Yttria-based coating and bulk compositions

Abstract

This paper describes plasma-resistant coating and bulk compositions that provide enhanced resistance to erosion and corrosion after exposure to harsh chemical environments (such as hydrogen-based and / or halogen-based chemicals) and / or after exposure to high-energy plasma. This paper also describes a method for coating articles with plasma-resistant coatings using electron beam ion-assisted deposition, physical vapor deposition, or plasma spraying. This paper further describes a method for processing wafers that results in a reduced number of yttrium-based particles.

Description

[0001] This application is a divisional application of application number 202180046285.0, filed on June 28, 2021, entitled "Yttrium Oxide-Based Coatings and Bulk Compositions". Technical Field

[0002] Embodiments of this disclosure generally relate to yttrium oxide-based protective coatings and bulk compositions for enhancing defect performance in semiconductor processing applications. Background Technology

[0003] In the semiconductor industry, devices are manufactured using multiple processes that produce structures of ever-decreasing size. As device geometry shrinks, controlling process uniformity and repeatability becomes increasingly challenging.

[0004] Existing manufacturing processes expose semiconductor processing chamber components (also known as processing chamber parts) to high-energy invasive plasma and / or corrosive environments that can be detrimental to the integrity of the semiconductor processing chamber components, and can further lead to challenges in controlling process uniformity and repeatability.

[0005] Therefore, certain semiconductor processing chamber components (e.g., gaskets, doors, covers, etc.) are coated with yttrium-based protective coatings or made from yttrium-based bulk compositions. Yttrium oxide (Y₂O₃) is commonly used in etched chamber components due to its excellent resistance to erosion and / or sputtering in invasive plasma environments.

[0006] It would be advantageous to obtain protective coatings and bulk compositions that provide both physical resistance to sputtering caused by high-energy invasive plasma and chemical resistance to corrosion caused by corrosive environments. Summary of the Invention

[0007] In some embodiments, this disclosure relates to a ceramic body composed of single-phase bulk yttrium aluminum garnet (YAG). The single-phase bulk crystalline YAG comprises yttrium oxide with a molar concentration varying from about 35 mol% to 40 mol% and alumina with a molar concentration varying from 60 mol% to 65 mol%. The single-phase bulk crystalline YAG has a density of about 98% or greater and a hardness greater than about 10 GPa.

[0008] In some embodiments, this disclosure relates to a method for coating a chamber component. The method includes performing electron beam ion-assisted deposition (electron beam IAD) to deposit a plasma-resistant protective coating. The plasma-resistant protective coating comprises a single-phase amorphous dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. The plasma-resistant protective coating has a porosity of substantially 0% (e.g., less than 0.1%) and an adhesion strength greater than about 25 MPa.

[0009] In some embodiments, this disclosure relates to a method for coating a chamber component. The method includes performing plasma spraying or physical vapor deposition (PVD) to deposit a plasma-resistant protective coating on the chamber component. The plasma-resistant protective coating comprises a dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. The plasma-resistant protective coating is at least about 90% amorphous. The average total number of yttrium-based particles released from the plasma-resistant protective coating after exposure to corrosive chemicals is less than 3 per 500 RF hours. Attached Figure Description

[0010] This disclosure is illustrated by way of example rather than limitation in the accompanying drawings, in which the same reference numerals indicate similar elements. It should be noted that in this disclosure, different references to "an" or "one" embodiments do not necessarily refer to the same embodiment, and such references imply at least one.

[0011] Figure 1 A cross-sectional view of one embodiment of the processing chamber is depicted.

[0012] Figure 2 The phase diagram of aluminum oxide and yttrium oxide is shown.

[0013] Figure 3 A cross-sectional side view of an article (e.g., a cover) covered by one or more protective coatings is shown.

[0014] Figure 4A A perspective view of a chamber cover having a protective coating or block composition according to an embodiment is shown.

[0015] Figure 4B A cross-sectional side view of a chamber cover having a protective coating or block composition according to an embodiment is shown.

[0016] Figure 5A1 , Figure 5A2 , Figure 5B1 and Figure 5B2 The chemical resistance of various bulk components subjected to accelerated chemical stress testing is shown.

[0017] Figure 6A Deposition mechanisms applicable to various deposition techniques utilizing high-energy particles, such as ion-assisted deposition (IAD), are described.

[0018] Figure 6B A schematic diagram of an IAD deposition apparatus is depicted.

[0019] Figure 7A1 , Figure 7A2 , Figure 7B1 , Figure 7B2 , Figure 7C1 , Figure 7C2 , Figure 7D1 and Figure 7D2 The chemical resistance of various anti-plasma protective coatings deposited via IAD is demonstrated after undergoing accelerated chemical stress testing.

[0020] Figure 8 A schematic diagram of a physical vapor deposition technique, according to an embodiment, is shown.

[0021] Figure 9 A schematic diagram of a plasma spraying deposition technique, according to an embodiment, is depicted.

[0022] Figure 10A1 , Figure 10A2 , Figure 10B1 , Figure 10B2 , Figure 10C1 , Figure 10C2 , Figure 10D1 and Figure 10D2 The chemical resistance of various plasma-resistant protective coatings deposited via plasma spraying after undergoing accelerated chemical stress testing is demonstrated.

[0023] Figure 11 A method for coating a chamber component with an anti-plasma protective coating, according to an embodiment, is shown.

[0024] Figure 12 A method for processing a wafer in a processing chamber according to an embodiment is described, the processing chamber comprising at least one chamber component coated with an anti-plasma protective coating or having a bulk composition.

[0025] Figure 13A The illustration shows total yttrium-based particles from a cap coated with an anti-plasma protective coating during a 770-hour radio frequency chamber marathon run of invasive chemicals, according to an embodiment.

[0026] Figure 13B The illustration shows total yttrium-based particles from a nozzle coated with an anti-plasma protective coating according to an embodiment during a 460-hour radio frequency chamber marathon run of invasive chemicals.

[0027] Figure 13C The illustration shows the total yttrium-based particles from a kit with a cap and nozzle coated with an anti-plasma protective coating according to an embodiment during treatment with invasive chemicals, compared to a kit with a cap and nozzle coated with a Y2O3-ZrO2 solid solution.

[0028] Figure 14The illustration shows the total yttrium-based particles from a kit with a cap, nozzle, and liner coated with an anti-plasma protective coating according to an embodiment during treatment with invasive chemicals, compared to kits coated with various comparative yttrium-based compositions.

[0029] Figure 15 Normalized erosion rates (nm / RF hours) were depicted for a comparison of a bulk YAG composition (bulk YAG), a first optimized bulk YAG composition (bulk YAG1 (optimized)) prepared by field-assisted sintering (FAS) according to an embodiment, and a second optimized bulk YAG composition (bulk YAG2 (optimized)) prepared by hot isostatic pressing (HIP) according to an embodiment. Detailed Implementation

[0030] Semiconductor manufacturing processes expose semiconductor processing chamber components to high-energy invasive plasma environments and corrosive environments. To protect the processing chamber components from these invasive environments, the chamber components are coated with protective coatings or made of bulk components resistant to such invasive plasma and corrosive environments.

[0031] Yttrium oxide (Y₂O₃) is commonly used in coatings for chamber components (e.g., etched chamber components) due to its excellent corrosion resistance. However, despite its good corrosion resistance, yttrium oxide is not chemically stable in invasive etching chemicals. Free radicals such as fluorine, chlorine, and bromine readily chemically erode yttrium oxide, leading to the formation of yttrium-based particles. These particles contribute to defects in etching applications. Therefore, various industries (e.g., the logic industry) have begun to set stringent specifications for yttrium-based defects on product wafers.

[0032] To meet these stringent specifications, it is beneficial to identify protective coating and bulk compositions that provide physical resistance to sputtering due to high-energy invasive plasma and chemical resistance to chemical erosion through invasive chemical environments.

[0033] In this disclosure, anti-plasma protective coating compositions and bulk compositions have been identified as having improved chemical stability compared to pure yttrium oxide (Y2O3) and other yttrium-based materials, while maintaining physical resistance to high-energy invasive plasmas compared to pure alumina (Al2O3).

[0034] In some embodiments, the protective coating described herein is a corrosion-resistant and erosion-resistant coating comprising a substantially amorphous (i.e., at least about 90% amorphous) dopant of alumina and yttrium oxide. In some embodiments, the protective coating is completely amorphous (i.e., 100% amorphous). Due to the substantially amorphous nature of the protective coating, greater flexibility may exist in tuning the amounts of alumina and yttrium oxide to achieve optimal chemical resistance (e.g., to harsh chemical environments) and physical resistance (e.g., to harsh plasma environments), as the composition is not limited to the bond arrangement of crystalline compositions or to... Figure 2 The phases depicted in the alumina-yttrium oxide phase diagram shown.

[0035] Without being interpreted as a limitation, it is believed that introducing more aluminum-based components into the coating makes it more chemically resistant to harsh chemical environments (e.g., acidic, hydrogen-based, and halogen-based environments), and that yttrium-based components in the coating provide it with physical resistance to high-energy plasma environments.

[0036] In one embodiment, the protective coating described herein may have a chemical composition of yttrium aluminum garnet (YAG) or (in terms of the amounts of yttrium, aluminum, and oxygen in the composition) close to that of YAG, but with mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, adhesion strength, crystallinity / amorphous properties, etc.) and chemical properties (e.g., chemical resistance) that provide enhanced chemical resistance and / or enhanced plasma resistance in invasive chemical environments (e.g., invasive halogen and / or hydroacidic environments) compared to other yttrium-based coatings and / or other YAG coatings prepared and / or deposited differently in accordance with this disclosure.

[0037] The anti-plasma protective coatings described herein can be deposited via ion-assisted deposition, physical vapor deposition, or plasma spraying. The deposition technique can be selected and optimized to obtain anti-plasma protective coatings with certain properties, such as high density, very low internal and / or surface porosity (or no porosity), amorphous content, adhesion strength, roughness, breakdown voltage, hermeticity, hardness, flexural strength, chemical stability, and physical stability.

[0038] The anti-plasma protective coating described herein can be applied to any number of chamber components and is particularly suitable for coating overlays and / or nozzles and / or liners. Processing wafers in a processing chamber having at least one chamber component coated with the anti-plasma protective coating described herein significantly reduces the number of yttrium-based particles generated during processing, reduces the wafer defect rate due to the presence of yttrium-based particles, reduces variability between multiple processes regarding yttrium-based particle formation and the associated defect rate, increases reliability, increases accuracy, increases reproducibility, increases predictability, increases yield, increases throughput, and reduces cost.

[0039] In some embodiments, this disclosure relates to anti-plasma bulk compositions that have improved chemical stability compared to pure yttrium oxide (Y2O3) and other yttrium-based materials, while maintaining physical resistance to high-energy invasive plasmas compared to pure alumina (Al2O3).

[0040] In some embodiments, any chamber component, and particularly the cap and / or nozzle and / or liner, comprises a ceramic body of single-phase bulk yttrium aluminum garnet (YAG), wherein the single-phase bulk YAG comprises yttrium oxide in molar concentrations varying from 35 mol% to 40 mol% and alumina in molar concentrations varying from 60 mol% to 65 mol%, wherein the single-phase bulk YAG has a density of about 98% or greater and a hardness greater than about 10 GPa. The single-phase bulk YAG disclosed in the embodiments has proven particularly effective and has been shown to be more effective than even other examples of bulk YAG ceramics in terms of chemical resistance and / or plasma erosion resistance. In the embodiments, the bulk ceramic body is fully crystalline. The bulk composition may be the result of a two-step sintering process including hot isostatic pressing (HIP). The process can be optimized to produce a bulk composition with certain properties, for example, such as high density, very low porosity (or substantially no porosity), hardness, chemical stability, and physical stability.

[0041] Even compared to other bulk YAG ceramics, processing wafers in a processing chamber having at least one chamber component made of the bulk composition described herein significantly reduces the number of yttrium-based particles generated during processing, reduces the wafer defect rate due to the presence of yttrium-based particles, reduces the variability between multiple processes regarding yttrium-based particle formation and the associated defect rate, increases reliability, increases accuracy, increases reproducibility, increases predictability, increases yield, increases throughput, and reduces cost.

[0042] Figure 1This is a cross-sectional view of a semiconductor processing chamber 100 having one or more chamber components coated with a plasma-resistant protective coating composition according to embodiments of the present disclosure or made of a bulk composition according to embodiments of the present disclosure. The processing chamber 100 can be used in processes in which an invasive plasma environment and / or an invasive chemical environment is provided. For example, the processing chamber 100 can be a chamber for a plasma etching reactor (also known as a plasma etcher), a plasma cleaner, etc.

[0043] Examples of chamber components that may include a plasma-resistant protective coating include: a substrate support assembly 148, an electrostatic chuck (ESC) 150, a ring (e.g., a processing kit ring or a single ring), a chamber wall, a base, a gas distribution plate, a nozzle, a liner, a liner kit, a shield, a plasma barrier, a flow equalizer, a cooling base, a chamber viewing port, a chamber cover 130, a nozzle, and the like. Any of these chamber components may also be made of a plasma- and chemical-resistant bulk composition according to embodiments described herein. In one particular embodiment, the chamber cover 130 and / or the liner 116 or 118 and / or the nozzle 132 are independently coated with a plasma-resistant protective coating or made of a plasma- and chemical-resistant bulk material according to embodiments described herein.

[0044] In some embodiments, the anti-plasma protective coating, described in more detail below, is a dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. The anti-plasma protective coating can be deposited by ion-assisted deposition (IAD) (such as electron beam ion-assisted deposition (electron beam IAD)), physical vapor deposition (PVD), and plasma spraying. Depending on the deposition technique, the anti-plasma protective coating is at least about 90% amorphous, at least about 92% amorphous, at least about 94% amorphous, at least about 96% amorphous, at least about 98% amorphous, or single-phase 100% amorphous.

[0045] In some embodiments, the anti-plasma protective coating comprises 35 mol% to 40 mol% yttrium oxide and 60 mol% to 65 mol% alumina. In some embodiments, the anti-plasma protective coating comprises 37 mol% to 38 mol% yttrium oxide and 62 mol% to 63 mol% alumina. In some embodiments, the total molar concentration of yttrium oxide and alumina in the anti-plasma protective coating reaches 100 mol%.

[0046] In some embodiments, the plasma-resistant protective coating comprises yttrium oxide in molar concentrations ranging from any of about 35 mol%, about 35.5 mol%, about 36 mol%, about 36.5 mol%, about 37 mol%, or about 37.5 mol% to about 38 mol%, about 38.5 mol%, about 39 mol%, about 39.5 mol%, about 40 mol%, about 45 mol%, about 50 mol%, about 55 mol%, about 60 mol%, about 65 mol%, about 70 mol%, about 75 mol%, about 80 mol%, about 85 mol%, about 90 mol%, or about 95 mol%, or any single value thereof or any subrange thereof.

[0047] In some embodiments, the plasma-resistant protective coating comprises aluminum oxide with a molar concentration ranging from any one of about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 25 mol%, about 30 mol%, about 35 mol%, about 40 mol%, about 45 mol%, about 50 mol%, about 55 mol%, about 60 mol%, about 60.5 mol%, about 61 mol%, about 61.5 mol%, or about 62 mol% to about 62.5 mol%, about 63 mol%, about 63.5 mol%, about 64 mol%, about 64.5 mol%, or about 65 mol%, or any single value thereto or any subrange thereof.

[0048] In some embodiments, the anti-plasma protective coating described herein consists of or is substantially composed of a single-phase amorphous dopant of alumina and yttrium oxide, wherein the alumina is present in the anti-plasma protective coating at a molar concentration varying from about 5 mol% to about 65 mol%, from 60 mol% to 65 mol%, or from 62 mol% to 63 mol%, and the yttrium oxide is present in the anti-plasma protective coating at a molar concentration varying from about 35 mol% to 95 mol%, from 35 mol% to 40 mol%, or from 37 mol% to 38 mol%.

[0049] In some embodiments, the anti-plasma protective coating described herein consists of or substantially of at least about 90% an amorphous dopant of alumina and yttrium oxide, wherein alumina is present in the anti-plasma protective coating at a molar concentration varying from about 5 mol% to about 65 mol%, from 60 mol% to 65 mol%, or from 62 mol% to 63 mol%, and yttrium oxide is present in the anti-plasma protective coating at a molar concentration varying from about 35 mol% to 95 mol%, from 35 mol% to 40 mol%, or from 37 mol% to 38 mol%.

[0050] In some embodiments, the bulk composition described in more detail below comprises a single-phase bulk crystalline yttrium aluminum garnet (YAG) comprising yttrium oxide in molar concentrations ranging from 35 mol% to 40 mol% and alumina in molar concentrations ranging from 60 mol% to 65 mol%. In some embodiments, the bulk composition is highly dense and has a density of about 98% or greater, about 98.5% or greater, about 99% or greater, about 99.5% or greater, or about 100% (e.g., approximately 0% porosity). In some embodiments, the bulk composition has a hardness of about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, or about 13 GPa or greater. In some embodiments, certain properties and characteristics of the bulk composition described herein (such as, but not limited to, density, hardness, etc.) may be modified to vary by up to 30% (e.g., 10 GPa ± 30% from 7 GPa to 13 GPa), up to 25% (e.g., 10 GPa ± 25% from 7.5 GPa to 12.5 GPa), up to 20% (e.g., 10 GPa ± 20% from 8 GPa to 12 GPa), up to 15% (e.g., 10 GPa ± 15% from 8.5 GPa to 11.5 GPa), up to 10% (e.g., 10 GPa ± 10% from 9 GPa to 11 GPa), or up to 5% (e.g., 10 GPa ± 5% from 9.5 GPa to 10.5 GPa). Therefore, the values ​​described for these material properties should be understood as exemplary achievable values.

[0051] In some embodiments, the single-phase bulk crystalline composition may be the result of a two-step sintering process including hot isostatic pressing (HIP). In some embodiments, the sintering process includes pressing raw ceramic powder into a shape (similar to ceramic processing), pressing them into sheets, and firing the ceramic to promote complete densification. The sintering process can be controlled to achieve optimized conditions and bulk composition properties, such as, but not limited to, high yield, high density, improved hardness, improved polishing, surface roughness, improved chemical stability, improved physical stability, and precise and accurate composition.

[0052] In some embodiments, the bulk composition comprises single-phase bulk crystalline yttrium aluminum garnet (YAG) comprising yttrium oxide in molar concentrations ranging from any one of about 35 mol%, about 35.5 mol%, about 36 mol%, about 36.5 mol%, about 37 mol%, or about 37.5 mol% to any one of about 38 mol%, about 38.5 mol%, about 39 mol%, about 39.5 mol%, or about 40 mol% or any single value thereof or any subrange thereof.

[0053] In some embodiments, the bulk composition comprises a single-phase bulk crystalline YAG comprising alumina with a molar concentration varying from any one of about 60 mol%, about 60.5 mol%, about 61 mol%, about 61.5 mol%, or about 62 mol% to about 62.5 mol%, about 63 mol%, about 63.5 mol%, about 64 mol%, about 64.5 mol%, or about 65 mol%, or any single value thereof or any subrange thereof.

[0054] In some embodiments, the bulk composition described herein consists of a single-phase bulk crystalline YAG, which comprises or substantially consists of alumina with a molar concentration from any of about 60 mol%, about 60.5 mol%, about 61 mol%, about 61.5 mol%, or about 62 mol% to about 62.5 mol%, about 63 mol%, about 63.5 mol%, about 64 mol%, about 64.5 mol%, or about 65 mol% and yttrium oxide with a molar concentration from any of about 35 mol%, about 35.5 mol%, about 36 mol%, about 36.5 mol%, about 37 mol%, or about 37.5 mol% to about 38 mol%, about 38.5 mol%, about 39 mol%, about 39.5 mol%, or about 40 mol%.

[0055] In some embodiments, such as as measured by X-ray diffraction (XRD), the described bulk composition is greater than about 90% crystallinity, greater than about 92% crystallinity, greater than about 94% crystallinity, greater than about 96% crystallinity, greater than about 98% crystallinity, greater than about 99% crystallinity, or about 100% crystallinity.

[0056] The crystalline composition of alumina and yttrium oxide follows the principle of Figure 2 The solid lines depicted in the alumina-yttrium oxide phase diagram are shown in the image. Therefore, the bulk composition of yttrium aluminum garnet (YAG) crystallizing at temperatures below approximately 2177 K will be limited to... Figure 2 The solid line A in the figure corresponds to the amounts of alumina and yttrium oxide (approximately 37-38 mol% yttrium oxide and approximately 62-63 mol% alumina). Similarly, the bulk composition of crystalline yttrium aluminum perovskite (YAP) at temperatures below approximately 2181 K will be limited to... Figure 2 The solid line B in the figure corresponds to the amounts of alumina and yttrium oxide (approximately 50 mol% yttrium oxide and approximately 50 mol% alumina). At temperatures below approximately 2223 K, the bulk composition of yttrium aluminum monoclinic (YAM) crystals will be limited to... Figure 2The solid line C corresponds to the amounts of alumina and yttrium oxide (approximately 65 mol% yttrium oxide and approximately 35 mol% alumina). Adding additional alumina or yttrium oxide to the bulk composition corresponding to any of the solid lines A, B, or C results in a mixture of two crystalline phases. For example, from solid line A and temperatures below approximately 2084 K, adding more alumina produces a mixture of crystalline YAG and crystalline alumina (region R1), while adding more yttrium oxide produces a mixture of crystalline YAG and crystalline YAP (region R2). Similarly, from solid line B and temperatures below approximately 2177 K, adding more alumina produces a mixture of crystalline YAG and crystalline YAP (region R2), while adding more yttrium oxide produces a mixture of crystalline YAM and crystalline YAP (region R3). From solid line C and temperatures below approximately 2181 K, adding more alumina produces a mixture of crystalline YAM and crystalline YAP (region R3), while adding more yttrium oxide produces a mixture of crystalline YAM and cubic yttrium aluminum (Cub2) (region R4).

[0057] In some embodiments, the bulk compositions described herein offer greater chemical resistance to corrosive chemicals, such as hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof, compared to other yttrium-based bulk compositions. Figure 5A1 , Figure 5A2 , Figure 5B1 and Figure 5B2 As shown. In some embodiments, the single-phase bulk crystalline YAG disclosed in the embodiments has been shown to provide greater chemical resistance to corrosive chemicals, such as hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof, compared to other examples of bulk YAG ceramics.

[0058] Figure 5A1 and Figure 5A2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 5A1 ) and afterwards ( Figure 5A2 Comparison of bulk YAG with that of solid YAG. Moderate chemical damage was observed in the bulk YAG after accelerated chemical resistance testing. For example, in... Figure 5A2 In this study, approximately 10% of the comparative block YAG was eroded. In other words, in... Figure 5A2 In addition to scratches, there are general changes in appearance that indicate chemical erosion. Figure 5B1 and Figure 5B2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 5B1 ) and afterwards ( Figure 5B2The bulk YAG according to the embodiment. No damage was observed in the bulk YAG after accelerated chemical resistance testing. Figure 5A1 and Figure 5A2 The comparative bulk YAG depicted in the paper has a density of approximately 92-98% and a hardness of approximately 9.3 GPa.

[0059] exist Figure 5B1 and Figure 5B2 The bulk YAG of the present invention described herein is prepared using a two-step sintering process (e.g., including hot isostatic pressing), and has a density of about 98% or greater and a hardness of about 13 GPa (i.e., with...). Figure 5A1 and Figure 5A2 The baseline comparison shows an approximately 33% improvement in hardness compared to YAG. Figure 5B1 and Figure 5B2 The bulk YAG of the present invention, as depicted, exhibits increased yield, a bottom surface roughness of about 10% or less (compared to about 94% in comparative bulk YAG), a side surface roughness of about 15% or less (compared to about 98% in comparative bulk YAG), improved pore quality demonstrated by an improved roughness of less than 50 microinches (compared to 50 microinches using comparative bulk YAG), and significantly reduced porosity compared to comparative bulk YAG. These properties (e.g., surface roughness and improved pore quality) were measured using profilometry. Furthermore, the bulk YAG of the present invention was subjected to [further details needed for accurate translation]. x No yttrium-based particles were observed after 100 RF hours of processing in the etching environment, thus demonstrating enhanced performance in reducing part-related particles.

[0060] In some embodiments, as measured by X-ray diffraction (XRD), the composition of the anti-plasma protective coating described herein is greater than about 90%, greater than about 92%, greater than about 94%, greater than about 96%, greater than about 98%, greater than about 99%, or about 100% amorphous. In some embodiments, the anti-plasma protective coating described herein does not have crystalline regions. Therefore, the anti-plasma protective coating described herein provides the flexibility to incorporate a larger amount of alumina and / or a larger amount of yttrium oxide, and is not limited to... Figure 2 The solid lines and composition mixtures depicted in the alumina-yttrium oxide phase diagram are shown in the figure.

[0061] For example, alumina is believed to provide greater chemical stability to harsh chemical environments, such as acidic, hydrogen-based, and halogen-based environments, so more alumina can be added to form coating compositions with improved chemical stability in harsh chemical environments. On the other hand, yttrium oxide is believed to provide greater physical stability to high-energy plasmas, so more yttrium oxide can be added to form coating compositions with improved physical stability in high-energy plasmas. Due to the amorphous nature of the coating composition, the amounts of alumina and yttrium oxide in the coating can be tuned to protect it while maintaining a substantially single amorphous phase. This is believed to be possible because of the amorphous nature of the coating, where the bonds between atoms can and do change (as opposed to being limited to) amorphous phases. Figure 2 The bond linkages in the crystalline composition of the alumina-yttrium oxide phase diagram are opposite.

[0062] In other words, in some embodiments, adding alumina to the amorphous protective coating having a composition of alumina and yttrium oxide corresponding to solid line A will comprise a single-phase amorphous dopant of yttrium oxide and alumina corresponding to either of the compositions in region R1 (ranging from more than 62 or 63 mol% alumina to less than 100 mol% alumina and from more than 0 mol% yttrium oxide to less than 37 or 38 mol% yttrium oxide), rather than a mixture of two crystalline phases of YAG and alumina as in a bulk crystalline composition. In some embodiments, the single-phase amorphous dopant of yttrium oxide and alumina having the composition in region R1 may be homogeneous or substantially homogeneous.

[0063] Similarly, adding alumina to an amorphous protective coating having a composition of alumina and yttrium oxide corresponding to solid line B will comprise a single-phase amorphous blend of yttrium oxide and alumina corresponding to either of the compositions in region R2 (ranging from more than 50 mol% alumina to less than 62 or 63 mol% alumina and from more than 37 or 38 mol% yttrium oxide to less than 50 mol% yttrium oxide), rather than a mixture of two crystalline phases of YAG and YAP as in a bulk crystalline composition. In some embodiments, the single-phase amorphous blend of yttrium oxide and alumina having the composition in region R2 may be homogeneous or substantially homogeneous.

[0064] Similarly, adding alumina to an amorphous protective coating having a composition of alumina and yttrium oxide corresponding to solid line C will comprise a single-phase amorphous dopant of yttrium oxide and alumina corresponding to either of the compositions in region R3 (ranging from more than 35 mol% alumina to less than 50 mol% alumina and from more than 50 mol% yttrium oxide to less than 65 mol% yttrium oxide), rather than a mixture of two crystalline phases of YAM and YAP as in a bulk crystalline composition. In some embodiments, the single-phase amorphous dopant of yttrium oxide and alumina having the composition in region R3 may be homogeneous or substantially homogeneous.

[0065] In some embodiments, adding yttrium oxide to an amorphous protective coating having a composition of alumina and yttrium oxide corresponding to solid line C will comprise a single-phase amorphous dopant of yttrium oxide and alumina corresponding to either of the compositions in region R4 (ranging from more than 0 mol% alumina to less than 35 mol% alumina and from more than 65 mol% yttrium oxide to less than 100 mol% yttrium oxide), rather than a mixture of two crystalline phases of YAM and Cub2 as in a bulk crystalline composition. In some embodiments, the single-phase amorphous dopant of yttrium oxide and alumina having the composition in region R4 may be homogeneous or substantially homogeneous.

[0066] In one embodiment, the protective coating described herein may have a chemical composition of yttrium aluminum garnet (YAG) or a chemical composition close to that of YAG (in terms of the amounts of yttrium, aluminum, and oxygen in the composition), but with mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, adhesion strength, crystallinity / amorphous properties, etc.) and / or chemical properties (e.g., chemical resistance) that provide enhanced chemical resistance and / or enhanced plasma resistance in invasive chemical environments (e.g., invasive halogen and / or hydroacidic environments) compared to other yttrium-based coatings and / or other YAG coatings prepared and / or deposited in a manner different from that disclosed.

[0067] In some embodiments, the plasma-resistant protective coatings described herein offer greater chemical resistance compared to other yttrium-based coating compositions prepared using the same process, as detailed below with reference to Figures 7 and 10.

[0068] Plasma-resistant protective coatings can be electron beam IAD deposited coatings, PVD deposited coatings, or plasma spray deposited coatings applied over various ceramics, including oxide-based ceramics, nitride-based ceramics, and / or carbide-based ceramics. Examples of oxide-based ceramics include SiO2 (quartz), Al2O3, Y2O3, and so on. Examples of carbide-based ceramics include SiC, Si-SiC, and so on. Examples of nitride-based ceramics include AlN, SiN, and so on. Electron beam IAD coating plug materials can be calcined powders, preforms (e.g., formed by pressing, hot pressing, etc.), sintered bodies (e.g., having a density of 50-100%), or processed bodies (e.g., ceramics, metals, or metal alloys).

[0069] Return to Figure 1 According to one embodiment, as shown in the figure, the cap 130, nozzle 132, and gasket 116 each have anti-plasma protective coatings 133, 134, and 136, respectively. In some embodiments, nozzle 132 is made from any of the bulk compositions described herein. In some embodiments, the nozzle is exclusively made (i.e., 100% of the nozzle) from a bulk composition of single-phase bulk crystalline yttrium aluminum garnet (YAG), said single-phase bulk crystalline yttrium aluminum garnet (YAG) comprising: 1) a molar concentration from any one of about 35 mol%, about 35.5 mol%, about 36 mol%, about 36.5 mol%, about 37 mol%, or about 37.5 mol% to about 38 mol%, about 38.5 mol%, about 39 mol%, or about 39.5 mol%. yttrium oxide varying from any of about 40 mol% or any single value or any subrange thereof; and 2) alumina with a molar concentration varying from any of about 60 mol%, about 60.5 mol%, about 61 mol%, about 61.5 mol%, or about 62 mol% to about 62.5 mol%, about 63 mol%, about 63.5 mol%, about 64 mol%, about 64.5 mol%, or about 65 mol% or any single value or any subrange thereof.

[0070] In some embodiments, it should be understood that any of the other chamber components (such as those listed above) may also include a plasma-resistant protective coating and / or be made of any of the bulk components described herein.

[0071] In one embodiment, the processing chamber 100 includes a chamber body 102 and a cover 130 enclosing an internal volume 106. The chamber body 102 may be made of aluminum, stainless steel, or other suitable materials. The chamber body 102 generally includes sidewalls 108 and a bottom 110. In some embodiments, any of the cover 130, sidewalls 108, and / or bottom 110 may include a plasma-resistant protective coating.

[0072] The outer liner 116 may be disposed adjacent to the sidewall 108 to protect the chamber body 102. The outer liner 116 may be manufactured and / or coated with a plasma-resistant protective coating 136. In one embodiment, the outer liner 116 is made of alumina.

[0073] The vent 126 may be defined within the chamber body 102 and may be coupled to the internal volume 106 to the pumping system 128. The pumping system 128 may include one or more pumps and throttle valves for evacuating and regulating the pressure of the internal volume 106 of the processing chamber 100.

[0074] A cover 130 may be supported on the sidewall 108 of the chamber body 102. The cover 130 may open to allow access to the internal volume 106 of the processing chamber 100 and, when closed, provide a seal for the processing chamber 100. A gas panel 158 may be coupled to the processing chamber 100 to supply processing gas and / or cleaning gas through a nozzle 132 to the internal volume 106. The cover 130 may be a ceramic such as Al2O3, Y2O3, YAG, SiO2, AlN, SiN, SiC, Si-SiC, or a ceramic compound comprising Y4Al2O9 and Y2O3-ZrO2 solid solutions. In one embodiment, the cover 130 may be made of any of the bulk compositions described herein. The nozzle 132 may also be ceramic, such as any of those ceramics mentioned with respect to the cover. In one embodiment, the nozzle 132 may be made of any of the bulk compositions described herein. The cover 130 and / or nozzle 132 may be coated with anti-plasma protective coatings 133 and 134, respectively.

[0075] Examples of processing gases that can be used to process the substrate in processing chamber 100 include halogen-containing gases and hydrogen-containing gases, such as C2F6, SF6, SiCl4, HBr, Br, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, SiF4, H2, Cl2, HCl, HF, etc., as well as other gases such as O2 or N2O. Examples of carrier gases include N2, He, Ar, and other gases inert to the processing gases (e.g., non-reactive gases). A substrate support assembly 148 is disposed in the internal volume 106 of processing chamber 100 below cover 130. The substrate support assembly 148 holds the substrate 144 during processing. A ring 146 (e.g., a single ring) may cover a portion of electrostatic chuck 150 and may protect the covered portion from exposure to plasma during processing. In one embodiment, ring 146 may be silicon or quartz.

[0076] The inner liner 118 may be coated on the periphery of the substrate support assembly 148. The inner liner 118 may be a halogen gas resist material, such as those discussed with reference to the outer liner 116. In one embodiment, the inner liner 118 may be made of the same material as the outer liner 116. Furthermore, in some embodiments, the inner liner 118 may be coated with a plasma-resistant protective coating or may be made of any of the bulk components described herein.

[0077] In one embodiment, the substrate support assembly 148 includes a mounting plate 162 for a support pedestal 152 and an electrostatic chuck 150. The electrostatic chuck 150 further includes a thermally conductive base 164 and an electrostatic disk 166 bonded to the thermally conductive base by an adhesive 138, which in one embodiment may be a polysiloxane adhesive. The mounting plate 162 is coupled to the bottom 110 of the chamber body 102 and includes channels for wiring utilities (e.g., fluid, power lines, sensor wires, etc.) to the thermally conductive base 164 and the electrostatic disk 166.

[0078] The thermally conductive base 164 and / or the electrostatic disk 166 may include one or more optional embedded heating elements 176, embedded thermal isolators 174, and / or conduits 168, 170 to control the lateral temperature distribution of the support assembly 148. The conduits 168, 170 may be fluidly coupled to a fluid source 172, which circulates temperature-regulating fluid through the conduits 168, 170. In one embodiment, the embedded isolator 174 may be disposed between the conduits 168, 170. The heater 176 is regulated by a heater power supply 178. The conduits 168, 170, and heater 176 can be used to control the temperature of the thermally conductive base 164, and to heat and / or cool the electrostatic disk 166 and the substrate (e.g., wafer) 144 being processed. The temperatures of the electrostatic disk 166 and the thermally conductive base 164 may be monitored using multiple temperature sensors 190, 192, which may be monitored using a controller 195.

[0079] The electrostatic disk 166 may further include a plurality of gas channels, such as grooves, mesas, and other surface features, that can be formed in the upper surface of the disk 166. The gas channels can be fluidly coupled to a heat transfer (or back-side) gas (such as He) source via holes drilled in the disk 166. In operation, back-side gas can be supplied to the gas channels under controlled pressure to enhance heat transfer between the electrostatic disk 166 and the substrate 144.

[0080] The electrostatic disk 166 includes at least one clamping electrode 180 controlled by a clamping power supply 182. The electrode 180 (or other electrodes disposed in the disk 166 or base 164) may be further coupled via a matching circuit 188 to one or more RF power supplies 184, 186 for maintaining a plasma formed by process gases and / or other gases within the processing chamber 100. The sources 184, 186 are typically capable of generating RF signals with frequencies from about 50 kHz to about 3 GHz and power up to about 10,000 watts. In some embodiments, the bulk components and / or coating components described herein exhibit high-energy plasma resistance upon exposure (e.g., to power up to about 10,000 watts).

[0081] Figure 3 A cross-sectional side view is shown of an article (e.g., a chamber component, such as a cover and / or door and / or liner and / or nozzle) that may be covered by one or more anti-plasma protective coatings.

[0082] See Figure 3 The body 305 of the chamber component 300 includes a coating stack 306 having a first anti-plasma protective coating 308 and a second anti-plasma protective coating 310. Alternatively, the article 300 may include only a single anti-plasma protective coating 308 on the body 305. In some embodiments, the body 305 is made of any of the bulk components described herein. In embodiments where the body 305 is made of any of the bulk components described herein, the body 305 may or may not be further coated with one or more anti-plasma protective coatings 308, 310.

[0083] In some embodiments, the various chamber components in the processing chamber may be coated with the anti-plasma protective coating described herein and / or made of any of the bulk components described herein, including but not limited to caps, cap liners, nozzles, substrate support assemblies, gas distribution plates, nozzles, electrostatic chucks, shadow frames, substrate support frames, processing kit rings, individual rings, chamber walls, bases, liner kits, shielding, plasma barriers, flow equalizers, cooling bases, chamber viewing ports, or chamber liners.

[0084] In one embodiment, the anti-plasma protective coatings 308 and 310 have a thickness of up to about 300 μm. In a further embodiment, the anti-plasma protective coatings have a thickness of less than about 20 micrometers, such as a thickness between about 0.5 micrometers and about 12 micrometers, a thickness between about 2 micrometers and about 12 micrometers, a thickness between about 2 micrometers and about 10 micrometers, a thickness between about 3 micrometers and about 7 micrometers, a thickness between about 4 micrometers and about 6 micrometers, or any subrange thereof or a single thickness value thereof. In one embodiment, the total thickness of the anti-plasma protective coating stack is 300 μm or less.

[0085] In some embodiments, the anti-plasma protective coating provides complete coverage of the underlying surface and is of uniform thickness. The uniform thickness of the coating across different portions of the coating can be demonstrated by a thickness variation of about 15% or less, about 10% or less, or about 5% or less in one portion of the coating compared to another portion of the coating (or based on the standard deviation derived from multiple thicknesses in different portions of the coating).

[0086] In some embodiments, multiple anti-plasma protective coatings (e.g., 308 and / or 310) are deposited on the body 305 of the article 300 using an electron beam ion-assisted deposition (EB-IAD) process, as per [reference to...]. Figures 6A to 6B More detailed description. The EB-IAD deposited plasma-resistant protective coating(s) may have relatively low film stress (e.g., compared to film stress caused by plasma spraying or sputtering). In some embodiments, the relatively low film stress can result in a very flat lower surface of the body 305, with a curvature of less than about 50 micrometers over the entire body for a 12-inch diameter body. In some embodiments, curvature measurements on the 12-inch wafer indirectly indicate low stress due to low curvature. In some embodiments, the cap flexural strength of a cap coated with the EB-IAD deposited plasma-resistant protective coating is about 412 MPa. In some embodiments, the cap flexural strength may be tested using a bending flexural test.

[0087] In some embodiments, the anti-plasma protective coating described herein does not exhibit any gaps, pinholes, or uncoated areas. In embodiments, as analyzed by cross-sectional morphology, the anti-plasma protective coating deposited by EB-IAD has essentially 0% porosity (i.e., no porosity). This low porosity allows chamber components to provide an effective vacuum seal during processing. Air tightness measurements can be performed using the sealing capability achieved by the anti-plasma protective coating. According to embodiments, it is approximately less than 3E-9 (cm²). 3 / s), less than 2E-9 (cm) 3 / s), or less than 1E-9 (cm) 3The He leak rate of ( / s) can be achieved using a 5-micron-thick EB-IAD deposited anti-plasma protection coating. In contrast, a He leak rate of approximately 1E-6 cubic centimeters per second (cm 3 / s) can be achieved using alumina. A lower He leak rate indicates improved sealing. The airtightness can be measured by the following steps: Place the coated specimen on top of the O-ring of the helium test stand and pump down the pressure until the manometer <E-9 Torr / s (or <1.3E-9 cm 3 / s), apply helium around the O-ring using a helium flow rate of approximately 30 sccm by slowly moving the helium source around the O-ring, and measure the leak rate.

[0088] In some embodiments, the EB-IAD deposited anti-plasma protection coating has a dense structure. For example, for applications on chamber lids, such a dense structure can have performance benefits. Additionally, the EB-IAD deposited anti-plasma protection coating can have a low crack density and high adhesion to the body 305, which can help reduce cracks (vertical and horizontal cracks) in the coating, delamination of the coating, generation of yttrium-based particles through the coating, and yttrium-based particle defects on the wafer. In some embodiments, the adhesion strength of the 5-micron-thick EB-IAD deposited anti-plasma protection coating to an aluminum substrate can be greater than approximately 25 MPa, greater than approximately 26 MPa, greater than approximately 27 MPa, or greater than approximately 28 MPa. In some embodiments, the adhesion strength can be measured via a tensile test in accordance with ASTM 633C or JIS H8666.

[0089] In some embodiments, the roughness of the anti-plasma protection coating can be approximately unchanged from the starting roughness of the underlying substrate being coated. For example, in some embodiments, the starting roughness of the substrate can be approximately 8 - 16 microinches and the roughness of the coating can be approximately unchanged. In some embodiments, the starting roughness of the underlying substrate can be less than approximately 8 microinches, e.g., approximately 4 to approximately 8 microinches, and the roughness of the anti-plasma protection coating can be approximately unchanged. The anti-plasma protection coating can have a surface roughness of approximately 8 microinches or lower or approximately 6 microinches or lower.

[0090] In some embodiments, the anti-plasma protection coating has a high hardness that can resist wear during plasma processing. According to an embodiment, the 5-micron-thick EB-IAD deposited anti-plasma protection coating has a hardness of approximately ≥7 GPa, e.g., approximately 8 GPa. The hardness of the coating is determined by nanoindentation in accordance with ASTM E2546-07.

[0091] According to an example, a 5-micron-thick EB-IAD deposited plasma-resistant protective coating has a breakdown voltage greater than 2,500 V / mil of coating. The breakdown voltage is determined according to JIS C 2110.

[0092] The anti-plasma protective coating described herein may contain trace metals, such as one or more of the following: Ca, Cr, Cu, Fe, Mg, Mn, Ni, K, Mo, Na, Ti, Zn. The trace metals are determined at a depth of 2 μm using laser ablation inductively coupled plasma mass spectrometry (LA ICPMS). In some embodiments, based on atomic percent or based on the weight percent of the anti-plasma protective coating, the anti-plasma protective coating described herein has a purity of about 99.5% or greater, about 99.6% or greater, about 99.7% or greater, about 99.8% or greater, or about 99.9% or greater.

[0093] Chamber components with an EB-IAD anti-plasma protective coating can be used in applications requiring a wide temperature range. For example, the anti-plasma protective coating described herein is stable at operating temperatures ranging from about 80°C to about 120°C.

[0094] It should be noted that the composition of the anti-plasma protective coating described herein (whether deposited by EB-IAD, PVD, plasma spraying, or any other deposition method contemplated herein) may be modified such that the material properties and characteristics identified above may vary by up to 10% in some embodiments or by up to 30% in others. Therefore, in some embodiments, the values ​​described for the properties of the anti-plasma protective coating should be understood as example achievable values. In some embodiments, the anti-plasma protective coating described herein should not be construed as limited to the values ​​provided.

[0095] In some embodiments, (multiple) plasma-resistant protective coatings (e.g., 308 and / or 310) are used as described above. Figure 8 A more detailed description of physical vapor deposition (PVD), such as regarding Figure 9 A more detailed description of plasma spraying, ion-assisted deposition (IAD) without electron beams, or any other suitable deposition process is applied to the body 305 of article 300.

[0096] As previously mentioned, various chamber components within the processing chamber may be coated with the anti-plasma protective coating described herein (via IAD, plasma spraying, or PVD deposition) and / or made from any of the bulk compositions described herein. In one embodiment, a chamber component made from the bulk compositions described herein and / or coated with the anti-plasma protective coating described herein includes one or more of a cap (e.g., 130), a nozzle (e.g., 132), and / or a liner (e.g., 116 and / or 118). In one embodiment, a chamber component is a cap that may be made from the bulk compositions described herein and / or coated with the anti-plasma protective coating described herein. In one embodiment, a chamber component is a nozzle that may be made from the bulk compositions described herein and / or coated with the anti-plasma protective coating described herein. In one embodiment, a chamber component is a liner that may be made from the bulk compositions described herein and / or coated with the anti-plasma protective coating described herein. In one embodiment, a chamber component is a kit of two or more of a cap, nozzle, and liner that may be made from the bulk compositions described herein and / or coated with the anti-plasma protective coating described herein.

[0097] Figure 4A A chamber cover 505 with an anti-plasma protective coating 510 according to an exemplary embodiment is shown (similar to...). Figure 1 A perspective view of the chamber cover 130 in the middle. Figure 4B An embodiment of a plasma-resistant protective coating 510 (similar to) is shown. Figure 1 A cross-sectional side view of the chamber cover 505 (coating 133 in the image). The chamber cover 505 includes an opening 520, which may be located at the center of the cover or elsewhere on the cover. The cover 505 may also have a lip 515 that contacts the wall of the chamber when the cover is closed. In one embodiment, the anti-plasma protective coating 510 does not cover the lip 515. To ensure that the anti-plasma protective coating does not cover the lip 515, a hard or soft mask that covers the lip 515 during deposition can be used. The mask can then be removed after deposition. Alternatively, the protective layer 510 may coat the entire surface. Thus, the protective layer 510 may be positioned on the sidewall of the chamber during processing.

[0098] like Figure 4B As shown, the anti-plasma protective coating 510 may have a sidewall portion 530 that coats the interior of the hole 520. The sidewall portion 530 of the protective layer 510 may be thicker near the surface of the cap 505 and may gradually become thinner as it goes deeper into the hole 520. In such embodiments, the sidewall portion 530 may not coat the entire sidewall of the hole 520.

[0099] Figure 6ADeposition mechanisms applicable to various deposition techniques utilizing high-energy particles, such as ion-assisted deposition (IAD), are described. Exemplary IAD methods include deposition processes combining ion bombardment, such as evaporation (e.g., activated reactive evaporation (ARE)), and sputtering in the presence of ion bombardment to form a plasma-resistant protective coating as described herein. One particular type of IAD performed in the embodiments is electron beam IAD (e-beam IAD). Any of the IAD methods can be performed in the presence of reactive gaseous substances such as O2, N2, halogens (e.g., fluorine), argon, etc. The reactive substances can burn off surface organic contaminants before and / or during deposition. Furthermore, in the embodiments, the IAD deposition process for ceramic target deposition relative to metal target deposition can be controlled by the partial pressure of O2 ions. Alternatively, the ceramic target may be used without oxygen or with reduced oxygen. In some embodiments, IAD deposition is performed in the presence of oxygen and / or argon. In some embodiments, IAD deposition is performed in the presence of fluorine to deposit a coating in which fluorine is incorporated into the coating. It is believed that the fluorine-containing coating is unlikely to interact with wafer processes that include similar environments (e.g., processes that utilize fluorine environments).

[0100] As shown in the figure, anti-plasma protective coating 615 (similar to...) Figure 1 Coatings 133, 134, and 136 in the middle, Figure 3 308 and / or 310 in Figure 4A and Figure 4B (510) is formed on article 610 or on any of the plurality of articles 610A, 610B (such as any of the previously described chamber components including a cap and / or nozzle and / or gasket) by accumulating deposited material 602 in the presence of high-energy particles 603 (such as ions). Deposited material 602 may include atoms, ions, free radicals, etc. High-energy particles 603 may bombard and compact the anti-plasma protective coating 615 during its formation.

[0101] In one embodiment, EB-IAD is used to form a plasma-resistant protective coating 615. Figure 6B A schematic diagram of an IAD deposition apparatus is depicted. As shown, a material source 650 provides a flux of deposition material 602, while a high-energy particle source 655 provides a flux of high-energy particles 603. Both deposition material 602 and high-energy particles 603 bombard articles 610, 610A, and 610B throughout the IAD process. The high-energy particle source 655 can be oxygen or other ion sources. The high-energy particle source 655 can also provide other types of high-energy particles, such as free radicals, neutrons, atoms, and nanoscale particles from particle generation sources (e.g., from plasma, reactive gases, or from the material source providing the deposition material).

[0102] The material source 650 used to provide the deposition material 602 (e.g., target body or plug material) can be a bulk sintered ceramic corresponding to the same ceramic constituting the anti-plasma protective coating 615. The material source can be or includes a bulk sintered ceramic compound body, such as bulk sintered YAG, bulk sintered Y2O3, and / or bulk sintered Al2O3, and / or other mentioned ceramics. In some embodiments, multiple material sources are used, such as a first material source of a bulk sintered Y2O3 target and a second material source of a bulk sintered Al2O3 target. Other target materials may also be used, such as powders, calcined powders, preforms (e.g., formed by pressing or hot pressing), or processed bodies (e.g., fused materials). During deposition, all different types of material sources 650 melt into a molten material source. However, different types of starting materials take different amounts of time to melt. Fused materials and / or processed bodies melt the fastest. Precast materials melt more slowly than fused materials, calcined powder melts more slowly than precast materials, and standard powder melts more slowly than calcined powder.

[0103] In some embodiments, the material source is a metallic material (e.g., a mixture of Y and Al, or two different targets, one Y and one Al). Such a material source can be bombarded with oxygen ions to form an oxide coating. Additionally or alternatively, oxygen (and / or oxygen plasma) may flow into the deposition chamber during the IAD process to allow sputtered or evaporated metallic Y and Al to interact with oxygen and form an oxide coating.

[0104] The IAD can utilize one or more plasmas or beams (e.g., electron beams) to provide the material and a high-energy ion source. Reactive materials may also be provided during the deposition of the anti-plasma coating. In one embodiment, the high-energy particles 603 include at least one of a non-reactive material (e.g., Ar) or a reactive material (e.g., O). In a further embodiment, reactive materials such as CO and halogens (Cl, F, Br, etc.) may be introduced during the formation of the anti-plasma protective coating to further increase the tendency to selectively remove the deposited material that is weakly bound to the anti-plasma protective coating 615.

[0105] Using the IAD process, high-energy particles 603 can be controlled independently of other deposition parameters via a high-energy ion (or other particle) source 655. The composition, structure, crystal orientation, grain size, and amorphous properties of the anti-plasma protective coating can be manipulated based on the energy (e.g., velocity), density, and incident angle of the high-energy ion flux.

[0106] Additional adjustable parameters are the temperature of the article during deposition and the duration of deposition. In one embodiment, the IAD deposition chamber (and chamber cap) is heated to an initial temperature of 70°C or higher prior to deposition. In one embodiment, the initial temperature is 50°C to 250°C. In another embodiment, the initial temperature is 50°C to 100°C. The temperature of the chamber and cap can then be maintained at the initial temperature during deposition. In one embodiment, the IAD chamber includes a heating lamp for performing the heating. In an alternative embodiment, the IAD chamber and cap are not heated. If the chamber is not heated, the chamber temperature naturally increases to about 70°C due to the IAD process. Higher temperatures during deposition can increase the density of the plasma-resistant protective coating, but can also increase the mechanical stress on the plasma-resistant protective coating. Active cooling can be added to the chamber during coating to maintain a low temperature. In one embodiment, the low temperature can be maintained at 70°C or below 70°C up to 0°C.

[0107] Additional adjustable parameters are the working distance 670 and the incident angle 672. The working distance 670 is the distance between the material source 650 and the products 610A, 610B. In one embodiment, the working distance is 0.2 meters to 2.0 meters, while in a particular embodiment, the working distance is 1.0 meter. Reducing the working distance increases the deposition rate and increases the effectiveness of ion energy. However, reducing the working distance below a certain point can decrease the uniformity of the protective layer. The incident angle is the angle at which the deposited material 602 impacts the products 610A, 610B. In one embodiment, the incident angle is 10-90 degrees.

[0108] IAD coatings can be applied to a wide range of surface conditions, with roughness ranging from approximately 0.1 microinches (μin) to approximately 180 microinches. However, smoother surfaces promote uniform coating coverage. Coating thickness can be as high as approximately 300 micrometers (μm). During production, the coating thickness on a part can be assessed by intentionally adding a rare-earth oxide-based developer (such as Nd₂O₃, Sm₂O₃, Er₂O₃, etc.) at the bottom of the coating stack. The thickness can also be accurately measured using an ellipsometry.

[0109] In the embodiments described herein, the IAD coating is amorphous. Compared to crystalline coatings, amorphous coatings are more conformal and reduce epitaxial cracking induced by lattice mismatch. In one embodiment, the anti-plasma protective coating described herein is 100% amorphous and has zero crystallinity. In some embodiments, the anti-plasma protective coating described herein is conformal and has low film stress.

[0110] Multiple electron beam guns can be used to co-deposit multiple targets to produce thicker coatings and layered architectures. For example, two targets with the same material type can be used simultaneously. Each target can be bombarded by a different electron beam gun. This can increase the deposition rate and thickness of the protective layer. In another example, the two targets can be different ceramic materials. For example, one target of Al or Al2O3 and another target of Y or Y2O3 can be used. A first electron beam gun can bombard the first target to deposit a first protective layer, and a second electron beam gun can subsequently bombard the second target to form a second protective layer with a different material composition than the first protective layer.

[0111] In the embodiments, a single target material (also known as plug material) and a single electron beam gun can be used to reach the anti-plasma protective coating described herein.

[0112] In one embodiment, multiple chamber components (e.g., multiple caps, multiple liners, or multiple nozzles) are processed in parallel within an IAD chamber. Each chamber component may be supported by a different fixture. Alternatively, a single fixture may be configured to hold multiple chamber components. The fixture may be able to move the supported chamber components during deposition.

[0113] In one embodiment, the clamp for holding the chamber component may be designed from a metallic component, such as cold-rolled steel or a ceramic component, such as Al2O3, Y2O3, etc. The clamp may be used to support the chamber component above or below the material source and electron beam gun. The clamp may have clamping capabilities to hold the chamber component for safer and easier handling and to hold the chamber component during coating. Furthermore, the clamp may have features for orienting or aligning the chamber component. In one embodiment, the clamp may be repositioned and / or rotated about one or more axes to change the orientation of the supported chamber component to the source material. The clamp may also be repositioned to change the working distance and / or angle of incidence before and / or during deposition. The clamp may have cooling or heating channels to control the temperature of the chamber component during coating. Because IAD is a line-of-sight process, the ability to reposition and rotate the chamber component enables maximum coating coverage of 3D surfaces, such as holes.

[0114] In some embodiments, the IAD-deposited anti-plasma protective coatings described herein provide greater chemical resistance to corrosive chemicals (e.g., hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof) compared to other yttrium-based coating compositions and / or other coatings that may have the same chemical composition but different mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, adhesion strength, crystallinity / amorphous properties, etc.) and / or chemical properties (e.g., chemical resistance). For example, in one embodiment, the IAD-deposited anti-plasma protective coating has a chemical composition corresponding to or close to that of YAG (in terms of the amounts of aluminum, yttrium, and oxygen), which provides enhanced chemical resistance and / or enhanced plasma resistance in invasive chemical environments (e.g., invasive halogen and / or hydroacidic environments) compared to other yttrium-based coatings and / or other YAG coatings prepared and / or deposited differently in accordance with this disclosure.

[0115] Compared to other yttrium-based coatings, the plasma-resistant protective coatings deposited by IAD described in this paper exhibit enhanced chemical resistance. Figure 7A1 , Figure 7A2 , Figure 7B1 , Figure 7B2 , Figure 7C1 , Figure 7C2 , Figure 7D1 and Figure 7D2 As shown in the image. Figure 7A1 and Figure 7A2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 7A1 ) and afterwards ( Figure 7A2 A coating of yttrium oxide (Y₂O₃) IAD deposited. Figure 7A2 After accelerated chemical resistance testing, the yttrium oxide IAD-deposited coating disappeared (i.e., Figure 7A2 The coating is depicted as 100% eroded. Figure 7B1 and Figure 7B2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 7B1 ) and afterwards ( Figure 7B2 A coating deposited by IAD consisting of ceramic compounds containing solid solutions of Y4Al2O9 and Y2O3-ZrO2. According to Figure 7B2 After accelerated chemical resistance testing, the IAD-deposited coating, composed of ceramic compounds containing Y4Al2O9 and Y2O3-ZrO2 solid solutions, almost disappeared (i.e., Figure 7B2 The coating was depicted as having 70% erosion. Figure 7C1 and Figure 7C2The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 7C1 ) and afterwards ( Figure 7C2 A coating deposited by IAD consisting of a Y2O3-ZrO2 solid solution. Figure 7C2 After accelerated chemical resistance testing, the IAD-deposited coating composed of Y2O3-ZrO2 solid solution disappeared (i.e., Figure 7C2 The coating is depicted as 100% eroded.

[0116] Figure 7D1 and Figure 7D2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 7D1 ) and afterwards ( Figure 7D2 A single-phase amorphous YAG coating deposited by IAD (i.e., having the same characteristics as) Figure 2 The alumina-yttrium oxide phase diagram depicted in the figure shows the composition of YAG corresponding to yttrium oxide and alumina (an amorphous single-phase dopant of yttrium oxide and alumina). No damage was observed in the IAD-deposited single-phase amorphous YAG coating after accelerated chemical resistance testing (i.e., ...). Figure 7D2 The coating with 0% erosion is depicted.

[0117] Figure 7A1 Until Figure 7D2 The plasma-resistant protective coating deposited by IAD according to the embodiments described herein exhibits improved chemical resistance to harsh chemical environments, such as harsh acidic environments and halogen- and / or hydrogen-based environments, compared to other yttrium-based IAD-deposited coatings. This chemical resistance also helps reduce the number of yttrium-based particles over extended processing times and correspondingly contributes to reducing wafer defect rates.

[0118] Not to be interpreted as restrictive, can be seen from Figures 7A1 to 7D2 It is understood that, in some embodiments, increasing the aluminum / alumina concentration in the anti-plasma coating composition deposited by IAD improves the chemical resistance of the coating (as determined based on acid stress testing).

[0119] The plasma-resistant protective coating described herein can be deposited using a physical vapor deposition (PVD) process. PVD processes can be used to deposit thin films with thicknesses ranging from a few nanometers to several micrometers. Various PVD processes share three basic characteristics: (1) evaporation of material from a solid source using high-temperature or gaseous plasma; (2) transport of the evaporated material to the surface of the article under vacuum; and (3) condensation of the evaporated material onto the article to create a thin film layer. Figure 8 The text describes an illustrative PVD reactor.

[0120] Figure 8 A deposition mechanism applicable to various PVD technologies and reactors is depicted. A PVD reactor chamber 800 may include a plate 810 adjacent to an article 820 and a plate 815 adjacent to a target 830. In some embodiments, multiple targets (e.g., two targets) may be used. Air may be removed from the reactor chamber 800 to create a vacuum. A gas (such as argon or oxygen) may then be introduced into the reactor chamber, a voltage may be applied to the plates, and a plasma containing electrons and positive ions (such as argon ions or oxygen ions) 840 may be generated. The ions 840 may be positive ions and may be attracted to the negatively charged plate 815, where they may bombard one or more targets 830 and release atoms 835 from the targets. The released atoms 835 may be transported and deposited onto the article 820 as a coating 825. The coating may have a single-layer architecture or may include a multi-layer architecture (e.g., layers 825 and 845).

[0121] Figure 8 Article 820 in the text can represent various semiconductor processing chamber components, including but not limited to substrate support assemblies, electrostatic chucks (ESCs), rings (e.g., processing kit rings or single rings), chamber walls, bases, gas distribution plates, gas lines, nozzles, spray nozzles, covers, liner, liner kits, shielding components, plasma barriers, flow equalizers, cooling bases, chamber viewing ports, chamber covers, etc.

[0122] Figure 8 The coating 825 (and optionally 845) may represent any of the plasma-resistant protective coatings described herein. Coating 825 (and optionally 845) may have the same aluminum / alumina, yttrium / yttrium, and oxygen composition as the coatings previously described. Similarly, plasma-resistant protective coating 825 (and optionally 845) may have any of the properties previously described, such as, but not limited to, amorphous percentage, porosity, density, adhesion strength, roughness, chemical resistance, physical resistance, hardness, purity, breakdown voltage, flexural strength, hermeticity, stability, etc.

[0123] Furthermore, after exposure to invasive chemical and / or invasive plasma environments over extended processing durations, the anti-plasma protective coating 825 (and optional 845) can exhibit a reduced defect rate (as assessed based on yttrium-based particle defects per wafer).

[0124] The anti-plasma protective coating described in this article can be deposited using a plasma spraying process, examples of which are shown in... Figure 9 Described in the text. Figure 9A cross-sectional view of a plasma spraying apparatus 900 according to an embodiment is depicted. The plasma spraying apparatus 900 is a type of thermal spraying system used to perform "slurry plasma spraying" ("SPS") deposition of ceramic materials. Although the following description will concern SPS technology, other standard plasma spraying techniques using dry powder mixtures can also be used to deposit the coatings described herein.

[0125] SPS deposition utilizes solution-based particle distribution (slurry) to deposit ceramic coatings on substrates. SPS can be performed by spraying slurry using atmospheric pressure plasma spraying (APPS), high-velocity oxygen-fuel (HVOF), thermal spraying, vacuum plasma spraying (VPS), and low-pressure plasma spraying (LPPS).

[0126] The plasma spraying apparatus 900 may include a sleeve 902 that encloses a nozzle anode 906 and a cathode 904. The sleeve 902 allows a gas flow 908 to pass through the plasma spraying apparatus 900 and between the nozzle anode 906 and the cathode 904. An external power source can be used to apply a voltage potential between the nozzle anode 906 and the cathode 904. This voltage potential generates an electric arc between the nozzle anode 906 and the cathode 904, which ignites the gas flow 908 to generate plasma gas. The ignited plasma gas flow 908 generates a high-speed plasma plume 914, which is directed out of the nozzle anode 906 and toward a substrate 920.

[0127] The plasma spraying apparatus 900 may be located in a chamber or an atmospheric chamber. In some embodiments, the gas flow 908 may be a gas or a mixture of gases, including but not limited to argon, oxygen, nitrogen, hydrogen, helium, and combinations thereof. In some embodiments, other gases, such as fluorine, may be introduced to incorporate some of the fluorine into the coating, making the coating more resistant to abrasion in fluorine-treated environments.

[0128] The plasma spraying apparatus 900 may be equipped with one or more fluid lines 912 to deliver slurry into a plasma plume 914. In some embodiments, the fluid lines 912 may be arranged on one side of the plasma plume 914 or symmetrically around the plasma plume 914. In some embodiments, such as Figure 9 As depicted, fluid lines 912 may be arranged vertically in the direction of the plasma plume 914. In other embodiments, fluid lines 912 may be adapted to deliver slurry into the plasma plume at different angles (e.g., 45°), or may be located at least partially inside the sleeve 902 to inject slurry into the plasma plume 914 internally. In some embodiments, each fluid line 912 may provide a different slurry, which can be used to vary the composition of the resulting coating across the substrate 920.

[0129] A slurry feeding system may be used to deliver slurry to fluid line 912. In some embodiments, the slurry feeding system includes a flow controller that maintains a constant flow rate during coating. Fluid line 912 may be rinsed with, for example, deionized water before and after the coating process. In some embodiments, a slurry container containing slurry fed to plasma spraying apparatus 900 is mechanically agitated during the coating process to keep the slurry homogeneous and prevent sedimentation.

[0130] Alternatively, in standard powder-based plasma spraying techniques, a powder delivery system comprising one or more powder containers filled with one or more different powders can be used to deliver powder into a plasma plume 914 (not shown).

[0131] The plasma plume 914 can reach very high temperatures (e.g., between approximately 3000°C and approximately 10000°C). When injected into the slurry plume 914, the high temperature experienced by the slurry (or multiple slurries) causes the slurry solvent to evaporate rapidly and melts the ceramic particles, thereby generating a particle stream 916 propelled toward the substrate 920. In plasma spraying technology based on standard powders, the high temperature of the plasma plume 914 also melts the powder delivered to the plasma plume 914 and propels the molten particles toward the substrate 920. After impacting the substrate 920, the molten particles can become flattened and rapidly solidify on the substrate, thereby forming a ceramic coating 918. The solvent can completely evaporate before the ceramic particles reach the substrate 920.

[0132] In some embodiments, plasma-resistant protective coatings deposited using plasma spraying deposition can have greater porosity compared to coatings deposited via electron beam IAD. For example, in some embodiments, plasma-sprayed plasma-resistant protective coatings can have porosity of up to about 10%, up to about 8%, up to about 6%, up to about 4%, up to about 3%, up to about 2%, up to about 1%, or up to about 0.5%. In some embodiments, porosity is measured using software via 1000x scanning electron microscopy (SEM) images to calculate the percentage area of ​​porosity.

[0133] Parameters that can affect the thickness, density, and roughness of ceramic coatings include slurry conditions, particle size distribution, slurry feed rate, plasma gas composition, gas flow rate, energy input, spraying distance, and substrate cooling.

[0134] Figure 9Article 920 in the text can represent various semiconductor processing chamber components, including but not limited to substrate support assemblies, electrostatic chucks (ESCs), rings (e.g., processing kit rings or single rings), chamber walls, bases, gas distribution plates, gas lines, nozzles, spray nozzles, covers, liner, liner kits, shielding components, plasma barriers, flow equalizers, cooling bases, chamber viewing ports, chamber covers, etc.

[0135] Figure 9 The coating 918 may represent any of the plasma-resistant protective coatings described herein. Coating 918 may have the same aluminum / alumina, yttrium / yttrium, and oxygen composition as the coatings previously described. Similarly, the anti-plasma protective coating 918 may have any of the previously described properties, such as, but not limited to, amorphous percentage (e.g., greater than any of about 80%, about 85%, about 90%, about 95%, or about 98% amorphous), porosity (e.g., less than any of about 2%, about 1.5%, about 1%, about 0.5%, or about 0.1%), density, adhesion strength (e.g., greater than any of about 18 MPa, about 20 MPa, about 23 MPa, about 25 MPa, about 28 MPa, or about 30 MPa), chemical resistance, physical resistance, hardness (e.g., greater than any of about 6 GPa, about 7 GPa, about 8 GPa, about 9 GPa, or about 10 GPa), purity, breakdown voltage (greater than about 800 V / mil, about 1000 V / mil, about 1250 V / mil, about 1500 V / mil, or about 2000 V / mil). (either V / mil), roughness, flexural strength, hermeticity, stability, etc. Furthermore, after exposure to invasive chemical and / or invasive plasma environments over extended processing durations, coating 918 can exhibit a reduced defect rate (e.g., assessed based on yttrium-based particle defects per wafer).

[0136] In some embodiments, plasma-deposited anti-plasma protective coatings, as described herein, offer greater chemical resistance to corrosive chemicals (e.g., hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof) compared to other yttrium-based coating compositions and / or other coatings that may have the same chemical composition but different mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, adhesion strength, crystalline / amorphous properties, etc.) and / or chemical properties (e.g., chemical resistance). For example, in one embodiment, a plasma-deposited anti-plasma protective coating has a chemical composition corresponding to or close to that of YAG (in terms of the amounts of aluminum, yttrium, and oxygen), which provides enhanced chemical resistance and / or enhanced plasma resistance in invasive chemical environments (e.g., invasive halogen and / or hydrogen-acidic environments) compared to other yttrium-based coatings and / or other YAG coatings prepared and / or deposited differently from this disclosure.

[0137] Compared to other yttrium-based coating compositions deposited via plasma spraying, the plasma-sprayed anti-plasma protective coating described herein exhibits enhanced chemical resistance. Figure 10A1 , Figure 10A2 , Figure 10B1 , Figure 10B2 , Figure 10C1 , Figure 10C2 , Figure 10D1 and Figure 10D2 As shown in the image. Figure 10A1 and Figure 10A2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 10A1 ) and afterwards ( Figure 10A2 A yttrium oxide (Y2O3) coating deposited by plasma spraying. Figure 10A2 Plasma-sprayed yttrium oxide coatings showed severe damage after accelerated chemical resistance testing (in more than 25% of the inspected coating area). Figure 10A2 The area of ​​the inspected coating is shown as having approximately 50% erosion. Figure 10B1 and Figure 10B2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 10B1 ) and afterwards ( Figure 10B2 A coating formed by plasma spraying, consisting of ceramic compounds comprising solid solutions of Y4Al2O9 and Y2O3-ZrO2. According to... Figure 10B2The plasma-sprayed coating, consisting of ceramic compounds containing solid solutions of Y4Al2O9 and Y2O3-ZrO2, showed localized moderate damage in 15% of the examined coating area after accelerated chemical resistance testing. Figure 10C1 and Figure 10C2 The description describes the exposure to invasive acid immersion for up to 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). Figure 10C1 ) and afterwards ( Figure 10C2 A coating consisting of a Y₂O₃-ZrO₂ solid solution was deposited by plasma spraying. According to... Figure 10C2 The plasma-sprayed coating, consisting of a Y2O3-ZrO2 solid solution, showed localized moderate to severe damage in 30% of the examined coating area after accelerated chemical resistance testing.

[0138] Figure 10D1 and Figure 10D2 The description, according to an embodiment, depicts the process of exposing the patient to an invasive acid immersion for up to 60 minutes in a concentrated halogen-based acid (e.g., HCl, HF, HBr). Figure 10D1 ) and afterwards ( Figure 10D2 The plasma-sprayed, essentially amorphous YAG coating (i.e., having a similar structure to) Figure 2 The composition of YAG on the alumina-yttrium oxide phase diagram depicted in the figure is at least 90% amorphous dopant of yttrium oxide and alumina. After accelerated chemical resistance testing, localized minor damage and essentially no damage were observed in plasma-sprayed, substantially amorphous YAG coatings (in approximately 0%–3% of the examined coating area).

[0139] Figure 10A1 Until Figure 10D2 The plasma-resistant protective coatings deposited via plasma spraying according to the embodiments described herein exhibit improved chemical resistance to harsh chemical environments, such as harsh acidic environments and halogen- and / or hydrogen-based environments, compared to other yttrium-based plasma-sprayed coatings. This chemical resistance also contributes to reducing the number of yttrium-based particles over extended processing times and correspondingly helps reduce wafer defect rates.

[0140] Not to be interpreted as restrictive, can be seen from Figures 10A1 to 10D2 It is understood that, in some embodiments, increasing the aluminum / alumina concentration in the plasma-sprayed coating composition improves the chemical resistance of the coating (as determined based on acid stress testing).

[0141] Figure 11An embodiment of a method 1100 for coating an article (such as a chamber component) with an anti-plasma protective coating according to an embodiment is shown. At block 1110 of process 1100, an article, such as a chamber component, is provided. The chamber component (e.g., a cap, nozzle, or gasket) may have a bulk sintered ceramic body having any of the bulk compositions previously described. Alternatively, the bulk sintered ceramic body may be Al2O3, Y2O3, SiO2, or a ceramic compound comprising Y4Al2O9 and Y2O3-ZrO2 solid solutions.

[0142] At box 1120, an ion-assisted deposition (IAD) process (such as EB-IAD), plasma spraying, or PVD is performed to deposit any of the corrosion-resistant and erosion-resistant plasma-resistant protective coatings described herein onto at least one surface of the chamber component. In one embodiment, an electron beam ion-assisted deposition (EB-IAD) process is performed to deposit the plasma-resistant protective coating. In one embodiment, plasma spraying is performed to deposit the plasma-resistant protective coating. In one embodiment, PVD is performed to deposit the plasma-resistant protective coating.

[0143] In some embodiments, the erosion-resistant and corrosion-resistant plasma-resistant protective coating can be deposited by EB-IAD and may comprise a single-phase amorphous dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. In some embodiments, the plasma-resistant protective coating comprises yttrium oxide with a molar concentration varying from 35 mol% to 40 mol% and alumina with a molar concentration varying from 60 mol% to 65 mol%. In some embodiments, the plasma-resistant protective coating comprises yttrium oxide with a molar concentration varying from 37 mol% to 38 mol% and alumina with a molar concentration varying from 62 mol% to 63 mol%.

[0144] The EB-IAD deposition process can be optimized to obtain a plasma-resistant coating having any of the compositions described herein and any of the properties described herein, for example, such as, but not limited to, 0% porosity, 100% amorphous, adhesion strength greater than about 25 MPa, roughness less than about 6 microinches, breakdown voltage greater than about 2,500 V / mil, hermeticity less than about 3E-9, hardness of about 8 GPa, flexural strength greater than about 400 MPa, stability at temperatures varying from about 80°C to about 120°C, chemical stability, or physical stability.

[0145] In some embodiments, the erosion-resistant and corrosion-resistant plasma-resistant protective coating may be deposited by plasma spraying or by physical vapor deposition and may comprise a substantially amorphous (e.g., greater than about 90% amorphous) dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. In some embodiments, the plasma-resistant protective coating comprises yttrium oxide with a molar concentration varying from 35 mol% to 40 mol% and alumina with a molar concentration varying from 60 mol% to 65 mol%. In some embodiments, the plasma-resistant protective coating comprises yttrium oxide with a molar concentration varying from 37 mol% to about 38 mol% and alumina with a molar concentration varying from 62 mol% to 63 mol%.

[0146] Physical vapor deposition or plasma spraying deposition processes can be optimized to obtain plasma-resistant coatings having any of the compositions or properties described herein, for example, such as, but not limited to, greater than 90% amorphousness, chemical stability, or physical stability.

[0147] Figure 12 A method 1200 for processing a wafer in a processing chamber comprising at least one chamber component made of and / or coated with any of the plasma-resistant protective coatings described herein. Method 1200 includes transferring the wafer into a processing chamber (1210) comprising at least one chamber component (e.g., a cover, gasket, door, nozzle, etc.) made of and / or coated with any of the plasma-resistant protective coatings described herein. Method 1200 further includes processing the wafer in the processing chamber under harsh chemical and / or high-energy plasma conditions (1220). The processing environment may include halogen-containing and hydrogen-containing gases such as C2F6, SF6, SiCl4, HBr, Br, NF3, CF4, CHF3, CH2F3, F, NF3, Cl2, CCl4, BCl3, SiF4, H2, Cl2, HCl, HF, etc., and other gases such as O2 or N2O. In one embodiment, the wafer may be processed in Cl2. In one embodiment, the wafer may be processed in H2. In another embodiment, the wafer may be processed in HBr. Method 1200 further includes passing the processed wafer out of the processing chamber (1230).

[0148] like Figures 13A to 13C and Figure 14As shown, according to embodiments, wafers processed according to the methods described herein in a processing chamber having at least one chamber component made of and / or coated with an anti-plasma protective coating of any of the bulk components described herein exhibit a low number of yttrium-based particle defects. For example, after exposure to corrosive chemicals, the average total number of yttrium-based particles released from any of the anti-plasma protective coatings and / or from any of the bulk components described herein is less than about 3 per 500 radio frequency hours (RFhr), less than about 2 per 500 RFhr, less than about 1 per 500 RFhr, or zero per 500 RFhr.

[0149] Figure 13A The number of yttrium-based particles produced after prolonged treatment in a harsh chemical environment (running invasive Cl2, H2, and fluorine-based chemicals) and high-energy plasma, according to embodiments, using a cap made of bulk YAG, was depicted. Similar results were observed for caps coated with YAG coatings deposited by plasma spraying, PVD, and IAD, according to embodiments. Figure 13A As shown, after an extended processing duration of approximately 770 radio frequency hours (RFhr), the number of yttrium-based particles is zero. In other words, after 770 RFhr, the cover has 100% zero yttrium-based particles. In some embodiments, the bulk composition described herein and / or the coating composition described herein have high-energy plasma resistance upon exposure, for example, to extended processing durations of up to approximately 10,000 watts of power, varying from any of approximately 200 RFhr, approximately 300 RFhr, or approximately 400 RFhr to any of approximately 500 RFhr, approximately 600 RFhr, approximately 700 RFhr, or approximately 800 RFhr, or any subrange or individual value thereof.

[0150] Figure 13B The number of yttrium-based particles produced, according to embodiments, through a nozzle made of bulk YAG under harsh chemical conditions (operating invasive Cl2, H2, and fluorine-based chemicals) and high-energy plasma for extended processing durations is depicted. Similar results were observed, according to embodiments, for nozzles coated with YAG coatings deposited via plasma spraying, PVD, and IAD. Figure 13B As shown, after an extended processing duration of approximately 460 RF hours, the number of yttrium-based particles is two. In other words, after 460 RF hours, the nozzle has more than 95% zero yttrium-based particles.

[0151] Figure 13CPerformance comparisons are depicted regarding the number of yttrium-based particles produced under harsh chemical conditions and high-energy plasma after extended processing durations for kits with nozzles and caps according to embodiments (e.g., each component is made of bulk YAG according to embodiments, with similar results observed for components coated with YAG coatings by plasma spraying, PVD, and IAD deposition according to embodiments) and comparative kits with comparative nozzles and comparative caps (e.g., each component is made of bulk ceramic of Y2O3-ZrO2 solid solution and / or coated with a Y2O3-ZrO2 solid solution coating by plasma spraying, PVD, or IAD deposition).

[0152] according to Figure 13C Compared to a kit with a cap and nozzle according to embodiments described herein, the comparison kit (having a comparison nozzle and a comparison cap) results in the average generation of more yttrium-based particles during extended processing (e.g., approximately 500 RF hours). For example, the average number of yttrium-based particles generated during extended processing using the comparison kit varies from approximately 1 to approximately 3 yttrium-based particles (or, including standard deviation, from 0 to approximately 6 yttrium-based particles). In contrast, the average number of yttrium-based particles generated during extended processing using the kit according to embodiments described herein is zero.

[0153] In addition, according to Figure 13C Compared to the cap and nozzle kit according to the embodiments described herein, the comparison kit (having a comparison nozzle and a comparison cap) exhibits greater variation between processing occasions. For example, the number of yttrium-based particles generated during processing using the comparison kit varies from zero to eight across multiple processing occasions. "Processing occasion" refers to a process performed in different occasions (e.g., at different times) using similar environments. In contrast, the number of yttrium-based particles generated during processing using the kit according to the embodiments described herein remains substantially unchanged across multiple processing occasions.

[0154] Therefore, in some embodiments, the kits according to the embodiments described herein are used to process wafers to reduce the number of yttrium-based particles generated, reduce wafer defect rates, increase accuracy, increase predictability, increase yield, increase throughput, and reduce costs.

[0155] according to Figure 14Compared to a kit with a cap, nozzle, and liner having a coating and / or bulk composition according to embodiments described herein, the three comparative kits (having a comparative nozzle, a comparative cap, and a comparative liner) resulted in an average production of more yttrium-based particles over an extended processing period (e.g., 500 RF hours). For example, in a comparative kit utilizing a chamber component comprising a bulk ceramic coating or made of a ceramic compound comprising a Y4Al2O9 and Y2O3-ZrO2 solid solution (in... Figure 14 The average number of yttrium-based particles generated during the extended treatment (designated K1) varied from about 1 to about 2.5 yttrium-based particles (or, including standard deviation, from 0 to about 5 yttrium-based particles). A comparative kit utilizing a chamber component coated or made of bulk ceramic comprising a Y2O3-ZrO2 solid solution (in...) Figure 14 The average number of yttrium-based particles generated during the extended treatment (designated as K2) varied from 0 to approximately 1 yttrium-based particle (or, including standard deviation, from 0 to approximately 2 yttrium-based particles). In utilizing... Figure 14 The kit designated K3 (comparison nozzle consisting of a Y2O3-ZrO2 solid solution coating or bulk composition, comparison liner consisting of a ceramic compound coating or bulk composition comprising Y4Al2O9 and Y2O3-ZrO2 solid solution, and cap according to embodiments described herein) exhibits an average number of yttrium-based particles ranging from 0 to less than 1 during extended processing. The kit comprising the nozzle, liner, and cap according to embodiments described herein (in...) Figure 14 The average number of yttrium-based particles generated during the processing (specified as K4) was zero.

[0156] In addition, according to Figure 14Compared to a kit that includes at least one component according to embodiments described herein, a comparative kit consisting of the following exhibits significant variation between processing scenarios: a) a Y₂O₃-ZrO₂ solid solution and b) a ceramic compound comprising Y₄Al₂O₉ and a Y₂O₃-ZrO₂ solid solution. For example, between multiple processing scenarios, the number of yttrium-based particles generated during processing using a comparative kit comprising a ceramic compound coated with a ceramic compound comprising a Y₄Al₂O₉ and a Y₂O₃-ZrO₂ solid solution or a chamber component made of said ceramic varies from zero to 5. Between multiple processing scenarios, the number of yttrium-based particles generated during processing using a comparative kit comprising a ceramic compound coated with a Y₂O₃-ZrO₂ solid solution or a chamber component made of said ceramic varies from zero to 3. In contrast, across multiple processing scenarios, the amount of yttrium-based particles generated during processing using a kit comprising a nozzle consisting of a Y₂O₃-ZrO₂ solid solution, a liner consisting of a ceramic compound comprising Y₄Al₂O₉ and a Y₂O₃-ZrO₂ solid solution, and a cap according to embodiments described herein, is significantly reduced. Furthermore, the kit comprising the nozzle, cap, and liner according to embodiments described herein remains substantially unchanged across multiple processing scenarios.

[0157] Figure 15 Normalized erosion rates (nm / RF hours) were depicted for a comparison of a bulk YAG composition (bulk YAG), a first optimized bulk YAG composition according to an embodiment prepared by field-assisted sintering (FAS) (bulk YAG1 (optimized)), and a second optimized bulk YAG composition according to an embodiment prepared by hot isostatic pressing (HIP) (bulk YAG2 (optimized)). The erosion rates were evaluated after exposing the bulk compositions to Cl2-CH4-HBr at 50 °C using a bias voltage of 150 V. Figure 15 The results described herein are also summarized in the table below. As can be seen from these results, the bulk composition according to the embodiments described herein exhibits enhanced erosion resistance compared to other bulk YAG compositions prepared differently from those disclosed herein.

[0158]

[0159] The foregoing description sets forth several specific details, such as examples of specific systems, components, methods, etc., to provide a good understanding of several embodiments of the present disclosure. However, it will be apparent to those skilled in the art that at least some embodiments of the present disclosure can be practiced without these specific details. In other examples, well-known components or methods are not described in detail or are provided in a simple block diagram format to avoid unnecessarily obscuring the present disclosure. Therefore, the specific details set forth are merely exemplary. Specific implementations may be modified from these exemplary details and still contemplated within the scope of this disclosure.

[0160] Throughout this specification, references to "an embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with an embodiment is included in at least one embodiment. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places throughout this specification do not necessarily all refer to the same embodiment. Additionally, the term "or" is intended to mean inclusive "or" rather than exclusive "or". When the terms "about" or "approximately" are used herein, this is intended to mean that the provided nominal values ​​are exactly within ±30%.

[0161] Although the operations of the methods described herein are illustrated and described in a specific order, the order of operations of each method may be changed, such that some operations may be performed in reverse order, or that some operations may be performed at least partially concurrently with other operations. In another embodiment, instructions or sub-operations of different operations may be performed in an intermittent and / or alternating manner.

[0162] It will be understood that the above description is intended to be illustrative and not restrictive. Numerous other embodiments will become apparent to those skilled in the art upon reading and understanding the above description. Therefore, the scope of this disclosure should be determined by reference to the full scope of the appended claims and their equivalents.

Claims

1. A method for coating a cavity component, comprising the following steps: Electron beam ion-assisted deposition (electron beam IAD) is performed to deposit a plasma-resistant protective coating on at least a portion of the processing chamber components. The plasma-resistant protective coating comprises a single-phase amorphous dopant of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and alumina with a molar concentration varying from about 5 mol% to about 65 mol%. The plasma-resistant protective coating has 0% porosity and an adhesion strength greater than about 25 MPa.

2. The method of claim 1, wherein the anti-plasma protective coating comprises a single-phase amorphous dopant of yttrium oxide with a molar concentration varying from 35 mol% to 40 mol% and alumina with a molar concentration varying from 60 mol% to 65 mol%.

3. The method of claim 2, wherein the anti-plasma protective coating comprises a single-phase amorphous dopant of yttrium oxide with a molar concentration varying from 37 mol% to 38 mol% and alumina with a molar concentration varying from 62 mol% to 63 mol%.

4. The method of claim 1, wherein the anti-plasma protective coating has one or more of the following: an airtightness of less than about 3E-9, a hardness of about 8 Gpa, a flexural strength of more than about 400 MPa, or stability at temperatures varying from about 80°C to about 120°C.

5. The method of claim 1, wherein the anti-plasma protective coating has a roughness of less than about 6 microinches.

6. The method of claim 1, wherein the anti-plasma protective coating at a thickness of 5 µm has a breakdown voltage greater than about 2,500 V / mil.

7. The method of claim 1, wherein the average total number of yttrium-based particles released from the anti-plasma protective coating after exposure to corrosive chemicals is less than 3 per 500 RF hours.

8. The method of claim 7, wherein the corrosive chemical substance comprises hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof.

9. The method of claim 8, wherein the corrosive chemical substance comprises one or more of HF, HBr, HCl, Cl2, or H2.

10. A method for coating a chamber component, comprising the following steps: Perform plasma spraying or physical vapor deposition (PVD) to deposit a plasma-resistant protective coating on the processing chamber components. The plasma-resistant protective coating comprises a mixture of yttrium oxide with a molar concentration varying from about 35 mol% to about 95 mol% and aluminum oxide with a molar concentration varying from about 5 mol% to about 65 mol%. The plasma-resistant protective coating is at least about 90% amorphous, and the average total number of yttrium-based particles released from the plasma-resistant protective coating after exposure to corrosive chemicals is less than 3 per 500 RF hours.

11. The method of claim 10, wherein the anti-plasma protective coating comprises a mixture of yttrium oxide with a molar concentration varying from 35 mol% to 40 mol% and alumina with a molar concentration varying from 60 mol% to 65 mol%.

12. The method of claim 10, wherein the anti-plasma protective coating comprises a mixture of yttrium oxide with a molar concentration varying from 37 mol% to 38 mol% and alumina with a molar concentration varying from 62 mol% to 63 mol%.

13. The method of claim 10, wherein the corrosive chemical substance comprises hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof.

14. The method of claim 13, wherein the corrosive chemical substance comprises one or more of HF, HBr, HCl, Cl2, or H2.

15. The method of claim 10, wherein the anti-plasma protective coating has a roughness of less than about 6 microinches.

16. The method of claim 10, wherein the anti-plasma protective coating at a thickness of 5 µm has a breakdown voltage greater than about 2,500 V / mil.

17. The method of claim 10, wherein the anti-plasma protective coating has an airtightness of less than about 3E-9.

18. The method of claim 10, wherein the anti-plasma protective coating has a hardness of about 8 GPa.

19. The method of claim 10, wherein the anti-plasma protective coating has a flexural strength greater than about 400 MPa.

20. The method of claim 10, wherein the anti-plasma protective coating is stable at temperatures ranging from about 80°C to about 120°C.

Images