Metal oxyfluoride films for chamber components

Abstract

To provide a method for avoiding problems of a significant decrease in etching rate, process drift, and chamber matching.SOLUTION: In a processing chamber 100 having one or more chamber components that include a M-O-F layer or coating, the coating 152 includes a Y-O-F coating or other yttrium-based oxy-fluoride coating produced by performing either a fluorination process on the yttrium-based oxide coating or an oxidation process on the yttrium-based fluorine coating.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] BACKGROUND OF THE DISCLOSURE Embodiments of the present disclosure generally relate to methods for converting metal fluoride and / or metal oxide coatings into MOF layers and coatings. Embodiments further relate to the in-situ formation of temporary metal fluoride and / or MOF layers on metal oxide surfaces.

[0002] Various manufacturing processes expose chamber components and their coating materials to high temperatures, high-energy plasmas, corrosive gas mixtures, high stresses, and combinations thereof. Rare earth oxides are often used in the fabrication of chamber components due to their resistance to erosion by plasma etching chemistries. However, exposure of rare earth oxides to fluorine-based plasmas can cause cracking and particle emission onto the wafer.

[0003] Furthermore, oxide coatings (e.g., YO) are permeable to water and can cause water adsorption. As a result, exposure of oxide coatings (e.g., YO) to air typically results in the formation of a brittle M(OH) layer (e.g., Y(OH)), where M is a metal, 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 the processed wafer. Furthermore, the M(OH) layer increases the leakage current in 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 yttrium-based particle problems on processed wafers. However, applying YF3 coatings to chamber components in etch reactors has been shown to cause significant etch rate degradation (e.g., as much as a 60% etch rate reduction), process drift, and chamber matching issues. Overview

[0005] In an example of a first method for forming a YOF layer or coating, an yttrium-containing coating (e.g., a YO coating or a YO-ZrO solid solution coating) is deposited on a surface of a chamber component for a first processing chamber. Alternatively, an MxOy coating can be deposited, where M is a metal (e.g., Al or a rare earth metal). The chamber component is heated to an elevated temperature of about 150-1000°C (e.g., 150-500°C). The chamber component is exposed to a fluorine source (e.g., HF, NF3, NF3 plasma, F2, F radicals, etc.) at the elevated temperature for a period of time. As a result, at least the surface of the yttrium-containing oxide coating is converted to a YOF layer or other yttrium-based oxyfluoride layer or coating. In some examples, the entire yttrium-containing oxide coating is converted to YOF or other yttrium-containing oxyfluoride. Alternatively, at least the surface of the MxOy coating is converted to a MOF layer.

[0006] In a second exemplary method for forming a YF layer or coating, atomic layer deposition (ALD), chemical vapor deposition (CVD), or ion-assisted deposition (IAD) is performed to deposit a YF3 coating having a thickness of about 10 nm to about 10 microns on a surface of a chamber component for a processing chamber. The chamber component is heated to an elevated temperature of about 150°C to about 1500°C. The chamber component is exposed to an oxygen source at the elevated temperature for about 12 to 24 hours. As a result, the YF3 coating is converted to a YF3 coating.

[0007] In an embodiment of a third method for forming a MOF layer or coating, a substrate is loaded into a process chamber having one or more chamber components containing a metal oxide coating. A fluorine-based plasma from a remote plasma source is introduced into the process chamber. The metal oxide coating reacts with the fluorine-based plasma to form a temporary MOF or metal fluoride layer on the metal oxide coating. A process utilizing a corrosive gas is then performed on the substrate. This process removes or adds to the temporary MOF or metal fluoride layer, while the temporary MOF or metal fluoride layer protects the metal oxide coating from the corrosive gas. [Brief explanation of the drawings]

[0008] The present disclosure is illustrated by way of example, and not limitation, in the figures of the accompanying drawings in which like reference numerals refer to like elements. It should be noted that different references to "an" or "one" embodiment in the present disclosure are not necessarily limited to the same embodiment, but such references mean at least one.

[0009] [Figure 1] 1 illustrates a cross-sectional view of one embodiment of a processing chamber. [Figure 2] 1 illustrates an example architecture for a manufacturing system, according to one embodiment of the present invention. [Figure 3A] 1 illustrates a process for forming a MOF layer on the surface of a metal oxide coating, according to one embodiment. [Figure 3B] FIG. 1 illustrates a cross-sectional side view of a chamber component including a Y2O3 coating and a YOF layer, according to one embodiment. [Figure 4A] 1 illustrates a process for converting a YF3 coating to a YOF coating, according to one embodiment. [Figure 4B] 1 illustrates a cross-sectional side view of a chamber component including a YOF coating according to one embodiment. [Figure 5]1 illustrates an in-situ process for forming a temporary MOF or metal fluoride layer on a metal oxide coating or metal oxide article prior to a manufacturing process according to one embodiment. [Figure 6A] 1 illustrates a process for stress relieving a yttrium-based coating by converting at least a portion of the yttrium-based coating to a YOF coating or layer, according to one embodiment. [Figure 6B] FIG. 1 shows a cross-sectional side view of a chamber component including a YOF / MOF coating on the body of the chamber component according to one embodiment. [Figure 7A] 1 shows a cross-sectional side view of a chamber component including a Y2O3 coating as observed by transmission electron microscopy (TEM), according to one embodiment. [Figure 7B] 7B illustrates the material composition of the chamber components of FIG. 7A. [Figure 8A] 1 shows a cross-sectional side view of a chamber component including a YOF coating after a fluorination treatment as observed by TEM, according to one embodiment. [Figure 8B] 8B illustrates the material composition of the chamber components of FIG. 8A. [Figure 9A] FIG. 1 shows a cross-sectional side view of a chamber component including alternating stacks of YOF and Al—OF layers after a fluorination treatment as observed by TEM, according to one embodiment. [Figure 9B] 9B illustrates the material composition of the chamber components of FIG. 9A. [Figure 10A] FIG. 1 shows a cross-sectional side view of a chamber component including alternating stacks of YOF and Al—OF layers after a fluorination treatment as observed by TEM, according to one embodiment. [Figure 10B] 10B illustrates the material composition of the chamber components of FIG. 10A. [Figure 11A] FIG. 1 shows a cross-sectional side view of a chamber component including a solid-sintered (bulk) ceramic consisting of a Y2O3-ZrO2 solid solution after a fluorination treatment as observed by TEM, according to one embodiment. [Figure 11B] 11B illustrates the material composition of the chamber components of FIG. 11A. [Figure 12A] FIG. 10 shows a cross-sectional side view of a chamber component including a coating of Al 2 O 3 after a fluorination treatment as observed by TEM, according to one embodiment. [Figure 12B] 12B illustrates the material composition of the chamber components of FIG. 12A. [Figure 13A] 1 shows a YOF coating resulting from fluorination of a Y2O3 coating, according to one embodiment. [Figure 13B] 1 shows a YZOF coating resulting from fluorination of a Y2O3-ZrO2 solid solution coating, according to one embodiment. [Figure 14] 1 shows an energy dispersive electroscopy (EDS) line scan showing the material composition of the YF3 coating. [Figure 15] 15 shows an EDS line scan showing the material composition of the YF3 coating including the YOF layer of FIG. 14 after oxidation treatment, according to one embodiment. [Figure 16A] FIG. 1 shows a cross-sectional side view of a chamber component including a coating of Y2O3 after a fluorination treatment in an HF acidic solution as observed by TEM, according to one embodiment. [Figure 16B] 16B illustrates the material composition of the chamber components of FIG. 16A. [Figure 17] Figure 1 shows an X-ray photoelectron spectroscopy (XPS) surface analysis showing the material composition of a YF3 coating deposited by ALD. [Figure 18] 18 shows an XPS surface analysis showing the material composition of the YOF coating formed from oxidation of the YF3 coating of FIG. 17, according to one embodiment. [Figure 19] The particle performance of YOF coating and YZOF coating is shown. Detailed Description of the Embodiments

[0010] Embodiments of the present invention relate to processes for forming YOF layers and coatings, as well as other MOF layers and coatings, where M is a metal (Al, rare earth, or a combination of metals). YOF coatings and layers, as well as other yttrium-containing oxyfluoride coatings and layers, are highly resistant to erosion and corrosion by fluorine-based plasmas. Furthermore, MOF coatings are generally resistant to fluorination by fluorine-based plasmas. Furthermore, MOF coatings may be resistant to the formation of M(OH) (e.g., Y(OH)). Furthermore, MOF coatings do not cause the etch rate degradation observed when YF is used to coat chamber components. As a result of these properties, YOF and other MOF coatings and layers described herein, when used on chamber components for processing chambers, result in significant particle reduction and improved etch rate uniformity and chamber-to-chamber uniformity. In embodiments, the term "MOF" refers to 1-99 at.% M, 1-99 at.% O, and 1-99 at.% F.

[0011] In some embodiments, the metal oxide coating is 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), or another deposition technique. The metal oxide coating can be represented as MxOy, where M is a metal (e.g., Al or a rare earth metal), and x and y are positive numbers (e.g., positive integers between 1 and 9). In some examples, the metal oxide coating can be Al2O3 or a rare earth oxide (e.g., Gd2O3, Yb2O3, Er2O3, or YO3). The metal oxide coating can be a more complex oxide (e.g., Y3Al5O 12 (YAG), Y4Al2O9(YAM), Y2O3 stabilized ZrO2(YSZ), Er3Al5O 12The metal oxide coating may be a composite ceramic including an MOF (EAG), a Y2O3-ZrO2 solid solution, or a composite ceramic including Y4Al2O9 and a Y2O3-ZrO2 solid solution). At least the surface of the metal oxide coating is converted to MOFs by exposing the metal oxide coating to a fluorine source (e.g., HF, NF3, F2, NF3 plasma, F radicals, etc.) at elevated temperatures for a period of time. This period of time may be about 0.1 to 72 hours (e.g., about 1 to 24 hours) in some embodiments.

[0012] Thin, dense coatings (e.g., coatings deposited using IAD and ALD) are prone to cracking when deposited on articles with a coefficient of thermal expansion (CTE) different from that of the thin, dense coating. Unlike thick, porous plasma-sprayed yttrium-based coatings, thin, dense yttrium-based coatings cannot withstand tensile stresses. Tensile stresses often cause through-cracks in thin, dense yttrium-based coatings, providing a direct path for highly reactive species to attack the underlying coated surface during processing. For example, the CTE of Y2O3 is approximately 6-8 ppm / K (also x10 -6 / ℃, ppm / ℃ and x10 -6 / K, which is equivalent), the CTE of YF3 is approximately 14 ppm / K, and the CTE of aluminum is approximately 22-25 ppm / K. If there is a CTE mismatch between the aluminum article and the Y2O3 or YF3 coating, dense YF3 and Y2O3 coatings on the aluminum can crack at processing temperatures (e.g., approximately 250-350°C) due to tensile stresses caused by the CTE mismatch. In some cases, cracking can be alleviated by heating the article during deposition of the thin, dense yttrium-based coating. However, some deposition processes (e.g., ALD) should be performed within a specific temperature range that is lower than the processing temperature range in which the article will be used. Therefore, increasing the deposition temperature for yttrium-based coatings may not be feasible.

[0013] The molar volume of YF3 is approximately 60% larger than that of YO3. For example, YF3 has a molar volume of 36.384 cm 3 / mol, and Y2O3 has a molar volume of approximately 22.5359 cm 3 / mol. YOF has a molar volume between the molar volumes of YO and YF. As a result, there is a volume expansion of up to about 60% when YO is converted to YF, and a smaller volume expansion when YO is converted to YOF. In embodiments, as described above, the yttrium-based oxide coating is subjected to a fluorination treatment to convert at least a portion of the yttrium-based coating into a YOF coating or layer. Due to the larger molar volume of YOF compared to YO, the conversion of the yttrium-based oxide coating to a YOF coating or layer introduces compressive stress into the coating at room temperature. The application of compressive stress at room temperature means that the tensile stress is reduced at processing temperatures (e.g., about 250-350°C). The reduced tensile stress at processing temperatures may reduce or eliminate cracking in thin, dense yttrium-based coatings.

[0014] In some embodiments, a YF or other yttrium-based fluoride (e.g., yttrium-based fluoride) coating is formed via ion-assisted deposition (IAD), atomic layer deposition (ALD), CVD, or another deposition technique. The YF or other yttrium-based fluoride coating is converted to a YOF or MOF by exposing the metal oxide coating to an oxygen source at elevated temperatures for a period of time.

[0015] In some embodiments, a YF3 coating or other yttrium-based fluoride coating is formed on an article having a lower CTE than the YF3 or other yttrium-based fluoride coating. For example, a YF3 or other yttrium-based fluoride coating can be formed on a graphite article having a CTE of about 4 ppm / K. Converting a YF3 coating to a YOF coating (or other yttrium-based fluoride coating to a MOF coating, where M is a combination of Y and another metal) can reduce the molar volume of the coating and reduce compressive stress within the coating at room and processing temperatures. This can reduce cracking during thermal cycling due to CTE mismatch.

[0016] In some embodiments, an in-situ fluorination treatment is performed to form a thin MOF layer (e.g., a thin YOF layer or a thin YZOF layer) or a thin metal fluoride layer (e.g., a thin YF3 layer) on the surface of a metal oxide coating on one or more chamber components before performing a manufacturing process on the substrate. For example, the in-situ fluorination treatment may be performed before a plasma etching process or a plasma cleaning process. The fluorination treatment may include introducing a fluorine-based plasma from a remote plasma source into a processing chamber including one or more chamber components. The fluorine-based plasma may be introduced using process parameter values ​​optimized for forming the thin MOF or metal fluoride layer and different from the parameters of a manufacturing process that will be performed later. The metal oxide coating reacts with the fluorine-based plasma to form a temporary MOF or metal fluoride layer on the metal oxide coating. Next, a manufacturing process utilizing a corrosive gas (e.g., a fluorine-based plasma or a reducing chemistry (e.g., an ammonia-based chemistry or a chlorine-based chemistry)) is performed on the substrate. Depending on the manufacturing process, the temporary MOF or metal fluoride layer may be removed or added to, but the temporary MOF or metal fluoride layer protects the metal oxide coating from corrosive gases.

[0017] In another embodiment, an in-situ fluorination treatment can include exposing one or more chamber components of a processing chamber to a fluorine-based acidic solution (e.g., an HF acidic solution and / or an NHF acidic solution). For example, fluorination can be performed using a fluorine-based acidic solution in a non-vacuum chamber (e.g., a chemical mechanical planarization (CMP) chamber or a chamber for a wet clean bench). The fluorine-based acidic solution can be introduced using process parameter values ​​optimized for the formation of a thin MOF or metal fluoride layer. The metal oxide coating reacts with the fluorine-based plasma to form a temporary MOF or metal fluoride layer on the metal oxide coating. Next, a manufacturing process utilizing a corrosive gas (e.g., a fluorine-based plasma or a reducing chemistry (e.g., an ammonia-based chemistry or a chlorine-based chemistry) is performed on the substrate. The manufacturing process can remove or add to the temporary MOF or metal fluoride layer, depending on the manufacturing process, while the temporary MOF or metal fluoride layer protects the metal oxide coating from the corrosive gas.

[0018] In some embodiments, an etch-back process is periodically performed to remove at least a portion of the temporary MOF or metal fluoride layer from the metal oxide coating. The etch-back process may be used to ensure that the thickness of the MOF or metal fluoride layer does not reach a threshold thickness. Beyond the threshold thickness, the MOF or metal fluoride layer may begin to release particles due to additional stress resulting from volume expansion due to the conversion of the metal oxide to MOF or metal fluoride. However, below the threshold thickness, particle adder can be mitigated or prevented.

[0019] As used herein, the term "heat treating" refers to subjecting a ceramic article to high temperatures (e.g., by 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, plasmas generated from halogen-containing gases (e.g., C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, SiF4, among others) and other gases (e.g., O2 or NO). A material's resistance to plasma is measured by its "etch rate" (ER), which may have units of angstroms per minute (Å / min), throughout the duration of operation and exposure of the coated component 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 may be taken after different treatment times. For example, measurements may be taken before treatment, after 50 hours of treatment, after 150 hours of treatment, after 200 hours of treatment, etc. Erosion rates of less than about 100 nm / RFHr are typical for plasma-resistant coating materials. A single plasma-resistant material may have multiple 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.

[0020] When the terms "about" and "approximately" are used herein, they are intended to mean that the stated nominal value is accurate to within ±10%. Some embodiments are described herein with reference to chamber components and other articles installed in a plasma etcher for semiconductor manufacturing. However, it should be understood that such plasma etchers 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 (e.g., a semiconductor processing chamber). For example, the article may be a chamber component for a plasma etcher, a plasma cleaner, a plasma propulsion system, or another processing chamber. Examples of chamber components that can benefit from embodiments of the invention include a substrate support assembly, an electrostatic chuck (ESC), a ring (e.g., a process kit ring or a single ring), a chamber wall, 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.

[0021] Additionally, embodiments are described herein with reference to MOF layers and coatings that reduce particle contamination when used in process chambers for plasma-rich processing. However, it should be understood that the MOF layers and coatings discussed herein also reduce particle contamination when used in process chambers for other processes, such as non-plasma etchers, non-plasma cleaners, chemical vapor deposition (CVD) chambers, physical vapor deposition (PVD) chambers, plasma-enhanced chemical vapor deposition (PECVD) chambers, plasma-enhanced physical vapor deposition (PEPVD) chambers, plasma-enhanced atomic layer deposition (PEALD) chambers, etc. Furthermore, the techniques discussed herein for forming MOF layers and coatings are applicable to articles other than chamber components for processing chambers.

[0022] Additionally, embodiments are described herein with reference to converting metal fluoride coatings (e.g., yttrium-based fluoride coatings) and metal oxide coatings (or portions of such coatings) to YOF and other MOF layers. However, it should be understood that the embodiments also apply to converting the surface of bulk metal oxides to MOFs. For example, the surface of a sintered YO ceramic article can be converted to YOF by the process described below with reference to FIGS. 3A and 5.

[0023] Furthermore, some embodiments are discussed with reference to yttrium-based oxides and / or yttrium-based fluorides. Erbium is completely miscible with yttrium. Therefore, it should be understood that these embodiments can be modified to achieve similar results by substituting any amount of yttrium with erbium. Thus, yttrium may be substituted with erbium in any of the embodiments discussed herein with respect to yttrium-based fluorides, yttrium-based oxides, and yttrium-based oxyfluorides. In embodiments, a portion of the yttrium may be substituted with erbium, or all of the yttrium may be substituted with erbium. Thus, any of the embodiments discussed herein may have 0% to 100% of the recited yttrium substituted with erbium. In one example, rather than YO, the coating may be a mixture of 1 to 99 mol% YO and 1 to 99 mol% Er. The resulting metal oxyfluoride may be Y-Er-OF, with the ratio of Y to Er being between 1:99 and 99:1.

[0024] FIG. 1 is a cross-sectional view of a processing chamber 100 (e.g., a semiconductor processing chamber) having one or more chamber components including a MOF layer or coating according to an embodiment of the invention. The processing chamber 100 may be used for processes in which a corrosive plasma environment is provided. For example, the processing chamber 100 may be a plasma etch reactor (also known as a plasma etcher), a plasma cleaner, or the like. Examples of chamber components that may include a MOF 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), a chamber wall, 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.

[0025] In one embodiment, the processing chamber 100 includes a chamber body 102 enclosing an interior volume 106 and a showerhead 130. 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 coupled to the showerhead base. Alternatively, the showerhead 130 may be replaced with a lid and nozzle in some embodiments, or with multiple pie-shaped showerhead compartments and plasma generation sections 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.

[0026] An outer liner 116 may be disposed adjacent the sidewall 108 to protect the chamber body 102. The outer liner 116 may be made of a halogen-containing gas resistant material (such as Al2O3 or Y2O3).

[0027] An exhaust port 126 may be defined 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 throttle valves and may be utilized to evacuate and regulate the pressure of the interior volume 106 of the processing chamber 100.

[0028] The showerhead 130 may be supported on the sidewall 108 of the chamber body 102 and / or on the top of the chamber body. The showerhead 130 (or lid) can be opened to allow access to the interior volume 106 of the processing chamber 100 and can provide a seal for the processing chamber 100 when closed. A gas panel 158 is coupled to the process chamber 100 and can supply process gases 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) coupled to the showerhead. The GDP can be, for example, Si or SiC. The GDP can further include multiple holes that align with the holes in the showerhead.

[0029] Examples of process gases that can be used to process substrates in the process chamber 100 include halogen-containing gases (e.g., C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, Cl2, CCl4, BCl3, and SiF4, among others) and other gases (e.g., O2 or N2O). Examples of carrier gases include N2, He, Ar, and other gases that are inert to the process gas (e.g., non-reactive gases).

[0030] A substrate support assembly 148 is disposed 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 that secures the substrate 144 during processing, a metal cooling plate coupled 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 (e.g., Al2O3 or YO3, etc.).

[0031] Depending on the embodiment, the showerhead 130 (or lid and / or nozzle), sidewall 108, bottom 110, substrate support assembly 148, outer liner 116, inner liner (not shown), or any of the other chamber components may include a MOF coating or a metal oxide coating having a MOF layer on the metal oxide coating. For example, the illustrated showerhead 130 includes a MOF coating 152. In some embodiments, the MOF layer is temporarily formed using an in-situ fluorination treatment before performing another process on the substrate 144. In some embodiments, the MOF coating 152 is a YOF coating. The YOF coating may have a single YOF phase or multiple different YOF phases. Some possible YOF phases that a YOF coating can have are YOF ht, YOF rt, YOF tet, YOF (e.g., YOFht-hp), ... 0.4 F 22 (For example, YO 0.4 F 22 ht-hp), Y5O4F7, Y6O5F8, Y7O6F9, and Y 17 O 14 F 23 In some embodiments, the MOF coating is a Y-Zr-OF coating.

[0032] FIG. 2 illustrates an exemplary structure of a manufacturing system 200 in accordance with an embodiment of the present invention. The manufacturing system 200 may be a ceramic manufacturing system. In one embodiment, the manufacturing system 200 includes processing equipment 201 connected to an equipment automation layer 215. The processing equipment 201 may include a furnace 202, a wet cleaner 203, a plasma spray system 204, an atomic layer deposition (ALD) system 205, an IAD system 206, a plasma etch reactor 207, a bead blaster (not shown), a CVD system (not shown), a plasma cleaner 208, and / or another processing chamber using a fluorine-based plasma. The manufacturing system 200 may further include one or more computing devices 220 connected to the equipment automation layer 215. In alternative embodiments, the manufacturing system 200 may include more or fewer components. For example, the manufacturing system 200 may include manual (e.g., offline) processing equipment 201 without the equipment automation layer 215 or the computing device 220.

[0033] The furnace 202 is a machine designed to heat an article (e.g., a ceramic article). The furnace 202 comprises an insulated chamber or oven that can apply a controlled temperature to an article (e.g., a ceramic article) inserted therein. In one embodiment, the chamber is sealed. The furnace 202 may comprise a pump for evacuating air from the chamber, thus creating a vacuum within the chamber. The furnace 202 may additionally or alternatively comprise a gas inlet for injecting gas (e.g., an inert gas (e.g., Ar or N) and / or a reactive gas (e.g., hydrogen fluoride (HF))) into the chamber. In an embodiment, the furnace 202 can be used to perform an HF heat treatment process.

[0034] The wet cleaner 203 is a device that includes a bath and a heating element. The wet cleaner 203 can clean articles (e.g., chamber components) using a wet cleaning process. The wet cleaner 203 includes a wet bath filled with an HF acidic solution or other fluorine-based acidic solution (e.g., an acidic solution containing fluoroantimonic acid, ammonium fluoride (and / or NHF), and / or sulfuric hydrofluoric acid). Chamber components having metal oxide coatings can be immersed in the HF acidic solution (or other fluorine-based acidic solution) at a temperature of about 0-100°C (or about room temperature to about 100°C) to convert at least a portion of the metal oxide to MOFs. In some embodiments, the HF acidic solution (or other fluorine-based acidic solution) can remove surface contaminants from the article and / or remove M(OH) layer oxides from the surface of the metal oxide coating. In one embodiment, an acidic solution containing about 0.05-50 vol% HF and 50-95 vol% water is used. In one embodiment, an acidic solution containing about 0.05 to 1.0 (or 0.05 to 0.1) vol % HF, 99.5 to 99.95 vol % as a buffer, and an amount of ammonium fluoride is used.

[0035] The plasma spray system 204 is a machine configured to plasma spray a ceramic coating onto a surface of an article. The plasma spray system 204 may be a low-pressure plasma spray (LPPS) system or an atmospheric pressure plasma spray (APPS) system. Both LPPS and APPS systems may be used to deposit porous, low-density plasma-resistant layers (e.g., second plasma-resistant layers for multi-layer plasma-resistant coatings). LPPS systems include a vacuum chamber that can be evacuated to low pressures (e.g., to a vacuum of 1 Mbar, 10 Mbar, 35 Mbar, etc.), while APPS systems may not include any vacuum chamber and instead include an open chamber or space.

[0036] In the plasma spray system 204, an arc is formed between two electrodes through which a gas flows. As the gas is heated by the arc, it 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 extremely high temperatures of the plasma jet melt the powder and propel the molten ceramic and / or metallic material toward the article. Upon impact with the article, the molten powder flattens and rapidly solidifies, forming a layer of ceramic coating that adheres to the article. Parameters that affect the thickness, density, and roughness of the plasma spray layer include powder type, powder 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, in which the powder is dispersed in a suspension before being injected into the plasma jet. In some embodiments, the plasma spray layer may have a porosity of approximately 2-5%. Porosity is a measure of voids (eg, air spaces) in a material and is the ratio of void volume to the total volume or material.

[0037] The ALD system 205 is a system that performs atomic layer deposition to form thin, dense, conformal layers on an article. ALD enables controlled, self-limiting deposition of materials through chemical reactions with the article's surface. In addition to conformal processing, ALD is also uniform. All exposed surfaces of the article, including high aspect ratio features (e.g., from about 10:1 to about 300:1), will have the same or nearly the same amount of deposited material. A typical reaction cycle for an ALD process begins with a precursor (i.e., a single chemical, A) flowing into the ALD chamber and adsorbing onto the article's surface in the first half of the reaction. Excess precursor is then flushed out of the ALD chamber, and a reactant (i.e., a single chemical, R) is introduced into the ALD chamber for the second half of the reaction, followed by a subsequent flush. In some embodiments, this process can be repeated to build up ALD layers with thicknesses up to about 1 micron.

[0038] Unlike other techniques commonly used to deposit coatings on articles (e.g., plasma spray coating and ion-assisted deposition), ALD techniques are capable of depositing material layers within (i.e., on the surfaces of) high aspect ratio features. Furthermore, ALD techniques produce relatively thin (i.e., 1 μm or less, or in some cases 10 μm or less) coatings that are non-porous (i.e., pinhole-free). As used herein, the term "non-porous" means the absence of pores, pinholes, or voids along the entire depth of the coating as measured by transmission electron microscopy (TEM).

[0039] The precursors used by the ALD system 205 to form the plasma-resistant layer depend on the plasma-resistant layer being formed. In some embodiments, the plasma-resistant layer is Al2O3 and is formed from an aluminum precursor (e.g., diethylaluminum ethoxide, tris(ethylmethylamido)aluminum, aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum, or tris(diethylamido)aluminum, etc.). In some embodiments, the plasma-resistant layer is YO3 or YF3 and is formed from an yttrium precursor (e.g., tris(N,N-bis(trimethylsilyl)amido)yttrium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III), or yttrium(III) butoxide). In some embodiments, the plasma-resistant layer is Er2O3 and is formed from an erbium precursor (e.g., tris-methylcyclopentadienyl erbium(III) (Er(MeCp)3), erbium borane amide (Er(BA)3), Er(TMHD)3, erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), and tris(butylcyclopentadienyl)erbium(III)).

[0040] The reactant used by the ALD system 205 to form the plasma resistant layer may be oxygen, water vapor, ozone, pure oxygen, oxygen radicals, or another oxygen source if the deposited plasma resistant layer is an oxide. If a YF3 plasma resistant layer is formed, the reactant may be a fluoride (e.g., TiF4).

[0041] CVD systems perform chemical vapor deposition (CVD), a chemical process in which an article is exposed to one or more volatile precursors that react with and / or decompose on the article to form a layer (e.g., to form a YF3 or YO3 layer).

[0042] The EB-IAD system 206 is a system that performs electron beam ion-assisted deposition. Alternatively, other types of IAD systems (e.g., activated reactive evaporation ion-assisted deposition (ARE-IAD) or ion beam sputter ion-assisted deposition (IBS-IAD)) can be used in embodiments. 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 (e.g., O, N, halogens, etc.).

[0043] For various types of IADs, a thin-film plasma-resistant layer is formed by the accumulation of deposition material in the presence of high-energy particles (e.g., ions). The deposition material may include atoms, ions, radicals, or a mixture thereof. The high-energy particles may bombard and compact the thin-film plasma-resistant layer as it is formed.

[0044] For IAD, a material source provides the deposition material flux, and a high-energy particle source provides the high-energy particle flux, both of which bombard the article through the IAD process. The high-energy particle source may be an oxygen or other ion source. The high-energy particle source can provide other types of high-energy particles, such as radicals, atoms, ions, and nano-sized particles, originating from a particle generating source (e.g., from a plasma, a reactive gas, or from a material source providing the deposition material). The material source (e.g., a target body) used to provide the deposition material may be a bulk-sintered ceramic corresponding to the same ceramic from which the plasma-resistant layer is constructed.

[0045] IAD may utilize one or more plasmas or beams to provide a material source and a source of high-energy ions. It may also provide reactive species during deposition of the plasma-resistant coating. In an IAD process, high-energy particles may be controlled by a high-energy ion (or other particle) source independent of other deposition parameters. The energy (e.g., velocity), density, and incidence angle of the high-energy ion flux may be selected to achieve a 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 duration of deposition. EB-IAD and IBS-IAD deposition are feasible over a wide range of surface conditions. However, IAD performed on polished surfaces may result in increased breakdown voltage.

[0046] The plasma etch reactor 207 is a process chamber that performs an etching process using plasma. The plasma cleaner 208 is a process chamber that performs a cleaning process using plasma. In an embodiment, the plasma etch reactor 207 and / or the plasma etch cleaner 208 can correspond to the process chamber 100 of FIG. 1.

[0047] The equipment automation layer 215 may interconnect some or all of the manufacturing machines 201 with the computing device 220, other manufacturing machines, metrology tools, and / or other devices. The equipment automation layer 215 may include a network (e.g., a location area network (LAN)), routers, gateways, servers, data stores, etc. The manufacturing machines 201 may connect to the equipment automation layer 215 via a SEMI Equipment Communications Standard / Generic Equipment Model (SECS / GEM) interface, via an Ethernet interface, and / or via other interfaces. In one embodiment, the equipment automation layer 215 enables process data (e.g., data collected by the manufacturing machines 201 during the performance of processes) to be stored in a data store (not shown). In an alternative embodiment, the computing device 220 connects directly to one or more manufacturing machines 201.

[0048] In one embodiment, some or all of the manufacturing machines 201 include a programmable controller capable of loading, storing, and executing process recipes. The programmable controller may control the temperature settings, gas and / or vacuum settings, time settings, etc. of the manufacturing machines 201. The programmable controller may include a primary 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 (e.g., a disk drive)). The primary memory and / or secondary memory may store instructions for performing the thermal treatment processes described herein.

[0049] The programmable controller may include a processing unit coupled to a main memory and / or a secondary memory (e.g., via a bus) for executing instructions. The processing unit may be a general-purpose processing unit (e.g., a microprocessor, a central processing unit, etc.). The processing unit may be a special-purpose processing unit (e.g., 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).

[0050] In one embodiment, the manufacturing machine 201 is programmed to execute recipes such as for the manufacturing machine to heat-treat an article, coat an article, etc. In one embodiment, the manufacturing machine 201 is programmed to execute process recipes 225 that implement multi-step process operations to manufacture an article or coating, as described with reference to Figures 3A, 4A, and 6A. In one embodiment, one or more manufacturing machines 201 are programmed to execute a process recipe for an in-situ fluorination process to protect chamber components before executing a process recipe for treating a substrate using a fluorine-based plasma, as described with reference to Figure 5. The computing device 220 can store one or more process recipes 225 and download the process recipes 225 to the manufacturing machine 201 to cause the manufacturing machine 201 to manufacture an article according to an embodiment of the present invention.

[0051] 3A illustrates a process 300 for converting at least the surface of a Y2O3 coating or other yttrium-based oxide coating to a YOF layer or other metal oxyfluoride layer or coating, according to one embodiment. Alternatively, process 300 can be performed to form a YOF layer or other metal oxyfluoride layer on the surface of a sintered ceramic article of Y2O3 or another metal oxide. It should be noted that process 300 can be modified to also apply to the formation of MOF layers from other metal oxide coatings. Some examples of other metal oxides that can be used in embodiments include Al2O3, Er2O3, Y2O3-stabilized ZrO2 (YSZ), Er3Al5O 12 Examples of yttrium-based oxide coatings include yttrium-based oxide coatings (EAG), yttrium-oxide-based aluminum alloys (YO-ZrO), and composite ceramics composed of yttrium-based aluminum alloys (YAlO) and yttrium-based aluminum alloys (YAlO). In one embodiment, the yttrium-based oxide coating comprises a stack of alternating layers of yttrium-based oxides (YO and ZrO and / or AlO). In some embodiments, the yttrium-based oxide coating is substantially thicker than the AlO layer (e.g., anywhere from 5 to 10 times thicker than the aluminum oxide layer). For example, when the yttrium-based oxide coating and other oxide layers are formed using ALD, the yttrium-based oxide coating may be formed by applying 8 to 10 ALD deposition cycles, while the additional oxide layers may be formed by applying 1 to 2 ALD deposition cycles, with each ALD deposition cycle producing approximately one monolayer.

[0052] In one embodiment, the metal oxide coating comprises or is a coating consisting of a solid solution of yttria and zirconia (Y2O3-ZrO2). In one embodiment, the Y2O3-ZrO2 solid solution may comprise 20-80 mol% Y2O3 and 20-80 mol% ZrO2. In a further embodiment, the Y2O3-ZrO2 solid solution comprises 30-70 mol% Y2O3 and 30-70 mol% ZrO2. In a further embodiment, the Y2O3-ZrO2 solid solution comprises 40-60 mol% Y2O3 and 40-60 mol% ZrO2. In a further embodiment, the Y2O3-ZrO2 solid solution comprises 50-80 mol% Y2O3 and 20-50 mol% ZrO2. In further embodiments, the Y2O3-ZrO2 solid solution includes 60-70 mol% Y2O3 and 30-40 mol% ZrO2. In other examples, the Y2O3-ZrO2 solid solution can include 45-85 mol% Y2O3 and 15-60 mol% ZrO2, 55-75 mol% Y2O3 and 25-45 mol% ZrO2, 58-62 mol% Y2O3, 38-42 mol% ZrO2, 68-72 mol% Y2O3, and 28-32 mol% ZrO2.

[0053] Any of the foregoing metal oxide coatings may contain one or more dopants, in combination comprising up to about 2 mol% of the coating. Such dopants may be rare earth oxides of the lanthanide series (e.g., Er (erbium), Ce (cerium), Gd (gadolinium), Yb (ytterbium), Lu (lutetium), etc.). Such dopants may additionally or alternatively include Al (aluminum) and / or Si (silicon).

[0054] The MOF layer formed will depend on the particular metal oxide coating used. Process 300 is described with reference to yttrium-based oxide coatings (e.g., YO) and YOF. However, it should be understood that process 300 is equally applicable to the formation of other MOF layers on other metal oxide coatings.

[0055] In block 305 of process 300, a YO coating or other yttrium-based oxide coating is deposited on the surface of a chamber component for a first processing chamber. The yttrium-based oxide coating can be deposited using any of the deposition techniques described herein (e.g., plasma spray, ALD, IAD, etc.). If APPS is performed, the yttrium-based oxide coating can have a thickness of about 100-300 microns and a porosity of about 2-5%. If SPS is performed, the yttrium-based oxide coating can have a thickness of about 50-100 microns and a porosity of about 1-3%. If IAD is performed, the yttrium-based oxide coating can have a thickness of about 1-20 microns and a porosity of less than about 0.1% (e.g., substantially 0%). If ALD is performed, the yttrium-based oxide coating can have a thickness of about 10 nm to about 10 microns (e.g., about 1 micron) and a porosity of about 0%. When ALD or IAD is performed, the yttrium-based oxide 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, a conformal layer discussed herein has conformal coverage of the underlying surface (including the coated surface features) with a uniform thickness having less than about ±20% thickness variation, ±10% thickness variation, ±5% thickness variation, or even less thickness variation.

[0056] Alternatively, in some embodiments, no yttrium-based oxide coating or other metal oxide coating is deposited. Instead, the chamber component body may be composed of a metal oxide (e.g., Al2O3 or YO3).

[0057] In block 310, the chamber components are placed in a second processing chamber and may be heated to an elevated temperature of approximately 50-500°C. In one embodiment, the chamber components are heated to approximately 150-350°C. The second processing chamber may be, for example, a furnace or a wet cleaner containing an HF acid bath (or an acid bath containing another fluorine-based acid solution (e.g., NHF or a mixture of HF and NHF)). In block 315, the chamber components are exposed to HF at an elevated temperature. Alternatively, the chamber components may be exposed to another fluorine source (e.g., NF3 gas, NF3 plasma, CF4 plasma (e.g., CF4 / Ar plasma), F2, and / or F radicals, etc.). If an HF acid solution (or other fluorine-based acid solution) is used, the HF acid solution (or other fluorine-based acid solution) may be maintained at a temperature of approximately 0-100°C (or from about room temperature to about 100°C). In such an embodiment, the second processing chamber may or may not be heated. The combination of exposure to high temperature and HF can be referred to as an HF heat treatment process.

[0058] In one embodiment, at block 320, a flow of HF gas (e.g., anhydrous hydrogen fluoride gas) is introduced into a second processing chamber including a chamber component. The flow rate of the HF gas may be approximately 100-1000 SCCM. In one embodiment, an O2 plasma is also flowed into the second processing chamber. A power of approximately 100-1000 Watts may be used for the O2 plasma. The O2 plasma may be generated by a remote plasma source in one embodiment. The elevated temperature in one embodiment is 150-200°C.

[0059] In one embodiment, at block 325, the chamber components are immersed in a HF acid bath solution (or other fluorine-based acid solution). The HF acid bath solution may contain approximately 50-99.5 vol% water and 0.5-50 vol% HF acid. In one embodiment, the HF acid bath solution includes approximately 0.5-1.0 vol% HF acid and approximately 99-99.95 vol% water. In one embodiment, the HF acid bath solution is any of the HF acid bath solutions described above, further including an ammonium fluoride (NHF) buffer. In one embodiment, the HF acid bath solution includes 0.5 mol% NHF buffer. In one embodiment, the temperature is 0-100°C. Alternatively, the temperature may be 250-350°C.

[0060] In one embodiment, an NF3 plasma or a CF4 plasma (e.g., a CF4 / Ar plasma) is flowed into the second chamber in block 328. The plasma may be an inductively coupled plasma (ICP) or a capacitively coupled plasma (CCP). The power of the plasma may be, for example, 150-500 watts.

[0061] Treatment in the presence of HF gas or acidic HF solution (or other fluorine source) causes a chemical reaction at the surface of the metal oxide coating (or metal oxide ceramic article) in which some of the oxygen bonds are replaced with fluorine bonds. In the case of acidic HF solution, the solution may not be heated as described above. As a result of the HF treatment, YO becomes YOF, which begins at the surface of the YO coating. Some example reactions are shown below: 6HF+Al2O3→2AlF3+3H2O 6HF+Y2O3→2YF3+3H2O 4HF+ZrO2 → ZrF4+2H2O

[0062] The water produced by the reaction may evaporate and / or become part of the HF acidic solution at the treatment temperature, leaving behind fluoride. Thus, a chemical reaction occurs at the surface of the article or coating that replaces some of the oxygen molecules in the yttrium oxide (or other metal oxide) coating with fluorine molecules. The depth of the reaction is a function of time and temperature. In some embodiments, the reaction may penetrate the surface of the article or coating from a depth of about 10 nm to a depth of about 5 μm or less (e.g., to about 200 nm). In some embodiments, the entire yttrium-based oxide coating (or other metal oxide coating) is converted to a YOF coating (or other MOF coating).

[0063] The fluorine concentration in the MOF layer and the depth or thickness of the metal oxide converted to the MOF layer depend on the composition of the metal oxide being fluorinated, the fluorine concentration in the fluorine-based plasma (or HF acid solution), the temperature, and the duration of the fluorination treatment. Experiments have shown that a relatively low-temperature fluorination treatment (e.g., below about 100°C) for 1 to 5 hours results in fluorination of the topmost 50 to 70 nm of a YO coating or YO bulk sintered article. High-temperature fluorination (e.g., above about 400°C) fluorinates the entire YO coating, resulting in a coating with a thickness of about 50 nm to about 5 μm (e.g., about 200 nm). Examples of fluorination treatment conditions and resulting metal oxyfluoride layers are shown below in Figures 7B to 12B.

[0064] Exposure of metal oxides to air generally results in the formation of a layer of -OH groups (e.g., forming an M(OH) layer) on the surface of the metal oxide. As noted above, the M(OH) layer has several undesirable effects. Exposure of an M(OH) layer (e.g., a Y(OH) layer) to HF at the temperatures described above converts the M-OH layer to an MOF layer in a manner similar to that of a metal oxide coating or article. Thus, the M(OH) layer can be removed by HF heat treatment. Furthermore, the MOF layer or coating is not susceptible to further formation of -OH groups on its surface.

[0065] In embodiments, where the yttrium-based oxide coating is an alternating stack of Y2O3 layers and additional oxide layers as described above, the Y2O3 layers can be converted to YOF layers, and the additional oxide layers can be converted to additional MOF layers.

[0066] In some embodiments, the chamber component includes magnesium (e.g., is an aluminum alloy containing magnesium). In one embodiment, in block 335, magnesium from the chamber component diffuses toward the surface of the chamber component and into the YOF coating or other MOF coating. The diffusion may occur as a result of the HF treatment. In block 340, the magnesium reacts with the MOF coating to form an MgF2 layer at the MOF coating interface. If all of the yttrium-based oxide coating has been converted to MOFs, the MOF coating interface may be the interface between the MOF coating and the chamber component. Alternatively, if not all of the yttrium-based oxide coating has been converted to MOFs, the MOF coating interface may be the interface between the MOF layer and the yttrium-based oxide coating. The MgF2 layer acts as a magnesium barrier layer, preventing magnesium from diffusing beyond the MgF2 layer. Similarly, other metals may diffuse toward the MOF layer and react with the MOF layer to form other metal fluoride barrier layers.

[0067] In some embodiments, the yttrium-based oxide coating may be subjected to a chemical treatment before and / or after the HF treatment, which may improve the quality (e.g., stability) of the MOF layer.

[0068] 3B shows a cross-sectional side view of a chamber component 350 including a Y2O3 coating 360 on a body 355 of the chamber component 350 and a YOF layer 365 on the Y2O3 coating 360, according to one embodiment. The chamber component 350 may have a metallic body (e.g., aluminum or an aluminum alloy (e.g., Al6061)) or a ceramic body (e.g., Al2O3, AlN, SiC, etc.).

[0069] 4A illustrates a process 400 for converting a YF3 coating or other rare earth fluoride coating to a YOF coating or other MOF coating, according to one embodiment. Process 400 may also be performed to convert other yttrium-based fluoride coatings to YOF coatings or other yttrium-based oxyfluorides. Examples of other yttrium-based fluoride coatings include YxFyZrz (where x, y, and z are positive integers or decimals), ErF3, YxErzFz (where x, y, and z are positive integers or decimals), and the like. For example, the yttrium-based fluoride can include a mixture of 20-80 mol% YF3 and 20-80 mol% ZrF4. Other examples include 45-85 mol% YF3 and 15-60 mol% ZrF4, 55-75 mol% YF3 and 25-45 mol% ZrF4, 58-62 mol% YF3 and 38-42 mol% ZrF4, 68-72 mol% YF3 and 28-32 mol% ZrF4. In other examples, the yttrium-based fluoride can include 50-90 mol% YF3 and 10-50 mol% ErF3, 10-90 mol% YF3 and 10-90 mol% ErF3, 30-70 mol% YF3 and 30-70 mol% ErF3, 60-80 mol% YF3 and 20-40 mol% ErF3, etc. Process 400 will be discussed with reference to the conversion of YF3 to YF. However, it should be understood that process 400 can be performed to convert other yttrium-based fluorides to yttrium-based oxyfluorides. Thus, YF in the following discussion may be substituted with other yttrium-based fluorides, and YOF in the following discussion may be substituted with other yttrium-based oxyfluorides.

[0070] In one example, the yttrium-based fluoride may be a YF3-ZrF4 solid solution, an alternating laminate of YF3 layers and AlF3 layers or other metal fluoride layers, or a composite ceramic including a first phase of Y-Al-F and a second phase of Y-Zr-F. The YF3-ZrF4 solid solution may include approximately 50-75 mol% YF3 and approximately 25-50 mol% ZrF4, and may be converted to Y-Zr-OF, where the Y to Zr ratio is approximately 1:1 to 3:1. In an embodiment, the YF3-ZrF4 solid solution may include 55-65 mol% YF3 and approximately 35-45 mol% ZrF4. In an embodiment, the YF3-ZrF4 solid solution may include 65-75 mol% YF3 and approximately 25-55 mol% ZrF4. In the case of an alternating laminate of YF3 and AlF3 (or other metal fluoride) layers, the YF3 layer may have a thickness of about 5 to 10 times that of the AlF3 or other metal fluoride layer. For example, the YF3 layer may have a thickness of about 5 to 100 angstroms, and the AlF3 layer may have a thickness of about 1 to 20 angstroms. The YF3 layer may be converted into a YOF layer having approximately the thickness of the original YF3 layer, and the AlF3 layer may be converted into an Al-OF layer having approximately the thickness of the original AlF3 layer. In the case of a composite ceramic, the first phase of Y-Al-F may be converted into Y-Al-OF, and the second phase may be converted into Y-Zr-OF.

[0071] In block 405 of process 400, ALD, CVD, or IAD is performed to deposit a YF3 or other rare earth fluoride coating on a chamber component for a processing chamber. If ALD is performed, the YF3 coating (or other yttrium-based fluoride coating) has a thickness of about 10 nm to 10 microns. If EB-IAD is performed, the YF3 coating (or other yttrium-based fluoride coating) has a thickness of about 0.5 to 10 microns. If CVD is performed, the YF3 coating (or other yttrium-based fluoride coating) has a thickness of about 100 nm to about 10 microns. In one embodiment, the IAD-deposited YF3 coating (or other yttrium-based fluoride coating) has a thickness of 5 microns. Both the ALD coating and the IAD coating are conformal coatings with very low porosity (e.g., no porosity) of about 0%. In embodiments, the YF3 coating (or other yttrium-based fluoride coating) may be an amorphous coating, as determined by X-ray powder diffraction (XRD) phase studies.

[0072] At block 410, the chamber components can be placed in a processing chamber (e.g., a furnace processing chamber) and heated to an elevated temperature of approximately 100-1500°C. Examples of temperatures to which the chamber components can be heated include 200°C, 250°C, 300°C, 400°C, 500°C, 600°C, 650°C, 750°C, and 800°C. At block 415, the chamber components are exposed to an oxygen source at the elevated temperature for a period of time. The oxygen source can be air, O2 gas, water vapor, O3 gas, O2 plasma, and / or other oxygen-based plasma or oxygen-based radicals. Other oxygen sources include ion bombardment of the YF3 coating (or other yttrium-based fluoride coating) using O2 ions and / or radicals. The combination of elevated temperature and exposure to an oxygen source can be referred to as an oxygen heat treatment process. In an embodiment, the time period can be 12-24 hours. In another embodiment, the time period can be 0.1-72 hours. In some embodiments, the processing chamber is or includes a metal, and the elevated temperature is between 150 and 650°C. In some embodiments, the elevated temperature is between 300 and 400°C. In some embodiments, the processing chamber is ceramic and has a coefficient of thermal expansion (CTE) that closely matches the CTE of the YF3 coating (or other yttrium-based fluoride coating). In such embodiments, the elevated temperature can reach 1500°C.

[0073] In one embodiment, at block 420, the YF3 coating (or other yttrium-based fluoride coating) is converted to a YOF coating (or other MOF coating). In one embodiment, a portion of the YF3 coating (or other yttrium-based fluoride coating) is converted to a YOF or other MOF layer (e.g., the surface of the YF3 coating is converted). In one embodiment, the entire YF3 coating (or other yttrium-based fluoride coating) is converted to a YOF or other MOF coating. The YOF coating can be a crack-free crystalline coating, as shown by XRD phase studies. Films with thicknesses of 10 microns or greater have been shown to experience vertical cracks when converted from YF3 to YOF. Thus, in an embodiment, a YF3 film less than 10 microns thick is used.

[0074] Heat treatment in the presence of an oxygen source causes a chemical reaction at the coating surface, replacing some of the fluorine bonds with oxygen bonds. Thus, a chemical reaction occurs at the surface of the article or coating that replaces some of the fluorine molecules in the YF3 coating with oxygen molecules. The depth of the reaction is a function of time and temperature.

[0075] In some embodiments, the chamber component includes magnesium (e.g., is an aluminum alloy containing magnesium). In one embodiment, at block 335, magnesium from the chamber component diffuses toward the surface of the chamber component and into the YOF coating. The diffusion may occur as a result of the HF treatment. At block 340, the magnesium reacts with the YOF coating to form a MgF2 layer at the YOF coating interface. If all of the YF3 coating is converted to YOF, the YOF coating interface may be the interface between the YOF coating and the chamber component.

[0076] In one example, a 1-micron-thick amorphous YF3 coating was exposed to air at 350°C for 12 hours. The results showed that the majority of the YF3 coating was converted to a crack-free, crystalline YOF coating. Specifically, the coating contained 83.7 wt.% YOF and 13.7 wt.% YF after oxygen heat treatment. In this example, the chamber components were Al6061 and contained magnesium. The magnesium diffused into the YOF coating, forming MgF2. Accordingly, XRD phase studies showed a minor phase of 2.6 wt.% MgF2 at the interface between the coating and the substrate. The emissivity of the as-deposited YF3 is 0.351, while the emissivity of the YOF layer is 0.149.

[0077] YOF has a smaller molar volume than YF3. Therefore, when a YF3 coating is converted to a YOF coating, the compressive stress of the YF3 coating can be reduced. Therefore, the conversion can be performed to adjust the "zero stress state" of the coating. The term "zero stress state" refers to a state in which the coating is not under any tensile or compressive stress (e.g., has no internal compressive or tensile stress). The zero stress state generally occurs at the deposition temperature.

[0078] 4B shows a cross-sectional side view of a chamber component 450 including a YOF coating 360 on a body 355 of the chamber component 350, according to one embodiment. The chamber component 350 may have a metallic body (e.g., aluminum or an aluminum alloy (e.g., Al6061)) or a ceramic body (e.g., Al2O3, AlN, SiC, etc.). The YOF coating 360 may originally be a YF3 coating or may be completed and converted to a YOF coating 460. Similar results can be achieved by converting other yttrium-based fluorides to yttrium-based oxyfluorides.

[0079] 5 illustrates an in-situ process 500 for forming a temporary YF3, yttrium-based oxyfluoride, or other MOF layer on a metal oxide coating prior to a manufacturing process, according to one embodiment, referred to herein as an in-situ fluorination treatment. Alternatively, process 500 can be performed to form a MOF (e.g., YF3 or yttrium-based oxyfluoride) layer on a sintered metal oxide chamber component that does not have a metal oxide coating. Furthermore, process 500 can also be performed to form a temporary YF3 or other metal fluoride layer on the surface of a metal oxide coating or article, rather than forming a MOF layer.

[0080] At block 505 of process 500, a substrate is loaded into a processing chamber. The processing chamber includes one or more chamber components having a metal oxide coating. The metal oxide coating (or sintered metal oxide article) may be Al2O3, Er2O3, Y2O3, Y2O3-stabilized ZrO2 (YSZ), Er3Al5O, to name a few. 12 The metal oxide coating may be an aluminum-oxide-coated (ALD) coating having a thickness of 10 nm to 1 micron, an iron-oxide-deposited (IAD) coating having a thickness of 1 to 10 microns, a plasma-sprayed coating having a thickness of 100 to 300 microns, an aluminum-oxide-coated (SPS) coating having a thickness of 50 to 100 microns, a chemical vapor deposition (CVD) coating, or another type of coating (e.g., an Al2O3 coating formed by anodization). Alternatively, the chamber component may be a bulk-sintered metal oxide ceramic article without a metal oxide coating.

[0081] At block 510, a fluorine-based plasma from a remote plasma source is introduced into a processing chamber in which one or more chamber components are located. Alternatively, a different fluorination source (e.g., HF gas) may be used. In one embodiment, a fluorine-based acidic solution (e.g., HF acidic solution) is used as the fluorination source.

[0082] At block 515, the metal oxide coating (or metal oxide article) is reacted with a fluorine-based plasma or other fluorine source to form a temporary MOF or metal fluoride layer on the metal oxide coating (or metal oxide article). The temporary MOF or metal fluoride layer can be a very thin layer that is not designed to last more than one process or a few processes. In embodiments, the temporary MOF layer can have a thickness of 1 to 50 nm (e.g., 1 to 5 nm).

[0083] In embodiments, a fluorine-based plasma may be introduced into the processing chamber while the chamber temperature is between about room temperature and about 1000°C. In further embodiments, the chamber may have a temperature between about room temperature and about 400°C. In embodiments, the fluorine-based plasma may be introduced into the processing chamber for about 0.5 to 10 minutes. The fluorine-based plasma may be any of the fluorine-based plasmas described above. In one embodiment, oxygen plasma and HF gas are used rather than a fluorine-based plasma.

[0084] In alternative embodiments, the fluorine-based acidic solution may be introduced into the processing chamber at a temperature from room temperature up to about 100°C. In embodiments, the acidic solution itself may be heated, and / or the chamber may be heated. In one embodiment, the fluorine-based acidic solution is a HF acidic solution containing 50-95 vol% water and 5-50 vol% HF acid. The fluorine-based acidic solution may be flowed into the chamber to completely or partially fill it. Alternatively, the fluorine-based acidic solution may be sprayed onto one or more chamber components to fluorinate them. The exposure time of one or more chamber components to the fluorine-based acidic solution may be about 0.5-10 minutes (e.g., 0.8 minutes, 1.0 minutes, 1.2 minutes, 1.5 minutes, etc.). In some examples, the exposure time may be shorter (e.g., about 0.2-0.4 minutes). After the exposure time, the chamber components may be rinsed (e.g., with DI water).

[0085] In some embodiments, the operation of block 505 is performed after the operation of block 515 and before the operation of block 520 .

[0086] At block 520, a fabrication process is performed. The fabrication process may be, for example, a plasma etching process or a plasma cleaning process, and may etch or clean a substrate (e.g., a wafer with semiconductor circuits formed thereon) secured in a processing chamber. The fabrication process may include the use of a corrosive gas (e.g., a fluorine-based plasma, a chlorine-based chemistry, an ammonia-based chemistry, etc., which would enable a plasma etching process or a plasma cleaning process). Due to the presence of an MOF layer or a metal fluoride layer on the metal oxide coating (or metal oxide article), the corrosive gas may not erode, corrode, or damage the metal oxide coating. In some embodiments (e.g., embodiments in which a chlorine-based chemistry or an ammonia-based chemistry is used), the corrosive gas may remove the entire MOF layer or the metal fluoride layer by the end of the fabrication process. Alternatively, the corrosive gas may remove only a portion of the MOF layer or the metal fluoride layer (e.g., when a chlorine-based chemistry or an ammonia-based chemistry is used). In some embodiments, the fabrication process includes a fluorine-based plasma under conditions that grow the MOF layer or the metal fluoride layer. In each of these examples, the MOF layer or metal fluoride layer can protect the underlying metal oxide coating and / or metal oxide article throughout the manufacturing process.

[0087] In-situ fluorination treatment may be performed prior to each manufacturing process that exposes the processing chamber to corrosive gases. The MOF or metal fluoride layer may have a much lower erosion rate than metal oxide coatings when exposed to reducing chemistries (e.g., chlorine, fluorine, and ammonia chemistries). As a result, the useful life of chamber components for the processing chamber may be significantly extended, process drift may be mitigated, and on-wafer particles due to chemical reactions between corrosive gases and metal oxide coatings may be mitigated. Furthermore, the MOF or metal fluoride layer may function as a diffusion barrier to block metal diffusion during the manufacturing process, potentially reducing metal contamination on processed substrates.

[0088] In some instances where the manufacturing process is a fluorine-based process (e.g., using fluorine gas or fluorine plasma), the manufacturing process itself may convert some portions of the metal oxide coating to metal fluorides or metal oxyfluorides. However, other manufacturing processes (e.g., processes using chlorine or ammonia) may not cause such conversion to metal fluorides or metal oxyfluorides. Furthermore, there are often large surfaces of chamber components with metal oxide coatings. It may take multiple iterations of the manufacturing process before a sufficient metal oxyfluoride or metal fluoride layer builds up on the metal oxide coating to protect it. During this time, process drift may occur due to changes in chamber conditions. In-situ fluorination treatment can function as an in-situ seasoning process, rapidly forming a metal oxyfluoride or metal fluoride layer, immediately protecting the metal oxide coating and mitigating process drift. Furthermore, in-situ fluorination treatment can be used to control the fluorination conditions and stress to achieve a target thickness of the MOF layer or metal fluoride. Controlling the fluorination conditions can prevent particle generation from the MOF layer or metal fluoride layer.

[0089] Experiments have determined that there is a first threshold layer thickness for the temporary MOF or metal fluoride layer above which particles are generated. Thus, in some embodiments, the thickness of the MOF or metal fluoride layer is further controlled by periodically performing an etch-back process. For example, an in-situ fluorination treatment may be performed at the beginning of each manufacturing process, or the etch-back treatment may be performed after the manufacturing process has been performed a threshold number of times (e.g., 5, 10, 24, 30, etc.). The etch-back process may be performed as an in-situ process, or may be performed periodically at the end of the manufacturing process or at the beginning of the manufacturing process prior to the fluorination treatment.

[0090] Thus, in one embodiment, a determination is made at block 525 whether to perform an etch-back process. This determination may be based on the thickness of the MOF or metal fluoride layer or other etch-back criteria. In one embodiment, it is time to perform the etch-back process when the MOF or metal fluoride layer reaches a first threshold thickness that is less than a second threshold thickness at which particle generation occurs. In one embodiment, the determination is made based on counting the number of iterations of the fabrication process that have been performed since the last time the etch-back process was performed. For example, this can be determined by testing how much thickness is added to the MOF or metal fluoride layer after each in-situ fluorination treatment and fabrication process iteration. This information can be used to determine when the MOF or metal fluoride layer has reached the first threshold thickness and satisfied the etch-back criteria.

[0091] Additionally or alternatively, a particle count test may be performed on the substrate after processing, and if the particle count of yttrium-containing particles increases by a threshold amount (e.g., the number of yttrium-containing particles reaches a threshold), a determination may be made that the etch-back criteria is met and an etch-back process should be performed.

[0092] If an etch-back process is not performed (e.g., the MOF layer or metal fluoride layer has not reached the first threshold thickness or the threshold particle count has not been reached), the method returns to block 505 and another substrate is loaded into the processing chamber for processing. If an etch-back process is performed, the method continues to block 530.

[0093] At block 530, an etch-back process is performed. In one embodiment, the etch-back process is performed after removing the substrate from the processing chamber, which prevents the etch-back process from affecting the substrate. Alternatively, in some cases, the etch-back process may be performed as an in-situ process after a fabrication process or before a subsequent fabrication process on another substrate.

[0094] The etch-back process is used to control the net thickness of the MOF or metal fluoride layer. The etch-back process is performed using a corrosive chemistry capable of etching metal fluorides or metal oxyfluorides. In one embodiment, the etch-back process is performed using silicon tetrachloride (SiCl4) gas or SiCl4 plasma. SiCl4 reacts with the metal fluoride or MOF layer to form SiFx (x can be any positive value), which is highly volatile and has a high vapor pressure. SiFx then reacts with the MOF or metal fluoride layer to form MFz (z can be any positive value), which can then be pumped out of the processing chamber. In one embodiment, the etch-back process is performed using a combination of SiCl4 gas or plasma and Cl2 gas or plasma. The addition of Cl2 to SiCl4 increases the etch-back rate of the MOF or metal fluoride layer. In one embodiment, approximately 1-5 SCCM of SiCl4 and optionally 1-5 SCCM of Cl2 are flowed into the processing chamber for 1-5 seconds. In one embodiment, approximately 1-2 SCCM of SiCl4 and optionally 1-2 SCCM of Cl2 are flowed into the processing chamber for 1-3 seconds.

[0095] In one embodiment, the processing chamber is equipped with an optical emission spectroscopy (OES) device. During the etch-back process, plasma is generated, at least a portion of which is from the MOF or metal fluoride layer being etched. The OES device can measure the intensity levels of various wavelengths of light output by the plasma. Based on the detection of the intensity levels of various wavelengths of light, the OES device can detect the optical signature of SiFx formed from etching the MOF or metal oxide with SiCl4. Additionally or alternatively, the optical signature of YClx can be detected using OES (where x can be any positive value). Once the MOF or metal fluoride layer is completely removed, SiFx and / or YCl will no longer be produced, and the detected wavelength intensity will change. Thus, the OES device can detect when the MOF or metal fluoride layer has been removed. At this point, the etch-back process can be terminated, and the gas / plasma can be pumped out of the processing chamber. Furthermore, the proportion of fluorine in the MOF or metal fluoride layer may decrease with depth, with a small amount of fluorine present near the interface with the metal oxide coating. The OES device can detect this change in fluorine content and can trigger the end of the etch-back process when a specific optical signature is detected. The specific optical signature may be an optical signature containing a certain amount of SiFx and / or YCl. Thus, the OES device may be used to perform a partial etch-back that ensures that some portion of the MOF layer or metal fluoride layer is still in an end-of-etch-back state.

[0096] Each of methods 300, 400, and 500 can at least partially convert metal fluoride or metal oxide coatings and / or articles to metal oxyfluoride (MOF) layers or coatings. Tests have shown that yttrium oxyfluoride layers or coatings and other metal oxyfluoride layers or coatings are stable and highly resistant to plasma erosion and reaction with fluorine-based chemistries. Furthermore, YOF coatings and other yttrium-based oxyfluoride coatings are inert to hydroxide attack (OH attack). Thus, yttrium hydroxide (Y(OH)) does not form when a YOF coating or layer is exposed to air. Tests have shown that particle levels are reduced when YOF coatings are used on chamber components. Furthermore, Cl * , Br * , F * and H * Even in the presence of seeds, the etching rate of the YOF coating is very stable and slow compared to the YF3 coating.

[0097] FIG. 6A illustrates a process 600 for stress-relieving a yttrium-based coating by converting at least a portion of the yttrium-based coating to a YOF coating or layer (or other yttrium-based oxyfluoride coating or layer), according to one embodiment. Process 600 is initially described with reference to converting a yttrium-based oxide coating to a yttrium-based oxyfluoride coating. However, method 600 can also be performed to convert a yttrium-based fluoride coating to a yttrium-based oxyfluoride coating. In an embodiment, the chamber component may be a metal chamber component, such as an aluminum component (e.g., pure aluminum or an aluminum alloy (e.g., Al6061)) or a stainless steel component. Aluminum has a CTE of approximately 22-25 ppm / K, and stainless steel has a CTE of approximately 13 ppm / K. However, yttrium-based coatings have significantly lower CTEs (e.g., approximately 6-8 ppm / K for YO). Other oxides also generally have lower CTEs. For example, the CTE of Al2O3 is 8 ppm / K. This CTE difference between the yttrium-based coating and the chamber components can cause the yttrium-based coating to crack during thermal cycling. Dense coatings (e.g., coatings produced by IAD, PVD, CVD, and ALD) are particularly susceptible to cracking during thermal cycling when formed on metal articles.

[0098] At block 605 of process 600, a yttrium-based coating is deposited on the surface of a chamber component for a first processing chamber. The yttrium-based oxide coating may be a Y2O3 coating, a coating comprised of a Y2O3-Er2O3 solid solution, a coating comprised of a Y2O3-ZrO2 solid solution, or other yttrium-based coating discussed herein. In some embodiments, the yttrium-based coating comprises an alternating stack of thicker Y2O3 layers and thinner layers of another metal oxide (e.g., ZrO2 or Al2O3). The thinner metal oxide layer can prevent crystal formation in the Y2O3 layer or limit the size of the crystals formed in the Y2O3 layer.

[0099] The yttrium-based coating may be a thin, dense oxide coating deposited using an IAD deposition process, a physical vapor deposition (PVD) deposition process, a chemical vapor deposition (CVD) deposition process, or, in embodiments, an ALD deposition process. In some embodiments, the yttrium-based coating may be deposited using a deposition temperature of approximately 100-300°C. For example, the chamber components may be heated to a temperature of 100-200°C during deposition. Thus, the yttrium-based coating may have a "zero stress state" at deposition temperatures of approximately 100-300°C, low compressive stress at room temperature, and high tensile stress at processing (operating) temperatures. The deposition temperature may be governed by the deposition process being performed and / or the characteristics of the chamber components. When the chamber components are at room temperature, the yttrium-based coating may be under slight compressive stress because the chamber components contract more than the yttrium-based coating as they cool below the deposition temperature. However, at processing temperatures higher than the deposition temperature, the chamber components expand more than the yttrium-based coating, placing the yttrium-based coating under tensile stress. The tensile stress can cause the yttrium-based coating to crack. In embodiments, the chamber component may subsequently be used at elevated processing temperatures of approximately 250-350° C. As a result, the difference in CTE between the yttrium-containing coating and the chamber component will place it under tensile stress during future processing.

[0100] The yttrium-based coating can have a very low porosity, in embodiments less than 1%, in further embodiments less than 0.1%, in embodiments about 0%, or in still further embodiments no porosity. When ALD is performed to form the yttrium-based coating, after one complete ALD deposition cycle, the yttrium-based coating can have a thickness of one atom to less than a few atoms (e.g., two to three atoms). Multiple ALD deposition cycles can be performed to deposit thicker yttrium-based coatings, with each deposition cycle adding one to a few atoms to the thickness. In embodiments, the yttrium-based coating can have a thickness of about 10 nm to about 1.5 μm. In further embodiments, the yttrium-based coating can have a thickness of about 300 nm to about 500 nm.

[0101] In some embodiments, the yttrium-based coating comprises a series of alternating layers of Y2O3 and an additional metal-containing oxide. For example, the yttrium-based coating can be a series of alternating layers of Y2O3 and Al2O3, a series of alternating layers of Y2O3 and ZrO2, etc. Using ALD, the chamber component can be exposed to one or more precursors for a period of time until the surface of the chamber component is fully adsorbed with the one or more precursors to form an adsorbed layer. The chamber component can then be exposed to a reactant to react with the adsorbed layer and grow a Y2O3 layer. This process can be repeated for up to about 5-10 cycles to grow a Y2O3 layer.

[0102] The chamber component bearing the YO layer may be exposed to one or more precursors for a period of time until the surface of the YO layer is fully adsorbed with one or more precursors to form an adsorbed layer. The chamber component may then be exposed to a reactant, which reacts with the adsorbed layer to grow an additional solid metal oxide layer. Thus, using ALD, an additional metal oxide layer is fully grown or deposited on the YO layer. In one example, the precursor may be an aluminum-containing precursor used in the first cycle, and the reactant may be H2O used in the second cycle. The metal oxide layer may be ZrO2, Al2O3, or other oxides. This process can be performed once to grow very thin metal oxide layers with thicknesses of less than a monolayer to a few atomic layers. For example, an Al2O3 monolayer grown with TMA and H2O typically has a growth rate of approximately 0.9-1.3 Å / cycle, while the lattice constants of Al2O3 (for a trigonal structure) are a-4.7 Å and c=13 Å.

[0103] The deposition of the YO layer and the additional metal oxide layer can be repeated n times to form a stack of alternating layers, where n is an integer value greater than 2. n may represent a finite number of layers selected based on the targeted thickness and properties. The stack of alternating layers may be considered a yttrium-based coating comprising multiple alternating sublayers.

[0104] In embodiments, the alternating layers may have a ratio of the thickness of the YO layer to the thickness of the additional metal oxide layer of about 5:1 to 10:1. Thus, the additional metal oxide layers may have a thickness that is 1 / 10 to 1 / 5 of the thickness of the YO layer. In one embodiment, eight ALD deposition cycles are performed for each YO layer, and one ALD deposition cycle is performed for each additional metal oxide layer. As a result, the YO layers may be amorphous. In another embodiment, ten ALD cycles are performed for each YO layer, and one ALD deposition cycle is performed for each additional metal oxide layer. As a result, the YO layers may be nanocrystalline, with crystal sizes on the order of one or a few nanometers. Alternatively, more, but fewer, ALD deposition cycles may be performed for the YO layers and / or the additional metal oxide layers.

[0105] As previously described, a Y2O3 layer is formed on the chamber component, followed by the formation of an additional metal oxide layer, followed by the formation of another Y2O3 layer, etc. However, in other embodiments, the first layer may be an additional metal oxide layer, the next layer may be a Y2O3 layer, followed by another additional metal oxide layer, etc.

[0106] In one embodiment, a stress relief layer (e.g., amorphous Al2O3 or another amorphous ceramic) is deposited prior to deposition of the yttrium-based coating. The stress relief layer may be deposited using the same deposition technique as the yttrium-based coating, or a different deposition technique. In an example where the stress relief layer is an alumina (Al2O3) stress relief layer, ALD may be performed until all reactive sites on the surface of the chamber component are consumed and an Al-containing adlayer is formed in the first half of the reaction, during which the chamber component is exposed to a first precursor (e.g., trimethylaluminum (TMA)) for a first time. After flushing out any remaining first precursor, a first reactant of HO can then be injected into the reactor containing the chamber component to begin the second half of the cycle. After the HO molecules react with the Al-containing adlayer produced by the first half of the reaction, an Al2O3 stress relief layer is formed.

[0107] The stress relief layer may be uniform, continuous, and conformal. In embodiments, the stress relief layer may be non-porous (e.g., have a porosity of 0%) or may have a porosity of nearly 0% (e.g., a porosity of 0% to 0.01%). Multiple full ALD deposition cycles may be performed, with each full cycle (e.g., including precursor introduction, rinsing, reactant introduction, and rinsing again) adding one to several atoms to the thickness, to deposit a thicker stress relief layer. In embodiments, the stress relief layer may have a thickness of about 10 nm to about 1.5 μm.

[0108] At block 610, the chamber components are heated to an elevated temperature of about 250-500°C (e.g., about 250-350°C). At block 615, the chamber components are exposed to a fluorine source at the elevated temperature for a period of time. In embodiments, the period of time may be about 0.1 hours to about 72 hours. In further embodiments, the period of time may be about 12-24 hours or about 1-12 hours. The fluorine source may be HF gas, NF3 gas, NF3 plasma, F2 gas, F radicals in a gas, or other fluorine source, as described at block 620.

[0109] At block 625, the yttrium-based coating is converted to a MOF coating or layer. F atoms diffuse through the yttrium-based coating and react with YO in the coating, forming YOF and possibly other fluorinated phases. The depth and percentage of conversion can be controlled by parameters (e.g., treatment time, temperature, type of F-containing gas, gas pressure, and chamber pressure). The target depth and percentage of the yttrium-based oxide coating to be converted to MOF can depend on the difference between the deposition temperature and the operating or processing temperature to adjust the "zero stress state" of the coating. For example, if the yttrium-based coating is a YO coating, the entire YO coating can be converted to YOF. If the yttrium-based coating is an alternating layer of YO and an additional metal oxide layer, the YO layer can be converted to a YOF layer, and the additional metal oxide layer can be converted to a MOF layer. In some cases, the additional metal oxide layer can be so thin that the material composition of the additional metal oxide layer does not change as a result of the fluorination treatment. Thus, the Y2O3 layer can be converted to a YOF layer, and the additional metal oxide layer may remain unchanged.

[0110] Compared with Y2O3, YO x F y has a larger molar volume (x and y can be positive values). Depending on the values ​​of x and y, YO x F y The molar volume of YF3 is 36.384 cm 3 / mol and the molar volume of 1 / 2Y2O3 form is 22.5359 cm 3 / mol. YOF coatings or layers of yttrium-based coatings (e.g., YO x F yThe conversion of YF3 to YOF3 results in a volume expansion, introducing additional internal compressive stress at temperatures below the deposition temperature, which is greater than the internal compressive stress of yttrium-based coatings at temperatures below the deposition temperature. As a result, the zero-stress state of the coating on the metal chamber component or other article shifts toward higher temperatures. Thus, when the chamber component is heated to a high processing temperature above the deposition temperature, the MOF coating or layer (e.g., YOF3 coating or layer) has reduced internal tensile stress, which is less than the internal tensile stress of yttrium-based coatings at temperatures above the deposition temperature. The volume expansion occurs because YF3 has a molar volume approximately 60% greater than that of YO3. The molar volume of YOF is between the molar volumes of YF3 and YO3. The reduced tensile stress can reduce or eliminate cracking in the YOF coating. YOF is a plasma-resistant coating that is resistant to erosion and corrosion by fluorine-based plasmas.

[0111] Process 600 is described as increasing the compressive stress of a yttrium-based coating on a chamber component having a CTE higher than the CTE of the yttrium-based coating. However, a similar process can also be performed to reduce the compressive stress of a yttrium-based coating on a chamber component having a CTE lower than the CTE of the yttrium-based coating. For example, the chamber component may be graphite (having a CTE of about 4 ppm / K), AlN (having a CTE of about 4.6 ppm / K), SiC (having a CTE of about 3.7 ppm / K), or SiN (having a CTE of about 2.8 ppm / K). In such cases, it may be desirable to reduce the compressive stress in the yttrium-based coating. This can be accomplished, for example, by starting with the deposition of a YF3 or other yttrium-based fluoride coating at block 605. The chamber components can then be exposed to an oxygen source (e.g., any of the oxygen sources described herein) at block 615 to convert the yttrium-based fluoride coating to a YOF coating or layer or other yttrium-based oxyfluoride coating or layer. In embodiments, exposure to an oxygen source (e.g., O plasma and / or O radicals) can be performed at a temperature of 200-300°C. The conversion of YF to YOF (or another yttrium-based fluoride to an yttrium-based oxyfluoride) results in volumetric shrinkage (e.g., due to a decrease in molar volume), which can introduce tensile stress and / or reduce compressive stress at room temperature and / or at elevated processing temperatures. Thus, process 600 can be performed to adjust stress within the yttrium-based oxide or yttrium-based fluoride coating. Examples of yttrium-based fluoride coatings that can be converted to yttrium-based oxyfluoride coatings are provided above with reference to FIG. 4A.

[0112] 6B shows a cross-sectional side view of a chamber component 650 including a YOF / MOF coating 670 on a body 655 of the chamber component 650, according to one embodiment. The chamber component 650 may have a metallic body (e.g., aluminum, an aluminum alloy (e.g., Al6061 or Al6063), stainless steel (e.g., SST316L), etc.) or a ceramic body (e.g., Al2O3, AlN, SiC, etc.). The YOF / MOF coating 670 may include alternating stacks of thicker YOF layers 660 and thinner MOF layers 665. Alternatively, the thinner layers may be M layers.

[0113] 7A shows a cross-sectional side view of a chamber component 710 including a Y2O3 coating 705 as viewed by transmission electron microscopy (TEM), according to one embodiment. A capping layer 715 is disposed on top of the Y2O3 coating 705 for purposes of generating a TEM image. Plane A1 shows the top of the Y2O3 coating 705, and plane B1 shows the interface between the chamber component 710 and the Y2O3 coating 705.

[0114] Figure 7B shows the material composition of the chamber components of Figure 7A. As shown, the capping layer 715 is made of Ir. The Y2O3 coating 705 is made of yttrium 725 and oxygen 720. The chamber component 710 is made of Si 735.

[0115] FIG. 8A shows a cross-sectional side view of a chamber component 810 including a YOF coating 805 after a fluorination treatment, as observed by transmission electron microscopy (TEM), according to one embodiment. The fluorination treatment was performed at 500°C for approximately 12 hours using an NF3 plasma with a power of 200 W. A capping layer 815 was disposed on the YOF coating 805 for the purpose of generating a TEM image. Surface A2 shows the top of the YOF coating 805, and surface B2 shows the interface between the chamber component 810 and the YOF coating 805. Strain measurements by X-ray diffraction (XRD) showed an increase in strain of approximately 1.34±0.13% at room temperature, with a crystallite size of 11.4±1.5 nm, equivalent to an increase in compressive stress at room temperature. In comparison, the yttria coating without the fluorination treatment had a strain of 0.22±0.14% and a crystallite size of 6.1±0.5 nm at room temperature. The increased compressive stress of the YOF coating at room temperature results in a lower film stress for this coating at operating temperatures (eg, about 100° C. or above).

[0116] FIG. 8B illustrates the material composition of the chamber component of FIG. 8A. As shown, the capping layer 815 is comprised of Ir. The YOF coating 805 is comprised of yttrium 825, oxygen 820, and fluorine 840. The chamber component 810 is comprised of Si 835. As shown, the YOF coating 805 contains approximately 30-50 at.% F, approximately 20-30 at.% O, and approximately 30-40 at.% Y, depending on the depth of the coating. The fluorination process replaces O molecules with F molecules throughout the YO coating 705.

[0117] FIG. 9A shows a cross-sectional side view of a chamber component 910 including an yttrium-based oxyfluoride coating 905 consisting of alternating layers of YOF and Al-OF after a fluorination treatment, as observed by transmission electron microscopy (TEM), according to one embodiment. The yttrium-based oxyfluoride coating was produced by fluorination of an yttrium-based oxide coating including alternating layers of YO and AlO. The fluorination treatment may be performed at 250° C. A capping layer 915 is disposed on the yttrium-based oxide coating 905 for the purpose of generating a TEM image. Surface A3 shows the top of the yttrium-based oxide coating 905, surface B3 shows the interface between the yttrium-based oxide coating and the alumina stress relief layer 912, and surface C3 shows the interface between the alumina stress relief layer 912 and the chamber component 910.

[0118] Figure 9B shows the material composition of the chamber component of Figure 9A. As shown, the capping layer 915 is composed of Ir. The yttrium-based oxide coating 905 is composed of yttrium 925, oxygen 920, fluorine 940, and aluminum 935. The stress relief layer is composed of oxygen 920 and aluminum 935. The chamber component 810 is composed of different ratios of aluminum 935 and oxygen 920.

[0119] Prior to fluorination, the yttrium-based oxyfluoride coating 905 was an yttrium-based oxide coating comprising alternating layers of YO and AlO. In some embodiments, the YO layer may be approximately 2 to 12 times thicker than the AlO layer. Examples of thickness ratios between the rare earth oxide sublayer and the additional metal oxide sublayer include 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, and 12:1. In some embodiments, the YO layer is formed using approximately 5 to 12 cycles of an ALD process, with each cycle forming one nanolayer (or slightly less than or slightly more than one nanolayer) of rare earth metal-containing oxide. Each AlO layer can be formed in one ALD cycle (or several ALD cycles) and can have a thickness of less than one atom to a few atoms. In embodiments, each Y2O3 layer can have a thickness of about 5-100 Angstroms, and each Al2O3 layer can have a thickness of about 1-20 Angstroms. In the illustrated embodiment, the thickness ratio of the Y2O3 layer to the Al2O3 layer is about 10:1. In embodiments, the Al2O3 layer can prevent the Y2O3 layer from becoming crystalline. As a result of the additional Al2O3 layer, the Y2O3 layer remains in a polycrystalline state.

[0120] As a result of the fluorination, the YO layer was converted to a YOF layer, and the AlO layer was converted to an Al-OF layer. Alternatively, some or all of the AlO layer may not be converted to an Al-OF layer. As shown, the at.% of fluorine varies from about 2 at.% to about 25 at.%. The F concentration is higher near the surface of the coating and lower near the bottom of the coating.

[0121] FIG. 10A shows a cross-sectional side view of another chamber component including an yttrium-based oxyfluoride coating 1005 including alternating layers of YOF and Al-OF after a fluorination treatment, as observed by transmission electron microscopy (TEM), according to one embodiment. The coating was produced by fluorination of an ALD coating including alternating layers of YO and AlO. The coating 1005 has a thickness of approximately 500 nm. A capping layer 1015 is disposed on the yttrium-based oxyfluoride coating 1005 for the purpose of generating a TEM image. Surface A4 shows the top of the yttrium-based oxyfluoride coating 1005, surface B4 shows the interface between the yttrium-based oxyfluoride coating 1005 and the alumina stress relief layer 1012, and surface C4 shows the interface between the alumina stress relief layer 1012 and the chamber component 1010.

[0122] FIG. 10B shows the material composition of the chamber component of FIG. 10A. As shown, the capping layer 1015 is composed of Ir. The yttrium-based oxyfluoride coating 1005 is composed of yttrium 1025, oxygen 1020, fluorine 1040, and aluminum 1035. The stress relief layer is composed of oxygen 1020 and aluminum 1035. The chamber component 1010 is composed of different ratios of aluminum 1035 and oxygen 1020. The fluorination treatment used to create the yttrium-based oxyfluoride coating 1005 was a remote inductively coupled plasma (ICP) process at 450°C using an NF3 plasma. As shown, the entire yttrium-based oxide coating was converted to the yttrium-based oxyfluoride coating 1005. The fluorine concentration in the coating 1005 varies from about 35 at.% to about 60 at.% and varies with depth. In particular, under these treatment conditions, the fluorine concentration is greater near the center and bottom of coating 1005 than at the top of coating 1005. Diffraction analysis showed that the YOF layer of coating 1005 remained polycrystalline after the fluorination treatment.

[0123] 11A shows a cross-sectional side view of a chamber component that is a solid-sintered (bulk) ceramic 1105 made of a YO-ZrO solid solution after a fluorination treatment as observed by transmission electron microscopy (TEM), according to one embodiment. A capping layer 1015 is disposed on top of the solid-sintered ceramic 1105 for the purpose of generating the TEM image. Plane A5 shows the top of the solid-sintered ceramic 1105.

[0124] FIG. 11B shows an EDS line scan illustrating the material composition of the chamber component of FIG. 11A. As shown, approximately the top 70 nm of the solid-sintered ceramic 1105 was converted from a YO-ZrO solid solution to Y-Zr-O. The EDS line scan shows concentrations of oxygen 1120, fluorine 1140, yttrium 1125, and zirconium 1150. The YO-ZrO solid solution initially contained approximately 60 mol% YO and approximately 40 mol% ZrO, and energy dispersive electroscopy (EDS) line scan results (as shown in FIG. 11A) show approximately 23 at.% Y, approximately 65 at.% O, and approximately 12 at.% Zr. After fluorination, the fluorine concentration changed from approximately 5 at.% to approximately 30 at.% in the top 100 nm of the solid-sintered ceramic 1105. The fluorination treatment conditions included a plasma power of 200 W, direct capacitively coupled plasma (CCP) of NF3 plasma, and a treatment time of 2 hours at 450 °C. The fluorination rate of the Y2O3-ZrO2 solid solution was slowed down by Zr occupying vacancies in the Y lattice. The fluorine concentration and depth of fluorination could be increased by increasing the treatment time and / or the density of fluorine radicals in the plasma.

[0125] Fluorination was performed on other bulk-sintered ceramic articles and coatings using similar test conditions: plasma power 200 W, direct CCP of NF3 plasma, and treatment time 450 °C for 2 hours. Under these conditions, fluorination of a 100 nm Y2O3 ALD coating prepared using the first Y precursor resulted in the entire coating being converted to a YOF coating, with the fluorine concentration varying from approximately 25 at.% to approximately 55 at.%. It was found that oxygen was nearly depleted at the surface of the coating, resulting in the formation of a nearly YF3 layer at the surface. Furthermore, the fluorine concentration gradually decreased with depth. Under these conditions, fluorination of another 100 nm Y2O3 ALD coating prepared using the second Y precursor resulted in the entire coating being converted to a YOF coating, with the fluorine concentration varying from approximately 20 at.% to approximately 30 at.%. The fluorine concentration was found to be slightly higher in the lower half of the coating than in the upper half. Subtle microstructural differences were found between the Y2O3ALD coatings produced with the first Y precursor and those produced with the second Y precursor, resulting in unexpected differences in fluorination.

[0126] Fluorination was performed on a 100 nm Al2O3 ALD coating using a plasma power of 200 W, direct CCP of NF3 plasma, and a treatment time of 2 hours at 450 °C. This fluorination resulted in fluorination of the top 20 nm of the coating. The fluorine concentration in the top 20 nm of the coating was approximately 5-7 at.% F. Thus, the top 20 nm was converted to an Al-OF coating with approximately 35 at.% Al, 5-7 at.% F, and 58-60 at.% O.

[0127] Fluorination was performed on bulk-sintered Y2O3 articles using direct CCP of NF3 plasma at 450 °C with a plasma power of 200 W for 2 h. Such fluorination resulted in fluorination of the top 150 nm of the article. The fluorine concentration was approximately 30-40 at.% in the top 50 nm and gradually decreased to approximately 5 at.% near the 150 nm depth.

[0128] 12A shows a cross-sectional side view of a chamber component 1265 including a coating 1205 of AlO on a SiO substrate 1265 after a fluorination treatment as observed by transmission electron microscopy (TEM), according to one embodiment. A capping layer 1215 is disposed on the coating 1205 for purposes of generating a TEM image. Surface A6 shows the top of the coating 1205. Surface B6 shows the bottom of the coating 1205 and the top of the chamber component 1265.

[0129] Figure 12B shows an EDS line scan illustrating the material composition of the chamber component in Figure 12A. As shown, the top 50 nm of the coating 1205 was converted from Al2O3 to Al-OF. The Al2O3 initially contained approximately 63-67 at.% Al and approximately 33-37 at.% O, resulting in the EDS line scan shown in Figure 12B. The EDS line scan shows concentrations of aluminum 1220, oxygen 1260, and fluorine 1240. After fluorination, the fluorine concentration changed from approximately 15 at.% at surface A6 to approximately 5 at.% or less at a depth of 50 nm. The fluorination treatment conditions included a plasma power of 450 W, direct CCP of CF3 / Ar plasma, and a treatment time of 5 hours. Notably, the fluorination of Al2O3 was significantly slower than that of YO3. The fluorine concentration and fluorination depth can be increased by increasing the treatment time and / or the density of fluorine radicals in the plasma.

[0130] Fluorination was also performed on other bulk-sintered ceramic articles and coatings using similar test conditions: plasma power 450 W, direct CCP of CF₃ / Ar plasma, and treatment times of 1 to 5 hours. Under these conditions, fluorination of a 100-nm Al₂O₃ ALD coating for 5 hours resulted in the conversion of the top 10 to 15 nm of the coating to Al-OF with a fluorine concentration of 3 to 30 at.%, and the fluorine concentration was approximately 30 at.% at a depth of approximately 3 to 5 nm. Under these conditions, fluorination of a 100-nm Y₂O₃ ALD coating for 5 hours resulted in the fluorination of the top 70 nm of the coating. The Y₂O₃ coating was converted to a Y₂F coating with a fluorine concentration of approximately 3 to 25 at.%, and the fluorine concentration was approximately 25 at.% at a depth of approximately 4 to 5 nm, and approximately 5 to 10 at.% at a depth of approximately 10 to 70 nm. Under these conditions, fluorination of a 5 μm Y₂O₃ ALD coating for 5 hours resulted in the fluorination of the top 70 nm of the coating. The Y2O3 coating was transformed into a YOF coating with a fluorine concentration of about 5–20 at.%, and the fluorine concentration was about 20 at.% at a depth of about 8–10 nm and gradually decreased with increasing depth.

[0131] Fluorination was performed on bulk sintered ceramic composite articles containing a Y2Al4O9 primary phase and a Y2O3-ZrO2 solid solution secondary phase using direct CCP plasma with CF3 / Ar plasma at a plasma power of 450 W for 5 hours. As a result of this fluorination, the top 20 nm of the article was fluorinated. Lamellar layers originally containing the Y2Al4O9 primary phase were converted to Y-Al-OF by the fluorination treatment, whereas lamellae originally containing the Y2O3-ZrO2 solid solution secondary phase were converted to Y-Zr-OF by the fluorination treatment. The fluorine concentration in the lamellae originally containing the secondary phase ranged from approximately 4 to 18 at.%.

[0132] FIG. 13A shows a YOF layer 1300 resulting from fluorination of a YO coating. Fluorination was performed using a remote fluorine plasma source. The YOF layer 1300 has a thickness of 138-182 nm. As shown, the YOF layer contains cracks 1305, 1310 and delaminations 1315. These cracks 1305, 1310 and delaminations 1315 can be mitigated by slowing down the fluorination process.

[0133] FIG. 13B shows a YZOF layer 1320 resulting from the fluorination of a Y2O3-ZrO2 solid solution coating. The illustrated YZOF layer 1320 is based on the fluorination of a Y2O3-ZrO2 coating containing 60 mol% Y2O3 and 40 mol% ZrO2. However, similar results can be obtained using 70 mol% Y2O3 and 30 mol% ZrO2. The YZOF layer has a thickness of approximately 32-60 nm. As shown, the YZOF layer 1320 exhibits no cracking or delamination. It has been discovered that the Y2O3-ZrO2 solid solution reacts with fluorine sources at a slower rate than Y2O3. Furthermore, the microstructural integrity of the fluorinated Y2O3-ZrO2 solid solution coating (e.g., YZOF layer 1320) has been shown to be excellent, with no cracking or delamination. As a result, the YZOF layer 1320 provides improved particle performance (reduced yttrium-based particle counts on the processed substrate) and increased beneficial lifetime.

[0134] Figure 14 shows an energy dispersive electroscopy (EDS) line scan illustrating the material composition of the YF31405 coating. As shown, the YF3 coating 1405 contains approximately 25-30 at.% Y1425 and approximately 60-70 at.% F1440. The YF3 coating further contains approximately 3-6 at.% F1420 and approximately 2-10 at.% C1422. The YF3 coating was deposited by IAD and has a thickness of approximately 5 μm.

[0135] FIG. 15 shows an EDS line scan illustrating the material composition of the YF3 coating 1405 of FIG. 14 after an oxidation process, according to one embodiment. The YF3 coating 1405 includes a YOF layer. The oxidation process was performed using microwave O plasma at a plasma power of 50 W and approximately 350°C. The O plasma was flowed with Ar at a 1:1 ratio. As shown, the oxidation process converted approximately the top 500 nm of the YF3 into a YOF layer. The O1520 concentration in the YOF layer was approximately 10-30 at.%, the F1540 concentration was approximately 30-50 mol%, and the O concentration was higher at the surface of the YF3 coating 1405. The C1522 concentration remained nearly unchanged.

[0136] 16A shows a cross-sectional side view of a chamber component 1605 including a coating of Y2O3 1610 after a fluorination treatment in an HF acidic solution as observed by TEM, according to one embodiment. The Y2O3 coating 1610 has a thickness of approximately 600 nm and was deposited by ALD. The fluorination treatment was carried out using an acidic solution containing approximately 49% HF with ultrasonic agitation for a treatment time of approximately 1 minute.

[0137] FIG. 16B illustrates the material composition of the chamber component of FIG. 16A. As shown, the Y2O3 coating 1610 includes a YOF layer at its top having a thickness of approximately 50 nm. The concentration of F1640 in the YOF layer is approximately 3-15 at.%, with a higher F concentration near the surface. The Y2O3 coating 1610 further includes approximately 60-70 at.% O1620 and approximately 19-24 at.% Y1625. The Y2O3 coating 1610 further includes C1680.

[0138] Fluorination treatments were performed on several different yttrium-based coatings using an acidic solution containing approximately 49% HF with ultrasonic agitation for approximately 1 minute. The fluorination treatments were performed on 1-micron-thick coatings containing alternating layers of YO and AlO (YO:AlO thickness ratio 10:1) deposited by zone-controlled ALD. As a result, the top 50 nm of the coating was converted to YOF with a fluorine concentration of approximately 5 at.%. Fluorination treatments using these conditions were also tested on 600-nm-thick YO coatings deposited by ALD without zone control. As a result, the top 500 nm of the coating was converted to YOF with a fluorine concentration of approximately 18 at.%. Fluorination treatments using these conditions were also tested on 50-nm-thick coatings consisting of a YO-ZrO solid solution. As a result, the top 25 nm of the coating was converted to Y-Zr-OF with a fluorine concentration of approximately 5 at.%.

[0139] In another embodiment, fluorination treatments were performed on various yttrium-based coatings using an acidic solution containing approximately 0.5 vol% HF, 0.5 molar NHF, 10 vol% H2O3, and the remainder water, with sonication of the acidic solution for 1 minute. These fluorination treatments were tested on 1-micron-thick coatings containing alternating layers of YO3 and Al2O3 (YO3 to Al2O3 thickness ratio of 10:1) deposited by zone-controlled ALD. As a result, the top 50 nm of the coating was converted to YOF with a fluorine concentration of approximately 1 at.%. These fluorination treatments were also tested on 600-nm-thick YO3 coatings deposited by non-zone-controlled ALD. As a result, the top 25 nm of the coating was converted to YOF with a fluorine concentration of approximately 2.5 at.%. These fluorination treatments were also tested on 50-nm-thick coatings consisting of a YO3-ZrO2 solid solution. As a result, the top 25 nm of the coating was converted to Y-Zr-OF with a fluorine concentration of approximately 1 at.%.

[0140] A fluorination treatment was performed, exposing the Y2O3 coating to a fluorine-based acid solution. Using this acid-based fluorination recipe, a 1-micron thick Y2O3 coating was tested.

[0141] 17 shows an X-ray photoelectron spectroscopy (XPS) surface analysis showing the material composition of the YF3 coating deposited by ALD. As shown, the YF3 coating contains F1740 and Y1725 and has a depth of 160 nm.

[0142] FIG. 18 shows an XPS surface analysis illustrating the material composition of a YOF coating formed from oxidation of the YF coating of FIG. 17, according to one embodiment. The oxidation process was performed using microwave O plasma at a plasma power of 50 W and approximately 350°C. The O plasma was flowed with Ar at a 1:1 ratio. As shown, the oxidation process converted the entire YF coating into a YOF coating with an oxygen concentration of approximately 35-60 at.%.

[0143] Figure 19 is a chart showing the number of YO particles detected on processed substrates on the y-axis and the number of high-frequency hours (RFH) on the x-axis. RFH indicates the number of processing hours under processing conditions. Figure 19 shows a first particle performance 1910 for a first processing chamber including a liner with YOF, a lid that is a composite ceramic containing a first phase of Y4Al2O9 (YAM) and a second phase that is a YO3-ZrO2 solid solution, and a quartz nozzle. Also shown is a second particle performance 1915 for a second processing chamber including a YZOF coating on the liner, lid, and nozzle. As shown, manufacturer specifications 1905 dictate that fewer than five YO particles with a size of 35 nm or greater should be added to substrates processed in the processing chamber. The first particle performance 1910 for the first processing chamber exceeded the specification 1905 of five adders in approximately 80-100 high-frequency hours. As shown, the second particle performance 1915 of the second processing chamber is much better than the first particle performance 1910, being limited to only 1-2 adders at approximately 60 and 70 high frequency hours. The YZOF coating demonstrates significantly lower particle counts on processed substrates, even after 250 high frequency hours. Furthermore, with the YZOF coating on the lid, nozzle, and liner, no zirconium-based particles (e.g., ZrO2 particles) were detected.

[0144] The foregoing description sets forth numerous specific details (e.g., examples of particular systems, components, methods, etc.) to provide a thorough understanding of some embodiments of the present invention. However, it will be apparent to one of ordinary skill 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 shown in simple block diagram form in order to avoid unnecessarily obscuring the present invention. Thus, the specific details set forth are merely exemplary. While particular embodiments may vary from these example details, they are still believed to be within the scope of the present disclosure.

[0145] Throughout this specification, "one embodiment" or "one embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Thus, the appearances of the phrase "in one embodiment" or "in one 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 accurate to within ±10% of the nominal value stated.

[0146] Although the operations of the methods herein are shown and described in a particular order, the order of the operations of each method may be changed such that certain operations are performed in reverse order, or certain operations may be performed, at least in part, in parallel with other operations. In alternative embodiments, the instructions of individual operations or sub-operations thereof may be intermittent and / or alternating.

[0147] It should be understood that the above description is illustrative, and not restrictive. Many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. The scope of the 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. depositing a yttrium-based oxide coating on a surface of a chamber component for a first processing chamber; heating the chamber components to an elevated temperature of about 150-1000°C; The chamber component is heated to a high temperature using a CF ４ , H.F., F. ２ , F radical or NF ３ for 0.1 to 72 hours; and converting at least the surface of the yttrium-based oxide coating to an yttrium-based oxyfluoride layer.

2. The chamber components are ３ The step of exposing to NF ３ The method of claim 1 , including the step of introducing a plasma.

3. The chamber component is ４ The step of exposing the chamber component to CF ４ The method of claim 1 , comprising introducing a plasma of and an Ar plasma.

4. The method of claim 1 , wherein the yttrium-based oxyfluoride layer has a thickness of about 10 nm to about 5 μm.

5. 2. The method of claim 1, wherein the yttrium-based oxide coating comprises a Y(OH) layer on the surface of the yttrium-based oxide coating, and wherein exposing the chamber component to the HF at the elevated temperature converts the Y(OH) layer to the yttrium-based oxyfluoride layer.

6. the chamber component includes a metal having a first coefficient of thermal expansion (CTE) greater than a second CTE of the yttrium-based oxide coating; depositing the yttrium-based oxide coating includes depositing the yttrium-based oxide coating by atomic layer deposition (ALD) or ion-assisted deposition (IAD) at a deposition temperature of about 100-300°C, wherein the yttrium-based oxide coating has an internal compressive stress below the deposition temperature and an internal tensile stress above the deposition temperature; 2. The method of claim 1, wherein converting the yttrium-based oxide coating to the yttrium-based oxyfluoride layer causes a volume expansion introducing: a) an additional internal compressive stress at the temperature below the deposition temperature that is greater than the internal compressive stress of the yttrium-based oxide coating at the temperature below the deposition temperature; and b) a reduced internal tensile stress at the temperature above the deposition temperature that is less than the internal tensile stress of the yttrium-based oxide coating at the temperature above the deposition temperature.

7. 7. The method of claim 6, wherein the entire yttrium-based oxide coating is converted into a yttrium-based oxyfluoride layer, and the yttrium-based oxyfluoride layer is resistant to cracking at temperatures between 250 and 350°C.

8. The yttrium-based oxide coating has a first thickness of Y ２ O ３ and an Al layer having a second thickness that is about 1 / 10 to 1 / 5 of the first thickness. ２ O ３ 7. The method of claim 6, wherein the yttrium-based oxyfluoride layers comprise alternating stacks of Y—O—F layers having the first thickness and Al—O—F layers having the second thickness.

9. The yttrium-based oxide coating is Y ２ O ３ -ZrO ２ 2. The method of claim 1, wherein the yttrium-based oxyfluoride layer comprises a solid solution, and the yttrium-based oxyfluoride layer comprises a Y-Z-O-F layer.

10. 1. A chamber component for a processing chamber, comprising: an article made of at least one of a metal or a ceramic; a yttrium-based oxyfluoride layer on at least one surface of the article, the yttrium-based oxyfluoride layer having a thickness of 10 nm to 300 μm; The yttrium-based oxyfluoride layer comprises: Y-O-F and Y-Al-O-F and Y-Zr-O-F and a composite ceramic including a first phase of Y—Al—O—F and a second phase of Y—Zr—O—F; A chamber component having a composition selected from the group consisting of:

11. The article is Y ２ O ３ , Y ４ Al ２ O ９ , Y ３ Al ５ O １２ , Y ２ O ３ -ZrO ２ Solid solutions, and Y ４ Al ２ O ９ The first phase and Y ２ O ３ -ZrO ２ a second composite ceramic comprising a second phase in solid solution; The sintered ceramic article is Y ２ O ３ and the yttrium-based oxyfluoride layer is Y—O—F; The sintered ceramic article is Y ４ Al ２ O ９ or Y ３ Al ５ O １２ and the yttrium-based oxyfluoride layer is Y—Al—O—F; The sintered ceramic article is ２ O ３ -ZrO ２ In a solid solution, the yttrium-based oxyfluoride layer is Y—Zr—O—F; or The sintered ceramic article is Y ４ Al ２ O ９ The first phase and Y ２ O ３ -ZrO ２ the second composite ceramic including the first phase of Y—Al—O—F and the second phase of Y—Zr—O—F, and the yttrium-based oxyfluoride layer is the composite ceramic including the first phase of Y—Al—O—F and the second phase of Y—Zr—O—F. The chamber component of claim 10 , wherein the chamber component is at least one of:

12. a yttrium-based coating on said at least one surface of said article, the yttrium-based oxyfluoride layer; a yttrium-based oxide layer between the yttrium-based oxyfluoride layer and the at least one surface of the article, the yttrium-based oxide layer comprising Y ２ O ３ , Y ４ Al ２ O ９ , Y ３ Al ５ O １２ , Y ２ O ３ -ZrO ２ Solid solutions and Y ４ Al ２ O ９ The first phase and Y ２ O ３ -ZrO ２ a second composite ceramic comprising a second phase in solid solution; The yttrium-based oxide layer is Y ２ O ３ and the yttrium-based oxyfluoride layer is Y—O—F; The yttrium-based oxide layer is Y ４ Al ２ O ９ or Y ３ Al ５ O １２ and the yttrium-based oxyfluoride layer is Y—Al—O—F; The yttrium-based oxide layer is Y ２ O ３ -ZrO ２ In a solid solution, the yttrium-based oxyfluoride layer is Y—Zr—O—F; or The yttrium-based oxide layer is Y ４ Al ２ O ９ The first phase and Y ２ O ３ -ZrO ２ the second composite ceramic including the first phase of Y—Al—O—F and the second phase of Y—Zr—O—F, wherein the yttrium-based oxyfluoride layer is the composite ceramic including the first phase of Y—Al—O—F and the second phase of Y—Zr—O—F; The chamber component of claim 10 , further comprising a yttrium-based coating that is at least one of:

13. 11. The chamber component of claim 10, wherein the yttrium-based oxyfluoride coating comprises alternating first layers having a first thickness and second layers having a second thickness that is about 1 / 10 to 1 / 5 of the first thickness, the first layers comprising Y—O—F and the second layers comprising Al—O—F.

14. depositing a yttrium-based oxide coating on a surface of a chamber component for a processing chamber; immersing the chamber component including the yttrium-based oxide in a fluorine-based acidic solution; and converting at least one surface of said yttrium-based oxide coating to an yttrium-based oxyfluoride layer using said fluorine-based acidic solution.

15. 15. The method according to claim 14, wherein the fluorine-based acidic solution is an HF acidic solution containing 50 to 95 vol. % water and 0.1 to 50 vol. % HF acid, and the fluorine-based acidic solution has a temperature of 0 to 100°C.

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