Yttrium oxide based coating and bulk compositions

Abstract

To provide a method for applying a protective coating on a chamber component that offers both physical resistance to sputtering resulting from high energy aggressive plasma and chemical resistance to corrosion arising from corrosive environments.SOLUTION: A method of coating a process chamber component comprises performing electron beam ion assisted deposition (e-beam IAD) to deposit a plasma resistant protective coating on at least a portion of the process chamber component, wherein the plasma resistant protective coating comprises a single phase amorphous blend of yttrium oxide at a molar concentration ranging from about 35 mol% to about 95 mol% and aluminum oxide at a molar concentration ranging from about 5 mol% to about 65 mol%, and wherein the plasma resistant protective coating has a porosity of 0% and an adhesion strength greater than about 25 MPa.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001]

[0001] Embodiments of the present disclosure generally relate to yttrium oxide-based protective coatings and bulk compositions for enhancing defect performance in semiconductor processing applications.

Background Art

[0002]

[0002] In the semiconductor industry, devices are manufactured by numerous manufacturing processes that produce structures of ever-decreasing size. As the device geometries shrink, it has become more difficult to control process uniformity and reproducibility.

[0003]

[0003] In existing manufacturing processes, semiconductor processing chamber components (also referred to as process chamber components) are exposed to high-energy aggressive plasmas and / or corrosive environments. This high-energy aggressive plasma and / or corrosive environment is detrimental to the integrity of semiconductor processing chamber components and can make the task of controlling process uniformity and reproducibility even more difficult.

[0004]

[0004] Therefore, certain semiconductor processing chamber components (e.g., liners, doors, covers, etc.) are coated with yttrium-based protective coatings or fabricated from yttrium-based bulk compositions. Yttria (Y2O3) is often used for etching chamber components because of its excellent erosion resistance and / or sputtering resistance in aggressive plasma environments.

[0005]

[0005] It would be advantageous to provide protective coatings and bulk compositions that provide both physical resistance to sputtering from high-energy aggressive plasmas and chemical resistance to corrosion from corrosive environments.

Summary of the Invention

[0006]

[0006] In certain embodiments, the present disclosure is directed to a ceramic body composed of single-phase bulk crystalline yttrium aluminum garnet (YAG). The single-phase bulk crystalline YAG contains yttrium oxide with a molar concentration in the range of about 35 mol% to 40 mol% and aluminum oxide with a molar concentration in the range of 60 mol% to 65 mol%. The single-phase bulk crystalline YAG has a density of about 98% or more and a hardness exceeding about 10 GPa.

[0007]

[0007] In certain embodiments, the present disclosure is directed to a method for coating a chamber component. The method includes performing electron beam ion assisted deposition (e-beam IAD) to deposit a plasma-resistant protective coating. The plasma-resistant protective coating includes a single-phase amorphous blend of yttrium oxide with a molar concentration in the range of about 35 mol% to about 95 mol% and aluminum oxide with a molar concentration in the range of 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 a bonding strength exceeding about 25 MPa.

[0008]

[0008] In certain embodiments, the present disclosure is directed to a method for coating a chamber component. This method includes performing plasma spraying or physical vapor deposition (PVD) to deposit a plasma-resistant protective coating on the processing chamber component. The plasma-resistant protective coating includes a blend of yttrium oxide with a molar concentration in the range of about 35 mol% to about 95 mol% and aluminum oxide with a molar concentration in the range of about 5 mol% to about 65 mol%. The plasma-resistant protective coating is about 90% amorphous. The average total number of yttrium-based particles released from the plasma-resistant protective coating when exposed to corrosive chemicals is less than 3 per 500 RF hours.

[0009]

[0009] The present disclosure is illustrated by way of example and not limitation in the accompanying drawings, in which like reference numerals indicate like elements. Note that various references to "an" or "one" embodiment in the present disclosure are not necessarily to the same embodiment, and such references are meant to mean at least one.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4A

Figure 4B

Figure 5A1 - 5B2

Figure 6A

Figure 6B

Figure 7A1 - 7D2

Figure 8

Figure 9

Figure 10A1 - 10D2

Figure 11

Figure 12

Figure 13A

Figure 13B

Figure 13C

Figure 14

Figure 15

DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0029] In semiconductor manufacturing processes, semiconductor processing chamber components are exposed to high-energy aggressive plasma environments and corrosive environments. To protect the processing chamber components from such aggressive environments, the chamber components are either coated with a protective coating or made from a bulk composition that is resistant to such aggressive plasma environments and corrosive environments.

[0012]

[0030] Yttria (Y2O3) is often used for coating chamber components (e.g., etching chamber components) due to its good erosion resistance. Despite its good erosion resistance, yttria is not chemically stable in aggressive etching chemistries. Radicals such as fluorine, chlorine, and bromide readily chemically attack yttria, leading to the formation of yttrium-based particles, which are a cause of defects in etching applications. Therefore, various industries (e.g., the logic industry) have begun to impose strict specifications on yttrium-based defects on product wafers.

[0013]

[0031] To meet such stringent specifications, it is beneficial to identify protective coating compositions and bulk compositions that provide both physical resistance to sputtering caused by high-energy aggressive plasmas and chemical resistance to chemical attack by aggressive chemical environments.

[0014]

[0032] In the present disclosure, the plasma-resistant protective coating compositions and bulk compositions are identified as having improved chemical stability compared to pure yttria (Y2O3) and other yttrium-based materials, and further maintaining physical resistance to high-energy aggressive plasmas compared to pure alumina (Al2O3).

[0015]

[0033] In certain embodiments, the protective coatings described herein are corrosion and erosion resistant coatings comprising a substantially amorphous (i.e., at least about 90% amorphous) blend of aluminum oxide and yttrium oxide. In certain embodiments, the protective coatings are completely amorphous (i.e., 100% amorphous). Since the composition is not limited to the bonding arrangements of crystalline compositions or the phases shown in the alumina - yttria phase diagram of FIG. 2, the substantially amorphous nature of the protective coatings allows for more flexible adjustment of the amounts of alumina and yttria, achieving optimal chemical resistance (e.g., to harsh chemical environments) and physical resistance (e.g., to harsh plasma environments).

[0016]

[0034] Without being limited thereto, introducing more aluminum - based components into the coating makes the coating more chemically resistant to harsh chemical environments (e.g., acidic environments, hydrogen - based environments, and halogen - based environments), and the yttrium - based components in the coating are thought to provide the coating with physical resistance to high - energy plasma environments.

[0017]

[0035] In one embodiment, the protective coatings described herein may have the chemical composition of yttrium aluminum garnet (YAG) (in terms of the amounts of yttrium, aluminum, and oxygen in the composition), or be close to the chemical composition of YAG, but provide improved chemical resistance and / or improved plasma resistance in aggressive chemical environments (e.g., aggressive halogen and / or hydrogen - acidic environments) compared to other yttrium - based coatings prepared and / or deposited differently and / or compared to other YAG coatings different from the present disclosure, and have mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, bond strength, crystallinity / amorphousness, etc.) and chemical properties (e.g., chemical resistance).

[0018]

[0036] The plasma-resistant protective coating described herein can be deposited by ion-assisted deposition, chemical vapor deposition, or plasma spraying. The deposition technique can be selected and optimized to achieve a plasma-resistant protective coating having certain properties, such as, for example, high density, very low internal and / or surface porosity (or non-porosity), amorphous content, bond strength, roughness, breakdown voltage, gas tightness, hardness, flexural strength, chemical stability, and physical stability.

[0019]

[0037] The plasma-resistant protective coating described herein can be coated on any number of chamber components, and is particularly considered suitable for coating lids and / or nozzles and / or liners. A processed wafer in a processing chamber having at least one chamber component coated with the plasma-resistant protective coating described herein can significantly reduce the number of yttrium-based particles generated during processing, reduce wafer defectiveness due to the presence of yttrium-based particles, reduce variability across a plurality of processes related to the formation of yttrium-based particles and the associated defectiveness, increase reliability, increase accuracy, improve reproducibility, increase predictability, increase yield, increase throughput, and reduce costs.

[0020]

[0038] In certain embodiments, the present disclosure is directed to a plasma-resistant bulk composition that has improved chemical stability compared to pure yttria (Y2O3) and other yttrium-based materials, and that further maintains physical resistance to high-energy aggressive plasmas compared to pure alumina (Al2O3).

[0021]

[0039] In certain embodiments, any chamber component, particularly the lid and / or nozzle and / or liner, comprises a ceramic body such as single-phase bulk crystalline yttrium aluminum garnet (YAG), and the single-phase bulk crystalline YAG comprises yttrium oxide with a molar concentration in the range of 35 mol% to 40 mol% and aluminum oxide with a molar concentration in the range of 60 mol% to 65 mol%. The single-phase bulk crystalline YAG has a density of about 98% or more and a hardness exceeding about 10 GPa. The single-phase bulk crystalline YAG disclosed in the embodiments has been shown to be particularly effective, especially more effective in chemical resistance and / or plasma erosion resistance than other examples of bulk YAG ceramics. The bulk ceramic body is completely crystalline in the embodiments. The bulk composition can be the result of a two-step sintering process including hot isotactic pressing (HIP). The process can be optimized for bulk compositions having certain properties such as high density, very low porosity (or substantially non-porous), hardness, chemical stability, and physical stability, to name a few.

[0022]

[0040] A processing wafer within a processing chamber having at least one chamber component made from the bulk composition described herein can significantly reduce the number of yttrium-based particles generated during processing, reduce wafer defectivity due to the presence of yttrium-based particles, reduce variability across multiple processes related to the formation of yttrium-based particles and the associated defectivity, enhance reliability, increase accuracy, improve reproducibility, increase predictability, increase yield, increase throughput, and reduce cost, even compared to other bulk YAG ceramics.

[0023]

[0041] FIG. 1 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 an embodiment of the present disclosure or fabricated from a bulk composition according to an embodiment of the present disclosure. The processing chamber 100 may be used in processes where an aggressive plasma environment and / or an aggressive chemical environment occur. For example, the processing chamber 100 can be a chamber for a plasma etching reactor (also called a plasma etcher), a plasma cleaner, etc.

[0024]

[0042] 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 process kit ring or a single ring), a chamber wall, a base, a gas supply plate, a plate, a showerhead, a liner, a liner kit, a shield, a plasma screen, a flow equalizer, a cooling base, a chamber viewport, a chamber lid 130, a nozzle, etc. Any of these chamber components may also be fabricated from a bulk composition having plasma resistance and chemical resistance according to the embodiments described herein. In certain embodiments, the chamber lid 130, and / or the liner 116 or 118, and / or the nozzle 132 are individually coated with a plasma-resistant protective coating or fabricated from a bulk material having plasma resistance and chemical resistance according to the embodiments described herein.

[0025]

[0043] In certain embodiments, the plasma-resistant protective coating, described in more detail below, is a blend of yttrium oxide in a molar concentration in the range of about 35 mole percent to about 95 mole percent and aluminum oxide in a molar concentration in the range of about 5 mole percent to about 65 mole percent. The plasma-resistant protective coating may be deposited by ion-assisted deposition (IAD) such as electron beam ion-assisted deposition (e-beam IAD), physical vapor deposition (PVD), or plasma spraying. Depending on the deposition technique, the plasma-resistant 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 100% single-phase amorphous.

[0026]

[0044] In certain embodiments, the plasma-resistant protective coating comprises yttrium oxide in a molar concentration in the range of 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration in the range of 60 mole percent to 65 mole percent. In certain embodiments, the plasma-resistant protective coating comprises yttrium oxide in a molar concentration in the range of 37 mole percent to 38 mole percent and aluminum oxide in a molar concentration in the range of 62 mole percent to 63 mole percent. In certain embodiments, the molar concentrations of yttrium oxide and aluminum oxide in the plasma-resistant protective coating add up to 100 mole percent.

[0027]

[0045] In certain embodiments, the plasma-resistant protective coating comprises yttrium oxide in a molar concentration in the range from any of about 35 mole percent, about 35.5 mole percent, about 36 mole percent, about 36.5 mole percent, about 37 mole percent, or about 37.5 mole percent to any of about 38 mole percent, about 38.5 mole percent, about 39 mole percent, about 39.5 mole percent, about 40 mole percent, about 45 mole percent, about 50 mole percent, about 55 mole percent, about 60 mole percent, about 65 mole percent, about 70 mole percent, about 75 mole percent, about 80 mole percent, about 85 mole percent, about 90 mole percent, or about 95 mole percent, or in a molar concentration of any single value therein or any sub-range therein.

[0028]

[0046] In certain embodiments, the plasma-resistant protective coating comprises aluminum oxide in a molar concentration in the range from any of about 5 mole percent, about 10 mole percent, about 15 mole percent, about 20 mole percent, about 25 mole percent, about 30 mole percent, about 35 mole percent, about 40 mole percent, about 45 mole percent, about 50 mole percent, about 55 mole percent, about 60 mole percent, about 60.5 mole percent, about 61 mole percent, about 61.5 mole percent, or about 62 mole percent to any of about 62.5 mole percent, about 63 mole percent, about 63.5 mole percent, about 64 mole percent, about 64.5 mole percent, or about 65 mole percent, or in a molar concentration of any single value therein or any sub-range therein.

[0029]

[0047] In certain embodiments, the plasma-resistant protective coating described herein consists of, or consists essentially of, a single-phase amorphous blend of aluminum oxide and yttrium oxide. In the plasma-resistant protective coating, aluminum oxide is present at a molar concentration in the range of from about 5 mole percent to about 65 mole percent, from 60 mole percent to 65 mole percent, or from 62 mole percent to 63 mole percent, and yttrium oxide is present at a molar concentration in the range of from about 35 mole percent to about 95 mole percent, from 35 mole percent to 40 mole percent, or from 37 mole percent to 38 mole percent.

[0030]

[0048] In certain embodiments, the plasma-resistant protective coating described herein consists of, or consists essentially of, an amorphous blend of at least about 90% aluminum oxide and yttrium oxide, and in the plasma-resistant protective coating, aluminum oxide is present at a molar concentration in the range of from about 5 mole percent to about 65 mole percent, from 60 mole percent to 65 mole percent, or from 62 mole percent to 63 mole percent, and yttrium oxide is present at a molar concentration in the range of from about 35 mole percent to about 95 mole percent, from 35 mole percent to 40 mole percent, or from 37 mole percent to 38 mole percent.

[0031]

[0049] In certain embodiments, the bulk composition, described in more detail below, is composed of single-phase bulk crystalline yttrium aluminum garnet (YAG) containing yttrium oxide at a molar concentration in the range of 35 mole percent to 40 mole percent and aluminum oxide at a molar concentration in the range of 60 mole percent to 65 mole percent. In certain embodiments, the bulk composition is of high density 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., about 0% porosity). In certain 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 certain embodiments, the specific properties and characteristics of the bulk compositions described herein (e.g., but not limited to, density and hardness) can be modified to vary by up to 30% (e.g., 10 GPa ± 30% ranges from 7 GPa to 13 GPa), up to 25% (e.g., 10 GPa ± 25% ranges from 7.5 GPa to 12.5 GPa), up to 20% (e.g., 10 GPa ± 20% ranges from 8 GPa to 12 GPa), up to 15% (e.g., 10 GPa ± 15% ranges from 8.5 GPa to 11.5 GPa), up to 10% (e.g., 10 GPa ± 10% ranges from 9 GPa to 11 GPa), or up to 5% (e.g., 10 GPa ± 5% ranges from 9.5 GPa to 10.5 GPa). Accordingly, the recited values of these material properties should be understood as examples of achievable values.

[0032]

[0050] In certain embodiments, the single-phase bulk crystalline composition can be the result of a two-step sintering process that includes hot isostatic pressing (HIP). In certain embodiments, the sintering process includes (similar to ceramic processing) compressing the raw ceramic powders into a certain shape, compressing them into sheets, and firing the ceramic to promote complete densification. The sintering process is controlled to obtain optimized conditions and bulk composition properties, such as, but not limited to, high yield, high density, improved hardness, improved grindability, surface roughness, improved chemical stability, improved physical stability, precise and accurate composition.

[0033]

[0051] In certain embodiments, the bulk composition consists of single-phase bulk crystalline yttrium aluminum garnet (YAG) containing yttrium oxide at a molar concentration in the range from any of about 35 mole percent, about 35.5 mole percent, about 36 mole percent, about 36.5 mole percent, about 37 mole percent, or about 37.5 mole percent to any of about 38 mole percent, about 38.5 mole percent, about 39 mole percent, about 39.5 mole percent, or about 40 mole percent, or at a molar concentration of any single value therein or any sub-range therein.

[0034]

[0052] In certain embodiments, the bulk composition consists of single-phase bulk crystalline yttrium aluminum garnet (YAG) containing aluminum oxide at a molar concentration in the range from any of about 60 mole percent, about 60.5 mole percent, about 61 mole percent, about 61.5 mole percent, or about 62 mole percent to any of about 62.5 mole percent, about 63 mole percent, about 63.5 mole percent, about 64 mole percent, about 64.5 mole percent, or about 65 mole percent, or at a molar concentration of any single value therein or any sub-range therein.

[0035]

[0053] In certain embodiments, the bulk compositions described herein consist of or consist essentially of aluminum oxide in a molar concentration in the range from any of about 60 mole percent, about 60.5 mole percent, about 61 mole percent, about 61.5 mole percent, or about 62 mole percent to any of about 62.5 mole percent, about 63 mole percent, about 63.5 mole percent, about 64 mole percent, about 64.5 mole percent, or about 65 mole percent, and yttrium oxide in a molar concentration in the range from any of about 35 mole percent, about 35.5 mole percent, about 36 mole percent, about 36.5 mole percent, about 37 mole percent, or about 37.5 mole percent to any of about 38 mole percent, about 38.5 mole percent, about 39 mole percent, about 39.5 mole percent, or about 40 mole percent, and are composed of single-phase bulk crystalline YAG.

[0036]

[0054] In certain embodiments, the bulk compositions described are crystalline with 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% crystallinity as measured by X-Ray Diffraction (XRD).

[0037]

[0055] The crystalline composition of alumina and yttria follows the solid line of the alumina-yttria phase diagram shown in Figure 2. Therefore, the bulk composition of crystalline yttrium aluminum garnet (YAG) at temperatures below about 2177K is limited to the amounts of alumina and yttria corresponding to solid line A in Figure 2 (about 37 to 38 mole percent yttria and about 62 to 63 mole percent alumina). Similarly, the bulk composition of crystalline yttrium aluminum perovskite (YAP) at temperatures below about 2181K is limited to the amounts of alumina and yttria corresponding to solid line B in Figure 2 (about 50 mole percent yttria and about 50 mole percent alumina). The bulk composition of crystalline yttrium aluminum monoclinic (YAM) at temperatures below about 2223K is limited to the amounts of alumina and yttria corresponding to solid line C in Figure 2 (about 65 mole percent yttria and about 35 mole percent alumina). If additional alumina and yttria are added to the bulk composition corresponding to any of solid lines A, B, or C, a mixture of two crystalline phase forms is formed. For example, from solid line A and at temperatures below about 2084K, adding more alumina results in a mixture of crystalline YAG and crystalline alumina (region R1), while adding more yttria results in a mixture of crystalline YAG and crystalline YAP (region R2). Similarly, from solid line B and at temperatures below about 2177K, adding more alumina results in a mixture of crystalline YAG and crystalline alumina (region R2), while adding more yttria results in a mixture of crystalline YAM and crystalline YAP (region R3). From solid line C and at temperatures below about 2181K, adding more alumina results in a mixture of crystalline YAG and crystalline YAP (region R3), while adding more yttria results in a mixture of crystalline YAM and cubic yttrium aluminum (Cub2) (region R4).

[0038]

[0056] In certain embodiments, the bulk compositions 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 bulk compositions, as shown in FIGS. 5A1, 5A2, 5B1, and 5B2. In certain embodiments, the single-phase bulk crystalline YAG disclosed in the embodiments has been shown to provide greater chemical resistance to corrosive chemicals (e.g., hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof) compared to other examples of bulk YAG ceramics.

[0039]

[0057] FIGS. 5A1 and 5A2 show a comparative bulk YAG (FIG. 5A1) before exposure to an aggressive acid dip and the YAG (FIG. 5A2) after 60 minutes of exposure in a concentrated halogen-based acid (e.g., HCl, HF, HBr). Moderate chemical damage is observed in the bulk YAG after the accelerated chemical resistance test. For example, in FIG. 5A2, approximately 10% of the comparative bulk YAG was attacked. In other words, in FIG. 5A2, except for scratches, a general change in appearance indicative of a chemical attack is observed. FIGS. 5A1 and 5A2 show the bulk YAG according to the embodiments before (FIG. 5B1) and after (FIG. 5B2) exposure to an aggressive acid dip for 60 minutes in a concentrated halogen-based acid (e.g., HCl, HF, HBr). No damage is observed in the bulk YAG after the accelerated chemical resistance test. The comparative bulk YAG shown in FIGS. 5A1 and 5A2 has a density of about 92 to 98% and a hardness of about 9.3 GPa.

[0040]

[0058] The bulk YAG of the present invention shown in FIGS. 5B1 and 5B2 is prepared using a two-step sintering process (including, for example, a hot isostatic pressing sintering process), and has a density of about 98% or more and a hardness exceeding about 13 GPa (i.e., about 33% improvement in hardness compared to the baseline comparison YAG of FIGS. 5A1 and 5A2). The bulk YAG of the present invention shown in FIGS. 5B1 and 5B2 has an improved yield, a bottom surface roughness of about 10% or less (about 94% for the comparison bulk YAG), a side surface roughness of about 15% or less (about 98% for the comparison bulk YAG), and shows improved pore quality demonstrated by a roughness improvement of 50 μin or less (50 μin for the comparison bulk YAG), and a reduced porosity compared to the comparison bulk YAG. These properties (such as the improvement in surface roughness and pore quality) were measured using shape measurement. Further, when the bulk YAG of the present invention was treated for 100 high-frequency hours in a TiOx etching environment, no yttrium-based particles were observed, and an improvement in the performance of reducing particles related to the parts was seen.

[0041]

[0059] In certain embodiments, the plasma-resistant protective coating composition described herein is amorphous by more than about 90%, more than about 92%, more than about 94%, more than about 96%, more than about 98%, more than about 99%, or about 100% as measured by X-ray diffraction (XRD). In certain embodiments, the plasma-resistant protective coating described herein has no crystalline regions therein. Thus, the plasma-resistant protective coating described herein provides the flexibility to incorporate more aluminum oxide and / or more yttrium oxide without being limited to the solid lines and compositional mixtures shown in the alumina-yttria phase diagram shown in FIG. 2.

[0042]

[0060] For example, aluminum oxide is considered to provide greater chemical stability against harsh chemical environments (e.g., acidic environments, hydrogen-based environments, and halogen-based environments). Therefore, more aluminum oxide may be added to form a coating composition with improved chemical stability in a harsh chemical environment. On the other hand, yttrium oxide is considered to provide greater physical stability against high-energy plasma. Therefore, more yttrium oxide may be added to form a coating composition with improved physical stability in high-energy plasma. Since the coating composition has an amorphous nature, it is possible to adjust the amounts of alumina and yttria in the protective coating while maintaining a substantially single amorphous phase. This is thought to be possible due to the amorphous nature of the coating where the interatomic bond links are variable and change (in contrast to the bond links of the crystalline compositions restricted by the alumina-yttria phase diagram in FIG. 2).

[0043]

[0061] In other words, in certain embodiments, adding alumina to an amorphous protective coating having a composition of alumina and yttria corresponding to solid line A results in a single-phase amorphous blend of yttria and alumina corresponding to any of the compositions in region R1 (alumina in the range of greater than 62 or 63 mole percent to 100 mole percent, and yttria in the range of greater than 0 mole percent to less than 37 or 38 mole percent), rather than a mixture of two crystalline phases of YAG and alumina like a crystalline bulk composition. In certain embodiments, the single-phase amorphous blend of yttria and alumina having the composition of region R1 may be homogeneous or substantially homogeneous.

[0044]

[0062] Similarly, when alumina is added to an amorphous protective coating having a composition of alumina and yttria corresponding to the solid line B, instead of a mixture of two crystalline phases of YAG and YAP like the crystalline bulk composition, it will contain a single-phase amorphous blend of yttria and alumina corresponding to any of the compositions in region R2 (alumina in the range of more than 50 mole percent to 62 or 63 mole percent, and yttria of more than 37 or 38 mole percent to less than 50 mole percent). In certain embodiments, the single-phase amorphous blend of yttria and alumina having the composition of region R2 may be homogeneous or substantially homogeneous.

[0045]

[0063] Similarly, when alumina is added to an amorphous protective coating having a composition of alumina and yttria corresponding to the solid line C, instead of a mixture of two crystalline phases of YAM and YAP like the crystalline bulk composition, it will contain a single-phase amorphous blend of yttria and alumina corresponding to any of the compositions in region R3 (alumina in the range of more than 35 mole percent to less than 50 mole percent, and yttria of more than 50 mole percent to less than 65 mole percent). In certain embodiments, the single-phase amorphous blend of yttria and alumina having the composition of region R3 may be homogeneous or substantially homogeneous.

[0046]

[0064] In certain embodiments, when alumina is added to an amorphous protective coating having a composition of alumina and yttria corresponding to the solid line C, instead of a mixture of two crystalline phases of YAM and Cub2 like the crystalline bulk composition, it will contain a single-phase amorphous blend of yttria and alumina corresponding to any of the compositions in region R4 (alumina in the range of more than 0 mole percent to less than 35 mole percent, and yttria of more than 65 mole percent to less than 100 mole percent). In certain embodiments, the single-phase amorphous blend of yttria and alumina having the composition of region R4 may be homogeneous or substantially homogeneous.

[0047]

[0065] In one embodiment, the protective coating described herein may have the chemical composition of yttrium aluminum garnet (YAG) (in terms of the amounts of yttrium, aluminum, and oxygen in the composition), or be close to the chemical composition of YAG, but compared to other yttrium-based coatings and / or compared to other YAG coatings prepared and / or deposited differently from the present disclosure, it has improved chemical resistance and / or improved plasma resistance in aggressive chemical environments (e.g., aggressive halogen and / or hydrogen acidic environments), and has mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, airtightness, bonding strength, crystallinity / amorphousness, etc.) and chemical properties (e.g., chemical resistance).

[0048]

[0066] In certain embodiments, the plasma-resistant protective coating described herein provides greater chemical resistance compared to other yttrium-based coating compositions prepared using the same process, as will be described in detail in connection with FIGS. 7 and 10 below.

[0049]

[0067] The plasma-resistant protective coating may be an electron beam IAD deposition coating, a PVD deposition coating, or a plasma spray deposition coating applied to various ceramics (e.g., oxide-based ceramics, nitride-based ceramics, and / or carbide-based ceramics). Examples of oxide-based ceramics include SiO2 (quartz), Al2O3, Y2O3, etc. Examples of carbide-based ceramics include SiC, Si-SiC, etc. Examples of nitride-based ceramics include AlN, SiN, etc. The electron beam IAD coating plug material may be a calcined powder, a preformed mass (e.g., a mass formed by green body pressing or hot pressing, etc.), a sintered body (e.g., a sintered body having a density of 50 to 100%), or a machined body (e.g., a ceramic, a metal, or a metal alloy).

[0050]

[0068] Returning to FIG. 1, according to one embodiment, as illustrated, the lid 130, nozzle 132, and liner 116 each have plasma-resistant protective coatings 133, 134, and 136. In certain embodiments, the nozzle 132 is fabricated from any of the bulk compositions described herein. In certain embodiments, the nozzle is made exclusively (i.e., 100% of the nozzle) from a bulk composition consisting of single-phase bulk crystalline yttrium aluminum garnet. This bulk composition is: 1) Yttrium oxide in a molar concentration of from any of about 35 mole percent, about 35.5 mole percent, about 36 mole percent, about 36.5 mole percent, about 37 mole percent, or about 37.5 mole percent to any of about 38 mole percent, about 38.5 mole percent, about 39 mole percent, about 39.5 mole percent, or about 40 mole percent, or any single value molar concentration therein or any sub-range molar concentration therein, and 2) Aluminum oxide in a molar concentration of from any of about 60 mole percent, about 60.5 mole percent, about 61 mole percent, about 61.5 mole percent, or about 62 mole percent to any of about 62.5 mole percent, about 63 mole percent, about 63.5 mole percent, about 64 mole percent, about 64.5 mole percent, or about 65 mole percent, or any single value molar concentration therein or any sub-range molar concentration therein is included.

[0051]

[0069] It should be understood that in certain embodiments, any of the other chamber components as listed above may include a plasma-resistant protective coating and / or may be fabricated from any of the bulk compositions described herein.

[0052]

[0070] In one embodiment, the processing chamber 100 includes a chamber body 102 and a lid 130 that surround an internal space 106. The chamber body 102 can typically be fabricated from aluminum, stainless steel, or other suitable materials. The chamber body 102 generally includes sidewalls 108 and a bottom 110. In certain embodiments, any of the lid 130, the sidewalls 108, and / or the bottom 110 can include a plasma-resistant protective coating.

[0053]

[0071] To protect the chamber body 102, an outer liner 116 can be disposed adjacent to the sidewalls 108. The outer liner 116 can be fabricated from and / or coated with a plasma-resistant protective coating 136. In one embodiment, the outer liner 116 is fabricated from aluminum oxide.

[0054]

[0072] An exhaust port 126 can be defined in the chamber body 102 and can connect the internal space 106 to a pump system 128. The pump system 128 can include one or more pumps and throttle valves. These are utilized to evacuate the internal space 106 of the processing chamber 100 and regulate the pressure in the internal space 106.

[0055]

[0073] The lid 130 can be supported on the side wall 108 of the chamber body 102. The lid 130 can enable access to the internal space 106 of the processing chamber 100 in the open state and can provide a seal to the processing chamber 100 in the closed state. The gas panel 158 is connected to the processing chamber 100 and can supply a processing gas and / or a cleaning gas to the internal space 106 through the nozzle 132. The lid 130 may be a ceramic such as Al2O3, Y2O3, YAG, SiO2, AlN, SiN, SiC, Si—SiC, or a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3—ZrO2. In one embodiment, the lid 130 may be fabricated from any of the bulk compositions described herein. The nozzle 132 may be ceramic, for example, any of the ceramics described above for the lid. In one embodiment, the nozzle 132 may be fabricated from any of the bulk compositions described herein. The lid 130 and / or the nozzle 132 can each be coated with a plasma-resistant protective coating 133, 134.

[0056]

[0074] Examples of processing gases that can be used to process a substrate within the 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, and especially other gases such as O2 or N2O. Examples of carrier gases include N2, He, Ar, and other gases (e.g., non-reactive gases) that are inert with respect to the processing gas. A substrate support assembly 148 is disposed within the internal space 106 of the processing chamber 100 below the lid 130. The substrate support assembly 148 holds the substrate 144 during processing. A ring 146 (e.g., a single ring) can cover a portion of the electrostatic chuck 150 and can protect the covered portion from exposure to plasma during processing. In one embodiment, the ring 146 may be silicon or quartz.

[0057]

[0075] The inner liner 118 can be coated at the periphery of the substrate support assembly 148. The inner liner 118 may be a halogen-containing gas resist material such as the materials described with reference to the outer liner 116. In one embodiment, the inner liner 118 can be made of the same material as the outer liner 116. Further, in certain embodiments, the inner liner 118 may be coated with a plasma-resistant protective coating or may be made of any of the bulk compositions described herein.

[0058]

[0076] In one embodiment, the substrate support assembly 148 includes a mounting plate 162 that supports a pedestal 152 and an electrostatic chuck 150. The electrostatic chuck 150 further includes a thermally conductive base 164 and an electrostatic pack 166 joined to the thermally conductive base by a bond 138 (which may be a silicone bond in one embodiment). The mounting plate 162 is connected to the bottom 110 of the chamber body 102 and includes passages for routing utilities (such as fluids, power lines, sensor reads, etc.) to the thermally conductive base 164 and the electrostatic pack 166.

[0059]

[0077] The thermally conductive base 164 and / or the electrostatic pack 166 may include one or more optional embedded heating elements 176, embedded insulation 174, and / or conduits 168, 170 to control the lateral temperature profile of the support assembly 148. The conduits 168, 170 may be fluidly connected to a fluid source 172 through which a temperature control fluid is circulated. The embedded insulation 174 may be disposed between the conduit 168 and the conduit 170 in one embodiment. The heater 176 is regulated by a heater power supply 178. The conduits 168, 170 and the heater 176 can be utilized to control the temperature of the thermally conductive base 164 and to control the heating and / or cooling of the electrostatic pack 166 and the substrate (e.g., wafer) 144 being processed. The temperatures of the electrostatic pack 166 and the thermally conductive base 164 can be monitored using a plurality of temperature sensors 190, 192. The plurality of temperature sensors 190, 192 can be monitored using a controller 195.

[0060]

[0078] The electrostatic chuck 166 may further include a plurality of gas passages, such as grooves, mesas, and other surface features, which may be formed on the upper surface of the chuck 166. The gas passages may be fluidly connected to a source of heat transfer (or backside) gas, such as He, via holes drilled in the chuck 166. During operation, the backside gas is supplied into the gas passages at a controlled pressure, which may improve the heat transfer between the electrostatic chuck 166 and the substrate 144.

[0061]

[0079] The electrostatic chuck 166 includes at least one clamp electrode 180 controlled by a chuck power supply 182. The electrode 180 (or other electrodes disposed in the chuck 166 or the base 164) may be further coupled to one or more RF power supplies 184, 186 via a matching circuit 188 to maintain a plasma formed from a process gas and / or other gases within the processing chamber 100. The sources 184, 186 are generally capable of generating RF signals having a frequency from about 50 kHz to about 3 GHz and a power of up to about 10,000 watts. In certain embodiments, the bulk compositions and / or the coating compositions described herein have high energy plasma resistance, for example, when exposed to a power of up to about 10,000 watts.

[0062]

[0080] FIG. 3 shows a cross-sectional side view of an article (e.g., a lid, and / or a door, and / or a liner, and / or a nozzle, etc., of a chamber component) that may be covered by one or more plasma resistant protective coatings.

[0063]

[0081] Referring to FIG. 3, the body 305 of the chamber component 300 includes a coating stack 306 having a first plasma-resistant protective coating 308 and a second plasma-resistant protective coating 310. Alternatively, the article 300 may include only a single plasma-resistant protective coating 308 on the body 305. In certain embodiments, the body 305 is fabricated from any of the bulk compositions described herein. In embodiments where the body 305 is fabricated from any of the bulk compositions described herein, the body 305 may or may not be further coated with one or more plasma-resistant protective coatings 308, 310.

[0064]

[0082] In certain embodiments, various chamber components within the processing chamber may be coated with the plasma-resistant protective coatings described herein and / or fabricated from any of the bulk compositions described herein. Such bulk compositions include, but are not limited to, lids, lid liners, nozzles, substrate support assemblies, gas supply plates, plates, showerheads, electrostatic chucks, shadow frames, substrate holding frames, processing kit rings, single rings, chamber walls, bases, liner kits, shields, plasma screens, flow equalizers, cooling bases, chambers, chamber viewports, or chamber liners.

[0065]

[0083] In one embodiment, the plasma-resistant protective coatings 308, 310 have a thickness of up to about 300 μm. In further embodiments, the plasma-resistant protective coating has a thickness of less than about 20 microns (e.g., a thickness of about 0.5 microns to about 12 microns, a thickness of about 2 microns to about 12 microns, a thickness of about 2 microns to about 10 microns, a thickness of about 3 microns to about 7 microns, a thickness of about 4 microns to about 6 microns, or any sub-range or single thickness value thereof). The total thickness of the plasma-resistant protective coating stack in one embodiment is 300 μm or less.

[0066]

[0084] In certain embodiments, the plasma-resistant protective coating provides complete coverage of the underlying surface and has a uniform thickness. That the coating has a uniform thickness across various sections of the coating can be demonstrated by the fact that a section of the coating varies in thickness by about 15% or less, about 10% or less, or about 5% or less compared to another section (or can be demonstrated based on the standard deviation obtained from the multiple thicknesses of various sections of the coating).

[0067]

[0085] In certain embodiments, one or more plasma-resistant 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 described in more detail in connection with FIGS. 6A and 6B. The one or more EB-IAD deposited plasma-resistant protective coatings can have a relatively low film stress (e.g., compared to film stress caused by plasma spraying or sputtering). In certain 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 microns across a 12-inch diameter body. In certain embodiments, the curvature measurements of a 12-inch wafer indirectly indicate low stress with low curvature. In certain embodiments, the bending strength of a lid coated with an EB-IAD deposited plasma-resistant protective coating is about 412 MPa. In certain embodiments, the bending strength of the lid may be tested by a bending test.

[0068]

[0086] In certain embodiments, the plasma-resistant protective coatings described herein do not exhibit gaps, pinholes, or uncoated regions. According to the analysis of the cross-sectional morphology, in one embodiment, the porosity of one or more EB-IAD deposited plasma-resistant protective coatings is substantially 0% (i.e., non-porous). Such low porosity can enable effective vacuum sealing of chamber components during processing. The airtightness measures the sealing ability achievable using the plasma-resistant protective coating. According to one embodiment, by using an EB-IAD deposited plasma-resistant protective coating with a thickness of 5 micrometers, a He leak rate of less than 3E-9 (cm 3 / s), less than 2E-9 (cm 3 / s), or less than 1E-9 (cm 3 / s) can be achieved. In contrast, using alumina, a He leak rate of approximately 1E-6 cubic centimeters per second (cm 3 / s) is possible. The lower the He leak rate, the better the sealing performance. The airtightness measurement is performed by placing a coupon coated on the O-ring of a helium test stand, reducing the pressure until the gauge reaches <E-9 torr / s (or <1.3E-9 cm 3 / s), slowly moving a helium source around the O-ring, applying helium around the O-ring using a helium flow rate of approximately 30 sccm, and measuring the leak rate.

[0069]

[0087] In certain embodiments, the EB-IAD deposited plasma-resistant protective coating has a dense structure and may have performance advantages, for example, when applied to a chamber lid. Further, the EB-IAD deposited plasma-resistant protective coating has a low crack density and high adhesion to the body 305, which is beneficial for reducing cracks (both in the vertical and horizontal directions) in the coating, delamination of the coating, generation of yttrium-based particles by the coating, and defects of yttrium-based particles on the wafer. In certain embodiments, the adhesion strength of a 5 μm thick EB-IAD deposited plasma-resistant protective coating to an aluminum substrate may be greater than about 25 MPa, greater than about 26 MPa, greater than about 27 MPa, or greater than about 28 MPa. In certain embodiments, the adhesion strength can be measured by a tensile test according to ASTM 633C or JIS H8666.

[0070]

[0088] In certain embodiments, the roughness of the plasma-resistant protective coating may not change significantly from the initial roughness of the underlying substrate being coated. For example, in certain embodiments, the initial roughness of the substrate may be about 8 to 16 microinches, and the roughness of the coating may not change significantly. In certain embodiments, the initial roughness of the underlying substrate may be less than about 8 microinches, for example, about 4 to about 8 microinches, and the roughness of the plasma-resistant protective coating may not change significantly. The plasma-resistant protective coating may have a surface roughness of about 8 microinches or less or about 6 microinches or less.

[0071]

[0089] In certain embodiments, the plasma-resistant protective coating has a high hardness that can resist wear during plasma processing. The EB-IAD deposited plasma-resistant protective coating with a thickness of 5 micrometers according to the embodiment has a hardness of about ≧7 GPa, for example, about 8 GPa. The hardness of the coating is determined by nanoindentation in accordance with ASTM E2546-07.

[0072]

[0090] The EB-IAD deposited plasma-resistant protective coating according to the embodiment, with a thickness of 5 micrometers, has a breakdown voltage exceeding 2500 V / mil coating. The breakdown voltage is determined in accordance with JIS C 2110.

[0073]

[0091] The plasma-resistant protective coating described herein may have trace metals such as one or more of Ca, Cr, Cu, Fe, Mg, Mn, Ni, K, Mo, Na, Ti, Zn. The trace metal levels are determined using laser ablation inductively coupled plasma mass spectrometry (LA ICPMS) at a depth of 2 μm. In certain embodiments, the plasma-resistant protective coating described herein has a purity of about 99.5% or more, about 99.6% or more, about 99.7% or more, about 99.8% or more, or about 99.9% or more, based on atomic % or wt% of the plasma-resistant protective coating.

[0074]

[0092] Chamber parts having the EB-IAD plasma-resistant protective coating can be used in applications subject to a wide range of temperatures. For example, the plasma-resistant protective coating described herein can be stable at operating temperatures in the range of about 80°C to about 120°C.

[0075]

[0093] It should be noted that the composition of the plasma-resistant protective coating described herein (regardless of whether it is deposited by EB-IAD, PVD, plasma spraying, or any other deposition method contemplated herein) can be modified such that the material properties and characteristics specified above can vary by up to 10% in certain embodiments or up to 30% in other embodiments. Accordingly, in certain embodiments, the values described for the properties of the plasma-resistant protective coating should be understood as exemplary achievable values. In certain embodiments, the plasma-resistant protective coating described herein should not be construed as being limited to the values provided.

[0076]

[0094] In certain embodiments, one or more plasma-resistant protective coatings (e.g., 308 and / or 310) are deposited on the body 305 of the article 300 using physical vapor deposition (PVD) which is described in more detail in connection with FIG. 8, plasma spraying which is described in more detail in connection with FIG. 9, an ion-assisted deposition (IAD) process without using an electron beam, or any other suitable deposition process.

[0077]

[0095] As described above, various chamber components within the processing chamber may be coated with a plasma-resistant protective coating (deposited by IAD, plasma spraying, or PVD as described herein) and / or may be fabricated from any one of the bulk compositions described herein. In one embodiment, chamber components fabricated from the bulk compositions described herein and / or coated with a plasma-resistant protective coating as described herein include one or more of a lid (e.g., 130), a nozzle (e.g., 132), and / or a liner (e.g., 116 and / or 118). In one embodiment, the chamber component is a lid that can be fabricated from the bulk compositions described herein and / or can be coated with a plasma-resistant protective coating as described herein. In one embodiment, the chamber component is a nozzle that can be fabricated from the bulk compositions described herein and / or can be coated with a plasma-resistant protective coating as described herein. In one embodiment, the chamber component is a liner that can be fabricated from the bulk compositions described herein and / or can be coated with a plasma-resistant protective coating as described herein. In one embodiment, the chamber component is a kit that includes two or more of a lid, a nozzle, and a liner, and the lid, the nozzle, and the liner can each be fabricated from the bulk compositions described herein and / or can be coated with a plasma-resistant protective coating as described herein.

[0078]

[0096] FIG. 4A is a perspective view of a chamber lid 505 (similar to chamber lid 130 of FIG. 1) having a plasma-resistant protective coating 510, according to one exemplary embodiment. FIG. 4B is a side cross-sectional view of a chamber lid 505 having a plasma-resistant protective coating 510 (similar to coating 133 of FIG. 1), according to one exemplary embodiment. Chamber lid 505 includes a hole 520. Hole 520 may be at the center of the lid or at other locations on the lid. Lid 505 may further have a lip 515 that contacts the chamber wall when closed. In one embodiment, plasma-resistant protective coating 510 does not cover lip 515. A hard mask or soft mask that covers lip 515 may be used during deposition to ensure that the plasma-resistant protective coating does not cover lip 515. This mask may then be removed after deposition. Alternatively, protective layer 510 can coat the entire surface of the lid. Thus, protective layer 510 may be placed on the sidewalls of the chamber during processing.

[0079]

[0097] As shown in FIG. 4B, plasma-resistant protective coating 510 may have a sidewall portion 530 that coats the interior of hole 520. Sidewall portion 530 of protective layer 510 may be thicker near the surface of lid 505 and gradually thinner towards the back of hole 520. In such an embodiment, sidewall portion 530 may not cover the entire sidewall of hole 520.

[0080]

[0098] FIG. 6A shows a deposition mechanism applicable to various deposition techniques using energy particles, such as ion-assisted deposition (IAD). Exemplary IAD methods incorporate ion collisions in the deposition process, such as vapor deposition under ion collisions (e.g., activated reactive evaporation (ARE)) and sputtering for forming the plasma-resistant protective coatings described herein. A particular type of IAD performed in an embodiment is electron beam IAD (e-beam IAD). Any IAD method can be performed in the presence of reactive gas species such as O2, N2, halogens (e.g., fluorine), argon, etc. The reactive species can burn surface organic contaminants before and / or during deposition. Further, in an embodiment, the IAD deposition process for ceramic target deposition versus metal target deposition can be controlled by the partial pressure of O2 ions. Alternatively, the ceramic target can be used in the absence of oxygen or with reduced oxygen. In a particular embodiment, the IAD deposition is performed in the presence of oxygen and / or argon. In a particular embodiment, the IAD deposition is performed in the presence of fluorine such that the coating is deposited with fluorine incorporated therein. The coating with fluorine incorporated is considered to have less potential for interaction with wafer processes involving similar environments (e.g., processes involving a fluorine environment).

[0081]

[0099] As shown, a plasma-resistant protective coating 615 (similar to coatings 133, 134, and 136 of FIG. 1, 308 and / or 310 of FIG. 3, 510 of FIGS. 4A and 4B) is formed on an article 610 or a plurality of articles 610A, 610B (e.g., any chamber component described above, including a lid and / or a nozzle and / or a liner) by the accumulation of a deposition material 602 in the presence of high-energy particles 603 such as ions. The deposition material 602 may include atoms, ions, radicals, etc. The energy particles 603 can collide with the coating when the plasma-resistant protective coating 615 is formed and compress the coating.

[0082]

[0100] In one embodiment, EB-IAD is utilized to form the plasma-resistant protective coating 615. FIG. 6B shows a schematic view of an IAD deposition apparatus. As shown, the material source 650 supplies a flux of deposition material 602, while the energy particle source 655 supplies a flux of energy particles 603, and both impinge on the articles 610, 610A, 610B throughout the IAD process. The energy particle source 655 may be oxygen or other ion sources. The energy particle source 655 may further supply other types of energy particles such as radicals, neutrons, atoms, and nano-sized particles from a particle generation source (e.g., plasma, reactive gas, or a material source supplying the deposition material).

[0083]

[0101] The material source (e.g., target body or plug material) 650 used to supply the deposition material 602 may be a bulk sintered ceramic corresponding to the same ceramic that should constitute the plasma-resistant protective coating 615. The material source may be a bulk sintered ceramic composite (e.g., bulk sintered YAG, bulk sintered Y2O3, and / or bulk sintered Al2O3), and / or other described ceramics, or may include them. 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, such as powders, calcined powders, preformed materials (e.g., formed by green body pressing or hot pressing), or machined bodies (e.g., molten materials) can also be used. All of the various types of material sources 650 are melted into a molten material source during deposition. However, depending on the type of starting material, the time required to melt varies. Molten materials and / or machined bodies are likely to melt the fastest. Preformed materials take longer to melt than molten materials, calcined powders melt slower than preformed materials, and standard powders melt slower than calcined powders.

[0084]

[0102] In some embodiments, the material source is a metallic material (e.g., a mixture of Y and Al, or two different targets, one being Y and the other being A). Oxygen ions can be collided with such a material source to form an oxide coating. Additionally or alternatively, during the IAD process, oxygen gas (and / or oxygen plasma) can be flowed into the deposition chamber to interact the sputtered or evaporated metal of Y and Al with oxygen to form an oxide coating.

[0085]

[0103] IAD can utilize one or more plasmas or beams (e.g., an electron beam) to provide a material and a high-energy ion source. The reactive species may be supplied during the deposition of the plasma-resistant coating. In one embodiment, the energy particles 603 include at least one of a non-reactive species (e.g., Ar) or a reactive species (e.g., O). In further embodiments, reactive species such as CO and halogens (Cl, F, Br, etc.) can also be introduced during the formation of the plasma-resistant protective coating, further enhancing the tendency to selectively remove the deposited material most weakly bonded to the plasma-resistant protective coating 615.

[0086]

[0104] In the IAD process, the energy particles 603 can be controlled by an energy ion (or other particle) source 655 separately from other deposition parameters. Depending on the energy (e.g., velocity), density, and incident angle of the energy ion flux, the composition, structure, crystal orientation, particle size, and amorphousness of the plasma-resistant protective coating can be manipulated.

[0087]

[0105] Adjustable additional parameters are the temperature of the article during deposition and the duration of deposition. In one embodiment, the IAD deposition chamber (and chamber lid) is heated to a starting temperature of 70 °C or higher before deposition. In one embodiment, the starting temperature is from 50 °C to 250 °C. In one embodiment, the starting temperature is from 50 °C to 100 °C. During deposition, the temperature of the chamber and lid can be maintained at the temperature of the starting temperature. In one embodiment, the IAD chamber includes a heat lamp for heating. In an alternative embodiment, the IAD chamber and lid are not heated. If the chamber is not heated, its temperature naturally rises to about 70 °C as a result of the IAD process. When the temperature during deposition is high, the density of the plasma-resistant protective coating may be high, but the mechanical stress of the plasma-resistant protective coating may also be high. In order to maintain a low temperature during coating, active cooling can be added to the chamber. In one embodiment, the low temperature can be maintained at any temperature from 70 °C or lower to 0 °C.

[0088]

[0106] Adjustable additional parameters include the working distance 670 and the angle of incidence 672. The working distance 670 is the distance between the material source 650 and the articles 610A, 610B. In one embodiment, the working distance is from 0.2 to 2.0 meters, and in certain embodiments the working distance is 1.0 meter. Shortening the working distance increases the deposition rate and enhances the effect of ion energy. However, if the working distance is shorter than a certain distance, the uniformity of the protective layer may decrease. The angle of incidence is the angle at which the deposited material 602 impinges on the articles 610A, 610B. In one embodiment, the angle of incidence is from 10 to 90 degrees.

[0089]

[0107] The IAD coating can be applied to a wide range of surface conditions having roughness from about 0.1 microinch (μin) to about 180 μin. However, if the surface is smoother, uniform coating coverage is promoted. The thickness of the coating can be up to about 300 microns (μm). During manufacturing, the thickness of the coating on the part can be evaluated by intentionally adding rare earth oxide based colored agents such as Nd2O3, Sm2O3, Er2O3, etc. to the bottom of the coating layer stack. Further, the thickness can be accurately measured by ellipsometry.

[0090]

[0108] In the embodiments described herein, the IAD coating is amorphous. Amorphous coatings are more conformal and can reduce epitaxial cracks generated by lattice mismatch compared to crystalline coatings. In one embodiment, the plasma resistant protective coating described herein is 100% amorphous with a zero crystallinity. In certain embodiments, the plasma resistant protective coating described herein is conformal and has low film stress.

[0091]

[0109] Multiple electron beam (e-beam) guns can be used to achieve Co deposition on multiple targets and generate thicker coatings or layered structures. For example, it is also possible to use two targets of the same material type simultaneously. Each target can also be irradiated by various different electron beam guns. Thereby, the deposition rate and the thickness of the protective layer can be increased. In another example, the two targets may be different ceramic materials respectively. For example, a target of Al or Al2O3 on one hand and a target of Y or Y2O3 on the other hand may be used. The first electron beam gun irradiates the first target to deposit the first protective layer, and then the second electron beam gun irradiates the second target to form a second protective layer having a different material composition from the first protective layer.

[0092]

[0110] In one embodiment, a single target material (also referred to as a plug material) and a single electron beam gun can be used to reach the plasma-resistant protective coating described herein.

[0093]

[0111] In one embodiment, a plurality of chamber parts (e.g., a plurality of lids or a plurality of liners or a plurality of nozzles) are processed in parallel within the IAD chamber. Each chamber part can be supported by a different fixture. Alternatively, a single fixture may be configured to hold a plurality of chamber parts. The fixture can move the supported chamber parts during deposition.

[0094]

[0112] In one embodiment, the fixture for holding the chamber parts can be designed from a metal part such as cold-rolled steel or a ceramic such as Al2O3, Y2O3. Using this fixture, the chamber parts can be supported above or below the material source and the electron beam gun. The fixture can have a chucking ability to chuck the chamber parts during coating for safer and easier handling. Further, the fixture can have features for orienting or positioning the chamber parts. In one embodiment, the fixture can be repositioned and / or rotated about one or more axes to change the orientation of the supported chamber parts relative to the source material. Further, the fixture may be repositioned to change the working distance and / or the angle of incidence before and during deposition. The fixture can have cooling channels or heating channels to control the temperature of the chamber parts during coating. Since IAD is a line of sight process, the ability to reposition and rotate the chamber parts can enable maximum coating coverage of 3D surfaces such as holes.

[0095]

[0113] In certain embodiments, the IAD-deposited plasma-resistant protective coating described herein provides higher chemical resistance to corrosive chemical substances (e.g., hydrogen-based chemical substances, halogen-based chemical substances, or mixtures thereof) compared to other yttrium-based bulk compositions and / or compared to other coatings that may have the same chemical composition but different mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, hermeticity, bond strength, crystallinity / amorphousness, etc.) and / or chemical properties (e.g., chemical resistance). For example, in one embodiment, the IAD-deposited plasma-resistant protective coating has a chemical composition corresponding to or close to that of YAG (in terms of the amounts of aluminum, yttrium, and oxygen), thereby providing improved chemical resistance and / or improved plasma resistance in aggressive chemical environments (e.g., aggressive halogen and / or hydrogen acidic environments) compared to other yttrium-based coatings and / or compared to other YAG coatings prepared and / or deposited differently from the present disclosure.

[0096]

[0114] The improved chemical resistance of the IAD-deposited plasma protection coatings described herein, compared to other yttrium-based coatings, is shown in FIGS. 7A1, 7A2, 7B1, 7B2, 7C1, 7C2, 7D1, and 7D2. FIGS. 7A1 and 7A2 show yttria (Y2O3) IAD-deposited coatings before (FIG. 7A1) and after (FIG. 7A2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 7A2, the yttria IAD-deposited coating has disappeared after the accelerated chemical resistance test (i.e., FIG. 7A2 shows that 100% of the coating has been attacked). FIGS. 7A1 and 7A2 show IAD-deposited coatings composed of ceramic compounds containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 before (FIG. 7B1) and after (FIG. 7B2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 7A2, the IAD-deposited coating composed of a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 has almost disappeared after the accelerated chemical resistance test (i.e., FIG. 7B2 shows that 70% of the coating has been attacked). FIGS. 7C1 and 7C2 show IAD-deposited coatings composed of Y2O3-ZrO2 solid solution before (FIG. 7C1) and after (FIG. 7C2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 7C2, the IAD-deposited coating composed of Y2O3-ZrO2 solid solution has disappeared after the accelerated chemical resistance test (i.e., FIG. 7C2 shows that 100% of the coating has been attacked).

[0097]

[0115] Figures 7D1 and 7D2 show the IAD-deposited single-phase amorphous YAG coating (i.e., an amorphous single-phase blend of yttria and alumina having a composition of yttria and alumina corresponding to YAG in the alumina-yttria phase diagram shown in FIG. 2) before (FIG. 7C1) and after (FIG. 7C2) exposure to aggressive acid immersion for 60 minutes in concentrated halogenated acids (e.g., HCl, HF, HBr) according to an embodiment. After the accelerated chemical resistance test, no damage was observed to the IAD-deposited single-phase amorphous YAG coating (i.e., FIG. 7A2 shows that 0% of the coating was attacked).

[0098]

[0116] Figures 7A1 - 7D2 illustrate that the plasma-resistant protective coating deposited by IAD according to the embodiments described herein exhibits improved chemical resistance to harsh chemical environments (e.g., harsh acidic environments, as well as halogen and / or hydrogen-based environments) compared to other yttrium-based IAD-deposited coatings. Further, such chemical resistance reduces the number of yttrium-based particles over long processing times, and thus wafer defects.

[0099]

[0117] Without being limited thereto, looking at FIGS. 7A1 through 7D2, in certain embodiments, it can be understood that as the aluminum / alumina concentration increases in the IAD-deposited plasma-resistant coating composition, the chemical resistance of the coating (determined based on the acid stress test) improves.

[0100]

[0118] The plasma-resistant protective coating described herein can be deposited using physical vapor deposition (PVD). The PVD process can be used to deposit thin films having a thickness in the range of a few nanometers to a few micrometers. Three basic characteristics are common to various PVD processes. (1) Evaporate the material from a solid source with the aid of a high-temperature plasma or a gas plasma. (2) Transport the evaporated material to the surface of the article in a vacuum. (3) Condense the evaporated material on the article to form a thin film layer. FIG. 8 shows an exemplary PVD reactor.

[0101]

[0119] Figure 8 shows a deposition mechanism applicable to various PVD techniques and reactors. The PVD reactor chamber 800 may include a plate 810 adjacent to the article 820 and a plate 815 adjacent to the target 830. In certain embodiments, multiple targets (e.g., two targets) may be used. Air may be evacuated from the reactor chamber 800 to form a vacuum. Then, a gas (e.g., argon gas or oxygen gas) is introduced into the reactor chamber, a voltage is applied to the plates, and a plasma including electrons and positive ions (e.g., 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. At the negatively charged plate 815, the ions 840 may collide with one or more targets 830, and atoms 835 may be released from the targets. The released atoms 835 may be transported and deposited onto the article 820 as a coating 825. The coating may be a single-layer structure or may include a multi-layer structure (e.g., layers 825 and 845).

[0102]

[0120] The article 820 of Figure 8 may represent various semiconductor processing chamber components (including, but not limited to, substrate support assemblies, electrostatic chucks (ESCs), rings (e.g., process kit rings or single rings), chamber walls, bases, gas supply plates, gas lines, showerheads, nozzles, lids, liners, liner kits, shields, plasma screens, flow equalizers, cooling bases, chamber viewports, chamber lids, etc.).

[0103]

[0121] The coating 825 (and optionally 845) of FIG. 8 may represent any of the plasma-resistant protective coatings described herein. The coating 825 (and optionally 845) may have a similar composition of aluminum / alumina, yttria / yttrium, and oxygen, like the coatings described above. Similarly, the plasma-resistant protective coating 825 (and optionally 845) may have any of the properties described above, including, but not limited to, amorphous fraction, porosity, density, bonding strength, roughness, chemical resistance, physical resistance, hardness, purity, breakdown voltage, bending strength, airtightness, stability, etc.

[0104]

[0122] Furthermore, the plasma-resistant protective coating 825 (and optionally 845) may show a reduction in defects (estimated based on yttrium-based particle defects per wafer) when exposed to an aggressive chemical environment and / or an aggressive plasma environment over a long processing time.

[0105]

[0123] The plasma-resistant protective coatings described herein can be deposited using a plasma spraying process, an example of which is shown in FIG. 9. FIG. 9 shows a cross-sectional view of a plasma spraying device 900 according to one embodiment. The plasma spraying device 900 is a type of thermal spraying system used to perform "slurry plasma spraying (SPS)" deposition of ceramic materials. The following description is provided in relation to the SPS technique, but other standard plasma spraying techniques using dry powder mixtures can also be utilized to deposit the coatings described herein.

[0106]

[0124] In SPS deposition, a solution-based distribution of particles (slurry) is utilized to deposit a ceramic coating on a substrate. SPS can be performed by spraying the slurry using atmospheric pressure plasma spray (APPS), high velocity oxy-fuel (HVOF), warm spraying, vacuum plasma spraying (VPS), and low pressure plasma spraying (LPPS).

[0107]

[0125] The plasma spraying device 900 may include a casing 902 that houses a nozzle anode 906 and a cathode 904. The casing 902 allows a gas flow 908 to pass through the plasma spraying device 900 and between the nozzle anode 906 and the cathode 904. An external power source may be used to apply a potential between the nozzle anode 906 and the cathode 904. This potential causes an arc to occur between the nozzle anode 906 and the cathode 904, and the arc ignites the gas flow 908 to generate a plasma gas. The ignited plasma gas flow 908 generates a high-speed plasma plume 914 directed from the nozzle anode 906 towards the substrate 920.

[0108]

[0126] The plasma spraying device 900 may be disposed within a chamber or an atmospheric pressure booth. In some embodiments, the gas flow 908 may be a gas or a mixed gas including, but not limited to, argon, oxygen, nitrogen, hydrogen, helium, and combinations thereof. In certain embodiments, other gases such as fluorine can be introduced to incorporate some fluorine into the coating and enhance the wear resistance in a fluorine-treated environment.

[0109]

[0127] The plasma spraying device 900 may include one or more fluid lines 912 for supplying the slurry into the plasma plume 914. In some embodiments, the plurality of fluid lines 912 may be arranged symmetrically around or on one side of the plasma plume 914. In some embodiments, the fluid lines 912 may be arranged to be orthogonal to the direction of the plasma plume 914, as shown in FIG. 9. In other embodiments, the fluid lines 912 may be adjusted to supply the slurry to the plasma plume at different angles (e.g., 45°), or may be arranged at least partially inside the casing 902 for injecting the slurry internally into the plasma plume 914. In some embodiments, each fluid line 912 may supply a different slurry. This slurry can be used to vary the composition of the coating obtained across the substrate 920.

[0110]

[0128] A slurry supply system can be used to supply the slurry to the fluid line 912. In some embodiments, the slurry supply system includes a flow controller to maintain a constant flow rate during the coating. The fluid line 912 can be cleaned before and after the coating process, for example, using deionized water. In some embodiments, the slurry container containing the slurry supplied to the plasma spraying device 900 is mechanically agitated during the coating process to keep the slurry homogeneous and prevent precipitation.

[0111]

[0129] Alternatively, in a standard powder-based plasma spraying technique, a powder supply system including one or more powder containers filled with one or more different powders can be utilized to supply the powder to the plasma plume 914 (not shown).

[0112]

[0130] The plasma plume 914 can reach very high temperatures (e.g., between about 3000°C and about 10000°C). When one or more slurries are injected into the plasma plume 914, the intense temperature experienced by the slurries can rapidly evaporate the slurry solvent, melt the ceramic particles, and generate a particle stream 916 that is propelled towards the substrate 920. In standard powder-based plasma spraying techniques, the intense temperature of the plasma plume 914 also melts the powder sent there and extrudes the molten particles towards the substrate 920. The molten particles can flatten upon impact with the substrate 920 and rapidly solidify on the substrate to form a ceramic coating 918. The solvent may be completely evaporated before the ceramic particles reach the substrate 920.

[0113]

[0131] The plasma spray deposited plasma resistant protective coating may be more porous in certain embodiments than that of the coating deposited by electron beam IAD. For example, in certain embodiments, the plasma spray deposited plasma resistant protective coating may have a 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 certain embodiments, the porosity is measured by a 1000x scanning electron microscope (SEM) image and software calculates the area ratio of the porosity.

[0114]

[0132] Parameters that can affect the thickness, density, and roughness of the ceramic coating include slurry conditions, particle size distribution, slurry feed rate, plasma gas composition, gas flow rate, energy input, spray distance, and substrate cooling.

[0115]

[0133] The article 920 of FIG. 9 can represent various semiconductor processing chamber components (including, but not limited to, substrate support assemblies, electrostatic chucks (ESCs), rings (e.g., process kit rings or single rings), chamber walls, bases, gas supply plates, gas lines, showerheads, nozzles, lids, liners, liner kits, shields, plasma screens, flow equalizers, cooling bases, chamber viewports, chamber lids, etc.).

[0116]

[0134] Coating 918 of FIG. 9 may represent any of the plasma-resistant protective coatings described herein. Coating 918 may have a similar composition of aluminum / alumina, yttria / yttrium, and oxygen, like the coatings described above. Similarly, the plasma-resistant protective coating 918 may have the properties described above, for example, but not limited to, the amorphous ratio (e.g., an amorphous percentage exceeding any of about 80%, about 85%, about 90%, about 95%, or about 98%), porosity (e.g., a porosity lower than any of about 2%, about 1.5%, about 1%, about 0.5%, or about 0.1%), density, bond strength (e.g., a bond strength exceeding 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., a hardness exceeding any of about 6 GPa, about 7 GPa, about 8 GPa, about 9 GPa, or about 10 GPa), purity, breakdown voltage (a breakdown voltage exceeding any of about 800 V / mil, about 1000 V / mil, about 1250 V / mil, about 1500 V / mil, or about 2000 V / mil), roughness, flexural strength, airtightness, stability, etc. Further, coating 918 may show a reduction in defects (estimated based on yttrium-based particle defects per wafer) when exposed to an aggressive chemical environment and / or an aggressive plasma environment over a long processing time.

[0117]

[0135] In certain embodiments, the plasma-resistant protective coatings deposited by plasma spraying described herein provide higher chemical resistance to corrosive chemicals (e.g., hydrogen-based chemicals, halogen-based chemicals, or mixtures thereof) compared to other yttrium-based bulk compositions and / or compared to other coatings that may have the same chemical composition but different mechanical properties (e.g., density, porosity, hardness, breakdown voltage, roughness, gas tightness, bond strength, crystallinity / amorphousness, etc.) and / or chemical properties (e.g., chemical resistance). For example, in one embodiment, the plasma-resistant protective coatings deposited by plasma spraying have a chemical composition corresponding to or close to that of YAG (in terms of the amounts of aluminum, yttrium, and oxygen), thereby providing improved chemical resistance and / or improved plasma resistance in aggressive chemical environments (e.g., aggressive halogen and / or hydrogen acidic environments) compared to other yttrium-based coatings and / or compared to other YAG coatings prepared and / or deposited differently from the present disclosure.

[0118]

[0136] Compared with other yttrium-based coating compositions deposited by plasma spraying, the improved chemical resistance of the plasma-sprayed plasma-resistant protective coatings described herein is shown in FIGS. 10A1, 10A2, 10B1, 10B2, 10C1, 10C2, 10D1, and 10D2. FIGS. 10A1 and 10A2 show yttria (Y2O3) coatings deposited by plasma spraying before (FIG. 10A1) and after (FIG. 10A2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 10A2, the plasma-sprayed yttria coating showed significant damage (e.g., FIG. 10A2 shows that approximately 50% of the coated area examined was attacked) after the accelerated chemical resistance test (in more than 25% of the coated area examined). FIGS. 10B1 and 10B2 show coatings deposited by plasma spraying consisting of a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 before (FIG. 10B1) and after (FIG. 10B2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 10B2, the plasma-sprayed coating consisting of a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 showed local and moderate damage (in 15% of the coated area examined) after the accelerated chemical resistance test. FIGS. 10C1 and 10C2 show coatings deposited by plasma spraying consisting of a Y2O3-ZrO2 solid solution before (FIG. 10C1) and after (FIG. 10C2) exposure to aggressive acid immersion for 60 minutes in concentrated halogen-based acids (e.g., HCl, HF, HBr). In FIG. 10C2, the plasma-sprayed coating consisting of a Y2O3-ZrO2 solid solution showed local and moderate to severe damage (in 30% of the coated area examined) after the accelerated chemical resistance test.

[0119]

[0137] Figures 10D1 and 10D2 show a plasma-sprayed substantially amorphous YAG coating (i.e., a blend of at least 90% amorphous single-phase yttria and alumina having a composition of yttria and alumina corresponding to YAG in the alumina-yttria phase diagram shown in FIG. 2) before (FIG. 10D1) and after (FIG. 10D2) exposure to aggressive acid immersion for 60 minutes in concentrated halogenated acids (e.g., HCl, HF, HBr) according to an embodiment. After the accelerated chemical resistance test, local and minor damage (in about 0% to 3% of the coated area examined) and substantially no damage were observed in the plasma-sprayed substantially amorphous YAG coating.

[0120]

[0138] Figures 10A1 - 10D2 illustrate that a plasma-sprayed plasma-resistant protective coating according to the embodiments described herein exhibits improved chemical resistance to harsh chemical environments (e.g., harsh acidic environments, and halogen and / or hydrogen-based environments) compared to other yttrium-based plasma-sprayed coatings. Further, such chemical resistance reduces the number of yttrium-based particles over long processing times, and thus wafer defects.

[0121]

[0139] Without being limitedly construed, from FIGS. 10A1 to 10D2, it can be understood that in certain embodiments, as the aluminum / alumina concentration increases in the plasma-sprayed coating composition, the chemical resistance of the coating (determined based on an acid stress test) improves.

[0122]

[0140] Figure 11 shows an embodiment of a method 1100 for coating an article such as a chamber component with a plasma-resistant protective coating according to an embodiment. In block 1110 of process 1100, an article such as a chamber component is provided. The chamber component (e.g., a lid or nozzle or liner) may have a bulk sintered ceramic body having any of the bulk compositions described above. Alternatively, the bulk sintered ceramic body may be a ceramic compound composed of Al2O3, Y2O3, SiO2, or a solid solution of Y4Al2O9 and Y2O3-ZrO2.

[0123]

[0141] In block 1120, an ion-assisted deposition (IAD) process (e.g., EB-IAD), or plasma spraying, or PVD is performed to deposit any of the corrosion-resistant and erosion-resistant plasma-resistant protective coatings described herein on at least one surface of the chamber component. In one embodiment, an electron beam ion-assisted deposition process (EB-IAD) 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.

[0124]

[0142] In certain embodiments, the corrosion-resistant and erosion-resistant plasma-resistant protective coating may be deposited by EB-IAD and may include a single-phase amorphous blend of yttrium oxide in a molar concentration in the range of about 35 mole percent to about 95 mole percent and aluminum oxide in a molar concentration in the range of about 5 mole percent to about 65 mole percent. In certain embodiments, the plasma-resistant protective coating includes yttrium oxide in a molar concentration in the range of 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration in the range of 60 mole percent to 65 mole percent. In certain embodiments, the plasma-resistant protective coating includes yttrium oxide in a molar concentration in the range of 37 mole percent to 38 mole percent and aluminum oxide in a molar concentration in the range of 62 mole percent to 63 mole percent.

[0125]

[0143] To achieve a plasma-resistant coating having any of the compositions described herein, including, but not limited to, a porosity of 0%, 100% amorphousness, a bonding strength exceeding about 25 MPa, a roughness less than about 6 μin, a breakdown voltage exceeding about 2500 V / mil, an airtightness less than about 3E-9, a hardness of about 8 GPa, a flexural strength exceeding about 400 MPa, stability at a temperature from about 80 °C to about 120 °C, chemical stability, or physical stability, etc., any of the properties described herein, the EB-IAD deposition process can be optimized.

[0126]

[0144] In certain embodiments, the corrosion- and erosion-resistant plasma-protective coating can be deposited by plasma spraying or physical vapor deposition and can include a substantially amorphous (e.g., exceeding about 90% amorphous) blend of yttrium oxide in a molar concentration in the range of about 35 mole percent to about 95 mole percent and aluminum oxide in a molar concentration in the range of about 5 mole percent to about 65 mole percent. In certain embodiments, the plasma-protective coating includes yttrium oxide in a molar concentration in the range of 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration in the range of 60 mole percent to 65 mole percent. In certain embodiments, the plasma-protective coating includes yttrium oxide in a molar concentration in the range of 37 mole percent to about 38 mole percent and aluminum oxide in a molar concentration in the range of 62 mole percent to 63 mole percent.

[0127]

[0145] To achieve a plasma-resistant coating having any of the compositions described herein and having any of the properties described herein, including, but not limited to, exceeding 90% amorphous, chemical stability, or physical stability, etc., the physical vapor deposition or plasma spraying deposition process can be optimized.

[0128]

[0146] FIG. 12 shows a method 1200 for processing a wafer in a processing chamber that includes at least one chamber component fabricated from any of the bulk compositions described herein and / or coated with any of the plasma-resistant protective coatings described herein. Method 1200 includes transferring a wafer into a processing chamber that includes at least one chamber component (e.g., a lid, a liner, a door, a nozzle, etc.) fabricated from any of the bulk compositions described herein and / or coated with any of the plasma-resistant protective coatings described herein (1210). Method 1200 further includes processing the wafer in the processing chamber in a harsh chemical environment and / or a high-energy plasma environment (1220). The processing environment includes 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, and in particular, other gases such as O2 or N2O. In one embodiment, the wafer can be processed in Cl2. In one embodiment, the wafer can be processed in H2. In one embodiment, the wafer can be processed in HBr. Method 1200 further includes transferring the processed wafer out of the processing chamber (1230).

[0129]

[0147] A wafer processed according to the method described herein in a processing chamber having at least one chamber component fabricated from any of the bulk compositions described herein and / or coated with a plasma-resistant protective coating according to an embodiment has fewer yttrium-based particle defects thereon, as shown in FIGS. 13A through 13C and FIG. 14. For example, when exposed to a corrosive chemical, the average total number of yttrium-based particles released from any of the plasma-resistant protective coatings described herein and / or from any of the bulk compositions is less than about 3 per 500 radio frequency hours (RFhrs), less than about 2 per 500 RFhrs, less than about 1 per 500 RFhrs, or zero per 500 RFhrs.

[0130]

[0148] FIG. 13A shows the number of yttrium-based particles generated after a long processing time under a harsh chemical environment (in the presence of aggressive Cl2, H2, and fluorine-based chemicals) and high-energy plasma by a lid fabricated from bulk YAG according to an embodiment. Similar results were observed for lids coated with a YAG coating deposited by plasma spraying, PVD, and IAD according to an embodiment. As shown in FIG. 13A, after a long processing time of about 770 radio frequency hours (RFhrs), the number of yttrium-based particles was zero. In other words, the lid passed 770 RFhr with 100% zero yttrium-based particles. In certain embodiments, the bulk composition and / or the coating composition described herein has high-energy plasma resistance when exposed to a power of up to about 10,000 watts over a long processing time in the range of, for example, any of about 200 RFhrs, about 300 RFhrs, or about 400 RFhrs to any of about 500 RFhrs, about 600 RFhrs, about 700 RFhrs, or about 800 RFhrs, or any sub-range or single value thereof.

[0131]

[0149] FIG. 13B shows the number of yttrium-based particles generated after a long processing time under a harsh chemical environment (in the presence of aggressive Cl2, H2, and fluorine-based chemicals) and high-energy plasma by a nozzle fabricated from bulk YAG according to an embodiment. Similar results were observed for nozzles coated with a YAG coating deposited by plasma spraying, PVD, and IAD according to an embodiment. As shown in FIG. 13B, after a long processing time of about 460 RFhrs, the number of yttrium-based particles was two. In other words, the nozzle passed 460 RFhr with more than 95% zero yttrium-based particles.

[0132]

[0150] Figure 13C shows a comparison of performance related to the number of yttrium-based particles generated by a kit of a nozzle and a lid according to an embodiment (e.g., each component is made of bulk YAG according to the embodiment, and similar results are observed for parts coated with a YAG coating deposited by plasma spraying, PVD, and IAD according to the embodiment), and a comparison kit of a nozzle for comparison and a lid for comparison (e.g., each component is made of a bulk ceramic made of a Y2O3-ZrO2 solid solution and / or coated with a coating made of a Y2O3-ZrO2 solid solution deposited by plasma spraying, PVD, or IAD) after a long processing time under a harsh chemical environment and high-energy plasma.

[0133]

[0151] In Figure 13C, the comparison kit (having a nozzle for comparison and a lid for comparison) resulted in generating significantly more yttrium-based particles on average during long-term processing (e.g., about 500 RFhrs) compared to the kit of the lid and nozzle according to the embodiments described herein. For example, the average number of yttrium-based particles generated during the long-term processing of the comparison kit was in the range of about 1 to about 3 (or, including the standard deviation, 0 to about 6 yttrium-based particles). In contrast, the average number of yttrium-based particles generated during the long-term processing of the kit according to the embodiments described herein was 0.

[0134]

[0152] Furthermore, in FIG. 13C, the kit to be compared (having the nozzle to be compared and the lid to be compared) showed significant variations depending on each processing occasion as compared with the kit of the lid and the nozzle according to the embodiments described herein. For example, the number of yttrium-based particles generated during the processing of the kit to be compared varied from 0 to 8 over a plurality of processing occasions. "Processing occasions" refers to processes performed in various scenarios (e.g., various times) (using similar environments). In contrast, the number of yttrium-based particles generated during the processing using the kit according to the embodiments described herein showed substantially no variation over a plurality of processing occasions.

[0135]

[0153] Therefore, in certain embodiments, the processing of wafers using the kits according to the embodiments described herein reduces the number of yttrium-based particles generated, reduces wafer defectiveness, increases accuracy, increases predictability, increases yield, increases throughput, and reduces costs.

[0136]

[0154] In FIG. 14, three comparison target kits (having a comparison target nozzle, a comparison target lid, and a comparison target liner) generated, on average, more yttrium-based particles during long-term processing (e.g., 500 RFhrs) compared to kits of lids, nozzles, and liners having the coatings and / or bulk compositions according to the embodiments described herein. The average number of yttrium-based particles generated during long-term processing of a comparison target kit (designated as K1 in FIG. 14) including chamber components coated or fabricated with a bulk ceramic composed of a ceramic compound containing Y4Al2O9 and a solid solution of Y2O3-ZrO2 was in the range of about 1 to about 2.5 (or, including the standard deviation, 0 to about 5 yttrium-based particles). The average number of yttrium-based particles generated during long-term processing of a comparison target kit (designated as K2 in FIG. 14) including chamber components coated or fabricated with a bulk ceramic composed of a Y2O3-ZrO2 solid solution was in the range of 0 to about 1 (or, including the standard deviation, 0 to about 2 yttrium-based particles). The average number of yttrium-based particles generated during long-term processing using a kit (designated as K3 in FIG. 14) including a comparison target nozzle composed of a Y2O3-ZrO2 solid solution coating or bulk composition, a ceramic compound composed of a coating or bulk composition of a solid solution of Y4Al2O9 and Y2O3-ZrO2, and a lid according to the embodiments described herein was in the range of 0 to less than 1. The average number of yttrium-based particles generated during processing using a kit (designated as K4 in FIG. 14) including a nozzle, a liner, and a lid according to the embodiments described herein was 0.

[0137]

[0155] Furthermore, in FIG. 14, a comparison kit consisting of a) a Y2O3-ZrO2 solid solution and b) a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 showed significant variations depending on each processing scenario compared to the kit containing at least one component according to the embodiments described herein. For example, the number of yttrium-based particles generated during processing using a comparison kit containing a chamber component coated or made of a ceramic consisting of a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2 varied from 0 to 5 over multiple processing scenarios. The number of yttrium-based particles generated during processing using a comparison kit containing a chamber component coated or made of a ceramic consisting of a Y2O3-ZrO2 solid solution varied from 0 to 3 over multiple processing scenarios. In contrast, the number of yttrium-based particles generated during processing using a kit containing a nozzle made of a Y2O3-ZrO2 solid solution, a liner made of a ceramic compound containing a solid solution of Y4Al2O9 and Y2O3-ZrO2, and a lid according to the embodiments described herein was significantly less. Furthermore, the kit containing a nozzle, lid, and liner according to the embodiments described herein showed substantially no variation over multiple processing scenarios.

[0138]

[0156] FIG. 15 shows the normalized erosion rates (nm / RF time) of a bulk YAG composition for comparison (bulk YAG), a first optimized bulk YAG composition according to an embodiment prepared through field-assisted sintering (FAS) (bulk YAG1 (optimized)), and a second optimized bulk YAG composition according to an embodiment prepared according to hot isostatic pressing (HIP) (bulk YAG2 (optimized)). The bulk composition was exposed to Cl2-CH4-HBr at 50° C. with a 150 V bias, and then the erosion rate was evaluated. The results shown in FIG. 15 are summarized in the following table. As can be seen from these results, the bulk compositions according to the embodiments described herein have improved erosion resistance compared to other bulk YAG compositions prepared in a manner different from the present disclosure. TIFF2025090584000002.tif36170

[0139]

[0157] The foregoing description presents many 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 instances, well-known components or methods are not described in detail or are presented in a simple block diagram format to avoid unnecessarily obscuring the present disclosure. Thus, the specific details presented are merely illustrative. Particular implementations may differ from these illustrative details and still be considered within the scope of the present disclosure.

[0140]

[0158] Throughout this specification, when reference is made to "one embodiment" or "an embodiment", it means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Additionally, the word "or" is intended to mean an inclusive "or" rather than an exclusive "or". When the words "about" or "approximately" are used in this specification, it is intended that the stated nominal value be accurate within ±30%.

[0141]

[0159] The operations of the methods in this specification are illustrated and described in a particular order, but the order of operations of each method may be changed so that a particular operation may be performed in the reverse order or so that a particular operation may be performed at least partially concurrently with other operations. In another embodiment, the instructions or sub-operations of the individual operations may be executed intermittently and / or alternately.

[0142]

[0160] It should be understood that the foregoing description is intended to be illustrative and not limiting. Upon reading and understanding the foregoing description, many other embodiments will be apparent to those skilled in the art. Accordingly, the scope of the present disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. 1. A processing chamber component comprising: a ceramic body of the processing chamber component, the ceramic body having at least an outer surface comprising crystalline yttrium aluminum garnet (YAG); Equipped with the crystalline YAG comprises yttrium oxide in a molar concentration ranging from 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration ranging from 60 mole percent to 65 mole percent; The process chamber component, wherein the crystalline YAG has a density of about 98% or greater and a hardness of greater than about 10 GPa.

2. The processing chamber part of claim 1 , wherein the crystalline YAG has a porosity of less than 0.1%.

3. The processing chamber part of claim 1 , wherein the crystalline YAG has a hardness greater than about 12 GPa.

4. 2. The processing chamber component of claim 1, wherein said ceramic body is comprised of said crystalline YAG, said crystalline YAG being single phase bulk crystalline YAG.

5. 10. The process chamber part of claim 1, wherein an average total number of yttrium-based particles released from said crystalline YAG upon exposure to corrosive chemicals is less than 3 per 500 radio frequency hours.

6. The processing chamber part of claim 5 , wherein the corrosive chemical comprises a hydrogen-based chemical, a halogen-based chemical, or a mixture thereof.

7. The corrosive chemical substance may be HF, HBr, HCl, Cl ２ , or H ２ The processing chamber part of claim 6 , comprising one or more of:

8. The processing chamber part of claim 1 , wherein the processing chamber part comprises at least one of a lid, a nozzle, or a liner.

9. 10. The processing chamber part of claim 1, wherein the crystalline YAG is the result of a two-stage sintering process that includes hot isostatic pressing (HIP).

10. 1. A method of coating a processing chamber part, comprising: performing electron beam ion assisted deposition (e-beam IAD) to deposit a plasma resistant protective coating on at least a portion of the processing chamber component; the plasma resistant protective coating comprising a single phase amorphous blend of yttrium oxide in a molar concentration ranging from about 35 mole percent to about 95 mole percent and aluminum oxide in a molar concentration ranging from about 5 mole percent to about 65 mole percent; The method of claim 1, wherein the plasma resistant protective coating has 0% porosity and a bond strength of greater than about 25 MPa.

11. 11. The method of claim 10, wherein the plasma resistant protective coating comprises a single phase amorphous blend of yttrium oxide in a molar concentration range of 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration range of 60 mole percent to 65 mole percent.

12. 12. The method of claim 11, wherein the plasma resistant protective coating comprises a single phase amorphous blend of yttrium oxide in a molar concentration range of 37 mole percent to 38 mole percent and aluminum oxide in a molar concentration range of 62 mole percent to 63 mole percent.

13. 11. The method of claim 10, wherein the plasma resistant protective coating has one or more of a roughness of less than about 6 μin at a thickness of 5 μm, a breakdown voltage of greater than about 2500 V / mil, a hermeticity of less than about 3E-9, a hardness of about 8 GPa, a flexural strength of greater than about 400 MPa, or a stability at temperatures ranging from about 80° C. to about 120° C.

14. 11. The method of claim 10, wherein the average total number of yttrium-based particles released from the plasma-resistant protective coating when exposed to corrosive chemicals is less than 3 per 500 radio frequency hours.

15. The method of claim 14 , wherein the corrosive chemical comprises a hydrogen-based chemical, a halogen-based chemical, or a mixture thereof.

16. The corrosive chemical may be HF, HBr, HCl, Cl ２ , or H ２ 16. The method of claim 15, comprising one or more of:

17. 1. A method of coating a processing chamber part, comprising: Performing plasma spray or physical vapor deposition (PVD) to deposit a plasma resistant protective coating on the processing chamber components Including, the plasma resistant protective coating comprises a blend of yttrium oxide in a molar concentration ranging from about 35 mole percent to about 95 mole percent and aluminum oxide in a molar concentration ranging from about 5 mole percent to about 65 mole percent; the plasma resistant protective coating is at least about 90% amorphous; The method, wherein an average total number of yttrium-based particles released from said plasma-resistant protective coating upon exposure to corrosive chemicals is less than 3 per 500 radio frequency hours.

18. 20. The method of claim 17, wherein the plasma resistant protective coating comprises a blend of yttrium oxide in a molar concentration range of 35 mole percent to 40 mole percent and aluminum oxide in a molar concentration range of 60 mole percent to 65 mole percent.

19. 20. The method of claim 18, wherein the plasma resistant protective coating comprises a blend of yttrium oxide in a molar concentration range of 37 mole percent to 38 mole percent and aluminum oxide in a molar concentration range of 62 mole percent to 63 mole percent.

20. 20. The method of claim 19, wherein the corrosive chemical comprises a hydrogen-based chemical, a halogen-based chemical, or a mixture thereof.

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