fluoride coating contains about 1 mol% to about 40 mol% or about 5 mol% to about 30 mol% of yttrium and about 1 mol% to about 40 mol% or about 1 mol% to about 20 mol% of zirconium, hafnium, or tantalum, or about 10 mol% to about 25 mol% of yttrium and about 5 mol% to about 17 mol% of Zr, Hf, or Ta, or about 15 mol% to about 21.5 mol% of yttrium and about 10 mol% to about 14.5 mol% of Zr, Hf, or Ta. In embodiments, the coating contains a mixture of Y and Er, wherein the molar percentage of the combination of Y and Er is about 5 mol% to about 30 mol% (e.g., it may contain 1-29 mol% of Y and 1-29 mol% of Er). The coating may additionally contain about 1 mol% to about 20 mol% of zirconium, hafnium, or tantalum.

[0030] In embodiments, the thickness of the composite metal fluoride coating or the rare earth metal-containing fluoride coating may be about 5 nm to about 10 μm, or about 5 nm to about 5 μm, or about 25 nm to about 5 μm, or about 50 nm to about 500 nm, or about 75 nm to about 200 nm. In some embodiments, the thickness of the composite metal fluoride coating or the rare earth metal-containing fluoride coating may be about 50 nm, or about 75 nm, or about 100 nm, or about 125 nm, or about 150 nm. The composite metal fluoride coating or the rare earth metal-containing fluoride coating may conformally cover one or more surfaces of the body of the article (including high aspect ratio features, such as pores) with a substantially uniform thickness. In one embodiment, the rare earth metal-containing fluoride coating has conformal coverage of the underlying surface (including the surface features of the coating) coated with a thickness variation of less than about + / - 20%, + / - 10%, + / - 5%, or even less.

[0031] In a further embodiment, the composite metal fluoride coating or the rare earth metal-containing fluoride coating does not contain a separate layer of fluoride containing a first metal and a second metal (or a third metal, a fourth metal, etc.). In particular, in some embodiments, the composite metal fluoride coating or the rare earth metal-containing fluoride coating may not be formed by a sequential atomic layer deposition cycle of multiple metals. Instead, in embodiments, the first metal and the second metal may, for example, be co-deposited on the article or the body of the article. Thus, the rare earth metal-containing fluoride coating may not have mechanical separation between the layer containing the first metal and the layer containing the second additional metal. As a further result of the co-deposition process, the composite metal fluoride coating or the rare earth metal-containing fluoride coating may contain a homogeneous mixture of the first metal (e.g., a rare earth metal) and the second metal without performing annealing, and may not include a concentration gradient of the first metal or the second metal caused by incomplete interdiffusion of materials in the coating.

[0032] In an alternative embodiment, a sequential atomic layer deposition (ALD) process is performed. For a sequential ALD process, a first metal precursor can be adsorbed onto the surface, and a fluorine-based reactant can react with the adsorbed first metal (e.g., rare earth metals, tantalum, etc.) to form a first metal fluoride layer. Subsequently, a second metal precursor can be adsorbed onto the first metal fluoride layer, and a fluorine-based reactant can react with the adsorbed second metal to form a second metal (e.g., zirconium, aluminum, hafnium, tantalum, silicon, etc.) fluoride layer. The metals from the first and second metal fluoride layers can then interdiffused with each other. When using a sequential deposition loop of the first and second metals to deposit a coating, annealing can be performed to affect the interdiffusion between layers. Such annealing can result in a concentration gradient of the metal phase (e.g., YF3 and ZrO2 to YZrF) from the surface toward the underlying article, and such coatings consistently lack homogeneity. Coatings as described herein, formed by co-deposition, create a homogeneous mixture of the first and second metals. Annealing is typically not performed to achieve interdiffusion.

[0033] According to an embodiment, a composite metal fluoride coating or a rare earth metal-containing fluoride coating can be formed by a multilayer stack having alternating material layers. In one embodiment, a buffer layer can be deposited on the surface of the article or the surface of the body of the article, and the composite metal fluoride coating or the rare earth metal-containing fluoride coating can be deposited on the buffer layer. The buffer layer may include, but is not limited to, alumina (e.g., Al2O3), silicon oxide (e.g., SiO2), aluminum nitride, or combinations thereof. In other embodiments, an ALD can be used to co-deposit a first metal (e.g., yttrium, erbium, tantalum, etc.) and a second metal (e.g., rare earth metal, zirconium, aluminum, hafnium, tantalum, etc.) onto the article (or co-deposit onto the buffer layer, if a buffer layer is used) to form a first co-deposited layer. A second layer of material (e.g., metal fluoride, rare earth metal fluoride, co-deposited rare earth metal zirconium oxide, etc.) can be deposited or co-deposited on the first co-deposited layer. Each deposition or co-deposition cycle can be repeated as many times as desired to achieve the final multilayer coating with the target composition and / or thickness.

[0034] The thickness of each layer in the multilayer composite metal fluoride coating or the rare earth metal-containing fluoride coating can be from about 10 nm to about 1.5 μm. In embodiments, the buffer layer (e.g., amorphous Al₂O₃) can have a thickness of about 1.0 μm, and the rare earth metal-containing fluoride layer can have a thickness of about 50 nm. The ratio of the thickness of the composite metal fluoride or rare earth metal-containing fluoride layer to the thickness of the buffer layer can be from 200:1 to 1:200, or from about 100:1 to 1:100, or from about 50:1 to about 1:50. The thickness ratio can be selected according to the specific chamber application.

[0035] A composite metal fluoride or rare earth metal fluoride coating can be grown or co-deposited using an ALD that utilizes a precursor for co-deposition of a first metal-containing fluoride layer containing tantalum and / or at least one rare earth metal (e.g., yttrium, erbium, etc.) and a second metal (e.g., RE, Zr, Ta, Hf, Al, Si). In one embodiment, the composite metal fluoride coating or rare earth metal-containing fluoride layer has a polycrystalline structure.

[0036] The buffer layer may comprise amorphous alumina or a similar material. The buffer layer provides robust mechanical properties and can enhance dielectric strength, allowing the composite metal fluoride or rare-earth metal-containing fluoride coating to adhere better to the component (e.g., formed of Al6061, Al6063, or ceramic), and prevents cracking of the composite metal fluoride or rare-earth metal-containing fluoride coating at temperatures up to about 350°C, or up to about 300°C, or up to about 250°C, or up to about 200°C, or about 200°C to about 350°C, or about 250°C to about 300°C. The coefficient of thermal expansion of such a metal article may be significantly higher than that of the composite metal fluoride coating or the rare-earth metal-containing fluoride coating. By first applying the buffer layer 209, the adverse effects of the mismatch in coefficients of thermal expansion between the article and the composite metal-containing fluoride coating can be controlled. Because ALD is used for deposition, it can coat the inner surfaces of high aspect ratio features (such as gas delivery orifices in nozzles or gas delivery lines), thus protecting the entire component from exposure to corrosive environments. In some embodiments, the buffer layer may comprise a material having a coefficient of thermal expansion between the value of the in-process article and the value of the coefficient of thermal expansion of the composite metal-containing fluoride coating. Additionally, the buffer layer can serve as a barrier layer to prevent metallic contaminants (e.g., trace metals such as Mg and Cu) from migrating from the component or article into the composite metal-containing fluoride coating. Adding an amorphous Al₂O₃ layer as a buffer layer under the composite metal fluoride coating can increase the overall heat resistance of the composite metal fluoride coating by mitigating elevated stresses concentrated in certain areas of the composite metal fluoride / Al 6061 interface.

[0037] This document also describes articles having a composite metal fluoride coating or a rare earth metal fluoride coating as described above. In embodiments, the articles can be any type of component for use in a semiconductor processing chamber, including but not limited to electrostatic chucks, gas delivery plates, chamber walls, chamber liners, doors, rings, nozzles, spray nozzles, plasma generation units, radio frequency electrodes, electrode housings, diffusers, and gas lines. The articles may comprise materials including but not limited to aluminum (Al), silicon (Si), copper (Cu), and magnesium (Mg). In embodiments, the articles may comprise ceramic materials including but not limited to alumina (AlxOy), silicon oxide (SixOy), aluminum nitride (AlN), or silicon carbide (SiC). In some embodiments, the article or the body of the article may be aluminum Al 6061 or Al 6063 material. In some embodiments, the surface of the article or the surface of the body of the article has a surface roughness of about 120 μin to about 180 μin, or about 130 μin to about 170 μin, or about 140 μin to about 160 μin.

[0038] The composite metal coating can be very dense, with a porosity of about 0% (e.g., in embodiments, the rare earth metal-containing fluoride coating can be non-porous). The composite metal fluoride coating can resist corrosion and erosion from plasma etching chemicals, such as CCl4 / CHF3 plasma etching chemicals, HCl3Si etching chemicals, and NF3-containing etching chemicals. Additionally, the composite metal fluoride coating with a buffer layer described herein can resist cracking and delamination at temperatures up to about 350°C. For example, a chamber component having the rare earth metal-containing fluoride coating and buffer layer described herein can be used in processes including heating to temperatures of about 200°C. The chamber component can undergo thermal cycling between room temperature and temperatures of about 200°C without introducing any cracks or delamination in the rare earth metal-containing fluoride coating.

[0039] In some embodiments, the article or the body of the article may include at least one feature (e.g., a pore), wherein the feature has an aspect ratio (L:D) of about 5:1 to about 300:1, or about 10:1 to about 200:1, or about 20:1 to about 100:1, or about 5:1 to about 50:1, or about 7:1 to about 25:1, or about 10:1 to about 20:1. A composite metal fluoride coating or a rare earth metal-containing fluoride coating may conformally cover the surface of the body of the article and the feature. In some embodiments, the article or the body of the article may include a feature (e.g., a channel) having a depth-to-width ratio (D:W) of about 5:1 to about 300:1, or about 10:1 to about 200:1, or about 20:1 to about 100:1, or about 5:1 to about 50:1, or about 7:1 to about 25:1, or about 10:1 to about 20:1. Composite metal fluoride coatings or rare earth metal fluoride coatings can conformally cover the body of the article and the surface of the aforementioned features.

[0040] In various embodiments, the high aspect ratio features of the article (as described above) can be effectively coated with the composite metal fluoride coating or the rare earth metal-containing fluoride coating described herein. The composite metal fluoride coating may have a single phase, two phases, or more than two phases. The composite metal fluoride coating or the rare earth metal-containing fluoride coating is conformal within the high aspect ratio features with a substantially uniform thickness as described above.

[0041] FIG1 is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components according to an embodiment described herein, the one or more chamber components being coated with a composite metal fluoride or a rare earth metal-containing fluoride coating. The base material of at least some components of the chamber may include one or more of the following: Al (e.g., AlxOy, AlN, Al 6061 or Al 6063), Si (e.g., SixOy, SiO2 or SiC), copper (Cu), magnesium (Mg), titanium (Ti), and stainless steel (SST). The processing chamber 100 may be used in processes in which a corrosive plasma environment (e.g., fluorinated plasma) with plasma processing conditions is provided. For example, the processing chamber 100 may be a chamber for a plasma etcher or plasma etching reactor, a plasma cleaner, a plasma-enhanced CVD or ALD reactor, etc. Examples of chamber components that may include a composite metal fluoride coating or a rare earth metal-containing fluoride coating include chamber components having complex shapes and features with a high aspect ratio as described above. Some exemplary chamber components include substrate support elements, electrostatic chucks, rings (e.g., process kit rings or single rings), chamber walls, bases, gas distribution plates, nozzles, gas lines, nozzles, covers, gaskets, gasket kits, protective covers, plasma shields, flow equalizers, cooling bases, chamber viewing ports, chamber covers, and so on.

[0042] In one embodiment, the processing chamber 100 includes a chamber body 102 enclosing an internal volume 106 and a nozzle 130. The nozzle 130 may include a nozzle base and a nozzle gas distribution plate. Alternatively, in some embodiments, the nozzle 130 may be replaced by a cap and a nozzle, or in other embodiments, by a plurality of pie-shaped nozzle compartments and a plasma generation unit. The chamber body 102 may be made of aluminum, stainless steel, or other suitable materials. The chamber body 102 typically includes sidewalls 108 and a bottom 110. An outer liner 116 may be disposed adjacent to the sidewalls 108 to protect the chamber body 102. Any of the nozzle 130 (or cap and / or nozzle), sidewalls 108, and / or bottom 110 may include a fluoride coating containing rare earth metals.

[0043] The discharge port 126 may be defined in the chamber body 102 and may be coupled to the internal volume 106 to the pump system 128. The pump system 128 may include one or more pumps and throttle valves for evacuating and regulating the pressure of the internal volume 106 of the treatment chamber 100.

[0044] The nozzle 130 may be supported on the sidewall 108 of the chamber body 102. The nozzle 130 (or cover) may be opened to allow access to the internal volume 106 of the processing chamber 100 and may provide a seal to the processing chamber 100 when closed. A gas panel 158 may be coupled to the processing chamber 100 to supply process gases and / or cleaning gases to the internal volume 106 through the nozzle 130 or the cover and nozzle. The nozzle 130 may be used for a processing chamber for dielectric etching (etching of dielectric materials). The nozzle 130 may include a gas distribution plate (GDP) having a plurality of gas delivery holes 132 throughout the GDP. The nozzle 130 may include a GDP bonded to an aluminum base or anodized aluminum base. The GDP may be made of Si or SiC, or may be a ceramic such as Y2O3, Al2O3, Y3Al5O12 (YAG), etc.

[0045] For a processing chamber used for conductor etching (etching of conductive materials), a cover may be used instead of a nozzle. The cover may include a central nozzle mounted in a central hole in the cover. The cover may be a ceramic such as Al2O3, Y2O3, or YAG, or a ceramic compound comprising a solid solution of Y2O3-ZrO2 and Y4Al2O9. The nozzle may also be a ceramic such as Y2O3 or YAG, or a ceramic compound comprising a solid solution of Y2O3-ZrO2 and Y4Al2O9.

[0046] Examples of process gases that can be used in the processing chamber 100 for processing the substrate include halogen-containing gases such as C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, and SiF4, as well as other gases such as O2 or N2O. Examples of carrier gases and purging gases include N2, He, Ar, and other gases that are inert to process gases (e.g., non-reactive gases).

[0047] A substrate support element 148 is disposed within the internal volume 106 of the processing chamber 100, below the nozzle 130 or cover. The substrate support element 148 includes a support member 136 that holds the substrate 144 during processing. The support member 136 is attached to an end of a shaft (not shown) coupled to the chamber body 102 via a flange 164. The substrate support element 148 may include, for example, a heater, an electrostatic chuck, a base, a vacuum chuck, or other substrate support element components.

[0048] Figure 2A depicts an embodiment of a co-deposition process 200 according to ALD technology for growing or depositing a fluoride coating rich in a first metal on an article of paper. Figure 2B depicts another embodiment of a co-deposition process according to ALD technology as described herein for growing or depositing a rare earth metal fluoride coating rich in a second metal on an article of paper. Figure 2C depicts another embodiment of a co-deposition process according to ALD technology as described herein. Figure 2D depicts another embodiment of a co-deposition process utilizing a co-mixture of rare earth metals and other metals according to ALD technology as described herein.

[0049] For the ALD co-deposition process, adsorbing at least two precursors onto a surface or reacting reactants with the adsorbed precursors can be referred to as a "half-reaction". During the first half-reaction, a first precursor (or a mixture of precursors) can be pulsed onto the surface of article 205 for a period of time sufficient to allow the precursor to be partially (or completely) adsorbed onto the surface. Because the precursor will adsorb onto several available sites on the surface, the adsorption is self-limiting, thereby forming a partially adsorbed layer of the first metal on the surface. Any site that has been adsorbed by the first metal of the precursor will become unavailable for further adsorption performed with subsequent precursors. Alternatively, some sites that have been adsorbed by the first metal of the first precursor can be replaced by a second metal of the second precursor adsorbed at that site. To complete the first half-reaction, a second precursor can be pulsed onto the surface of article 205 for a period of time sufficient to allow the second metal of the second precursor to be (partially or completely) adsorbed onto available sites on the surface (and possibly replacing the first metal of the first precursor), which forms a co-deposited adsorbed layer on the surface.

[0050] The co-deposition cycle of the ALD process begins with a first precursor (i.e., chemical A or a mixture of chemicals A and B) flowing into the ALD chamber and partially (or completely) adsorbing onto the surface of the article (including the surfaces of pores and features within the article). A second precursor (i.e., chemical B) may flow into the ALD chamber and adsorb onto the remaining exposed surfaces of the article. Excess precursor is then flushed out / purified (i.e., with inert gas) of the ALD chamber before the reactant (i.e., chemical R) is introduced and subsequently flushed out. Alternatively or additionally, the chamber may be purged during a first half-reaction between the deposition of the first and second precursors. For ALD, the final thickness of the material depends on the number of reaction cycles run, as each reaction cycle will grow a layer of a certain thickness, which may be an atomic layer or part of an atomic layer.

[0051] In addition to being a conformal process, ALD is also a uniform process and can form very thin films, for example, films with a thickness of about 3 nm or greater. All exposed surfaces of the article will have the same or approximately the same amount of deposited material. ALD technology can deposit thin material layers at relatively low temperatures (e.g., from about 25°C to about 350°C), so it does not damage or deform any material of the part. In addition, ALD technology can also deposit material layers within complex features of the part (e.g., high aspect ratio features). Furthermore, ALD technology typically produces relatively thin (i.e., 1 micrometer or less) coatings without pores (i.e., without pinholes), which can reduce crack formation during deposition.

[0052] An ALD can be used to grow or deposit a composite metal fluoride coating or a rare earth metal fluoride coating using a precursor containing a first metal (e.g., a rare earth metal precursor, a tantalum precursor, etc.), a precursor containing a second metal, and a fluorine-containing reactant (e.g., hydrogen fluoride or other fluorine-containing substances). In some embodiments, the precursor containing the first metal may contain yttrium, erbium, lanthanum, diurethane, scandium, zonal, samarium, dysprosium, or tantalum.

[0053] In the embodiments, the precursor containing the first metal and the precursor containing the second metal (and in the case of a composite metal coating, the precursor containing the third metal and the precursor containing the fourth metal, etc.) are independently selected from yttrium-containing precursors, such as tris(N,N-bis(trimethylsilyl)pyramine)yttrium(III), yttrium(III) butoxide, or cyclopentadienylyttrium compounds (e.g., such as tris(cyclopentadienyl)yttrium(Cp3Y), tris(methylcyclopentadienyl)yttrium((CpMe)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, or tris(ethylcyclopentadienyl)yttrium)). Other yttrium-containing precursors that may be used include yttrium-containing amide compounds (e.g., tris(N,N'-di-i-propylformamidinato)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dionate)yttrium, or tris(bis(trimethylsilyl)amino)lanthanum) and yttrium-containing β-diketone compounds. In some embodiments, rare-earth metal-containing fluoride precursors may include erbium. Erbium-containing precursors include, but are not limited to, erbium-containing cyclopentadienyl compounds, erbium-containing amide compounds, and erbium-containing β-diketone compounds. Examples of erbium-containing precursors include trimethylcyclopentadienylerbium(III) (Er(MeCp)3), borane-nitrogenylerbium (Er(BA)3), Er(TMHD)3, tris(2,2,6,6-tetramethyl-3,5-heptadecyl)erbium(III) and tris(butylcyclopentadienyl)erbium(III) for ALD. Zirconium-containing precursors may include, but are not limited to, zirconium-containing cyclopentadienyl compounds, zirconium-containing nitrogenyl compounds, and zirconium-containing β-diketone compounds. Examples of zirconium-containing precursors include zirconium bromide(IV), zirconium chloride(IV), tert-butoxide zirconium(IV), tetra(diethylamino)zirconium(IV), tetra(dimethylamino)zirconium(IV), tetra(ethylmethylnitroamino)zirconium(IV), or cyclopentadienylzirconium compounds for ALD. Some examples of zirconium-containing precursors include tetra(dimethylamino)zirconium, tetra(diethylamino)zirconium, tetra(N,N'-dimethylformamidinyl)zirconium, tetra(ethylmethylamino)hafnium, penta(dimethylamino)tantalum, and tris(2,2,6,6-tetramethylheptane-3,5-diketone)erbium.

[0054] In some embodiments, the precursor containing the first metal and the precursor containing the second metal may be independently selected from: cyclopentadienyl precursor, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, amidoyl precursor, tris(N,N'-diisopropylmethylammonium)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dione)yttrium, tris(bis(trimethylsilyl)amino)lanthanum, aminoyl precursor and β-diketoyl precursor.

[0055] In some embodiments, a mixture of two precursors is introduced (i.e., co-mixed) together, wherein the mixture comprises a first percentage of a precursor containing a first metal and a second percentage of a precursor containing a second metal. For example, the mixture of precursors may comprise about 1 wt% to about 90 wt%, or about 5 wt% to about 80 wt%, or about 20 wt% to about 60 wt% of a precursor containing a first metal and about 1 wt% to about 90 wt%, or about 5 wt% to about 80 wt%, or about 20 wt% to about 60 wt% of a precursor containing a second metal. The mixture may comprise a ratio of a precursor containing a first metal (e.g., yttrium, tantalum, etc.) to a precursor containing a second metal suitable for forming a target type of fluoride material. The atomic ratio of the precursor containing the first metal (e.g., yttrium, tantalum, etc.) to the precursor containing the second metal can be about 200:1 to about 1:200, or about 100:1 to about 1:100, or about 50:1 to about 1:50, or about 25:1 to about 1:25, or about 10:1 to about 1:10, or about 5:1 to about 1:5.

[0056] In one embodiment, an atomic layer deposition (ALD) method is used to co-deposit a composite metal fluoride coating or a rare earth metal-containing fluoride coating onto the surface of the article. Co-depositing the rare earth metal-containing fluoride coating may include contacting the surface with a precursor containing a first metal (e.g., a rare earth metal-containing precursor) for a first duration to form a partially metal-adsorbed layer. The precursor containing the first metal may be one of a rare earth metal-containing precursor, a zirconium-containing precursor, a tantalum-containing precursor, a hafnium-containing precursor, or an aluminum-containing precursor. Subsequently, the partially metal-adsorbed layer is contacted with a precursor containing a second metal, different from the precursor containing the first metal, for a second duration to form a co-adsorbed layer containing both the first and second metals. The precursor containing the second metal may be at least one of a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, a tantalum-containing precursor, or an aluminum-containing precursor. Afterward, the co-adsorbed layer is contacted with a fluorine source reactant to form a rare earth metal-containing fluoride coating. In some embodiments, the coating may contain about 1 mol% to about 40 mol% or about 5 mol% to about 30 mol% of a rare earth metal or tantalum and about 1 mol% to about 40 mol% or about 1 mol% to about 20 mol% of a second metal. Alternatively, the rare earth metal-containing fluoride coating may comprise a homogeneous mixture of the first metal and the second metal.

[0057] Referring to FIG. 2A, a first metal (M1)-second metal (M2) co-deposition scheme 200 for depositing a rare earth metal-containing fluoride coating on article 205 is described. Article 205 may be introduced into a first metal-containing precursor 210 (e.g., a rare earth metal-containing precursor) for a duration until the surface portion of article 205 is partially adsorbed with the first metal-containing precursor 210 to form a partially metal-adsorbed layer 215. Subsequently, article 205 may be introduced into a second metal-containing precursor 220 for a duration until the remaining exposed surface of the article is adsorbed with the second metal-containing precursor 220 to form a co-adsorbed layer 225 containing both the first and second metals. The first metal-containing precursor exposed to the uncoated surface (i.e., all adsorption sites are available) can be adsorbed onto the surface more effectively than the second metal-containing precursor exposed to the partially adsorbed surface. Therefore, the co-adsorbed layer 225 can be rich in the first metal, i.e., it can contain a higher concentration of first metal atoms than the second metal. Next, according to the embodiments described herein, article 205 can be introduced into reactant 230 for a duration to react with co-adsorbed layer 225 to grow a solid fluoride layer (e.g., YxZryFz or YF3-Zr solid solution) of rare earth metal-containing fluoride coating 235. The precursor can be any precursor as described above. The co-deposition of the first and second metals and the introduction of the reactant are referred to as the M1-M2 co-deposition loop. The M1-M2 co-deposition loop can be repeated m times until the desired coating thickness is achieved.

[0058] Referring to FIG. 2B, an M2-M1 co-deposition scheme 202 for depositing a rare-earth metal-containing fluoride coating on article 205 is described. Article 205 may be introduced into a precursor 220 containing a second metal for a duration until a portion of the surface of article 205 is adsorbed with the precursor 220 containing the second metal to form a partial second metal adsorption layer 216. Subsequently, article 205 may be introduced into a precursor 210 containing a first metal for a duration until the remaining exposed surface of the article is adsorbed with the precursor 220 containing the first metal to form a co-adsorption layer 226. The co-adsorption layer 226 may be rich in the second metal. Next, according to the embodiments described herein, article 205 may be introduced into a first reactant 230 to react with the co-adsorption layer 225 to grow a solid layer (e.g., YZrF) of a rare-earth metal-containing fluoride coating 236. The precursor may be any precursor as described above. The co-deposition of the second metal and the first metal and the introduction of the reactant are referred to as the M2-M1 co-deposition loop. The M2-M1 co-deposition cycle can be repeated n times until the desired coating thickness is achieved.

[0059] Each layer of the rare-earth metal-containing fluoride coatings 235, 236 can be uniform, continuous, and conformal. In embodiments, the rare-earth metal-containing fluoride coatings 235, 236 can be non-porous (e.g., having a porosity of 0) or have a porosity of approximately 0 (e.g., a porosity of 0% to 0.01%). In some embodiments, after a single ALD deposition loop, each layer of the rare-earth metal-containing fluoride coatings 235, 236 can have a thickness of less than one atomic layer to several atoms. Some organometallic precursor molecules are large. After reacting with reactants, large organic ligands can disappear, leaving much smaller metal atoms. A complete ALD loop (e.g., including the introduction of a precursor followed by the introduction of reactants) can result in a layer smaller than a single atomic layer. Co-deposition scheme 200 can include repeating m co-deposition loops to achieve a target thickness of coating 235. Similarly, co-deposition scheme 202 can include repeating n co-deposition loops to achieve a target thickness of coating 236. M and N can be positive integer values.

[0060] The relative concentrations of the first metal (e.g., rare earth metals, Ta, etc.) and the second metal can be controlled by the type of precursor used, by the temperature of the ALD chamber during the period when the precursor is adsorbed onto the surface of the article, by the amount of time a particular precursor remains in the ALD chamber, and by the partial pressure of the precursor. For example, using tris(N,N-bis(trimethylsilyl)pyramine)yttrium(III) precursor can result in a lower yttrium oxide atom percentage than using cyclopentadienylyttrium precursor.

[0061] In some embodiments, two or more types of metal precursors are adsorbed onto the surface of article 205 in a single co-deposition loop. For example, a co-deposition loop may include adsorbing a yttrium precursor onto the surface, then adsorbing a zirconium precursor onto the surface, and then adsorbing a hafnium precursor onto the surface. Each subsequent precursor may adsorb a lower amount of the relevant metal onto the surface. Accordingly, the order in which various precursors are adsorbed onto the surface to create the co-adsorbed layer may be selected to achieve a target ratio of two or more different metals. An example additional co-deposition scheme that may be performed includes an M1-M2-M3 co-deposition scheme in which a first metal (M1) is adsorbed onto the surface, followed by a second metal (M2) being adsorbed onto the surface, then a third metal (M3) being adsorbed onto the surface, and then a fluorine source reactant is introduced. Another example co-deposition scheme that may be performed includes an M2-M1-M3 co-deposition scheme in which a second metal (M2) is adsorbed onto the surface, followed by a first metal (M1) being adsorbed onto the surface, then a third metal (M3) being adsorbed onto the surface, and then a fluorine source reactant is introduced. Another example co-deposition scheme that can be performed includes the M3-M1-M2 co-deposition scheme, in which a third metal (M3) is adsorbed onto the surface, followed by the adsorption of a first metal (M1) onto the surface, then the adsorption of a second metal (M2) onto the surface, and then the introduction of a fluorine source reactant. More precursors can also be adsorbed onto the surface to produce more complex metal fluorides. The more metals used, the greater the number of possible permutations.

[0062] Referring to FIG. 2C, in some embodiments, a multilayer stack can be deposited on article 205 using a co-deposition ALD process 203. An optional buffer layer 209, as described above, can be deposited on article 205. In an example where the buffer layer 209 is alumina (Al2O3), in the first half-reaction, article 205 (e.g., an Al 6061 substrate) can be introduced with an aluminum-containing precursor (e.g., trimethylaluminum (TMA)) (not shown) for a duration until all reaction sites on the surface are consumed. The remaining alumina-containing precursor can be flushed out of the reaction chamber, and then reactants of H2O (not shown) or another oxygen source can be planted in the reactor to begin the second half-cycle. After the H2O molecules react with the Al-containing adsorbed layer generated by the first half-reaction, an Al2O3 buffer layer 209 can be formed.

[0063] The buffer layer 209 may be uniform, continuous, and conformal. In embodiments, the buffer layer 209 may be non-porous (e.g., having 0 porosity) or have approximately 0 porosity (e.g., a porosity of 0% to 0.01%). Multiple complete ALD deposition loops may be performed to deposit the buffer layer 209 with the target thickness, wherein each complete loop (e.g., including the introduction of an aluminum-containing precursor, rinsing, the introduction of H2O reactants, and re-rinsing) increases the thickness by an additional atom to a fraction of several atoms. In embodiments, the buffer layer 209 may have a thickness of about 10 nm to about 1.5 µm, or about 10 nm to about 15 nm, or about 0.8 µm to about 1.2 µm.

[0064] Subsequently, an M1-M2 co-deposition cycle as described above with respect to FIG. 2A or an M2-M1 co-deposition cycle as described above with respect to FIG. 2B may be performed on the article 205 having an optional buffer layer 209. The buffer layer 209, rather than the surface of the article or the surface of the body of the article, will be partially adsorbed by a precursor 210 containing the first metal or a second precursor 220 to form a partially metal adsorbed layer 215. Afterward, the precursor may be flushed from the ALD chamber with an inert gas (e.g., nitrogen), and then an M1-M2 co-deposition cycle as described above with respect to FIG. 2B or an M2-M1 co-deposition cycle as described above with respect to FIG. 2A may be performed on the article 205 having the optional buffer layer 209 and the M1-M2 coating 235.

[0065] The rare-earth metal-containing fluoride layer produced by the M1-M2 co-deposition cycle may contain a first percentage of a first metal and a second percentage of a second metal. The M2-M1 co-deposition cycle produces an additional layer containing a third percentage of the first metal and a fourth percentage of the second metal. In embodiments, the third percentage may be lower than the first percentage, and the fourth percentage may be higher than the third percentage. Thus, using two co-deposition cycles, a multilayer coating having a buffer layer 209, an M1-M2 layer 235, and an M2-M1 layer 236 can be formed. As previously described, any one or both cycles in the co-deposition cycle may be repeated m times or n times, where m and n are each positive integers and represent the number of co-deposition cycles. In some embodiments, the ratio of m to n may be 1:50 to about 50:1, or about 1:25 to about 25:1, or about 1:10 to about 10:1, or about 1:2 to about 2:1, or 1:1. The co-deposition cycles may be performed continuously and / or alternately to construct the coating. The alternating layers 235 and 236 described in Figure 2C are formed in a 1:1 co-deposition loop, wherein for each monolayer of the M2-M1 coating, there is a single layer of the M1-M2 coating. However, in other embodiments, other patterns may exist. For example, two M1-M2 co-deposition loops may be followed by one M2-M1 co-deposition loop (2:1), and this sequence may then be repeated.

[0066] According to various embodiments, the M1-M2 co-deposition cycle can be represented as m*(M1 + M2 + F), where m is a positive integer and represents the number of M1-M2 co-deposition cycles, M1 represents the amount of the deposited first metal (e.g., yttrium) in moles (%), M2 represents the amount of the deposited second metal (moles %), and F represents the amount of deposited fluorine (moles %). The M2-M1 co-deposition cycle can be represented as n*(M2 + M1 + F), where n is a positive integer and represents the number of M2-M1 co-deposition cycles, M2 represents the amount of the deposited second metal (moles %), M1 represents the amount of the deposited first metal (e.g., yttrium) in moles (moles %), and F represents the amount of deposited fluorine (moles %).

[0067] As shown in Figure 2C, the target composition of the rare-earth metal-containing fluoride coating can be achieved using the following formula: K*[m*(M1 + M2 + O) + n*(M2 + M1 + O)], where K is a positive integer and represents the number of superloops performed to achieve the target thickness. By adjusting K, m, and n, the desired composition (e.g., the desired ratio of the first metal to the second metal) can be obtained in the coating regardless of the chemical properties of the precursor.

[0068] Figure 2C illustrates co-deposition using two different metals. However, in a further embodiment, co-deposition can be performed with more than two metals, as described above. If more than two different metals are used, more than two different co-deposition sequences can be performed. For example, for co-deposition of three metals, the following co-deposition schemes can be mixed to achieve a coating with the target composition: M1+M2+M3+F, M1+M3+M2+F, M2+M1+M3+F, M2+M3+M1+F, M3+M1+M2+F, M3+M2+M1+F. Accordingly, the target composition can be achieved using the following formula: K*[a*(M1+M2+M3+F) + b*(M1+M3+M2+F) + c*(M2+M1+M3+F) + d*(M2+M3+M1+F) + e*(M3+M1+M2+F) + f*(M3+M2+M1+F)], where a, b, c, d, e, and f are non-negative integers. For each co-deposition scheme, the molar percentage of each of M1, M2, and M3 can be determined experimentally. Similarly, for the co-deposition of four metals, the following co-deposition schemes can be combined to achieve a coating with the target composition: M1+M2+M3+M4+F, M1+M3+M4+M2+F, M1+M4+M2+M3+F, M1+M3+M2+M4+F, M1+M4+M3+M2+F, M1+M2+M4+M3+F, M2+M1+M3+M4+F, M2+M3+M4+M1+F, M2+M4+M1+M3+F, M2+M1+M4+M3+F, M2+M3+M1 +M4+F, M2+M4+M3+M1+F, M3+M1+M2+M4+F, M3+M2+M4+M1+F, M3+M4+M1+M2+F, M3+M1+M4+M2+F, M3+M2+M1+M4+F, M3+M 4+M2+M1+F, M4+M1+M2+M3+F, M4+M2+M3+M1+F, M4+M3+M1+M2+F, M4+M1+M3+M2+F, M4+M2+M1+M3+F, M4+M3+M3+M1+F.Accordingly, the target component can be achieved using the following formula: K*[a*(M1+M2+M3+M4+F)+b*(M1+M3+M4+M2+F)+c*(M1+M4+M2+M3+F)+d*(M1+M3+M2+M4+F)+e*(M1+M4+M3+M2+F)+f*(M1+M2+M4+M3+F)+g*(M2+M1+M3+M4+F)+h*(M2+M3+M4+M1+F)+i*(M2+M4+M1+M3+F)+j*(M2+M1+M4+M3+F)+k(M2+M3+M1+M4+F)+l*(M2+M4+M3+M 1+F)+m*(M3+M1+M2+M4+F)+n*(M3+M2+M4+M1+F)+o*(M3+M4+M1+M2+F)+p*(M3+M1+M4+M2+F)+q*(M3+M2+M1+M4+F)+r*(M3+M4+M2+M1+O)+s*(M4+M1+M2+M3+F)+t*(M4+M2+M3+M1+F)+u*(M4+M3+M1+M2+F)+v*(M4+M1+M3+M2+F)+w*(M4+M2+M1+M3+F)+x*(M4+M3+M3+M1+F)], where a to x are non-negative integers.

[0069] The dose-time ratio can be expressed as the ratio of the exposure time of the first metal (e.g., yttrium) precursor to the exposure time of the second metal precursor. It should be noted that while the dose-time and ratio of the precursor materials are controllable, the adhesion, adhesion coefficient, and chemical interactions between the precursor and the surface may not be controllable. The pressure and temperature of the ALD chamber also affect the adsorption of the precursor on the surface. For example, Zr is slightly more reactive than Y, and therefore coatings obtained with a mixture of zirconium and yttrium can be zirconium-rich. Under equilibrium conditions in the chamber, the dose-time can be adjusted to achieve the desired composition. Under equilibrium conditions, the composition is limited by the chemical reactivity of the precursor and the adhesion coefficient of the material. In some embodiments, there is no purification between the introduction of the precursor containing the first metal and the precursor containing the second metal, as this could affect the adsorption of the material onto the article.

[0070] In an embodiment, the ratio of a first number of M2-M1 co-deposition loops to a second number of M1-M2 co-deposition loops can be selected to produce a target first mol% of the first metal and a target second mol% of the second metal. Furthermore, multiple deposition superloops can be performed, wherein each deposition superloop includes performing a first number of M1-M2 co-deposition loops and performing a second number of M2-M1 deposition loops.

[0071] The ratio of the thickness of the fluoride layer containing the first metal to the thickness of the buffer layer can be from 200:1 to 1:200, or from about 100:1 to 1:100, or from about 50:1 to about 1:50. Higher ratios of the thickness of the fluoride layer containing the first metal to the thickness of the buffer layer (e.g., 200:1, 100:1, 50:1, 20:1, 10:1, 5:1, 2:1, etc.) provide better resistance to corrosion and erosion, while lower ratios (e.g., 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, 1:200) provide better heat resistance (e.g., improved resistance to cracking and / or delamination caused by thermal cycling). The thickness ratio can be selected according to the specific chamber application. In the example, for capacitively coupled plasma environments with high sputtering rates, a 1µm top layer can be deposited on a 50nm buffered Al2O3 layer. For high-temperature chemical or radical environments without high-energy ion bombardment, a 100nm top layer with a 500nm underlayer may be optimal.

[0072] Referring to FIG. 2D, the article 205 can be inserted into the ALD chamber. In this embodiment, the co-deposition method includes simultaneously co-doping at least two precursors onto the surface of the article. The article 205 may be introduced into the mixture of precursors 210, 220 for a duration until the surface of the article or the surface of the body of the article is completely adsorbed with the mixture of precursors 210, 220 to form a co-adsorbed layer 227. A mixture of two precursors A and B (such as a yttrium-containing precursor and another rare earth metal fluoride precursor) is co-injected into the chamber in any ratio (AxBy) (e.g., A90 + B10, A70 + B30, A50 + B50, A30 + B70, A10 + A90, etc.) and adsorbed onto the surface of the article. In these examples, x and y are expressed as the atomic ratio (moles%) of Ax + By. For example, A90 + B10 is 90 mol% A and 10 mol% B. In some embodiments, at least two precursors are used; in other embodiments, at least three precursors are used; and in still further embodiments, at least four precursors are used. Next, the article 205 having the co-adsorption layer 227 can be introduced into the reactant 230 to react with the co-adsorption layer 227 to grow a solid rare-earth metal-containing fluoride coating 235. As shown, the co-deposition of the co-concentrated rare-earth metal-containing coating 235 can be repeated m times to obtain the desired coating thickness, where m is an integer value greater than 1.

[0073] Depending on the type of process, ALD processes can be performed at different temperatures. The optimal temperature range for a particular ALD process is referred to as the "ALD temperature window." Temperatures below the ALD temperature window can result in poor growth rates and non-ALD type deposition. Temperatures above the ALD temperature window can result in reactions occurring via chemical vapor deposition (CVD). The ALD temperature window can be from about 100 °C to about 650 °C. In some embodiments, the ALD temperature window is from about 20 °C to about 200 °C, or from about 25 °C to about 150 °C, or from about 100 °C to about 120 °C, or from about 20 °C to 125 °C.

[0074] The ALD process allows for conformal rare-earth metal-containing fluoride coatings of uniform thickness on articles and surfaces with complex geometries, high aspect ratio holes (e.g., pores), and three-dimensional structures. Sufficient exposure time for each precursor on the surface allows the precursor to disperse and fully react with the entire surface, including all its three-dimensional complexities. The exposure time for obtaining conformal ALD in high aspect ratio structures is proportional to the square of the aspect ratio and can be predicted using modeling techniques. Furthermore, ALD technology is advantageous compared to other commonly used coating techniques because it allows for in-situ, on-demand material synthesis of specific components or formulations without the lengthy and arduous fabrication of source materials such as powder feedstocks and sintering targets.

[0075] Another possible ALD deposition technique involves the sequential deposition of multiple different metal fluoride layers, followed by interdiffusion between the layers. This may include introducing a first precursor of a first metal, followed by the introduction of a first reactant to form a first metal fluoride layer. Subsequently, a second precursor of a second metal may be introduced, followed by the introduction of either a first reactant or a second reactant to form a second metal fluoride layer. In some embodiments, an annealing operation may then be performed.

[0076] In some embodiments, two or more of the above-described ALD deposition techniques can be combined to produce a uniform metal fluoride coating. For example, co-deposition and co-doping can be combined, co-deposition and sequential deposition can be combined, and / or co-doping and sequential deposition can be combined. In an example, a mixture of yttrium and erbium precursors can be implanted into an ALD chamber to adsorb yttrium and erbium onto the surface of the article. Subsequently, a mixture of zirconium and hafnium precursors can be implanted into an ALD chamber to further adsorb zirconium and hafnium onto the surface. Subsequently, a fluorine source reactant can be implanted into an ALD chamber to form a YvErwZrxHfyFz coating.

[0077] Figure 3A illustrates a method 300 for forming a rare-earth metal-containing fluoride coating via a co-deposition ALD process. Method 300 can be used to coat any article described herein. Method 300 may optionally be initiated by selecting precursors for forming the coating. The composition selection and formation method may be performed by the same entity or by multiple entities.

[0078] At block 305, method 300 may optionally include cleaning the article with an acid solution. In one embodiment, the article is immersed in an acid solution bath. In an embodiment, the acid solution may be a hydrofluoric acid (HF) solution, a hydrochloric acid (HCl) solution, a nitric acid (HNO3) solution, or a combination thereof. The acid solution can remove surface contaminants from the article and / or remove oxides from the surface of the article. Cleaning the article with an acid solution can improve the quality of coatings deposited using ALD. In one embodiment, an acid solution containing about 0.1-5.0 vol% HF is used to clean a chamber component made of quartz. In one embodiment, an acid solution containing about 0.1-20 vol% HCl is used to clean an article made of Al2O3. In one embodiment, an acid solution containing about 5-15 vol% HNO3 is used to clean an article made of aluminum and additional metals.

[0079] At frame 310, the article is loaded into an ALD deposition chamber. At frame 325, method 300 includes optionally depositing a buffer layer on the surface of the article or the surface of the body of the article using ALD. At frame 320, ALD is performed to co-deposit a fluoride coating containing a rare earth metal on the article. At least one M1-M2 co-deposition loop 330 is performed. At frame 335, the M1-M2 co-deposition loop includes introducing a precursor containing a first metal into an ALD chamber containing an article (with or without a buffer layer). The precursor containing the first metal contacts the surface of the article or the surface of the article body to form a partially metal-adsorbed layer. At frame 340, a precursor containing a second metal is introduced into an ALD chamber containing an article having a partially metal-adsorbed layer. The precursor containing the second metal contacts the remaining exposed surface of the article or the body of the article to form an M1-M2 co-adsorbed layer. At frame 345, the reactants are introduced into the ALD chamber and react with the M1-M2 co-adsorption layer to form a rare earth metal-containing fluoride coating.

[0080] Figure 3B illustrates a method 302 for forming a rare-earth metal-containing fluoride coating via a co-deposition ALD process. Method 302 can be used to coat any article described herein. Method 302 may optionally be initiated by selecting precursors for forming the coating. The composition selection and formation method may be performed by the same entity or by multiple entities.

[0081] At block 305, method 302 may optionally include cleaning the article with an acid solution. At block 310, the article is loaded into an ALD deposition chamber. At block 325, method 302 includes optionally depositing a buffer layer on the surface of the article or the surface of the body of the article using ALD. At block 321, ALD is performed to co-deposit a fluoride coating containing a rare earth metal on the article. At least one M2-M1 co-deposition loop 331 is performed. At block 336, the M2-M1 co-deposition loop includes introducing a precursor containing a second metal into an ALD chamber containing an article (with or without a buffer layer). The precursor containing the second metal contacts the surface of the article or the surface of the article body to form an adsorbed layer containing a portion of the metal. At block 341, a precursor containing a first metal is introduced into an ALD chamber containing an article having an adsorbed layer of the second metal. The precursor containing the first metal contacts the remaining exposed surfaces of the article or the body of the article to form an M2-M1 co-adsorbed layer. At frame 346, the reactants are introduced into the ALD chamber and react with the M2-M1 co-adsorption layer to form a rare earth metal-containing fluoride coating.

[0082] Figure 3C illustrates a combined method 303 for forming a multilayer coating as described herein, comprising performing at least one M1-M2 co-deposition loop at block 330. Subsequently, the ALD chamber is purged with an inert gas at block 332. At block 350, at least one M2-M1 co-deposition loop is performed to form a fluoride coating containing rare earth metals. As described above, the co-deposition loops can be repeated any number of times and in any order to obtain the desired composition of the rare earth metal-containing coating. Although not shown, in some embodiments, annealing can be performed on the deposited coating. Annealing temperatures up to about 500 °C can be used for coatings where the second metal is aluminum.

[0083] Figure 3D illustrates a method 304 for co-depositing a rare-earth metal-containing fluoride coating by co-doping according to embodiments described herein. At block 305, method 304 may optionally include cleaning the article with an acid solution. At block 310, the article is loaded into an ALD deposition chamber. At block 325, method 302 includes optionally depositing a buffer layer on the surface of the article or the surface of the body of the article using ALD.

[0084] At box 322, ALD is performed to co-deposit a rare-earth metal-containing fluoride coating on article 205 by co-doping. At least one co-deposition loop 332 is performed. At box 355, the co-deposition loop includes introducing a mixture of a precursor containing a first metal and a precursor containing a second metal into an ALD chamber containing an article (with or without a buffer layer). The precursors containing the first metal and the precursors containing the second metal may independently comprise metals selected from: rare-earth metals, zirconium, aluminum, hafnium, and tantalum. The mixture of precursors contacts the surface of the article or the surface of the body of the article to form a co-adsorbed layer. At box 360, reactants are introduced into the ALD chamber and react with the co-adsorbed layer to form a rare-earth metal-containing fluoride coating. The co-deposition loop can be repeated as many times as necessary to achieve the desired coating thickness.

[0085] According to an embodiment, the method may include: co-depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition. Co-depositing the rare earth metal-containing fluoride coating may include: contacting the surface with a first precursor for a first duration to form a partial first metal adsorption layer, wherein the first precursor is selected from rare earth metal-containing precursors, zirconium-containing precursors, hafnium-containing precursors, tantalum-containing precursors, or aluminum-containing precursors; contacting a portion of the metal adsorption layer with a second precursor different from the first precursor for a second duration to form a co-adsorption layer comprising a first metal and a second metal, wherein the second precursor is selected from rare earth metal-containing precursors, zirconium-containing precursors, hafnium-containing precursors, tantalum-containing precursors, or aluminum-containing precursors; and contacting the co-adsorption layer with reactants to form a rare earth metal-containing fluoride coating. In some embodiments, the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, and the rare earth metal-containing fluoride coating may be a homogeneous mixture of the first metal and the second metal.

[0086] According to an embodiment, co-depositing a fluoride coating containing rare earth metals includes: performing at least one M1-M2 co-depositation cycle, which includes: contacting a surface with a precursor containing a first metal to form a partial first metal adsorption layer; subsequently contacting the partial first metal adsorption layer with a precursor containing a second metal to form an M1-M2 co-adsorption layer; and contacting the M1-M2 co-adsorption layer with a reactant. At least one M1-M2 co-depositation cycle can produce a layer containing a first percentage of the first metal and a second percentage of the second metal.

[0087] In an embodiment, co-depositing a fluoride coating containing rare earth metal may further include: performing at least one M2-M1 co-depositation cycle, which includes: contacting the surface with a precursor containing a second metal to form a partial second metal adsorption layer; subsequently contacting the partial metal adsorption layer with the rare earth metal precursor to form an M2-M1 co-adsorption layer; and contacting the M2-M1 co-adsorption layer with a reactant. At least one M2-M1 co-depositation cycle may produce an additional layer comprising a third percentage of a first metal and a fourth percentage of a second metal, wherein the third percentage is lower than the first percentage and the fourth percentage is higher than the second percentage.

[0088] The method according to the embodiments described herein may further include: selecting a ratio of a first number of M1-M2 co-deposition loops and a second number of M2-M1 co-deposition loops, which yields a target first mole % of the first metal and a target second mole % of the second metal; and performing a plurality of deposition superloops, wherein each deposition superloop includes performing the first number of M1-M2 co-deposition loops and performing the second number of M2-M1 deposition loops. According to an embodiment, performing at least one M1-M2 co-deposition loop may include: contacting the surface with a rare earth metal-containing precursor for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds; contacting a portion of the first metal adsorption layer with a precursor containing a second metal for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds; and contacting the M1-M2 co-adsorption layer with a reactant for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds; and performing at least one M2-M1 co-deposition loop. Performing at least one M2-M1 co-deposition loop may include: contacting the surface with a precursor containing a second metal for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds; contacting a portion of the metal adsorption layer with a precursor containing a rare earth metal for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds; and contacting the M2-M1 co-adsorption layer with a reactant for about 50 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 5 seconds to about 60 seconds, or about 10 seconds to about 60 seconds.

[0089] The following examples are illustrated to aid in understanding the embodiments described herein and should not be construed as specifically limiting the embodiments described and claimed herein. Such changes (including alternative embodiments of all equivalent embodiments now known or developed hereafter), as well as minor variations in formulation or experimental design, that would be within the view of someone skilled in the art should be considered to fall within the scope of the embodiments contained herein. These examples can be achieved by performing the methods described herein. Example 1—The effect of fluorine on Y2O3 coatings

[0090] A yttrium oxide coating was deposited on a chamber component using atomic layer deposition (ALD). The coated substrate was subjected to 3000 cycles of nitrogen trifluoride (NF3) plasma in a chemical vapor deposition chamber at 450 °C. A cross-sectional side-view transmission electron microscopy (TEM) image of the Y2O3 coating on the substrate was obtained. A transmission electron microscopy energy-dispersive X-ray spectroscopy (TEM / EDS) line scan of the Y2O3 coating was also obtained. During the NF3 treatment of the Y2O3 substrate, uncontrolled fluorine (F) diffusion / reaction into the Y2O3 damaged the coating and the underlying substrate. Fluorine (1) caused surface degradation of the coating; (2) erosion and the resulting particle generation; (3) diffusion through the coating; and (4) increased the risk of coating cracking and delamination. Example 2 – Comparison of Al2O3, Y2O3 and YF3 prepared by ALD

[0091] Samples with Al2O3, Y2O3, or YF3 coatings were prepared using an ALD deposition method. The thickness of the Al2O3 coating was 500 nm, the thickness of the Y2O3 coating was 100 nm, and the thickness of the YF3 coating was 100 nm. Each sample was exposed to CF4 inductively coupled plasma for 34 RF hours at 75°C and 300 W of RF source power.

[0092] After exposure to CF4 plasma, while neither the YF3 nor Y2O3 coatings experienced a reduction in thickness (e.g., etch rate was approximately 0), the YF3 coating did not exhibit microstructure degradation, whereas the Y2O3 coating underwent significant microstructure degradation. The Y2O3 coating exhibited dense nanocracks and delamination, while the YF3 coating did not. Without being bound by any particular theory, it is believed that when the Y2O3 coating is exposed to fluorine plasma, fluorine diffuses into the coating and displaces oxygen molecules, causing volume expansion of the Y2O3 coating, which in turn leads to nanocracks and delamination. Before the occurrence of nanocracks, both the Y2O3 and YF3 coatings acted as diffusion barrier layers and prevented metals in the coated article from diffusing through the coating and contaminating the treated substrate. However, the nanocracks in the Y2O3 coating cause it to cease acting as a diffusion barrier layer, as the nanocracks allow metals to diffuse through the coating. Furthermore, the nanocracks cause the Y2O3 coating to peel off and generate particulate contamination on the treated substrate. In contrast, the YF3 coating remains a good diffusion barrier layer because no nanocracks are formed in it, and it does not cause particulate contamination even after repeated exposure to fluorine-rich plasma. When fluorine is used instead of oxygen in the coating, although fluorine can diffuse into the YF3 coating, the YF3 coating does not undergo volume expansion, thus preventing the formation of nanocracks and delamination. The Al2O3 coating underwent significant etching, reducing its thickness from 500 nm to approximately 225 nm (i.e., approximately 275 nm was etched away).

[0093] Comparisons of other rare earth oxides with rare earth fluorides have also demonstrated similar results to those shown above for YF3 and Y2O3. For example, a comparison of YxZryOz and YxZryFz coatings exposed to CF4 plasma showed that the YxZryOz coating experienced nanocracks (and therefore no longer functioned as a diffusion barrier layer, leading to particulate contamination), while the YxZryFz coating did not experience nanocracks (and therefore functioned as a diffusion barrier layer and did not cause particulate contamination). Similar results were observed for comparisons of other monometallic and polymetallic rare earth fluorides with other monometallic and polymetallic rare earth fluorides.

[0094] The foregoing description sets forth numerous specific details, such as examples of specific systems, components, methods, etc., to provide a good understanding of several embodiments of the invention. However, it will be apparent to those skilled in the art that at least some embodiments of the invention can be practiced without these specific details. On the other hand, well-known components or methods have not been described in detail or presented in simple block diagram form so as not to unnecessarily obscure the invention. Therefore, the specific details set forth are merely exemplary. Specific implementations may be derived from these exemplary details and are still considered to be within the scope of the invention.

[0095] Throughout this specification, references to "an embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Therefore, throughout this specification, the phrase "in an embodiment" appearing in multiple places does not necessarily refer to the same embodiment. Additionally, the term "or" is intended to indicate an inclusive "or" rather than an exclusive "or." When the terms "about" or "approximately" are used herein, they are intended to indicate that the presented nominal values ​​are exactly within ±10%.

[0096] Although the operations of the methods are shown and described herein in a specific order, the order of operations of each method may be changed such that certain operations may be performed in reverse order or that an operation may be performed at least partially simultaneously with other operations. In another embodiment, instructions or sub-operations of different operations may be performed in an intermittent and / or alternating manner.

[0097] It should be understood that the above description is intended to be illustrative and not restrictive. Many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. Therefore, the scope of the invention should be determined by reference to the appended claims and their equivalents. [Simplified Explanation of the Diagram]

[0009] In the accompanying drawings, this disclosure is illustrated by way of example rather than by way of limitation, in which similar reference numerals indicate similar elements. It should be noted that in this disclosure, different references to "a" or "an" embodiment do not necessarily refer to the same embodiment, and such references mean at least one.

[0010] Figure 1 depicts a cross-sectional view of the processing chamber.

[0011] Figure 2A depicts an embodiment of a co-deposition process according to the atomic layer deposition technique described herein.

[0012] Figure 2B depicts another embodiment of a co-deposition process according to the atomic layer deposition technique described herein.

[0013] Figure 2C depicts another embodiment of a co-deposition process according to the atomic layer deposition technique described herein.

[0014] Figure 2D depicts another embodiment of a co-deposition process according to the atomic layer deposition technique described herein.

[0015] Figure 3A illustrates a method for forming a rare earth metal-containing fluoride coating using atomic layer deposition as described herein.

[0016] Figure 3B illustrates a method for forming a rare earth metal-containing fluoride coating using atomic layer deposition as described herein.

[0017] Figure 3C illustrates a method for forming a rare earth metal-containing fluoride coating using atomic layer deposition as described herein.

[0018] Figure 3D illustrates a method for forming a rare earth metal-containing fluoride coating using atomic layer deposition as described herein. [Biomaterial Storage]

[0099] Domestic Storage Information (Please note in order of storage institution, date, and number) None

[0100] Overseas Deposit Information (Please note in the order of deposit country, institution, date, and number) None

Claims

1. A coated article, comprising: One main body; A buffer layer is deposited on a surface of the host body, wherein the buffer layer is non-porous, and the buffer layer comprises silicon oxide, aluminum nitride, or a combination thereof; and a rare-earth metal-containing fluoride coating is deposited on a surface of the buffer layer, wherein the rare-earth metal-containing fluoride coating is non-porous. The rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal (M1) and about 1 mol% to about 40 mol% of a second metal (M2), the rare earth metal-containing fluoride coating having a formula M1xM2yFz and being oxygen-deficient, wherein the first metal and the second metal are independently selected from the group consisting of: a rare earth metal, zirconium, hafnium, aluminum and tantalum, wherein the first metal is different from the second metal, and wherein each of the aforementioned variables x, y and z is in the range of 0.1 to 10, and wherein the rare earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal and the second metal, wherein the rare earth metal-containing fluoride coating is a co-deposited coating comprising multiple layers, each layer comprising the first metal and the second metal, and wherein the rare earth metal-containing fluoride coating is free from surface fluorination and metal phase separation.

2. The coated article as claimed in claim 1, wherein the rare earth metal-containing fluoride coating has a thickness of about 5 nm to about 10 µm.

3. The coated article as claimed in claim 1, wherein the article is a component of a processing chamber, the components of which are selected from the group consisting of: a chamber wall, a nozzle, a spray nozzle, a plasma generating unit, a radio frequency electrode, an electrode housing, a diffuser, and a gas line.

4. The coated article as claimed in claim 1, wherein the body comprises a material selected from the group consisting of aluminum, steel, silicon, copper, and magnesium.

5. The coated article as claimed in claim 1, wherein the first metal comprises a rare earth metal selected from the group consisting of: yttrium, erbium, lanthanum, diurethane, scandium, zonesium, samarium, and dysprosium.

6. The coated article as claimed in claim 1, wherein the first metal comprises yttrium, and wherein the rare earth metal-containing fluoride coating comprises a zirconium at a concentration of about 1 mole% to about 40 mole%.

7. The coated article as claimed in claim 1, wherein the rare earth metal-containing fluoride coating comprises a component selected from a group consisting of YxZryFz and YxHfyFz.

8. The coated article as claimed in claim 1, wherein the rare earth metal-containing fluoride coating comprises a co-adsorption layer and a product of a fluorine-containing reactant, the co-adsorption layer comprising the first metal and the second metal.

9. A coated article, comprising: One main body; A buffer layer is deposited on a surface of the host body, wherein the buffer layer is non-porous, and the buffer layer comprises silicon oxide, aluminum nitride, or a combination thereof; and a rare-earth metal-containing fluoride coating is deposited on a surface of the buffer layer, wherein the rare-earth metal-containing fluoride coating is non-porous. The rare-earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal (M1), about 1 mol% to about 40 mol% of a second metal (M2), and further comprises a third metal (M3) different from the first metal and the second metal. The rare-earth metal-containing fluoride coating has the formula M1xM2yM3wFz and is oxygen-deficient. The first metal, the second metal, and the third metal are independently selected from the group consisting of yttrium, erbium, lanthanum, diurethane, scandium, zonesium, samarium, dysprosium, zirconium, hafnium, and tantalum. Each of the aforementioned variables x, y, w, and z is in the range of 0.1 to 10. The rare-earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal, the second metal, and the third metal. The rare earth metal-containing fluoride coating is a multi-layer co-deposited coating, each layer including the first metal, the second metal and the third metal, and the rare earth metal-containing fluoride coating has no surface fluorination and no metal phase separation.

10. The coated article as claimed in claim 9, wherein the buffer layer has a thickness of about 10 nm to about 1.5 µm.

11. The coated article as claimed in claim 9, wherein the buffer layer comprises amorphous alumina.

12. The coated article as claimed in claim 9, wherein the ratio of the thickness of the rare earth metal-containing fluoride coating to the thickness of the buffer layer is from about 200:1 to about 1:

200.

13. The coated article as claimed in claim 9, wherein the rare earth metal-containing fluoride coating is uniform on the angstrom scale.

14. The coated article as claimed in claim 9, wherein the rare earth metal-containing fluoride coating is free from interdiffusion of one or more metal phases.

15. The coated article as claimed in claim 9, wherein the rare earth metal-containing fluoride coating does not undergo phase separation.

16. The coated article as claimed in claim 9, wherein the rare earth metal-containing fluoride coating comprises a component selected from the group consisting of YxTayZrwFz and ErxTayZrwFz.

17. The coated article as claimed in claim 9, wherein the rare earth metal-containing fluoride coating comprises a component selected from the group consisting of ErxZryHfwFz and ErxHfyYwFz.

18. A coated article comprising: One main body; A buffer layer on a surface of the body, wherein the deposited buffer layer is non-porous, wherein the buffer layer comprises silicon oxide, aluminum nitride, or a combination thereof; and a rare-earth metal-containing fluoride coating on a surface of the buffer layer, wherein the deposited rare-earth metal-containing fluoride coating is non-porous, wherein the rare-earth metal-containing fluoride coating comprises a material selected from the group consisting of: YxZryHfwFz, YxErvZryHfwFz, YxTauHfwFz, ErvTauHfwFz, and YxErvTauHfwFz, and ErvZryHfwFz, wherein each of the aforementioned variables x, y, w, z, v, and u is in the range of 0.1 to 10, wherein the rare-earth metal-containing fluoride coating comprises a homogeneous mixture of a plurality of metals within the material. The rare earth metal-containing fluoride coating is a multi-layer co-deposited coating, each layer comprising multiple metals within the material, and wherein the rare earth metal-containing fluoride coating has no surface fluorination and no metal phase separation.

19. The coated article as claimed in claim 18, wherein the buffer layer has a coefficient of thermal expansion between the coefficient of thermal expansion of the article and the coefficient of thermal expansion of the rare earth metal-containing fluoride coating.

20. A coating method comprising the steps of: co-depositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, wherein the step of co-depositing the rare earth metal-containing fluoride coating comprises the step of: contacting the surface with a precursor containing a first metal or a precursor containing a second metal for a first duration to form a partial metal adsorption layer comprising a first metal (M1) or a second metal (M2), wherein the precursor containing the first metal or the precursor containing the second metal is selected from the group consisting of: a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, an aluminum-containing precursor, and a tantalum-containing precursor, and wherein the first duration is at least 50 milliseconds; The metal adsorption layer is contacted with the precursor containing the second metal or the precursor containing the first metal for a second duration to form a co-adsorption layer comprising the first metal (M1) and the second metal (M2), wherein the first metal and the second metal are different, and wherein the second duration is at least 50 milliseconds; and the co-adsorption layer is contacted with a fluorine-containing reactant to form the rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of the first metal and about 1 mol% to about 40 mol% of the second metal, and wherein the rare earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal and the second metal.

21. The coating method of claim 20, wherein the step of co-depositing the rare earth metal-containing fluoride coating comprises the following steps: performing at least one M1-M2 co-deposition cycle, comprising the following steps: contacting the surface with the precursor containing the first metal to form the partial metal adsorption layer; subsequently contacting the partial metal adsorption layer with the precursor containing the second metal to form an M1-M2 co-adsorption layer; and contacting the M1-M2 co-adsorption layer with the fluorine-containing reactant.

22. The coating method of claim 21, wherein the step of co-depositing the rare earth metal-containing fluoride coating further comprises the following steps: performing at least one M2-M1 co-deposition cycle, comprising the following steps: contacting the surface with the precursor containing the second metal to form a second partial metal adsorption layer; subsequently contacting the second partial metal adsorption layer with the precursor containing the first metal to form an M2-M1 co-adsorption layer; and contacting the M2-M1 co-adsorption layer with the fluorine-containing reactant.

23. The coating method as described in claim 22, wherein: Performing the at least one M1-M2 co-deposition loop includes the following steps: contacting the surface with the precursor containing the first metal for about 50 milliseconds to about 60 seconds; contacting the partial metal adsorption layer with the precursor containing the second metal for about 50 milliseconds to about 60 seconds; and contacting the M1-M2 co-adsorption layer with the fluorine-containing reactant for about 50 milliseconds to about 60 seconds; and performing the at least one M2-M1 co-deposition loop includes the following step: contacting the surface with the precursor containing the second metal for about 50 milliseconds to about 60 seconds; The second metal adsorption layer is brought into contact with the precursor containing the first metal for approximately 50 milliseconds to approximately 60 seconds. And to bring the M2-M1 co-adsorption layer into contact with the fluorine-containing reactant for about 50 milliseconds to about 60 seconds.

24. The coating method as claimed in claim 20, wherein the precursor containing the first metal and the precursor containing the second metal are independently selected from the group consisting of: a cyclopentadienyl precursor, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, trimethylcyclopentadienyl erbium(III) (Er(MeCp)3), tris(butylcyclopentadienyl)erbium(III), amidine precursor, tris(N,N'-diisopropylmethylamidine) Yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dione)yttrium, tris(bis(trimethylsilyl)pyramidinyl)lanthanum, pyramidinyl precursor, boranepyramidinyl erbium (Er(BA)3), β-diketone precursor, erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione), tris(dimethylamino)(cyclopentadienyl)zirconium, tetra(dimethylamino)zirconium, tetra(diethylamino)zirconium, tetra(N,N'-dimethyl-formamidinyl)zirconium, tetra(ethylmethylamino)hafnium, and penta(dimethylamino)tantalum.

25. The coating method of claim 20 further comprises the following steps: before contacting the co-adsorption layer with the fluorine-containing reactant, contacting the co-adsorption layer with a third precursor to adsorb a third metal, wherein the third precursor is selected from the group consisting of: a yttrium precursor, an erbium precursor, a zirconium precursor, a hafnium precursor, a silicon precursor, a tantalum precursor, a lanthanum precursor, a diurethane precursor, a scandium precursor, a zirconium precursor, a samarium precursor, and a dysprosium precursor.

26. The coating method of claim 20 further comprises the steps of: depositing a buffer layer on the surface of the article by atomic layer deposition, and co-depositing the rare earth metal-containing coating on the buffer layer, wherein the buffer layer comprises at least one of alumina, silicon oxide, or aluminum nitride.

27. The coating method as claimed in claim 20, wherein the rare earth metal-containing fluoride coating comprises a component selected from a group consisting of: YxZryFz, YxEryFz, ErxZryFz, LaxZryFz, LuxZryFz, ScxZryFz, GdxZryFz, SmxZryFz, DyxZryFz, YxHfyFz, ErxHfyFz, LaxHfyFz, LuxHfyFz, ScxHfyFz, GdxHfyFz, SmxHfyFz, DyxHfyFz, and combinations thereof, wherein each of the aforementioned variables x, y, and z is in the range of 0.1 to 10.

28. A coating method comprising the steps of: co-depositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, wherein co-depositing the rare earth metal-containing fluoride coating comprises the steps of: performing at least one co-doping cycle, comprising the steps of: contacting the surface with a mixture of a first precursor and a second precursor for a first duration to form a co-adsorption layer, wherein the first precursor and the second precursor are each selected from a group consisting of: a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, an aluminum-containing precursor, and a tantalum-containing precursor, and wherein the first duration is at least 50 milliseconds; and contacting the co-adsorption layer with a fluorine-containing reactant to form the rare earth metal-containing fluoride coating. The rare earth metal-containing fluoride coating comprises a first metal (M1) and a second metal (M2), wherein the first metal and the second metal are independently selected from a group consisting of: a rare earth metal, zirconium, hafnium, aluminum and tantalum, wherein the first metal is different from the second metal, and wherein the rare earth metal-containing fluoride coating comprises a homogeneous mixture of the first metal and the second metal.

29. The coating method of claim 28, wherein the mixture further comprises a third precursor comprising a metal different from the first metal of the first precursor and the second metal of the second precursor.

30. The coating method as claimed in claim 29, wherein the third precursor is selected from a group consisting of: a yttrium precursor, an erbium precursor, a zirconium precursor, a hafnium precursor, a silicon precursor, a tantalum precursor, a lanthanum precursor, a diurethane precursor, a scandium precursor, a zirconium precursor, a samarium precursor, and a dysprosium precursor.

31. The coating method as claimed in claim 28, wherein the at least one co-mixing cycle produces a layer comprising about 1 mol% to about 40 mol% of the first metal (M1) and about 1 mol% to about 40 mol% of the second metal (M2).

32. The coating method as described in claim 31, wherein: Performing the M1-M2 co-adsorption cycle includes the following steps: contacting the surface with a mixture of the first precursor and the second precursor for about 50 milliseconds to about 60 seconds to form an M1-M2 co-adsorption layer, wherein the ratio of M1:M2 is greater than 1; and contacting the M1-M2 co-adsorption layer with the fluorine-containing reactant for about 50 milliseconds to about 60 seconds. And performing the M2-M1 co-adsorption cycle includes the following steps: contacting the surface with the precursor containing the second metal and the precursor containing the first metal for about 50 milliseconds to about 60 seconds to form an M2-M1 co-adsorption layer, wherein the ratio of M2:M1 is greater than 1; and contacting the M2-M1 co-adsorption layer with the fluorine-containing reactant for about 50 milliseconds to about 60 seconds.

33. The coating method as claimed in claim 28, wherein the precursor containing the first metal and the precursor containing the second metal are independently selected from the group consisting of: a cyclopentadienyl precursor, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, trimethylcyclopentadienyl erbium(III) (Er(MeCp)3), tris(butylcyclopentadienyl)erbium(III), amidine precursor, tris(N,N'-diisopropylmethylamidine) Yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dione)yttrium, tris(bis(trimethylsilyl)pyramidinyl)lanthanum, pyramidinyl precursor, boranepyramidinyl erbium (Er(BA)3), β-diketone precursor, erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedione), tris(dimethylamino)(cyclopentadienyl)zirconium, tetra(dimethylamino)zirconium, tetra(diethylamino)zirconium, tetra(N,N'-dimethyl-formamidinyl)zirconium, tetra(ethylmethylamino)hafnium, and penta(dimethylamino)tantalum.

34. The coating method of claim 28 further comprises the steps of: depositing a buffer layer on the surface of the article by atomic layer deposition, and co-depositing the rare earth metal-containing coating on the buffer layer, wherein the buffer layer comprises at least one of alumina, silicon oxide, or aluminum nitride.

35. The coating method as claimed in claim 28, wherein the rare earth metal-containing fluoride coating comprises a component selected from a group consisting of: YxZryFz, YxEryFz, ErxZryFz, LaxZryFz, LuxZryFz, ScxZryFz, GdxZryFz, SmxZryFz, DyxZryFz, YxHfyFz, ErxHfyFz, LaxHfyFz, LuxHfyFz, ScxHfyFz, GdxHfyFz, SmxHfyFz, DyxHfyFz, and combinations thereof, wherein each of the aforementioned variables x, y, and z is in the range of 0.1 to 10.

36. A coating method comprising the steps of: depositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, wherein the step of depositing the rare earth metal-containing fluoride coating comprises the following steps: contacting the surface with a first precursor for a first duration to form a first metal adsorption layer, wherein the first duration is at least 50 milliseconds; contacting the first metal adsorption layer with a fluorine-containing reactant to form a first metal fluoride layer; contacting the first metal layer with a second precursor for a second duration to form a second metal adsorption layer, wherein the second duration is at least 50 milliseconds; contacting the second metal adsorption layer with the fluorine-containing reactant or an alternative fluorine-containing reactant to form a second metal fluoride layer; forming the rare earth metal-containing fluoride coating from the first metal fluoride layer and the second metal fluoride layer, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal. The first metal and the second metal are independently selected from a group consisting of a rare earth metal, hafnium, and tantalum, wherein the first metal is different from the second metal.

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