Metal oxyfluoride coating for chamber components and coating method thereof

Abstract

A chamber component is provided with a metal oxyfluoride coating containing YF3, ZrF4, or a combination thereof, and a metal oxide consisting of Y2O3 and ZrO2. The metal oxyfluoride coating contains 5 mol% to 90 mol% YF3 or ZrF4 and 10 mol% to 95 mol% metal oxide. The metal oxyfluoride coating is amorphous and contains 35 to 50 atomic % yttrium (Y), 0.3 to 10 atomic % zirconium (Zr), 5 to 57 atomic % oxygen (O), and 3 to 65 atomic % fluorine (F).

Description

[Technical Field]

[0001] BACKGROUND OF THE INVENTION 1. Field of the Invention Embodiments of the present disclosure generally relate to methods of coating articles with coatings comprising metal oxyfluorides. The present disclosure also relates to coatings comprising metal oxyfluorides that are amorphous.

[0002] During various manufacturing processes, chamber components and their coating materials are exposed to high temperatures, high-energy plasmas, corrosive gas mixtures, high stresses, and combinations of these. Rare earth oxides are frequently used in the fabrication of chamber components because they are resistant to erosion by plasma etching chemistries. However, exposure of rare earth oxides to fluorine-based plasmas can cause cracking and particle flaking onto the wafer.

[0003] Oxide coatings such as YO are permeable to moisture and can cause moisture adsorption. As a result, when oxide coatings such as YO are exposed to air, a brittle M(OH) layer (e.g., Y(OH)) (where M is the metal) typically forms on the surface of the oxide coating. Tests have shown that multiple -OH groups exist on the surface of YO exposed to air. The M(OH) layer is brittle and can release particles onto processed wafers. Furthermore, the M(OH) layer increases the leakage current of metal oxide coatings (e.g., YO).

[0004] In some instances, YF3 has been used as a coating on chamber components. The use of YF3 coatings can mitigate the problem of yttrium-based particles on processed wafers. However, the application of YF3 coatings to chamber components in etch reactors has been shown to result in significant etch rate degradation (e.g., up to 60% etch rate reduction), process drift, and chamber matching issues. Overview

[0005] In one embodiment, a method is provided. The method includes providing a metal oxyfluoride source containing YF3, ZrF4, or a combination thereof, and metal oxides consisting of yttrium oxide (YO3) and zirconium oxide (ZrO2), where the metal oxyfluoride source contains about 5 mol% to about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% to about 95 mol% metal oxide. The method also includes vapor deposition, sputter deposition, or evaporation of the metal oxyfluoride source to form a metal oxyfluoride coating on an article. The metal oxyfluoride coating contains about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F). The formed metal oxyfluoride coating is amorphous.

[0006] In another embodiment, a thin film is provided, the thin film comprising a metal oxyfluoride comprising about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F), and the thin film is amorphous.

[0007] In another embodiment, a process is provided. The process includes depositing a metal oxyfluoride coating on a surface of a chamber component. The metal oxyfluoride coating includes yttrium fluoride (YF), zirconium fluoride (ZrF), or a combination thereof, and a metal oxide consisting of yttrium oxide (YO) and zirconium oxide (ZrO), wherein the YF or ZrF is about 5 mol% to about 90 mol% and the metal oxide is about 10 mol% to about 95 mol%. The metal oxyfluoride coating is amorphous.

[0008] In yet another embodiment, a method is provided. The method includes providing a metal fluoride source comprising YF3, ZrF4, or a combination thereof, and a metal oxide source comprising yttrium oxide (YO3) and zirconium oxide (ZrO2), wherein the metal oxide source comprises about 0.1 mol% to about 20 mol% ZrO2. The method also includes vapor-depositing, sputter-depositing, or evaporating the metal fluoride source while simultaneously and independently vapor-depositing, sputter-depositing, or evaporating the metal oxide source to form a metal oxyfluoride coating on an article. The evaporation and deposition rates from the metal fluoride source and the metal oxide source, respectively, can form a metal oxyfluoride coating containing about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F). The metal oxyfluoride coating that is formed is amorphous. [Brief explanation of the drawings]

[0009] The present disclosure is illustrated by way of example, and not by way of limitation, in the accompanying drawings, in which like reference numerals indicate similar elements. It should be noted that different references to "one embodiment" in the present disclosure do not necessarily refer to the same embodiment, and that such references mean at least one embodiment. [Figure 1] 1 illustrates a cross-sectional view of one embodiment of a processing chamber. [Figure 2] 1 illustrates a process for forming a MOF layer on the surface of a metal oxide coating according to one embodiment. [Figure 3] 1A-1C show cross-sectional side views of chamber components including MOF layers according to embodiments. [Figure 4] 1 shows an example of a manufacturing system architecture. Detailed Description of the Embodiments

[0010] Embodiments disclosed herein describe coated articles, coated chamber components, methods for coating articles and chamber components, methods for reducing or eliminating defects in semiconductor processing chambers, and methods for using coated articles and chamber components, as well as processing chambers containing coated articles and chamber components. Coatings are applied to articles and / or chamber components to reduce reactions between the component materials and reactive chemicals and / or plasmas (resulting in the formation of particles and other trace metal contaminants). The coatings can also reduce defects and extend the seasoning time of the articles and / or chamber components. The coatings can be or include metal oxyfluoride layers, where the metals can include a combination of yttrium (Y) and zirconium (Zr). It has been found that defects are reduced when the coating is in an amorphous state, and the amorphous state improves plasma resistance during chemical and etching processes. The inventors have discovered that incorporating oxygen into either the Y or Zr fluorides, or both, inhibits crystallization and creates an amorphous state.

[0011] Previous approaches to coating articles or chamber components have used fluorine-free yttrium oxide and yttrium-zirconium binary oxide compositions. These compositions have slow seasoning times and increased particle defects on processed substrates (e.g., wafers). In the disclosed coatings, combining Y and Zr oxides with Y or Zr fluorides, or both, has been found to shorten seasoning times and reduce particle defects. Thus, embodiments improve the lifetime of chamber components by using more amorphous coatings to protect them from the corrosive environment of plasma processes. Y-Zr-OF coatings and layers are highly resistant to erosion and corrosion by fluorine-based plasmas. Furthermore, Y-Zr-OF coatings generally resist fluorination by fluorine-based plasmas. As a result of these properties, the Y-Zr-OF coatings and layers described herein significantly reduce particles, improve wafer processing throughput, and process stability, and also improve etch rate uniformity and chamber-to-chamber uniformity when used on chamber components in processing chambers.

[0012] Furthermore, with conventional approaches to coating articles or chamber components, there are two primary failure mechanisms for coatings in the field. In the first failure mechanism, the etch rate of the processing chamber affects the lifetime of the coated chamber component or coated article. Consequently, the etch rate eventually causes the coating to wear out. In the second failure mechanism, reaction products are generated during processing and can accumulate on the chamber component or article coating. These reaction products can flake off the coating, causing particle contamination and / or altering the chamber process chemistry, thereby affecting, for example, the wafer etch rate. Therefore, any chamber component coating must be able to withstand varying etch rates and avoid the accumulation of reaction products on the chamber component. To achieve this, the inventors have discovered that coatings in an amorphous state exhibit slower wear, lower etch rates, and greater resistance to reaction products than coatings in a crystalline state.

[0013] It has been found that rendering the metal oxyfluoride coating amorphous reduces defects during the etching process. Furthermore, the coating can provide chemical and / or etch resistance in a plasma environment. The metal oxyfluoride coating can include a combination of YF3, ZrF4, and YO3-ZrO2, which is amorphous when applied to a surface. This combination in the coating has been found to provide faster in-chamber seasoning times to reach stable wafer etch rates compared to YO3 or YO3-ZrO2 oxide compositions. Furthermore, the disclosed metal oxyfluoride coatings have been found to have superior chemical resistance and produce fewer particle defects on chamber components, such as wafers, than YO3, YAG, or YF3. Furthermore, the metal oxyfluoride coatings are denser and more amorphous than YO3 or YO3-ZrO2 oxide compositions, resulting in faster seasoning times and less / slower drift during use.

[0014] In embodiments disclosed herein, a coating method is provided. The method includes providing a metal oxyfluoride precursor including YF3, ZrF4, or a combination thereof, and a metal oxide including yttrium oxide (YO) and zirconium oxide (ZrO). In some embodiments, the metal oxyfluoride precursor includes about 5 mol% to about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% to about 95 mol% metal oxide. The method further includes vapor-depositing, sputter-depositing, or vapor-depositing the metal oxyfluoride precursor to form a metal oxyfluoride coating on an article. The metal oxyfluoride coating can have about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F). In embodiments, the metal oxyfluoride coating is amorphous. When the coating is amorphous, a denser coating can be formed, limiting the surface area that can become fluorinated or react with the chamber environment during processing in the processing chamber. Thus, the coating can season the chamber part or article and reach equilibrium with the process at a faster rate than a crystalline coating.

[0015] Without being bound by any particular theory, the addition of fluorine to metal oxides to achieve an amorphous state disrupts the crystalline structure during the condensation and crystallization process during the coating process, promoting the amorphization of the coating. The thermodynamically stable crystalline structure of metal oxyfluorides is more complex and requires higher atomic arrangement than the cubic crystalline structure of metal oxides such as Y2O3 and ZrO2. Because complex crystalline structures are kinetically unfavorable during physical vapor deposition of the coating, amorphization, or the amorphous state, is favored and suppressed.

[0016] In some embodiments, the metal oxyfluoride coating can be formed by atmospheric pressure plasma spraying (APPS), low pressure plasma spraying (LPPS), suspension plasma spraying (SPS), ion-assisted deposition (IAD), chemical vapor deposition (CVD), atomic layer deposition (ALD), magnetron sputtering physical vapor deposition (MSPVD), plasma-enhanced chemical vapor deposition (PECVD), plasma-enhanced atomic layer deposition (PEALD), or other deposition techniques. In some embodiments, the bulk metal oxyfluoride material can be formed by hot pressing, cold pressing, spark plasma sintering, reverse co-precipitation, or similar processes. The bulk metal oxyfluoride material can be used in ceramic products (e.g., nozzles, lids, chamber liners, etc.). The bulk metal oxyfluoride material can also be bonded to chamber components using diffusion bonding, metallurgical bonding, or the like. In such embodiments, the bulk metal oxyfluoride material can be used as a protective layer on chamber components.

[0017] In some embodiments, the metal oxyfluoride source can include about 50 mol% YF3, ZrF4, or a combination thereof, and about 50 mol% metal oxide. In other embodiments, the metal oxyfluoride source can include about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% metal oxide. In yet other embodiments, the metal oxyfluoride source can include about 5 mol% YF3, ZrF4, or a combination thereof, and about 95 mol% metal oxide. In some embodiments, the metal oxyfluoride source can include about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 50 mol%, about 75 mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol% YF, ZrF, or a combination thereof, and about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 50 mol%, about 75 mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol% metal oxide.

[0018] In some embodiments, the metal oxides can include Y2O3 and ZrO2. In some embodiments, Y2O3 can comprise about 80%, about 85%, about 90%, or about 95% based on the total mole percent of the metal oxides. In some embodiments, ZrO2 can comprise about 2%, about 5%, about 10%, about 15%, or about 20% based on the total mole percent of the metal oxides.

[0019] In some embodiments, the metal oxyfluoride source can include about 50 mol% YF3 or ZrF4 and about 50 mol% metal oxide. The metal oxide can include about 80%, about 85%, about 90%, or about 95% Y2O3 and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO2, based on the total mole percent of the metal oxides. In other embodiments, the metal oxyfluoride source can include about 90 mol% YF3, ZrF4, or a combination thereof and about 10 mol% metal oxide. The metal oxide can include about 80%, about 85%, about 90%, or about 95% Y2O3 and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO2, based on the total mole percent of the metal oxides. In yet other embodiments, the metal oxyfluoride source can include about 5 mole percent YF, ZrF, or a combination thereof, and about 95 mole percent metal oxide, which can include about 80%, about 85%, about 90%, or about 95% Y2O3 and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO2, based on the total mole percent of the metal oxide.

[0020] In some embodiments, the article may include a semiconductor processing chamber part or a processing chamber part for other manufacturing processes (e.g., displays, photovoltaics, etc.) Examples of processing chamber parts include lids, nozzles, chucks (e.g., electrostatic chucks), chamber liners, windows, heaters, etc.

[0021] In some embodiments, the metal oxyfluoride coating is comprised of a Y—Zr—OF layer.

[0022] In another embodiment of the present disclosure, a coating is provided, the coating comprising a metal oxyfluoride having about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F), and the coating is amorphous.

[0023] In some embodiments of the coating, the coating can coat at least one surface of a chamber component of a semiconductor processing device.

[0024] In yet another embodiment of the present disclosure, a process is provided that includes forming a metal oxyfluoride material on a surface of a chamber component, the metal oxyfluoride material including yttrium fluoride (YF) or zirconium fluoride (ZrF) and a metal oxide consisting of yttrium oxide (YO) and zirconium oxide (ZrO), wherein the YF is about 5 mol % to about 90 mol % and the metal oxide is about 10 mol % to about 95 mol %, and the metal oxyfluoride material is amorphous.

[0025] In some embodiments, the process can further include heating the chamber components.

[0026] In some embodiments of the process, the metal oxyfluoride material has about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F).

[0027] In some embodiments, the metal oxyfluoride material can include about 50 mol% YF3, ZrF4, or a combination thereof, and about 50 mol% metal oxide. In other embodiments, the metal oxyfluoride material can include about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% metal oxide. In yet other embodiments, the metal oxyfluoride material can include about 5 mol% YF3, ZrF4, or a combination thereof, and about 95 mol% metal oxide.

[0028] In some embodiments of the process, the method of forming the metal oxyfluoride coating can include performing one of: performing a plasma spray process to deposit the metal oxyfluoride coating; performing atomic layer deposition (ALD) to deposit the metal oxyfluoride coating; performing ion-assisted deposition (IAD) to deposit the metal oxyfluoride coating; performing an air plasma spray process to deposit the metal oxyfluoride coating; performing vapor deposition to deposit the metal oxyfluoride coating; performing physical vapor deposition (PVD) or electron beam physical vapor deposition (EBPVD) to deposit the metal oxyfluoride coating; performing a magnetron sputtering process to deposit the metal oxyfluoride coating; or performing a suspension plasma spray process to deposit the metal oxyfluoride coating.

[0029] In some embodiments, the metal oxyfluoride material is a bulk material that can be used as a protective layer on a chamber component or as the chamber component itself. In such embodiments, forming the metal oxyfluoride material can include performing a spark plasma sintering process to form the metal oxyfluoride material, performing a hot pressing process to form the metal oxyfluoride material, performing a cold isostatic pressing process to form the metal oxyfluoride material, or performing a reverse co-precipitation process to form the metal oxyfluoride material.

[0030] In some embodiments of the process, the thickness of the metal oxyfluoride material (eg, coating or layer) is from about 10 nm to about 300 μm.

[0031] Another embodiment of the present disclosure provides a method. The method can include providing a metal oxyfluoride precursor containing YF3, ZrF4, or a combination thereof, and metal oxides consisting of yttrium oxide (YO3) and zirconium oxide (ZrO2), where the metal oxyfluoride precursor contains about 0.1 mol% to about 20 mol% ZrO2. The method can also include performing one of vapor deposition, physical vapor deposition (PVD), electron beam physical vapor deposition (EBPVD), sputter deposition, or evaporation of the metal oxyfluoride precursor to form a metal oxyfluoride coating on an article. The metal oxyfluoride coating has about 35-50 atomic % yttrium (Y), about 0.3-10 atomic % zirconium (Zr), about 5-57 atomic % oxygen (O), and about 3-65 atomic % fluorine (F). The formed metal oxyfluoride coating is amorphous.

[0032] In some embodiments of the method, the metal oxyfluoride source can include about 50 mol% YF3, ZrF4, or a combination thereof, and about 50 mol% metal oxide. In other embodiments, the metal oxyfluoride source includes about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% metal oxide. In yet other embodiments, the metal oxyfluoride source includes about 5 mol% YF3, ZrF4, or a combination thereof, and about 95 mol% metal oxide. In some embodiments, the metal oxyfluoride source can include about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 50 mol%, about 75 mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol% YF, ZrF, or a combination thereof, and about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 50 mol%, about 75 mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol% metal oxide.

[0033] In some embodiments, the metal oxides can include Y2O3 and ZrO2. In some embodiments, Y2O3 can be present at about 80%, about 85%, about 90%, or about 95% based on the total mole percent of the metal oxides. In some embodiments, ZrO2 can be present at about 2%, about 5%, about 10%, about 15%, or about 20% based on the total mole percent of the metal oxides.

[0034] In some embodiments, the metal oxyfluoride source can include about 50 mol% YF, ZrF, or a combination thereof, and about 50 mol% metal oxide. The metal oxide can include about 80%, about 85%, about 90%, or about 95% YO and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO, based on the total mole percent of the metal oxide. In other embodiments, the metal oxyfluoride source can include about 90 mol% YF, ZrF, or a combination thereof, and about 10 mol% metal oxide. The metal oxide can include about 80%, about 85%, about 90%, or about 95% YO and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO, based on the total mole percent of the metal oxide. In yet other embodiments, the metal oxyfluoride source can include about 5 mole percent YF, ZrF, or a combination thereof, and about 95 mole percent metal oxide, which can include about 80%, about 85%, about 90%, or about 95% Y2O3 and about 2%, about 5%, about 10%, about 15%, or about 20% ZrO2, based on the total mole percent of the metal oxide.

[0035] In some embodiments, the article may include a semiconductor processing chamber part or a processing chamber part for other manufacturing processes (e.g., displays, photovoltaics, etc.) Examples of processing chamber parts include lids, nozzles, chucks (e.g., electrostatic chucks), chamber liners, windows, heaters, etc.

[0036] In some embodiments, the metal oxyfluoride coating is comprised of a Y—Zr—OF layer.

[0037] In some embodiments, the metal oxyfluoride coating is formed by ion-assisted deposition (IAD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), electron beam physical vapor deposition (EBPVD), sputter deposition, evaporation, or other deposition techniques. The metal oxyfluoride coating can be formed by combining YF3 with a metal oxide, such as yttrium oxide, zirconium oxide, or a combination thereof. The metal oxyfluoride coating can be formed to be amorphous and not have a crystalline structure. Having a coating with an amorphous structure is believed to limit the surface area that can react with the chamber environment and / or be fluorinated or oxidized. Therefore, the chamber parts can be seasoned and reach equilibrium faster than conventionally coated chamber parts.

[0038] As used herein, the term "heat treating" refers to subjecting a ceramic article to high temperatures, such as in a furnace. "Plasma-resistant material" refers to a material that is resistant to erosion and corrosion due to exposure to plasma treatment conditions. Plasma treatment conditions include, among others, C2F6, SF6, SiCl4, HBr, NF 3、 CF 4、These include plasmas generated from halogen-containing gases such as CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, and SiF4, as well as other gases such as O2 and NO. The plasma resistance of a material is measured by its "etch rate" (ER), which may be measured in angstroms per minute (Å / min), during operation and exposure of the coated part to the plasma. Plasma resistance can also be measured by its erosion rate, which has units of nanometers per radio frequency hour (nm / RFHr), where 1 RFHr represents 1 hour of treatment under the plasma treatment conditions. Measurements can be taken after different treatment times. For example, measurements can be taken before treatment, after 50 treatment hours, after 150 treatment hours, after 200 treatment hours, etc. Erosion rates of less than about 100 nm / RFHr are common for plasma-resistant coating materials. A single plasma-resistant material may have several different plasma resistance or erosion rate values. For example, a plasma-resistant material may have a first plasma resistance or erosion rate associated with a first type of plasma and a second plasma resistance or erosion rate associated with a second type of plasma.

[0039] The terms "about" and "approximately," when used herein, mean that the nominal value presented is accurate to within ±10%. Some embodiments are described herein with respect to chamber components and other articles installed in a plasma etching apparatus for semiconductor manufacturing. However, it should be understood that such plasma etching apparatuses can also be used in the manufacture of microelectromechanical systems (MEMS) devices. Furthermore, the articles described herein may be other structures exposed to plasma or other corrosive environments. The articles discussed herein may be chamber components for a processing chamber, such as a semiconductor processing chamber. For example, the article may be a plasma etching apparatus, a plasma cleaner, a plasma propulsion system, or a chamber component for other processing chambers. Examples of chamber components that may benefit from embodiments of the present invention include a substrate support assembly, an electrostatic chuck (ESC), a ring (e.g., a process kit ring or a single ring), chamber walls, a base, a gas distribution plate, a faceplate, a showerhead, a nozzle, a lid, a liner, a liner kit, a shield, a plasma screen, a flow equalizer, a cooling base, a chamber viewport, a chamber lid, etc.

[0040] Additionally, embodiments are described herein for MOF layers, components, and coatings that reduce particle contamination when used in processing chambers for plasma-rich processes. However, it should be understood that the MOF layers, components, and coatings described herein can also reduce particle contamination when used in processing chambers for other processes, such as non-plasma etching equipment, non-plasma cleaning equipment, chemical vapor deposition (CVD) chambers, physical vapor deposition (PVD) chambers, plasma-enhanced chemical vapor deposition (PECVD) chambers, plasma-enhanced physical vapor deposition (PEPVD) chambers, and plasma-enhanced atomic layer deposition (PEALD) chambers. Furthermore, the techniques described herein for forming MOF layers and coatings can be applied to articles other than chamber components for processing chambers.

[0041] Referring to the drawings, FIG. 1 is a cross-sectional view of a processing chamber 100 (e.g., a semiconductor processing chamber) including one or more chamber parts including a metal oxyfluoride layer or coating according to an embodiment of the present invention. The processing chamber 100 can be used for processes in which a corrosive plasma environment is provided. For example, the processing chamber 100 can be a plasma etch reactor (also referred to as a plasma etcher), a plasma cleaner, or the like. Examples of chamber components that can be formed from metal oxyfluorides or that can include a metal oxyfluoride layer or coating include a substrate support assembly 148, an electrostatic chuck (ESC), a ring (e.g., a process kit ring or a single ring), chamber walls, a base, a showerhead 130, a gas distribution plate, a liner, a liner kit, a shield, a plasma screen, a flow equalizer, a cooling base, a chamber viewport, a chamber lid, a nozzle, a process kit ring, etc.

[0042] In one embodiment, a metal oxyfluoride component, layer, or coating can be formed using a metal oxyfluoride precursor. The metal oxyfluoride precursor can include YF3, ZrF4, or a combination thereof, and a metal oxide. The metal oxide can be yttrium oxide (YO3) and zirconium oxide (ZrO2). The metal oxyfluoride component, layer, or coating can include 35-50 atomic % Y, 0.3-10 atomic % Zr, 5-57 atomic % O, and 3-65 atomic % F. In an embodiment, the metal oxyfluoride component, layer, or coating is amorphous.

[0043] In one embodiment, the processing chamber 100 includes a chamber body 102 and a showerhead 130 that enclose an interior volume 106. The showerhead 130 may or may not include a gas distribution plate. For example, the showerhead may be a multi-piece showerhead including a showerhead base and a showerhead gas distribution plate bonded to the showerhead base. Alternatively, the showerhead 130 may be replaced by a lid and a nozzle in some embodiments, or by multiple pie-shaped showerhead compartments and plasma generation units in other embodiments. The chamber body 102 may be fabricated from aluminum, stainless steel, or other suitable materials. The chamber body 102 generally includes a sidewall 108 and a bottom 110. Any of the showerhead 130 (or lid and / or nozzle), sidewall 108, and / or bottom 110 may include a metal oxyfluoride coating.

[0044] An outer liner 116 may be disposed adjacent the sidewall 108 to protect the chamber body 102. The outer liner 116 may be a halogen-containing gas resistant material such as Al2O3 or YO3. In some embodiments, the outer liner 116 may be coated with a metal oxyfluoride coating.

[0045] An exhaust port 126 may be formed in the chamber body 102 to couple the interior volume 106 to a pumping system 128. The pumping system 128 may include one or more pumps and a throttle valve used to evacuate and regulate the pressure in the interior volume 106 of the processing chamber 100.

[0046] The showerhead 130 can be supported on the sidewall 108 of the chamber body 102 and / or on top of the chamber body. The showerhead 130 (or lid) can be opened to provide access to the interior volume 106 of the processing chamber 100 and can be closed to enclose the processing chamber 100. A gas panel 158 can be coupled to the processing chamber 100 and supply process and / or cleaning gases to the interior volume 106 through the showerhead 130 or the lid and nozzles. The showerhead 130 can be used in processing chambers used for dielectric etching (etching of dielectric materials). The showerhead 130 includes multiple gas supply holes 132 throughout the showerhead 130. The showerhead 130 can be aluminum, anodized aluminum, an aluminum alloy (e.g., Al6061), or anodized aluminum alloy. In some embodiments, the showerhead includes a gas distribution plate (GDP) bonded to the showerhead. The GDP can be, for example, Si or SiC. Additionally, the GDP can include a plurality of holes that align with the holes in the showerhead.

[0047] Examples of process gases that can be used to process substrates in the process chamber 100 include C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, Cl2, CCl 4、 Examples of suitable carrier gases include halogen-containing gases such as BCl3 and SiF4, and other gases such as O2 and N2O. Examples of carrier gases include N2, He, Ar, and other gases that are inert (e.g., non-reactive) to the process gases. Fluorine-based gases can cause fluoride deposits to build up in standard showerhead holes or form a contamination layer in the showerhead holes. However, the holes 132 of the showerhead 130 can be made resistant to such fluoride buildup by the metal oxyfluoride coating 152.

[0048] The substrate support assembly 148 is positioned within the interior volume 106 of the processing chamber 100 below the showerhead 130. The substrate support assembly 148 holds a substrate 144 (e.g., a wafer) during processing. The substrate support assembly 148 may include an electrostatic chuck to secure the substrate 144 during processing, a metal cooling plate bonded to the electrostatic chuck, and / or one or more additional components. An inner liner (not shown) may cover the periphery of the substrate support assembly 148. The inner liner may be a halogen-containing gas-resistant material such as Al2O3 or YO3.

[0049] In embodiments, the showerhead 130 (or lid and / or nozzle), sidewalls 108, bottom 110, substrate support assembly 148, outer liner 116, inner liner (not shown), or other chamber components may be composed of a metal oxyfluoride and / or include a metal oxyfluoride coating. For example, as shown, the showerhead 130 includes a metal oxyfluoride coating 152. In some embodiments, the MOF coating is a Y-Zr-OF coating.

[0050] FIG. 2 illustrates a process 200 for applying a coating to a surface of an article, according to embodiments. In some embodiments, the coating can be formed using a metal oxyfluoride precursor. In block 205, a metal oxyfluoride precursor is provided. In one embodiment, the metal oxyfluoride precursor includes YF3, ZrF4, or a combination thereof, and a metal oxide. The metal oxide includes Y2O3, ZrO2, or a combination thereof. In one embodiment, to prepare the metal oxyfluoride precursor, the YF3, ZrF4, or a combination thereof and the metal oxide may comprise powders or pellets and be physically mixed. In another embodiment, to prepare the metal oxyfluoride precursor, the YF3, ZrF4, or a combination thereof and the metal oxide comprise powders or pellets and are thermo-physically fused together by hot pressing, hot isostatic pressing, cold isostatic pressing, or a similar process. In yet other embodiments, metal fluorides such as YF3 or ZrF4 and oxide materials such as YO3 or ZrO2 may be fused and reacted by electric arc melting, electron beam melting, or similar processes. In some embodiments, the metal oxyfluoride source may be heat-treated to improve the chemical homogeneity of the material. In one embodiment, the metal oxyfluoride source comprises about 5 mol% to about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% to about 95 mol% metal oxide. In some embodiments, the metal oxyfluoride source comprises about 50 mol% YF3, ZrF4, or a combination thereof, and about 50 mol% metal oxide. In other embodiments, the metal oxyfluoride source comprises about 90 mol% YF3, ZrF4, or a combination thereof, and about 10 mol% metal oxide. In yet another embodiment, the metal oxyfluoride source comprises about 5 mol% YF, ZrF, or a combination thereof, and about 95 mol% metal oxide. In one embodiment, the metal oxide may comprise about 90% Y2O3 and about 10% ZrO2, based on the total mol% of the metal oxides. In another embodiment, the metal oxide may comprise about 95% Y2O3 and about 5% ZrO2, based on the total mol% of the metal oxides.In yet other embodiments, the metal oxide may comprise about 80%-95% Y2O3 and about 5-15% ZrO2, based on the total mole percent of the metal oxides.

[0051] After preparing the metal oxyfluoride source 205, a deposition or formation process, such as vapor deposition, sputtering, evaporation, or the like, is performed to apply the metal oxyfluoride source in block 210. The deposition or formation process may include a plasma spray process, atomic layer deposition (ALD), ion-assisted deposition (IAD), atmospheric plasma spray process, magnetron sputtering, electron beam physical vapor deposition (EBPVD), thermal evaporation physical vapor deposition, spark plasma sintering, hot pressing, cold isostatic pressing, reverse co-precipitation, or a suspension plasma spray process. The deposition or formation process is performed to form a metal oxyfluoride coating or bulk material on the article 215.

[0052] When performing an APPS process, the metal oxyfluoride coating can have a thickness of about 100-300 microns and a porosity of about 2-5%. When performing an SPS process, the metal oxyfluoride coating can have a thickness of about 25-100 microns and a porosity of about 0.1-3%. When performing an IAD process, the metal oxyfluoride coating can have a thickness of about 1-20 microns and a porosity of less than about 0.1% (e.g., substantially 0%). When performing an ALD process, the metal oxyfluoride coating can have a thickness of about 10 nm to about 1 micron and a porosity of about 0%. The metal oxyfluoride coating is a conformal coating. As used herein, the term "conformal" as applied to a layer refers to a layer that covers the features of an article with a substantially uniform thickness. In one embodiment, the conformal layer described herein has conformal coverage of the underlying surface (including the coated surface features) with a uniform thickness of less than about + / - 20% thickness variation, + / - 10% thickness variation, + / - 5% thickness variation, or even less.

[0053] In one embodiment, the metal oxyfluoride coating comprises about 35-50 atomic % Y, about 0.3-10 atomic % Zr, about 5-57 atomic % O, and about 3-65 atomic % F. Metal oxyfluoride coatings having the above atomic percentages are amorphous. The metal oxyfluoride coating on the article has a uniform thickness. It has been found that the inclusion of fluoride in the feedstock in combination with the metal oxide disrupts the crystalline structure, rendering the coating amorphous.

[0054] Another method for coating an article involves depositing a metal oxyfluoride coating on the surface of the chamber component. The deposited metal oxyfluoride coating has the same composition as the coating described above with respect to the metal oxyfluoride source material in block 205 of FIG. 2. After depositing the metal oxyfluoride coating, the chamber component can be heated. The metal oxyfluoride coating can have a thickness of about 10 nm to about 300 μm.

[0055] FIG. 3 is a cross-sectional side view of a chamber component 300 having a body 305 formed thereon with a metal oxyfluoride coating 310 according to one embodiment. The chamber component 300 can have a metal body (e.g., aluminum or an aluminum alloy such as Al6061) or a ceramic body (e.g., Al2O3, AlN, SiC, etc.). The metal oxyfluoride coating 310 includes a metal oxyfluoride containing approximately 35-50 atomic % Y, approximately 0.3-10 atomic % Zr, approximately 5-57 atomic % O, and approximately 3-65 atomic % F. In one embodiment, the metal oxyfluoride coating 310 is amorphous. As shown in FIG. 3, the metal oxyfluoride coating 310 coats at least one surface of the semiconductor processing equipment chamber component 300.

[0056] FIG. 4 illustrates an exemplary architecture of a manufacturing system 400. The manufacturing system 400 may be a manufacturing system for applying coatings to articles, such as chamber components. In one embodiment, the manufacturing system 400 includes a manufacturing machine 401 (e.g., processing equipment) connected to an equipment automation layer 415. The manufacturing machine 401 may include a furnace 402, a wet cleaner 403, a plasma spray system 404, an electron beam physical vapor deposition (EBPVD), an evaporative thermal physical vapor deposition, an atomic layer deposition (ALD) system 405, an IAD system 406, a plasma etch reactor (not shown), a bead blaster (not shown), a CVD system (not shown), a plasma cleaner (not shown), and / or other processing chambers that use fluorine-based plasma. In some embodiments, the manufacturing machine 401 may also include polishing equipment, plating systems, sputtering systems, oxidation systems, and / or other machines. Additionally, the manufacturing system 400 may include one or more computing devices 420 connected to the equipment automation layer 415. In alternative embodiments, manufacturing system 400 may include more or fewer components. For example, manufacturing system 400 may include manually operated (e.g., offline) processing equipment 401 without including equipment automation layer 415 or computing device 420.

[0057] The furnace 402 is a machine designed to heat articles such as ceramic articles. The furnace 402 includes an insulated chamber, or oven, capable of providing a controlled temperature to an article (e.g., a ceramic article) inserted therein. In one embodiment, the chamber is hermetically sealed. The furnace 402 may include a pump for evacuating air from the chamber and creating a vacuum therein. Additionally or alternatively, the furnace 402 may include a gas inlet for delivering gas (e.g., an inert gas such as Ar or N2, and / or a reactive gas such as hydrogen fluoride (HF)) into the chamber. In an embodiment, the furnace 402 may be used to perform an HF heat treatment process.

[0058] The wet cleaner (wet cleaning device) 403 is a cleaning device that cleans items (e.g., articles) using a wet cleaning process. The wet cleaner 403 includes a wet bath filled with liquid, and substrates are immersed in the wet bath for cleaning. The wet cleaner 403 can improve the cleaning effect by using ultrasound to agitate the wet bath during cleaning. This is referred to herein as wet bath ultrasonic treatment.

[0059] In some embodiments, the wet cleaner 403 includes a first wet cleaner containing deionized water (DI) and a second wet cleaner containing an acidic solid. The acidic solution may be, in embodiments, a hydrofluoric acid (HF) solution, a hydrochloric acid (HCl) solution, a nitric acid (HNO) solution, or a combination thereof. The acidic solution can remove surface contaminants from the article and / or remove oxides from the surface of the article. In one embodiment, an acidic solution containing approximately 0.05-50 vol% HF and 50-95 vol% water is used. In one embodiment, an acidic solution containing approximately 0.05-1.0 (or 0.05-0.1) vol% HF and a certain amount of ammonium fluoride as a buffer is used.

[0060] Wet cleaner 403 can clean articles at multiple stages during processing, for example, after polishing a substrate, before plating (e.g., electroplating), before applying a coating, etc.

[0061] In other embodiments, alternative types of cleaning machines may be used to clean the items, such as dry cleaning machines, which may clean the items by applying heat, gas, plasma, etc.

[0062] The plasma spray system 404 is an apparatus configured to apply a coating to a surface of an article by plasma spraying. The plasma spray system 404 may be a low-pressure plasma spray (LPPS) system or an atmospheric pressure plasma spray (APPS) system. Both LPPS and APPS systems can be used to deposit a porous, low-density plasma-resistant layer (e.g., a second plasma-resistant layer in a multi-layer plasma-resistant coating). LPPS systems include a vacuum chamber that can be pumped down to a reduced pressure (e.g., 1 Mbar, 10 Mbar, 35 Mbar, etc.). APPS systems, on the other hand, do not include a vacuum chamber but instead include an open chamber or space.

[0063] In the plasma spray system 404, an arc is formed between two electrodes through which gas flows. The gas, heated by the arc, expands and accelerates through the shaping nozzle of the plasma torch, creating a high-velocity plasma jet. Powders of ceramic and / or metallic materials are injected into the plasma jet by a powder feed system. The high temperature of the plasma jet melts the powder, and the molten ceramic and / or metallic material is propelled toward the article. Upon impact with the article, the molten powder flattens and rapidly solidifies, forming a ceramic coating layer that adheres to the article. Parameters that affect the thickness, density, and roughness of the plasma spray layer include the powder type, powder particle size distribution, powder feed rate, plasma gas composition, gas flow rate, energy input, pressure, and torch offset distance. Alternatively, suspension plasma spraying (SPS) can be performed, where the powder is dispersed in a liquid suspension and then injected into the plasma jet. In some embodiments, the plasma spray layer can have a porosity of approximately 2-5%. Porosity is a measure of voids (e.g., voids) in a material and represents the ratio of void volume to the total volume of the material.

[0064] The ALD system 405 is a system that forms thin, dense conformal layers on an article by atomic layer deposition (ALD). ALD allows for controlled, self-limiting deposition of material through chemical reactions with the article surface. In addition to being a conformal process, ALD is also a uniform process. The same or nearly the same amount of material is deposited on all exposed surfaces of an article, including high aspect ratio features (e.g., about 10:1 to about 300:1). A typical reaction cycle of an ALD process begins with a precursor (i.e., a single chemical, A) being injected into the ALD chamber and adsorbed on the surface of the article in a first half-reaction. The excess precursor is then pumped out of the ALD chamber, after which a reactant (i.e., a single chemical, R) is introduced into the ALD chamber for a second half-reaction and then pumped out. In some embodiments, this process is repeated to form an ALD layer up to about 1 micron thick.

[0065] Unlike other techniques commonly used to coat articles, such as plasma spray coating and ion-assisted deposition, ALD techniques are capable of depositing material layers over high aspect ratio features (i.e., at the surface of the features). Furthermore, ALD techniques produce coatings that are relatively thin (i.e., 1 μm or less) and non-porous (i.e., pinhole-free). As used herein, the term "non-porous" refers to the absence of pores, pinholes, or voids throughout the entire depth of the coating as measured by transmission electron microscopy (TEM).

[0066] CVD systems perform chemical vapor deposition (CVD), a chemical process in which an article is exposed to one or more volatile precursors that react or decompose with the article to form a layer (e.g., a metal oxyfluoride (Y-Zr-OF) layer).

[0067] The EB-IAD system 406 is a system that performs electron beam ion-assisted deposition. Alternatively, embodiments may use other types of IAD systems, such as activated reactive evaporation ion-assisted deposition (ARE-IAD) or ion beam sputtering ion-assisted deposition (IBSIAD). EB-IAD can be performed by evaporation. IBS-IAD can be performed by sputtering a solid target material (e.g., a solid metal target). Both IAD methods can be performed in the presence of reactive gas species, such as O, N, or halogens.

[0068] In various types of IADs, the thin-film plasma-resistant layer is formed by depositing a deposition material in the presence of high-energy particles, such as ions. The deposition material may include atoms, ions, radicals, or a mixture thereof. The high-energy particles may impact and compress the thin-film plasma-resistant layer during its formation.

[0069] In IAD, a material source provides a flux of deposition material, and a high-energy particle source provides a flux of high-energy particles that bombard the article throughout the IAD process. The high-energy particle source can be a source of oxygen or other ions. The high-energy particle source can also provide other types of high-energy particles, such as radicals, atoms, ions, or nano-sized particles, that originate from a particle generation source (e.g., plasma, reactive gas, or material source that provides the deposition material). The material source (e.g., target body) used to provide the deposition material is a bulk-sintered ceramic that corresponds to the same ceramic that constitutes the plasma-resistant layer.

[0070] IAD can utilize one or more plasmas or beams to provide the material and a source of high-energy ions. Reactive species can also be supplied during the deposition of the plasma-resistant coating. In the IAD process, high-energy particles can be controlled by a high-energy ion (or other particle) source, independently of other deposition parameters. The energy (e.g., velocity), density, and incidence angle of the high-energy ion flux can be selected to achieve the target composition, structure, crystal orientation, and grain size of the plasma-resistant layer. Additional adjustable parameters are the temperature of the article during deposition and the deposition time. EB-IAD and IBS-IAD deposition can be performed over a wide range of surface conditions. However, performing IAD on polished surfaces can sometimes improve breakdown voltage.

[0071] The equipment automation layer 415 can interconnect some or all of the manufacturing machines 401 with computing devices 420, other manufacturing machines, metrology tools, and / or other devices. The equipment automation layer 415 can include a network (e.g., a location area network (LAN)), routers, gateways, servers, data stores, etc. The manufacturing machines 401 can connect to the equipment automation layer 415 via a SEMI Equipment Communications Standard / Generic Equipment Model (SECS / GEM) interface, an Ethernet interface, and / or other interfaces. In one embodiment, the equipment automation layer 415 enables process data (e.g., data collected by the manufacturing machines 401 during process execution) to be stored in a data store (not shown). In other embodiments, the computing devices 220 connect directly to one or more manufacturing machines 201.

[0072] In one embodiment, some or all of the manufacturing machines 401 include a programmable controller capable of loading, saving, and executing process recipes. The programmable controller can control the temperature settings, gas and / or vacuum settings, time settings, etc. of the manufacturing equipment 401. The programmable controller can include a main memory (e.g., read-only memory (ROM), flash memory, dynamic random access memory (DRAM), static random access memory (SRAM), etc.) and / or a secondary memory (e.g., a data storage device such as a disk drive). The main memory and / or secondary memory can store instructions for performing the thermal treatment processes described herein.

[0073] The programmable controller may also include a processing device coupled to a main memory and / or a secondary memory (e.g., via a bus) for executing instructions. The processing device may be a general-purpose processing device such as a microprocessor, central processing unit, etc. The processing device may also be a special-purpose processing device such as an application-specific integrated circuit (ASIC), a field-programmable gate array (FPGA), a digital signal processor (DSP), a network processor, etc. In one embodiment, the programmable controller is a programmable logic controller (PLC).

[0074] In one embodiment, the manufacturing machine 401 is programmed to execute a recipe for heat treating an article, coating an article, etc. In one embodiment, the manufacturing machine 401 is programmed to execute a process recipe 425 that performs operations of a multi-step process for manufacturing an article or coating, as shown in Figure 2. In one embodiment, one or more manufacturing machines 401 are programmed to execute a process recipe for a process that applies a metal oxyfluoride source to protect chamber parts before executing a process recipe for processing a substrate using a plasma, as described with reference to Figure 2. The computing device 420 can store one or more process recipes 425 that can be downloaded to the manufacturing machine 401 to cause the manufacturing machine 401 to manufacture an article in accordance with embodiments of the present invention.

[0075] The foregoing description provides numerous specific details, including examples of specific systems, components, methods, etc., to provide a thorough understanding of some embodiments of the present invention. However, it will be apparent to those skilled in the art that at least some embodiments of the present invention may be practiced without these specific details. In other instances, well-known components or methods have not been described in detail or have been presented in simplified block diagram form in order to avoid unnecessarily obscuring the present invention. Thus, the specific details described are merely exemplary. Particular embodiments may vary from these illustrative details and still be deemed to be within the scope of the present invention.

[0076] Throughout this specification, the phrase "one embodiment" or "embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the appearances of "one embodiment" or "embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." When the term "about" or "approximately" is used herein, it is intended to mean that the stated nominal value is accurate to within ±10%.

[0077] Although the operations of the methods herein are shown and described in a particular order, the order of operations within each method may be changed. Certain operations may be performed in reverse order, and certain operations may be performed at least partially concurrently with other operations. In other embodiments, instructions or sub-operations of different operations may be performed intermittently and / or interleaved.

[0078] It should be understood that the above description is intended to be illustrative, and not limiting. Many other embodiments will become apparent to those skilled in the art upon reading and understanding the above description. The scope of the present invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. YF ３ , ZrF ４ or a combination thereof with yttrium oxide (Y ２ O ３ ) and zirconium oxide (ZrO ２ providing a metal oxyfluoride source comprising a metal oxide consisting of 5 mol % to 90 mol % YF ３ , ZrF ４ or a combination thereof, and comprising 10 mol% to 95 mol% metal oxide; 1. The method of claim 1, wherein the metal oxyfluoride coating is formed on the article by vapor deposition, sputter deposition, or vapor deposition of a metal oxyfluoride precursor, the metal oxyfluoride coating comprising 35-50 atomic % yttrium (Y), 0.3-10 atomic % zirconium (Zr), 5-57 atomic % oxygen (O), and 3-65 atomic % fluorine (F); The method wherein the metal oxyfluoride coating is amorphous.

2. The metal oxyfluoride source was 50 mol % YF ３ , ZrF ４ or a combination thereof, and 50 mole % of a metal oxide.

3. The metal oxides are 90% Y, based on the total mole percent of the metal oxides. ２ O ３ and 10% ZrO ２ The method of claim 2 , comprising:

4. The metal oxides are 95% Y, based on the total mole percent of the metal oxides. ２ O ３ and 5% ZrO ２ The method of claim 2 , comprising:

5. The metal oxyfluoride source was 90 mol % YF ３ , ZrF ４ or a combination thereof, and 10 mole % of a metal oxide.

6. The metal oxides are 90% Y, based on the total mole percent of the metal oxides. ２ O ３ and 10% ZrO ２ The method of claim 5 , comprising:

7. The metal oxyfluoride source was 5 mol % YF ３ , ZrF ４ or a combination thereof, and 95 mole % of the metal oxide.

8. The metal oxides are 90% Y, based on the total mole percent of the metal oxides. ２ O ３ and 10% ZrO ２ The method of claim 7, comprising:

9. The method of claim 1 , wherein the article comprises a semiconductor processing chamber part.

10. The method of claim 1 , wherein the metal oxyfluoride coating comprises a Y—Zr—O—F layer.

11. A thin film, a metal oxyfluoride containing 35 to 50 atomic % yttrium (Y), 0.3 to 10 atomic % zirconium (Zr), 5 to 57 atomic % oxygen (O), and 3 to 65 atomic % fluorine (F); A thin film that is amorphous.

12. The thin film of claim 11 coating at least one surface of a chamber component of a semiconductor processing apparatus.

13. 1. A method comprising depositing a metal oxyfluoride coating on a surface of a chamber component, the metal oxyfluoride coating being yttrium fluoride (YF ３ ) or zirconium fluoride (ZrF ４ ) and yttrium oxide (Y ２ O ３ ) and zirconium oxide (ZrO ２ and a metal oxide consisting of YF ３ or ZrF ４ is 5 mol % to 90 mol %, and the metal oxide is 10 mol % to 95 mol %, The method wherein the metal oxyfluoride coating is amorphous.

14. The method of claim 13, comprising heating the chamber components to a temperature range of about 600 to 1400°C.

15. 14. The method of claim 13, wherein the metal oxyfluoride coating comprises 35-50 atomic % yttrium (Y), 0.3-10 atomic % zirconium (Zr), 5-57 atomic % oxygen (O), and 3-65 atomic % fluorine (F).

16. The metal oxyfluoride coating is 50 mol % YF ３ , ZrF ４ or a combination thereof, and 50 mole % of a metal oxide.

17. The metal oxyfluoride coating is 90 mol % YF ３ , ZrF ４ or a combination thereof, and 10 mole % of a metal oxide.

18. The metal oxyfluoride coating was 5 mol % YF ３ , ZrF ４ or a combination thereof, and 95 mole % of the metal oxide.

19. The step of depositing a metal oxyfluoride coating comprises: performing a plasma spray process to deposit a metal oxyfluoride coating; performing atomic layer deposition (ALD) to deposit a metal oxyfluoride coating; performing ion-assisted deposition (IAD) to deposit a metal oxyfluoride coating; performing electron beam physical vapor deposition (EBPVD) to deposit a metal oxyfluoride coating; performing thermal evaporation physical vapor deposition to deposit a metal oxyfluoride coating; performing an air plasma spray process to deposit a metal oxyfluoride coating; performing magnetron sputtering to deposit a metal oxyfluoride coating; performing spark plasma sintering to deposit a metal oxyfluoride coating; performing a heat press to deposit a metal oxyfluoride coating; performing cold isostatic pressing to deposit a metal oxyfluoride coating; performing a co-evaporation physical vapor deposition process to deposit a metal oxyfluoride coating; performing reverse co-precipitation to deposit a metal oxyfluoride coating; or The method of claim 13 , comprising performing one of performing a suspension plasma spray process to deposit the metal oxyfluoride coating.

20. The method of claim 13, wherein the metal oxyfluoride coating has a thickness of about 10 nm to about 300 μm.

21. YF ３ , ZrF ４ or a combination thereof with yttrium oxide (Y ２ O ３ ) and zirconium oxide (ZrO ２ providing a metal fluoride source comprising a metal oxide source comprising 0.1 mol % to 20 mol % ZrO ２ and performing one of vapor deposition, sputter deposition, or vapor deposition of a metal fluoride source and simultaneously and independently performing one of vapor deposition, sputter deposition, or vapor deposition of a metal oxide source to form a metal oxyfluoride coating on the article; A method for producing a metal oxyfluoride coating by evaporation and deposition rates from a metal fluoride source and a metal oxide source, respectively, the metal oxyfluoride coating comprising 35 to 50 atomic % yttrium (Y), 0.3 to 10 atomic % zirconium (Zr), and 5 to 57 atomic % oxygen (O), wherein the metal oxyfluoride coating is amorphous.

22. The deposition rate of each of the metal fluoride source and the metal oxide source is about 50 mol % YF ３ , ZrF ４ 22. The method of claim 21, further comprising forming a composite deposition flux comprising about 50 mole percent metal oxides, or a combination thereof.

23. The metal oxide is about 90% Y, based on the total mole percent of the metal oxide. ２ O ３ and about 10% ZrO ２ 23. The method of claim 22, comprising:

24. The metal oxide is about 95% Y, based on the total mole percent of the metal oxide. ２ O ３ and about 5% ZrO ２ 23. The method of claim 22, comprising:

25. The deposition rate of each of the metal fluoride source and the metal oxide source is about 90 mol % YF ３ , ZrF ４ 22. The method of claim 21, further comprising forming a composite deposition flux comprising: a) a metal oxide; or a combination thereof; and about 10 mole percent metal oxide.

26. The metal oxide is about 90% Y, based on the total mole percent of the metal oxide. ２ O ３ and about 10% ZrO ２ 26. The method of claim 25, comprising:

27. The deposition rate of each of the metal fluoride source and the metal oxide source is about 5 mol % YF ３ , ZrF ４ or a combination thereof to form a composite deposition flux comprising about 95 mole % metal oxide.

28. The metal oxide is about 90% Y, based on the total mole percent of the metal oxide. ２ O ３ and about 10% ZrO ２ 28. The method of claim 27, comprising:

29. The method of claim 21 , wherein the article comprises a semiconductor processing chamber part.

30. 22. The method of claim 21, wherein the metal oxyfluoride coating comprises a Y-Zr-O-F layer.

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