Erosion-resistant metal fluoride coating deposited by atomic layer deposition method

Abstract

To provide an article coated with erosion-resistant metal fluorides.SOLUTION: An article includes a body, and a rare earth metal-containing fluoride coating on the surface of the body. The rare earth metal-containing fluoride coating contains a first metal of about 1 mol% to about 40 mol%, and a second metal of about 1 mol% to about 40 mol%. The first metal and the second metal are selected independently from the group consisting of rare earth metals, zirconium, hafnium, aluminum and tantalum. The first metal is different from the second metal. The rare earth metal-containing fluoride coating may contain a homogeneous mixture of the first metal and the second metal, but the coating is free from mechanical interlayer separation.SELECTED DRAWING: Figure 3A

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to erosion resistant metal fluoride coatings, coated articles, and methods of forming such coatings using atomic layer deposition.

[0002] In the semiconductor industry, devices are fabricated by many manufacturing processes that produce structures of ever-increasing size. Some manufacturing processes, such as plasma etching and plasma cleaning processes, expose a substrate to a high velocity plasma stream to etch or clean the substrate. Plasma can be highly corrosive and can corrode the processing chamber and other surfaces and components exposed to the plasma. This corrosion can generate particles that often contaminate the substrate during processing and contribute to device defects. Fluorine-containing plasmas, which can contain fluoride ions and radicals, are particularly harsh and can generate particles from the interaction of the plasma with materials in the processing chamber. Fluorine-containing plasmas can damage protective coatings and underlying materials on chamber components. This can degrade the surface of the protective coating and increase the risk of cracking and delamination. Drift in radical recombination rates resulting from gradual fluorination of chamber surfaces can also cause wafer processing drift.

[0003] As device geometries shrink, the susceptibility to defects increases and particulate contamination requirements (i.e., on-wafer 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 made of Al2O3, AlN, SiC, Y2O3, quartz, and ZrO2. Different ceramics have different material properties (plasma resistance, stiffness, bending strength, thermal shock resistance, etc.). Different ceramics also have different material costs. Thus, some ceramics have good plasma resistance, some are low cost, and some have good bending 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, but such plasma spray coatings cannot penetrate and coat high aspect ratio features such as showerhead holes. While some deposition techniques can coat high aspect ratio features, the resulting coatings may erode in certain plasma environments, e.g., fluorine-containing plasmas, forming particles, or suffer from mechanical separation of layers of material due to poor interdiffusion within the coating. Overview

[0005] An article of interest for embodiments described herein comprises a body and a rare earth metal-containing fluoride coating on a surface of the body, the rare earth metal-containing fluoride coating comprising from about 1 mol % to about 40 mol % of a first metal and from about 1 mol % to about 40 mol % of a second metal, the first metal and the second metal being independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum and tantalum, the first metal being different from the second metal, and the rare earth metal-containing fluoride coating comprising an intimate mixture of the first metal and the second metal.

[0006] Further embodiments are directed to a method comprising codepositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, the codepositing comprising the steps of contacting the surface with a first precursor for a first period of time to form a partial metal adsorbed layer comprising a first metal (M1), the first precursor being 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 contacting the partial metal adsorbed layer with a second precursor, different from the first precursor, for a second period of time to form a partial metal adsorbed layer comprising the first metal (M1) and a second metal (M2). and a second metal precursor 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 the first metal is different from the second metal; and contacting the coadsorbed layer with a reactant to form a rare earth metal-containing fluoride coating, the rare earth metal-containing fluoride coating comprising about 1 mol % to about 40 mol % of the first metal and about 1 mol % to about 40 mol % of the second metal, the rare earth metal-containing fluoride coating comprising a homogeneous mixture of the first metal and the second metal.

[0007] According to various embodiments, the described method includes codepositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, the codepositing the rare earth metal-containing fluoride coating comprising performing at least one co-injection cycle, contacting the surface with a mixture of a first precursor and a second precursor for a first period of time to form a co-adsorbed layer, the first precursor and the second precursor each being 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 contacting the coadsorbed layer with a fluorine-containing reactant to form a rare earth metal-containing fluoride coating, the rare earth metal-containing fluoride coating comprising from about 1 mol % to about 40 mol % of a first metal and from about 1 mol % to about 40 mol % of a second metal, the first metal and the second metal being independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum and tantalum, the first metal being different from the second metal, and the rare earth metal-containing fluoride coating comprising an intimate mixture of the first metal and the second metal.

[0008] According to various embodiments, methods described herein include depositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, the step of depositing the rare earth metal-containing fluoride coating comprising the steps of contacting the surface with a first precursor for a first period of time to form a first metal adsorbed layer, contacting the first metal adsorbed 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 period of time to form a second metal adsorbed layer, and contacting the second metal adsorbed layer with the fluorine-containing reactant. and forming a rare earth metal-containing fluoride coating from the first metal fluoride layer and the second metal fluoride layer, the rare earth metal-containing fluoride coating comprising from about 1 mol % to about 40 mol % of a first metal and from about 1 mol % to about 40 mol % of a second metal, the first metal and the second metal being independently selected from the group consisting of rare earth metals, zirconium, hafnium and tantalum, and the first metal being different from the second metal. [Brief description of the drawings]

[0009] The present disclosure is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings in which like reference numerals indicate like elements. It should be noted that different references to "an" or "one" embodiment in this disclosure are not necessarily references to the same embodiment, and such references mean at least one. [Figure 1] A cross-sectional view of a processing chamber is shown. [Figure 2A] 1 illustrates one embodiment of a co-deposition process according to the atomic layer deposition technique described herein. [Figure 2B] 1 illustrates another embodiment of a co-deposition process according to the atomic layer deposition technique described herein. [Figure 2C] 1 illustrates another embodiment of a co-deposition process according to the atomic layer deposition technique described herein. [Figure 2D] 1 illustrates another embodiment of a co-deposition process according to the atomic layer deposition technique described herein. [Figure 3A]FIG. 1 illustrates a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition methods described herein. [Figure 3B] FIG. 1 illustrates a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition methods described herein. [Figure 3C] FIG. 1 illustrates a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition methods described herein. [Figure 3D] FIG. 1 illustrates a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition methods described herein. Detailed Description

[0010] The embodiments described herein relate to composite metal-containing fluoride coatings that include a mixture of multiple metals. The embodiments also relate to coated articles and methods of forming such composite metal-containing fluoride coatings using atomic layer deposition. The composite metal-containing fluoride coating may include a first metal (M1) and a second metal (M2), where the first metal and the second metal are independently selected from rare earth metals (RE), zirconium, tantalum, hafnium, and aluminum, and the first metal is different from the second metal. In certain embodiments, the rare earth metal-containing fluoride coating may include three or more metals (e.g., M1, M2, M3, M4, etc.), where each metal is independently selected from rare earth metals, zirconium, tantalum, hafnium, and aluminum. For example, the rare earth metal-containing fluoride coating may include a first metal (M1), a second metal (M2), and a third metal (M3). x M2 y F z (For example, Y x Zr y F z , Y x Er y F z , Y x Ta y F z etc.), M1 w M2 x M3 y F z (For example, Y w ErxF z , Yw Z rx Hf y F z etc.), M1 v M2 w M3 x M4 y F z (For example, Y v Er w Z rx Hf y F z ), and / or in the form of more complex composite metal fluoride coatings with more mixed metals. As discussed in more detail below, multiple different metals (e.g., first metal, second metal, etc.) may be co-deposited on the article using non-line-of-sight techniques such as atomic layer deposition (ALD). Alternatively, multiple different metal fluorides may be deposited sequentially and then interdiffused to form a composite metal fluoride coating. The coating is resistant to plasma chemistries used in semiconductor processing, such as bromine-containing plasmas having bromine ions and bromine radicals. Without being bound to a particular theory, it is believed that the incorporation of a second metal (M2) or a third, fourth, etc. (i.e., M3, M4, etc.) into the coating reduces voids in the material, thereby reducing the diffusion of fluorine (e.g., from a CF4 plasma) into the coating.

[0011] According to embodiments described herein, the coating comprises multiple metals (e.g., RE) co-deposited in a single adsorbed layer. w M y F z , Y x Zr y F z or RE w Y x Zr y F z). In some embodiments, the at least one metal is a rare earth metal. The at least one rare earth metal may be selected from yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, or dysprosium. In certain embodiments, the coating may be formed from tantalum and at least one additional metal. 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), in embodiments. According to embodiments, the composite metal-containing fluoride coating 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 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.

[0012] In certain embodiments, the coating comprises at least one rare earth metal (e.g., as a first metal) and at least one additional (e.g., second) metal (e.g., a rare earth metal) co-deposited in a single adsorbed layer. w M y F z , Y x Zr y F z or RE w Y x Zr y F z), the at least one rare earth metal may be selected from yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, 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 embodiments, the rare earth metal-containing fluoride coating may contain about 5 mol% to about 30 mol%, or about 10 mol% to about 25 mol%, or about 15 mol% to about 20 mol% of the at least one 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 the at least one additional metal.

[0013] The coating provides resistance to erosion by plasmas (e.g., fluorine-containing plasmas) used in semiconductor processing and chamber cleaning. Thus, the coating provides good particle and process stability performance during such processing and cleaning. As used herein, the term "erosion-resistant coating" or "plasma-resistant coating" refers to a coating that has a particularly low erosion rate when exposed to certain plasmas, chemicals, and radicals (e.g., fluorine-based plasmas, chemicals and / or radicals, chlorine-based plasmas, chemicals and / or radicals, etc.). The co-deposition method results in a coating that eliminates surface fluorination that can lead to wafer processing drift, achieves a much more uniform coating on the angstrom scale, and improves phase control (e.g., lack of interdiffusion that leaves YF3 and other metal phases in the coating). According to embodiments, the co-deposition method results in a coating having a homogenous mixture of metal and metal, and without being bound to a particular theory, it is believed that voids are eliminated in the co-deposited coating (compared to oxide films), thereby preventing fluorine diffusion into the coating. For example, coatings containing mixtures of Y2O3 and ZrO2 deposited by deposition techniques other than ALD, or by ALD using sequential deposition techniques, may experience one or more phase separations in some locations. This may result in some voids in the Y2O3 phase, which may increase the susceptibility to fluorination. In contrast, coatings containing mixtures of Y2O3 and ZrO2 deposited by codeposition and / or co-injection techniques may experience some phase separations in some locations. x Zr y F z ALD deposition of co-deposition metals (e.g., YF-ZrF solid solutions) can reduce or eliminate phase separation, resulting in a homogenous mixture of Y and Zr. Co-deposition methods also offer the flexibility to adjust the ratio of deposited metals, e.g., by adjusting the number and / or pulse time, temperature, pressure, etc. This flexibility allows for the formation of coatings with specific molar ratios of two or more metals.

[0014] In various embodiments, the composite metal fluoride coating is a bimetallic composition (M1 × M2y F z ), 3rd metal composition (M1 w M2 x M3 y F z ), four metal compositions (M1 v M2 w M3 x M4 y F z ), five metal compositions (M1 u M2 v M3 w M4 x M5 y F z ), 6 metal compositions (M1 t M2 u M3 v M4 w M5 x M6 y F z ), etc. In each complex metal fluoride coating, the variables t, u, v, w, x, y, z may be positive integers or decimal values. Some exemplary values ​​of t, u, v, w, x, y, z may range from about 0.1 to about 10. In some embodiments, the complex metal fluoride coating is a rare earth metal-containing fluoride coating. In various embodiments, the rare earth metal-containing fluoride coating is a rare earth metal-containing fluoride coating. x Zr y F z , Er x Zr y F z , Y w Er x Zr y F z , Y w Er x Hf y F z , Y w Z rx Hf y F z , Er w Z rx Hf y F z , Y v Er w Z rx Hf y F z , Y x Hf y Fz , Er x Hf y F z , Y x Ta y F z , Er x Ta y F z , Y w Er x Ta y F z , Y w Ta x Zr y F z , Y w Ta x Hf y F z , Er w Ta x Zr y F z Er w Ta x Hf y F z and Y v Er w Ta x Hf y F z In one embodiment, the rare earth metal-containing fluoride coating comprises YZrF, which has an atomic ratio of yttrium to zirconium of about 3. In another embodiment, the rare earth metal-containing fluoride coating comprises YZrOF, which has an atomic ratio of yttrium to zirconium of about 4.6. In further embodiments, the rare earth metal-containing fluoride coating comprises La w Y x Zr y F z , Lu w Y x Zr y F z , Sc w Y x Zr y F z , Gd w Y x Zr y F z , Sm w Y x Zr y F z , D.Y. w Y xZr y F z , La w Y x Zr y F z , Lu w Y x Ta y F z , Sc w Y x Ta y F z , Gd w Y x Ta y F z , Sm w Y x Ta y F z , D.Y. w Y x Ta y F z , Er w Y x Hf y F z , La w Y x Hf y F z , Lu w Y x Hf y F z , Sc w Y x Hf y F z , Gd w Y x Hf y F z , Sm w Y x Hf y F z , D.Y. w Y x Hf y F z In some embodiments, the coating may comprise a composition selected from RE w Z rx Al y F z (For example, Y w Z rx Al y F z ). Other complex fluorides may also be used.

[0015] Examples of yttrium-containing fluoride compounds that can form plasma-resistant coatings include YF, Y x Al y F z , Y x Zr y F z , Y x Hf y F z , Y a Z rx Al y F z , Y a Z rx Hf y F z , Y a Hf x Al y F z , Y v Zr w Hf x Al y F z Or Y x Er y F z The yttrium content in the coating may range from about 0.1 mol% to nearly 100 mol%. For yttrium-containing fluorides, the yttrium content may range from about 0.1 mol% to nearly 100 mol% and the fluorine content may range from about 0.1 mol% to nearly 100 mol%.

[0016] Examples of erbium-containing fluoride compounds that can form plasma-resistant coatings include Er2O3, Er x Al y F z (For example, Er3Al5F 12 ), Er x Zr y F z , Er x Hf y F z , Er a Z rx Al y F z , Er a Z rx Hf y F z, Er a Hf x Al y F z , Y x Er y F z and Er a Y x Zr y F z (e.g., single-phase solid solutions of Y2O3, ZrO2, and Er2O3). The erbium content in the plasma resistant coating may range from about 0.1 mol% to nearly 100 mol%. For erbium-containing fluorides, the erbium content may range from about 0.1 mol% to nearly 100 mol%, and the fluorine content may range from about 0.1 mol% to nearly 100 mol%.

[0017] Advantageously, Y2O3 and Er2O3 are miscible. For any combination of Y2O3 and Er2O3, a single-phase solid solution may be formed. For example, a mixture of slightly more than 0 mol% Er2O3 and slightly less than 100 mol% Y2O3 may be combined and co-deposited to form a plasma-resistant coating that is a single-phase solid solution. Additionally, a mixture of slightly more than 0 mol% Er2O3 and slightly less than 100 mol% Y2O3 may be combined to form a plasma-resistant coating that is a single-phase solid solution. Y x Er y F zThe plasma resistant coating may contain from greater than 0 mol% to less than 100 mol% YF3 to greater than 0 mol% to less than 100 mol% ErF3. 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, 50-59 mol% YF3 and 41-50 mol% ErF3, and the like. YF3, 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. x Er y F z A single-phase solid solution of may have a monoclinic cubic state at temperatures below about 2330°C.

[0018] Advantageously, ZrO2 can be combined with YF3 and ErF3 to produce a mixture of zirconium, YF3 and ErF3 (e.g., Er a Y x Zr y F z ) may form a single-phase solid solution containing Y a Er x Zr y F z The solid solutions of Y may have cubic, hexagonal, tetragonal and / or cubic fluorite structures. a Er x Zr y F zThe solid solution may include from greater than 0 mol% to 60 mol% Zr, from greater than 0 mol% to 99 mol% ErF3, and from greater than 0 mol% to 99 mol% YF3. Some notable amounts of ZrO2 that may 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 may be used include 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, and 90 mol%.

[0019] Y a Z rx Al y F z The plasma resistant coating may include greater than 0 mol% to 60 mol% Zr, greater than 0 mol% to 99 mol% YF3, and greater than 0 mol% to 60 mol% Al. Some notable amounts of ZrO2 that may 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 may 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 may be used include 2 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, and 60 mol%. In one embodiment, Y a Z rx Al y F z The plasma resistant coating of this embodiment contains 42 mol % YF3, 40 mol % Zr and 18 mol % Al and has a lamellar structure. a Z rx Al y F z The plasma-resistant coating contains 63 mol % YF3, 10 mol % Zr and 27 mol % ErF3 and has a lamellar structure.

[0020] In embodiments, the rare earth metal-containing fluoride coating includes 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 further embodiments, the composite metal fluoride coating includes about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol% 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 various embodiments, the composite metal fluoride coating comprises about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol% yttrium, and about 1 mol% to about 40 mol%, or about 1 mol% to about 20 mol% zirconium, hafnium, or tantalum, or about 10 mol% to about 25 mol% yttrium, and about 5 mol% to about 17 mol% Zr, Hf, or Ta, or about 15 mol% to about 21.5 mol% yttrium, and about 10 mol% to about 14.5 mol% Zr, Hf, or Ta. In various embodiments, the coating comprises a mixture of Y and Er, where the combined mol% of Y and Er is about 5 mol% to about 30 mol% (e.g., 1-29 mol% Y and 1-29 mol% Er). The coating may further comprise about 1 mol% to about 20 mol% zirconium, hafnium, or tantalum.

[0021] In embodiments, the thickness of the composite metal fluoride coating or 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 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 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 gas holes) with a substantially uniform thickness. In one embodiment, the rare earth metal-containing fluoride coating conformally coats an underlying surface, the surface being coated with a uniform thickness (including the coated surface features), the uniformity being less than about + / - 20% thickness variation, + / - 10% thickness variation, + / - 5% thickness variation, or even less thickness variation.

[0022] In further embodiments, the composite metal fluoride coating or the rare earth metal-containing fluoride coating does not include separate layers including a fluoride of a first metal and a fluoride of a second metal (or a third metal, a fourth metal, etc.). In particular, in certain embodiments, the composite metal fluoride coating or the rare earth metal-containing fluoride coating may not be formed by sequential atomic layer deposition cycles of multiple metals. Rather, in embodiments, for example, the first metal and the second metal may be co-deposited on the article or the body of the article. As a result, the rare earth metal-containing fluoride coating may avoid mechanical separation between the layer containing the first metal and the layer containing the additional second metal. The composite metal fluoride coating or the rare earth metal-containing fluoride coating may include a homogenous mixture of the first metal (e.g., a rare earth metal) and the second metal without performing annealing. It may also not include a concentration gradient of the first metal or the second metal resulting from incomplete interdiffusion of materials within the coating.

[0023] In alternative embodiments, sequential atomic layer deposition (ALD) processes are performed. For sequential ALD processes, a first metal precursor may be adsorbed on a surface, and a fluorine-based reactant may react with the adsorbed first metal (e.g., rare earth metal, tantalum, etc.) to form a first metal fluoride layer. A second metal precursor may then be adsorbed on the first metal fluoride layer, and a fluorine-based reactant may react with the adsorbed second metal to form a second metal (e.g., zirconium, aluminum, hafnium, tantalum, silicon, etc.) fluoride layer. Metals from the first and second metal fluoride layers may then interdiffuse into each other. When a coating is deposited using sequential deposition cycles of a first metal and a second metal, annealing may be performed to affect interdiffusion between the layers. Such annealing can result in a concentration gradient of the metallic phase (e.g., YF3 and ZrO2 to YZrF) from the surface to the underlying article, and such coatings lack homogeneity throughout. The co-deposition coatings described herein form a homogeneous mixture of the first and second metals. Generally, annealing is not performed to effect interdiffusion.

[0024] According to embodiments, the composite metal fluoride coating or the rare earth metal-containing fluoride coating may be formed from a multi-layer stack having alternating layers of materials. In one embodiment, a buffer layer may be deposited on the surface of the article or the body of the article, and the composite metal fluoride coating or the rare earth metal-containing fluoride coating may be deposited on the buffer layer. The buffer layer may include, but is not limited to, aluminum oxide (e.g., Al2O3), silicon oxide (e.g., SiO2), aluminum nitride, or combinations thereof. In other embodiments, a first metal (e.g., yttrium, erbium, tantalum, etc.) and a second metal (e.g., rare earth metal, zirconium, aluminum, hafnium, tantalum, etc.) may be co-deposited on the article (or on the buffer layer, if used) using ALD to form a first codeposition layer. For example, a second layer of material, such as a metal fluoride, a rare earth metal fluoride, or a co-deposited rare earth metal zirconium oxide, may be deposited or co-deposited on the first codeposition layer. Each deposition or co-deposition cycle may be repeated as many times as desired to achieve a target composition and / or thickness of the final multi-layer coating.

[0025] The thickness of each layer in the multi-layer composite metal fluoride coating or rare earth metal-containing fluoride coating may be about 10 nm to about 1.5 μm. In embodiments, the buffer layer (e.g., amorphous Al2O3) may have a thickness of about 1.0 μm and the rare earth metal-containing fluoride layer may 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 may be 200:1 to 1:200, or about 100:1 to 1:100, or about 50:1 to about 1:50. The thickness ratio may be selected according to the particular chamber application.

[0026] Complex metal fluoride or rare earth metal-containing fluoride coatings may be grown or co-deposited using ALD with precursors for the co-deposition of a first metal-containing fluoride layer comprising 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 complex metal fluoride coating or rare earth metal-containing fluoride layer has a polycrystalline structure.

[0027] The buffer layer may include amorphous aluminum oxide or similar material. The buffer layer may provide robust mechanical properties, increase dielectric strength, provide better adhesion of the composite metal fluoride or rare earth metal-containing fluoride coating to components (e.g., formed from Al6061, Al6063, or ceramics), and prevent 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 from about 200° C. to about 350° C., or from about 250° C. to about 300° C. Such metal articles have a thermal expansion coefficient significantly greater than that of the composite metal fluoride or rare earth metal-containing fluoride coating. The detrimental effects of a thermal expansion coefficient mismatch between the article and the composite metal-containing fluoride coating may be addressed by first providing a buffer layer 209. Since ALD is used for deposition, the inner surface of high aspect ratio features such as gas supply holes in a showerhead or gas supply line can be coated, thus protecting the entire component from exposure to corrosive environments. In some embodiments, the buffer layer may include a material having a thermal expansion coefficient between the value of the thermal expansion coefficient of the article and the value of the thermal expansion coefficient of the composite metal-containing fluoride coating. Furthermore, the buffer layer may act as a barrier to prevent migration of metal contaminants (e.g., trace metals such as Mg, Cu, etc.) 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 may increase the thermal resistance of the composite metal fluoride coating as a whole. This is due to the relaxation of high stresses concentrated in some areas of the composite metal fluoride / Al6061 interface.

[0028] Also described herein are articles having composite metal fluoride coatings or rare earth metal-containing fluoride coatings as described above. In embodiments, the article may be any type of component for use in a semiconductor processing chamber, examples of which include, but are not limited to, electrostatic chucks, gas distribution plates, chamber walls, chamber liners, doors, rings, showerheads, nozzles, plasma generating units, radio frequency electrodes, electrode housings, diffusers, and gas lines. The article may contain materials including, but are not limited to, aluminum (Al), silicon (Si), copper (Cu), and magnesium (Mg). In embodiments, the article may be a material such as aluminum oxide (Al). x O y ), silicon oxide (Si x O y The article may comprise a ceramic material including, but not limited to, aluminum nitride (AlN) or silicon carbide (SiC) materials. In some embodiments, the article or the body of the article may be an aluminum Al6061, Al6063 material. In some embodiments, the surface of the article or 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.

[0029] The composite metal coatings may be very dense with approximately 0% porosity (e.g., in embodiments, the rare earth metal-containing fluoride coating may be void of porosity). The composite metal fluoride coatings may be resistant to corrosion and erosion by plasma etch chemistries, such as CCl4 / CHF3 plasma etch chemistries, HCl3Si etch chemistries, and NF3-containing etch chemistries. Additionally, the composite metal fluoride coatings described herein with buffer layers may be resistant to cracking and delamination at temperatures up to approximately 350°C. For example, the rare earth metal-containing fluoride coatings and chamber components with buffer layers described herein may be used in processes that include heating to temperatures of approximately 200°C. The chamber components may be thermally cycled between room temperature and temperatures of approximately 200°C without cracking or delaminating the rare earth metal-containing fluoride coating.

[0030] In some embodiments, the article or body of the article includes at least one feature (e.g., a gas hole) that may have an aspect ratio of length to diameter (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. The composite metal fluoride coating or rare earth metal-containing fluoride coating may conformally cover the surfaces of the article body and the features. In some embodiments, the article or body of the article includes features (e.g., channels) that have an aspect ratio of depth to width (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. The composite metal fluoride coating or rare earth metal-containing fluoride coating may conformally cover the surfaces of the body of the article and the features.

[0031] In various embodiments, high aspect ratio features of an article (as described above) may be effectively coated with a composite metal fluoride coating or rare earth metal-containing fluoride coating as described herein. The composite metal fluoride coating may have one phase, two phases, or more than two phases. The composite metal fluoride coating or rare earth metal-containing fluoride coating is conformal within the high aspect ratio features and has a substantially uniform thickness as described above.

[0032] 1 is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components coated with a complex metal fluoride or rare earth metal-containing fluoride coating according to embodiments described herein. The substrate of at least some of the chamber components is, for example, Al. x O y , AlN, Al6061 or Al6063, for example, Si x O y , Si, such as SiO2 or SiC, copper (Cu), magnesium (Mg), titanium (Ti), and stainless steel (SST). The process chamber 100 may be used for processes in which a corrosive plasma environment (e.g., fluorine-containing plasma) having plasma processing conditions occurs. For example, the process chamber 100 may be a chamber for a plasma etcher or plasma etch reactor, a plasma cleaner, a plasma 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 high aspect ratios as discussed above. Some exemplary chamber components include a substrate support assembly, an electrostatic chuck, a ring (e.g., a process kit ring or a single ring), a chamber wall, a base, a gas distribution plate, a showerhead, a gas line, a nozzle, a lid, a liner, a liner kit, a shield, a plasma screen, a flow balancer, a cooling base, a chamber viewport, a chamber lid, etc.

[0033] In one embodiment, the processing chamber 100 comprises a chamber body 102 and a showerhead 130 that surround an interior volume 106. The showerhead 130 may comprise a showerhead base and a showerhead gas distribution plate. Alternatively, the showerhead 130 may be replaced by a lid and a nozzle in some embodiments, or by a plurality of fan-shaped showerhead sections and a plasma generating unit in other embodiments. The chamber body 102 may be fabricated from aluminum, stainless steel, or other suitable materials. The chamber body 102 generally comprises a sidewall 108 and a bottom 110. An outer liner 116 may be disposed adjacent the sidewall 108 to protect the chamber body 102. Any of the showerhead 130 (or lid and / or nozzle), the sidewall 108, and / or the bottom 110 may comprise a rare earth metal-containing fluoride coating.

[0034] An exhaust port 126 may be defined in the chamber body 102 and may connect the interior volume 106 to a pumping system 128. The pumping system 128 may include one or more pumps and a throttle valve and may be utilized to evacuate and regulate the pressure in the interior volume 106 of the processing chamber 100.

[0035] The showerhead 130 may be supported by the sidewall 108 of the chamber body 102. The showerhead 130 (or lid) may be open to allow access to the interior volume 106 of the processing chamber 100, or closed to seal the processing chamber 100. A gas panel 158 may be connected to the processing chamber 100 to supply process and / or cleaning gases to the interior volume 106 through the showerhead 130 or the lid and nozzles. The showerhead 130 may be used in processing chambers used for dielectric etching (etching dielectric materials). The showerhead 130 may include a gas distribution plate (GDP) having a plurality of gas supply holes 132 therethrough. The showerhead 130 may include a GDP bonded to an aluminum base or an anodized aluminum base. The GDP may be made of Si or SiC, or may be made of Y2O3, Al2O3, Y3Al5O 12 It may also be a ceramic such as (YAG).

[0036] For processing chambers used for conductor etching (etching conductive materials), a lid may be used instead of a showerhead. The lid may include a central nozzle that fits into a central hole in the lid. The lid may be a ceramic such as Al2O3, Y2O3, YAG, or a ceramic compound including Y4Al2O9 and a solid solution of Y2O3-ZrO2. The nozzle may also be a ceramic such as Y2O3, YAG, or a ceramic compound including Y4Al2O9 and a solid solution of Y2O3-ZrO2.

[0037] Examples of process gases that may be used to process a substrate in the process chamber 100 include halogen-containing gases (such as C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, and SiF4, among others), as well as gases such as O2 or N2O. Examples of carrier and purge gases include N2, He, Ar, and other gases that are inert (e.g., non-reactive) with respect to the process gases.

[0038] The substrate support assembly 148 is disposed within the interior volume 106 of the processing chamber 100, below the showerhead 130 or lid. The substrate support assembly 148 includes a support 136 that holds a substrate 144 during processing. The support 136 is attached to the end of a shaft (not shown) that is coupled to the chamber body 102 via a flange 164. The substrate support assembly 148 may include, for example, a heater, an electrostatic chuck, a susceptor, a vacuum chuck, or other substrate support assembly components.

[0039] FIG 2A illustrates one embodiment of a co-deposition process 200 by an ALD technique, in which a first metal-rich fluoride coating is grown or deposited on an article. FIG 2B illustrates another embodiment of a co-deposition process by an ALD technique described herein, in which a second metal-rich rare earth metal fluoride coating is grown or deposited on an article. FIG 2C illustrates another embodiment of a co-deposition process by an ALD technique described herein. FIG 2D illustrates another embodiment of a co-deposition process utilizing co-injection of a rare earth metal with another metal by an ALD technique described herein.

[0040] In the case of an ALD codeposition process, both the adsorption of at least two precursors to the surface and the reaction of the adsorbed precursors with the reactants may be referred to as a "half-reaction." During the first half-reaction, a first precursor (or a mixture of precursors) may be pulsed to the surface of the article 205 for a sufficient time to allow the precursor to be partially (or completely) adsorbed on the surface. This adsorption is self-limiting because the precursor adsorbs to many available sites on the surface, forming a partial adlayer of the first metal on the surface. Sites already adsorbed with the first metal of the precursor are unavailable for further adsorption with a subsequent precursor. Alternatively, some sites adsorbed with the first metal of the first precursor may be replaced with a second metal of the second precursor that is adsorbed on the site. To complete the first half-reaction, a second precursor may be pulsed to the surface of the article 205 for a sufficient time to allow the second metal of the second precursor to be adsorbed (partially or completely) on available sites on the surface (or to replace the first metal of the first precursor) to form a codeposited adlayer on the surface.

[0041] A co-deposition cycle of an ALD process begins with a first precursor (i.e., chemical A, or a mixture of chemicals A and B) flooding the ALD chamber and being partially (or completely) adsorbed on the surface of the article (including the surface of holes and features in the article). A second precursor (i.e., chemical B) may be flooded into the ALD chamber and adsorbed on the remaining exposed surfaces of the article. The excess precursor may then be flushed / purged (i.e., with an inert gas) from the ALD chamber, after which a reactant (i.e., chemical R) may be introduced into the ALD chamber and subsequently flushed away. Alternatively or additionally, the chamber may be purged during the first half-reaction between the deposition of the first precursor and the deposition of the second precursor. In the case of ALD, the final thickness of the material depends on the number of reaction cycles that are performed, since each reaction cycle grows a layer of a particular thickness, such as an atomic layer or a fraction of an atomic layer.

[0042] Apart from being a conformal process, ALD is also a uniform process and can form very thin films, for example having a thickness of about 3 nm or more. All exposed surfaces of the article have the same or nearly the same amount of material deposited on them. ALD techniques can deposit thin layers of material at relatively low temperatures (e.g., about 25° C. to about 350° C.), so they do not damage or deform any material of the component. Additionally, ALD techniques can also deposit layers of material within complex features (e.g., high aspect ratio features) of the component. Furthermore, ALD techniques generally produce relatively thin (i.e., 1 μm or less) coatings that are porosity-free (i.e., pinhole-free). This can eliminate crack formation during deposition.

[0043] Composite metal fluoride coatings or rare earth metal-containing fluoride coatings may be grown or deposited using ALD with a first metal-containing precursor (e.g., a rare earth metal-containing precursor, a tantalum-containing precursor, etc.), a second metal-containing precursor, and a fluorine-containing reactant (e.g., hydrogen fluoride or other fluorine-containing material). In some embodiments, the first metal-containing precursor may include yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, dysprosium, or tantalum.

[0044] In embodiments, the first metal-containing precursor and the second metal-containing precursor (e.g., the third metal-containing precursor and the fourth metal-containing precursor in the case of a composite metal coating) are independently selected from yttrium-containing precursors, such as tris(N,N-bis(trimethylsilyl)amido)yttrium(III), yttrium(III) butoxide, or yttrium cyclopentadienyl compounds, such as tris(cyclopentadienyl)yttrium (CpY), tris(methylcyclopentadienyl)yttrium ((CpMe)Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, or tris(ethylcyclopentadienyl)yttrium. Other yttrium-containing precursors that may be used include yttrium-containing amide-based compounds (e.g., tris(N,N'-diisopropylformamidinato)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dionato)yttrium, or tris(bis(trimethylsilyl)amido)lanthanum), and yttrium-containing β-diketonate-based compounds. In some embodiments, the rare earth metal-containing fluoride precursor may include erbium. Erbium-containing precursors include, but are not limited to, erbium-containing cyclopentadienyl compounds, erbium-containing amide-based compounds, and erbium-containing β-diketonate-based compounds. Examples of erbium-containing precursors for ALD include tris-methylcyclopentadienyl erbium(III) (Er(MeCp)3), erbium borane amide (Er(BA)3), Er(TMHD)3, erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and tris(butylcyclopentadienyl)erbium(III). Zirconium-containing precursors can include, but are not limited to, zirconium-containing cyclopentadienyl compounds, zirconium-containing amide-based compounds, and zirconium-containing β-diketonate-based compounds.Examples of zirconium-containing precursors for ALD include zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, tetrakis(diethylamido)zirconium(IV), tetrakis(dimethylamido)zirconium(IV), tetrakis(ethylmethylamido)zirconium(IV), or zirconium cyclopentadienyl compounds. Examples of zirconium-containing precursors include tetrakis(dimethylamido)zirconium, tetrakis(diethylamido)zirconium, tetrakis(N,N'-dimethylformamidinato)zirconium, tetra(ethylmethylamido)hafnium, pentakis(dimethylamido)tantalum, and tris(2,2,6,6-tetramethyl-heptane-3,5-dionato)erbium.

[0045] In some embodiments, the first metal-containing precursor and the second metal-containing precursor may be independently selected from cyclopentadienyl-based precursors, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, amidinate-based precursors, tris(N,N'-diisopropylformamidinate)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dionate)yttrium, tris(bis(trimethylsilyl)amido)lanthanum), amide-based precursors, and β-diketonate-based precursors.

[0046] In some embodiments, a mixture of two precursors is introduced together (i.e., co-injected), where the mixture includes a first proportion of a first metal-containing precursor and a second proportion of a second metal-containing precursor. For example, the mixture of precursors may include about 1 wt% to about 90 wt%, or about 5 wt% to about 80 wt%, or about 20 wt% to about 60 wt% of the first metal-containing precursor 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 the second metal-containing precursor. The mixture may have a ratio of first metal (e.g., yttrium, tantalum, etc.)-containing precursor to the second metal-containing precursor that may be suitable to form a desired type of fluoride material. The atomic ratio of the first metal (e.g., yttrium, tantalum, etc.) containing precursor to the second metal containing precursor may be from about 200:1 to about 1:200, or from about 100:1 to about 1:100, or from about 50:1 to about 1:50, or from about 25:1 to about 1:25, or from about 10:1 to about 1:10, or from about 5:1 to about 1:5.

[0047] In one embodiment, a composite metal fluoride coating or a rare earth metal-containing fluoride coating is codeposited on a surface of an article using atomic layer deposition. Co-depositing a rare earth metal-containing fluoride coating may include contacting the surface with a first metal-containing precursor (e.g., a rare earth metal-containing precursor) for a first period of time to form a partial metal adsorbed layer. The first metal-containing precursor 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. The partial metal adsorbed layer is then contacted with a second metal-containing precursor different from the first metal-containing precursor for a second period of time to form a co-adsorbed layer comprising the first metal and the second metal. The second metal-containing precursor 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. The co-adsorbed layer is then contacted with a fluorine source reactant to form a rare earth metal-containing fluoride coating. In certain embodiments, the coating may include 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. Additionally, the rare earth metal-containing fluoride coating may include a homogeneous mixture of the first metal and the second metal.

[0048] Referring to FIG. 2A, a first metal (M1)-second metal (M2) co-deposition method 200 for depositing a rare earth metal-containing fluoride coating on an article 205 is described. The article 205 may be introduced to a first metal-containing precursor 210 (e.g., a rare earth metal-containing precursor) for a period of time until the surface of the article 205 is partially adsorbed with the first metal-containing precursor 210, forming a partial metal adsorbed layer 215. The article 205 may then be introduced to a second metal-containing precursor 220 for a period of time until the remaining exposed surfaces of the article are adsorbed with the second metal-containing precursor 220, forming a co-adsorbed layer 225 comprising the first metal and the second metal. The first metal-containing precursor exposed to an uncoated surface (i.e., with all available adsorption sites) may be more efficiently adsorbed to the surface than the second metal-containing precursor exposed to a partially adsorbed surface. Thus, the co-adsorbed layer 225 is rich in the first metal. That is, the article 205 may include a higher atomic concentration of the first metal than the second metal. The article 205 is then introduced into a reactant 230 for a period of time to react with the co-adsorbed layer 225 to form a solid fluoride layer (e.g., Y x Zr y F z or YF3-Zr solid solution) may be grown. The precursor may be any of the precursors mentioned above. The co-deposition of the first and second metals with the introduction of reactants is called M1-M2 co-deposition cycle. The M1-M2 co-deposition cycle may be repeated m times to eventually achieve a coating of the desired thickness.

[0049] Referring to FIG. 2B, an M2-M1 co-deposition method 202 for depositing a rare earth metal-containing fluoride coating on an article 205 is described. The article 205 may be introduced to a second metal-containing precursor 220 for a period of time until the surface of the article 205 is partially adsorbed with the second metal-containing precursor 220 to form a partial second metal adsorbed layer 216. The article 205 may then be introduced to a first metal-containing precursor 210 for a period of time until the remaining exposed surface of the article is adsorbed with the first metal-containing precursor 220 to form a co-adsorbed layer 226. The co-adsorbed layer 226 may be rich in the second metal. The article 205 may then be introduced to a first reactant 230 to react with the co-adsorbed layer 225 to grow a solid layer of a rare earth metal-containing fluoride coating 236 (e.g., YZrF) according to embodiments described herein. The precursor may be any of the precursors described above. The co-deposition of the second metal and the first metal with the introduction of the reactant is called the M2-M1 co-deposition cycle. The M2-M1 co-deposition cycle can be repeated n times until a coating of a desired thickness is achieved.

[0050] Each layer of the rare earth metal-containing fluoride coating 235, 236 may be uniform, continuous, and conformal. In embodiments, the rare earth metal-containing fluoride coating 235, 236 may be porosity-free (e.g., zero porosity) or may have near-zero porosity (e.g., 0% to 0.01%). In some embodiments, after one ALD deposition cycle, each layer of the rare earth metal-containing fluoride coating 235, 236 may have a thickness of less than one atomic layer to a few atoms. Some organometallic precursor molecules are large. After reacting with reactants, the large organic ligands are gone, leaving much smaller metal atoms. One complete ALD cycle (e.g., including introduction of precursors followed by introduction of reactants) may result in less than one atomic layer. In the co-deposition method 200, the co-deposition cycle may be repeated m times to reach a target thickness of the coating 235. Similarly, the co-deposition method 202 may repeat the co-deposition cycle n times to reach a target thickness of the coating 236. m and n may be positive integer values.

[0051] The relative concentrations of the first metal (e.g., rare earth metal, Ta, etc.) and the second metal may be controlled by the type of precursor used, the temperature of the ALD chamber during adsorption of the precursor on the surface of the article, the time a particular precursor remains in the ALD chamber, and the partial pressure of the precursor. For example, the use of a tris(N,N-bis(trimethylsilyl)amido)yttrium(III) precursor may result in a lower atomic % of yttria than the use of a yttrium cyclopentadienyl precursor.

[0052] In some embodiments, three or more metal precursors are adsorbed onto the surface of the article 205 in one codeposition cycle. For example, the codeposition cycle may include adsorption of an yttrium precursor onto the surface, followed by adsorption of a zirconium precursor onto the surface, followed by adsorption of a hafnium precursor onto the surface. Each subsequent precursor may have a smaller amount of the associated metal adsorbed onto the surface. Thus, the order in which each precursor is adsorbed onto the surface to form a coadsorbed layer may be selected to achieve a target ratio of two or more different metals. Additional exemplary co-deposition methods that may be performed include M1-M2-M3 co-deposition methods, in which a first metal (M1) is adsorbed onto the surface, followed by a second metal (M2) is adsorbed onto the surface, followed by a third metal (M3) is adsorbed onto the surface, followed by introduction of a fluorine source reactant. Another exemplary co-deposition method that may be performed includes M2-M1-M3 co-deposition methods. In this codeposition method, the second metal (M2) is adsorbed on the surface, followed by the first metal (M1), followed by the third metal (M3), followed by the introduction of the fluorine source reactant. Another exemplary codeposition method that can be performed includes the M3-M1-M2 codeposition method, in which the third metal (M3) is adsorbed on the surface, followed by the first metal (M1), followed by the second metal (M2), followed by the introduction of the fluorine source reactant. Another exemplary codeposition method that can be performed includes the M3-M2-M1 codeposition method, in which the third metal (M3) is adsorbed on the surface, followed by the second metal (M2), followed by the first metal (M1), followed by the introduction of the fluorine source reactant. More precursors may be adsorbed on the surface to create more complex complex metal fluorides. The more metals used, the more permutations possible.

[0053] Referring to FIG. 2C, in some embodiments, a multilayer stack may be deposited on the article 205 using a co-deposition ALD process 203. An optional buffer layer 209, as described above, may be deposited on the article 205. In an example where the buffer layer 209 is alumina (Al2O3), in a first half-reaction, the article 205 (e.g., an Al6061 substrate) may be introduced to an aluminum-containing precursor (e.g., trimethylaluminum (TMA)) (not shown) for a period of time until all reactive sites on the surface are exhausted. The remaining aluminum-containing precursor may be flushed out of the reaction chamber, and then H2O or other oxygen source reactant (not shown) may be injected into the reactor to initiate the second half-reaction. After the H2O molecules react with the Al-containing adlayer produced by the first half-reaction, a buffer layer 209 of Al2O3 may be formed.

[0054] The buffer layer 209 may be uniform, continuous, and conformal. In embodiments, the buffer layer 209 may be porosity-free (e.g., zero porosity) or may have near-zero porosity (e.g., 0% to 0.01%). Multiple full ALD deposition cycles may be performed to deposit the buffer layer 209 with a target thickness. Each full cycle (e.g., including introduction of an aluminum-containing precursor, flushing away, introduction of HO reactant, and flushing away again) further increases the thickness by a fraction of an atom to a few atoms. In embodiments, the thickness of the buffer layer 209 may be 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.

[0055] 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 with the optional buffer layer 209. The buffer layer 209, rather than the surface of the article or the bulk of the article, becomes partially adsorbed with the first metal-containing precursor 210 or the second precursor 220 to form a partially adsorbed layer 215. The precursors are then flushed out of the ALD chamber using 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 with the optional buffer layer 209 and the M1-M2 coating layer 235.

[0056] The rare earth metal-containing fluoride layer resulting from the M1-M2 codeposition cycle may include a first percentage of the first metal and a second percentage of the second metal. The M2-M1 codeposition cycle results in an additional layer including 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, two codeposition cycles may be used to form a multi-layer coating having a buffer layer 209, an M1-M2 layer 235, and an M2-M1 layer 236. As is conventional, either or both of the codeposition cycles may be repeated m or n times, where m and n are each integers greater than zero and represent the number of codeposition 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. Co-deposition cycles may be performed sequentially and / or alternatingly to build up the coating. The alternating layers 235 and 236 described with respect to FIG. 2C were formed by co-deposition cycles in a 1:1 manner, where there is one layer of M1-M2 coating layers for every one layer of M2-M1 coating layers. However, in other embodiments, there may be other patterns. For example, two M1-M2 co-deposition cycles may be followed by one M2-M1 co-deposition cycle (2:1), and then the sequence may be repeated once more.

[0057] According to various embodiments, the M1-M2 codeposition cycles may be expressed as m*(M1+M2+F), where m is an integer greater than zero and represents the number of M1-M2 codeposition cycles, M1 represents the amount (mol%) of the deposited first metal (e.g., yttrium), M2 represents the amount (mol%) of the deposited second metal, and F represents the amount (mol%) of the deposited fluorine. The M2-M1 codeposition cycles may be expressed as n*(M2+M1+F), where n is an integer greater than zero and represents the number of M2-M1 codeposition cycles, M2 represents the amount (mol%) of the deposited second metal, M1 represents the amount (mol%) of the deposited first metal (e.g., yttrium), and F represents the amount (mol%) of the deposited fluorine.

[0058] As shown in FIG. 2C, the target composition of the rare earth metal-containing fluoride layer may be achieved using the following formula: K*[m*(M1+M2+O)+n*(M2+M1+O)] where K is an integer greater than zero and represents the number of supercycles performed to achieve a target thickness. By adjusting K, m, and n, a coating of a desired composition (e.g., a desired ratio of a first metal to a second metal) can be achieved regardless of the precursor chemistry.

[0059] FIG. 2C shows the co-deposition with two different metals. However, in further embodiments, co-deposition may be performed with three or more metals, as described above. When using three or more metals, there are three or more sequences of co-deposition that may be performed. For example, in the case of co-deposition of three metals, the following co-deposition methods may be mixed to achieve a coating of 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. Thus, the following formula may be used to achieve the target composition: 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. The number of moles of M1, M2, and M3 in each co-deposition process may be determined by experiment. Similarly, in the case of four metal co-deposition, the following co-deposition processes may be mixed to achieve a coating of 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+M4+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+M2+M1+F. Thus, the following formula may be used to achieve the target composition: 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+M1+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+F) +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+M2+M1+F)] where a through x are non-negative integers.

[0060] The injection time ratio may be expressed as the ratio of the first metal (e.g., yttrium) precursor exposure time to the second metal precursor exposure time. It should be noted that the injection time and time ratio of the precursor materials are controllable. On the other hand, the attachment of the precursor to the surface, the attachment coefficient and chemical interaction may not be controllable. The pressure and temperature of the ALD chamber also affect the adsorption of the precursor to the surface. For example, the reactivity of zirconium is slightly higher than yttrium, so a coating obtained using a mixture of zirconium and yttrium may be rich in zirconium. Under equilibrium conditions in the chamber, the injection time may be adjusted to achieve the desired composition. At equilibrium, the composition is limited by the chemical reactivity of the precursors and the attachment coefficient of the materials. In some embodiments, there is no purge between the introduction of the first metal-containing precursor and the second metal-containing precursor, as this may affect the adsorption of the materials to the article.

[0061] In embodiments, a ratio of the first number of M1-M2 co-deposition cycles to the second number of M2-M1 co-deposition cycles may be selected to result in a first target mol % of the first metal and a second target mol % of the second metal. Additionally, multiple deposition supercycles may be performed, where each deposition supercycle includes performing a first number of M1-M2 co-deposition cycles and performing a second number of M2-M1 deposition cycles.

[0062] The ratio of the thickness of the first metal-containing fluoride layer to the thickness of the buffer layer may be 200:1 to 1:200, or about 100:1 to 1:100, or about 50:1 to about 1:50. A higher ratio of the thickness of the first metal-containing fluoride layer to the thickness of the buffer layer (e.g., 200:1, 100:1, 50:1, 20:1, 10:1, 5:1, 2:1, etc.) may provide better corrosion and erosion resistance. On the other hand, a lower ratio of the thickness of the first metal-containing fluoride layer to the thickness of the buffer layer (e.g., 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, 1:200) may provide better thermal resistance (e.g., improved resistance to cracking and / or delamination caused by thermal cycling). The thickness ratio may be selected according to the particular chamber application. In one embodiment, for a capacitively coupled plasma environment with a high sputter rate, a 1 μm top layer may be deposited on a 50 nm buffer Al2O3 layer. For a high temperature chemical or radical environment without vigorous ion bombardment, a 100 nm top layer with a 500 nm bottom layer may be optimal.

[0063] Referring to FIG. 2D, an article 205 may be inserted into an ALD chamber. In this embodiment, the co-deposition process includes simultaneously co-injecting at least two precursors onto the surface of the article. The article 205 may be introduced into a mixture of precursors 210, 220 for a period of time until the surface of the article or the body of the article is fully adsorbed with the mixture of precursors 210, 220 to form a co-adsorbed layer 227. A mixture of two precursors A and B (e.g., yttrium-containing precursors and other rare earth metal fluoride precursors) may be co-injected into the chamber in any number of ratios 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 atomic ratios (mol%) relative to 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 further embodiments, at least four precursors are used. The article 205 having the co-adsorbed layer 227 may then be introduced to reactant 230 to react with the co-adsorbed layer 227 and grow a solid rare earth metal-containing fluoride coating 235. As shown, the co-injection co-deposition of the rare earth metal-containing coating 235 may be repeated m times to achieve a desired coating thickness, where m is an integer value greater than 1.

[0064] ALD processes may be performed at various temperatures depending on the type of process. The optimal temperature range for a particular ALD process is called the "ALD temperature window." Temperatures below the ALD temperature window may result in low growth rates and non-ALD type deposition. Temperatures above the ALD temperature window may result in reactions occurring via chemical vapor deposition (CVD) mechanisms. The ALD temperature window may range 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.

[0065] ALD processing allows for conformal rare earth metal-containing fluoride coatings with uniform thickness on articles and surfaces with complex geometries, high aspect ratio holes (e.g., pores), and three-dimensional structures. By allowing sufficient exposure time for each precursor to the surface, the precursors can distribute and react completely across the surface (including all of the complex three-dimensional features). The exposure time utilized to obtain conformal ALD on high aspect ratio structures is proportional to the square of the aspect ratio and can be predicted using modeling techniques. Furthermore, ALD techniques are advantageous over other commonly used coating techniques because they allow for the synthesis of materials with specific compositions or formulations on demand in situ, without the need for lengthy and difficult fabrication of raw materials (e.g., powder feedstocks and sintered targets).

[0066] Another possible ALD deposition technique involves the sequential deposition of multiple different metal fluoride layers followed by interdiffusion between the layers. This involves introducing a first precursor for a first metal and then a first reactant to form a first metal fluoride layer. A second precursor for a second metal may then be introduced, followed by the first reactant or the second reactant to form a second metal fluoride layer. An annealing operation may then be performed in some embodiments.

[0067] In some embodiments, two or more of the above-mentioned ALD deposition techniques may be combined to produce a homogenous metal fluoride coating. For example, codeposition may be combined with co-injection, codeposition may be combined with sequential deposition, and / or co-injection may be combined with sequential deposition. In one example, a mixture of yttrium and erbium precursors may be injected into the ALD chamber to adsorb yttrium and erbium on the surface of the article. A mixture of zirconium and hafnium precursors may then be injected into the ALD chamber to further adsorb zirconium and hafnium on the surface. A fluorine source reactant may then be injected into the ALD chamber to adsorb Y. v Er w Z rx Hfy F z A coating may be formed.

[0068] 3A illustrates a method 300 for forming a rare earth metal-containing fluoride coating by a codeposition ALD process. Method 300 may be used to coat any of the articles described herein. Method 300 may optionally begin with selecting a precursor for forming the coating. The selection of the composition and the method of formation may be performed by persons of the same organization or by persons of multiple organizations.

[0069] The method 300 may optionally include cleaning the article with an acidic solution at block 305. In one embodiment, the article is immersed in a bath of the acidic solution. In embodiments, the acidic solution may be a hydrofluoric acid (HF) solution, a hydrochloric acid (HCl) solution, a nitric acid (HNO3) solution, or a combination thereof. The acidic solution may remove surface contaminants from the article and / or remove oxides from the surface of the article. Cleaning the article with an acidic solution may improve the quality of a coating deposited using ALD. In one embodiment, an acidic solution containing about 0.1-5.0 vol.% HF is used to clean chamber components made of quartz. In one embodiment, an acidic solution containing about 0.1-20 vol.% HCl is used to clean articles made of Al2O3. In one embodiment, an acidic solution containing about 5-15 vol.% HNO3 is used to clean articles made of aluminum and additional metals.

[0070] At block 310, the article is loaded into an ALD deposition chamber. At block 325, the method 300 optionally includes depositing a buffer layer on the surface of the article or the body of the article using ALD. At block 320, ALD is performed to codeposit a rare earth metal-containing fluoride coating on the article. At least one M1-M2 co-deposition cycle 330 is performed. The M1-M2 co-deposition cycle includes introducing a first metal-containing precursor into the ALD chamber housing the article (with or without a buffer layer) at block 335. The first metal-containing precursor contacts the surface of the article or the body of the article to form a partial metal adsorbed layer. At block 340, a second metal-containing precursor is introduced into the ALD chamber housing the article with the partial metal adsorbed layer. The second metal-containing precursor contacts the remaining exposed surface of the article or the body of the article to form the M1-M2 co-adsorbed layer. At block 345, reactants are introduced into the ALD chamber to react with the M1-M2 coadsorbed layer and form a rare earth metal-containing fluoride coating.

[0071] 3B illustrates a method 302 for forming a rare earth metal-containing fluoride coating by a codeposition ALD process. Method 302 may be used to coat any of the articles described herein. Method 302 may optionally begin with selecting a precursor for forming the coating. The selection of the composition and the method of formation may be performed by persons from the same organization or by persons from multiple organizations.

[0072] Method 302 may optionally include cleaning the article with an acidic solution at block 305. At block 310, the article is loaded into an ALD deposition chamber. At block 325, method 302 optionally includes depositing a buffer layer on the surface of the article or the body of the article using ALD. At block 321, ALD is performed to codeposit a rare earth metal-containing fluoride coating on the article. At least one M2-M1 codeposition cycle 331 is performed. The M2-M1 codeposition cycle includes introducing a second metal-containing precursor into the ALD chamber housing the article (with or without the buffer layer) at block 336. The second metal-containing precursor contacts the surface of the article or the body of the article to form a partial metal-containing adsorbed layer. At block 341, the first metal-containing precursor is introduced into the ALD chamber housing the article having the second metal adsorbed layer. The first metal-containing precursor contacts the remaining exposed surface of the article or body of the article to form a M2-M1 coadsorbed layer. At block 346, reactants are introduced into the ALD chamber to react with the M2-M1 coadsorbed layer to form a rare earth metal-containing fluoride coating.

[0073] FIG. 3C illustrates a composite method 303 for forming a multilayer coating as described herein, which includes performing at least one M1-M2 codeposition cycle at block 330. The ALD chamber is then purged with an inert gas at block 332. At least one M2-M1 codeposition cycle is performed at block 350 to form a rare earth metal-containing fluoride coating. As described above, the codeposition cycle may be repeated any number of times and in any order to achieve a rare earth metal-containing coating of a desired composition. Although not shown, in some embodiments, the deposited coating may be annealed. When the second metal is aluminum, an annealing temperature of up to about 500° C. may be used for the coating.

[0074] 3D illustrates a method 304 of co-depositing a rare earth metal-containing fluoride coating by co-implantation according to embodiments described herein. The method 304 may optionally include cleaning the article with an acidic solution at block 305. At block 310, the article is loaded into an ALD deposition chamber. At block 325, the method 302 optionally includes depositing a buffer layer on a surface of the article or body of the article using ALD.

[0075] At block 322, ALD is performed to co-deposit, by co-injection, a rare earth metal-containing fluoride coating on the article 205. At least one codeposition cycle 332 is performed. The codeposition cycle includes, at block 355, introducing a mixture of a first metal-containing precursor and a second metal-containing precursor into an ALD chamber housing the article (with or without a buffer layer). The first metal-containing precursor and the second metal-containing precursor may independently comprise a metal selected from a rare earth metal, zirconium, aluminum, hafnium, and tantalum. The mixture of precursors contacts the surface of the article or the body of the article to form a co-adsorbed layer. At block 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 codeposition cycle may be repeated as many times as necessary to achieve a coating of a desired thickness.

[0076] According to various embodiments, a method may include codepositing a rare earth metal-containing fluoride coating on a 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 period of time to form a partial first metal adsorbed layer, the first precursor being selected from a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, a tantalum-containing precursor, or an aluminum-containing precursor, contacting the partial metal adsorbed layer with a second precursor different from the first precursor for a second period of time to form a co-adsorbed layer comprising the first metal and the second metal, the second precursor being selected from a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, a tantalum-containing precursor, or an aluminum-containing precursor, and contacting the co-adsorbed layer with a reactant to form the rare earth metal-containing fluoride coating. In certain embodiments, the rare earth metal-containing fluoride coating includes 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 can be a homogenous mixture of the first metal and the second metal.

[0077] According to various embodiments, the process of codepositing a rare earth metal-containing fluoride coating includes performing at least one M1-M2 codeposition cycle that includes contacting the surface with a first metal-containing precursor to form a partial first metal adsorbed layer, followed by contacting the partial first metal adsorbed layer with a second metal-containing precursor to form an M1-M2 coadsorbed layer, and contacting the M1-M2 coadsorbed layer with a reactant. The at least one M1-M2 codeposition cycle can result in a layer that includes a first proportion of the first metal and a second proportion of the second metal.

[0078] In various embodiments, the step of codepositing a rare earth metal-containing fluoride coating may further include performing at least one M2-M1 codeposition cycle comprising contacting the surface with a second metal-containing precursor to form a partial second metal adsorbed layer, followed by contacting the partial metal adsorbed layer with a rare earth metal-containing precursor to form an M2-M1 coadsorbed layer, and contacting the M2-M1 coadsorbed layer with a reactant. The at least one M2-M1 codeposition cycle may result in an additional layer comprising a third proportion of the first metal and a fourth proportion of the second metal, the third proportion being lower than the first proportion and the fourth proportion being higher than the second proportion.

[0079] Methods according to embodiments described herein may further include selecting a ratio of a first number of M1-M2 co-deposition cycles and a second number of M2-M1 co-deposition cycles resulting in a first target mol % of the first metal and a second target mol % of the second metal, and performing a plurality of deposition super-cycles, each deposition super-cycle including performing a first number of M1-M2 co-deposition cycles and performing a second number of M2-M1 deposition cycles. According to embodiments, performing at least one M1-M2 codeposition cycle may include contacting the surface with a rare earth metal-containing precursor for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds; contacting the partial first metal adsorbed layer with a second metal-containing precursor for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds; contacting the M1-M2 coadsorbed layer with a reactant for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds; and performing at least one M2-M1 codeposition cycle. Performing at least one M2-M1 co-deposition cycle can include contacting the surface with a second metal-containing precursor for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds; contacting the partial metal adsorbed layer with a rare earth metal-containing precursor for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds; and contacting the M2-M1 co-adsorbed layer with a reactant for between about 50 milliseconds and about 60 seconds, or between about 1 second and about 60 seconds, or between about 5 seconds and about 60 seconds, or between about 10 seconds and about 60 seconds.

[0080] The following examples are provided to aid in the understanding of the embodiments described herein and should not be construed as specifically limiting the embodiments described and claimed herein. Such variations, including the substitution of all equivalents now known or later developed within the knowledge of a person skilled in the art, and changes in the scheme or minor changes in experimental design should be considered within the scope of the embodiments incorporated herein. These examples may be achieved by carrying out the methods described herein.

[0081] Example 1 - Effect of Fluorine on Y2O3 Coatings Atomic layer deposition was used to deposit yttrium oxide coatings on chamber components. The coated substrates were exposed to 3,000 cycles of nitrogen trifluoride (NF3) plasma at a temperature of 450°C in a chemical vapor deposition chamber. Side-sectional transmission electron microscopy (TEM) images of the Y2O3 coating on the substrate were obtained. Transmission electron microscopy energy dispersive x-ray spectroscopy (TEM / EDS) line scans of the Y2O3 coating were also obtained. During NF3 treatment of the Y2O3 substrate, the coating and underlying substrate were damaged due to uncontrolled diffusion / reaction of fluorine (F) into the Y2O3. Fluorine (1) caused surface degradation of the coating, (2) eroded and thus generated particles, (3) diffused through the coating, and (4) increased the risk of cracking and delamination of the coating.

[0082] Example 2 - Comparison of Al2O3, Y2O3 and YF3 coatings produced by ALD Sample coupons with Al2O3, Y2O3 or YF3 coatings were prepared using ALD deposition. The Al2O3 coating was 500 nm thick, the Y2O3 coating was 100 nm thick, and the YF3 coating was 100 nm thick. Each sample was exposed to CF4 inductively coupled plasma for 34 RF hours at a temperature of 75° C. and a radio frequency source power of 300 W.

[0083] After exposure to CF4 plasma, both the YF3 and Y2O3 coatings did not decrease in thickness (i.e., the etch rate was near zero) and the YF3 coating did not suffer from microstructural degradation, whereas the Y2O3 coating suffered from significant microstructural degradation. The Y2O3 coating exhibited dense nanocracks and delamination, whereas the YF3 coating did not. Without being bound to a particular theory, it is believed that when the Y2O3 coating is exposed to fluorine plasma, fluorine diffuses into the coating and displaces oxygen molecules, which causes a volume expansion of the Y2O3 coating, resulting in nanocracks and delamination of the coating. Before nanocracks, the Y2O3 and YF3 coatings act as diffusion barriers to prevent metals in the coated article from diffusing through the coating and contaminating the processed substrate. However, when nanocracks are present in the Y2O3 coating, the Y2O3 coating no longer functions as a diffusion barrier, because the nanocracks allow metals to diffuse through the coating. Furthermore, the nanocracks cause the Y2O3 coating to peel off, resulting in particle contamination on the treated substrate. In contrast, the YF3 coating does not develop nanocracks, so it remains a good diffusion barrier and does not cause particle contamination even after repeated exposure to fluorine-rich plasmas. If fluorine is used in the coating instead of oxygen, the YF3 coating does not undergo volume expansion, and therefore does not form nanocracks or peel off, although fluorine can diffuse into the YF3 coating. The Al2O3 coating underwent significant etching, with the thickness decreasing from 500 nm to about 225 nm (i.e., about 275 nm was etched away).

[0084] Similar conditions to those shown above for YF3 and Y2O3 have been demonstrated for other rare earth oxides versus rare earth fluorides. For example, Y exposed to a CF4 plasma x Zr y O z Coating and Y x Zr y Fz In comparison with coating, Y x Zr y O z The coating has been shown to suffer from nanocracks (and therefore no longer acts as a diffusion barrier, leading to particle contamination). x Zr y F z The coating is free of nanocracks (thus acting as a diffusion barrier and not causing particulate contamination). The same results occur for comparisons of other mono- and poly-metallic rare earth oxides with mono- and poly-metallic rare earth fluorides.

[0085] The foregoing description sets forth numerous specific details, such as examples of specific systems, components, methods, and the like, to provide a thorough understanding of some embodiments of the present invention. However, it will be apparent to those skilled in the art that at least some embodiments of the present invention may be practiced without such specific and detailed descriptions. In other instances, well-known components or methods are not described in detail or are presented in simple block diagram form to avoid unnecessarily obscuring the present invention. Thus, the specific and detailed descriptions are merely exemplary. Particular implementations may differ from these exemplary descriptions and still be considered to be within the scope of the present invention.

[0086] References throughout this specification to "an embodiment" or "one embodiment" mean that a particular configuration, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in one embodiment" in various places throughout this specification do not necessarily all refer to the same embodiment. Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". When the term "about" or "approximately" is used herein, it is intended to mean that the nominal value presented is accurate to within ±10%.

[0087] Although the operations of the methods herein are shown and described in a particular order, the order of the operations of each method may be changed such that certain operations are performed in the reverse order or certain operations are performed at least partially in parallel with other operations. In alternative embodiments, instructions of different operations or sub-operations may be performed intermittently and / or alternatingly.

[0088] It should be understood that the above description is intended to be illustrative, and not limiting. Many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. The scope of the present invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. 1. A method comprising the steps of: codepositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition, the step of codepositing the rare earth metal-containing fluoride coating comprising: contacting the surface with a first metal-containing precursor or a second metal-containing precursor for a first period of time to form a partial metal adsorption layer comprising a first metal (M1) or a second metal (M2), wherein the first metal-containing precursor or the second metal-containing 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; contacting the partial metal adsorbed layer with a second metal-containing precursor or a first metal-containing precursor for a second period of time to form a co-adsorbed layer comprising a first metal (M1) and a second metal (M2), wherein the first metal is different from the second metal; contacting the coadsorbed layer with a reactant to form a rare earth metal-containing fluoride coating; 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 method, wherein the rare earth metal-containing fluoride coating comprises an intimate mixture of a first metal and a second metal.

2. The step of codepositing a rare earth metal-containing fluoride coating comprises: performing at least one M1-M2 codeposition cycle; contacting the surface with a first metal-containing precursor to form a partial metal adsorption layer; subsequently contacting the partial metal adsorbed layer with a second metal-containing precursor to form an M1-M2 coadsorbed layer; contacting the M1-M2 coadsorbed layer with a reactant; 2. The method of claim 1, wherein at least one M1-M2 codeposition cycle results in a layer comprising a first proportion of a first metal and a second proportion of a second metal.

3. The step of codepositing a rare earth metal-containing fluoride coating comprises: performing at least one M2-M1 codeposition cycle; contacting the surface with a second metal-containing precursor to form a second partial metal adsorbed layer; subsequently contacting the second partial metal adsorbed layer with a first metal-containing precursor to form an M2-M1 coadsorbed layer; contacting the M2-M1 coadsorbed layer with a reactant; 3. The method of claim 2, wherein at least one M2-M1 codeposition cycle results in an additional layer comprising a third percentage of the first metal and a fourth percentage of the second metal, the third percentage being less than the first percentage and the fourth percentage being greater than the second percentage.

4. selecting a ratio of a first number of M1-M2 codeposition cycles to a second number of M2-M1 codeposition cycles, the ratio resulting in a first target mol % of the first metal and a second target mol % of the second metal; 4. The method of claim 3, further comprising: performing a plurality of deposition super cycles, each deposition super cycle including performing a first number of M1-M2 co-deposition cycles and performing a second number of M2-M1 co-deposition cycles.

5. performing at least one M1-M2 codeposition cycle; contacting the surface with a first metal-containing precursor for about 50 milliseconds to about 60 seconds; contacting the partial metal adsorbate with a second metal-containing precursor for about 50 milliseconds to about 60 seconds; contacting the M1-M2 coadsorbed layer with a reactant for about 50 milliseconds to about 60 seconds; performing at least one M2-M1 codeposition cycle, contacting the surface with a second metal-containing precursor for about 50 milliseconds to about 60 seconds; contacting the second partial metal adsorbed layer with the first metal-containing precursor for about 50 milliseconds to about 60 seconds; and contacting the M2-M1 coadsorbed layer with the reactant for about 50 milliseconds to about 60 seconds.

6. The first metal-containing precursor and the second metal-containing precursor are independently selected from the group consisting of cyclopentadienyl-based precursors, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, tris-methylcyclopentadienyl erbium(III) (Er(MeCp)3), tris(butylcyclopentadienyl)erbium(III), amidinate-based precursors, tris(N,N'-diisopropylformamidinate)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dione, 2. The method of claim 1, wherein the cation exchange material is selected from the group consisting of tris(bis(trimethylsilyl)amido)lanthanum), amide-based precursors, erbium borane amide (Er(BA)3), β-diketonate-based precursors, erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(dimethylamino)(cyclopentadienyl)zirconium, tetrakis(dimethylamido)zirconium, tetrakis(diethylamido)zirconium, tetrakis(N,N'-dimethylformamidinato)zirconium, tetra(ethylmethylamido)hafnium, and pentakis(dimethylamido)tantalum.

7. 10. The method of claim 1, further comprising contacting the coadsorbed layer with a third precursor to adsorb a third metal thereon, followed by contacting the coadsorbed layer with a reactant, wherein the third precursor is selected from the group consisting of an yttrium precursor, an erbium precursor, a zirconium precursor, a hafnium precursor, a silicon precursor, a tantalum precursor, a lanthanum precursor, a lutetium precursor, a scandium precursor, a gadolinium precursor, a samarium precursor, and a dysprosium precursor.

8. 10. The method of claim 1, further comprising depositing a buffer layer on the surface of the article by atomic layer deposition and codepositing a rare earth metal-containing coating on the buffer layer, the buffer layer comprising at least one of aluminum oxide, silicon oxide, or aluminum nitride.

9. The rare earth metal-containing fluoride coating is ｘ Zr ｙ F ｚ , Y ｘ Er ｙ F ｚ , Er ｘ Zr ｙ F ｚ , La ｘ Zr ｙ F ｚ , Lu ｘ Zr ｙ F ｚ , Sc ｘ Zr ｙ F ｚ , Gd ｘ Zr ｙ F ｚ , Sm ｘ Zr ｙ F ｚ , Dy ｘ Zr ｙ F ｚ , Y ｘ Hf ｙ F ｚ , Er ｘ Hf ｙ F ｚ , La ｘ Hf ｙ F ｚ , Lu ｘ Hf ｙ F ｚ , Sc ｘ Hf ｙ F ｚ , Gd ｘ Hf ｙ F ｚ , Sm ｘ Hf ｙ F ｚ , Dy ｘ Hf ｙ F ｚ and combinations thereof.

10. Codepositing a rare earth metal-containing fluoride coating onto a surface of an article using atomic layer deposition A method comprising the steps of: The step of codepositing a rare earth metal-containing fluoride coating comprises: performing at least one co-injection cycle; contacting the surface with a mixture of a first precursor and a second precursor for a first period of time to co-adsorb forming a layer, the first precursor and the second precursor each being a rare earth metal-containing precursor; Zirconium-containing precursors, hafnium-containing precursors, aluminum-containing precursors, and titanium-containing precursors. a nitrile-containing precursor selected from the group consisting of: The coadsorbed layer is contacted with a fluorine-containing reactant to form a rare earth metal-containing fluoride coating. and forming a groove, The rare earth metal-containing fluoride coating comprises a first proportion of a first metal and a second proportion of a second metal, the first metal and the second metal being independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum and tantalum, the first metal being different from the second metal; The rare earth metal-containing fluoride coating comprises a homogeneous mixture of a first metal and a second metal. How to do it.

11. The mixture includes a third precursor having a metal different from the first metal of the first precursor and the second metal of the second precursor. The method of claim 10 further comprising a precursor.

12. 12. The method of claim 11, wherein the third precursor is selected from the group consisting of an yttrium precursor, an erbium precursor, a zirconium precursor, a hafnium precursor, a silicon precursor, a tantalum precursor, a lanthanum precursor, a lutetium precursor, a scandium precursor, a gadolinium precursor, a samarium precursor, and a dysprosium precursor.

13. 11. The method of claim 10, wherein at least one co-implantation cycle forms a rare earth metal-containing fluoride coating having a layer comprising about 1 mol % to about 40 mol % of the first metal and about 1 mol % to about 40 mol % of the second metal.

14. 11. The method of claim 10, wherein at least one co-implantation cycle results in an additional layer comprising a third percentage of the first metal and a fourth percentage of the second metal, the third percentage being less than the first percentage and the fourth percentage being greater than the second percentage.

15. selecting a ratio of a first number of M1-M2 codeposition cycles to a second number of M2-M1 codeposition cycles, the ratio resulting in a first target mol % of the first metal and a second target mol % of the second metal; 11. The method of claim 10, further comprising: performing a plurality of co-deposition super-cycles, each deposition super-cycle including performing a first number of M1-M2 co-deposition cycles and performing a second number of M2-M1 co-deposition cycles.

16. The step of performing an M1-M2 coinfusion cycle comprises: contacting the surface with a mixture of a first metal precursor and a second metal precursor for about 50 milliseconds to about 60 seconds to form a M1-M2 co-adsorbed layer, wherein the ratio of M1:M2 is greater than 1; contacting the M1-M2 coadsorbed layer with a reactant for about 50 milliseconds to about 60 seconds; The step of performing an M2-M1 coinfusion cycle comprises: contacting the surface with a mixture of a second metal precursor and a first metal precursor for about 50 milliseconds to about 60 seconds to form an M2-M1 coadsorbed layer, wherein the ratio of M2:M1 is greater than 1; and contacting the M2-M1 coadsorbed layer with the reactant for about 50 milliseconds to about 60 seconds.

17. The first metal-containing precursor and the second metal-containing precursor are independently selected from the group consisting of cyclopentadienyl-based precursors, tris(methylcyclopentadienyl)yttrium ((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, tris-methylcyclopentadienyl erbium(III) (Er(MeCp)3), tris(butylcyclopentadienyl)erbium(III), amidinate-based precursors, tris(N,N'-diisopropylformamidinate)yttrium, tris(2,2,6,6-tetramethyl-heptane-3,5-dione 11. The method of claim 10, wherein the cation exchange material is selected from the group consisting of tris(bis(trimethylsilyl)amido)lanthanum), amide-based precursors, erbium borane amide (Er(BA)3), β-diketonate-based precursors, erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(dimethylamino)(cyclopentadienyl)zirconium, tetrakis(dimethylamido)zirconium, tetrakis(diethylamido)zirconium, tetrakis(N,N'-dimethylformamidinato)zirconium, tetra(ethylmethylamido)hafnium, and pentakis(dimethylamido)tantalum.

18. 11. The method of claim 10, further comprising depositing a buffer layer on the surface of the article by atomic layer deposition and codepositing a rare earth metal-containing coating on the buffer layer, the buffer layer comprising at least one of aluminum oxide, silicon oxide, or aluminum nitride.

19. The rare earth metal-containing fluoride coating is ｘ Zr ｙ F ｚ , Y ｘ Er ｙ F ｚ , Er ｘ Zr ｙ F ｚ , La ｘ Zr ｙ F ｚ , Lu ｘ Zr ｙ F ｚ , Sc ｘ Zr ｙ F ｚ , Gd ｘ Zr ｙ F ｚ , Sm ｘ Zr ｙ F ｚ , Dy ｘ Zr ｙ F ｚ , Y ｘ Hf ｙ F ｚ , Er ｘ Hf ｙ F ｚ , La ｘ Hf ｙ F ｚ , Lu ｘ Hf ｙ F ｚ , Sc ｘ Hf ｙ F ｚ , Gd ｘ Hf ｙ F ｚ , Sm ｘ Hf ｙ F ｚ , Dy ｘ Hf ｙ F ｚ and combinations thereof.

20. Depositing a rare earth metal-containing fluoride coating on a surface of an article using atomic layer deposition. A method comprising the steps of: The step of depositing a rare earth metal-containing fluoride coating comprises: contacting the surface with a first precursor for a first period of time to form a first metal adsorbate layer; Contacting the first metal adsorbate layer with a fluorine-containing reactant to form a first metal fluoride layer. The process and contacting the first metal layer with a second precursor for a second period of time to form a second metal adsorption layer. With contacting the second metal adsorbate layer with a fluorine-containing reactant or an alternative fluorine-containing reactant to form a second metal fluoride layer; The first metal fluoride layer and the second metal fluoride layer form a rare earth metal-containing fluoride coating. and forming a groove; 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 a second metal, the first metal and the second metal being independently and wherein the first metal is selected from the group consisting of rare earth metals, hafnium, and tantalum. It's a different way.

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