Tantalum carbide / graphite composite material and preparation method thereof

Abstract

The invention discloses a tantalum carbide / graphite composite material and a preparation method thereof. The tantalum carbide / graphite composite material comprises a graphite substrate, a hafnium-doped tantalum carbide film layer and a tantalum carbide film layer, wherein the hafnium-doped tantalum carbide film layer is positioned between the graphite substrate and the tantalum carbide film layer. The hafnium-doped tantalum carbide film layer has certain plasticity (ductility), serves as a buffer layer, is arranged between the graphite substrate and the tantalum carbide film layer, and can relieve thermal stress accumulation in the heating and cooling processes in the use process of the composite material, so that the thermal shock resistance of the composite material is improved, and the service life of the film layer and the composite material is prolonged.

Description

Technical Field

[0001] This application relates to the field of epitaxial growth consumables, specifically to tantalum carbide / graphite composite materials and their preparation methods. Background Technology

[0002] Graphite disks for semiconductors are one of the key consumables in the epitaxial growth process of MOCVD (Metal-Organic Chemical Vapor Deposition) equipment. Graphite has excellent properties such as high temperature resistance, high thermal conductivity, and high high temperature strength, making it the preferred material for epitaxial substrate disks. However, graphite is prone to oxidation, corrosion, and wear, and it easily produces powder, which contaminates the epitaxial growth chamber environment and reduces the quality of epitaxial products. Therefore, directly using graphite substrates in semiconductor epitaxial film growth chambers still has performance defects. To compensate for this defect, a protective film layer can be coated on the surface of the graphite substrate to optimize the performance of graphite components.

[0003] Film coating technology is a widely used surface treatment process that involves coating a substrate material with a layer of metal, alloy, ceramic, or other material to achieve or enhance certain target properties. Currently, the mainstream film preparation technologies include: brush coating, embedding, magnetron sputtering deposition, ion beam assisted deposition, pulsed laser deposition, liquid phase pulsed discharge deposition, and chemical vapor deposition.

[0004] Tantalum carbide is an important high-strength, corrosion-resistant, and chemically stable high-temperature structural material with a melting point as high as 3880℃. It has excellent resistance to oxidation, acid and alkali corrosion, thermal shock, and airflow erosion. At the same time, it has low gas permeability and good chemical and mechanical compatibility with graphite materials, making it one of the preferred materials for protective film layers on graphite substrates.

[0005] However, tantalum carbide ceramic materials have a relatively large coefficient of thermal expansion, approximately 6.29 × 10⁻⁶. -6 / K, while the coefficient of thermal expansion of commonly used graphite substrates is typically 4×10. -6 / K-5×10 -6 The difference in thermal expansion coefficients between / K results in large residual stress in TaC (tantalum carbide) films during preparation and use. When the peak shear stress at the film interface exceeds the bonding strength of the film, the film will detach, thus affecting the service life of the product.

[0006] Therefore, current tantalum carbide / graphite composite materials and their preparation methods still need improvement. Summary of the Invention

[0007] This application is based on the inventor's discoveries and understanding of the following facts and problems: To address the issue of membrane detachment affecting product lifespan, current approaches primarily focus on reducing the difference in thermal expansion coefficients between the membrane material and the substrate material. This reduces stress buildup caused by the difference in thermal expansion coefficients, thus mitigating membrane detachment. However, the selection of substrate materials is relatively limited, and materials with perfectly matched thermal expansion coefficients from low to high temperatures are almost nonexistent. Furthermore, in certain application scenarios, specific performance requirements for the substrate material may exist, making substrate material replacement unsuitable. Therefore, there is an urgent need for a new, widely applicable thermal stress-adaptive membrane.

[0008] The inventors discovered that if the plasticity of the film material itself can be improved, the film will dissipate some of the thermal stress during temperature rise and fall due to its own plastic deformation, thereby helping to improve the life of the film.

[0009] Based on first-principles calculations, it is predicted that in hafnium-doped tantalum carbide ceramics, the addition of vacancies in carbon atoms alters the chemical environment surrounding each atom. The electrons of Hf / Ta, originally bound by carbon atoms, transition to near the Fermi level, allowing the material to exhibit certain metallic properties. Using the Pugh ratio as the criterion for the brittle-to-ductile transition of the system, Ta... 0.8 Hf 0.2 C 0.8 The Pugh ratio of the ceramic is 0.41, which is far below the 0.6 standard for the brittle-ductile transition (a material with a Pugh ratio below 0.6 is considered to have good ductility).

[0010] Meanwhile, tantalum carbide and hafnium carbide, as important ultra-high temperature ceramic materials, both possess a NaCl-type face-centered cubic crystal structure, and the radius difference between Hf atoms (radius 0.1585 nm) and Ta atoms (radius 0.1457 nm) is less than 15%. Therefore, they are theoretically infinitely miscible, forming ternary ultra-high temperature ceramics. Furthermore, the solid solution ceramics of both inherit their excellent thermophysical properties, with melting points reaching up to 4300 K.

[0011] In view of this, this application proposes the following new process. Compared with the existing process, the new process is characterized by using hafnium-doped tantalum carbide ceramic with better plasticity as a buffer layer material, which is disposed between the graphite substrate and the tantalum carbide film layer to improve the thermal shock resistance of graphite-based products.

[0012] This application aims to at least partially alleviate or resolve at least one of the aforementioned problems.

[0013] In one aspect of this application, a tantalum carbide / graphite composite material is proposed. In some embodiments of this application, the tantalum carbide / graphite composite material includes a graphite matrix, a hafnium-doped tantalum carbide film layer, and a tantalum carbide film layer, wherein the hafnium-doped tantalum carbide film layer is located between the graphite matrix and the tantalum carbide film layer. The hafnium-doped tantalum carbide film layer has a certain degree of plasticity (ductility) and, as a buffer layer, is disposed between the graphite matrix and the tantalum carbide film layer. During the use of the composite material, it can alleviate the accumulation of thermal stress during heating and cooling processes, thereby improving the thermal shock resistance of the composite material and extending the service life of the film layer and the composite material.

[0014] In some embodiments of this application, the hafnium-doped tantalum carbide film layer comprises the chemical formula Ta x Hf 1-x C y The material has a particle size distribution of x (0.7-0.9) and y (0.7-0.9). A film meeting these conditions exhibits good ductility and can significantly improve the thermal shock resistance of the composite material.

[0015] In some embodiments of this application, the thickness of the hafnium-doped tantalum carbide film is 5 μm-10 μm; and / or, the thickness of the tantalum carbide film is 10 μm-50 μm. This is beneficial for further improving the overall performance of the composite material.

[0016] In some embodiments of this application, the tantalum carbide / graphite composite material further includes an isolation layer located between the graphite matrix and the hafnium-doped tantalum carbide film. The isolation layer comprises one or more of boron nitride, an iridium / rhenium composite film, tungsten, zirconium, hafnium, tungsten carbide, zirconium carbide, and hafnium carbide. The isolation layer can at least partially slow down the diffusion of carbon from the graphite matrix to the hafnium-doped tantalum carbide film, thereby allowing the hafnium-doped tantalum carbide film to maintain good plasticity for a longer period. This is beneficial for further improving the thermal shock resistance of the composite material, and thus further extending the service life of the film and the composite material.

[0017] In some embodiments of this application, the thickness of the isolation layer is 1 μm-5 μm. An isolation layer of this thickness can provide good isolation and effectively alleviate the problem of carbon diffusion from the graphite matrix.

[0018] In another aspect of this application, a method for preparing the aforementioned tantalum carbide / graphite composite material is proposed. In some embodiments of this application, the method for preparing the aforementioned tantalum carbide / graphite composite material includes: (1) placing a graphite matrix in a reaction chamber; (2) introducing a first carbon source, a first tantalum source, a hafnium source, hydrogen, and a first carrier gas into the reaction chamber, and forming a hafnium-doped tantalum carbide film layer on the graphite matrix using chemical vapor deposition; (3) introducing a second carbon source, a second tantalum source, hydrogen, and a second carrier gas into the reaction chamber, and forming a tantalum carbide film layer on the side of the hafnium-doped tantalum carbide film layer away from the graphite matrix using chemical vapor deposition. The tantalum carbide / graphite composite material prepared by the above method possesses all the characteristics and advantages of the aforementioned composite material, which will not be repeated here.

[0019] In some embodiments of this application, the method for preparing the aforementioned tantalum carbide / graphite composite material satisfies at least one of the following conditions: in step (2), the reaction temperature is 1000℃-2000℃; in step (2), the pressure of the reaction chamber is 1000Pa-70000Pa; in step (3), the reaction temperature is 1000℃-2000℃; in step (3), the pressure of the reaction chamber is 1000Pa-70000Pa; the first carbon source and the second carbon source each independently include at least one of methane, ethane, propane, butane, ethylene, propylene, and butene; the flow rate of the first carbon source and the flow rate of the second carbon source each independently are 20 sccm-125 sccm; the first tantalum source and the second tantalum source each independently include five Tantalum chloride; the feeding rate of the first tantalum source and the feeding rate of the second tantalum source are each independently 1 g / min-80 g / min; the hafnium source includes hafnium tetrachloride; the ratio of the feeding rate of the first tantalum source to the feeding rate of the hafnium source is 3.5-4.5; in step (2), the hydrogen flow rate is 10 sccm-1000 sccm; in step (3), the hydrogen flow rate is 10 sccm-1000 sccm; the first carrier gas and the second carrier gas each independently include argon; the flow rate of the first carrier gas is 1 slm-100 slm; the flow rate of the second carrier gas is 1 slm-100 slm; in step (2), the deposition time is 0.5 h-10 h; in step (3), the deposition time is 0.5 h-10 h.

[0020] In some embodiments of this application, an isolation layer is formed on the graphite substrate before forming the hafnium-doped tantalum carbide film. The isolation layer comprises one or more of boron nitride, an iridium / rhenium composite film, tungsten, zirconium, hafnium, tungsten carbide, zirconium carbide, and hafnium carbide. During the preparation and use of the composite material, the isolation layer can at least partially prevent the outward diffusion of carbon from the graphite matrix.

[0021] In some embodiments of this application, a nitrogen source, a boron source, hydrogen gas, and a dilution gas are introduced into the reaction chamber, and the isolation layer is formed using a chemical vapor deposition method. The isolation layer prepared using the above method can form a film layer with uniform thickness and relatively dense structure.

[0022] In some embodiments of this application, the step of forming the isolation layer satisfies at least one of the following conditions: the nitrogen source includes ammonia; the flow rate of the nitrogen source is 0.5 slm-50 slm; the boron source includes boron trichloride; the flow rate of the boron source is 0.5 slm-50 slm; the flow rate of hydrogen is 0.5 slm-50 slm; the dilution gas includes nitrogen; the flow rate of the dilution gas is 0.5 slm-50 slm; the reaction temperature is 300℃-1000℃; the pressure of the reaction chamber is 200 Pa-14000 Pa; and the deposition time is 10 min-300 min. Attached Figure Description

[0023] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 A schematic diagram of the structure of a tantalum carbide / graphite composite material according to an embodiment of this application is shown; Figure 2 A schematic diagram of the structure of a tantalum carbide / graphite composite material according to another embodiment of this application is shown; Figure 3 The energy spectrum of the hafnium-doped tantalum carbide film in Example 3 is shown.

[0024] Explanation of reference numerals in the attached figures: 1: Graphite substrate; 2: Hafnium-doped tantalum carbide film; 3: Tantalum carbide film; 4: Isolation layer. Detailed Implementation

[0025] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0026] In one aspect of this application, a tantalum carbide / graphite composite material is proposed. In some embodiments of this application, reference is made to... Figure 1The tantalum carbide / graphite composite material comprises a graphite matrix 1, a hafnium-doped tantalum carbide film 2, and a tantalum carbide film 3, with the hafnium-doped tantalum carbide film 2 located between the graphite matrix 1 and the tantalum carbide film 3. The hafnium-doped tantalum carbide film has good plasticity; by acting as a buffer layer between the graphite matrix and the tantalum carbide film, it can dissipate some of the thermal stress during temperature rises and falls through its own plastic deformation, thereby helping to extend the lifespan of the film and the overall service life of the composite material.

[0027] In some embodiments of this application, the hafnium-doped tantalum carbide film layer 2 may include the chemical formula Ta x Hf 1-x C y The material has a particle size distribution of x (0.7-0.9) and y (0.7-0.9). This is beneficial for further improving the plasticity of the film, which in turn helps to dissipate thermal stress during temperature rise and fall, thereby further extending the service life of the film and the composite material.

[0028] In some embodiments of this application, Ta x Hf 1-x C y In the material, x can be 0.7, 0.75, 0.8, 0.85, 0.9, etc., and y can be 0.7, 0.75, 0.8, 0.85, 0.9, etc.

[0029] In some specific embodiments of this application, Ta x Hf 1-x C y In the material, x can be 0.8 and y can be 0.8, meaning that the hafnium-doped tantalum carbide film layer 2 can include materials with the chemical formula Ta 0.8 Hf 0.2 C 0.8 The material, therefore, the hafnium-doped tantalum carbide film layer has good plasticity. During temperature rise and fall, it can effectively dissipate some of the thermal stress through its own plastic deformation, alleviate the accumulation of thermal stress, and improve the problem of thermal stress accumulation affecting the film life due to the mismatch of thermal expansion coefficients between the film layer and the substrate. In some specific embodiments, the hafnium-doped tantalum carbide film layer 2 can be made of the chemical formula Ta 0.8 Hf 0.2 C 0.8 The material composition.

[0030] In some embodiments of this application, the thickness of the hafnium-doped tantalum carbide film 2 is 5 μm-10 μm. For example, the thickness of the hafnium-doped tantalum carbide film 2 can be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, etc. This film thickness within the above range is beneficial for further extending the service life of the film and the composite material.

[0031] In some embodiments of this application, the thickness of the tantalum carbide film 3 is 10 μm-50 μm. For example, the thickness of the tantalum carbide film 3 can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, etc. A film thickness within the above range can improve the high-temperature corrosion resistance of the composite material.

[0032] In other embodiments of this application, reference is made to Figure 2 The tantalum carbide / graphite composite material also includes an isolation layer 4, which is located between the graphite matrix 1 and the hafnium-doped tantalum carbide film layer 2. The isolation layer 4 comprises one or more of boron nitride, an iridium / rhenium composite film layer, tungsten, zirconium, hafnium, tungsten carbide, zirconium carbide, and hafnium carbide. The film layer formed by these materials, acting as an isolation layer, can at least partially prevent the graphite matrix from diffusing and damaging the plasticity of the hafnium-doped tantalum carbide film layer, thereby further improving the overall performance of the composite material and extending its service life.

[0033] In some embodiments of this application, the isolation layer 4 may include a metallic iridium / rhenium composite film (iridium has good adhesion to graphite but poor adhesion to tantalum carbide, so metallic rhenium needs to be introduced as a transition layer to achieve the best effect), high-temperature resistant metals such as metallic tungsten, metallic zirconium, and metallic hafnium, or high-temperature resistant ceramic materials such as boron nitride, tungsten carbide, zirconium carbide, and hafnium carbide. In some specific embodiments, the isolation layer 4 may be composed of a metallic iridium / rhenium composite film, high-temperature resistant metals such as metallic tungsten, metallic zirconium, and metallic hafnium, or high-temperature resistant ceramic materials such as boron nitride, tungsten carbide, zirconium carbide, and hafnium carbide. This effectively slows down the outward diffusion of carbon from the graphite matrix during use, which can damage the plasticity of the hafnium-doped tantalum carbide film, thereby further improving the overall performance of the composite material.

[0034] In some embodiments of this application, the thickness of the isolation layer 4 can be 1 μm-5 μm, for example, the thickness of the isolation layer 4 can be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, etc. Isolation layers of the above thicknesses can at least partially prevent carbon in the graphite matrix from diffusing outwards, thereby at least partially preventing carbon from filling Ta. x Hf 1-x C y The carbon vacancies in the material allow the hafnium-doped tantalum carbide film to maintain good plasticity.

[0035] In another aspect of this application, a method for preparing the aforementioned tantalum carbide / graphite composite material is provided. In some embodiments of this application, the method for preparing the aforementioned tantalum carbide / graphite composite material may include the following steps: (1) Place the graphite matrix into the reaction chamber.

[0036] In some specific embodiments of this application, the graphite substrate may be a graphite disk.

[0037] In some embodiments of this application, the graphite substrate can be cleaned and dried before being placed in the reaction chamber to remove impurities from the surface of the graphite substrate.

[0038] In some embodiments of this application, after the graphite substrate is placed in the reaction chamber, the temperature is raised only after confirming that the airtightness of the reaction system meets the standard.

[0039] (2) Introduce a first carbon source, a first tantalum source, a hafnium source, hydrogen and a first carrier gas into the reaction chamber, and form a hafnium-doped tantalum carbide film on a graphite substrate by chemical vapor deposition.

[0040] In some embodiments of this application, the first carbon source may include at least one gaseous hydrocarbon such as methane, ethane, propane, butane, ethylene, propylene, and butene. In some specific embodiments, the first carbon source may be methane or propylene.

[0041] In some embodiments of this application, the flow rate of the first carbon source can be between 20 sccm and 125 sccm. For example, the flow rate of the first carbon source can be 20 sccm, 35 sccm, 50 sccm, 80 sccm, 100 sccm, 125 sccm, etc. A flow rate within the above range can provide sufficient carbon source for chemical vapor deposition, thereby improving the utilization rate of the first tantalum source and hafnium source.

[0042] In some embodiments of this application, the first tantalum source may include tantalum pentachloride (TaCl5). The above-mentioned raw material can provide tantalum element for chemical vapor deposition, and the by-products have low corrosivity and no obvious adverse effects on equipment life and safety.

[0043] In some embodiments of this application, the feeding rate of the first tantalum source can be 1 g / min to 80 g / min, for example, the feeding rate of the first tantalum source can be 1 g / min, 5 g / min, 10 g / min, 30 g / min, 50 g / min, 80 g / min, etc. A feeding rate of the first tantalum source within a suitable range is beneficial to the formation of the target film.

[0044] In some embodiments of this application, the hafnium source may include hafnium tetrachloride (HfCl4). The above-mentioned raw materials can provide hafnium, and the byproducts are relatively equipment-friendly, unlikely to corrode the equipment or adversely affect the safety of the equipment and operators.

[0045] In some embodiments, the ratio of the feeding speed of the first tantalum source to the feeding speed of the hafnium source can be 3.5-4.5. For example, the ratio can be 3.5, 3.8, 4, 4.2, 4.5, etc. Thus, the tantalum to hafnium ratio is close to 4:1, which is beneficial for forming a film with good plasticity. In this application, the feeding speed refers to the mass of material fed per unit time.

[0046] In some embodiments, in step (2), the hydrogen flow rate can be 10 sccm-1000 sccm, for example, the hydrogen flow rate can be 10 sccm, 50 sccm, 100 sccm, 300 sccm, 500 sccm, 700 sccm, 1000 sccm, etc. The above-mentioned hydrogen flow rates can promote the reduction of tantalum and hafnium sources, and can promote the cracking of carbon sources, thereby promoting the formation of hafnium-doped tantalum carbide.

[0047] In some embodiments, the first carrier gas may include argon. In some embodiments, the flow rate of the first carrier gas may be 1 slm-100 slm, for example, the flow rate of the first carrier gas may be 1 slm, 10 slm, 30 slm, 50 slm, 100 slm, etc. The first carrier gas at the above flow rates can act as a dilution and carrier gas, can reduce the partial pressure of the reactants, and can carry away byproducts.

[0048] In some embodiments of this application, in step (2), the reaction temperature is 1000℃-2000℃, for example, the reaction temperature can be 1000℃, 1200℃, 1350℃, 1500℃, 1800℃, 2000℃, etc. Within the above temperature range, the raw materials can undergo chemical reaction to form hafnium-doped tantalum carbide and deposit it on the graphite matrix.

[0049] In some embodiments of this application, in step (2), the pressure of the reaction chamber is 1000 Pa to 70000 Pa. For example, the pressure of the reaction chamber can be 1000 Pa, 5000 Pa, 10000 Pa, 30000 Pa, 50000 Pa, 70000 Pa, etc. The above pressure conditions are conducive to the chemical vapor deposition reaction and to the formation of a hafnium-doped tantalum carbide film with good plasticity.

[0050] In some embodiments of this application, in step (2), the deposition time is 0.5h-10h, for example, the deposition time can be 0.5h, 1h, 2.5h, 5h, 8h, 10h, etc. Within the above range, a hafnium-doped tantalum carbide film layer of suitable thickness can be deposited.

[0051] (3) Introduce a second carbon source, a second tantalum source, hydrogen gas and a second carrier gas into the reaction chamber, and use chemical vapor deposition to form a tantalum carbide film on the side of the hafnium-doped tantalum carbide film away from the graphite substrate.

[0052] In some embodiments of this application, in step (3), the second carbon source may include at least one of gaseous hydrocarbons such as methane, ethane, propane, butane, ethylene, propylene, and butene.

[0053] In some embodiments of this application, in step (3), the flow rate of the second carbon source can be 20 sccm-125 sccm. For example, the flow rate of the second carbon source can be 20 sccm, 40 sccm, 50 sccm, 70 sccm, 100 sccm, 110 sccm, or 125 sccm. Thus, the carbon source is sufficient, which is beneficial to improving the utilization rate of the second tantalum source.

[0054] In some embodiments of this application, the second tantalum source includes tantalum pentachloride. The above-mentioned raw materials can provide tantalum element, and the byproducts generated from the reaction using these raw materials have low corrosivity and are less likely to cause damage to equipment and operators.

[0055] In some embodiments, the feeding rate of the second tantalum source is 1 g / min to 80 g / min. For example, the feeding rate of the second tantalum source can be 1 g / min, 5 g / min, 10 g / min, 30 g / min, 50 g / min, 80 g / min, etc.

[0056] In some embodiments, in step (3), the hydrogen flow rate is 10 sccm-1000 sccm, for example, the hydrogen flow rate can be 10 sccm, 50 sccm, 100 sccm, 400 sccm, 600 sccm, 800 sccm, 1000 sccm, etc. This promotes the reduction of the tantalum source and the cracking of the carbon source, thereby facilitating the formation of the tantalum carbide film.

[0057] In some embodiments, the second carrier gas may include argon. In some embodiments, the flow rate of the second carrier gas is 1 slm-100 slm, for example, the flow rate of the second carrier gas may be 1 slm, 5 slm, 20 slm, 50 slm, 70 slm, 100 slm, etc. The second carrier gas at the above flow rates can act as a dilution and carrier gas, can reduce the partial pressure of the reactants, and can carry away byproducts.

[0058] In some embodiments, in step (3), the reaction temperature is 1000℃-2000℃. For example, the reaction temperature can be 1000℃, 1250℃, 1350℃, 1500℃, 1750℃, 2000℃, etc. Within the above temperature range, each raw material can form tantalum carbide through chemical reaction and deposit it on the graphite matrix.

[0059] In some embodiments, in step (3), the pressure of the reaction chamber is 1000 Pa to 70000 Pa. For example, the pressure of the reaction chamber can be 1000 Pa, 5000 Pa, 10000 Pa, 30000 Pa, 50000 Pa, 70000 Pa, etc. The above pressure conditions are conducive to the chemical vapor deposition reaction and to the formation of a uniform tantalum carbide film.

[0060] In some embodiments, the deposition time in step (3) is 0.5h-10h, for example, the deposition time can be 0.5h, 1.5h, 3h, 5h, 7h, 10h, etc. Within the above range, a film layer of suitable thickness can be deposited.

[0061] In some embodiments of this application, before forming the hafnium-doped tantalum carbide film, an isolation layer can be formed on the graphite substrate. This isolation layer includes one or more of boron nitride, iridium / rhenium composite films, tungsten, zirconium, hafnium, tungsten carbide, zirconium carbide, and hafnium carbide. During subsequent film preparation and use of the composite material product, the isolation layer can at least partially prevent carbon diffusion from the graphite substrate, mitigating or even preventing the problem of carbon diffusion into the hafnium-doped tantalum carbide film leading to decreased film plasticity.

[0062] In some embodiments of this application, a nitrogen source, a boron source, hydrogen gas, and a dilution gas can be introduced into the reaction chamber to form an isolation layer using a chemical vapor deposition method. The boron nitride isolation layer can prevent carbon from diffusing outward from the graphite matrix, thereby facilitating the formation of a hafnium-doped tantalum carbide film with good plasticity. Furthermore, during the use of the composite material, the hafnium-doped tantalum carbide film can maintain good plasticity, thus extending the service life of the composite material.

[0063] In some embodiments of this application, the nitrogen source may include ammonia. In some embodiments, the flow rate of the nitrogen source is 0.5 slm-50 slm, for example, the flow rate of the nitrogen source may be 0.5 slm, 1 slm, 5 slm, 10 slm, 30 slm, 50 slm, etc.

[0064] In some embodiments of this application, the boron source may include boron trichloride (BCl3). In some embodiments, the flow rate of the boron source is 0.5 slm-50 slm, for example, the flow rate of the boron source may be 0.5 slm, 3 slm, 5 slm, 10 slm, 20 slm, 35 slm, 50 slm, etc.

[0065] Ammonia can provide nitrogen, and boron trichloride can provide boron; setting the flow rates of the nitrogen and boron sources within appropriate ranges is beneficial for the formation of the boron nitride isolation layer.

[0066] In some embodiments, the hydrogen flow rate is 0.5 slm-50 slm, for example, the hydrogen flow rate can be 0.5 slm, 3 slm, 5 slm, 10 slm, 20 slm, 35 slm, 50 slm, etc. Hydrogen at these flow rates can reduce the boron source, thereby promoting the formation of boron nitride.

[0067] In some embodiments, the diluent gas may include nitrogen. In some embodiments, the flow rate of the diluent gas may be 0.5 slm-50 slm, for example, the flow rate may be 0.5 slm, 3 slm, 5 slm, 10 slm, 20 slm, 35 slm, 50 slm, etc. The diluent gas at the above flow rates can play a role in dilution and protection, thereby benefiting the safety of experimental equipment and operators.

[0068] In some embodiments, during the formation of the boron nitride isolation layer, the reaction temperature is 300℃-1000℃. For example, the reaction temperature can be 300℃, 450℃, 600℃, 800℃, 1000℃, etc. At the above temperatures, the nitrogen source, boron source, and hydrogen can undergo a chemical reaction to generate boron nitride and deposit it on the graphite substrate.

[0069] In some embodiments, during the formation of the boron nitride isolation layer, the pressure in the reaction chamber is 200 Pa to 14000 Pa. For example, the pressure in the reaction chamber can be 200 Pa, 500 Pa, 1000 Pa, 5000 Pa, 7000 Pa, 10000 Pa, 12000 Pa, 14000 Pa, etc. The above pressures facilitate the chemical reaction of the raw materials to generate boron nitride, which is then deposited on the graphite substrate to obtain the boron nitride isolation layer.

[0070] In some embodiments, the deposition time during the formation of the boron nitride isolation layer is 10 min to 300 min. For example, the deposition time can be 10 min, 30 min, 50 min, 80 min, 100 min, 150 min, 200 min, 250 min, 300 min, etc. Within the above range, a boron nitride isolation layer of suitable thickness can be formed, thereby effectively isolating the graphite matrix and preventing carbon from diffusing outward.

[0071] In some embodiments of this application, the boron nitride isolation layer may also be formed using other methods, such as magnetron sputtering, PECVD (plasma-enhanced chemical vapor deposition), etc.

[0072] In some embodiments of this application, a layer of high-temperature resistant metals such as tungsten, zirconium, or hafnium can be deposited on the surface of a graphite substrate using sputtering or CVD methods as an isolation layer. In other embodiments of this application, an iridium / rhenium composite film can be formed on a graphite substrate using sputtering or CVD methods. First, a layer of iridium is formed on the surface of the graphite substrate, and then a layer of rhenium is formed on the iridium. Iridium has good adhesion to graphite, and rhenium, as a transition layer, can improve the adhesion between the iridium / rhenium composite film and tantalum carbide.

[0073] In summary, this application employs a chemical vapor deposition method to first form a hafnium-doped tantalum carbide film on a graphite substrate, followed by the formation of a tantalum carbide film. The hafnium-doped tantalum carbide film can dissipate some thermal stress during temperature rises and falls through its own plastic deformation, thereby mitigating the problem of shortened film life caused by thermal stress accumulation. Furthermore, before forming the hafnium-doped tantalum carbide film, an isolation layer can be formed on the graphite substrate. This isolation layer can mitigate the outward diffusion of carbon from the graphite substrate during subsequent film preparation and use of the graphite-based product, thus forming a hafnium-doped tantalum carbide film with good plasticity and maintaining good plasticity for a longer period during use, further extending the film's lifespan. The above method is controllable and beneficial for improving the yield of composite material preparation.

[0074] The present application will be described below through specific embodiments. Those skilled in the art will understand that the specific embodiments below are merely illustrative and do not limit the scope of the present application in any way. Furthermore, in the following embodiments, unless otherwise specified, the materials and equipment used are commercially available. If specific processing conditions and methods are not explicitly described in the later embodiments, conditions and methods known in the art can be used for processing.

[0075] Example 1 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1600℃ and the reaction chamber pressure is controlled to 50000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The flow rate of propylene is 20 sccm, the flow rate of argon is 10 slm, the flow rate of hydrogen is 100 sccm, the feeding rate of tantalum pentachloride is 10 g / min, and the feeding rate of hafnium tetrachloride is 2.3 g / min. The process is maintained for 80 min. 4. The reaction chamber temperature is 1600℃, the reaction chamber pressure is controlled to 50000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 25sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0076] Example 2 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the chamber temperature rises to 800℃ and the pressure in the reaction chamber is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, and boron trichloride are introduced. The flow rates of ammonia are 3 slm, nitrogen is 30 slm, hydrogen is 10 slm, and boron trichloride is 1 slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1200℃ and the reaction chamber pressure is controlled to 10000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The propylene flow rate is gradually increased from 20sccm to 25sccm within 80min, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the tantalum pentachloride feeding rate is 10g / min, and the hafnium tetrachloride feeding rate is 2.3g / min. 4. The reaction chamber temperature is 1200℃, the reaction chamber pressure is controlled to 10000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 25sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0077] Example 3 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1200℃ and the reaction chamber pressure is controlled to 10000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The propylene flow rate is gradually increased from 50sccm to 65sccm within 80min, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the tantalum pentachloride feeding rate is 10g / min, and the hafnium tetrachloride feeding rate is 2.3g / min. 4. The reaction chamber temperature is 1200℃, the reaction chamber pressure is controlled to 10000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 65sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0078] Example 4 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1200℃ and the reaction chamber pressure is controlled to 10000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The propylene flow rate is gradually increased from 100sccm to 125sccm within 80min, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the tantalum pentachloride feeding rate is 10g / min, and the hafnium tetrachloride feeding rate is 2.3g / min. 4. The reaction chamber temperature is 1200℃, the reaction chamber pressure is controlled to 10000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 125sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0079] Example 5 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1800℃ and the reaction chamber pressure is controlled to 10000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The propylene flow rate is gradually increased from 100sccm to 125sccm within 80min, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the tantalum pentachloride feeding rate is 10g / min, and the hafnium tetrachloride feeding rate is 2.3g / min. 4. The reaction chamber temperature is 1800℃, the reaction chamber pressure is 10000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 125sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0080] Example 6 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. After the reaction chamber temperature is raised to 1800℃ and the reaction chamber pressure is controlled to 10000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride and propylene gas are introduced. The flow rate of propylene is 100 sccm, the flow rate of argon is 10 slm, the flow rate of hydrogen is 100 sccm, the feeding rate of tantalum pentachloride is 10 g / min, and the feeding rate of hafnium tetrachloride is 2.3 g / min. The process conditions are maintained for 120 min. 4. The process is completed and the temperature is lowered to room temperature.

[0081] Example 7 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 1600℃ and the reaction chamber pressure is controlled to 50000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The flow rate of propylene is 20 sccm, the flow rate of argon is 10 slm, the flow rate of hydrogen is 100 sccm, the feeding rate of tantalum pentachloride is 10 g / min, and the feeding rate of hafnium tetrachloride is 2.3 g / min. The process is maintained for 80 min. 3. The reaction chamber temperature is 1600℃, the reaction chamber pressure is controlled to 50000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 25sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 4. The process is completed and the temperature is lowered to room temperature.

[0082] Example 8 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. 2. After the reaction chamber temperature is raised to 1600℃ and the reaction chamber pressure is controlled to 50000pa and reaches equilibrium, hydrogen, argon and zirconium tetrachloride are introduced. The argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the zirconium tetrachloride feeding rate is 10g / min, and the process is maintained for 20min. 3. After the reaction chamber temperature is 1600℃ and the reaction chamber pressure is controlled to 50000pa and reaches equilibrium, hydrogen, argon, tantalum pentachloride, hafnium tetrachloride and propylene gases are introduced. The flow rate of propylene is 20 sccm, the flow rate of argon is 10 slm, the flow rate of hydrogen is 100 sccm, the feeding rate of tantalum pentachloride is 10 g / min, and the feeding rate of hafnium tetrachloride is 2.3 g / min. The process is maintained for 80 min. 4. The reaction chamber temperature is 1600℃, the reaction chamber pressure is controlled to 50000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 25sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 5. The process is completed and the temperature is lowered to room temperature.

[0083] Comparative Example 1 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. After reaching the target temperature, adjust the pressure conditions in the reaction chamber. 2. After the process parameters such as reaction chamber temperature (1200℃) and pressure (10000pa) reach the target conditions, argon, hydrogen, tantalum pentachloride and propylene gas are introduced. The propylene flow rate is 20 sccm, the argon flow rate is 5 slm, the tantalum pentachloride feeding rate is 10 g / min, and the hydrogen flow rate is 100 sccm. After 120 min, the introduction of propylene, hydrogen and tantalum pentachloride is stopped, and the argon flow rate is changed to keep the gas introduction constant. 3. The process is completed and the temperature is lowered to room temperature.

[0084] Comparative Example 2 1. Place the cleaned and dried graphite component to be formed into the reaction chamber. After confirming that the airtightness of the reaction system meets the standard, start heating. After reaching the target temperature, adjust the pressure conditions in the reaction chamber. 2. After the reaction chamber temperature is raised to 800℃ and the reaction chamber pressure is controlled to 7000pa and reaches equilibrium, hydrogen, nitrogen, ammonia, boron trichloride and other gases are introduced. The flow rates of ammonia are 3slm, nitrogen is 30slm, hydrogen is 10slm, and boron trichloride is 1slm. After 90 minutes, the process ends, the gas introduction is stopped, a vacuum is drawn, and the temperature is raised again. 3. The reaction chamber temperature is raised to 1600℃, the reaction chamber pressure is controlled to 50000pa, the argon flow rate is 10slm, the hydrogen flow rate is 100sccm, the propylene flow rate is 25sccm, the tantalum pentachloride feeding rate is 13g / min, the hafnium tetrachloride feeding is stopped, and the process conditions are maintained for 40min. 4. The process is completed and the temperature is lowered to room temperature.

[0085] Characterization data and effect data of the examples and comparative products The thermal shock resistance of the samples prepared in the examples and comparative examples was tested using the following methods: The sample to be tested was placed in a sealed furnace. After evacuation, the furnace was heated to 2000℃ (room temperature - 1000℃, heating rate 15℃ / min; 1000-1600℃, heating rate 10℃ / min; 1600-2000℃, heating rate 5℃ / min). After reaching 2000℃, the temperature was maintained for 30 minutes. Heating was then stopped, and the sample was allowed to cool naturally. This cycle was repeated until the film showed obvious damage. The number of cycles was recorded, and the test results were recorded in Table 1.

[0086] Table 1

[0087] As shown in Table 1, compared with Comparative Examples 1 and 2, Examples 1-5 and Example 8 all formed an isolation layer, a hafnium-doped tantalum carbide film layer, and a tantalum carbide film layer (protective coating), resulting in a significant increase in the number of thermal shock resistance cycles of the products. Compared with Comparative Example 1, Example 7 formed a hafnium-doped tantalum carbide film layer between the graphite substrate and the tantalum carbide film layer, resulting in a significant increase in the number of thermal shock resistance cycles of the products in Example 7. Compared with Example 7, Examples 1-5 and Example 8 had an isolation layer between the graphite substrate and the hafnium-doped tantalum carbide film layer, resulting in superior thermal shock resistance performance of the products. Compared with Example 5, Example 6 did not form the topmost tantalum carbide film layer. It can be seen that setting a boron nitride isolation layer and a hafnium-doped tantalum carbide film layer is beneficial to improving the thermal shock resistance performance of the products. In Example 5, after the formation of the tantalum carbide film layer, because the plasticity of the tantalum carbide film layer is lower than that of the hafnium-doped tantalum carbide film layer, the difference in the coefficient of thermal expansion between the tantalum carbide film layer and the substrate will accelerate the accumulation of thermal stress, thus reducing the thermal shock resistance performance.

[0088] By scanning the cross-sections of the products in Examples 1-5, it can be seen that the thickness of the hafnium-doped tantalum carbide film is in the range of 5μm-10μm, the thickness of the tantalum carbide film is in the range of 10μm-50μm, and the thickness of the isolation layer is in the range of 1μm-5μm.

[0089] Figure 3 The EDS test results of the hafnium-doped tantalum carbide film in Example 3 are shown. The atomic ratio of Ta, Hf and C is close to 4:1:4.

[0090] In the description of this application, the terms "upper" and "lower" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this application and do not require this application to be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this application.

[0091] In the description of this specification, references to terms such as "one embodiment," "another embodiment," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples, without contradiction. Additionally, it should be noted that in this specification, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features.

[0092] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A tantalum carbide / graphite composite material, characterized by, The tantalum carbide / graphite composite material comprises a graphite base, a hafnium-doped tantalum carbide film layer and a tantalum carbide film layer, the hafnium-doped tantalum carbide film layer being located between the graphite base and the tantalum carbide film layer.

2. The tantalum carbide / graphite composite of claim 1, wherein, The hafnium-doped tantalum carbide film layer comprises a material with a chemical formula of Ta x Hf 1-x C y , wherein x is 0.7-0.9, and y is 0.7-0.

9.

3. The tantalum carbide / graphite composite of claim 1, wherein, The thickness of the hafnium-doped tantalum carbide film layer is 5-10 μm; and / or, the thickness of the tantalum carbide film layer is 10-50 μm.

4. The tantalum carbide / graphite composite of any one of claims 1-3, wherein, The tantalum carbide / graphite composite material further comprises an isolation layer, the isolation layer being located between the graphite base and the hafnium-doped tantalum carbide film layer, the isolation layer comprising one or more of boron nitride, a metal iridium / rhenium composite film layer, metal tungsten, metal zirconium, metal hafnium, tungsten carbide, zirconium carbide, hafnium carbide.

5. The tantalum carbide / graphite composite of claim 4, wherein The thickness of the isolation layer is 1-5 μm.

6. A method of producing the tantalum carbide / graphite composite material according to any one of claims 1 to 5, characterized by, Comprise: (1) placing a graphite base into a reaction chamber; (2) introducing a first carbon source, a first tantalum source, a hafnium source, hydrogen and a first carrier gas into the reaction chamber, and using a chemical vapor deposition method to form a hafnium-doped tantalum carbide film layer on the graphite base; (3) introducing a second carbon source, a second tantalum source, hydrogen and a second carrier gas into the reaction chamber, and using a chemical vapor deposition method to form a tantalum carbide film layer on the side of the hafnium-doped tantalum carbide film layer away from the graphite base.

7. The method of claim 6, wherein, At least one of the following conditions is met: In step (2), the reaction temperature is 1000-2000℃; In step (2), the pressure in the reaction chamber is 1000-70000 Pa; In step (3), the reaction temperature is 1000-2000℃; In step (3), the pressure in the reaction chamber is 1000-70000 Pa; The first carbon source and the second carbon source each independently comprises at least one of methane, ethane, propane, butane, ethylene, propylene, butylene; The flow rate of the first carbon source and the flow rate of the second carbon source are each independently 20-125 sccm; The first tantalum source and the second tantalum source each independently comprises tantalum pentachloride; The feeding speed of the first tantalum source and the feeding speed of the second tantalum source are each independently 1-80 g / min; The hafnium source comprises hafnium tetrachloride; The ratio of the feeding speed of the first tantalum source to the feeding speed of the hafnium source is 3.5-4.5; In step (2), the flow rate of hydrogen is 10-1000 sccm; In step (3), the flow rate of hydrogen is 10-1000 sccm; The first carrier gas and the second carrier gas each independently comprises argon; The flow rate of the first carrier gas is 1-100 slm; The flow rate of the second carrier gas is 1-100 slm; In step (2), the deposition time is 0.5-10 h; In step (3), the deposition time is 0.5-10 h.

8. The method according to claim 6 or 7, characterized in that, Before forming the hafnium-doped tantalum carbide film layer, an isolation layer is formed on the graphite base, the isolation layer comprising one or more of boron nitride, a metal iridium / rhenium composite film layer, metal tungsten, metal zirconium, metal hafnium, tungsten carbide, zirconium carbide, hafnium carbide.

9. The method of claim 8, wherein, A nitrogen source, a boron source, hydrogen and a dilution gas are introduced into the reaction chamber, and a chemical vapor deposition method is used to form the isolation layer.

10. The method of claim 9, wherein, The step of forming the isolation layer meets at least one of the following conditions: The nitrogen source includes ammonia; The flow rate of the nitrogen source is 0.5 slm-50 slm; The boron source includes boron trichloride; The flow rate of the boron source is 0.5 slm-50 slm; The flow rate of hydrogen is 0.5 slm-50 slm; The diluting gas includes nitrogen; The flow rate of the diluent gas is 0.5 slm-50 slm; The reaction temperature is 300℃-1000℃; The pressure in the reaction chamber is 200 Pa - 14000 Pa; The deposition time is 10 min to 300 min.

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