Hybrid coatings for chamber components

Abstract

An apparatus includes a body configured to support a substrate, a first coating, conformal on a surface of the body, that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane, and a second coating, on the first coating, having a hardness that greater than or equal to about 8 gigapascals.

Description

HYBRID COATINGS FOR CHAMBER COMPONENTSTECHNICAL FIELD

[0001] Embodiments of the disclosure relate generally to processing chambers, and more particular to hybrid coatings, for chamber components of processing chambers (e.g., substrate support assemblies and / or heaters), that provide corrosion resistance and hardness.BACKGROUND

[0002] In the semiconductor industry, devices are fabricated by a number of manufacturing processes producing structures of an ever-decreasing size. Some electronic device manufacturing processes, such as deposition processes, etch processes and / or clean processes, can be performed using highly corrosive process gases, and may corrode chamber components of processing chambers and other surfaces. Additionally, some electronic device manufacturing processes are plasma-enhanced or plasma-assisted processes that involve the use plasma, which can further damage chamber components.SUMMARY

[0003] Described in embodiments herein is an apparatus including a body configured to support a substrate, a first coating, conformal on a surface of the body, that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane, and a second coating, on the first coating, having a hardness that greater than or equal to about 8 gigapascals.

[0004] Also described in embodiments herein is a method includes conformally depositing, via atomic layer deposition on a surface of a body configured to support a substrate, a first coating that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane, and depositing, on the first coating via physical vapor deposition, a second coating having a hardness that is greater than or equal to about 8 gigapascals.

[0005] Also described in embodiments herein is a method includes forming, via a conversion coating process on a surface of a body configured to support a substrate, a firstcoating that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane, and depositing, on the first coating via physical vapor deposition, a second coating having a hardness that is greater than or equal to about 8 gigapascals.BRIEF DESCRIPTION OF THE DRAWINGS

[0006] The present disclosure is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings in which like references indicate similar elements. It should be noted that different references to “an” or “one” embodiment in this disclosure are not necessarily to the same embodiment, and such references mean at least one.

[0007] FIG. 1 depicts a sectional view of a processing chamber, in accordance with some embodiments.

[0008] FIG. 2 depicts a substrate support assembly with components having a hybrid coating, in accordance with some embodiments.

[0009] FIGS. 3A-3B are block diagrams illustrating an example process of forming a hybrid coating on a chamber component, in accordance with some embodiments.

[0010] FIG. 4 is a diagram illustrating an example of an atomic layer deposition (ALD) process that can be used to form a hybrid coating on a chamber component, in accordance with some embodiments.

[0011] FIG. 5 is a diagram illustrating an example of a physical vapor deposition (PVD) process that can be used to form a hybrid coating on a chamber component, in accordance with some embodiments.

[0012] FIG. 6 is a flow chart depicting a process for forming a hybrid coating on a chamber component, in accordance with some embodiments.DETAILED DESCRIPTION

[0013] A substrate can be placed on a substrate support apparatus of a substrate support assembly (e.g., heater assembly) of a processing chamber for processing. For example, a substrate support apparatus can include at least one of a heater, a pedestal, a chuck (e.g., electrostatic chuck (ESC)), etc. If the substrate support apparatus does not have a sufficient high surface hardness, mechanical rubbing of grains of the material of the substrate supportapparatus that occur between a substrate and the substrate support apparatus can cause wear and particle formation. For example, mechanical rubbing can be caused by movement of the substrate. The mechanical rubbing can cause erosion of the substrate support apparatus and can cause particles to dislodge and settle on a backside of the substrate during processing. Moreover, the grains can react with radical species generated by the process gas, which can lead to contamination.

[0014] Embodiments described herein address these and other drawbacks by implementing hybrid coatings for chamber components of processing chambers. A hybrid coating is a multilayer coating that includes at least two layers of different materials. For example, a hybrid coating can include a first coating, conformal to the surface of a body, to provide corrosion resistance to at least one process gas, and a second coating formed on the first coating to reduce mechanical rubbing caused by a substrate. In some embodiments, the first coating is resistant to corrosion by corrosive chemistries and / or plasma, and the second coating has a sufficiently high hardness to provide wear resistance. For example, the second coating can have a higher hardness than the first coating. For example, corrosive chemistries and / or plasma may pass through pores, cracks, grain boundaries, etc. in the second coating, but may be blocked by the first coating, which can provide plasma and corrosion resistance and protects an underlying body of the chamber component. The second coating may regularly come into contact with other surfaces, such as backsides of substrates (e.g., wafers), and may resist wear due to a high hardness of the second coating. Accordingly, in some embodiments, the hybrid coating reduces the amount of backside particles on substrates due to low corrosion of the chamber component (provided by the first coating) and / or low wear of the chamber component (provided by the second coating). Further details regarding implementing hybrid coatings for chamber components of processing chambers will now be described below with reference to FIGS. 1- 6

[0015] FIG. 1 is a sectional view of a processing chamber 100 having one or more chamber components that are coated with a hybrid coating, in accordance with some embodiments. The base materials of the chamber may include one or more of aluminum (Al), titanium (Ti) and stainless steel (SST). The processing chamber 100 may be used for processes in which a corrosive plasma environment having plasma processing conditions is provided. For example, the processing chamber 100 may be a chamber for a plasma etcher or plasma etch reactor, a plasma cleaner, a plasma-enhanced chemical vapor deposition (CVD) reactor, a plasma- enhanced atomic layer deposition (ALD) reactor, and so forth.

[0016] In one embodiment, the processing chamber 100 includes a chamber body 102 and a showerhead 130 that encloses an interior volume 106. The showerhead 130 may include a showerhead base and a showerhead gas distribution plate. Alternatively, the showerhead 130 may be replaced by a lid and a nozzle in some embodiments, or by multiple pie shaped showerhead compartments and plasma generation units in other embodiments. The chamber body 102 may be fabricated from aluminum, stainless steel or other suitable material such as titanium (Ti). The chamber body 102 generally includes sidewalls 108 and a bottom 110. An outer liner 116 may be disposed adjacent the sidewalls 108 to protect the chamber body 102.

[0017] An exhaust port 126 may be defined in the chamber body 102, and may couple the interior volume 106 to a pump system 128. The pump system 128 may include one or more pumps and throttle valves utilized to evacuate and regulate the pressure of the interior volume 106 of the processing chamber 100.

[0018] The showerhead 130 may be supported on the sidewall 108 of the chamber body 102. The showerhead 130 (or lid) may be opened to allow access to the interior volume 106 of the processing chamber 100, and may provide a seal for the processing chamber 100 while closed. A gas panel 158 may be coupled to the processing chamber 100 to provide process and / or cleaning gases to the interior volume 106 through the showerhead 130 or lid and nozzle. Showerhead 130 may be used for processing chambers used for dielectric etch (etching of dielectric materials). The showerhead 130 may include a gas distribution plate (GDP) and may have multiple gas delivery holes 132 throughout the GDP. The showerhead 130 may include the GDP bonded to an aluminum base or an anodized aluminum base. The GDP may be made from Si or SiC, or may be a ceramic such as Y2O3, AI2O3, Y3AI5O12 (YAG), and so forth.

[0019] For processing chambers used for conductor etch (etching of conductive materials), a lid may be used rather than a showerhead. The lid may include a center nozzle that fits into a center hole of the lid. The lid may be a ceramic such as AI2O3, Y2O3, YAG, or a ceramic compound comprising Y4AI2O9 and a solid-solution of Y2O3-ZrO2. The nozzle may also be a ceramic, such as Y2O3, YAG, or the ceramic compound comprising Y4AI2O9 and a solidsolution of Y2O3-ZrO2.

[0020] Examples of processing gases that may be used to process substrates in the processing chamber 100 include halogen-containing gases, such as C2F6, SFe, SiCh, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Ch, CCI4, BCI3 and SiF4, among others, and other gases such as O2, or N2O. Examples of carrier gases include N2, He, Ar, and other gases inert to process gases (e.g., non-reactive gases).

[0021] A heater assembly 148 is disposed in the interior volume 106 of the processing chamber 100 below the showerhead 130 or lid. The heater assembly 148 includes a support 150 that holds a substrate 144 during processing. The support 150 is attached to the end of a shaft (also referred to as a pedestal) 152 that is coupled to the chamber body 102 via a flange 154. The support 150, shaft 152 and flange 154 may be constructed of a heater material containing AIN, an aluminum alloy, or another suitable material. The support 150 may further include mesas 156 (e.g., dimples or bumps). The support may additionally include wires, for example, tungsten wires (not shown), embedded within the heater material of the support 150. In one embodiment, the support 150 may include metallic heater and sensor layers that are sandwiched between AIN ceramic layers. Such an assembly may be sintered in a high- temperature furnace to create a monolithic assembly. The layers may include a combination of heater circuits, sensor elements, ground planes, radio frequency grids and metallic and ceramic flow channels. The heater assembly 148 may provide a heater temperature up to about 650 °C under vacuum conditions (e.g., about 1 mTorr to about 5 Torrs) in some embodiments.

[0022] In some embodiments, the processing chamber 100 is configured to perform an etch process. For example, the processing chamber 100 can be configured to perform selective atomic layer etching (ALE), selective ALE can be performed by using.

[0023] Generally, selective ALE can be performed by exposing a substrate formed from a first material to a plasma to convert the substrate into an intermediate structure. The intermediate structure can include a substrate layer including the first material, and a modified substrate layer including a second material different from the first material. The intermediate structure can then be exposed to a process gas to enable a ligand exchange mechanism that removes the modified substrate layer and leaves the substrate layer. One example of a process gas that can enable a ligand exchange mechanism is boron trichloride.

[0024] For example, if the substrate includes hafnium oxide, then the substrate can be exposed to a fluorine-containing plasma (e.g., nitrogen trifluoride plasma) to convert the substrate into an intermediate structure that includes a hafnium dioxide layer and a hafnium tetrafluoride layer. The intermediate structure can then be exposed to a process gas to enable the ligand exchange method that removes the hafnium tetrafluoride layer and leaves the hafnium dioxide layer. For example, boron trichloride can react with the hafnium tetrafluoride layer to form boron trifluoride and hafnium tetrachloride.

[0025] As another example, if the substrate includes molybdenum, then the substrate can be exposed to a fluorine-containing plasma (e.g., nitrogen trifluoride plasma) to convert thesubstrate into an intermediate structure that includes a molybdenum layer and a molybdenum fluoride layer. The intermediate structure can then be exposed to a process gas to enable the ligand exchange method that removes the molybdenum fluoride layer and leaves the molybdenum layer. For example, boron trichloride can react with the molybdenum fluoride layer to form boron trifluoride and molybdenum chloride.

[0026] As yet another example, if the substrate includes aluminum oxide, then the substrate can be exposed to a fluorine-containing plasma (e.g., nitrogen trifluoride plasma) to convert the substrate into an intermediate structure that includes an aluminum oxide layer and an aluminum trifluoride layer. The intermediate structure can then be exposed to a process gas to enable the ligand exchange method that removes the aluminum trifluoride layer and leaves the aluminum oxide layer. For example, boron trichloride can react with the aluminum trifluoride layer to form boron trifluoride and aluminum trichloride.

[0027] In some embodiments, at least one component of the processing chamber 100 is formed from a ceramic material. Examples of ceramic material include aluminum nitride (AIN), aluminum oxide (AI2O3), silicon carbide (SiC), or other suitable ceramic material having a comparable chemical resistance and mechanical, thermal and / or electrical properties. In some embodiments, a chamber component is formed from a metal or metal alloy. For example, at least one component of the processing chamber 100 can be formed from aluminum (Al), and Al alloy, etc.

[0028] A hybrid coating 160 can be formed on at least one component of the processing chamber. For example, the hybrid coating 160 may be deposited on the support 150 or on all surfaces of the heater assembly 148 (including the support 150, shaft 152 and flange 154) within the chamber 100.

[0029] The hybrid coating 160 can include a first coating that is corrosion resistant to at least one process gas (e.g., precursor), For example, the at least one process gas can include at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, etc. Accordingly, the first coating can primarily function as a corrosion resistant layer of the hybrid coating 160. The first coating of the hybrid coating 160 can be formed on the surface of a component of the processing chamber 100 via a process that enables the first coating to be conformally formed on the surface of the component of the processing chamber 100. The first coating may be dense, and may protect an underlying surface of the coated chamber component from attack by process gases, plasma, corrosive chemistry, etc. Further details regarding the first coating and methods of forming the first coating will be described below with reference to FIGS. 2-6.

[0030] The hybrid coating 160 can further include a second coating having a hardness that is greater than or equal to about 8 gigapascals (GPa). In some embodiments, the second coating has a hardness that ranges from about 12 GPa to about 25 GPa. In some embodiments, the second coating has a hardness that exceeds 25 GPa. Accordingly, the second coating can primarily function as a wear resistant layer of the hybrid coating 160. The second coating may be less dense than the first coating and / or may include one or more cracks, grains, etc. through which process gases, plasma, chemistry, etc. may penetrate the second coating. However, such process gases, plasma, corrosive chemistry, etc. may encounter the first coating and be stopped by the first coating. Further details regarding the second coating and methods of forming the second coating will be described below with reference to FIGS. 2-6.

[0031] FIG. 2 is a diagram of a substrate support assembly 200, in accordance with some embodiments. For example, the substrate support assembly can correspond to the heater assembly 148 of FIG. 1. As shown in FIG. 2, the apparatus 200 can include a body 202 including a substrate support apparatus (“support”) 205 attached to an end of an interior shaft 210. For example, the support 205 can include at least one of a heater, a pedestal, a chuck (e.g., electrostatic chuck), etc. The interior shaft 210 can be situated within the interior volume of the processing chamber (not shown). The interior shaft 210 can be attached to an exterior shaft 215 via a flange 220. The support 205 can include mesas 206, which can be connected to electrical components (not shown) embedded within the heater material of the support 205. In some embodiments, the body 202 includes at least one ceramic material (e.g., AIN, AI2O3 and / or SiC). In some embodiments, the body 202 includes at least one metal or metal alloy (e.g., Al or an Al alloy). At least the body 202 may be exposed to corrosive gases and / or plasmas within the processing chamber. Additionally, mechanical rubbing can be caused by a substrate that is placed on the support. To improve the lifespan of the body 202, at least a portion of the body 202 can be coated with a hybrid coating 230. The hybrid coating 230 is a multi-layer coating that includes at least two layers of different materials. For example, the hybrid coating 230 can include a first coating, conformal to the surface of the body 200, to provide corrosion resistance, and a second coating formed on the first coating to reduce mechanical rubbing. In some embodiments, a heater coated with the hybrid coating may have the same or substantially the same thermal conductivity and heating capacity as an uncoated heater. Further details regarding the body 202 and the hybrid coating 230, including the first coating and the second coating, will now be described in further detail below with reference to FIGS. 3A-3B.

[0032] FIG. 3A is a diagram 300A showing a body 310 and the formation of a coating 320 on the body 202, according to some embodiments. In some embodiments, the body 310corresponds to a substrate support assembly (e.g., the substrate support assembly 200 of FIG. 2). For example, the body 310 can include a substrate support apparatus (“support”) 312 (e.g., the support 205 of FIG. 2) and a shaft 314 (e.g., the interior shaft 210 of FIG. 2). For example, the support 312 can include at least one of a heater, a pedestal, a chuck (e.g., electrostatic chuck), etc.

[0033] The coating 320 is conformal to the surface of the body 310. The coating 320 can provide corrosion, plasma, and / or wear resistance. In some embodiments, the coating 320 provides corrosion resistance to one or more process gases. For example, the coating 320 can provide corrosion resistance to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, hexafluoroethane, etc. The coating 320 can provide plasma resistance to reduce plasma interactions and improve a component’ s durability without impacting its performance. In some embodiments, the coating 320 provides corrosion, plasma, and / or wear resistance at operating temperatures that range from about -10 °C to about 550 °C.

[0034] In some embodiments, the coating 320 includes at least one of: a silicon oxide, a silicon nitride, a silicon oxynitride, a magnesium fluoride, an aluminum oxide, a yttrium fluoride, a yttrium oxide, a yttrium aluminum oxide, a yttrium zirconium oxide, a hafnium aluminum oxide, etc.

[0035] In some embodiments, the coating 320 has a thickness that ranges from about 100 nanometers (nm) to about 2000 nm. In some embodiments, the coating 320 has a thickness that ranges from about 400 nm to about 1000 nm. In some embodiments, the coating 320 has a thickness that ranges from about 400 nm to about 500 nm.

[0036] The resistance of the coating 320 to corrosion, plasma and / or wear may be measured through “etch rate” (ER), which may have units of micron / hour (pm / hr) or Angstrom / hour (A / hr), throughout the duration of the coated components’ operation and exposure to plasma. Measurements may be taken after different processing times. For example, measurements may be taken before processing, or at about 50 processing hours, or at about 150 processing hours, or at about 200 processing hours, and so on. Variations in the composition of the coating 320 grown or deposited on the heater support and / or other components may result in multiple different erosion rate values. Additionally, the coating 320 with a single composition exposed to various plasmas could have multiple different plasma resistances or erosion rate values. For example, a plasma resistant material may have a first plasma resistance or erosion rateassociated with a first type of plasma and a second plasma resistance or erosion rate associated with a second type of plasma.

[0037] The coating 320 can be conformally formed on the body 202. Any suitable process can be used to conformally form the coating 320 on the surface of the body 310 in accordance with embodiments described herein.

[0038] In some embodiments, the coating 320 is conformally formed on the body 310 via ALD. ALD can enable the formation of a conformal coating 320 having approximately zero porosity (e.g., porosity-free or pinhole-free) on the surface of the body 310, which may reduce or eliminate crack formation during ALD. ALD can further enable the coating 320 to have an approximately uniform thickness on the body 310. That is, the same or approximately the same amount of material of the coating 320 can be deposited on the surfaces of the body 310. The coating 320 conformally formed on the body 310 via ALD may maintain the electrical properties and relative shape and geometric configuration of the component so as to not disturb its functionality. The coating 320 conformally formed on the body 310 via ALD may also reduce the volatility of the material of the body 310 and may form reactants having a lower vapor pressure than the component’s underlying materials. ALD can be performed at a relatively low temperature (e.g., about 25 °C to about 350 °C) so that the process does not cause significant damage or deformation to the body 310. Additionally, ALD can be used to deposit the coating 320 within complex features (e.g., high aspect ratio features) of the component. Further details regarding forming the coating 320 on the body 202 via ALD will be described below with reference to FIGS. 4 and 6.

[0039] In some embodiments, the coating 320 is conformally formed on the surface of the body 202 via a conversion coating process. A conversion coating process is a type of coating process by which a surface of the body undergoes a chemical or electrochemical reaction to form a coating on the surface. A conversion coating process can be performed by immersing the body in a chemical bath or spraying it with a solution that causes a reaction on the surface of the body. This reaction transforms the surface of the body into a different compound corresponding to the first coating. Further details regarding forming the coating 320 on the body 202 via a conversion coating process will be described below with reference to FIG. 6.

[0040] In some embodiments, the coating 320 is conformally formed on the surface of the body 202 via a plating process. One example of a plating process that can be used to form the first coating is an electroplating process. Another example of a plating process that can be used to form the first coating is an electroless plating process, which is a plating process that can beperformed without the use of an electric current (e.g., autocatalytic). One example an electroless plating process is electroless nickel plating (ENP). Further details regarding forming the coating 320 on the body 202 via a plating process will be described below with reference to FIG. 6

[0041] FIG. 3B is a diagram 300B showing the formation of a coating 330 on the coating 320. In some embodiments, the coating 330 reduces mechanical rubbing, wear on a substrate and / or the body 202, and / or backside substrate defects. More specifically, hardness (e.g., microhardness) of the coating 330 can be greater than the hardness of the coating 320, and the hardness of the coating 330 can be sufficiently high to reduce mechanical rubbing and / or backside substrate defects. Accordingly, the hardness of the coating 330 can correspond to damage tolerance, and thus higher hardness can improve durability and service life of the body 310.

[0042] In some embodiments, the coating 330 has a hardness that is greater than or equal to about 8 GPa. In some embodiments, the coating 330 has a hardness that ranges from about 12 GPa to about 25 GPa. In some embodiments, the coating 330 has a hardness that exceeds 25 GPa.

[0043] The coating 330 can include any suitable material in accordance with embodiments described herein. In some embodiments, the coating 330 includes at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamondlike carbon (DLC), etc.

[0044] The coating 330 can have any suitable thickness in accordance with embodiments described herein. In some embodiments, the coating 330 has a thickness that ranges from about 1 micrometer (pm) to about 100 pm. In some embodiments, the coating 330 has a thickness that ranges from about 2 pm to about 50 pm. In some embodiments, the coating 330 has a thickness that ranges from about 3 pm to about 20 pm.

[0045] Any suitable process can be used to form the coating 330 on the coating 320 in accordance with embodiments described herein. In some embodiments, the coating 330 is formed on the coating 320 via PVD. For example, the coating 330 can be formed using an evaporation or vacuum deposition process. Other examples of PVD processes that can be used to form the coating include sputtering, ion-assisted deposition, etc. Further details regarding forming the coating 330 will be described below with reference to FIGS. 5-6.

[0046] In some embodiments, a coefficient of thermal expansion of the coating 330 matches or approximately matches a coefficient of thermal expansion of a substrate. As a result, there can be reduced rubbing between the substrate and the support 312 with changes in temperature(e.g., which are generally caused by different rates of expansion and contraction between the substrate and the support 312). In some embodiments, the hybrid coating including the coating 320 and the coating 330 enables a reduced thermal stress as compared to prior practices. In some embodiments, the coating 320 includes a silicon oxide and the coating 330 includes a silicon nitride.

[0047] As shown, in some embodiments, coating 320 is formed on all surfaces of a substrate support, and coating 330 is formed on a single surface of the substrate support (e.g., the surface on which a substrate will rest).

[0048] FIG. 4 is a diagram 400 illustrating an example an ALD process that can be used to form a hybrid coating on an article 410, in accordance with some embodiments. For example, the article 410 can correspond to a chamber component (e.g., the support 312 and / or the shaft 314 of the substrate support assembly of FIGS. 3A-3B). The article 410 may represent various materials of semiconductor process chamber components including but not limited to a high temperature heater support and / or all surfaces of a heater assembly within a processing chamber. The article 410 may be made from a ceramic material (e.g., AIN, AI2O3 or SiC), a metal or metal alloy (e.g., Al or an Al alloy), etc. In some embodiments, the article 410 includes a high temperature heater formed from a heater material having a thermal conductivity of about 50 W / mK to about 300 W / mK, or about 100 W / mK to about 250 W / mK, about 150 W / mK to about 200 W / mK, or about 180 W / mK. The heater material may also have a specific heat capacity of about 0.15 cal / g-°C at 25 °C to about 0.30 cal / g-°C at 25 °C, or about 0.20 cal / g- °C at 25 °C to about 0.25 cal / g-°C at 25 °C, or about 0.25 cal / g-°C at 25 °C. The heater material may also have a coefficient of linear thermal expansion of about 4.6 to about 5.7 pm / m-°C.

[0049] The ALD process can be used to conformally form, on the article 410, a corrosion / plasma resistant coating of a hybrid coating (e.g., the coating 320 of FIGS. 3A-3B). ALD can cause the surface roughness of the corrosion / plasma resistant coating to match the surface roughness of the surface of the article 410.

[0050] Various types of ALD processes exist, and the specific type of ALD process may be selected based on several factors such as the surface to be coated, the coating material, chemical interaction between the surface and the coating material, etc. ALD is generally performed to grow a thin film layer by repeatedly exposing the surface to be coated to pulses of gaseous chemical precursors that chemically react with the surface one at a time in a self-limiting manner. A typical reaction cycle of an ALD process starts with a precursor flooded into an ALD chamber and adsorbed onto surfaces of the article (including surfaces of pore walls withinthe article). Excess precursor can then be flushed out of the ALD chamber (e.g., purged) before a reactant is introduced into the ALD chamber and subsequently flushed out. For ALD, the final thickness of material is dependent on the number of reaction cycles that are run, because each reaction cycle will grow a layer of a certain thickness that may be one atomic layer or a fraction of an atomic layer. For ALD, either adsorption of a precursor onto a surface or a reaction of a reactant with the adsorbed precursor may be referred to as a “half-reaction.” During a first half reaction, a precursor is pulsed onto a surface of the article 410 for a period of time sufficient to allow the precursor to fully adsorb onto the surface. The adsorption is selflimiting as the precursor will adsorb onto a finite number of available sites on the surface, forming a uniform and / or continuous adsorption layer on the surface. Any sites that have already adsorbed with a precursor will become unavailable for further adsorption with the same precursor unless and / or until the adsorbed sites are subjected to a treatment that will form new available sites on the uniform continuous coating. Exemplary treatments may be plasma treatment, treatment by exposing the uniform continuous adsorption layer to radicals, or introduction of a different precursor able to react with the most recent uniform continuous layer adsorbed to the surface. In some embodiments, two or more precursors are injected together and adsorbed onto the surface of an article. The excess precursors are pumped out until an oxygen-containing reactant is injected to react with the adsorbates to form a component layer (e.g., of Y2O3-AI2O3). This fresh layer can then be ready adsorb the precursors in the next cycle.

[0051] For example, as shown in FIG. 4, the article 410 may be introduced to a first precursor 460 for a first duration until a surface of article 410 is fully adsorbed with the first precursor 460 to form an adsorption layer 414. Subsequently, article 410 may be introduced to a first reactant 465 to react with the adsorption layer 414 to grow a solid layer 416 (e.g., so that the layer 416 is fully grown or deposited, where the terms grown and deposited may be used interchangeably herein). In one embodiment, the first precursor 460 may be a precursor for any of SiCL, YFX, Y2O3, Y3AI5O12, AI2O3, MgF2, A1YX, AlZrxOy, HfAlxOy, such as an Si precursor, a Y precursor, an Al precursor, an Mg precursor, a Zr precursor, an Hf precursor, or combinations thereof. The first reactant 465 may be oxygen, water vapor, ozone, oxygen radicals, or another oxygen source if layer 416 is an oxide. If layer 416 is a fluoride, the first reactant 465 may be a fluorine source. Accordingly, ALD may be used to form the layer 416.

[0052] Layer 416 may be uniform, continuous and conformal. Layer 416 may be porosity free (e.g., have a porosity of zero) or have an approximately zero porosity in embodiments (e.g., a porosity of 0% to 0.01%). Layer 416 may have a thickness of less than one atomic layer to a few atoms in some embodiments after a single ALD deposition cycle. Some metalorganicprecursor molecules are large. After reacting with the reactant 465, large organic ligands may be gone, leaving much smaller metal atoms. One full ALD cycle (e.g., that includes introduction of precursors 460 followed by introduction of reactants 465) may result in the formation of a layer with an average thickness less than a single unit cell.

[0053] Multiple full ALD deposition cycles may be implemented to deposit a thicker layer 416, with each full cycle (e.g., including introducing precursor 460, flushing, introducing reactant 465, and again flushing) adding to the thickness by an additional fraction of an atom to a few atoms. As shown, the process can be repeated n times (e.g., n cycles) to grow the layer 416, where n is a positive integer.

[0054] ALD processes may be conducted at various temperatures depending on the type of process. The optimal temperature range for a particular ALD process is referred to as the “ALD temperature window.” Temperatures below the ALD temperature window may result in poor growth rates and non- ALD type deposition. Temperatures above the ALD temperature window may result in reactions taken place via a chemical vapor deposition (CVD) mechanism. The ALD temperature window may range from about 100°C to about 650°C. In some embodiments, the ALD temperature window is from about 20°C to about 200°C, or about 25°C to about 150°C, or about 100°C to about 120°C, or about 20°C to 125°C. Further details regarding performing ALD to form a hybrid coating are described above with reference to FIG. 3A and will now be described below with reference to FIG. 6.

[0055] FIG. 5 is a diagram 500 illustrating an example system 500 configured to perform PVD that can be used to form a hybrid coating, in accordance with some embodiments. In some embodiments, the system 500 is configured to perform evaporation or vacuum deposition. Evaporation or vacuum deposition is a process that includes heating a solid target material in a vacuum chamber until it vaporizes and condenses into a thin film on a substrate. This can allow atoms, molecules and / or compounds to travel without colliding with residual gases in the chamber. Evaporation or vacuum deposition can be a low temperature process. In some embodiments, evaporation or vacuum deposition is performed at a temperature that ranges from about 150 °C to about 250 °C.

[0056] For example, as shown in FIG. 5, the system 500 can include a vacuum chamber 510, a body support 520, a body 530 attached to the body support 520, and a PVD target material 540. The system 500 can be used to form a second coating on a first coating that is conformally formed on a surface of the body 530. More specifically, to perform evaporation or vacuum deposition using the system 500, the PVD target material 540 can be heated in the vacuum chamber 510 until it vaporizes into a vapor flux 550 that condenses into a thin film on the body530. This can allow atoms, molecules and / or compounds to travel without colliding with residual gases in the chamber. In some embodiments, evaporation or vacuum deposition is a low temperature process. In some embodiments, evaporation or vacuum deposition is performed at a temperature that ranges from about 150 °C to about 250 °C. The resulting second coating can have a crystal structure ranging from amorphous to polycrystalline. Further details regarding performing PVD to form a hybrid coating are described above with reference to FIG. 3B and will now be described below with reference to FIG. 6.

[0057] FIG. 6 is a flow chart depicting a method 600 for forming a hybrid coating on a chamber component of a processing chamber, in accordance with embodiments described herein. Method 600 may be used to coat any articles described herein.

[0058] At block 610, a surface of a body configured to support a substrate can be cleaned. In some embodiments, the body is a body of a chamber component of a processing chamber. For example, the chamber component can be a substrate support apparatus. For example, the substrate support apparatus can include at least one of a pedestal, a heater, etc. The body can include any suitable material in accordance with embodiments described herein. In some embodiments, the body includes a ceramic material. For example, the ceramic material can include AIN.

[0059] Cleaning the surface of the body can include removing remove contaminants from the surface of the body and / or removing an oxide from the surface of the body. For example, cleaning the surface of the body may improve a quality of a coating deposited on the body (e.g., via ALD or other deposition process). In some embodiments, cleaning the surface of the body includes bathing the body in an acid solution. Examples of acid solutions include solutions including at least one of hydrofluoric acid (HF), hydrochloric acid (HC1), nitric acid (HNO3), etc. In some embodiments, an acid solution containing about 0.1 vol% to about 5.0 vol% HF is used to clean chamber components made of quartz. In some embodiments, an acid solution containing about 0.1 vol% to about 20 vol% HC1 is used to clean articles made of AI2O3. In some embodiments, an acid solution containing about 5 to about 15 vol% HNO3 is used to clean articles made of aluminum and other metals.

[0060] At block 620, the body is loaded into a first deposition chamber. In some embodiments, the first deposition chamber is configured to perform at least one of ALD, a conversion coating process, or a plating process, as will be described in further detail.

[0061] At block 630, a first coating that is corrosion resistant to at least one process gas is conformally formed on the surface of the body. In some embodiments, the at least one process gas includes at least one of boron trichloride, nitrogen trifluoride, hafnium tetrachloride,aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, hexafluoroethane, etc. The first coating can have any suitable thickness in accordance with some embodiments described herein. In some embodiments, the first coating is also plasma resistant.

[0062] The first coating can have any suitable thickness in accordance with embodiments described herein. In some embodiments, the first coating has a thickness that ranges from about 100 nm to about 2000 nm. In some embodiments, the first coating has a thickness that ranges from about 400 nm to about 1000 nm. In some embodiments, the first coating has a thickness that ranges from about 400 nm to about 500 nm. In some embodiments, the first coating is porosity-free or approximately porosity-free, and may have a thickness variation of about ±5% or less, ±10% or less, or ±20% or less.

[0063] The first coating can include any suitable material in accordance with embodiments. In some embodiments, the first coating includes at least one of: a silicon oxide, a silicon nitride, a silicon oxynitride, a magnesium fluoride, an aluminum oxide, a yttrium fluoride, a yttrium oxide, a yttrium aluminum oxide, a yttrium zirconium oxide, a hafnium aluminum oxide, or a combination thereof.

[0064] In some embodiments, the first coating is conformally formed on the surface of the body via ALD at block 632. Any suitable number of ALD cycles can be performed to form the first coating having a suitable thickness.

[0065] In some embodiments, the first coating is conformally formed on the surface of the body via a conversion coating process at block 634.

[0066] In some embodiments, the conversion coating process forms the first coating as a barrier thick oxide (BTO). In some embodiments, the first coating formed as a BTO has a thickness that ranges between about 10 nm to about 2000 nm.

[0067] In some embodiments, the conversion coating process is an anodization process. More specifically, the anodization process is an electrochemical process that can be used to form the first coating. For example, the anodization process can include preparing the surface of the body by removing contaminants, submerging the body in an electrolyte solution (e.g., an acid-based electrolyte solution), and applying an electric current while the body is in the electrolyte solution to turn the body into an anode. Ions from the electrolyte solution (e.g., oxygen ions) can react with the surface of the body to form an anodized layer (e.g. an oxide layer) that bonds to the body. The properties of the first coating (e.g., thickness) can be controlled by controlling process parameters such as current / voltage, type of electrolytesolution, temperature of the electrolyte solution, immersion time, etc. The anodized layer can be porous. In some embodiments, pores of the anodized layer are sealed to reduce the porosity of the anodized layer. For example sealing the pores can include hydrating the anodized layer (e.g., the oxide layer). In some embodiments, the first coating conformally formed on the surface of the body using an anodization process has a thickness that ranges between about 25 pm to about 2000 pm. In some embodiments, the anodization process is a barrier thick anodization (BTA) process. BTA is electrochemical oxide passivation process to convert a metal top surface (e.g., aluminum alloy) to a metal oxide (e.g., aluminum oxide) in a wet chemical bath.

[0068] Another example of a conversion coating process that can be used to conformally form the first coating on the surface of the body at block 634 is plasma electrolytic oxidation (PEO). PEO is similar to an anodization process, but is typically performed at higher voltages than typical anodization processes to cause plasma to discharge as microarcs or sparks on the surface of the body. These plasma discharges can cause extreme heating and cooling along the surface of the body, which forms the first coating on the surface of the body. The electrolyte solution used in PEO can be an aqueous solution including one or more types of salts (e.g., silicates, phosphates or aluminates). In some embodiments, the first coating conformally formed on the surface of the body using PEO has a thickness that ranges between about 100 nm to about 10000 nm.

[0069] Another example of a conversion coating process that can be used to conformally form the first coating on the surface of the body at block 634 is an acid passivation process. In some embodiments, the first coating conformally formed on the surface of the body using the acid passivation process has a thickness that ranges between about 5 nm to about 8 nm. The acid passivation process can be performed by rinsing an aluminum component in deionized water for at least one minute, drying the aluminum component for at least one minute, exposing the aluminum component to nitric acid having a concentration of at least 30 percent, at a temperature below 10° C., for between one and 30 minutes, rinsing the aluminum component in deionized water for at least one minute, drying the aluminum component for at least one minute, exposing the aluminum component to ammonium hydroxide for between one second and one minute, rinsing the aluminum component in deionized water for at least one minute, and drying the aluminum component for at least one minute. In some embodiments, the nitric acid has a concentration of about least about 60%. In some embodiments, the nitric acid has a temperature that is less than or equal to about 5 °C. In some embodiments, the aluminum component is exposed to the nitric acid by soaking the aluminum component for between oneminute and 15 minutes. In some embodiments, the aluminum component is exposed to the ammonium hydroxide by dipping the aluminum component in the ammonium hydroxide for between one second and 10 seconds.

[0070] In some embodiments, the first coating is conformally formed on the surface of the body via a plating process at block 636. One example of a plating process that can be used to form the first coating is an electroless plating process, which is a plating process that can be performed without the use of an electric current (e.g., autocatalytic). One example an electroless plating process is ENP. For example, performing an electroless plating process (e.g., ENP) can include preparing the surface of the body by removing contaminants, and submerging the body in an electroless plating solution. The electroless plating solution can be designed to support an autocatalytic redox reaction to form the first coating on the surface of the body while the body is submerged in the electroless plating solution. For example, the electroless plating solution can include suitable salts that can provide suitable ions (e.g., nickel salt providing nickel ions for ENP), and a reducing agent that reacts with the ions in the redox reaction to form the first coating on the surface of the body. The redox reaction can continue without additional external energy until the body is removed from the electroless plating solution. The electroless plating solution can further include additional agents to improve the electroless plating process. For example, the electroless plating solution can further include complexing agents that bind to the ions to maintain their solubility and to prevent precipitation, and / or stabilizers (e.g., buffers) to maintain stability of the plating solution and control pH levels to achieve a suitable plating rate and / or quality. The properties of the first coating (e.g., thickness) can be controlled by controlling process parameters such as current / voltage, type of electroless plating solution, temperature of the electroless plating solution, pH of the electroless plating solution, immersion time, etc. In some embodiments, the first coating conformally formed on the surface of the body using a plating process has a thickness that ranges between about 0.5 pm to about 100 pm.

[0071] At block 640, the body is loaded into a second deposition chamber. In some embodiments, the second deposition chamber is configured to perform at least PVD. In some embodiments, the second deposition chamber is the same as the first deposition chamber. In some embodiments, the first and second deposition chambers are different. For example, loading the body into the second deposition chamber can include causing a transfer robot to transfer the body from the first deposition chamber to the second deposition chamber.

[0072] At block 650, a second coating is formed on the first coating to reduce mechanical rubbing. More specifically, to reduce mechanical rubbing, the second coating can have asuitable hardness (e.g., microhardness). In some embodiments, the second coating has a hardness that is greater than or equal to about 8 GPa. In some embodiments, the second coating has a hardness that ranges from about 10 GPa to about 25 GPa.

[0073] The second coating can have any suitable thickness in accordance with embodiments described herein. In some embodiments, the second coating has a thickness that ranges from about 1 gm to about 100 gm. In some embodiments, the second coating has a thickness that ranges from about 2 gm to about 50 gm. In some embodiments, the second coating has a thickness that ranges from about 3 gm to about 20 gm.

[0074] The second coating can include any suitable material in accordance with embodiments described herein. In some embodiments, the second coating includes at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, DLC, or a combination thereof.

[0075] In some embodiments, the second coating is formed via PVD. For example, PVD can include evaporation or vacuum deposition, sputtering, ion-assisted deposition, etc.

[0076] In some embodiments, the first coating includes an oxide coating and the second coating includes a nitride coating. For example, the first coating can include a silicon oxide (e.g., SiCh) and the second coating can include a silicon nitride (e.g., SisN^. Further details regarding blocks 610-650 are described above with reference to FIGS. 1-5.

[0077] The preceding description sets forth numerous specific details such as examples of specific systems, components, methods, and so forth, in order to provide a good understanding of several embodiments of the present invention. It will be apparent to one skilled in the art, however, that at least some embodiments of the present invention may be practiced without these specific details. In other instances, well-known components or methods are not described in detail or are presented in simple block diagram format in order to avoid unnecessarily obscuring the present invention. Thus, the specific details set forth are merely exemplary. Particular implementations may vary from these exemplary details and still be contemplated to be within the scope of the present invention.

[0078] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrase “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. In addition, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.” When the term “about” or“approximately” is used herein, this is intended to mean that the nominal value presented is precise within ±10%.

[0079] 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 altered so that certain operations may be performed in an inverse order or so that certain operation may be performed, at least in part, concurrently with other operations. In another embodiment, instructions or sub-operations of distinct operations may be in an intermittent and / or alternating manner.

[0080] It is to be understood that the above description is intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reading and understanding the above description. The scope of the invention should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

AMENDED CLAIMS received by the International Bureau on 11 August 2025 (11.08.2025)1. An apparatus comprising: body configured to support a substrate; first coating, conformal on a surface of the body, that is corrosion resistant to at least one of boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane; and second coating on the first coating, the second coating having a hardness that is greater than or equal to about 8 gigapascals and comprising at least one of a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.

2. The apparatus of claim 1, wherein the first coating comprises at least one of a silicon oxide, a silicon nitride, a silicon oxynitride, a magnesium fluoride, an aluminum oxide, a yttrium fluoride, a yttrium oxide, a yttrium aluminum oxide, a yttrium zirconium oxide, a hafnium aluminum oxide, or a combination thereof.3.

4. The apparatus of claim 1, wherein the first coating comprises a silicon oxide, and wherein the second coating comprises a silicon nitride.

5. The apparatus of claim 1, wherein the first coating has a thickness that ranges from about 200 nanometers to about 600 nanometers, and wherein the second coating has a thickness that ranges from about 3 micrometers to about 20 micrometers.

6. The apparatus of claim 1, wherein the second coating has a hardness that ranges between about 10 gigapascals to about 25 gigapascals.

7. The apparatus of claim 1, wherein the body comprises aluminum nitride.

8. A method comprising: conformally forming, via atomic layer deposition on a surface of a body configured to support a substrate, a first coating that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane; and depositing, on the first coating via physical vapor deposition, a second coating having a hardness that is greater than or equal to about 8 gigapascals a second coating on the first coating, the second coating having a hardness that is greater than or equal to about 8 gigapascals and comprising at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.

9. The method of claim 8, wherein the first coating comprises at least one of: a silicon oxide, a silicon nitride, a silicon oxynitride, a magnesium fluoride, an aluminum oxide, a yttrium fluoride, a yttrium oxide, a yttrium aluminum oxide, a yttrium zirconium oxide, a hafnium aluminum oxide, or a combination thereof.10.

11. The method of claim 8, wherein the first coating comprises a silicon oxide, and wherein the second coating comprises a silicon nitride.

12. The method of claim 8, wherein the first coating has a thickness that ranges from about 200 nanometers to about 600 nanometers, and wherein the second coating has a thickness that ranges from about 3 micrometers to about 20 micrometers.

13. The method of claim 8, wherein the second coating has a hardness that ranges between about 10 gigapascals to about 25 gigapascals.

14. The method of claim 8, wherein the body comprises aluminum nitride.

15. A method comprising: conformally forming, via a conversion coating process on a surface of a body configured to support a substrate, a first coating that is corrosion resistant to at least one of: boron trichloride, nitrogen trifluoride, hafnium tetrachloride, aluminum trichloride, oxygen gas, chlorine gas, fluorine gas, chlorine trifluoride, hydrogen fluoride, hydrogen gas, ammonia, tungsten hexafluoride, tetrafluoromethane, titanium tetrachloride, molybdenum pentachloride, ozone, tetrafluorosilane, or hexafluoroethane; and depositing, on the first coating via physical vapor deposition, a second coating having a hardness that is greater than or equal to about 8 gigapascals a second coating on the first coating, the second coating having a hardness that is greater than or equal to about 8 gigapascals and comprising at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.

16. The method of claim 15, wherein the first coating comprises at least one of: a silicon oxide, a silicon nitride, a silicon oxynitride, a magnesium fluoride, an aluminum oxide, a yttrium fluoride, a yttrium oxide, a yttrium aluminum oxide, a yttrium zirconium oxide, a hafnium aluminum oxide, or a combination thereof.17.

18. The method of claim 15, wherein the first coating has a thickness that ranges from about 200 nanometers to about 600 nanometers, and wherein the second coating has a thickness that ranges from about 3 micrometers to about 20 micrometers.

19. The method of claim 15, wherein the second coating has a hardness that ranges between about 10 gigapascals to about 25 gigapascals.

20. The method of claim 15, wherein the body comprises aluminum nitride.STATEMENT UNDER ARTICLE 19 (1)Claim 1 amended; claim 2 unchanged; claim 3 canceled; claims 4 to 7 unchanged; claim 8 amended; claim 9 unchanged; claim 10 canceled; claims 11 to 14 unchanged; claim 15 amended; claim 16 unchanged; claim 17 canceled; claims 18 to 20 unchanged.(i) Basis for the amendment: Claim 1 has been amended at lines 9-11 to add “and comprising at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.” The basis for this amendment can be found in original claim 3 and paragraphs [0043] and [0074] of the specification as filed.(ii) Basis for the amendment: Claim 8 has been amended at lines 10-12 to add “and comprising at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.” The basis for this amendment can be found in original claim 10 and paragraphs [0043] and [0074] of the specification as filed.(iii) Basis for the amendment: Claim 15 has been amended at lines 10-12 to add “and comprising at least one of: a silicon nitride, a silicon oxide, a silicon oxynitride, silicon, a boron nitride, a boron carbide, diamond-like carbon, or a combination thereof.” The basis for this amendment can be found in original claim 17 and paragraphs [0043] and [0074] of the specification as filed.

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