Corrosion-resistant metal fluoride coating deposited by atomic layer deposition.

Abstract

To provide an article formed by coating the surface of a treatment chamber or other components exposed to plasma, with an erosion-resistant metal fluoride.SOLUTION: In an article including a rare earth metal-containing fluoride coating on the surface of the body, the rare earth metal-containing fluoride coating contains a first metal as much as about 1 mol% to about 40 mol%, and a second metal as much as about 1 mol% to about 40 mol%, the first metal and the second metal are selected independently from a group comprising a rare earth metal, zirconium, hafnium, aluminum and tantalum, the first metal is different from the second metal, and the rare earth metal-containing fluoride coating contains a homogeneous mixture of the first metal and the second metal.SELECTED DRAWING: Figure 3A

Description

[Technical Field]

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

[0002] In the semiconductor industry, devices are fabricated through numerous manufacturing processes that produce increasingly smaller structures. Some manufacturing processes, such as plasma etching and plasma cleaning, involve exposing a substrate to a high-speed plasma stream to etch or clean it. Plasma can be highly corrosive, potentially corroding the processing chamber and other surfaces and components exposed to it. This corrosion can generate particles, which often contaminate the substrate during processing, contributing to device defects. Fluorine-containing plasmas, which can contain fluoride ions and radicals, are particularly harsh, and particle generation can occur from the interaction between the plasma and materials within the processing chamber. Fluorine-containing plasmas can damage protective coatings on chamber components and the underlying materials. This can degrade the surface of the protective coating, increasing the risk of cracking and delamination. Drifts in radical recombination rates resulting from gradual fluorination of the chamber surface can also cause wafer processing drift.

[0003] As device shapes become smaller, susceptibility to defects increases, and the requirements for particulate contaminants (i.e., on-wafer performance) become more stringent. To minimize particulate contamination caused 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, flexural strength, thermal shock resistance, etc.). Different ceramics also have different material costs. Therefore, there are ceramics with excellent plasma resistance, low-cost ceramics, and even ceramics with excellent flexural strength and / or thermal shock resistance.

[0004] Plasma spray coatings formed from Al2O3, AlN, SiC, Y2O3, quartz, and ZrO2 can reduce particle generation from chamber components, but these types of 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 and form particles in certain plasma environments, such as fluorine-containing plasmas, or suffer from mechanical separation of material layers due to insufficient interdiffusion within the coating. Summary

[0005] The articles to which the embodiments described herein pertain comprise a body and a rare-earth metal-containing fluoride coating on the surface of the body, wherein the rare-earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, 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 distinct from the second metal, and the rare-earth metal-containing fluoride coating comprising a homogeneous mixture of the first metal and the second metal.

[0006] Further embodiments of the method include a step of co-depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition, wherein the step of co-depositing the rare earth metal-containing fluoride coating includes a step of contacting the surface with a first precursor during a first period to form a partial metal adsorption layer containing 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 a step of contacting the partial metal adsorption layer with a second precursor different from the first precursor during a second period to form a partial metal adsorption layer containing a first metal (M1) and a second metal The process includes a step of forming a co-adsorption layer containing a metal (M2), wherein the second metal precursor is selected from the group consisting of rare earth metal-containing precursors, zirconium-containing precursors, hafnium-containing precursors, aluminum-containing precursors, and tantalum-containing precursors, and the first metal is different from the second metal; and a step of contacting the co-adsorption layer with a reactant to form a rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating contains about 1 mol% to about 40 mol% of the first metal and about 1 mol% to about 40 mol% of the second metal, and the rare earth metal-containing fluoride coating contains a homogeneous mixture of the first metal and the second metal.

[0007] According to various embodiments, the described method includes a step of co-depositing a rare earth metal-containing fluoride coating onto the surface of an article using atomic layer deposition, wherein the step of co-depositing the rare earth metal-containing fluoride coating is a step of performing at least one co-injection cycle, wherein during a first period the surface is brought into contact with a mixture of a first precursor and a second precursor to form a co-adsorbent layer, the first precursor and the second precursor each comprise a group consisting of a rare earth metal-containing precursor, a zirconium-containing precursor, a hafnium-containing precursor, an aluminum-containing precursor and a tantalum-containing precursor. The process includes a step selected from the above, and a step of contacting a co-adsorption layer with a fluorine-containing reactant to form a rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, 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 a homogeneous mixture of the first metal and the second metal.

[0008] According to various embodiments, the method described herein includes a step of depositing a rare earth metal-containing fluoride coating on the surface of an article using atomic layer deposition, the step of depositing the rare earth metal-containing fluoride coating comprising: a step of contacting the surface with a first precursor during a first period to form a first metal adsorption layer; a step of contacting the first metal adsorption layer with a fluorine-containing reactant to form a first metal fluoride layer; a step of contacting the first metal fluoride layer with a second precursor during a second period to form a second metal adsorption layer; and a step of contacting the second metal adsorption layer with its fluorine-containing reactant. The process includes the steps of forming a second metal fluoride layer by contacting it with a responding substance or a further fluorine-containing reacting substance, and forming a rare earth metal-containing fluoride coating from the first metal fluoride layer and the second metal fluoride layer, wherein the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, and the first metal and the second metal are independently selected from the group consisting of rare earth metals, zirconium, hafnium and tantalum, and the first metal is different from the second metal. [Brief explanation of the drawing]

[0009] The drawings in this disclosure are shown as examples, not as limitations, and similar reference numerals indicate similar elements. It should be noted that different references to “one” or “one” embodiment in this disclosure do not necessarily refer to the same embodiment, and such references mean at least one. [Figure 1] A cross-sectional view of the processing chamber is shown. [Figure 2A] This specification shows one embodiment of co-deposition treatment using the atomic layer deposition technique described herein. [Figure 2B] Another embodiment of co-deposition processing using the atomic layer deposition technique described herein is shown. [Figure 2C] Another embodiment of co-deposition processing using the atomic layer deposition technique described herein is shown. [Figure 2D] Another embodiment of co-deposition processing using the atomic layer deposition technique described herein is shown. [Figure 3A]A diagram showing a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition method described in this specification. [Figure 3B] A diagram showing a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition method described in this specification. [Figure 3C] A diagram showing a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition method described in this specification. [Figure 3D] A diagram showing a method of forming a rare earth metal-containing fluoride coating using the atomic layer deposition method described in this specification. Detailed Description

[0010] The embodiments described herein relate to composite metal-containing fluoride coatings comprising 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). Here, 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.), and each metal is independently selected from rare earth metals, zirconium, tantalum, hafnium, and aluminum. For example, the rare earth metal-containing fluoride coating may be M1 z , w M2 y F z (e.g., 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 (e.g., 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 W w Z rx Hf y F z ), and / or more complex composite metal fluoride coatings having more mixed metals may also be present. As will be discussed in more detail below, multiple different metals (e.g., a first metal, a second metal, etc.) may be co-deposited onto an article using off-line techniques such as atomic layer deposition (ALD). Alternatively, multiple different metal fluorides may be sequentially deposited and then interdiffused to form a composite metal fluoride coating. The coating is resistant to the chemical properties of plasmas used in semiconductor processing, e.g., bromine-containing plasmas with bromine ions and bromine radicals. Without being bound by any particular theory, it is thought that incorporating 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 into the coating (e.g., from a CF4 plasma).

[0011] According to embodiments described herein, the coating comprises multiple metals (e.g., RE) co-deposited on a single adsorption layer. w M y F z , Y x Zr y F z or RE w Y x Zr y F z) may be formed from tantalum and at least one additional metal. In some embodiments, 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 in some embodiments from rare earth metals (RE), zirconium (Zr), aluminum (Al), hafnium (Hf), silicon (Si), and hafnium (Hf). According to some 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., a second) metal (e.g., RE) co-deposited on a single adsorption layer. w M y F z , Y x Zr y F z or RE w Y x Zr y F z) may be formed from the following. 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 some 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 some embodiments, the rare earth metal-containing fluoride coating may contain at least one rare earth metal in about 5 mol% to about 30 mol%, or about 10 mol% to about 25 mol%, or about 15 mol% to about 20 mol%, and at least one additional metal in about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, or about 10 mol% to about 20 mol%.

[0013] The coating provides resistance to erosion by plasmas (e.g., fluorine-containing plasmas) used in semiconductor processing and chamber cleaning. Therefore, the coating provides good particle performance and processing stability during such processing and cleaning. In this specification, the terms “erosion-resistant coating” or “plasma-resistant coating” refer to coatings that have particularly low erosion rates 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.). Co-deposition results in a coating that eliminates surface fluorination, which can lead to wafer processing drift, and achieves a much more uniform coating on the angstrom scale, improving phase control (e.g., lack of interdiffusion leaving YF3 and other metal phases within the coating). According to various embodiments, co-deposition results in a coating having a homogeneous mixture of metals, and without being bound by specific theories, it is considered that voids are eliminated within the co-deposited coating (compared to oxide films), thereby preventing the diffusion of fluorine into the coating. For example, in coatings containing a mixture of Y2O3 and ZrO2 deposited by deposition techniques other than ALD, or deposited by ALD using sequential deposition techniques, one or more phase separations may occur at several locations. This may result in some voids in the Y2O3 phase, which may consequently increase susceptibility to fluorination. In contrast, Y2O3 deposited using co-deposition and / or co-injection techniques... x Zr y F z ALD deposition of (e.g., YF-ZrF solid solution) can reduce or eliminate phase separation, resulting in a homogeneous mixture of Y and Zr. Co-deposition also offers the flexibility to adjust the ratio of deposited metals, for example, by adjusting the number and / or pulse duration, 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 has a composition of two metals (M1 × M2y F z )、 consisting of 3 metals (M1 w M2 x M3 y F z )、 consisting of 4 metals (M1 v M2 w M3 x M4 y F z )、 consisting of 5 metals (M1 u M2 v M3 w M4<\(0000071\)>M5<\(0000072\)>F<\(0000073\)>)、 consisting of 6 metals (M1<\(0000074\)>M2<\(0000075\)>M3<\(0000076\)>M4<\(0000077\)>M5<\(0000078\)>M6<\(0000079\)>F<\(0000080\)>) etc. may be included. In each composite 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 be in the range from about 0.1 to about 10. In some embodiments, the composite metal fluoride coating is a rare earth metal-containing fluoride coating. In various embodiments, the rare earth metal-containing fluoride coating is Y<\(0000081\)>Zr<\(0000082\)>F<\(0000083\)>, Er<\(0000084\)>Zr<\(0000085\)>F<\(0000086\)>, Y<\(0000087\)>Er<\(0000088\)>Zr<\(0000089\)>F<\(0000090\)>, Y<\(0000091\)>Er<\(0000092\)>Hf<\(0000093\)>F<\(0000094\)>, Y<\(0000095\)>Z<\(0000096\)>Hf<\(0000097\)>F<\(0000098\)>, Er<\(0000099\)>Z<\(0000100\)>Hf<\(0000101\)>F<\(0000102\)>, Y[[ID=​​​​​​​​​​​​​z Er x Hf y F z , Y x Ta y F z Er x Ta y F z , Y w W 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 W w Ta x Hf y F z and Y v W w Ta x Hf y F z Selected from: In one embodiment, the rare earth metal-containing fluoride coating contains YZrF, where the atomic ratio of yttrium to zirconium is about 3. In another embodiment, the rare earth metal-containing fluoride coating contains YZrOF, where the atomic ratio of yttrium to zirconium is about 4.6. In further embodiments, the rare earth metal-containing fluoride coating is 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 DY 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 DY 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 DY w Y x Hf y F z It may include a composition selected from the following. In some embodiments, the coating is RE w Z rx Al y F z (For example, Y w Z rx Al y F z ) may be included. Other composite fluorides may 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 W y F z It may also contain yttrium. The yttrium content in the coating may range from about 0.1 mol% to nearly 100 mol%. In the case of yttrium-containing fluoride, 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 zEr a Hf x Al y F z , Y x W y F z and Er a Y x Zr y F z (For example, single-phase solid solutions of Y2O3, ZrO2, and Er2O3) may be included. The erbium content in the plasma-resistant coating may range from about 0.1 mol% to nearly 100 mol%. In the case of 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] Beneficially, Y2O3 and Er2O3 are miscible. A single-phase solid solution can be formed for any combination of Y2O3 and Er2O3. For example, a plasma-resistant coating that is a single-phase solid solution may be formed by co-depositing a mixture of Er2O3 slightly above 0 mol% and Y2O3 slightly below 100 mol%. Furthermore, a plasma-resistant coating that is a single-phase solid solution may be formed by combining a mixture of Er2O3 slightly above 0 mol% and Y2O3 slightly below 100 mol%. x W y F zThe plasma-resistant coating may contain YF3 from more than 0 mol% to less than 100 mol% to ErF3 from more than 0 mol% to less than 100 mol%. 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. This includes F3, 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 W y F z The single-phase solid solution may have a monoclinic cubic state at temperatures below approximately 2330°C.

[0018] Beneficial, ZrO2 can be combined with YF3 and ErF3 to form a mixture of zirconium, YF3 and ErF3 (e.g., Er a Y x Zr y F z A single-phase solid solution containing ) may be formed. a W x Zr y F z The solid solution may have a cubic, hexagonal, tetragonal, and / or cubic fluorite structure. a W x Zr y F zThe solid solution may contain more than 0 mol% to 60 mol% of Zr, more than 0 mol% to 99 mol% of ErF3, and more than 0 mol% to 99 mol% of 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 contain more than 0 mol% to 60 mol% of Zr, more than 0 mol% to 99 mol% of YF3, and more than 0 mol% to 60 mol% of Al. Some notable amounts of ZrO2 that can be used include 2 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 30 mol%, 50 mol%, and 60 mol%. Some notable amounts of YF3 that can be used include 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, and 90 mol%. Some notable amounts of Al2O3 that can be used include 2 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, and 60 mol%. In one embodiment, Y a Z rx Al y F z The plasma-resistant coating contains 42 mol% YF3, 40 mol% Zr, and 18 mol% Al, and has a lamellar structure. In another embodiment, Y 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 some embodiments, the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a primary metal (e.g., rare earth metals such as Y and Er, or tantalum) and about 1 mol% to about 40 mol% of a secondary metal (e.g., rare earth metals, Zr, Hf, Ta, Al, Si). In further embodiments, the composite metal fluoride coating comprises about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, of Ta and about 1 mol% to about 40 mol%, or about 1 mol% to about 20 mol%, of a secondary metal (e.g., RE, Zr, Hf, Al, Si). In some embodiments, the composite metal fluoride coating comprises about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, of yttrium, and about 1 mol% to about 40 mol%, or about 1 mol% to about 20 mol%, of zirconium, hafnium, or tantalum, or about 10 mol% to about 25 mol%, of yttrium, and about 5 mol% to about 17 mol%, of Zr, Hf, or Ta, or about 15 mol% to about 21.5 mol%, of yttrium, and about 10 mol% to about 14.5 mol%, of Zr, Hf, or Ta. In some 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% (for example, it may contain 1 to 29 mol% of Y and 1 to 29 mol% of Er). The coating may further contain about 1 mol% to about 20 mol%, of zirconium, hafnium, or tantalum.

[0021] In some 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 an 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 covers the substrate surface, and this surface is covered with a uniform thickness (including the covered surface features), where the thickness variation is less than approximately + / -20%, + / -10%, + / -5%, or smaller.

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

[0023] In alternative embodiments, sequential atomic layer deposition (ALD) is performed. For sequential ALD, a first metal precursor may be adsorbed onto the surface, and a fluorinated reactant may react with the adsorbed first metal (e.g., a rare earth metal, tantalum, etc.) to form a first metal fluoride layer. Subsequently, a second metal precursor may be adsorbed onto the first metal fluoride layer, and a fluorinated reactant may react with the adsorbed second metal to form a second metal (e.g., zirconium, aluminum, hafnium, tantalum, silicon, etc.) fluoride layer. Then, the metals from the first and second metal fluoride layers may interdiffuse with each other. When a coating is deposited using a sequential deposition cycle of the first and second metals, annealing may be performed to influence interdiffusion between the layers. This type of annealing can create a concentration gradient of the metallic phase from the surface toward the substrate article (e.g., YZrF from YF3 and ZrO2), and the resulting coating lacks overall homogeneity. The co-deposition coating described herein forms a homogeneous mixture of the first and second metals. Generally, annealing to induce interdiffusion is not performed.

[0024] According to various embodiments, the composite metal fluoride coating or rare earth metal-containing fluoride coating may be formed from a multilayer stack having alternating material layers. In one embodiment, a buffer layer may be deposited on the surface of an article or the body of an article, and the composite metal fluoride coating or 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 a combination 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 (or on, if a buffer layer is used) an article using ALD to form a first co-deposited 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 co-deposited layer. Each deposition or co-deposition cycle can be repeated a desired number of times to achieve the target composition and / or target thickness of the final multilayer coating.

[0025] The thickness of each layer in a multilayer composite metal fluoride coating or rare earth metal-containing fluoride coating may range from about 10 nm to about 1.5 μm. In some 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 specific chamber application.

[0026] The composite metal fluoride or rare earth metal-containing fluoride coating may be grown or co-deposited with a precursor using ALD. However, this precursor is a precursor for co-deposition of a first metal-containing fluoride layer containing tantalum and / or at least one rare earth metal (e.g., yttrium, erbium, etc.) and a second metal (e.g., RE, Zr, Ta, Hf, Al, Si). In one embodiment, the composite metal fluoride coating or rare earth metal-containing fluoride layer has a polycrystalline structure.

[0027] The buffer layer may contain amorphous aluminum oxide or a similar material. The buffer layer provides robust mechanical properties, increases dielectric strength, provides better adhesion of the composite metal fluoride or rare earth metal-containing fluoride coating to the constituent material (e.g., formed from Al6061, Al6063, or ceramic), and can prevent cracking of the composite metal fluoride or rare earth metal-containing fluoride coating at the following 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 coefficient of thermal expansion significantly larger than that of the composite metal fluoride coating or rare earth metal-containing fluoride coating. The harmful effects of the mismatch in coefficients of thermal expansion between the article and the composite metal-containing fluoride coating may be addressed by first providing the buffer layer 209. Since ALD is used for deposition, it can coat the inner surfaces of high aspect ratio features such as showerheads or gas supply holes in gas supply lines, thus protecting the entire component from exposure to corrosive environments. In some embodiments, the buffer layer may include a material having a coefficient of thermal expansion between the coefficient of thermal expansion of the article and the coefficient of thermal expansion of the composite metal-containing fluoride coating. Furthermore, the buffer layer can act as a barrier to prevent the migration of metallic contaminants (e.g., trace metals such as Mg and Cu) from the component or article into the composite metal-containing fluoride coating. Adding an amorphous Al2O3 layer as a buffer layer beneath the composite metal-fluoride coating may increase the overall thermal resistance of the composite metal-fluoride coating. This is due to the relief of high stresses concentrated in several areas of the composite metal-fluoride / Al6061 interface.

[0028] This specification also describes articles having composite metal fluoride coatings or rare earth metal-containing fluoride coatings as described above. In various 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 supply plates, chamber walls, chamber liners, doors, rings, shower heads, nozzles, plasma generation units, high-frequency electrodes, electrode housings, diffusers, and gas lines. The article may contain, but are not limited to, materials including aluminum (Al), silicon (Si), copper (Cu), and magnesium (Mg). In various embodiments, the article may contain aluminum oxide (Al x O y ), silicon oxide (Si x O y The material may contain, but is not limited to, ceramic materials including aluminum nitride (AlN) or silicon carbide (SiC) material. In some embodiments, the article or body of the article may be made of aluminum Al6061 or Al6063 material. In some embodiments, the surface roughness of the surface of the article or body of the article is 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 are extremely dense, and their porosity can be approximately 0% (for example, in some embodiments, rare earth metal-containing fluoride coatings may be porosity-free). The composite metal-containing fluoride coatings may be resistant to corrosion and erosion due to the chemical properties of plasma etching. These chemical properties include the chemical properties of CCl4 / CHF3 plasma etching, HCl3Si etching, and NF3-containing etching. Furthermore, the composite metal-containing fluoride coatings described herein, having a buffer layer, 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 having a buffer layer as described herein may be used in processes that include heating to a temperature of approximately 200°C. Even when the chamber components undergo thermal repetitions between room temperature and approximately 200°C, no cracking or delamination will occur in 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 vent), the aspect ratio (L:D) of the length to diameter of the feature may be about 5:1 to about 300:1, or about 10:1 to about 200:1, or about 20:1 to about 100:1, or about 5:1 to about 50:1, or about 7:1 to about 25:1, or about 10:1 to about 20:1. A composite metal fluoride coating or a rare earth metal-containing fluoride coating may conformally cover the surface of the body of the article and the feature. In some embodiments, the article or body of the article includes features (e.g., channels), and the aspect ratio (D:W) of the depth to width of the features may be about 5:1 to about 300:1, or about 10:1 to about 200:1, or about 20:1 to about 100:1, or about 5:1 to about 50:1, or about 7:1 to about 25:1, or about 10:1 to about 20:1. A composite metal fluoride coating or a rare earth metal-containing fluoride coating may conformally cover the surface of the body of the article and the features.

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

[0032] Figure 1 is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components. These chamber components are coated with composite metal fluoride or rare earth metal-containing fluoride coatings according to embodiments described herein. The substrate of at least some of the chamber components is, for example, Al x O y Al, such as AlN, Al6061 or Al6063, for example, Si x O y The material may include one or more of the following: Si such as SiO2 or SiC, copper (Cu), magnesium (Mg), titanium (Ti), and stainless steel (SST). The processing chamber 100 may be used for processing that generates a corrosive plasma environment having a plasma processing state (e.g., fluorine-containing plasma). For example, the processing chamber 100 may be a chamber for a plasma etcher or plasma etching reactor, a plasma cleaner, or a reactor for plasma CVD or ALD. 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 having high aspect ratios as described 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 shower head, 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, and a chamber lid.

[0033] In one embodiment, the processing chamber 100 comprises a chamber body 102 surrounding an internal volume 106 and a shower head 130. The shower head 130 may comprise a shower head base and a shower head gas distribution plate. Alternatively, the shower head 130 may be replaced in some embodiments by a lid and nozzles, or in other embodiments by a plurality of fan-shaped shower head compartments and a plasma generation unit. The chamber body 102 may be manufactured from aluminum, stainless steel, or other suitable material. The chamber body 102 generally comprises side walls 108 and a bottom 110. An outer liner 116 may be positioned adjacent to the side walls 108 to protect the chamber body 102. The shower head 130 (or lid and / or nozzles), the side walls 108, and / or the bottom 110 may be coated with a rare earth metal-containing fluoride coating.

[0034] An exhaust port 126 may be defined within the chamber body 102, and the internal volume 106 may be connected to a pump system 128. The pump system 128 may include one or more pumps and throttle valves, which may be used to evacuate the internal volume 106 of the processing chamber 100 and adjust the pressure.

[0035] The shower head 130 may be supported by the side wall 108 of the chamber body 102. The shower head 130 (or lid) may be open to allow access to the internal volume 106 of the processing chamber 100, and while closed, the processing chamber 100 can be sealed. A gas panel 158 may be connected to the processing chamber 100 to supply processing gas and / or cleaning gas to the internal volume 106 through the shower head 130 or the lid and nozzle. The shower head 130 may be used in a processing chamber used for dielectric etching (etching dielectric materials). The shower head 130 may comprise a gas distribution plate (GDP) having a plurality of gas supply holes 132 throughout. The shower head 130 may comprise a GDP bonded to an aluminum base or an anodized aluminum base. The GDP may be made from Si or SiC, or Y2O3, Al2O3, Y3Al5O 12 Ceramic materials such as (YAG) may also be used.

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

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

[0038] The substrate support assembly 148 is located under the showerhead 130 or lid within the internal volume 106 of the processing chamber 100. The substrate support assembly 148 includes a support 136 for holding the substrate 144 during processing. The support 136 is attached to the end of a shaft (not shown) which is connected 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] Figure 2A shows one embodiment of co-deposition treatment 200 using ALD technology, in which a fluoride coating rich in a first metal is grown or deposited on an article. Figure 2B shows another embodiment of co-deposition treatment using ALD technology as described herein, in which a rare earth metal fluoride coating rich in a second metal is grown or deposited on an article. Figure 2C shows another embodiment of co-deposition treatment using ALD technology as described herein. Figure 2D shows another embodiment of co-deposition treatment using ALD technology as described herein, utilizing co-injection of rare earth metals and other metals.

[0040] In the ALD co-deposition process, both the adsorption of at least two precursors onto the surface and the reaction between the adsorbed precursors and the reactants may be referred to as "half-reactions." During the first half-reaction, the first precursor (or a mixture of precursors) may be rhythmically delivered to the surface of article 205 for a sufficient amount of time to partially (or completely) adsorb the precursor onto the surface. This adsorption is self-limiting because the precursor adsorbs onto numerous available sites on the surface, forming a partially adsorbed layer of the first metal on the surface. Sites already adsorbed with the first metal of the precursor become unavailable for further adsorption with subsequent precursors. Alternatively, some sites adsorbed with the first metal of the first precursor may be replaced with the second metal of the second precursor adsorbed on those sites. To complete the first half-reaction, the second precursor may be rhythmically delivered to the surface of article 205 for a sufficient amount of time to partially or completely adsorb the second metal of the second precursor onto available sites on the surface (or replace the first metal of the first precursor) to form a co-deposition adsorption layer on the surface.

[0041] The co-deposition cycle of the ALD process begins with a first precursor (i.e., chemical A, or a mixture of chemicals A and B) overflowing into the ALD chamber and being partially (or completely) adsorbed onto the surface of the article (including the surfaces of holes and features within the article). A second precursor (i.e., chemical B) may then be overflowed into the ALD chamber and adsorbed onto the remaining exposed surfaces of the article. The excess precursor may then be flushed out / purged from the ALD chamber (i.e., with an inert gas), followed by the introduction of a reactant (i.e., chemical R) into the ALD chamber, and then the reactant may be flushed out. 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 performed, as each reaction cycle grows a layer of a specific thickness, such as one atomic layer or a fraction of one atomic layer.

[0042] Aside from being a conformal process, ALD is also a uniform process, capable of forming very thin films, for example, with a thickness of approximately 3 nm or more. The same or nearly identical amount of material is deposited on all exposed surfaces of the article. Because ALD technology can deposit thin layers of material at relatively low temperatures (e.g., approximately 25°C to 350°C), it does not damage or deform any of the constituent materials. Additionally, ALD technology can also deposit layers of material within complex features of constituent materials (e.g., high aspect ratio features). Furthermore, ALD technology generally produces relatively thin (i.e., less than 1 μm) coatings that are pore-free (i.e., pinhole-free). This eliminates the possibility of crack formation during deposition.

[0043] A composite metal fluoride coating or a rare earth metal-containing fluoride coating may be grown or deposited using ALD together 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 various embodiments, the first metal-containing precursor and the second metal-containing precursor (in the case of a composite metal coating, the third metal-containing precursor and the fourth metal-containing precursor, etc.) are independently selected from yttrium-containing precursors. Examples of yttrium-containing precursors include tris(N,N-bis(trimethylsilyl)amide)yttrium(III), yttrium(III) butoxide, or yttrium cyclopentadienyl compounds (e.g., tris(cyclopentadienyl)yttrium (Cp3Y), tris(methylcyclopentadienyl)yttrium ((CpMe)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, or tris(ethylcyclopentadienyl)yttrium). Other yttrium-containing precursors that can be used include yttrium-containing amide compounds (e.g., tris(N,N'-diisopropylformamidinate)yttrium, tris(2,2,6,6-tetramethylheptane-3,5-dionate)yttrium, or tris(bis(trimethylsilyl)amide)lanthanum), and yttrium-containing β-diketnate compounds. In some embodiments, the rare earth metal-containing fluoride precursor may also contain erbium. Erbium-containing precursors include, but are not limited to, erbium-containing cyclopentadienyl compounds, erbium-containing amide compounds, and erbium-containing β-diketnate compounds. Examples of erbium-containing precursors for ALD include tris-methylcyclopentadienylerbium(III) (Er(MeCp)3), erbium boranamide (Er(BA)3), Er(TMHD)3, erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptane dionate), and tris(butylcyclopentadienyl)erbium(III). Zirconium-containing precursors may include, but are not limited to, zirconium-containing cyclopentadienyl compounds, zirconium-containing amide compounds, and zirconium-containing β-diketnate compounds.Examples of zirconium-containing precursors for ALD include zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, tetrakis(diethylamide)zirconium(IV), tetrakis(dimethylamide)zirconium(IV), tetrakis(ethylmethylamide)zirconium(IV), or zirconium cyclopentadienyl compounds. Examples of zirconium-containing precursors include tetrakis(dimethylamide)zirconium, tetrakis(diethylamide)zirconium, tetrakis(N,N'-dimethylformamidinate)zirconium, tetra(ethylmethylamide)hafnium, pentakis(dimethylamide)tantalum, and tris(2,2,6,6-tetramethylheptane-3,5-dioneate)erbium.

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

[0046] In some embodiments, a mixture of two precursors is introduced together (i.e., co-injected). Here, the mixture comprises a first proportion of a first metal-containing precursor and a second proportion of a second metal-containing precursor. For example, the precursor mixture may contain 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 has a ratio of the first metal (e.g., yttrium, tantalum, etc.)-containing precursor to the second metal-containing precursor, and the ratio may be suitable for forming the target type of fluoride material. The atomic ratio of the primary metal (e.g., yttrium, tantalum, etc.)-containing precursor to the secondary metal-containing precursor may be about 200:1 to about 1:200, or about 100:1 to about 1:100, or about 50:1 to about 1:50, or about 25:1 to about 1:25, or about 10:1 to about 1:10, or about 5:1 to about 1:5.

[0047] In one embodiment, a composite metal fluoride coating or a rare earth metal-containing fluoride coating is co-deposited onto the surface of an article using atomic layer deposition. The co-depositing step of the rare earth metal-containing fluoride coating may include a step of contacting the surface with a first metal-containing precursor (e.g., a rare earth metal-containing precursor) during a first period to form a partially 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. Subsequently, the partially metal-adsorbed layer is contacted with a second metal-containing precursor, different from the first metal-containing precursor, during a second period to form a co-adsorbed layer containing the first and second metals. 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 contain about 1 mol% to about 40 mol%, or about 5 mol% to about 30 mol%, of a rare earth metal or tantalum, and about 1 mol% to about 40 mol%, or about 1 mol% to about 20 mol%, of a secondary metal. Furthermore, the rare earth metal-containing fluoride coating may contain a homogeneous mixture of the primary and secondary metals.

[0048] Referring to Figure 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 for a period of time into a first metal-containing precursor 210 (e.g., a rare earth metal-containing precursor) until the surface of the article 205 is partially adsorbed with the first metal-containing precursor 210, forming a partially metal-adsorbed layer 215. Subsequently, the article 205 may be introduced for a period of time into a second metal-containing precursor 220 until the remaining exposed surface of the article is adsorbed with the second metal-containing precursor 220, forming a co-adsorbed layer 225 containing both the first and second metals. The first metal-containing precursor exposed to an uncoated surface (i.e., having all available adsorption sites) can be adsorbed to the surface more efficiently than the second metal-containing precursor exposed to a partially adsorbed surface. Therefore, the co-adsorbed layer 225 is rich in the first metal. That is, it may contain the first metal at a higher atomic concentration than the second metal. Next, article 205 is introduced into the reactant 230 for a period of time to react with the co-adsorption layer 225 to form a solid fluoride layer (e.g., Y) of the rare earth metal-containing fluoride coating 235 according to the embodiments described herein. x Zr y F z Alternatively, a YF3-Zr solid solution may be grown. The precursor may be any of the above precursors. The co-deposition of the first and second metals with the introduction of reactants is called the M1-M2 co-deposition cycle. By repeating the M1-M2 co-deposition cycle m times, a coating of the desired thickness can finally be achieved.

[0049] Referring to Figure 2B, an M2-M1 co-deposition method 202 for depositing a rare-earth metal-containing fluoride coating on article 205 is described. Article 205 may be introduced into a second metal-containing precursor 220 for a period of time until the surface of article 205 is partially adsorbed by the second metal-containing precursor 220, forming a partially adsorbed second metal layer 216. Subsequently, article 205 may be introduced into a first metal-containing precursor 210 for a period of time until the remaining exposed surface of the article is adsorbed by the first metal-containing precursor 220, forming a co-adsorbed layer 226. The co-adsorbed layer 226 may be rich in the second metal. Next, article 205 may be introduced into a first reactant 230 and reacted with the co-adsorbed layer 225 to grow a solid layer (e.g., YZrF) of the rare-earth metal-containing fluoride coating 236 according to the embodiments described herein. The precursor may be any of the above precursors. The co-deposition of a secondary metal and a primary metal, accompanied by the introduction of reactants, is called the M2-M1 co-deposition cycle. By repeating the M2-M1 co-deposition cycle n times, a coating of the desired thickness can eventually be achieved.

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

[0051] The relative concentrations of the primary metal (e.g., rare earth metals, such as Ta) and the secondary metal may be controlled by the type of precursor used, the temperature of the ALD chamber during adsorption of the precursor onto the surface of the article, the time a particular precursor remains in the ALD chamber, and the partial pressure of the precursor. For example, using a tris(N,N-bis(trimethylsilyl)amide)yttrium(III) precursor may result in a lower atomic percentage of yttria than using a yttrium cyclopentadienyl precursor.

[0052] In some embodiments, three or more metal precursors are adsorbed onto the surface of article 205 in a single co-deposition cycle. For example, the co-deposition cycle may include the adsorption of a yttrium precursor onto the surface, followed by the adsorption of a zirconium precursor onto the surface, followed by the adsorption of a hafnium precursor onto the surface. With each subsequent precursor, a smaller amount of the associated metal may be adsorbed onto the surface. Thus, by selecting the order in which each precursor is adsorbed onto the surface to form a co-adsorption layer, a target ratio of two or more different metals can be achieved. Further exemplary co-deposition methods that can be performed include the M1-M2-M3 co-deposition method, in which a first metal (M1) is adsorbed onto the surface, followed by the adsorption of a second metal (M2), followed by the adsorption of a third metal (M3), followed by the introduction of a fluorine source reactant. Another exemplary co-deposition method that can be performed includes the M2-M1-M3 co-deposition method. In this co-deposition method, the second metal (M2) is adsorbed onto the surface, followed by the first metal (M1), followed by the third metal (M3), and then the fluorine-source reactant is introduced. Another exemplary co-deposition method that can be performed is the M3-M1-M2 co-deposition method. In this co-deposition method, the third metal (M3) is adsorbed onto the surface, followed by the first metal (M1), followed by the second metal (M2), and then the fluorine-source reactant is introduced. Another exemplary co-deposition method that can be performed is the M3-M2-M1 co-deposition method. In this co-deposition method, the third metal (M3) is adsorbed onto the surface, followed by the second metal (M2), followed by the first metal (M1), and then the fluorine-source reactant is introduced. More precursors may be adsorbed onto the surface to create more complex composite metal fluorides. The more metals used, the greater the number of possible rearrangements.

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

[0054] The buffer layer 209 may be uniform, continuous, and conformal. In some embodiments, the buffer layer 209 may be porosity-free (e.g., zero porosity) or have near-zero porosity (e.g., 0% to 0.01%). Multiple complete ALD deposition cycles may be performed to deposit a buffer layer 209 having a target thickness. Each complete cycle (e.g., including the introduction and removal of an aluminum-containing precursor, the introduction of an H2O reactant, and another removal) further increases the thickness by a fraction of an atom to several atoms. In some 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] Next, the M1-M2 co-deposition cycle described above with respect to Figure 2A, or the M2-M1 co-deposition cycle described above with respect to Figure 2B, may be performed on an article 205 having an optional buffer layer 209. The buffer layer 209, rather than the surface or body of the article, partially adsorbs the first metal-containing precursor 210 or the second precursor 220, and attempts to form a partially adsorbed layer 215. After that, the precursor is flushed out of the ALD chamber using an inert gas (e.g., nitrogen), and then the M1-M2 co-deposition cycle described above with respect to Figure 2B, or the M2-M1 co-deposition cycle described above with respect to Figure 2A, may be performed on an article 205 having an optional buffer layer 209 and an M1-M2 coating layer 235.

[0056] The rare-earth metal-containing fluoride layer resulting from the M1-M2 co-deposition cycle may contain a first proportion of the first metal and a second proportion of the second metal. The M2-M1 co-deposition cycle results in an additional layer containing a third proportion of the first metal and a fourth proportion of the second metal. In some embodiments, the third proportion may be lower than the first proportion and the fourth proportion may be higher than the third proportion. Thus, by using two co-deposition cycles, a multilayer coating having a buffer layer 209, an M1-M2 layer 235, and an M2-M1 layer 236 can be formed. Conventionally, either or both of the co-deposition cycles may be repeated m or n times, where m and n are integers greater than zero and represent the number of co-deposition cycles. In some embodiments, the ratio of m to n may be 1:50 to about 50:1, or about 1:25 to about 25:1, or about 1:10 to about 10:1, or about 1:2 to about 2:1, or 1:1. The coating can be fabricated by performing co-deposition cycles continuously and / or alternately. The alternating layers 235 and 236, as described with respect to Figure 2C, were formed in a 1:1 manner by the co-deposition cycle. Here, there is one layer of the M1-M2 coating layer for each of the M2-M1 coating layers. However, other patterns may exist in other embodiments. For example, two M1-M2 co-deposition cycles may be followed by one M2-M1 co-deposition cycle (2:1), and then this sequence may be repeated once more.

[0057] According to various embodiments, the M1-M2 co-deposition cycle can be represented as m*(M1+M2+F), where m is an integer greater than zero and represents the number of M1-M2 co-deposition cycles, M1 represents the amount (mol%) of deposited primary metal (e.g., yttrium), M2 represents the amount (mol%) of deposited secondary metal, and F represents the amount (mol%) of deposited fluorine. The M2-M1 co-deposition cycle can be represented as n*(M2+M1+F), where n is an integer greater than zero and represents the number of M2-M1 co-deposition cycles, M2 represents the amount (mol%) of deposited secondary metal, M1 represents the amount (mol%) of deposited primary metal (e.g., yttrium), and F represents the amount (mol%) of deposited fluorine.

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

[0059] Figure 2C shows co-deposition using two different metals. However, in further embodiments, co-deposition may be performed using three or more metals, as described above. When using three or more metals, there can be three or more possible co-deposition sequences. 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: namely, M1+M2+M3+F, M1+M3+M2+F, M2+M1+M3+F, M2+M3+M1+F, M3+M1+M2+F, and M3+M2+M1+F. Therefore, the target composition may be achieved using the following formula. K*[a*(M1+M2+M3+F)+b*(M1+M3+M2+F)+c*(M2+M1+M3+F)+d*(M2+M3+M1+F)+e*(M3+M1+M2+F)+f*(M3+M2+M1+F)] Here, a, b, c, d, e, and f are non-negative integers. The number of moles of M1, M2, and M3 in each co-deposition method may be determined experimentally. Similarly, in the case of co-deposition of four metals, the following co-deposition methods may be mixed to achieve a coating of the target composition: namely, M1+M2+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+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. Therefore, the target composition may be achieved using the following formula. K*[a*(M1+M2+M3+M4+F)+b*(M1+M3+M4+M2+F)+c*(M1+M4+M2+M3+F)+d*(M1+M3+M2+M4+F)+e*(M1+M4+M3+M2+F)+f*(M1+M2+M4+M3+ F)+g*(M2+M1+M3+M4+F)+h*(M2+M3+M4+M1+F)+i*(M2+M4+M1+M3+F)+j*(M2+M1+M4+M3+F)+k(M2+M3+M1+M4+F)+l*(M2+M4+M3+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)] Here, a through x are non-negative integers.

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

[0061] In some embodiments, the 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 obtain a first target mol% of the first metal and a second target mol% of the second metal as a result. Furthermore, multiple deposition supercycles may be performed, where each deposition supercycle includes the steps of performing a first number of M1-M2 co-deposition cycles and 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 1:50. A higher ratio of the first metal-containing fluoride layer to the buffer layer (e.g., 200:1, 100:1, 50:1, 20:1, 10:1, 5:1, 2:1, etc.) may provide higher corrosion and erosion resistance. On the other hand, a lower ratio of the first metal-containing fluoride layer to the buffer layer (e.g., 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, 1:200) may provide higher heat resistance (e.g., improved resistance to cracking and / or delamination caused by thermal cycling). The thickness ratio may be selected according to the specific chamber application. In one embodiment, for a capacitively coupled plasma environment with a high sputtering rate, a 1 μm top layer may be deposited on a 50 nm buffer Al2O3 layer. For high-temperature chemical or radical environments without active ion bombardment, a 100 nm top layer with a 500 nm bottom layer may be optimal.

[0063] Referring to Figure 2D, article 205 may be inserted into the ALD chamber. In this embodiment, the co-deposition process includes the step of simultaneously co-injecting at least two precursors onto the surface of the article. Article 205 may be introduced into a mixture of precursors 210 and 220 for a period of time until the surface of the article or the body of the article is completely adsorbed with the mixture of precursors 210 and 220, forming a co-adsorption layer 227. A mixture of two precursors A and B (e.g., a yttrium-containing precursor and another rare-earth metal fluoride precursor) is 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 embodiments, 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. Subsequently, the article 205 having the co-adsorption layer 227 may be introduced into the reactant 230 and reacted with the co-adsorption layer 227 to grow a solid rare earth metal-containing fluoride coating 235. As shown in the figure, the co-deposition by co-injection of the rare earth metal-containing coating 235 may be repeated m times to achieve a desired coating thickness, where m is an integer greater than 1.

[0064] ALD processing may be carried out at various temperatures depending on the type of processing. The optimal temperature range for a particular ALD processing 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 caused by the chemical vapor deposition (CVD) mechanism. The ALD temperature window may be in the range of about 100°C to about 650°C. In some embodiments, the ALD temperature window is about 20°C to about 200°C, or about 25°C to about 150°C, or about 100°C to about 120°C, or about 20°C to 125°C.

[0065] ALD processing enables conformal rare-earth metal-containing fluoride coatings with uniform thickness on articles and surfaces with complex geometric shapes, high aspect ratio holes (e.g., micropores), and three-dimensional structures. By providing sufficient exposure time for each precursor to the surface, the precursors can be dispersed and reacted completely across the entire surface (including all complex three-dimensional features). The exposure time used 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 technology has advantages over other commonly used coating techniques because it allows for the synthesis of materials in specific compositions or formulations on demand, eliminating the need for the long and difficult production of raw materials (such as powder materials and sintered targets).

[0066] Another usable 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 the first metal, followed by introducing a first reactant to form the first metal fluoride layer. Subsequently, a second precursor for the second metal may be introduced, followed by introducing either the first or second reactant to form the second metal fluoride layer. In some embodiments, an annealing operation may then be performed.

[0067] In some embodiments, two or more of the above-described ALD deposition techniques may be combined to produce a homogeneous metal fluoride coating. For example, co-deposition and co-injection may be combined, co-deposition and sequential deposition may be combined, and / or co-injection and sequential deposition may be combined. In one embodiment, a mixture of yttrium precursor and erbium precursor may be sprayed into the ALD chamber to adsorb yttrium and erbium onto the surface of the article. Subsequently, a mixture of zirconium precursor and hafnium precursor may be sprayed into the ALD chamber to further adsorb zirconium and hafnium onto the surface. Subsequently, a fluorine source reactant may be sprayed into the ALD chamber to adsorb Y v W w Z rx Hfy F z A coating may be formed.

[0068] Figure 3A shows Method 300 for forming a rare-earth metal-containing fluoride coating by co-deposition ALD treatment. Method 300 may be used to coat any article described herein. Method 300 may optionally begin with the selection of a precursor for forming the coating. The selection of composition and the formation method may be carried out by the same organization or by multiple organizations.

[0069] Method 300 may optionally include a step in block 305 of cleaning the article with an acidic solution. In one embodiment, the article is immersed in a bath of the acidic solution. In various 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 is capable of removing surface contaminants from the article and / or oxides from the surface of the article. The step of cleaning the article with an acidic solution may improve the quality of the coating deposited using ALD. In one embodiment, a quartz chamber component is cleaned using an acidic solution containing about 0.1 to 5.0 vol% HF. In one embodiment, an Al2O3 article is cleaned using an acidic solution containing about 0.1 to 20 vol% HCl. In one embodiment, an article made of aluminum and additional metal is cleaned using an acidic solution containing about 5 to 15 vol% HNO3.

[0070] In block 310, the article is loaded into the ALD deposition chamber. In block 325, method 300 optionally includes the step of depositing a buffer layer on the surface of the article or the body of the article using ALD. In block 320, ALD is performed to co-deposit a rare-earth metal-containing fluoride coating onto the article. At least one M1-M2 co-deposition cycle 330 is performed. The M1-M2 co-deposition cycle includes the step in block 335 of introducing a first metal-containing precursor into the ALD chamber containing the article (with or without the buffer layer). The first metal-containing precursor comes into contact with the surface of the article or the body of the article to form a partially metal-adsorbed layer. In block 340, a second metal-containing precursor is introduced into the ALD chamber containing the article having the partially metal-adsorbed layer. The second metal-containing precursor comes into contact with the remaining exposed surfaces of the article or the body of the article to form the M1-M2 co-adsorbed layer. In block 345, the reactant is introduced into the ALD chamber and reacted with the M1-M2 co-adsorption layer to form a rare earth metal-containing fluoride coating.

[0071] Figure 3B shows method 302 for forming a rare earth metal-containing fluoride coating by co-deposition ALD treatment. Method 302 may be used to coat any article described herein. Method 302 may optionally begin with the selection of a precursor for forming the coating. The selection of composition and the formation method may be carried out by the same organization or by multiple organizations.

[0072] Method 302 may optionally include a step in block 305 of cleaning the article with an acidic solution. In block 310, the article is loaded into the ALD deposition chamber. In block 325, Method 302 optionally includes a step of depositing a buffer layer on the surface of the article or the body of the article using ALD. In block 321, ALD is performed to co-deposit a rare-earth metal-containing fluoride coating onto the article. At least one M2-M1 co-deposition cycle 331 is performed. The M2-M1 co-deposition cycle includes a step in block 336 of introducing a second metal-containing precursor into the ALD chamber containing the article (with or without the buffer layer). The second metal-containing precursor comes into contact with the surface of the article or the body of the article to form a partially metal-containing adsorbent layer. In block 341, the first metal-containing precursor is introduced into the ALD chamber containing the article having the second metal adsorbent layer. The first metal-containing precursor comes into contact with the article or the remaining exposed surface of the article's body to form an M2-M1 co-adsorption layer. In block 346, the reactant is introduced into the ALD chamber and reacts with the M2-M1 co-adsorption layer to form a rare earth metal-containing fluoride coating.

[0073] Figure 3C shows a composite method 303 for forming a multilayer coating as described herein, which includes the step of performing at least one M1-M2 co-deposition cycle in block 330. Subsequently, the ALD chamber is purged with an inert gas in block 332. At least one M2-M1 co-deposition cycle is performed in block 350 to form a rare earth metal-containing fluoride coating. As described above, the co-deposition 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, annealing temperatures up to about 500°C may be used for coating.

[0074] Figure 3D shows method 304 for co-depositing rare earth metal-containing fluoride coatings according to embodiments described herein by co-injection. Method 304 may optionally include a step of cleaning the article with an acidic solution in block 305. In block 310, the article is loaded into the ALD deposition chamber. In block 325, method 302 optionally includes a step of depositing a buffer layer on the surface of the article or the body of the article using ALD.

[0075] In block 322, ALD is performed to co-deposit a rare earth metal-containing fluoride coating onto article 205 by co-injection. At least one co-deposition cycle 332 is performed. The co-deposition cycle includes the step of introducing a mixture of a first metal-containing precursor and a second metal-containing precursor into an ALD chamber containing the article (with or without a buffer layer) in block 355. The first and second metal-containing precursors may independently contain metals selected from rare earth metals, zirconium, aluminum, hafnium, and tantalum. The mixture of precursors comes into contact with the surface of the article or the body of the article to form a co-adsorption layer. In block 360, reactants are introduced into the ALD chamber and reacted with the co-adsorption layer to form a rare earth metal-containing fluoride coating. The co-deposition cycle may be repeated as many times as necessary to achieve a coating of the desired thickness.

[0076] According to various embodiments, the method may include a step of co-depositing a rare earth metal-containing fluoride coating onto the surface of an article using atomic layer deposition. The step of co-depositing the rare earth metal-containing fluoride coating may include a step of contacting the surface with a first precursor during a first period to form a partial first metal adsorption layer, wherein the first precursor is 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; a step of contacting the partial metal adsorption layer with a second precursor different from the first precursor during a second period to form a co-adsorption layer containing the first metal and the second metal, wherein the second precursor is 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 a step of contacting the co-adsorption layer with a reactant to form a rare earth metal-containing fluoride coating. In certain embodiments, the rare earth metal-containing fluoride coating comprises about 1 mol% to about 40 mol% of a first metal and about 1 mol% to about 40 mol% of a second metal, and the rare earth metal-containing fluoride coating may be a homogeneous mixture of the first metal and the second metal.

[0077] According to various embodiments, the co-deposition of a rare-earth metal-containing fluoride coating includes a step of performing at least one M1-M2 co-deposition cycle, which includes a step of contacting the surface with a first metal-containing precursor, to form a partially first metal adsorption layer; a step of subsequently contacting the partially first metal adsorption layer with a second metal-containing precursor to form an M1-M2 co-adsorption layer; and a step of contacting the M1-M2 co-adsorption layer with a reactant. As a result of at least one M1-M2 co-deposition cycle, a layer containing a first proportion of the first metal and a second proportion of the second metal may be obtained.

[0078] In some embodiments, the co-deposition of a rare-earth metal-containing fluoride coating may further include: performing at least one M2-M1 co-deposition cycle, which includes contacting the surface with a second metal-containing precursor, to form a partially second metal adsorbed layer; subsequently, contacting the partially metal adsorbed layer with a rare-earth metal-containing precursor to form an M2-M1 co-adsorbed layer; and contacting the M2-M1 co-adsorbed layer with a reactant. As a result of at least one M2-M1 co-deposition cycle, an additional layer may be obtained containing a third proportion of the first metal and a fourth proportion of the second metal, where the third proportion is lower than the first proportion and the fourth proportion is higher than the second proportion.

[0079] The methods according to the embodiments described herein include the steps of selecting a ratio of the number of M1-M2 co-deposition cycles to the number of M2-M1 co-deposition cycles, thereby obtaining a first target mol% of the first metal and a second target mol% of the second metal; and performing a plurality of deposition supercycles, each deposition supercycle further comprising the steps of performing a first number of M1-M2 co-deposition cycles and performing a second number of M2-M1 deposition cycles. According to various embodiments, the step of performing at least one M1-M2 co-deposition cycle may include the steps of: contacting the surface with a rare earth metal-containing precursor for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds; contacting a partially first metal adsorption layer with a second metal-containing precursor for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds; contacting the M1-M2 co-adsorption layer with a reactant for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds; and performing at least one M2-M1 co-deposition cycle. The steps of performing at least one M2-M1 co-deposition cycle may include: contacting the surface with a second metal-containing precursor for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds; contacting the partially metal-adsorbed layer with a rare-earth metal-containing precursor for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds; and contacting the M2-M1 co-adsorbed layer with the reactant for about 50 milliseconds to about 60 seconds, or for about 1 second to about 60 seconds, or for about 5 seconds to about 60 seconds, or for about 10 seconds to about 60 seconds.

[0080] The following examples are provided to aid in understanding the embodiments described herein and should not be construed as specifically limiting the embodiments described herein and claimed. Any modifications, including the substitution of all currently known or subsequently developed equivalents, and any changes or minor modifications to the scheme in experimental designs, which are within the scope of the embodiments incorporated herein, 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 coating Yttrium oxide coatings were deposited on chamber components using atomic layer deposition (DPL). The coated substrates were exposed to a nitrogen trifluoride (NF3) plasma at 450°C for 3,000 cycles in a chemical vapor deposition chamber. Side-section transmission electron microscope (TEM) images of the Y2O3 coating on the substrates were obtained. Transmission electron microscope energy-dispersive X-ray spectroscopy (TEM / EDS) line scans of the Y2O3 coatings were also obtained. During the NF3 treatment of the Y2O3 substrates, the coating and the underlying substrate were damaged by 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 prepared by ALD Sample cut specimens with Al2O3, Y2O3, or YF3 coatings were prepared using ALD deposition. The thickness of the Al2O3 coating was 500 nm, the Y2O3 coating was 100 nm, and the YF3 coating was 100 nm. Each sample was exposed to CF4 inductively coupled plasma for 34 RF hours at a temperature of 75°C and a high-frequency power supply of 300 W.

[0083] After exposure to CF4 plasma, neither the YF3 nor the Y2O3 coatings showed a decrease in thickness (i.e., the etching rate was nearly zero), and the YF3 coating did not show any degradation of its microstructure, while the Y2O3 coating suffered significant degradation of its microstructure. The Y2O3 coating exhibited dense nanocracks and delamination, while the YF3 coating did not. Without being bound by any particular theory, it is thought that when a Y2O3 coating is exposed to fluorine plasma, fluorine diffuses into the coating, replacing oxygen molecules, which causes volume expansion of the Y2O3 coating, resulting in nanocracks and delamination of the coating. Before the formation of nanocracks, the Y2O3 and YF3 coatings act as diffusion barriers, preventing 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 ceases to function as a diffusion barrier because the nanocracks allow metals to diffuse through the coating. Furthermore, nanocracks peel off the Y2O3 coating, causing particulate contamination on the treated substrate. In contrast, the YF3 coating does not develop nanocracks, and therefore remains a good diffusion barrier, not causing particulate contamination even after repeated exposure to fluorine-rich plasma. When fluorine is used instead of oxygen in the coating, fluorine may diffuse into the YF3 coating, but the YF3 coating does not undergo volume expansion and therefore does not form nanocracks or peel off. The Al2O3 coating underwent significant etching, with its thickness reduced from 500 nm to approximately 225 nm (i.e., approximately 275 nm was etched away).

[0084] Similar conditions to those described above for YF3 and Y2O3 have also been demonstrated for comparisons of other rare earth oxides versus rare earth fluorides. For example, Y exposed to 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 be covered in nanocracks (and therefore no longer function as a diffusion barrier, causing particle contamination). On the other hand, Y x Zr y F z The coating does not exhibit nanocracks (and therefore acts as a diffusion barrier, preventing particulate contamination). The same results are obtained when comparing other single-metallic and polymetallic rare-earth oxides with single-metallic and polymetallic rare-earth fluorides.

[0085] The above description provides numerous specific details, such as examples of specific systems, components, and methods, in order 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 can be carried out without such specific and detailed descriptions. In other examples, well-known components or methods are not described in detail or are presented in simple block diagram form to avoid unnecessarily obscuring the invention. Thus, the specific and detailed descriptions are merely illustrative. Certain embodiments may differ from these illustrative descriptions but are still considered to fall within the scope of the present invention.

[0086] Throughout this specification, whenever the terms "in a particular embodiment" or "in one embodiment" are used, it means that any specific configuration, structure, or characteristic described in relation to that embodiment is included in at least one embodiment. Therefore, even if the phrases "in a particular embodiment" or "in one embodiment" appear in various places throughout this specification, they do not necessarily all refer to the same embodiment. Furthermore, the term "or" is intended to mean inclusive, not exclusive. Where the terms "about" or "approximately" are used in this specification, it is intended that the presented nominal values ​​are accurate within a range of ±10%.

[0087] Although the operations of the methods described herein are shown and described in a specific order, the order of the operations of each method may be changed so that certain operations are performed in reverse order, or some operations are performed at least partially in parallel with others. In another embodiment, instructions or suboperations of different operations may be performed intermittently and / or alternately.

[0088] It should be understood that the above description is illustrative and not limiting. By reading and understanding the above description, many other embodiments will become apparent to those skilled in the art. Therefore, the scope of the invention should be determined by reference to the appended claims, together with the entire scope of equivalents to which such claims are entitled.

Claims

1. Articles, The main unit and A buffer layer on the surface of the main body, which is pore-free and contains silicon oxide, aluminum nitride, or a combination thereof, The buffer layer is coated with a rare earth metal-containing fluoride on its surface. Rare earth metal-containing fluoride coatings do not contain pores. The rare earth metal-containing fluoride coating contains 1 mol% to 40 mol% of a primary metal and 1 mol% to 40 mol% of a secondary metal, M1 ｘ M2 ｙ F ｚ It has the following structure, does not contain oxygen, and the first and second metals are independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum, and tantalum, and the first metal is different from the second metal, The rare earth metal-containing fluoride coating contains a homogeneous mixture of a primary metal and a secondary metal. The rare earth metal-containing fluoride coating is a co-deposited coating consisting of multiple layers, each layer containing a first metal and a second metal. Articles coated with rare earth metal-containing fluoride that do not exhibit phase separation.

2. The rare earth metal-containing fluoride coating has a thickness of 5 nm to 10 μm, or The articles are components of a processing chamber selected from the group consisting of chamber walls, shower heads, nozzles, plasma generation units, high-frequency electrodes, electrode housings, diffusers, and gas lines, or The body contains a material selected from the group consisting of aluminum, steel, silicon, copper, and magnesium, or The first metal includes a rare earth metal selected from the group consisting of yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, and dysprosium, or The first metal contains yttrium, and the rare earth metal-containing fluoride coating contains zirconium in a concentration of 1 mol% to 40 mol%, or The rare earth metal-containing fluoride coating is Y ｘ Zr ｙ F ｚ 、Y ｘ Zr ｙ F ｚ 、Er ｘ Zr ｙ F ｚ 、Y ｗ Zr ｘ Hf ｙ F ｚ 、Er ｗ Zr ｘ Hf ｙ F ｚ 、Y ｖ Er ｗ Zr ｘ Hf ｙ F ｚ 、Y ｘ Hf ｙ F ｚ 、Er ｘ Hf ｙ F ｚ 、Y ｘ Ta ｙ F ｚ 、Er ｘ Ta ｙ F ｚ 、Y ｗ Ta ｘ Hf ｙ F ｚ 、Er<000004" +Ta ｘ Hf ｙ F ｚ and Y ｖ Er ｗ Ta ｘ Hf ｙ F ｚ The article according to claim 1, comprising a composition selected from the group consisting of

3. A step of depositing a buffer layer on the surface of the main body, wherein the deposited buffer layer does not contain pores and includes silicon oxide, aluminum nitride, or a combination thereof. A method comprising the step of co-depositing a porosity-free rare-earth metal-containing fluoride coating onto the surface of a buffer layer using atomic layer deposition, The process of co-depositing a rare earth metal-containing fluoride coating is, A step of bringing a surface into contact with a first metal-containing precursor or a second metal-containing precursor during a first period to form a surface including a partially metal-adsorbed layer containing 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. A step of bringing a surface containing a partially metal adsorption layer into contact with a second metal-containing precursor or a first metal-containing precursor during the second period to form a co-adsorption layer containing a first metal (M1) and a second metal (M2), wherein the first metal is different from the second metal. The process includes a step of bringing a co-adsorption layer into contact with a reactant to form a rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating has an M1xM2yFz structure and is oxygen-free. The rare earth metal-containing fluoride coating contains 1 mol% to 40 mol% of a primary metal and 1 mol% to 40 mol% of a secondary metal. The rare earth metal-containing fluoride coating comprises a homogeneous mixture of a primary metal and a secondary metal, and the rare earth metal-containing fluoride coating is a method that does not involve phase separation.

4. The process of co-depositing a rare earth metal-containing fluoride coating is, A step of performing at least one M1-M2 codeposition cycle, A step of bringing the surface into contact with a first metal-containing precursor to form a surface including a partially metal-adsorbed layer, Next, the surface containing the partially metal adsorption layer is brought into contact with a second metal-containing precursor to form an M1-M2 co-adsorption layer. The process includes a step of bringing the M1-M2 co-adsorption layer into contact with a reactant, The method according to claim 3, wherein a layer containing a first proportion of a first metal and a second proportion of a second metal is obtained by at least one M1-M2 codeposition cycle.

5. The process of co-depositing a rare earth metal-containing fluoride coating is, A step of performing at least one M2-M1 codeposition cycle, A step of bringing the surface into contact with a second metal-containing precursor to form a surface including a second partial metal adsorption layer, Next, the surface including the second partial metal adsorption layer is brought into contact with the first metal-containing precursor to form an M2-M1 co-adsorption layer. The process further includes a step of bringing the M2-M1 co-adsorption layer into contact with a reactant, The method according to claim 4, wherein at least one M2-M1 codeposition cycle yields an additional layer containing 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.

6. A step of selecting the ratio of the first number of M1-M2 co-deposition cycles to the second number of M2-M1 co-deposition cycles, wherein as a result of the selection, a first target mol% of the first metal and a second target mol% of the second metal are obtained. The method according to claim 5, further comprising the step of performing a plurality of sedimentation supercycles, each sedimentation supercycle comprising the step of performing a first number of M1-M2 co-sedimentation cycles and the step of performing a second number of M2-M1 co-sedimentation cycles.

7. The step of performing at least one M1-M2 co-deposition cycle is: A step of bringing the surface into contact with a first metal-containing precursor for 50 milliseconds to 60 seconds, A step of bringing a surface containing a partially metal adsorption layer into contact with a second metal-containing precursor for 50 milliseconds to 60 seconds, The process includes the step of bringing the M1-M2 co-adsorption layer into contact with the reactant for 50 milliseconds to 60 seconds. The step of performing at least one M2-M1 co-deposition cycle is: A step of bringing the surface into contact with a second metal-containing precursor for 50 milliseconds to 60 seconds, A step of bringing a surface containing a second partial metal adsorption layer into contact with a first metal-containing precursor for 50 milliseconds to 60 seconds, The method according to claim 5, comprising the step of bringing the M2-M1 co-adsorbent layer into contact with a reactant for 50 milliseconds to 60 seconds.

8. The first metal-containing precursor and the second metal-containing precursor are independently: cyclopentadienyl precursor, tris(methylcyclopentadienyl)yttrium((CH3Cp)3Y), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(ethylcyclopentadienyl)yttrium, tris-methylcyclopentadienylerbium(III)(Er(MeCp)3), tris(butylcyclopentadienyl)erbium(III); amidinate precursor, tris(N,N'-diisopropylformamidinate)yttrium, tris(2,2,6,6-tetramethylheptane-3,5-diona The method according to claim 3, selected from the group consisting of yttrium, tris(bis(trimethylsilyl)amide)lanthanum, amide precursors, erbium boranamide (Er(BA)3), β-diketnate precursors, erbium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(dimethylamino)(cyclopentadienyl)zirconium, tetrakis(dimethylamide)zirconium, tetrakis(diethylamide)zirconium, tetrakis(N,N'-dimethylformamidinate)zirconium, tetra(ethylmethylamide)hafnium, and pentakis(dimethylamide)tantalum.

9. The method according to claim 3, further comprising the step of contacting a co-adsorption layer with a third precursor to adsorb a third metal, and then contacting the co-adsorption layer with a reactant, wherein the third precursor is selected from the group consisting of yttrium precursor, erbium precursor, zirconium precursor, hafnium precursor, silicon precursor, tantalum precursor, lanthanum precursor, lutetium precursor, scandium precursor, gadolinium precursor, samarium precursor, and dysprosium precursor.

10. The rare earth metal-containing fluoride coating is Y 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 The method according to claim 3, comprising a composition selected from the group consisting of these and combinations thereof.

11. A step of depositing a buffer layer on the surface of the main body, wherein the deposited buffer layer does not contain pores and includes silicon oxide, aluminum nitride, or a combination thereof. A method comprising the step of co-depositing a porosity-free rare-earth metal-containing fluoride coating onto the surface of a buffer layer using atomic layer deposition, The process of co-depositing a rare earth metal-containing fluoride coating is, A step of performing at least one co-injection cycle, A step of forming a co-adsorbent layer by bringing the surface into contact with a mixture of a first precursor and a second precursor during a first period, wherein the first precursor and the second precursor are each 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. The process includes a step of contacting a co-adsorption layer with a fluorine-containing reactant to form a rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating has an M1xM2yFz structure and does not contain oxygen. The rare earth metal-containing fluoride coating comprises 1 mol% to 40 mol% of a first metal and 1 mol% to 40 mol% of a second metal, where the first and second metals are independently selected from the group consisting of rare earth metals, zirconium, hafnium, aluminum, and tantalum, and the first metal differs from the second metal. The rare earth metal-containing fluoride coating contains a homogeneous mixture of the first and second metals. The rare earth metal-containing fluoride coating method does not involve phase separation.

12. The method according to claim 11, wherein the mixture further comprises a third precursor containing a metal different from the first metal of the first precursor and the second metal of the second precursor, the metal of the third precursor being selected from the group consisting of yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, dysprosium, zirconium, hafnium, and tantalum, and the homogeneous mixture further comprises the metal of the third precursor.

13. A step of depositing a buffer layer on the surface of the main body, wherein the deposited buffer layer does not contain pores and includes silicon oxide, aluminum nitride, or a combination thereof. A method comprising the step of depositing a porosity-free rare-earth metal-containing fluoride coating onto the surface of a buffer layer using atomic layer deposition, The process of depositing a rare earth metal-containing fluoride coating is as follows: The process involves bringing the surface into contact with a first precursor during the first period to form a first metal adsorption layer, A step of bringing a first metal adsorption layer into contact with a fluorine-containing reactant to form a first metal fluoride layer, The process involves bringing the first metal fluoride layer into contact with the second precursor during the second period to form a second metal adsorption layer, A step of forming a second metal fluoride layer by contacting the second metal adsorption layer with the fluorine-containing reactant or an alternative fluorine-containing reactant, A step of annealing a first metal fluoride layer and a second metal fluoride layer to form a rare earth metal-containing fluoride coating, wherein the rare earth metal-containing fluoride coating has an M1xM2yFz structure and is oxygen-free, and the step includes the following: The rare earth metal-containing fluoride coating contains a homogeneous mixture of the primary and secondary metals. The rare earth metal-containing fluoride coating contains 1 mol% to 40 mol% of a first metal and 1 mol% to 40 mol% of a second metal, where the first and second metals are independently selected from the group consisting of rare earth metals, hafnium, and tantalum, and the first metal is different from the second metal. The rare earth metal-containing fluoride coating method does not involve phase separation.

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