Atomic layer deposition coatings for high-temperature ceramic components

Abstract

To provide an atomic layer deposition coated article for high temperature articles and a method of coating the coated article.SOLUTION: In a coated article, coating including an article suitable for use in a processing chamber 100 and a coating formed on the exterior and interior surfaces of the article includes a rare earth metal-containing ceramic and is substantially uniform, conformal, and non-porous.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Embodiments of this disclosure relate to articles, coated chamber components, and methods for coating chamber components with ceramic coatings. The ceramic coating may include a rare-earth metal-containing layer that coats all surfaces of the component (e.g., a high-temperature heater or an electrostatic chuck). The ceramic coating may be formed using an off-line technique such as atomic layer deposition (ALD). Background

[0002] Various semiconductor manufacturing processes utilize high temperatures, high-energy plasmas, mixtures of corrosive gases, high stress, and combinations thereof. Due to these extreme conditions, chamber components are often eroded, and particulate contaminants are generated.

[0003] Typically, protective coatings are deposited on chamber components using various methods, including thermal spraying, sputtering, plasma spraying, or vapor deposition. These techniques generally fail to deposit conformal and uniform coatings on the complex structural features of the components. Therefore, the complexity of the component's geometry imposes design constraints. Furthermore, these techniques are generally unsuitable for coating heater components without significantly impacting heater performance, as relatively thick coatings are required to achieve the same level of protection as a thinner, less defect-density film. [Overview of the project]

[0004] Embodiments of this specification describe atomic layer deposition coatings for high-temperature articles. In one aspect, the coated article comprises an article suitable for use in a processing chamber, the article comprising an outer surface and an internal channel comprising an inner surface that is difficult to reach for in-line deposition processing. The coated article further comprises a coating formed on the outer and inner surfaces of the article, the coating comprising a rare earth metal-containing ceramic, the rare earth metal-containing ceramic being Y2O3, YZrO, Y x Zr y O z 、YZrOF、Y3Al5O 12 、Y4Al2O9、YF3、Y x O y F z 、YOF、Er2O3、Er3Al5O 12 、ErF3、E x O y F z 、ErOF、La2O3、Lu2O3、Sc2O3、ScF3、ScOF、Gd2O3、Sm2O3、Dy{2}O3, and combinations thereof. In some embodiments, the coating is substantially uniform, conformal, and non-porous.

[0005] In another aspect, the coated article comprises an article suitable for use in a processing chamber, an amorphous carbon adhesion layer formed on the article, and a coating formed on the amorphous carbon adhesion layer, the coating comprising a rare earth metal-containing ceramic, the rare earth metal-containing ceramic being Y2O3, YZrO, Y x Zr y O z 、YZrOF、Y3Al5O 12 、Y{4}Al{2}O{9}, YF3, Y x O y F z 、YOF、Er2O3、Er3Al5O 12 、ErF3、E x O y F zThe material is selected from the group consisting of ErOF, La2O3, Lu2O3, Sc2O3, ScF3, ScOF, Gd2O3, Sm2O3, Dy2O3, and combinations thereof. In some embodiments, the coating is substantially uniform, conformal, and non-porous.

[0006] In another embodiment, a method for forming a coated article includes the steps of supplying an article suitable for use in a processing chamber, wherein the article has a first coefficient of thermal expansion; selecting a molar ratio of a first rare earth metal-containing ceramic compound to a second rare earth metal-containing ceramic compound, wherein a ceramic coating comprising the first and second rare earth metal-containing ceramic compounds in the selected molar ratio is deposited on the surface of the article by atomic layer deposition, thereby obtaining a ceramic coating having a second coefficient of thermal expansion, wherein the second coefficient of thermal expansion is within 10% of the first coefficient of thermal expansion; and performing atomic layer deposition to deposit the ceramic coating on the surface of the article. [Brief explanation of the drawing]

[0007] In the drawings of the attached documents, the same reference numerals are shown as examples, not as limitations, and similar reference numerals indicate similar elements. [Figure 1] A cross-sectional view of the processing chamber is shown. [Figure 2A] This specification shows one embodiment of the deposition process using the atomic layer deposition technique described herein. [Figure 2B] Another embodiment of the deposition process using the atomic layer deposition technique described herein is shown. [Figure 2C] Another embodiment of the deposition process using the atomic layer deposition technique described herein is shown. [Figure 3] The following are exemplary susceptors with ceramic coatings formed according to various embodiments. [Figure 4] The following are exemplary heater assemblies with ceramic coatings formed according to various embodiments. [Figure 5] The following are cross-sectional side views of exemplary components with internal channels formed according to various embodiments. [Figure 6A] The images show cross-sectional views of the surface of a component in which a single layer is formed, according to various embodiments. [Figure 6B] The images show cross-sectional views of the surfaces of components in which multiple layers are formed according to various embodiments. [Figure 7] This document describes a method for forming a ceramic coating using atomic layer deposition according to various embodiments. [Figure 8] These are transmission electron microscope images of graphite substrates on which adhesive layers and ceramic layers are formed according to various embodiments. Detailed explanation

[0008] The embodiments described herein deal with coated articles and methods for depositing coatings onto articles. The coating may be a rare earth metal-containing layer (e.g., a yttrium-containing oxide layer or a yttrium-containing fluoride layer). Alternatively, the coating may be a multilayer coating comprising one or more adhesive layers and one or more ceramic layers. The deposition process may be an off-target process such as atomic layer deposition (ALD).

[0009] Existing ceramic heaters and coating methods have several drawbacks. For example, when the heater is exposed to plasma, and especially when the heater is formed from bulk ceramics such as AlN, Al2O3, or SiC-coated graphite, the sputter yield and erosion rate are usually high. For example, SiC and TaC-coated graphite heaters are incompatible with fluorine-containing chemicals. Plasma spraying and SiC-coated graphite heaters are non-conformal. Therefore, their geometric complexity is subject to design constraints. Furthermore, the difficulty in adjusting the coefficient of thermal expansion (CTE) of existing heater coatings limits their application to substrates with different CTEs at high temperatures. Most heater coatings are thick coatings, which exacerbate this CTE mismatch problem.

[0010] The embodiments of this disclosure solve some of the problems of existing heater technologies. For example, the advantages of the embodiments of this disclosure include the ability of rare earth oxide and oxyfluoride ALD coatings to provide conformal coverage to heaters, electrostatic chucks, and other complex-shaped components. These complex-shaped components include complex, high-aspect-ratio internal geometries that cannot be reached with line-of-sight deposition technologies. Furthermore, heaters coated with rare earth oxide and oxyfluoride ALD coatings exhibit low sputter yields under high-energy plasma shock and have high resistance to degradation by chemical / radical attack (e.g., from NF3 radicals). Heaters coated with rare earth oxide and oxyfluoride ALD coatings can also withstand higher temperatures (e.g., be exposed without damage) compared to other coating technologies. Other coating technologies utilize much thicker coatings, which generate higher stresses when CTE mismatches are present. Heaters coated with rare earth oxide and oxyfluoride ALD coatings also naturally exhibit very high oxidation resistance. Furthermore, ALD coatings have the effect that, in various embodiments, improved protection can be achieved by adjusting the ratio of different constituent materials within the ALD coating (e.g., the molar ratio of two or more metals), thereby matching the coated CTE with the CTE of various substrates.

[0011] The heater may be formed from aluminum nitride (AlN) material, or other suitable material having equivalent chemical resistance and mechanical, thermal, and electrical properties. Electricity may be supplied by embedding wires (e.g., tungsten wires) in the heater material. In various embodiments, the heater material may be AlN ceramic, silicon carbide (SiC) ceramic, aluminum oxide (Al2O3) ceramic, graphite, or any combination thereof. Different heater materials have different reaction properties, and when one composition is exposed to high temperature, low vacuum pressure, and intense chemical reactions, it may form reactants with a higher vapor pressure than another composition. For example, when a typical high-temperature heater with AlN ceramic material is exposed to nitrogen trifluoride (NF3) plasma under high temperature (e.g., up to about 650°C) and vacuum (e.g., about 50 milliliters to about 200 milliliters), this reaction produces aluminum trifluoride (AlF3). The vapor pressure of aluminum trifluoride is approximately log(p / kPa) = 11.70 - 14950(T / K). Therefore, AlF3 can sublimate and deposit on other components in the chamber. In subsequent processing steps, the deposited material may detach, peel, or otherwise separate from other chamber components, depositing as particles on the wafer and creating defects.

[0012] ALD enables controlled, self-limiting deposition of material through a chemical reaction with the surface of an article. In addition to being a conformal process, ALD is also a uniform process, and can form very thin films, for example, with a thickness of about 3 nm or more. The same or nearly the same amount of material is deposited on all exposed surfaces of the article. As described herein, this heater may have the same or substantially the same thermal conductivity and heating capacity as an uncoated heater. A typical reaction cycle of the ALD process begins with a precursor (i.e., a single chemical A) flowing into the ALD chamber and being adsorbed onto the surface of the article (including the surface of the pore walls within the article). After the excess precursor is discharged from the ALD chamber, a reactant (i.e., a single chemical R) is introduced into the ALD chamber and then discharged. In the case of ALD, the final thickness of the material depends on the number of reaction cycles performed, because in each reaction cycle, a layer of a certain thickness, either one atomic layer or a fraction of an atomic layer, is grown.

[0013] ALD technology allows for the deposition of thin layers of material at relatively low temperatures (e.g., approximately 25°C to 350°C), thus avoiding damage or deformation of any constituent materials. Furthermore, ALD technology can also deposit layers of material within complex features of constituent materials (e.g., high aspect ratio features). In addition, ALD technology generally produces non-porous (i.e., pinhole-free), relatively thin (i.e., less than 1 μm) coatings. This eliminates the possibility of crack formation during deposition.

[0014] Figure 1 is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components coated with a coating layer according to various embodiments. The base material of the processing chamber 100 may include one or more of aluminum (Al), titanium (Ti), and stainless steel (SST). The processing chamber 100 may be used for processing in which a corrosive plasma environment with plasma processing conditions is provided. For example, the processing chamber 100 may be a chamber for a plasma etcher or plasma etching reactor, a plasma cleaner, a plasma-enhanced chemical vapor deposition (CVD) or ALD reactor, etc. Examples of chamber components that may have a coating layer (e.g., ceramic coating) include a substrate support assembly 148, an electrostatic chuck (ESC) assembly 150, a ring (e.g., a process kit ring or single ring), a chamber wall, a base, a gas distribution plate, a shower head, a liner, a liner kit, a shield, a plasma screen, a flow equalizer, a cooling base, a chamber viewport, a chamber lid, and the like. Various techniques may be used to deposit the coating on the components. Examples include ALD, sputtering, ion-assisted deposition, plasma spray coating, CVD, and other suitable techniques that will be understood by those skilled in the art. As shown in the illustration, according to one embodiment, the substrate support assembly 148 has a ceramic coating layer 136. However, it should be understood that any of the other chamber components listed above may also have a coating layer.

[0015] Another example of a chamber component that may have a coating is a high-temperature heater assembly. In some embodiments, the coating, which is described in more detail below, is applied by ALD. ALD enables the application of a conformal coating of substantially uniform thickness, and this coating is porosity-free on all types of components having complex shapes and high aspect ratio features.

[0016] In some embodiments, ALD may be used with a rare earth metal-containing precursor and a reactant consisting of or containing oxygen, fluorine, or nitrogen to grow or deposit a coating containing rare earth metals. The rare earth metal-containing precursor may include yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, or dysprosium. To grow or deposit an additional or alternative coating, ALD may be used with a precursor to deposit an adhesive layer having the same or similar material as the constituent material of the substrate to be deposited. For example, an aluminum-containing precursor and a nitrogen-containing reactant may be used to form AlN, or an aluminum-containing precursor and an oxygen-containing reactant may be used to form aluminum oxide (Al2O3). To grow or deposit a stack layer or wear-resistant layer on top of the adhesive layer, ALD may be used with one or more precursors containing rare earth metals. In some embodiments, sputtering, ion-assisted deposition, plasma spray coating, or CVD may be used to deposit the wear-resistant layer. The stacked layer may have alternating thin layers of a rare earth metal-containing material and another oxide, fluoride, or nitride material (such as Al2O3, AlN, Y2O3, YF3, etc.).

[0017] In one embodiment, the rare earth metal-containing layer has a polycrystalline structure. In another embodiment, the rare earth metal-containing layer may have an amorphous structure. The rare earth metal-containing layer may contain yttrium, erbium, lanthanum, lutetium, scandium, gadolinium, samarium, and / or dysprosium. For example, the rare earth metal-containing layer may contain yttria (Y2O3), yttrium fluoride (YF3), yttrium oxyfluoride (YF3). x O y F z ), yttrium zirconium oxide (YZrO), erbium oxide (Er2O3), erbium fluoride (ErF3), erbium oxyfluoride (Er x O y F z ), erbium aluminum oxide (Er3Al5O 12), dysprosium oxide (Dy2O3), dysprosium fluoride (DyF3), dysprosium oxyfluoride (Dy x O y F z ), gadolinium oxide (Gd2O3), gadolinium fluoride (GdF3), gadolinium oxyfluoride (Gd x O y F z ), may also include scandium oxide (Sc2O3), scandium fluoride (ScF3), scandium oxyfluoride (ScOF), etc. In various embodiments, the rare earth metal layer is polycrystalline Y2O3, YF3, or Y x O y F z In other embodiments, the rare earth metal layer is amorphous Y2O3, YF3, or Y x O y F z In one embodiment, the rare earth metal-containing material may be co-deposited with another material. For example, the rare earth metal-containing oxide may be mixed with one or more other rare earth compounds (such as Y2O3, gadolinium oxide (Gd2O3), and / or erbium (e.g., Er2O3)). For coating, the yttrium-containing oxide may be, for example, Y x Dy y O z , Y x Gd y O z or Y x W y O z This may also be done. The yttrium-containing oxide may be Y2O3 having a cubic structure of space group Ia-3(206). The subscripts x, y, and z may be independently set to values ​​in the range of 0.1 to 10, for example.

[0018] In one embodiment, the rare earth metal-containing layer is Y2O3, Y x Zr y O z YZrOF, Y3Al5O 12 (YAG), Y4Al2O9(YAM), YF3, Y x O y F z Er2O3, Er3Al5O 12(EAG), ErF3, Er x O y F z , La2O3, Lu2O3, Sc2O3, ScF3, Sc x O y F z It is one of Gd2O3, Sm2O3Dy2O3, or Nd2O3. In addition, the rare earth metal-containing layer is YAlO3 (YAP), Er4Al2O9 (EAM), ErAlO3 (EAP), Gd4Al2O9, GdAlO3, Nd3Al5O 12 The materials may be ceramic compounds consisting of Nd4Al2O9, NdAlO3, a solid solution of Y4Al2O9 and Y2O3-ZrO2, or other coating compositions described herein, as well as ternary varieties of lanthanum, lutetium, scandium, gadolinium, samarium, or dysprosium, or other rare earth metal-containing compounds discussed herein. Any of the aforementioned rare earth metal-containing materials may contain trace amounts of other materials. These other materials include ZrO2, Al2O3, SiO2, B2O3, Er2O3, Nd2O3, Nb2O5, CeO2, Sm2O3, Yb2O3, or other oxides.

[0019] In some embodiments, the rare earth metal-containing layer contains amounts of Y2O3, ZrO2, and / or Al2O3 selected from the following compositions: 50-75 mol% of Y2O3, 10-30 mol% of ZrO2, and 10-30 mol% of Al2O3; 40-99 mol% of Y2O3, 1-60 mol% of ZrO2, and 0-10 mol% of Al2O3; 60-75 mol% of Y2O3, 20-30 mol% of ZrO2, and 0-5 mol% of Al2O3; or 60-70 mol% of Y2O3, 30-40 mol% of ZrO2, and 0-10 mol% Al2O3 in the range of 50-60 mol%, Y2O3 in the range of 50-60 mol%, and ZrO2 in the range of 40-50 mol%, or Y2O3 in the range of 40-60 mol%, ZrO2 in the range of 30-50 mol%, and Al2O3 in the range of 10-20 mol%, or Y2O3 in the range of 40-50 mol%, ZrO2 in the range of 20-40 mol%, and Al2O3 in the range of 20-40 mol%, or Y2O3 in the range of 70-90 mol%, ZrO2 in the range of 0-20 mol%, and Al2O3 in the range of 10-20 mol% It is either O3, or Y2O3 in the range of 60-80 mol%, ZrO2 in the range of 0-10 mol%, and Al2O3 in the range of 20-40 mol%, or Y2O3 in the range of 40-60 mol%, ZrO2 in the range of 0-20 mol%, and Al2O3 in the range of 30-40 mol%, or Y2O3 in the range of 30-60 mol%, ZrO2 in the range of 0-20 mol%, and Al2O3 in the range of 30-60 mol%, or Y2O3 in the range of 20-40 mol%, ZrO2 in the range of 20-80 mol%, and 0-60 mol Al2O3 in the range of 1% or Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 20-30 mol%, and Al2O3 in the range of 50-60 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 20-30 mol%, and Al2O3 in the range of 40-50 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 10-20 mol%, and Al2O3 in the range of 50-60 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 10-20 mol%,and Al2O3 in the range of 40-50 mol%, Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 20-30 mol%, and Al2O3 in the range of 50-60 mol%, Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 20-30 mol%, and Al2O3 in the range of 40-50 mol%, Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 10-20 mol%, and 50- Al2O3 in the range of 60 mol%, Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 10-20 mol%, Al2O3 in the range of 40-50 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 40-50 mol%, Al2O3 in the range of 10-20 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 40-50 mol%, and in the range of 20-30 mol% It is either Al2O3 in the range of 0-10 mol%, Y2O3 in the range of 50-60 mol%, and Al2O3 in the range of 10-20 mol%, Y2O3 in the range of 0-10 mol%, ZrO2 in the range of 50-60 mol%, and Al2O3 in the range of 20-30 mol%, Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 40-50 mol%, and Al2O3 in the range of 10-20 mol% It is either Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 40-50 mol%, and Al2O3 in the range of 20-30 mol%, or Y2O3 in the range of 10-20 mol%, ZrO2 in the range of 50-60 mol%, and Al2O3 in the range of 10-20 mol%, or Y2O3 in the range of 10-20 mol%, or ZrO2 in the range of 50-60 mol%, and Al2O3 in the range of 20-30 mol%.

[0020] In some embodiments, the rare earth metal-containing layer contains amounts of Y2O3 and ZrO2 selected from the following compositions: namely, Y2O3 in the range of 1 to 99 mol% and ZrO2 in the range of 1 to 99 mol%, Y2O3 in the range of 1 to 50 mol% and ZrO2 in the range of 50 to 99 mol%, Y2O3 in the range of 50 to 99 mol% and ZrO2 in the range of 1 to 50 mol%, Y2O3 in the range of 50 to 75 mol%, and ZrO2 in the range of 25 to 50 mol%, or Y2O3 in the range of 40 to 61 mol%. And ZrO2 in the range of 39-60 mol%, Y2O3 in the range of 65-99 mol%, and ZrO2 in the range of 1-35 mol%, Y2O3 in the range of 65-80 mol%, and ZrO2 in the range of 20-35 mol%, Y2O3 in the range of 60-70 mol%, and ZrO2 in the range of 30-40 mol%, Y2O3 in the range of 1-11 mol%, and ZrO2 in the range of 89-99 mol%. or Y2O3 in the range of 11-21 mol% and ZrO2 in the range of 79-89 mol%, or Y2O3 in the range of 21-31 mol% and ZrO2 in the range of 69-79 mol%, or Y2O3 in the range of 31-41 mol% and ZrO2 in the range of 59-69 mol%, or Y2O3 in the range of 41-51 mol% and ZrO2 in the range of 49-59 mol%, or Y2O in the range of 51-61 mol% 3. ZrO2 in the range of 39-49 mol%, Y2O3 in the range of 61-71 mol%, and ZrO2 in the range of 29-39 mol%, Y2O3 in the range of 71-81 mol%, and YF3 in the range of 19-29 mol%, or Y2O3 in the range of 81-91 mol%, and YF3 in the range of 9-19 mol%, or Y2O3 in the range of 91-99 mol%, and YF3 in the range of 1-9 mol%.

[0021] In some embodiments, the rare earth metal-containing layer contains amounts of Y2O3, ZrO2, Er2O3, Gd2O3, and / or SiO2 selected from the following compositions: namely, 40-45 mol% of Y2O3, 0-10 mol% of ZrO2, 35-40 mol% of Er2O3, 5-10 mol% of Gd2O3, and 5-15 mol% of SiO2; or 30-60 mol% of Y2O3, 0-20 mol% of ZrO2, 20-50 mol% of Er2O3, 0-10 mol% of Gd2O3, and 0-30 mol% of SiO2; or 30-45 mol% of Y2O3, 5-15 mol% of ZrO2, 25-60 mol% of Er2O3, and 0-25 mol% of Gd2O3.

[0022] In some embodiments, the rare earth metal-containing layer contains amounts of Y2O3 and YF3 selected from the following compositions: namely, Y2O3 in the range of 1 to 99 mol% and YF3 in the range of 1 to 99 mol%, Y2O3 in the range of 1 to 10 mol% and YF3 in the range of 90 to 99 mol%, Y2O3 in the range of 11 to 20 mol% and YF3 in the range of 80 to 89 mol%, Y2O3 in the range of 21 to 30 mol% and YF3 in the range of 70 to 79 mol%, Y2O3 in the range of 31 to 40 mol%, and YF3 in the range of 60 to 69 mol%, or Y2O3 in the range of 41 to 50 mol%. The YF3 is in the range of 50-59 mol%, Y2O3 is in the range of 51-60 mol%, YF3 is in the range of 40-49 mol%, Y2O3 is in the range of 61-70 mol%, YF3 is in the range of 30-39 mol%, Y2O3 is in the range of 71-80 mol%, YF3 is in the range of 20-29 mol%, Y2O3 is in the range of 81-90 mol%, YF3 is in the range of 10-19 mol%, Y2O3 is in the range of 91-99 mol%, and YF3 is in the range of 1-9 mol%.

[0023] The ranges mentioned above are illustrative, and it should be understood that there may be some variation in the limits of each compound. For example, if it is stated as "Y2O3 in the range of 41-50 mol%", it should be understood to include all possible amounts of Y2O3 from 41 mol% to 50 mol%, and from approximately 41 mol% to approximately 50 mol%, taking into account approximations and measurement uncertainties.

[0024] Refer again to Figure 1. In one embodiment, the processing chamber 100 includes a chamber body 102 and a shower head 130, which surround an internal volume 106. The shower head 130 may include a shower head base and a shower head gas distribution plate. Alternatively, the shower head 130 may be replaced with a lid and nozzle in some embodiments, or with a plurality of fan-shaped shower head compartments and a plasma generation unit in other embodiments. The chamber body 102 may be manufactured from aluminum, stainless steel, or other suitable material such as titanium. The chamber body 102 generally includes side walls 108 and a bottom 110. One or more of the shower head 130 (or lid and / or nozzle), side walls 108, and / or bottom 110 may have a coating layer.

[0025] The outer liner 116 may be positioned adjacent to the side wall 108 to protect the chamber body 102. The outer liner 116 may be manufactured and / or coated with a coating layer. In one embodiment, the outer liner 116 is made of aluminum oxide.

[0026] The exhaust port 126 may be defined within the chamber body 102, and the internal volume 106 may be connected to the pump system 128 via the exhaust port 126. The pump system 128 may include one or more pumps and throttle valves, which may be used to exhaust and regulate the pressure of the internal volume 106 of the processing chamber 100.

[0027] The shower head 130 may be supported on the side wall 108 of the chamber body 102. The shower head 130 (or lid) may be open to allow access to the internal volume 106 of the processing chamber 100, or closed to provide airtightness to the processing chamber 100. A gas panel 158 may be connected to the processing chamber 100 to supply processing gas and / or cleaning gas to the internal volume 106 via the shower head 130 or the lid and nozzle. The shower head 130 may be used in a processing chamber used for dielectric etching (etching dielectric materials). The shower head 130 comprises a gas distribution plate (GDP) 133, the GDP 133 having a plurality of gas supply holes 132 throughout its entirety. The shower head 130 may comprise the GDP 133 bonded to a shower head base 104 made of aluminum or anodized aluminum. The GDP 133 may be made of Si or SiC, or of a ceramic such as Y2O3, Al2O3, or YAG.

[0028] For processing chambers used for conductive etching (etching conductive materials), a lid may be used instead of a showerhead. The lid may have a central nozzle that fits into the central hole of the lid. The lid may be made of ceramic. The ceramic may be Al2O3, Y2O3, YAG, or a ceramic compound consisting of a solid solution of Y4Al2O9 and Y2O3-ZrO2. The nozzle may also be made of ceramic. The ceramic may be Y2O3, YAG, or a ceramic compound consisting of a solid solution of Y4Al2O9 and Y2O3-ZrO2. Optionally, the lid, showerhead base 104, GDP 133, and / or the nozzle may be coated with a ceramic coating.

[0029] Examples of processing gases that can be used to process the substrate in the processing chamber 100 include halogen-containing gases (particularly C2F6, SF6, SiCl4, HBr, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, and SiF4, etc.) as well as gases such as O2 or N2O. The coating layer may be resistant to erosion by some or all of these gases and / or by the plasma generated from these gases. Examples of carrier gases include N2, He, Ar, and other gases that are inert to the processing gas (e.g., non-reactive gases).

[0030] The substrate support assembly 148 is placed in the internal volume 106 of the processing chamber 100 under the shower head 130 or lid. The substrate support assembly 148 holds the substrate 144 during processing. A ring 146 (e.g., a single ring) may cover a portion of the ESC assembly 150 and protect the covered portion from exposure to the plasma during processing. In one embodiment, the ring 146 may be silicon or quartz.

[0031] The inner liner 118 may be coated around the substrate support assembly 148. The inner liner 118 may be made of a halogen-containing gas resistant material (such as the material described for the outer liner 116). In one embodiment, the inner liner 118 may be made from the same material as the outer liner 116. Furthermore, the inner liner 118 may be coated with a ceramic coating.

[0032] In one embodiment, the substrate support assembly 148 comprises a mounting plate 162 supporting a base 152 and an ESC assembly 150. The ESC assembly 150 further comprises a thermally conductive base 164 and an electrostatic pack 166 bonded to the thermally conductive base by an adhesive 138. In one embodiment, the adhesive may be a silicone adhesive. The upper surface of the electrostatic pack 166 is covered by a ceramic coating layer 136 in the illustrated embodiment. In one embodiment, the ceramic coating layer 136 is located on the upper surface of the electrostatic pack 166. In another embodiment, the ceramic coating layer 136 is located on the entire exposed surface of the ESC assembly 150. This exposed surface includes the outer and periphery of the thermally conductive base 164 and the electrostatic pack 166. The mounting plate 162 is connected to the bottom 110 of the chamber body 102 and includes passages for routing utilities (e.g., fluids, power lines, sensor leads, etc.) to the thermally conductive base 164 and the electrostatic pack 166.

[0033] The thermally conductive base 164 and / or electrostatic pack 166 may include one or more optional embedded heating elements 176, embedded insulation 174, and / or conduits 168, 170 to control the lateral temperature profile of the substrate support assembly 148. The conduits 168, 170 are fluidically connected to a fluid source 172, which may circulate a temperature-regulating fluid through the conduits 168, 170. In one embodiment, the embedded insulation 174 may be placed between the conduits 168, 170. The heating elements 176 are regulated by a heater power supply 178. The temperature of the thermally conductive base 164 may be controlled using the conduits 168, 170 and the heating elements 176 to heat and / or cool the electrostatic pack 166 and the substrate (e.g., wafer) 144 being processed. The temperatures of the electrostatic pack 166 and the thermally conductive base 164 may be monitored using a plurality of temperature sensors 190, 192. A controller 195 may be used to monitor these multiple temperature sensors.

[0034] The electrostatic pack 166 may further include a plurality of gas channels, such as grooves, mesas, and other surface features. These gas channels may be formed on the upper surface of the pack 166 and / or the ceramic coating layer 136. The gas channels may be fluidically connected to a heat transfer (or back surface) gas source, such as helium, through holes drilled in the pack 166. During operation, back surface gas may be supplied to the gas channels at a controlled pressure to enhance heat transfer between the electrostatic pack 166 and the substrate 144. The electrostatic pack 166 includes at least one clamp electrode 180 controlled by a chucking power supply 182. The electrode 180 (or other electrodes located on the pack 166 or base 164) may be further connected to one or more high-frequency power supplies 184, 186 via a matching circuit 188 to maintain the plasma formed from the processing gas and / or other gases in the processing chamber 100. Power supplies 184 and 186 can generally generate high-frequency signals with frequencies ranging from approximately 50 kHz to approximately 3 GHz and power outputs of up to approximately 10,000 watts.

[0035] ALD technology enables conformal coatings with relatively uniform thickness and zero porosity (i.e., non-porous) on the surfaces of chamber components and on features with complex geometries, including internal shapes unattainable by conventional in-line deposition techniques. The coatings are plasma-resistant, reducing plasma interactions without affecting performance and potentially improving the durability of the components. Thin coatings deposited with ALD can maintain the electrical properties, relative shape, and geometric configuration of the components without interfering with their function. The coatings can also reduce the volatility of the component materials and may form reactants with lower vapor pressures than the component's substrate material.

[0036] The plasma resistance of a coating can be measured by its "etching rate" (ER). This etching rate is measured in micrometers per hour (μm / hr) or angstroms per hour (Å / hr). The measurement period is the entire duration that the coated component is in operation and exposed to plasma. The processing time before measurement may vary. For example, measurements may be performed before processing, or at approximately 50 processing hours, or at approximately 150 processing hours, or at approximately 200 processing hours, etc. Variations in the composition of the coating grown or deposited on the heater support and / or other components can result in a number of differing plasma resistance or erosion rate values. Furthermore, even with a single composition, coatings exposed to various plasmas may have a number of differing plasma resistance or erosion rate values. For example, a plasma-resistant material may have a first plasma resistance or erosion rate associated with a first type of plasma, and a second plasma resistance or erosion rate associated with a second type of plasma.

[0037] Figure 2A shows one embodiment of deposition process 200 by ALD technology for growing or depositing a coating on an article (e.g., a heater support, an entire heater assembly, or part of an electrostatic chuck). Figure 2B shows one embodiment of deposition process 201 by ALD technology, in which a multilayer plasma-resistant coating is grown or deposited on an article. Figure 2C shows another embodiment of deposition process 202 by ALD technology as described herein.

[0038] There are various types of ALD (Automated Laser Development) processes, and a specific type can be selected based on several factors. These factors include the surface to be coated, the coating material, and the chemical interaction between the surface and the coating material. The general principle of various ALD methods involves a process in which a thin film layer is grown by repeatedly exposing the surface to be coated to pulses of a gaseous chemical precursor. Here, the precursor chemically reacts with the surface one at a time in a self-limiting manner.

[0039] Figures 2A-2C show an article 210 having a surface. Article 210 may represent various materials for semiconductor processing chamber components, where the semiconductor processing chamber components include, but are not limited to, the high-temperature heater support and / or the entire surface of the heater ensemble within the processing chamber. Article 210 may be made from AlN-containing materials, dielectrics such as ceramics, metal-ceramic composites (e.g., Al2O3 / SiO2, Al2O3 / MgO / SiO2, SiC, Si3N4, AlN / SiO2, etc.), metals (aluminum, stainless steel, etc.), graphite, or other suitable materials, and may further include materials such as AlN, Si, SiC, Al2O3, and SiO2. In one embodiment, article 210 is a high-temperature heater made of 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, or about 150 W / mK to about 200 W / mK, or about 180 W / mK. The specific heat capacity of the heater material may also be about 0.15 cal / g°C to about 0.30 cal / g°C at 25°C, or about 0.20 cal / g°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 CTE of about 4.6 to about 5.7 μm / m°C. In one embodiment, article 210 is a high-temperature heater for a semiconductor processing chamber, manufactured, for example, from an AlN ceramic material. Such materials react with fluorine plasma (e.g., NF3) in the processing chamber during cleaning to form AlF3. AlF3 has a high vapor pressure, and therefore this reactant sublimes and deposits on other components in the chamber. In subsequent processing steps, the deposited AlF3 detaches, peels off, or is otherwise pulled away from other chamber components, contaminating the wafers there with particles.

[0040] In the case of ALD, both the adsorption of the precursor onto the surface and the reaction between the adsorbed precursor and the reactant may be referred to as "half-reactions." During the first half-reaction, the precursor is rhythmically delivered to the surface of article 210 for a period long enough for the precursor to be completely adsorbed onto the surface. Adsorption is self-limiting because the precursor is adsorbed to a finite number of available locations on the surface, forming a uniform and continuous adsorption layer on the surface. Locations where the precursor is already adsorbed cannot be used to further adsorb the same precursor unless and / or until the adsorbed locations undergo a process that creates new available locations on the uniform and continuous coating. Typical processes include plasma treatment, treatment by exposing the uniform and continuous adsorption layer to radicals, or introduction of a different precursor adsorbed on the surface that can react with the latest uniform and continuous layer.

[0041] In some embodiments, two or more precursors are injected together and adsorbed onto the surface of article 210. Excess precursors are discharged, and then an oxygen-containing reactant (or fluorine-containing reactant) is injected and reacts with the adsorbate to form a constituent layer (e.g., Y2O3-Al2O3). This new layer can be used for the adsorption of precursors in the next cycle.

[0042] In Figure 2A, article 210 may be introduced into the first precursor 260 over a first period until the surface of article 210 is completely adsorbed by the first precursor 260 to form an adsorption layer 214. Subsequently, article 210 may be introduced into the first reactant 265 to react with the adsorption layer 214 and grow a solid layer 216. (For example, to completely grow or deposit the layer 216. Hereinafter, the terms grow and deposit may be used interchangeably.) In the case of a single-layer coating, the first precursor 260 may be Y2O3, YF3, or Y x O y F zIt may also be used as a precursor for rare earth metal-containing materials such as yttrium precursors, zirconium precursors, and erbium precursors. When an adhesive layer is used, the first precursor 260 may be an Al-containing precursor in some embodiments. If layer 216 is an oxide, the first reactant 265 may be oxygen, water vapor, ozone, oxygen radicals, or another oxygen source. If layer 216 contains AlN, the first reactant 265 may be, for example, NH3 nitrogen radicals or another nitrogen source. If layer 216 is a fluoride, a fluorine-containing reactant may be used. Thus, layer 216 can be formed using ALD. Layer 216 may be a single-layer coating or one layer (i.e., an adhesive layer) of a multilayer coating.

[0043] In one embodiment, where layer 216 is an AlN adhesive layer, article 210 (e.g., the surface of a high-temperature heater) may be introduced into a first precursor 260 (e.g., trimethylaluminum i.e., a TMA precursor) over a first period until all reaction sites on the surface of the article are consumed. The remaining first precursor 260 is discharged, and then a first reactant 265 of NH3 is injected into the reactor to start a second half-cycle. After the NH3 molecules react with the Al-containing adsorbent layer produced in the first half-reaction, the AlN layer 216 is formed.

[0044] Layer 216 can be uniform, continuous, and conformal. Layer 216 is porosity-free (e.g., has zero porosity) or, in some embodiments, has near-zero porosity (e.g., porosity from 0% to 0.01%). In some embodiments, after a single ALD deposition cycle, layer 216 can have a thickness ranging from less than one atomic layer to several atoms. Some organometallic precursor molecules are large. After reacting with reactant 265, large organic ligands may disappear, leaving much smaller metal atoms. A single complete ALD cycle (e.g., including the introduction of precursor 260 followed by the introduction of reactant 265) can form a layer with an average thickness smaller than a single unit cell. For example, the growth rate of AlN monolayers grown with TMA and NH3 is typically about 1.0 Å / cycle, while the AlN lattice constants are a=3.111 Å and c=4.981 Å (for a hexagonal structure).

[0045] Multiple complete ALD deposition cycles may be performed to deposit a thicker layer 216. Each complete cycle (e.g., including the introduction and efflux of precursor 260, introduction of reactant 265, and efflux again) adds one to several atoms to the thickness. As shown, up to n complete cycles may be performed to grow layer 216, where n is an integer greater than 1. In some embodiments, the thickness of layer 216 may be about 5 nm to about 10 μm, or about 25 nm to about 5 μm, or about 50 nm to about 500 nm, or about 75 nm to about 200 nm. In some embodiments, the thickness of the coating may be about 50 nm, or about 75 nm, or about 100 nm, or about 125 nm, or about 150 nm. If layer 216 is an adhesive layer, the thickness of the adhesive layer may be about 1 nm to about 50 nm, or about 2 nm to about 25 nm, or about 5 nm to about 10 nm. In certain embodiments, the thickness of the adhesive layer is approximately 1 nm, or approximately 5 nm, or approximately 10 nm, or approximately 15 nm.

[0046] If layer 216 is a coating containing one or more rare earth metal-containing materials, layer 216 provides strong plasma resistance and mechanical properties without significantly affecting the thermal and electrical properties of the heater. Layer 216 protects the components from erosion, enhances or maintains dielectric strength, and may be resistant to cracking at temperatures up to about 500°C, or up to about 550°C, or between about 500°C and about 550°C. If layer 216 is an adhesive layer, it can improve the adhesion of the rare earth metal-containing layer (or stack layer) to the components and prevent cracking of the coating at temperatures up to about 650°C.

[0047] Figure 2B shows a deposition process 201 including the deposition of layer 216 as an adhesive or barrier layer, as described with reference to Figure 2A. However, the deposition process 201 in Figure 2B further includes the deposition of a further layer 220 to form a multilayer plasma-resistant coating. Thus, after layer 216 is completed, the article 210 having layer 216 may be introduced into one or more additional precursors 270 over a second period until layer 216 is completely adsorbed in the one or more additional precursors 270 to form an adsorption layer 218. Subsequently, the article 210 may be introduced into reactants 275 to react with the adsorption layer 218 to grow a solid rare-earth metal-containing oxide layer 220 (for example, to fully grow or deposit a second layer 220). This solid rare-earth metal-containing oxide layer 220 is also referred to as the second layer 220 for simplicity. In this embodiment, layer 216 may be an adhesive or barrier layer containing AlN. Therefore, the second layer 220 is completely grown or deposited on top of layer 216 using ALD. In one embodiment, the precursor 270 may be a yttrium-containing precursor used in the first half-cycle, and the reactant 275 may be H2O used in the second half-cycle.

[0048] The second layer 220 may form a yttrium-containing oxide layer or another rare-earth metal-containing oxide layer. This layer can be uniform, continuous, and conformal. The porosity of the second layer 220 may be very low, less than 1%, less than 0.1% in some embodiments, about 0%, or even non-porous in some embodiments. The second layer 220 may have a thickness of less than one atom to several atoms (e.g., 2-3 atoms) after one complete ALD deposition cycle. Multiple ALD deposition steps may be performed to deposit a thicker second layer 220, with each step adding one to several atoms to the thickness. As shown in the figure, the second layer 220 may have a target thickness by repeating the complete deposition cycle m times, where m is an integer greater than 1. In some embodiments, the second layer 220 may have a thickness of about 5 μm from about 5 ALD cycles (e.g., about 0.9 Å / cycle and 2 half-reactions). If the second layer 220 is the first layer of the stack, its thickness may be approximately 500 nm from about 5 ALD cycles, or approximately 250 nm from about 6 ALD cycles, or approximately 100 nm from about 7 ALD cycles, or approximately 50 nm from about 8 ALD cycles. In various embodiments, the thickness of the second layer 220 of the stack is approximately 5 to 15 ALD cycles, or approximately 6 to 14 ALD cycles, or approximately 7 to 13 ALD cycles, or approximately 8 to 10 ALD cycles.

[0049] The ratio of the thickness of the second layer 220 to the thickness of the layer 216 may range from 200:1 to 1:200. A higher ratio of the thickness of the second layer 220 to the thickness of the layer 216 (e.g., 200:1, 100:1, 50:1, 20:1, 10:1, 5:1, 2:1, etc.) results in better corrosion and erosion resistance. On the other hand, a lower ratio of the thickness of the second layer 220 to the thickness of the layer 216 (e.g., 1:2, 1:5, 1:10, 1:20, 1:50, 1:100, 1:200) results in better heat resistance (e.g., improved resistance to cracking and / or delamination caused by thermal cycling).

[0050] The second layer 220 may be any of the rare earth metal-containing oxide layers discussed herein. For example, the second layer 220 may be Y2O3, YF3, or Y x O y F z alone or in combination with one or more other rare earth metal materials. In some embodiments, the second layer 220 is a single-phase material formed from a mixture of at least two rare earth metal-containing precursors co-deposited by ALD (e.g., one or more combinations of Y2O3, Er2O3, and Al2O3). For example, the second layer 220 may be Y x Er y O z or Y x Al y O z of which one may be. In one embodiment, layer 216 is amorphous AlN and the second layer 220 is a polycrystalline or amorphous yttrium-containing oxide compound (e.g., Y2O3, Y x Al y O z , Y x Er y O z , etc.), alone or in a single phase with one or more other rare earth metal-containing materials. In another embodiment, article 210 is a graphite article, layer 216 is amorphous carbon, and the second layer 220 is a polycrystalline or amorphous yttrium-containing compound (e.g., Y2O3, YZrO, YF3, Y x Al y O z , Y x Er y O z etc.). Layer 216 can not only enhance adhesion but also function as a stress relaxation layer deposited prior to the deposition of the yttrium-containing oxide layer.

[0051] In some embodiments, the second layer 220 may include Er2O3, Y2O3, or Al2O3. In some embodiments, the second layer 220 is Er x Al y O z (e.g., Er3Al5O 12 ), Y x Al y Oz and Y x Er y O z or Er a Y x Al y O z is at least one multi-component material of (for example, single-phase solid solutions of Y2O3, Al2O3, and Er2O3).

[0052] In some embodiments, the thickness of layer 216 may be from about 1 nm to about 50 nm, or from about 2 nm to about 25 nm, or from about 5 nm to about 10 nm. In certain embodiments, the thickness of layer 216 is about 1 nm, or about 5 nm, or about 10 nm, or about 15 nm. The thickness of the rare earth metal-containing layer may be from about5 nm to about 10 μm, or from about 25 nm to about 5 μm, or from about 50 nm to about 500 nm, or from about 75 nm to about 200 nm. In some embodiments, the thickness of the second layer 220 may be about 50 nm, or about 75 nm, or about 100 nm, or about 125 nm, or about 150 nm. In certain embodiments, the total thickness of the coating including layer 216 and the second layer 220 may be about 50 nm, or about 75 nm, or about 100 nm, or about 125 nm, or about 150 nm.

[0053] Referring to FIG. 2C, in some embodiments, the multilayer coating includes three or more layers. Specifically, the coating may include a stack including a series of alternating layers of another material (for example, AlN, ZrO, Y2O3, or other compounds disclosed herein) and rare earth metal-containing oxide layers, or may include a series of alternating layers of layer 216 and rare earth metal-containing oxide layers. In some embodiments, the rare earth metal-containing oxide layer is a layer of alternating sub-layers. For example, the rare earth metal-containing oxide layer may be a series of alternating sub-layers of Y2O3 and AlN, a series of alternating sub-layers of Y2O3 and ZrO2, or a series of alternating sub-layers of Y2O3 and Al2O3.

[0054] Refer to Figure 2C. Article 210 having layer 216 may be inserted into the deposition chamber. Layer 216 may be formed as described with reference to Figure 2A or Figure 2B. Article 210 may be introduced into one or more precursors 280 containing one or more rare earth metal materials for a period of time until layer 216 is completely adsorbed on one or more precursors 280 to form layer 222. Subsequently, article 210 may be introduced into reactant 282 to react with layer 222 and grow layer 224. Thus, the rare earth metal-containing layer 224 is completely grown or deposited on layer 216 using ALD. In one embodiment, precursor 280 may be a yttrium-containing precursor used in the first half-cycle, and reactant 282 may be H2O used in the second half-cycle. The rare earth metal-containing layer 224 may be a first oxide of Y2O3, Er2O3, ZrO2, or another oxide.

[0055] Article 210 having layer 216 and metal oxide layer 224 may be introduced into one or more precursors 284 for a period of time until layer 224 is completely adsorbed on one or more precursors 284 to form layer 226. Subsequently, article 210 may be introduced into reactant 286 to react with layer 226 and grow an additional layer 228. Thus, the additional layer 228 (which may be made of the same material as layer 224) is completely grown or deposited on top of the rare earth metal-containing layer 224 using ALD.

[0056] As shown in the diagram, the deposition of the rare earth metal-containing layer 224 and the aluminum oxide layer 228 may be repeated n times to form an alternating layer stack 237, where n is an integer greater than 2, and n represents a finite number of layers selected based on the target thickness and properties. The alternating layer stack 237 may be considered as a rare earth metal-containing oxide layer containing multiple alternating sublayers. Thus, the precursor 280, reactant 284, precursor 284 and reactant 286 may be introduced repeatedly in a continuous manner to grow or deposit additional alternating layers 230, 232, 234, 236, etc. Each of the layers 224, 224, 230, 232, 234, 236, etc. may be a very thin layer with an average thickness ranging from less than one atomic layer to several atomic layers.

[0057] The alternating layers 224-236 described above have a 1:1 ratio. Here, there is a single layer of the first metal oxide for each scattered layer. However, in other embodiments, there may be different ratios between different types of layers, such as 2:1, 3:1, or 4:1. For example, in one embodiment, two Y2O3 layers may be deposited for each scattered layer of a different material. Furthermore, the stack 237 of the alternating layers 224-236 has been described as having two types of metal layers alternately in a continuous sequence. However, in other embodiments, three or more types of metal layers may be deposited in the alternating stack 237. For example, the stack 237 may contain three different alternating layers.

[0058] After the alternating layer stack 237 is formed, an annealing treatment may be performed to diffuse the alternating layers of different materials into each other, forming a composite oxide having a single phase or multiple phases. Thus, after the annealing treatment, the alternating layer stack 237 can become a single rare earth metal-containing oxide layer 238. For example, if the layers in the stack are Y2O3 and Al2O3, the resulting rare earth metal-containing oxide layer 238 will be Y3Al5O 12 (YAG) phase may be included.

[0059] Each layer of the rare-earth metal-containing material can have a thickness of about 5 to 10 angstroms and can be formed by performing about 1 to about 10 ALD treatment cycles, where each cycle forms a nanolayer (or slightly smaller or larger than a nanolayer) of the rare-earth metal-containing material. In one embodiment, each layer of the rare-earth metal-containing oxide is formed using about 6 to about 8 ALD cycles. Each scattered layer can be formed in about 1 to about 2 ALD cycles (or several ALD cycles) and can have a thickness of less than one atom to several atoms. Each layer of the rare-earth metal-containing material may have a thickness of about 5 to 100 angstroms, and each layer of the second oxide may have a thickness of about 1 to 20 angstroms in some embodiments and 1 to 4 angstroms in further embodiments. The stack 237 of the alternating layers may have a total thickness of about 5 nm to about 3 μm. Thin scattered layers between the layers of the rare-earth metal-containing material can prevent crystal formation in the rare-earth metal-containing layers. This allows for the growth of amorphous yttria layers.

[0060] In the embodiments described with reference to Figures 2A-2C, the surface reaction (e.g., half-reaction) is carried out sequentially, and in some embodiments, the various precursors and reactants are not in contact. Before introducing a new precursor or reactant, the chamber in which the ALD treatment is carried out may be purged with an inert carrier gas (such as nitrogen or air) to remove any unreacted precursors and / or surface precursor reaction byproducts. The precursors differ for each layer, and the second precursor for the yttrium-containing oxide layer or other rare-earth metal-containing oxide layer may be a mixture of two rare-earth metal-containing precursors to promote the co-deposition of these compounds and form a single-phase material layer. In some embodiments, at least two precursors are used, in other embodiments, at least three precursors are used, and in further embodiments, at least four precursors are used.

[0061] ALD processing may be performed at various temperatures depending on the type of processing. The optimal temperature range for a particular ALD processing is called the "ALD temperature window." Temperatures below the ALD temperature window may result in low growth rates and non-ALD type deposition. At temperatures above the ALD temperature window, reactions may occur by CVD mechanisms. The ALD temperature window may be in the range of about 100°C to about 650°C. In some embodiments, the ALD temperature window is about 20°C to about 200°C, or about 25°C to about 150°C, or about 100°C to about 120°C, or about 20°C to 125°C.

[0062] ALD processing enables conformal coatings of uniform thickness on articles and surfaces with complex geometric shapes, high aspect ratio holes (e.g., pores), and three-dimensional structures. By exposing each precursor to the surface for a sufficient amount of time, the precursors disperse and can react completely with the entire surface, including all of the complex three-dimensional features. The exposure time used to achieve conformal ALD on high aspect ratio structures is proportional to the square of the aspect ratio and can be predicted using modeling techniques. Furthermore, ALD technology is advantageous over other commonly used coating technologies because it allows for material synthesis in specific compositions or formulations on demand, eliminating the need for the long and difficult production of raw materials (such as powder materials and sintered targets). In some embodiments, ALD is used to coat articles with aspect ratios ranging from approximately 3:1 to 300:1.

[0063] Using the ALD technology described herein, Y x Al y O z (For example, Y3 Al5O 12 ), Y x W y O z , Y x W y F z , or Y w W x O y F zSuch multi-component films can be grown, deposited, or co-deposited. For this purpose, for example, rare earth metal-containing oxides are grown alone or in combination with one or more other oxides using a suitable mixture of precursors. The other oxides are described above and will be described in more detail in the following examples.

[0064] In some embodiments, a wear-resistant layer containing one or more rare-earth metal-containing materials may be deposited on top of the stack layer. The wear-resistant layer may have a thickness of about 5 nm to about 5000 nm, about 5 nm to about 1000 nm, about 100 nm to about 5000 nm, or about 100 nm to about 500 nm.

[0065] Herein, we refer to various high-temperature components that can be coated with rare-earth metal-containing coatings by ALD. Figure 3 shows an exemplary susceptor 300 for an ALD chamber. The susceptor 300 has a protective coating (such as the rare-earth metal-containing ceramic coating described herein). In one embodiment, the thin-film protective coating coats only the top surface of the susceptor. Alternatively, the thin-film protective coating coats both the top and bottom surfaces of the susceptor. The thin-film protective layer may also coat the side walls and inner surface of the susceptor. The susceptor 300 may be used to support and uniformly heat multiple wafers simultaneously. The susceptor 300 may be radiantly heated using a resistance heating element or a lamp. In one embodiment, the susceptor 300 includes a thermally conductive base such as graphite. The susceptor 300 may have a disc-like shape that can be large enough to support multiple substrates (e.g., multiple wafers). In one embodiment, the diameter of the susceptor is greater than 1 meter.

[0066] The susceptor 300 may include one or more recesses (also called pockets) 301-306. Each recess may be configured to support a wafer or other substrate during processing. In the illustrated embodiment, the susceptor 300 includes six recesses 301-306. However, other susceptors may have more or fewer recesses. Each of the recesses 301-306 includes various surface features. Examples of surface features of recess 301 include an outer ring 308, a plurality of mesas 306, and channels or gas channels between the mesas 306. In some embodiments, the features may have a height of about 10-80 micrometers.

[0067] The recesses 301-306 and surface features (e.g., mesa 306 and outer ring 308) may be fluidically coupled to a heat transfer (or backside) gas source (e.g., He through holes drilled in the susceptor 300). During operation, the backside gas can be supplied to the gas channel at a controlled pressure to enhance heat transfer between the susceptor 300 and the substrate.

[0068] The susceptor 300 may further include lift pin holes 310. For example, the susceptor 300 may have three lift pin holes, which may support lift pins (e.g., Al2O3 lift pins). The lift pins enable the loading and unloading of wafers into and out of the susceptor 300. The susceptor 300 may also include a recess 315, which may be used to fasten the susceptor to a rotating spindle. The recess 315 may include a hole 320, which may be used to mechanically secure the susceptor 300 to the rotating spindle.

[0069] In some embodiments, the susceptor 300 may be formed from graphite and coated using ALD to form a rare-earth metal-containing coating. To promote adhesion of the rare-earth metal-containing coating to the susceptor 300, an adhesive layer (such as a carbon layer deposited by CVD) may be formed on the susceptor 300.

[0070] Figure 4 shows coated components of the heater assembly 400 according to various embodiments. The heater assembly 400 may be provided by adapting the processing chamber 100. For example, the heater assembly 400 may be placed under the showerhead 130 or lid within the internal volume 106 of the processing chamber 100. The heater assembly 400 includes a support 405 for holding a substrate (e.g., a wafer) during processing, and the support 405 is attached to the end of an internal shaft 410. The internal shaft 410 may be placed within the internal volume of the processing chamber 100. The internal shaft 410 may be attached to an external shaft 415 via a flange 420, and the external shaft 415 may be coupled to the chamber body 102 of the processing chamber 100 by a flange (not shown). The support 405 includes a mesa 406, which is connected to electrical components (not shown) embedded in the heater material of the support 405. All surfaces that may be exposed to corrosive gases and plasma within the processing chamber are coated with coating 425 (e.g., ceramic coating) according to the embodiments described herein.

[0071] The support 405, shafts 410, 415, and flange 420 may be made from a heater material containing AlN (e.g., AlN ceramic). In one embodiment, the support 405 may comprise a metal heater and sensor layer sandwiched between AlN ceramic layers. Such assemblies may be sintered in a high-temperature furnace to create a single, integrated assembly. These layers may include a heater circuit, sensor elements, a grounding surface, a high-frequency grid, and a combination of metal and ceramic flow channels. The heater assembly 400 can provide heater temperatures up to about 650°C under vacuum conditions (e.g., about 1 milliliter to about 5 torr).

[0072] The coating 425 may include one or more rare earth metal-containing oxide materials on the surface of the support 405 and / or on the entire surface of the heater assembly 400, which may be exposed to corrosive gases or plasma in the processing chamber. The coating 425 may be a single-layer coating or a multi-layer coating, and generally has little to no effect on the thermal properties of the material of the support 405 or on the performance of the heater assembly 400. In some embodiments, the coating may have a thickness of about 5 nm to about 10 μm, or about 25 nm to about 5 μm, or about 50 nm to about 500 nm, or about 75 nm to about 200 nm. In some embodiments, the thickness of the coating may be about 50 nm, or about 75 nm, or about 100 nm, or about 125 nm, or about 150 nm.

[0073] Figure 5 shows a cross-sectional side view of an exemplary component 500 with an internal channel formed therein, according to various embodiments. Component 500 is a typical example of the top surface of a susceptor, heater, or electrostatic chuck, as described above. For example, component 500 may be a susceptor, and the total diameter of this susceptor may be 1 meter. It should be understood that the features of component 500 are not depicted to a specific scale, and are simply intended to illustrate the internal channel and its connections within component 500.

[0074] In some embodiments, the body 502 of the component 500 may be formed from one or more materials. In some embodiments, the body 502 may be formed from a single material. Examples of such materials include graphite, aluminum oxide, silicon carbide, and metal oxides (such as ceramics or rare-earth metal-containing ceramics).

[0075] The component 500 has multiple channels formed for gas flow. These channels may be used to generate a vacuum or distribute gas. The channels include a central opening 508 penetrating the lower surface 506 of the component 500, a main opening 510 intersecting the central opening 508, a first cavity 518, a second cavity 522, a cavity conduit 520 connecting the first cavity 518 to the second cavity 522, and a chucking hole 516 along the upper surface 504 of the component 500. In some embodiments, parts of the component 500 may be manufactured separately and joined together to define the internal channels.

[0076] The main opening 510 provides a gas passage between the central opening 508 and other channels. These other channels include other channels (not shown) that may be formed within the component 500. In some embodiments, the main opening 510 passes through the component 500 at least partially or completely. The main opening 510 may be formed, for example, using a gun drill. A plug 512 is provided to seal the end of the main opening 510.

[0077] The depth of the main opening 510 may be, for example, in the range of about 0.3 meters to about 0.8 meters, and in some embodiments, it may be about 0.5 meters. The diameter of the main opening 510 may be in the range of about 3 mm to about 10 mm, and in some embodiments, it may be about 6 mm. In some embodiments, the aspect ratio (depth:diameter) of the main opening 510 may be in the range of 250:1 to 30:1, or any range between ratios where the first number is an integer and the second number is 1 (for example, 200:1 to 40:1, 100:1 to 70:1, etc.).

[0078] The depth of the central opening 508 from the bottom surface 506 to the inner surface 514 may be, for example, in the range of about 15 mm to about 22 mm, and in certain embodiments, it may be about 18 mm. The diameter of the central opening 508 may be, for example, in the range of about 2 mm to 5 mm, and in certain embodiments, it may be about 3 mm. In certain embodiments, the aspect ratio of the central opening may be in the range of 22:1 to 4:1, or any range between ratios where the first number is an integer and the second number is 1 (for example, 18:1 to 6:1, 10:1 to 5:1, etc.).

[0079] In some embodiments, the first cavity 518 and the second cavity 522 are connected by a cavity conduit 520, which is distributed to allow for a uniform gas flow through the chucking hole 516. In some embodiments, the chucking hole 516 may be used to provide a vacuum for securing the wafer to the upper surface 504 of the component 500. In some embodiments, the length of each of the first cavity 518 or the second cavity 522 may range from about 50 mm to about 100 mm, and in certain embodiments, it may be about 75 mm. The diameter of each of the first cavity 518 or the second cavity 522 may range, for example, from about 2 mm to 6 mm, and in certain embodiments, it may be about 3 mm. In certain embodiments, the aspect ratio of the central opening may range from 50:1 to 8:1, or any range between ratios where the first number is an integer and the second number is 1 (e.g., 50:1 to 10:1, 30:1 to 20:1, etc.). In some embodiments, the diameters of the chucking hole 516 and the hollow conduit 520 may be in the range of approximately 0.5 mm to approximately 3 mm, approximately 0.5 mm to 1 mm, approximately 1 mm to approximately 3 mm, or approximately 1 mm to approximately 1.5 mm.

[0080] During use in plasma processing, the component 500 is exposed to plasma, and a plasma-resistant coating (e.g., a ceramic coating as described herein) is beneficial against this plasma. Since the internal channels of the component 500 are also likely to be exposed to plasma, it is beneficial to coat their inner surfaces 514. For example, coating 530 is shown to coat the upper surface 504 and the lower surface 506 of the component 500. To coat the inner surface 514, which is difficult to reach in line-of-sight deposition processing, coating 530 may be deposited using ALD processing as described herein.

[0081] Figure 6A shows a cross-sectional view of a coated article 600 having a single coating 604 coated on article 602. Similarly, Figure 6B shows a cross-sectional view of a coated article 650 having multiple coatings coated on article 652. Articles 602 and 652 may represent any of the articles / components described herein and may be formed from suitable materials such as AlN, Al2O3, graphite, or rare-earth metal-containing ceramics.

[0082] Coating 604 may be an ALD coating containing any of the rare earth metal-containing ceramics discussed herein. For example, coating 604 may be an ALD Y2O3 coating, and article 602 may be formed from AlN.

[0083] Coatings 654 and 656 may be formed from the same or different materials. In some embodiments, one or more of coatings 654 and 656 may contain rare earth metal-containing ceramics. In some embodiments, additional coatings may be formed. In some embodiments, coating 654 may be an adhesive layer that facilitates bonding between article 652 and coating 656. For example, article 652 may be formed from graphite (e.g., crystalline or semicrystalline graphite) with coating 654 being a CVD carbon bonding layer containing amorphous carbon formed by CVD, and coating 656 being an ALD Y2O3 coating or another ALD rare earth oxide coating. The carbon bonding layer may be a pyrolysis carbon bonding layer. This pyrolysis carbon bonding layer can facilitate bonding of the ALD rare earth oxide coatings. In another embodiment, article 652 may be formed from AlN with coating 654 being an ALD Al2O3 coating, and coating 656 being an ALD Y2O3 coating.

[0084] In some embodiments, each of articles 602 and 652 may have a different CTE than its respective coating. The greater the mismatch in CTE between two adjacent materials, the more likely one of those materials will eventually crack, delaminate, or lose its bond with the other. In some embodiments, the coating 604 may be formed, for example, to minimize the mismatch in CTE between the coating 604 and article 602, so that the difference between the two CTEs is within 10% of the CTE of article 602. This can be achieved by varying the ratio of rare-earth metal-containing compounds present in the coating 604, as will be explained in more detail with respect to Figure 7.

[0085] Figure 7 shows a method 700 for forming a ceramic coating using atomic layer deposition according to various embodiments. Method 700 may be used to coat any article / component described herein.

[0086] Method 700 begins with block 710, where an article is supplied. The article may be any of the articles / components described herein (e.g., high-temperature heater, electrostatic chuck, susceptor). The article may be formed from one or more materials (e.g., AlN, Al2O3, graphite). The article may be a component represented, for example, as article 210 in Figures 2A-2C. In one embodiment, the article may be a heater, electrostatic chuck, nozzle, gas distribution plate, shower head, electrostatic chuck component, chamber wall, liner, liner kit, gas line, lid, chamber lid, nozzle, single ring, process kit ring, base, shield, plasma screen, flow equalizer, cooling base, chamber viewport, bellows, faceplate, or selective modulator. In another embodiment, the article may be a high-temperature susceptor (e.g., represented by susceptor 300 in Figure 3). In another embodiment, the article is a high-temperature heater (for example, represented by heater assembly 400 in Figure 4). In yet another embodiment, the article is an electrostatic chuck (for example, represented by ESC assembly 150 in Figure 1).

[0087] In block 720, select one or more rare earth metal-containing ceramic compounds. The ceramic compounds are Y2O3, Y x Zr y O z YZrOF, Y3Al5O 12 Y4Al2O9, YF3, Y x O y F z Er2O3, Er3Al5O 12 ErF3, ZrO2, HfO2, E x O y F z , La2O3, Lu2O3, Sc2O3, ScF3, Sc x O y F z It may contain one or more of Gd2O3, Sm2O3, and Dy2O3.

[0088] In the optional block 730, by selecting two ceramic compounds and the molar ratio between them, a ceramic coating containing the selected molar ratio of ceramic compounds is deposited on the surface of an article by atomic layer deposition, resulting in a ceramic coating having a CTE within 10% of the article's first CTE. By adjusting the ratio of ceramic compounds, it is possible to produce ALD coatings that substantially reduce or eliminate the CTE mismatch between the coating and the article.

[0089] The CTEs of various ceramic compounds in the range of 40°C to 400°C are as follows: Y2O3 is 7.2 × 10⁻⁶. -6 / ℃, ZrO2 is 10.5 × 10 -6 / ℃, Al2O3 is 7.2 × 10 -6 / ℃, AlN is 4.6 × 10 -6 / ℃, SiC is 4×10 -6 / ℃, SiN is 2.8 × 10 -6 / ℃, La2O3 is 12.6 × 10 -6 / ℃, and Er2O3 is 6 × 10 -6 / ℃. Preparation of a coating containing two compounds in different ratios is a linear combination of the CTEs of the compounds, i.e., CTE coating =R A CTE A +R B CTE B It can also be calculated as follows: Here, R is the mole percent of a particular compound. For example, the molar ratio of Y2O3 to ZrO2 in a 3:1 ratio is calculated as follows: 0.66 × 7.2 + 0.33 × 10.5 = 8.2 × 10 -6 / ℃.

[0090] In some embodiments, the first ceramic compound comprises a rare earth oxide, and the second ceramic compound comprises a rare earth oxyfluoride or rare earth fluoride. In some embodiments, the first ceramic compound comprises Y2O3, and the second ceramic compound comprises Y x O y F z Includes.

[0091] In block 740, ALD is performed (for example, as described with respect to Figures 2A-2C) to deposit a ceramic compound, a combination of ceramic compounds, or a combination of two compounds in a selected ratio onto the article to produce a coated article. In some embodiments, an additional coating is deposited. For example, multiple layers of a rare earth metal-containing compound may be formed. In some embodiments, an adhesive layer is first deposited onto the article. This adhesive layer may be deposited by ALD, CVD, or other deposition methods (e.g., a CVD carbon layer).

[0092] In some embodiments, the compounds are deposited in alternating layers by ALD to achieve a desired ratio. For example, to achieve a Y2O3 to ZrO2 ratio of 3:1, three alternating deposits of Y2O3 followed by one deposit of ZrO2 are performed to achieve the desired thickness. In some embodiments, the compounds are co-deposited or deposited by co-adding precursors of the compounds (e.g., using a mixture of a first metal-containing precursor and a second metal-containing precursor).

[0093] The following embodiments are provided to aid in understanding the embodiments described herein and should not be construed as specifically limiting the embodiments described herein and claimed. Any modifications, including the substitution of all currently known or subsequently developed equivalents, and any changes or minor modifications of the scheme in experimental designs, which are within the scope of the embodiments incorporated herein, should be considered within the scope of the embodiments incorporated herein. These embodiments can be achieved by performing the above method 700.

[0094] The coated article may further include a ceramic coating (e.g., a rare earth metal-containing coating). In one embodiment, the composition of the coating is Y2O3, Y x Zr y O z YZrOF, Y3Al5O 12 Y4Al2O9, ZrO2, YF3, Y x O y F zEr2O3, Er3Al5O 12 , ErF3, E x O y F z , La2O3, Lu2O3, Sc2O3, ScF3, Sc x O y F z , Gd2O3, GdF3, Gd x O y F z It may be Sm2O3, Dy2O3, or a combination thereof. In one embodiment, the coating may be deposited using ALD (for example, as described with respect to Figures 4A-4C).

[0095] The coated article may further include an adhesive layer between the constituent elements and the coating layer. In one embodiment, the adhesive layer is an amorphous carbon layer.

[0096] In one exemplary embodiment, a 2 μm thick ALD coating of polycrystalline Y2O3 is formed on an AlN substrate.

[0097] In another exemplary embodiment, a 50 nm thick ALD coating of polycrystalline YZrO is formed on an Al2O3 substrate.

[0098] In another exemplary embodiment, a 160 nm thick ALD coating of polycrystalline YF3 is formed on an AlN substrate.

[0099] In another exemplary embodiment, an ALD coating of Y2O3, YZrO, or YF3 is formed on an Al2O3 buffer layer formed on an AlN substrate. The Al2O3 buffer layer can prevent the formation of a reaction interface layer between the rare earth metal-containing coating and the AlN substrate.

[0100] In another exemplary embodiment, an ALD coating of crystalline Y2O3 is formed on an adhesive layer. This adhesive layer is formed on a crystalline graphite substrate. The adhesive layer may be an amorphous carbon layer deposited by CVD. This amorphous carbon layer facilitates bonding between the crystalline graphite and Y2O3. This exemplary embodiment is shown in Figure 8. Figure 8 shows a transmission electron microscope image of the graphite substrate on which the adhesive layer and ceramic layer are formed.

[0101] This particular embodiment, which uses a conformal coating of rare-earth metal-containing ceramic on a graphite article with a carbon layer placed between them, is advantageous over other types of intermediate layers, such as a SiC layer. Graphite is relatively inexpensive, has high thermal conductivity and high thermal shock resistance, but is porous and contains impurities. Furthermore, graphite is readily eroded by fluorine-based plasma, so coating the graphite body to fill the pores and providing a plasma-resistant layer to prevent contamination of the treated substrate by graphite impurities is beneficial. While conformal plasma-resistant coatings as described herein are beneficial for coating graphite articles, the porosity and roughness of the graphite surface can degrade the quality of the coating. By utilizing an amorphous carbon adhesive layer, which is denser than the underlying sintered graphite substrate, adhesion between the ceramic layer and the substrate under high-temperature operation can be improved.

[0102] These aforementioned embodiments are not intended to be limiting, and other embodiments not expressly disclosed may be included. These other embodiments may be one of several combinations or rearrangements of the various embodiments described herein.

[0103] The above description provides numerous specific and detailed examples of particular systems, components, methods, etc., intended to help readers understand some of the embodiments of this disclosure. However, it will be apparent to those skilled in the art that at least some of the embodiments of this disclosure can be implemented without such specific and detailed descriptions. In other examples, well-known components or methods are not described in detail or are presented in simple block diagram form to avoid unnecessarily obscuring the embodiments of this disclosure. Therefore, the specific and detailed descriptions are merely illustrative. Certain embodiments may differ from these illustrative descriptions but are still considered to be within the scope of this disclosure.

[0104] It should be noted that different references to “one” or “one” embodiment in this disclosure do not necessarily refer to the same embodiment, and such references mean at least one. Where “one embodiment” or “one embodiment” is used throughout this specification, it means that a particular configuration, structure, or characteristic described in relation to that embodiment is included in at least one embodiment. Thus, where the expression “in one embodiment” or “in one embodiment” appears in various places throughout this specification, it does not necessarily mean that all of them refer to the same embodiment. Furthermore, the term “or” is intended to mean inclusive “or” rather than exclusive “or.” Where the terms “about” or “approximately” are used in this specification, it is intended that the presented nominal values ​​are accurate within a range of ±1%.

[0105] Although the operations of the methods described herein are shown and described in a specific order, the order of the operations of each method may be changed so that certain operations are performed in reverse order, or some operations are performed at least partially in parallel with others. In another embodiment, instructions or suboperations of different operations may be performed intermittently and / or alternately.

[0106] It should be understood that the above description is illustrative and not limiting. By reading and understanding the above description, many other embodiments will become apparent to those skilled in the art. Accordingly, the scope of this disclosure should be determined based on the appended claims, together with the entire scope of equivalents to which such claims are entitled.

Claims

1. Coated articles, An article suitable for use in a processing chamber and formed to be mechanically coupled inside the processing chamber, Outer appearance and, An internal channel including an inner surface that is difficult to reach in line of sight deposition processing, wherein the outer and inner surfaces of the internal channel correspond to surfaces that are exposed to plasma when used in the processing chamber during plasma processing, An article having carbon adhesive layers formed on the outer and inner surfaces of the article, A multilayer coating formed on a carbon adhesive layer, comprising an alternating continuous layer of at least two types of layer materials, At least one layer material is Y ｘ , ３ , ３ , ３ , ｚ , ｚ , ｘ , ｘ , ３ , ３ , １２ , ３ , ｚ , ２ , ５ , ２ , ｙ , ２ , ３ , ｙ , ２ , ３ , ２ , ｙ , ２ , ３ O ３ 、Y ｘ Zr ｙ O ｚ 、YZrOF、Y ３ Al ５ O １２ 、Y ４ Al ２ O ９ 、YF ３ 、YOF、Y ｘ O ｙ F ｚ 、Er ２ O ３ 、Er ３ Al ５ O １２ 、ErF ３ 、Er ｘ O ｙ F ｚ 、La ２ O ３ 、Lu ２ O ３ 、Sc ２ O ３ 、ScF ３ 、Sc ｘ O ｙ F ｚ 、Gd ２ O ３ 、GdF ３ 、Gd ｘ O ｙ F ｚ 、Sm<000​​​​​​​ A coated article comprising a multilayer coating that is uniform, conformal, and non-porous.

2. The coated article according to claim 1, wherein the aspect ratio of the main openings forming the flow path of the internal channel is 30:1 to 250:

1.

3. The coated article according to claim 1, wherein the article is a high-temperature article selected from a heater, an electrostatic chuck, or a susceptor.

4. The coated article according to claim 1, wherein the multilayer coating has a thickness of approximately 100 nm to approximately 5000 nm.

5. The items are AlN, Al ２ O ３ The coated article according to claim 1, comprising a composition selected from the group consisting of , and graphite.

6. The coated article according to claim 1, wherein the thermal expansion coefficient of the multilayer coating is within 10% of the thermal expansion coefficient of the article.

7. The coated article according to claim 1, wherein the multilayer coating comprises a first type of layer material and a second type of layer material, the first type of layer material being Y2O3 and the second type of layer material being YxOyFz.

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