Formation of metal film on electroless metal plating surface

Abstract

[0003] Embodiments of the present disclosure relate to articles, coated chamber components, and techniques for coating chamber components and systems. In particular, a chamber component and a method for forming a chamber component are disclosed, the chamber component including a substrate and a first layer disposed on the substrate, the first layer including a metal having a first atomic concentration. The chamber component further includes a second layer disposed on the first layer, the second layer including a metal having a second atomic concentration at least 5% higher than the first atomic concentration.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE

[0001] Embodiments of the present disclosure relate to corrosion-resistant coated articles, coated chamber components, and methods of forming and using such coated articles and chamber components. [Background technology]

[0002]

[0002] Various semiconductor manufacturing processes use high temperatures, high energy plasmas (e.g., remote and direct fluorine plasmas such as NF3, CF4), mixtures of corrosive gases, corrosive cleaning chemicals (e.g., hydrofluoric acid), and combinations thereof. These extreme conditions can cause reactions between the plasma or corrosive gases and the materials of components within the chamber, resulting in the formation of metal fluorides, particles, other trace metal contaminants, and high vapor pressure gases (e.g., AlF x ) can form. Such gases can easily sublimate and deposit on other components within the chamber. During subsequent processing steps, the deposited material can be released as particles from other components and fall onto the wafer, causing defects. Additional problems caused by such reactions include deposition rate drift, etch rate drift, reduced film uniformity, and reduced etch uniformity. It would be beneficial to reduce these defects with a stable, non-reactive coating over the reactive material to limit the sublimation and / or formation of particles and metallic contaminants on components within the chamber. Summary of the Invention

[0003]

[0003] According to one embodiment, the present specification discloses a chamber component for a processing chamber including a substrate, a first layer disposed on the substrate and including a metal having a first atomic concentration, and a second layer disposed on the first layer and including a metal having a second atomic concentration that is at least 5% higher than the first atomic concentration.

[0004] In another embodiment, disclosed herein is a method for maintaining a plasma environment comprising fluorine radicals and exposing a layered structure to the plasma environment at a temperature greater than 250° C. The layered structure includes a substrate and a first layer disposed on the substrate, the first layer including a metal having a first atomic concentration less than 90%.

[0005] In yet another embodiment, a processing chamber is disclosed that includes a chamber component, the chamber component including a substrate and a first layer disposed on the substrate, the first layer including a metal having a first atomic concentration, the chamber component further including a second layer disposed on the first layer, the second layer including a metal having a second atomic concentration that is at least 5% higher than the first atomic concentration.

[0006]

[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 reference numerals indicate like elements. It should be noted that different references to "an" or "one" embodiment in the present disclosure are not necessarily to the same embodiment, and such references mean at least one. [Brief explanation of the drawings]

[0007] [Figure 1] 7 is a cross-sectional view of a semiconductor processing chamber having one or more chamber components coated with an electroless metal plating coating having a layer of pure (or nearly pure) metal, according to some embodiments. [Figure 2A]

[0008] 1 shows a cross-sectional view of an article having an electroless metal plating coating modified with a layer of pure (or nearly pure) metal thereon, according to some embodiments. [Figure 2B]

[0009] 1 illustrates a cross-sectional view of another article having an electroless metal plating coating having a layer of pure (or nearly pure) metal and a layer of metal fluoride coating formed thereon, according to some embodiments. [Figure 3]

[0010] FIG. 1 is an exemplary diagram of a processing system capable of modifying an electroless metal plating coating with a layer of pure (or nearly pure) metal, according to some embodiments. [Figures 4A-4C]

[0011] In some embodiments, the transmission electron microscope images show example images of a stack of coating layers formed on a substrate, including an electroless nickel plating coating layer, a pure (or nearly pure) nickel layer, and a nickel fluoride coating layer, after treatment of the electroless nickel plating coating with fluorine radicals at temperatures of 250° C. (FIG. 4A), 300° C. (FIG. 4B), and 350° C. (FIG. 4C). [Figure 5]

[0012] FIG. 1 is a schematic diagram of an exemplary method for manufacturing a stack of coating layers formed on a substrate and including an electroless metal plating coating layer, a pure (or nearly pure) metal layer, and a metal fluoride coating layer, according to some embodiments. [Figure 6]

[0013] 1 illustrates an exemplary method for forming a pure (or nearly pure) metal layer from an electroless metal plating coating using fluorine radicals, according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0008]

[0014]

[0003] Embodiments disclosed herein describe coated articles, coated chamber components, methods for coating articles and chamber components, methods for reducing or removing particles from semiconductor processing chambers, methods for using the coated articles and chamber components, and processing chambers including coated chamber components. For example, substrates can be coated with nickel, which is useful in high-temperature applications (e.g., temperatures higher than those required for sputtering resistance). Nickel has mechanical properties (e.g., elastic modulus, tensile strength, elongation, hardness, fatigue limit) that exceed those of other metals (e.g., aluminum) and alloys used in low-temperature applications. Nickel can be used in applications at temperatures up to about 800°C for bulk nickel substrates and about 1,000°C if the substrate is ceramic.

[0009]

[0015] To further reduce reactions of component materials with reactive chemicals and / or plasmas to form metal fluorides, particles, other trace metal contaminants, and / or high vapor pressure gases, a metal fluoride (e.g., nickel fluoride) coating can be formed on the surface of the component, e.g., on a nickel coating. For example, a stable metal fluoride coating can be formed by contact with fluorine gas at a temperature of, e.g., about 100°C to about 500°C for a period of about 1 hour to about 72 hours.

[0010]

[0016] The component substrate may be formed of bulk metallic materials, bulk ceramic materials, aluminum alloys, aluminum nitride (AlN), alumina (Al2O3), stainless steel, quartz, iron, cobalt, titanium, magnesium, copper, zinc, chromium, or other metals and / or combinations thereof.

[0018] Exemplary substrates include, but are not limited to, semiconductor chamber components and / or tools positioned in the upper portion of the processing chamber (e.g., showerhead, faceplate, liner, electrostatic chuck, edge ring, blocker plate) and semiconductor chamber components and / or tools positioned in the lower portion of the processing chamber (e.g., sleeve, lower liner, bellows, gas box). Certain semiconductor processing chamber components that may have the metal fluoride coatings described herein may have portions with high aspect ratios (e.g., length-to-diameter or length-to-width ratios of about 1000:1, about 500:1, about 400:1, about 300:1, 200:1, 100:1, etc.), and the surfaces of the portions with high aspect ratios may be coated with the metal fluoride coatings described herein. In embodiments, the semiconductor process chamber components may be suitable for high temperature applications.

[0011]

[0017] In some embodiments, a substrate can be coated with an electroless metal plating coating using an electroless deposition process. For example, the electroless metal plating coating layer can be a nickel-phosphorus coating layer, which can be in an amorphous state. The electroless deposition process can form a metal plating coating directly on the surface of the substrate. The electroless metal plating coating can be contacted with fluorine to form a metal fluoride coating. An exemplary metal fluoride coating as defined above is Ni x F y In an embodiment, the coating is a converted conformal nickel fluoride coating that provides improved chamber performance and beneficial chemical, thermal, plasma, and radical erosion / corrosion resistance.

[0012]

[0018] Electroless metal plating of substrates, such as electroless nickel plating (ENP), is significantly less expensive than using bulk metals, such as nickel. Furthermore, ENP offers advantages over electrochemical plating, including more uniform thickness around complex surface structures and the ability to plate inside high-aspect-ratio features and cover internal features. However, under certain conditions, ENP coatings offer less protection than pure nickel coatings. For example, ENP-coated samples are more reactive to many corrosive substances than pure nickel. Furthermore, ENP coatings may be less resistant to high temperatures (e.g., 200–300 °C) than pure nickel due to the crystallization and subsequent chemical segregation of nickel and phosphorus.

[0013]

[0019] Aspects and embodiments of the present disclosure address these and other challenges of existing metal plating technologies by providing a technique that allows for the efficient and cost-effective coating of electroless metal plated samples with pure (or nearly pure) metal films. A pure or nearly pure metal layer can be formed on an electroless metal plated coating by exposing the electroless metal plated coating to fluorine radicals at elevated temperatures (e.g., above 250°C) for a period of time (e.g., 1-72 hours). The fluorine radicals can be generated by a remote plasma source using various fluorine-rich substances (e.g., gases), such as molecular fluorine, nitrogen trifluoride, hydrogen fluoride, etc. The pure (or nearly pure) metal can then be further coated with a protective Ni (Ni) film. x F y A coating may be applied.

[0014]

[0020] FIG. 1 is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components coated with an electroless metal plating coating having a layer of pure (or nearly pure) metal, according to some embodiments. The processing chamber 100 can be used for processes in which a corrosive plasma environment having plasma processing conditions is provided. For example, the processing chamber 100 can be a chamber for a plasma etcher or plasma etch reactor, a plasma cleaner, a plasma-enhanced CVD, ALD, etch, or EPI reactor, etc. Examples of chamber components that may include an electroless metal plating coating having a layer of pure (or nearly pure) metal are those that are at risk of exposure to fluorine chemicals and corrosive environments during processing. Such chamber components can be heaters, electrostatic chucks, faceplates, showerheads, liners, blocker plates, gas panels, edge rings, bellows, and / or any other tools in the processing chamber, located at the top or bottom of the chamber. The electroless metal plating coating modified with a layer of pure (or nearly pure) metal can be applied by such chamber components, for example, as described in further detail below.

[0015]

[0021] In one embodiment, the processing chamber 100 includes a chamber body 102 and a showerhead 130 surrounding an interior region 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 sections and a plasma generation unit in other embodiments. The chamber body 102 may be fabricated from aluminum, stainless steel, titanium, and / or other suitable materials. The chamber body 102 generally includes a sidewall 108 and a bottom 110. An outer liner 116 may be disposed adjacent to the sidewall 108 to protect the chamber body 102.

[0016]

[0022] An exhaust port 126 may be defined in the chamber body 102 and couple the interior region 106 to a pumping system 128. The pumping system 128 may include one or more pumps and a throttle valve utilized to evacuate and regulate the pressure in the interior region 106 of the processing chamber 100.

[0017]

[0023] 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 region 106 of the processing chamber 100 and may provide a seal for the processing chamber 100 when closed. A gas panel 158 may be coupled to the processing chamber 100 to supply process gases and / or cleaning gases to the interior region 106 through the showerhead 130 or lid and nozzles. The showerhead 130 may be used in processing chambers used for dielectric etching (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 a GDP bonded to an aluminum base or an anodized aluminum base. The GDP may be made of Si or SiC, or may be made of YO, AlO, YAlO, or other suitable materials. 12 It may also be a ceramic such as YAG.

[0018]

[0024] A processing chamber used for conductor etching (etching of conductive materials) may use a lid rather than a showerhead. The lid may include a central nozzle that fits into the central hole of the lid. The lid may be a ceramic, such as Al2O3, Y2O3, YAG, or a ceramic compound including a solid solution of Y4Al2O9 and Y2O3-ZrO2. The nozzle may also be a ceramic, such as Y2O3, YAG, or a ceramic compound including a solid solution of Y4Al2O9 and Y2O3-ZrO2.

[0019]

[0025] Examples of process gases that can be used to process substrates in the process chamber 100 include halogen-containing gases such as C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, and SiF4, among others, and other gases such as O2 or N2O. Examples of carrier gases include N2, He, Ar, and other gases that are inert (e.g., non-reactive) with respect to the process gas.

[0020]

[0026] The heater assembly 148 is disposed within the interior region 106 of the processing chamber 100 below the showerhead 130 or lid. The heater assembly 148 includes a support 150 that holds the substrate 144 during processing. The support 150 is attached to the end of a shaft 152 that is connected to the chamber body 102 via a flange. The support 150, shaft 152, and flange may be composed of a heater material that includes AlN, such as AlN ceramic. The support 150 may further include a mesa (e.g., a recess or protrusion). The support may also include a wire, such as a tungsten wire (not shown), embedded within the heater material of the support 150. In one embodiment, the support 150 may include a metal heater and sensor layer sandwiched between AlN ceramic layers. Such an assembly may be sintered in a high-temperature furnace to produce a monolithic assembly. The layers may include heater circuitry, a sensor element, a ground plane, a radio frequency grid, and a combination of metal and ceramic flow channels.

[0021]

[0027] Electroless metal plating coatings having a pure (or nearly pure) metal layer according to embodiments described herein can be deposited on at least a portion of any surface of the chamber components described herein (and those not shown in FIG. 1 ) that may be exposed to processing chemicals used in a processing chamber. Exemplary chamber components that can be protected with the pure (or nearly pure) metal layer described herein include, but are not limited to, an electrostatic chuck, a nozzle, a gas distribution plate, a showerhead (e.g., 130), an electrostatic chuck component, a chamber wall (e.g., 108), a liner (e.g., 116), a liner kit, a gas line, a chamber lid, a nozzle, a shingle ring, a process kit ring, an edge ring, a base, a shield, a plasma screen, a flow equalizer, a cooling base, a chamber viewport, a bellows, any portion of a heater assembly (including the support 150, the shaft 152, and the flange), a faceplate, a blocker plate, etc.

[0022]

[0028] 2A shows a cross-sectional view of an article 200 having an electroless metal plating coating modified with a layer of pure (or nearly pure) metal thereon, according to some embodiments. The article 200 may include a substrate 210 made of a ceramic (e.g., an oxide-based ceramic, a nitride-based ceramic, or a carbide-based ceramic), a metal (e.g., aluminum, stainless steel, titanium, and / or other suitable metals and / or combinations thereof), or a metal alloy, quartz, and combinations thereof. Examples of oxide-based ceramics include SiO (quartz), AlO, YO, etc. Examples of carbide-based ceramics include SiC, Si-SiC, etc. Examples of nitride-based ceramics include AlN, SiN, etc. In some embodiments, the substrate 210 may be aluminum, anodized aluminum, an aluminum alloy (e.g., Al6061), or an anodized aluminum alloy. In some embodiments, the substrate 210 may be stainless steel, nickel-chromium alloy, nickel, austenitic nickel-chromium based superalloys (e.g., Inconel®), iron, cobalt, titanium, magnesium, copper, zinc, chromium, etc. The terms "substrate," "article," and "chamber component" may be used interchangeably herein.

[0023]

[0029] In some embodiments, as depicted in FIG. 2A , substrate 210 may include electroless nickel plating (ENP) coating layer 220 or an electroless metal plating where the metal is different from nickel. Hereinafter, ENP is often referred to for brevity and clarity, but it should be understood that similar techniques may be used to produce pure (or nearly pure) layers of other metals. ENP coating layer 220 may be formed on article 200 to improve the performance of article 200 in high-temperature applications (e.g., temperatures higher than those required for sputtering resistance). In some embodiments, nickel possesses mechanical properties—physical properties exhibited when a force is applied (e.g., modulus of elasticity, tensile strength, elongation, hardness, fatigue limit, etc.)—that may be lacking in other metals (e.g., aluminum and other metals and alloys used in low-temperature applications). ENP coating layer 220 may be used in applications at temperatures up to about 800°C for bulk metal substrates and about 1,000°C for ceramic substrates. In embodiments, the ENP coating layer 220 can have a thickness of about 1 μm to about 50 μm, or about 5 μm to about 45 μm, or about 10 μm to about 40 μm, or about 15 μm to about 35 μm, or about 20 μm to about 30 μm, or any individual thickness or subrange within these ranges. The ENP coating layer 220 can be contacted with a fluorine radical gas at an elevated temperature (e.g., as described in more detail below in conjunction with FIGS. 3-5 ) to remove at least some phosphorus atoms from the ENP coating layer 220 and convert a portion of the ENP coating layer 220 to a pure (or nearly pure) nickel layer 230. The reaction temperature, exposure time, and fluorine radical gas flow rate can be adjusted to achieve a desired (target) purity of the nickel layer 230 and / or a target thickness (depth) of the nickel layer 230 according to embodiments herein.

[0024]

[0030] In some embodiments, the thickness of the pure (or nearly pure) nickel layer 230 can be between 5 nm and 1000 nm, or any subrange of thickness or single value therein. The thickness and properties of the pure (or nearly pure) nickel layer 230 described herein, according to embodiments herein, depend on the type and parameters of the fluorine-rich gas used to form the layer 230. These properties can be adjusted and tailored depending on the intended use of the coated article.

[0025]

[0031] FIG. 2B shows a cross-sectional view of another article 202 having an electroless metal plating coating having a layer of pure (or nearly pure) metal and a layer of metal fluoride coating formed thereon, according to some embodiments. The article 202 may include a substrate 210, an ENP coating layer 220, and a pure (or nearly pure) nickel layer 230, for example, substantially as described in connection with FIG. 2A. As shown in FIG. 2B, at least a portion of the pure (or nearly pure) nickel layer 230 may be coated with a nickel fluoride coating layer 240 in accordance with embodiments herein. In embodiments, the nickel fluoride coating layer 240 may be formed using a thermal molecular fluorine gas (F) conversion process (Ni + F = NiF). The thermal molecular fluorine gas conversion process may include subjecting the article 202 to a pre-wet clean (e.g., using hydrofluoric acid, nitric acid, or a combination thereof) and a bakeout in a thermal reactor (e.g., at a temperature of about 25° C. to about 90° C.). Articles (e.g., parts and / or components) to be reacted with fluorine gas can be loaded into the reactor. The reactor can be placed under vacuum conditions, for example, at a pressure of about 10 mTorr to about 50 mTorr. Once evacuated, the temperature within the reactor can be raised to about 100°C to about 500°C. It is noteworthy that at higher temperatures, the nickel fluoride coating can grow (i.e., thicken) at a faster rate than at lower temperatures. When the nickel fluoride coating layer 240 is formed at a temperature of about 300°C, the resulting coating thickness can be about 200 nm. The thickness of the nickel fluoride coating layer 240 can increase at the same temperature with prolonged exposure to fluorine gas.

[0026]

[0032] Conversion coatings formed by either the molecular fluorine gas process or the fluorine radical process have an adhesion strength to the surface of a substrate of greater than about 20 mN with a 2 μm diamond stylus, or greater than 100 mN with a 10 μm diamond stylus, using a Scratch Adhesion Test based on ASTM C1624, D7187, G171, or other equivalent standards. The resulting conversion coatings are conformal and capable of coating complex features, including high aspect ratio features of the substrate (e.g., aspect ratios of length to diameter or length to width of about 100:1 to about 1000:1). The resulting metal fluoride coating thickness can be about 5 nm to about 5,000 nm, or about 10 nm to about 4,000 nm, or about 25 nm to about 3,000 nm, or about 50 nm to about 2,500 nm, or about 100 nm to about 2,000 nm, or about 250 nm to about 1,000 nm, or any individual thickness or subrange within these broad ranges. The coating thickness can be a function of the reaction time between the fluorine gas or radicals and the surface of the coating. The resulting conversion coating can be crystalline and dense (e.g., having about 0% or no porosity) and can provide superior ion bombardment resistance compared to amorphous coatings. The metal fluoride coatings described herein provide fluorine plasma and / or radical erosion resistance, as well as oxygen, hydrogen, and nitrogen plasma resistance due to their stable properties. Because the metal fluoride coatings described herein already contain metal fluoride and can be considered pre-saturated with fluorine. When exposed to fluorine, the metal fluoride coating absorbs the fluorine like a sponge.

[0027]

[0033] In embodiments, the metal fluoride coating comprises nickel fluoride and is anhydrous. Anhydrous metal fluoride coatings may be non-hygroscopic unless mixed with hydrated nickel fluoride. Anhydrous converted nickel fluoride coatings are crystalline and may retain moisture only through physical absorption when exposed to moisture. In particular, NiF passivated at 300°C is anhydrous and non-hygroscopic unless mixed with hydrated NiF. Anhydrous NiF forms rutile-type tetragonal crystals. Anhydrous NiF exposed to moisture absorbs water only through physical absorption. Anhydrous NiF is practically insoluble at a value of 0.02 g / 100 mL. Hydrated NiF (NiF·4H₂O) is formed from hydroxide, nitrate, or carbonate solutions. When reacted with HF acid, the hydrate converts to anhydrous NiF at 350°C in dry HF. NiF2·4H2O is a stable hydrate, but other hydrates (NiF2·2H2O and NiF2·3H2O) are unstable. Hydrated NiF2 (NiF2·4H2O) dissolves in water at 4.03 g / 100 mL saturated solution.

[0028]

[0034] In one example, the substrate may initially include an electroless metal plating coating on the surface of the substrate. The substrate material may be, but is not limited to, one or more of a metal (e.g., aluminum, stainless steel, and / or titanium, nickel), a ceramic (e.g., alumina, silica, and / or aluminum nitride), and / or a combination thereof. The electroless metal plating coating may be contacted with fluorine gas to convert one or more metals in the metal plating coating to metal fluorides to form a metal fluoride coating. In an embodiment, the metal fluoride coating may be a homogeneous or substantially homogeneous metal fluoride coating in that at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, or at least about 100% of the one or more metals in the electroless metal plating coating are converted to metal fluorides.

[0029]

[0035] In an embodiment, the nickel fluoride coating layer 240 is Ni x F y(Accordingly, if a metal M different from nickel is used, the formula may be M x F y In embodiments, x may be 1 and y may range from 1 to 3. In other embodiments, nickel fluoride coating layer 240 may be Ni x P z F w (e.g., x is 1 and z is 2) and / or Ni x Au z Ag w F y In embodiments, the thickness of nickel fluoride coating layer 240 can range from about 5 nm to about 5000 nm, or any subrange of thickness or single value therein. The thickness and properties of the metal fluoride coatings described herein depend on the parameters of the fluorine gas or fluorine radical conversion process according to embodiments herein. These properties can be tailored depending on the intended use of the coated article.

[0030]

[0036] 3 is an exemplary diagram of a processing system 300 capable of modifying an electroless metal plating coating with a layer of pure (or nearly pure) metal, according to some embodiments. The article 302 may be placed in a process chamber, such as a remote plasma source (RPS) chamber 340 connected to a remote plasma source (RPS) 350. The RPS 350 may receive a source gas 352 via an inlet 354. The source gas 352 may include a fluorine-rich gas, such as nitrogen fluoride (NF), molecular fluorine (F), hydrogen fluoride (HF), chlorine trifluoride (ClF), etc., and a carrier gas, such as argon, neon, krypton, xenon, and / or other suitable low-reactivity gases. In one exemplary embodiment, the source gas 352 is fluorinated at a flow rate of 100-700 cm. 3The source gas 352 may be supplied to the RPS 350 at an exemplary flow rate of 1000 s / sec, although it should be understood that the flow rate is system specific and may have significant variations from system to system. In one exemplary embodiment, the source gas 352 may include 35% (e.g., by mass or partial pressure) fluorine-rich gas and 65% inert gas. In some embodiments, the source gas 352 may include 20-50% (e.g., by mass or partial pressure) fluorine-rich gas and 50-80% inert gas.

[0031]

[0037] The RPS 350 can dissociate the fluorine-rich gas component of the source gas 352 to generate fluorine radicals 360 (schematically represented by black dots). In some embodiments, the dissociation can be performed using an energy source 356, such as an inductive energy source or a microwave energy source, that supplies energy to the RPS 350. The fluorine radicals 360 can be supplied from the RPS 350 to the RPS processing chamber 340 via a channel 370, where the surface of the article 302 can be exposed to the fluorine radicals 360. In some embodiments, the article 302 can include a substrate 310 and an ENP coating layer 320. The fluorine radicals 360 can remove at least a portion of the phosphorus from the ENP coating layer 320, for example, by forming one or more phosphorus fluoride compounds, such as PF3, PF5, P2F4, etc. As a result, a pure (or nearly pure) nickel layer 330 can be formed on top (in the direction of FIG. 3 ) of the ENP coating layer 320.

[0032]

[0038] The temperature within the RPS processing chamber 340 can be controlled using a heating element 342 and a temperature sensor 344. The temperature can be 260°C, 270°C, 300°C, 320°C, 330°C, 350°C, 370°C, 400°C, 500°C, or higher. Increasing the temperature within the RPS processing chamber 340 can increase the purity of the nickel layer 330. For example, at lower temperatures (e.g., around 290-300°C), the nickel layer 330 can have a lower purity (e.g., 90-95% Ni), while at higher temperatures (e.g., 340-360°C), the nickel layer 330 can have a higher purity (e.g., 98-99.5% Ni).

[0033]

[0039] The pressure in the RPS processing chamber 340 may be measured using a pressure sensor 346. The pressure may be controlled by adjusting the flow of source gas 352 into the RPS 350, the flow of fluorine radicals 360 from the RPS 350 to the RPS processing chamber 340, and / or the flow of output gas 362 via exhaust 348, which may be coupled to a pumping system operating similarly to pumping system 128 of FIG. 1 and may include one or more pumps and throttle valves utilized to evacuate and adjust the pressure in the RPS processing chamber 340. In some embodiments, the pressure in the RPS processing chamber 340 may be at or about 1 Torr. In some embodiments, the pressure in the RPS processing chamber 340 may be in the range of 0.1 Torr to 10 Torr.

[0034]

[0040] The article 302 may be exposed to the fluorine radicals 360 for a target time, such as 1 hour, 2 hours, 12 hours, 24 hours, 48 ​​hours, 72 hours, and / or any other target time. The target time may be determined based on the target thickness of the pure (or nearly pure) nickel layer 330 desired to be formed on the ENP coating layer 320.

[0035]

[0041] After the pure (or nearly pure) nickel layer 330 is formed on the ENP coating layer 320, the article 302 may be removed from the RPS chamber 340 and subjected to fluorine gas exchange (or any other suitable technique) to form a nickel fluoride coating on the pure (or nearly pure) nickel layer 330. In some embodiments, the article 302 may be subjected to fluorine gas exchange while in the RPS chamber 340, e.g., exposed to different reactive gases delivered via channels 370.

[0036]

[0042] In some embodiments, Figures 4A-4C show example images of stacks of coating layers formed on a substrate, including an electroless nickel plating coating layer, a pure (or nearly pure) nickel layer, and a nickel fluoride coating layer. The left panels of Figures 4A-4C show transmission electron microscope (TEM) images of each example stack of coating layers, and the right panels of Figures 4A-4C show the chemical (elemental) composition of the corresponding stacks obtained using accompanying electron energy loss spectroscopy (EELS) data. The example stacks of coating layers shown in Figures 4A-4C were formed using fluorine radicals obtained by dissociation of NF3 gas.

[0037]

[0043] FIG. 4A shows a TEM image of a coating layer stack that has undergone treatment with fluorine radicals for an ENP coating in an RPS processing chamber (e.g., a chamber similar to RPS chamber 340 in FIG. 3) at a temperature of 250° C. and a pressure of 1.5 Torr. The bottom layer is ENP layer 402, which is 5 μm thick (the image shows a roughly 150 nm portion of ENP layer 402) and is composed (on average) of approximately 80% nickel and 20% phosphorus. The second layer (from the bottom) is nickel fluoride layer 406, which is approximately 35 nm thick and is composed of approximately 72% fluoride and 28% nickel. (The iridium layer 408 and carbon layer 410 are placed on the stack to facilitate TEM imaging and do not form part of the coating layer stack.) As shown in FIG. 4A, under the described conditions, no significant formation of a pure (or nearly pure) nickel layer occurs.

[0038]

[0044] Figure 4B shows a TEM image of a coating layer stack that was treated with fluorine radicals in an RPS processing chamber environment at a temperature of 300°C and a pressure of 1.5 Torr for the ENP coating. The ENP layer 402 is composed (on average) of approximately 74% nickel, 12% phosphorus, 7% oxygen, 6% carbon, and trace amounts of other elements (e.g., fluorine). A substantially pure nickel layer 404 is formed on top of the ENP layer 402. As shown in Figure 4B, the substantially pure nickel layer 404 is approximately 19-27 nm thick and is approximately 86% nickel, 6% oxygen, 5% carbon, and trace amounts of other elements. A nickel fluoride layer 406 formed on top of the substantially pure nickel layer 404 is approximately 78-84 nm thick and is approximately 59% fluoride and 34% nickel. (The iridium layer 408 and carbon layer 410 are placed on the stack to facilitate TEM imaging and do not form part of the coating layer stack.)

[0039]

[0045] FIG. 4C shows a TEM image of a coating layer stack that has been treated with fluorine radicals for the ENP coating in an RPS processing chamber environment at a temperature of 350° C. and a pressure of X. The ENP layer 402 is made up of (on average) approximately 78% nickel, 22% phosphorus, and trace amounts of other elements (such as carbon). A pure (or nearly pure) nickel layer 404 is formed on the ENP layer 402. As shown in FIG. 4C, the pure (or nearly pure) nickel layer 404 is approximately 50 nm thick and is approximately 98% nickel (with trace amounts of other elements, such as oxygen). A nickel fluoride layer 406 formed on the pure (or nearly pure) nickel layer 404 is approximately 90 nm thick and is approximately 72% fluoride and approximately 27% nickel. (The iridium layer 408 and carbon layer 410 are placed on the stack to facilitate TEM imaging and do not form part of the coating layer stack.)

[0040]

[0046] 5 is a schematic diagram of an exemplary method for manufacturing a stack of coating layers formed on a substrate, the stack including an electroless metal plating coating layer, a pure (or nearly pure) metal layer, and a metal fluoride coating layer, according to some embodiments. As shown, the substrate 210 may have a contaminant layer 502 disposed thereon. The substrate 210 may be subjected to a cleaning step 510 to strip the contaminant layer 502 from the substrate 210. The substrate 210 may be treated using an electroless metal plating process 520, such as an ENP process, to deposit an ENP coating layer 220 on the substrate 210. The substrate 210 with the ENP coating layer 220 may be exposed to fluorine radicals (step 530) to convert a portion (e.g., the top) of the ENP coating layer 220 to a pure (or nearly pure) nickel layer 230. A nickel fluoride layer 240 may then be formed using fluorine gas conversion 540. The resulting stack 550 includes the substrate 210, the ENP coating layer 220, the pure (or nearly pure) nickel layer 230, and the nickel fluoride layer 240.

[0041]

[0047] FIG. 6 illustrates an exemplary method 600 for forming a pure (or nearly pure) metal layer from an electroless metal plating coating using fluorine radicals, according to some embodiments. Method 600 may be performed using processing system 300 of FIG. 3 . At block 610, method 600 may include maintaining a plasma environment at a temperature greater than 250° C. The plasma environment may include fluorine radicals. In some embodiments, maintaining the plasma environment may include the operations illustrated in the top portion of FIG. 6 . More specifically, at block 612, method 600 may include receiving a source gas via a remote plasma source. The source gas may include a fluorine-rich gas and an inert gas. In some embodiments, the fluorine-rich gas may be or include at least one of nitrogen trifluoride (NF), molecular fluorine (F), or hydrogen fluoride (HF), chlorine trifluoride (ClF), or other suitable gases containing fluorine. In some embodiments, the mass fraction of the inert gas in the source gas may be between 50% and 80%, and the mass fraction of the fluorine-rich gas in the source gas may be between 20% and 50%. At block 614, the method 600 may include dissociating at least a portion of the source gas into one or more products. The one or more products may include fluorine radicals. At block 616, the method 600 may include providing fluorine radicals to the plasma environment.

[0042]

[0048] In some embodiments, the temperature of the plasma environment may exceed 290° C. In some embodiments, the temperature of the plasma environment may exceed 340° C. In some embodiments, the plasma environment may be maintained at a pressure of 10 Torr or less.

[0043]

[0049] At block 620, the method 600 may continue by exposing the layered structure to a plasma environment. The layered structure may include a substrate and a first layer disposed on the substrate. In some embodiments, the first layer may include a metal having a first atomic concentration of less than 85%, less than 90%, less than 95%, etc. In some embodiments, the first layer is an electroless metal plating layer. In some embodiments, the first layer is an electroless nickel plating layer. In some embodiments, the electroless metal plating layer is amorphous. In some embodiments, exposing the layered structure to the plasma environment may include the operations illustrated in the bottom callout of FIG. 6. More specifically, at block 622, the method 600 may include exposing the layered structure to the plasma environment for a predetermined time associated with forming a second layer of a target thickness. In some embodiments, the second layer may be formed from the first layer. Forming the second layer may include removing at least a portion of the phosphorus from the first layer (e.g., ENP) using fluorine radicals. In some embodiments, the second layer may have an atomic concentration of phosphorus of 5% or less. In some embodiments, the second layer may be free (or nearly free) of phosphorus. In some embodiments, the second layer may include nickel having a second atomic concentration of 90% or more, 95% or more, 98% or more, 99% or more, or 99.5% or more. In some embodiments, the second atomic concentration may be at least 5% higher than the first atomic concentration. In some embodiments, the second layer may be or include a crystalline layer of nickel. In some embodiments, the predetermined period of time may be greater than 1 hour. In some embodiments, the method 600 may further include coating the second layer with a third layer at block 630. For example, the third layer may be nickel fluoride Ni. x F y It may contain compounds.

[0044]

[0050] The foregoing description sets forth numerous specific details, including examples of specific systems, components, methods, etc., to provide a thorough understanding of some embodiments of the present disclosure. However, it will be apparent to one of ordinary skill in the art that at least some embodiments of the present disclosure 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 form in order to avoid unnecessarily obscuring the present disclosure. Thus, the specific subject matter described is merely illustrative. Particular embodiments can vary from these illustrative details and still be considered within the scope of the present disclosure.

[0045]

[0051] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to a "precursor" includes not only a single precursor but also a mixture of two or more precursors; reference to a "reactant" includes not only a single reactant but also a mixture of two or more reactants, etc.

[0046]

[0052] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that 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. Furthermore, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." When the terms "about" or "approximately" are used herein, this is intended to mean that the stated nominal value is accurate to within ±10%, such as "about 10" including 9 to 11.

[0047]

[0053] The term "at least about" in reference to a measured quantity refers to normal variations in that measured quantity, and any greater, as would be expected by one of ordinary skill in the art when making the measurement and exercising a level of care commensurate with the purpose of the measurement and the precision of the measuring device. In certain embodiments, the term "at least about" includes the recited number minus 10% and any greater amount, e.g., "at least about 10" includes 9 and anything greater than 9. The term can also be expressed as "about 10 or greater." Similarly, the term "less than about" typically includes the recited number plus 10% and any smaller amount, e.g., "less than about 10" includes 11 and anything less than 11. The term can also be expressed as "about 10 or less."

[0048]

[0054] The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each individual value falling within the range, unless otherwise indicated herein, and each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any examples or exemplary language (e.g., "etc.") provided herein is intended merely to highlight particular materials and methods and is not intended to limit the scope. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0049]

[0055] 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 may be performed in reverse order, or certain operations may be performed at least in part concurrently with other operations. In alternative embodiments, instructions of separate steps or substeps may be intermittent and / or alternating.

[0050]

[0056] It is to be understood that the foregoing description is intended to be illustrative, and not limiting. Many other embodiments will become apparent to those skilled in the art upon reading and understanding the above description. The scope of the present disclosure should, therefore, be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. 1. A chamber component for a processing chamber, comprising: A substrate; a first layer disposed on the substrate and including a metal having a first atomic concentration; a second layer disposed on the first layer, the second layer comprising a metal having a second atomic concentration at least 5% greater than the first atomic concentration; a chamber component comprising:

2. The chamber component of claim 1 , wherein the metal comprises nickel.

3. The chamber component of claim 1 , wherein the first layer comprises an amorphous layer of an electroless nickel plated layer.

4. The chamber component of claim 1 , wherein the second layer comprises a crystalline layer of nickel.

5. The chamber component of claim 1 , further comprising a third layer disposed on the second layer, the third layer comprising a nickel fluoride layer.

6. 6. The chamber component of claim 5, wherein the first layer comprises phosphorus having an atomic concentration of 10 percent or greater, and the second layer comprises either no phosphorus or phosphorus having an atomic concentration of 5 percent or less.

7. The substrate is made of aluminum alloy, aluminum nitride (AlN), alumina (Al ２ O ３ ), nickel (Ni), stainless steel, nickel-chromium alloy, austenitic nickel-chromium based superalloy, pure nickel, quartz, iron, cobalt, titanium, magnesium, copper, zinc, or chromium.

8. The chamber component of claim 1 , wherein the second atomic concentration is greater than or equal to 95 percent.

9. The chamber component of claim 8 , wherein the second atomic concentration is greater than or equal to 99 percent.

10. 10. The chamber component of claim 1, wherein the substrate comprises a surface of a tool of a semiconductor processing chamber, the tool comprising at least one of a heater, an electrostatic chuck, a faceplate, a showerhead, a liner, a blocker plate, a gas box, an edge ring, or a bellows.

11. maintaining a plasma environment containing fluorine radicals at a temperature above 250°C; exposing a layered structure to the plasma environment, wherein the layered structure: a substrate, and a first layer disposed on the substrate, the first layer including a metal having a first atomic concentration less than 90 percent; exposing the layered structure to said plasma environment; A method comprising:

12. maintaining the plasma environment; receiving a source gas by a remote plasma source (RPS), the source gas comprising a fluorine-rich gas, the fluorine-rich gas comprising: nitrogen trifluoride, molecular fluorine, chlorine trifluoride, or hydrogen fluoride receiving a source gas including at least one of: dissociating at least a portion of the source gas into one or more products including the fluorine radicals; providing the fluorine radicals to the plasma environment; The method of claim 11 , comprising:

13. 13. The method of claim 12, wherein the source gas further comprises an inert gas, the mass fraction of the inert gas in the source gas being between 50% and 80%, and the mass fraction of the fluorine-rich gas in the source gas being between 20% and 50%.

14. 14. The method of claim 13, wherein the temperature is greater than 290°C.

15. 15. The method of claim 14, wherein the temperature is greater than 340°C.

16. The method of claim 11 , further comprising maintaining the plasma environment at a pressure of 10 Torr or less.

17. 12. The method of claim 11 , wherein exposing the layered structure to the plasma environment occurs for a predetermined time in conjunction with forming a second layer of a target thickness, the second layer being formed from the first layer and comprising nickel having a second atomic concentration that is at least 5% greater than the first atomic concentration.

18. 18. The method of claim 17, wherein the predetermined time period is greater than one hour.

19. 18. The method of claim 17, further comprising coating the second layer with a third layer comprising nickel fluoride.

20. The method of claim 11 , wherein the first layer comprises an electroless nickel plated layer.

21. 1. A processing chamber comprising: A substrate; a first layer disposed on the substrate and including a metal having a first atomic concentration; a second layer disposed on the first layer, the second layer comprising a metal having a second atomic concentration at least 5% greater than the first atomic concentration; a chamber component comprising: a processing chamber comprising:

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