A plasma-assisted oxidized silicon carbide coated chamber component and method of making the same

Abstract

The application belongs to the technical field of semiconductor manufacturing equipment, and provides a plasma-assisted oxidized silicon carbide coating chamber component and a preparation method thereof; and aims to solve the technical problems of short service life of the coating of the existing chamber component, easy generation of particle pollution, and cleaning difficulty, etc., the method comprising multiple-step cleaning and plasma activation pretreatment on the chamber component, growing a silicon carbide main coating through a chemical vapor deposition method, and performing halogen etching on the coating surface to improve the activity; subsequently, a gradient composite protective layer is generated in situ on the silicon carbide surface through a plasma-assisted oxidation process, and the composite layer comprises a functional layer introduced by an organometallic precursor; through the construction of the gradient composite protective layer, the corrosion resistance, high-temperature stability and service life of the chamber component are improved, and the adhesion of parasitic deposition is reduced, so that the cleaning and maintenance of the component are more efficient and convenient.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor manufacturing equipment technology, and relates to a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method. Background Technology

[0002] In critical thin-film deposition processes in semiconductor manufacturing, such as chemical vapor deposition (CVD), the internal components of the reaction chamber must operate in extremely harsh environments, including high temperatures, high vacuum, and corrosive chemical atmospheres. To protect these core components and ensure the purity of the process environment, a dense silicon carbide (SiC) protective coating is typically prepared on their surface. However, during the thin-film deposition process, in addition to growing the thin film on the target wafer, process precursors inevitably deposit undesirable parasitic deposits on the SiC coating surface of the chamber components. Once these parasitic deposits accumulate to a certain extent, they easily peel off, forming microparticles that contaminate the wafer and severely impact product yield and reliability. Therefore, periodic shutdowns for cleaning of the chamber are necessary. Existing cleaning technologies, whether physical methods or chemical gas etching, while removing parasitic deposits, also cause irreversible damage to the SiC protective coating itself. This damage significantly shortens the lifespan of the chamber components, increases the frequency of spare parts replacement and equipment downtime, thereby substantially increasing the operating costs of semiconductor manufacturing. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method. After conventional silicon carbide coating preparation, a gradient composite protective layer is generated in situ through plasma-assisted oxidation. This protective layer contains a functional layer introduced by an organometallic precursor, thereby meeting the needs of actual production.

[0004] To achieve this objective, the present invention adopts the following technical solution:

[0005] In a first aspect, the present invention provides a method for preparing a plasma-assisted oxidation silicon carbide coated chamber assembly, the method comprising:

[0006] S1. The chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying. The cleaned substrate is transferred to the atomic layer etching reaction chamber, vacuumed and atomic layer etching is performed to obtain the activated chamber assembly.

[0007] S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum and subjected to a deposition process to obtain the deposition chamber assembly;

[0008] S3, the deposition chamber assembly is further processed in the CVD reaction chamber to perform a halogen etching process, resulting in an etched chamber assembly;

[0009] S4, the etched chamber assembly continues to be processed in the CVD reaction chamber to undergo a plasma-assisted oxidation process, resulting in a plasma-assisted oxidized silicon carbide coated chamber assembly.

[0010] The initial ultrasonic solvent cleaning process in step S1 utilizes the dissolving properties of solvents with different polarities to remove organic contaminants and inorganic ions from the substrate surface. Following this, atomic layer etching is performed, using high-energy argon plasma to physically sputter the outermost layer of the substrate, exposing the clean underlying crystal structure. Simultaneously, the introduced chemical precursor reacts with surface atoms to generate volatile products, achieving material exfoliation and ultimately obtaining a chemically pure activated interface with high surface energy, providing favorable conditions for subsequent film nucleation and growth. The chemical vapor deposition stage in step S2 involves the adsorption, decomposition, and chemical reaction of precursor gases on the activated substrate surface at high temperatures to form a silicon carbide film. Hydrogen gas serves not only as a carrier gas and dilution gas but also reduces any residual oxides that may be present on the surface during the high-temperature calcination stage.

[0011] The mechanism of step S3, halogen etching, is not macroscopic material removal, but a refined surface reactivation process. Chlorine-based plasma selectively reacts with high-energy sites, micro-defects, or amorphous regions on the silicon carbide surface at specific temperatures, generating volatile chlorosilane products. This smooths the surface and forms a uniform layer of chlorine-based functional group terminals, providing highly uniform nucleation sites for subsequent plasma-assisted oxidation. Step S4, plasma-assisted oxidation, is the core of constructing the gradient functional layer. The purpose of introducing methane in the first stage is to form a silicon carbide-carbon oxide transition layer between silicon carbide and the oxide layer. By establishing a continuous chemical bonding and thermal expansion coefficient gradient, stress concentration at the heterogeneous material interface is effectively alleviated. The second stage introduces a tris(trimethylsiloxy)borane single-source precursor. When this molecule decomposes in plasma, it can uniformly co-deposit boron, silicon, and oxygen elements, forming a dense borosilicate glass network. In this network, boron acts as a network modifier, lowering the softening point and viscosity of the glassy phase. Under the high-temperature conditions of component operation, when thermal stress causes microcracks to form, this low-viscosity phase undergoes viscous flow, filling and healing the cracks, thereby achieving active structural repair. The third stage involves adjusting plasma parameters, reducing power and increasing pressure. The mechanism is to alter the plasma ionization rate and particle mean free path, leading to a decrease in the density of the deposited oxide layer, forming a relatively chemically active, porous surface layer. This layer serves as a sacrificial layer preferentially etched during subsequent cleaning. The final high-temperature heat treatment step, through thermally driven atomic diffusion, further densifies the entire oxide stack and ensures complete oxidation of all components, ultimately resulting in a structurally stable and functionally synergistic gradient self-healing protection system.

[0012] As a preferred technical solution of the present invention, in S1, the temperature of vacuum drying is 150-160℃, for example, it can be 150℃, 151℃, 152℃, 153℃, 154℃, 155℃, 156℃, 157℃, 158℃, 159℃ or 160℃, but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0013] In some optional embodiments, the vacuum drying time is 20-30 min, for example, it can be 20 min, 21 min, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min or 30 min, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0014] In some optional embodiments, the atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 2-3 minutes. After completion, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm. For example, it can be: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 2.0 min, 2.1 min, 2.2 min, 2.3 min, 2.4 min, 2.5 min, 2.6 min, 2.7 min, 2.8 min, 2.9 min, or 3.0 min. After completion, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm. However, it is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0015] As a preferred embodiment of the present invention, in S2, the deposition procedure is as follows: hydrogen gas is introduced at a flow rate of 2000 sccm, the temperature is raised to 1000-1010℃, and held for 30-40 minutes; while maintaining the temperature, the chamber pressure is adjusted to 10 Torr, and trichloromethylsilane vapor is introduced into the chamber through hydrogen gas at a flow rate of 50 sccm, while hydrogen gas is introduced simultaneously as both a reaction gas and a dilution gas at a flow rate of 500 sccm. Under these conditions, deposition begins for 60-70 minutes; after deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 15-20 minutes; Ar atmosphere is maintained, and the temperature is lowered to below 100℃. For example, it could be as follows: Introduce hydrogen gas at a flow rate of 2000 sccm, raise the temperature to 1000℃, 1001℃, 1002℃, 1003℃, 1004℃, 1005℃, 1006℃, 1007℃, 1008℃, 1009℃, or 1010℃, and hold for 30 min, 31 min, 32 min, 33 min, 34 min, 35 min, 36 min, 37 min, 38 min, 39 min, or 40 min respectively; maintain a constant temperature, adjust the chamber pressure to 10 Torr, and introduce trichloromethylsilane vapor into the chamber through hydrogen gas at a flow rate of 50 sccm, while simultaneously introducing hydrogen gas as both a reactant and diluent gas at a flow rate of 500 sccm. Under the above conditions, begin deposition for 60 min, 61 min, 62 min, 63 min, 64 min, 65 min, 66 min, 67 min, 68 min, 69 or 70 min. After deposition, retain only hydrogen gas at a flow rate of 500 sccm to purge the chamber for 15.0 min, 15.5 min, 16.0 min, 16.5 min, 17.0 min, 17.5 min, 18.0 min, 18.5 min, 19.0 min, 19.5 or 20.0 min. Use an Ar atmosphere and cool to below 100°C, but this is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0016] As a preferred technical solution of the present invention, in S3, the halogen etching procedure is as follows: the chamber is evacuated to a vacuum and heated to 800-820°C, chlorine gas and hydrogen chloride are introduced, the chlorine gas flow rate is 50 sccm and the hydrogen chloride flow rate is 20 sccm, the chamber pressure is adjusted to stabilize at 20 Torr, chemical etching is performed under these conditions for 3-4 minutes, and after etching, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 10-12 minutes. For example, the chamber could be evacuated to a vacuum and heated to 800℃, 802℃, 804℃, 806℃, 808℃, 810℃, 812℃, 814℃, 816℃, 818℃, or 820℃. Chlorine and hydrogen chloride gas could then be introduced at a flow rate of 50 sccm for chlorine and 20 sccm for hydrogen chloride. The chamber pressure could be stabilized at 20 Torr. Under these conditions, chemical etching could be performed for 3.0 min, 3.1 min, 3.2 min, 3.3 min, 3.4 min, 3.5 min, and 3.6 min. For etching, the time intervals are 3.7 min, 3.8 min, 3.9 min, or 4.0 min. After etching, only argon gas at a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 10.0 min, 10.2 min, 10.4 min, 10.6 min, 10.8 min, 11.0 min, 11.2 min, 11.4 min, 11.6 min, 11.8 min, or 12.0 min. However, the values ​​are not limited to those listed, and other unlisted values ​​within this range are also applicable.

[0017] As a preferred embodiment of the present invention, in S4, the plasma-assisted oxidation process is as follows: oxygen, argon, and methane are introduced, with an oxygen flow rate of 50 sccm, an argon flow rate of 200 sccm, a methane flow rate of 5 sccm, a power of 150 W, a pressure of 80 mTorr, and a duration of 2-3 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced, with an oxygen flow rate of 100 sccm, an argon flow rate carrying tris(trimethylsiloxy)borane vapor of 50 sccm, a power of 300 W, a pressure of 50 mTorr, and a duration of 6-7 min; then oxygen and argon are introduced again, with a power of 100 W, a pressure of 150 mTorr, and a duration of 2-3 min; finally, oxygen is introduced, and the temperature is raised to 900-910℃ and held for 30-35 min. For example, it could be: introducing oxygen, argon, and methane, with an oxygen flow rate of 50 sccm, an argon flow rate of 200 sccm, a methane flow rate of 5 sccm, a power of 150 W, a pressure of 80 mTorr, and a duration of (2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0) min; then introducing oxygen and argon carrying tris(trimethylsiloxy)borane vapor, with an oxygen flow rate of 100 sccm, an argon carrying tris(trimethylsiloxy)borane vapor flow rate of 50 sccm, a power of 300 W, a pressure of 50 mTorr, and a duration of 6.0 min, 6.1 min, 6.2 min, 6.3 min, 6.4 min, 6.5 min, 6.6 min, 6.7 min, 6.8 min, 6.9, or 7. 0 min; then introduce oxygen and argon at a power of 100W and a pressure of 150mTorr for 2.0 min, 2.1 min, 2.2 min, 2.3 min, 2.4 min, 2.5 min, 2.6 min, 2.7 min, 2.8 min, 2.9 min, or 3.0 min; finally introduce oxygen and heat to 900℃, 901℃, 902℃, 903℃, 904℃, 905℃, 906℃, 907℃, 908℃, 909℃, or 910℃ and hold for 30 min, 30.5 min, 31 min, 31.5 min, 32 min, 32.5 min, 33 min, 33.5 min, 34 min, 34.5 min, or 35 min, but not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0018] In some optional embodiments, the preparation method of the tris(trimethylsiloxy)borane includes: dispersing boric acid in anhydrous toluene to form a suspension, then adding hexamethyldisilazane to the suspension, heating to 110-115°C, refluxing and stirring for 6-7 hours, filtering and distilling to obtain tris(trimethylsiloxy)borane, wherein the mass-to-volume ratio of boric acid, anhydrous toluene, and hexamethyldisilazane is (62-65) g: 500 mL: (258-262) g, for example... The values ​​can be (62, 62.3, 62.6, 62.9, 63.2, 63.5, 63.8, 64.1, 64.4, 64.7 or 65) g: 500 mL: (258, 258.4, 258.8, 259.2, 259.6, 260.0, 260.4, 260.8, 261.2, 261.6 or 262) g, but are not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0019] In a second aspect, the present invention provides a plasma-assisted oxidation silicon carbide coated chamber assembly prepared by the preparation method described in the first aspect.

[0020] Compared with existing technologies, the beneficial effects of this invention are as follows: First, by constructing a gradient composite structure and introducing an interface transition layer, this invention effectively alleviates the stress between heterogeneous materials, improves the bonding strength between the protective layer and the silicon carbide substrate, and makes it less prone to peeling off during harsh thermal cycling. Second, by introducing a low-viscosity phase that can flow at high temperatures into the dense barrier layer, it can heal microcracks generated during operation in real time, fundamentally changing the wear mode of the coating and extending the overall service life of the chamber assembly. Third, the loose sacrificial surface layer designed in this invention allows the periodic cleaning process to preferentially remove parasitic deposits and the sacrificial layer without damaging the underlying core functional layer and silicon carbide main coating, effectively solving the problem of substrate damage caused by existing cleaning technologies. Attached Figure Description

[0021] Figure 1 This is a SEM image of the surface of the deposition chamber assembly provided in Embodiment 1 of the present invention.

[0022] Figure 2 This is a cross-sectional SEM image of the deposition chamber assembly provided in Embodiment 1 of the present invention. Detailed Implementation

[0023] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include those that make any obvious substitutions and modifications to the embodiments described herein.

[0024] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone any further purification treatment.

[0025] Example 1

[0026] This embodiment provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method, the preparation method specifically including the following steps:

[0027] S1, the chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying at 155°C for 25 min. The cleaned substrate is transferred to the atomic layer etching reaction chamber, evacuated and subjected to atomic layer etching to obtain the activated chamber assembly. The atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 2.5 min. After the process is completed, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm.

[0028] S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum, and a deposition process is performed to obtain the deposition chamber assembly. The deposition process is as follows: hydrogen gas is introduced at a flow rate of 2000 sccm, the temperature is raised to 1005℃, and held for 35 min; while maintaining the temperature, the chamber pressure is adjusted to 10 Torr, and trichloromethylsilane vapor is introduced into the chamber through hydrogen gas at a flow rate of 50 sccm. At the same time, hydrogen gas is introduced as both the reaction gas and the dilution gas at a flow rate of 500 sccm. Under these conditions, deposition begins for 65 min; after deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 18 min; Ar atmosphere is maintained, and the temperature is lowered to below 100℃.

[0029] S3, the deposition chamber assembly continues to be processed in the CVD reaction chamber, and a halogen etching process is performed to obtain the etched chamber assembly. The halogen etching process is as follows: the chamber is evacuated to a vacuum and heated to 810°C. Chlorine gas and hydrogen chloride are introduced. The flow rate of chlorine gas is 50 sccm and the flow rate of hydrogen chloride is 20 sccm. The chamber pressure is adjusted to be stable at 20 Torr. Under these conditions, chemical etching is performed for 3.5 min. After the etching is completed, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 11 min.

[0030] S4, the etching chamber assembly continues processing in the CVD reaction chamber, undergoing a plasma-assisted oxidation process to obtain a plasma-assisted oxidized silicon carbide coated chamber assembly. The plasma-assisted oxidation process is as follows: oxygen, argon, and methane are introduced, with an oxygen flow rate of 50 sccm, an argon flow rate of 200 sccm, a methane flow rate of 5 sccm, a power of 150 W, a pressure of 80 mTorr, and a duration of 2.5 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced, with an oxygen flow rate of 100 sccm and an argon carrying tris(trimethylsiloxy)borane vapor... The flow rate was 50 sccm, the power was 300 W, the pressure was 50 mTorr, and the duration was 6.5 min. Then oxygen and argon were introduced at a power of 100 W and a pressure of 150 mTorr for 2.5 min. Finally, oxygen was introduced, and the temperature was raised to 905℃ and held for 32 min. The preparation method of the tris(trimethylsiloxy)borane includes: dispersing 63 g of boric acid in 500 mL of anhydrous toluene to form a suspension, then adding 260 g of hexamethyldisilazane to the suspension, raising the temperature to 112℃, refluxing and stirring for 6.5 h, and filtering and distilling to obtain tris(trimethylsiloxy)borane.

[0031] Figure 1 The SEM image of the deposition chamber assembly provided in the embodiment shows a β-SiC film with high density and good crystallinity. Figure 2 The SEM image of the deposition chamber assembly provided in this embodiment shows that the β-SiC thin film has a dense structure and good adhesion to the substrate.

[0032] Example 2

[0033] This embodiment provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method, the preparation method specifically including the following steps:

[0034] S1, the chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying at 152°C for 28 min. The cleaned substrate is transferred to the atomic layer etching reaction chamber, evacuated and subjected to atomic layer etching to obtain the activated chamber assembly. The atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 2.2 min. After the process is completed, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm.

[0035] S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum, and a deposition process is performed to obtain the deposition chamber assembly. The deposition process is as follows: hydrogen gas is introduced at a flow rate of 2000 sccm, the temperature is raised to 1002℃, and held for 38 min; while maintaining the temperature, the chamber pressure is adjusted to 10 Torr, and trichloromethylsilane vapor is introduced into the chamber through hydrogen gas at a flow rate of 50 sccm. At the same time, hydrogen gas is introduced as both the reaction gas and the dilution gas at a flow rate of 500 sccm. Under these conditions, deposition begins for 62 min; after deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 16 min; Ar atmosphere is maintained, and the temperature is lowered to below 100℃.

[0036] S3, the deposition chamber assembly continues to be processed in the CVD reaction chamber, and a halogen etching process is performed to obtain the etched chamber assembly. The halogen etching process is as follows: the chamber is evacuated to a vacuum and heated to 805°C. Chlorine gas and hydrogen chloride are introduced. The flow rate of chlorine gas is 50 sccm and the flow rate of hydrogen chloride is 20 sccm. The chamber pressure is adjusted to be stable at 20 Torr. Under these conditions, chemical etching is performed for 3.8 min. After the etching is completed, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 10.5 min.

[0037] S4, the etching chamber assembly continues processing in the CVD reaction chamber, undergoing a plasma-assisted oxidation process to obtain a plasma-assisted oxidized silicon carbide coated chamber assembly. The plasma-assisted oxidation process is as follows: oxygen, argon, and methane are introduced, with an oxygen flow rate of 50 sccm, an argon flow rate of 200 sccm, a methane flow rate of 5 sccm, a power of 150 W, a pressure of 80 mTorr, and a duration of 2.8 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced, with an oxygen flow rate of 100 sccm and an argon carrying tris(trimethylsiloxy)borane vapor... The flow rate was 50 sccm, the power was 300 W, the pressure was 50 mTorr, and the duration was 6.2 min. Then oxygen and argon were introduced at a power of 100 W and a pressure of 150 mTorr for 2.2 min. Finally, oxygen was introduced, and the temperature was raised to 908℃ and held for 34 min. The preparation method of the tris(trimethylsiloxy)borane includes: dispersing 64 g of boric acid in 500 mL of anhydrous toluene to form a suspension, then adding 259 g of hexamethyldisilazane to the suspension, raising the temperature to 114℃, refluxing and stirring for 6.2 h, and filtering and distilling to obtain tris(trimethylsiloxy)borane.

[0038] Example 3

[0039] This embodiment provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method, the preparation method specifically including the following steps:

[0040] S1, the chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying at 158°C for 22 min. The cleaned substrate is transferred to the atomic layer etching reaction chamber, evacuated and subjected to atomic layer etching to obtain the activated chamber assembly. The atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 2.8 min. After the process is completed, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm.

[0041] S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum, and a deposition process is performed to obtain the deposition chamber assembly. The deposition process is as follows: hydrogen gas is introduced at a flow rate of 2000 sccm, the temperature is raised to 1008℃, and held for 32 min; while maintaining the temperature, the chamber pressure is adjusted to 10 Torr, and trichloromethylsilane vapor is introduced into the chamber through hydrogen gas at a flow rate of 50 sccm. At the same time, hydrogen gas is introduced as both the reaction gas and the dilution gas at a flow rate of 500 sccm. Under these conditions, deposition begins for 68 min; after deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 19 min; Ar atmosphere is maintained, and the temperature is lowered to below 100℃.

[0042] S3, the deposition chamber assembly continues to be processed in the CVD reaction chamber, and a halogen etching process is performed to obtain the etched chamber assembly. The halogen etching process is as follows: the chamber is evacuated to a vacuum and heated to 818°C. Chlorine gas and hydrogen chloride are introduced. The flow rate of chlorine gas is 50 sccm and the flow rate of hydrogen chloride is 20 sccm. The chamber pressure is adjusted to be stable at 20 Torr. Chemical etching is performed under these conditions for 3.2 min. After the etching is completed, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 11.5 min.

[0043] S4, the etching chamber assembly continues processing in the CVD reaction chamber, undergoing a plasma-assisted oxidation process to obtain a plasma-assisted oxidized silicon carbide coated chamber assembly. The plasma-assisted oxidation process is as follows: oxygen, argon, and methane are introduced, with an oxygen flow rate of 50 sccm, an argon flow rate of 200 sccm, a methane flow rate of 5 sccm, a power of 150 W, a pressure of 80 mTorr, and a duration of 2.1 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced, with an oxygen flow rate of 100 sccm and an argon flow rate of [missing information - likely a specific flow rate]. The reaction was carried out at 50 sccm, 300 W, 50 mTorr, and for 6.8 min; then oxygen and argon were introduced at 100 W, 150 mTorr, and for 2.8 min; finally, oxygen was introduced, and the temperature was raised to 902 °C and held for 31 min. The preparation method of the tris(trimethylsiloxy)borane includes: dispersing 62.5 g of boric acid in 500 mL of anhydrous toluene to form a suspension, then adding 261.5 g of hexamethyldisilazane to the suspension, raising the temperature to 111 °C, refluxing and stirring for 6.8 h, filtering and distilling to obtain tris(trimethylsiloxy)borane.

[0044] Example 4

[0045] This embodiment provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method, the preparation method specifically including the following steps:

[0046] S1, the chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying at 160°C for 20 min. The cleaned substrate is transferred to the atomic layer etching reaction chamber, evacuated and subjected to atomic layer etching to obtain the activated chamber assembly. The atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200 W, and plasma bombardment is performed for 3 min. After the process is completed, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm.

[0047] S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum, and a deposition process is performed to obtain the deposition chamber assembly. The deposition process is as follows: hydrogen gas is introduced at a flow rate of 2000 sccm, the temperature is raised to 1010℃, and held for 30 min; while maintaining the temperature, the chamber pressure is adjusted to 10 Torr, and trichloromethylsilane vapor is introduced into the chamber through hydrogen gas at a flow rate of 50 sccm. At the same time, hydrogen gas is introduced as both the reaction gas and the dilution gas at a flow rate of 500 sccm. Under these conditions, deposition begins for 70 min; after deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 15 min; Ar atmosphere is maintained, and the temperature is lowered to below 100℃.

[0048] S3, the deposition chamber assembly continues to be processed in the CVD reaction chamber, and a halogen etching process is performed to obtain the etched chamber assembly. The halogen etching process is as follows: the chamber is evacuated to a vacuum and heated to 820°C. Chlorine gas and hydrogen chloride are introduced. The flow rate of chlorine gas is 50 sccm and the flow rate of hydrogen chloride is 20 sccm. The chamber pressure is adjusted to be stable at 20 Torr. Chemical etching is performed under these conditions for 4 min. After the etching is completed, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 12 min.

[0049] S4, the etching chamber assembly continues processing in the CVD reaction chamber, undergoing a plasma-assisted oxidation process to obtain a plasma-assisted oxidized silicon carbide coated chamber assembly. The plasma-assisted oxidation process is as follows: oxygen, argon, and methane are introduced at a flow rate of 50 sccm, argon at 200 sccm, and methane at 5 sccm, with a power of 150 W, a pressure of 80 mTorr, and a duration of 3 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced at a flow rate of 100 sccm. Argon flow rate is 50 sccm, power is 300 W, pressure is 50 mTorr, and duration is 7 min; then oxygen and argon are introduced, power is 100 W, pressure is 150 mTorr, and duration is 3 min; finally, oxygen is introduced, and the temperature is raised to 910℃ and held for 35 min. The preparation method of the tris(trimethylsiloxy)borane includes: dispersing 65 g of boric acid in 500 mL of anhydrous toluene to form a suspension, then adding 262 g of hexamethyldisilazane to the suspension, raising the temperature to 115℃, refluxing and stirring for 7 h, filtering and distilling to obtain tris(trimethylsiloxy)borane.

[0050] Comparative Example 1

[0051] This comparative example provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method. The difference between this example and Example 1 is that argon gas carrying tris(trimethylsiloxy)borane vapor is not introduced into the plasma-assisted oxidation process in S4. Other process parameters and operating conditions are exactly the same as in Example 1.

[0052] Comparative Example 2

[0053] This comparative example provides a plasma-assisted oxidation silicon carbide coated chamber assembly and its preparation method. The difference between this example and Example 1 is that in the plasma-assisted oxidation process in S4, oxygen and argon carrying tris(trimethylsiloxy)borane vapor are directly introduced into the etched surface of the chamber assembly. Other process parameters and operating conditions are exactly the same as in Example 1.

[0054] Thermal shock resistance test method: Heat the muffle furnace to 1000℃ and stabilize it. Use quartz tongs to quickly place the sample in the center of the furnace chamber and start timing. Hold the sample at this temperature for 15 minutes to ensure it reaches complete thermal equilibrium. After holding, quickly open the furnace door and immediately remove the hot sample from the furnace using quartz tongs. Place the sample on the pre-positioned heat-insulating quartz support within 3 seconds. Turn on the gas source and ensure the airflow velocity at the nozzle outlet is stable at ≥20m / s. Continuously purge and cool the sample surface for 60 seconds, or until the sample surface temperature drops below 200℃. After the sample has completely cooled to room temperature, use an optical microscope to examine the sample surface for cracks, blistering, or peeling. If the sample is intact, repeat the test. One complete process from high-temperature removal to airflow cooling is recorded as one thermal shock cycle. Continue cycling until the sample fails, and record the number of cycles. If the sample does not fail after the number of cycles reaches the preset limit (200 times), the test can be terminated. If, under an optical microscope, a new crack with a length exceeding 50µm is observed on the sample surface for the first time, or if any phenomenon such as coating blistering or edge peeling occurs, it is considered to have failed.

[0055] Thermal cycling corrosion life test method: The sample is placed in the reaction chamber, evacuated, and then high-purity argon gas (flow rate 500 sccm) is introduced as a protective atmosphere. The temperature is programmed to rise to 1200℃ at a rate of 15℃ / min and held for 60 minutes while maintaining the argon atmosphere. The temperature is then reduced from 1200℃ to 900℃ at a rate of 10℃ / min. At 900℃, the argon gas is stopped, and corrosive gases are introduced: chlorine gas 50 sccm and hydrogen chloride gas 20 sccm. The chamber pressure is adjusted to 20 Torr, and corrosion is carried out under these conditions for 3 minutes. After corrosion, a large flow rate of high-purity argon gas (2000 sccm) is introduced to purge for 15 minutes to thoroughly remove any residual corrosive gases from the chamber. Under argon protection, the temperature is programmed to cool to room temperature, completing one thermal cycling corrosion life test cycle. After 20 cycles, the sample is removed, and the sample surface is observed using an optical microscope. If any obvious cracks, coating blistering, or film peeling are observed, the sample is considered to have failed.

[0056] The test results are shown in Table 1.

[0057] Table 1 Test results of chamber components in Examples 1-4 and Comparative Examples 1-2

[0058]

[0059] As shown in Table 1, compared to Example 1, Comparative Example 1 exhibits decreased thermal shock resistance and a shorter thermal cycling corrosion life; Comparative Example 2 also shows decreased thermal shock resistance and a shorter thermal cycling corrosion life. This is because Comparative Example 1 does not introduce argon gas carrying tris(trimethylsiloxy)borane vapor, lacking boron doping. The dense layer is pure SiO2, which has lower fracture toughness than borosilicate glass. Thermal stress leads to crack formation, thus reducing the thermal shock resistance and thermal cycling corrosion life of Comparative Example 1. In Comparative Example 2, oxygen and argon gas carrying tris(trimethylsiloxy)borane vapor are directly introduced onto the surface of the etching chamber assembly. Due to the difference in thermal expansion coefficients between silicon carbide and borosilicate glass / SiO2, stress is generated at the interface during each rapid cooling, causing the coating to peel off due to thermal shock and fail.

[0060] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a silicon carbide coated chamber assembly by plasma-assisted oxidation, characterized in that, The preparation method includes: S1. The chamber assembly is sequentially immersed in acetone, isopropanol and deionized water for ultrasonic cleaning and vacuum drying. The cleaned substrate is transferred to the atomic layer etching reaction chamber, vacuumed and atomic layer etching is performed to obtain the activated chamber assembly. S2, the activation chamber assembly is loaded into the CVD reaction chamber, evacuated to a vacuum and subjected to a deposition process to obtain the deposition chamber assembly; S3, the deposition chamber assembly is further processed in the CVD reaction chamber to perform a halogen etching process, resulting in an etched chamber assembly; S4, the etched chamber assembly continues to be processed in the CVD reaction chamber to undergo a plasma-assisted oxidation process, resulting in a plasma-assisted oxidized silicon carbide coated chamber assembly.

2. The method for preparing a silicon carbide coated chamber assembly by plasma-assisted oxidation according to claim 1, characterized in that, In S1: The atomic layer etching process is as follows: argon gas is introduced at a flow rate of 50 sccm, the chamber pressure is stabilized to 100 mTorr, the power is 200W, and plasma bombardment is performed for 2-3 minutes. After the process is completed, an additional argon carrier gas carrying the InCl3 precursor is introduced at a flow rate of 10 sccm.

3. The method for preparing a silicon carbide coated chamber assembly by plasma-assisted oxidation according to claim 1, characterized in that, In S2: The deposition procedure is as follows: Hydrogen gas is introduced at a flow rate of 2000 sccm, and the temperature is raised to 1000-1010℃ and held for 30-40 minutes. While maintaining the temperature, the chamber pressure is adjusted to 10 Torr. Trichloromethylsilane vapor is introduced into the chamber via hydrogen gas at a flow rate of 50 sccm, while hydrogen gas is simultaneously introduced as both a reaction gas and a dilution gas at a flow rate of 500 sccm. The deposition time is 60-70 minutes. After deposition, only hydrogen gas is retained at a flow rate of 500 sccm to purge the chamber for 15-20 minutes. The chamber is then cooled to below 100℃ under an argon atmosphere.

4. The method for preparing a silicon carbide coated chamber assembly by plasma-assisted oxidation according to claim 1, characterized in that, In S3: The halogen etching procedure is as follows: the chamber is evacuated to a vacuum and heated to 800-820°C. Chlorine and hydrogen chloride are introduced, with a chlorine flow rate of 50 sccm and a hydrogen chloride flow rate of 20 sccm. The chamber pressure is adjusted to stabilize at 20 Torr. The etching time is 3-4 min. After etching, only argon gas with a flow rate of 2000 sccm is introduced to thoroughly purge the chamber for 10-12 min.

5. The method for preparing a plasma-assisted oxidation silicon carbide coated chamber assembly according to claim 1, characterized in that, In S4: The plasma-assisted oxidation procedure is as follows: oxygen, argon, and methane are introduced at a flow rate of 50 sccm, 200 sccm, and 5 sccm, with a power of 150 W and a pressure of 80 mTorr for 2-3 min; then oxygen and argon carrying tris(trimethylsiloxy)borane vapor are introduced at a flow rate of 100 sccm and 50 sccm, with a power of 300 W and a pressure of 50 mTorr for 6-7 min; then oxygen and argon are introduced again at a power of 100 W and a pressure of 150 mTorr for 2-3 min; finally, oxygen is introduced, and the temperature is raised to 900-910℃ and held for 30-35 min.

6. The method for preparing a plasma-assisted oxidation silicon carbide coated chamber assembly according to claim 5, characterized in that, The preparation method of the tris(trimethylsiloxy)borane includes: Boric acid was dispersed in anhydrous toluene to form a suspension, and then hexamethyldisilazane was added to the suspension. The mixture was heated to 110-115°C and stirred under reflux for 6-7 hours. The mixture was then filtered and distilled to obtain tris(trimethylsiloxy)borane.

7. The method for preparing a silicon carbide coated chamber assembly by plasma-assisted oxidation according to claim 6, characterized in that, The mass-to-volume ratio of boric acid, anhydrous toluene and hexamethyldisilazane is (62-65) g: 500 mL: (258-262) g.

8. A plasma-assisted oxidized silicon carbide coated chamber assembly obtained by the preparation method according to any one of claims 1-7.

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