High-temperature-resistant device and manufacturing method thereof
By generating an oxide layer on a tantalum substrate and then performing a carbonization reaction to form a tantalum carbide layer, the problem of easy peeling of TaC coating in SiC single crystal manufacturing is solved, providing high-temperature stability and high density, making it suitable for high-temperature devices.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- IND TECH RES INST
- Filing Date
- 2024-11-27
- Publication Date
- 2026-05-12
AI Technical Summary
In the current technology for manufacturing SiC single crystals, graphite crucibles are used to deposit TaC as a protective layer. This layer is prone to cracking or peeling due to thermal shock, which leads to the carrier gas corroding the carbon substrate. Furthermore, TaC crystals produced by CVD have low flexibility.
A tantalum oxide layer is generated by oxidizing the tantalum substrate, and then a carbonization reaction is carried out in an inert atmosphere to form a tantalum carbide layer as a surface protective layer for high-temperature resistant devices. The process is simple, environmentally friendly and non-toxic, and the film thickness can be adjusted and has high uniformity.
The problem of easy peeling of TaC coating has been solved, enabling stable use at high temperatures. It has high density and high reusability, and is suitable for high-temperature devices such as crucibles and aerospace mechanism parts.
Smart Images
Figure CN122013138A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a high-temperature resistant device, and specifically to a high-temperature resistant device suitable for growing high-purity semi-insulating silicon carbide powder and its manufacturing method. Background Technology
[0002] Silicon carbide (SiC) possesses excellent physicochemical properties and is suitable for applications in semiconductor processes, wireless communication, and power module industries. However, the manufacturing process of SiC single crystals requires temperatures above 1800°C and necessitates the use of hydrogen (H2), argon (Ar), ammonia (NH3), hydrocarbons, or other hydrocarbons as carrier gases. Because the reaction of ammonia produces Si2N4, SiC on carbon substrates is prone to corrosion, cracking, or peeling after the vaporization reaction at temperatures above 1500°C.
[0003] To reduce crystal growth or epitaxial defects, tantalum carbide (TaC) is typically deposited onto a graphite crucible as a protective layer, and a highly dense TaC coating is obtained using chemical vapor deposition (CVD). However, TaC produced by CVD exhibits low flexibility due to its directional growth. This also means that when the TaC-coated graphite crucible is subjected to thermal shock, cracking or peeling can cause rapid corrosion of the carbon substrate by NH3, H2, and other substances in the carrier gas. Summary of the Invention
[0004] This invention relates to a high-temperature resistant device and its manufacturing method, which can produce tantalum carbide as a surface protective layer for the high-temperature resistant device under normal pressure, which is resistant to high temperatures and does not easily fall off.
[0005] According to an embodiment of the present invention, a method for manufacturing a high-temperature resistant device includes providing a tantalum substrate as the device body, oxidizing the tantalum substrate in an oxygen-containing environment to generate a tantalum oxide layer on the surface of the tantalum substrate, wherein the oxidation treatment temperature is between 100°C and 1100°C, and then burying the oxidized tantalum substrate in a carbon-containing material and performing a carbonization reaction in an inert gas to transform the tantalum oxide layer into a tantalum carbide layer.
[0006] In one embodiment of the present invention, the oxygen-containing environment includes oxygen, water vapor, inert gas, or a combination thereof.
[0007] In one embodiment of the present invention, the pressure of the above oxidation treatment is atmospheric pressure.
[0008] In one embodiment of the present invention, the oxidation treatment time is between 15 minutes and 120 minutes.
[0009] In one embodiment of the present invention, the above-mentioned tantalum oxide layer is in the form of the chemical formula Ta x O yThis indicates that y / x is between 0.5 and 2.5.
[0010] In one embodiment of the present invention, the inert gas includes argon, helium, or a combination thereof.
[0011] In one embodiment of the present invention, the pressure of the carbonization reaction is atmospheric pressure, the reaction temperature is between 1500°C and 2100°C, and the reaction time is between 15 minutes and 2 hours.
[0012] In one embodiment of the present invention, the carbon-containing material includes carbon powder, graphite powder, activated carbon, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), sucrose, glucose, or a combination thereof.
[0013] In one embodiment of the present invention, decarbonization may be performed after the above-described carbonization reaction.
[0014] According to another embodiment of the present invention, a high-temperature resistant device includes a tantalum substrate and a tantalum carbide layer. The tantalum carbide layer is a layer formed on the surface of the tantalum substrate, wherein the thickness of the tantalum carbide layer is between 2 μm and 100 μm.
[0015] In another embodiment of the present invention, the specific surface area of the tantalum carbide layer is between 0.1 cm². 2 / g to 2cm 2 / g.
[0016] In another embodiment of the present invention, the above-mentioned high-temperature resistant device includes a crucible, aerospace mechanism accessories, high-temperature reaction vessel accessories, or crystal growth accessories.
[0017] Based on the above, the present invention produces a device for high-temperature applications by reacting tantalum substrate in an atmosphere furnace to generate TaC from carbon in situ. Therefore, it not only has the advantages of simple process, environmental protection and non-toxicity, adjustable film thickness and high uniformity, high film density and high reusability, but also solves the problem of coating peeling caused by traditional TaC coating methods. Attached Figure Description
[0018] Figure 1 This is a flowchart illustrating the manufacturing process of a high-temperature resistant device according to an embodiment of the present invention.
[0019] Figure 2A yes Figure 1 A simplified diagram of the oxidation treatment in step 110;
[0020] Figure 2B yes Figure 1 A simplified diagram of the carbonization reaction in step 120;
[0021] Figure 3This is a scanning electron microscope (SEM) image of the sample of Experimental Example 3 of the present invention;
[0022] Figure 4 This is a SEM image of the sample from Experimental Example 27 of the present invention;
[0023] Figure 5 This is a SEM image of the sample from Experimental Example 4 of the present invention;
[0024] Figure 6 This is a SEM image of the sample from Experimental Example 14 of the present invention;
[0025] Figure 7 This is a SEM image of the sample from Comparative Example 1;
[0026] Figure 8 This is a SEM image of the sample from Comparative Example 2. Detailed Implementation
[0027] Figure 1 This is a flowchart illustrating the manufacturing process of a high-temperature resistant device according to an embodiment of the present invention.
[0028] Please refer to Figure 1 First, in step 100, a tantalum substrate is provided as the device body. The tantalum substrate refers to a substrate whose entire material is tantalum, which may be a sheet substrate, a strip substrate, a spherical substrate, or a substrate made into a specific structure.
[0029] Then, in step 110, the tantalum substrate is oxidized in an oxygen-containing environment to form a tantalum oxide layer on the surface of the tantalum substrate, wherein the tantalum oxide has the chemical formula Ta x O y This indicates that y / x is between 0.5 and 2.5, where y / x = 0.5 in a low-oxygen environment and y / x = 2.5 in an oxygen-rich environment. The aforementioned oxygen-containing environment includes oxygen, water vapor, inert gases, or combinations thereof, such as a combination of oxygen and an inert gas or water vapor and an inert gas. In one embodiment, the aforementioned oxygen-containing environment refers to an environment with an oxygen content of 1 vol% to 100 vol%. In one embodiment, the temperature of the aforementioned oxidation treatment is between 100°C and 1100°C, for example, between 120°C and 1100°C, between 500°C and 1100°C, or between 120°C and 500°C. In one embodiment, the pressure of the aforementioned oxidation treatment is atmospheric pressure, for example, 1 atm. In one embodiment, the time of the aforementioned oxidation treatment is between 15 minutes and 120 minutes, for example, between 30 minutes and 120 minutes. Figure 2A A simplified diagram of the oxidation process in step 110 is shown, wherein the tantalum substrate 200 can be placed in an alumina crucible 210 and subjected to the above oxidation process.
[0030] Then, in step 120, the oxidized tantalum substrate is embedded in a carbon-containing material and subjected to a carbonization reaction in an inert gas to transform the tantalum oxide layer into a tantalum carbide layer. The carbon-containing material includes, but is not limited to, carbon powder, graphite powder, activated carbon, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), sucrose, glucose, or a combination thereof. In one embodiment, the inert gas includes argon, helium, or a combination thereof. In one embodiment, the carbonization reaction is carried out at atmospheric pressure, for example, 1 atm. In one embodiment, the reaction temperature is between 1500°C and 2100°C. In one embodiment, the reaction time is between 15 minutes and 2 hours. Figure 2B A simplified diagram of the carbonization reaction in step 120 is shown, wherein the oxidized tantalum substrate 200a can be placed in a graphite crucible 220 containing carbon material 230 and undergo the above carbonization reaction.
[0031] After step 120, step 130, carbon removal, can be performed. For example, the remaining carbon-containing substances can be removed by high-temperature treatment, wherein the high-temperature treatment temperature is about 800℃ to 900℃, in an atmospheric environment, and the holding time is about 1h to 2h, but it is not limited to this.
[0032] Another embodiment of the present invention is a high-temperature resistant device formed using the above process. Therefore, the high-temperature resistant device includes a tantalum substrate and a tantalum carbide layer, wherein the tantalum carbide layer is formed on the surface of the tantalum substrate. Such a high-temperature resistant device can be used at temperatures exceeding 1000°C, for example, as a crucible, aerospace component, high-temperature reaction vessel component, or crystal growth component. In this embodiment, the thickness of the tantalum carbide layer is, for example, between 2 μm and 100 μm. A thickness of 2 μm or more meets the uniformity requirements; a thickness of less than 100 μm reduces the probability of film separation. In this embodiment, the specific surface area of the tantalum carbide layer is between 0.1 cm². 2 / g to 2cm 2 / g. If the specific surface area of the tantalum carbide layer is 0.1cm², then... 2 Below / g, the effect of adsorbing carrier gas may be poor; if the specific surface area of the tantalum carbide layer is less than 2cm², the effect may be poor. 2 If the content exceeds / g, it may cause instability in the membrane structure and reduce mechanical strength.
[0033] The following experiments are listed to verify the implementation effect of this disclosure, but this disclosure is not limited to the following content.
[0034] <raw material>
[0035] <Experimental Examples 1-29>
[0036] First, a sheet-like tantalum substrate is prepared. Then, the tantalum substrate is placed in an alumina crucible and subjected to the oxidation treatments listed in Table 1 under atmospheric pressure. The oxidation treatment is carried out in an atmospheric furnace. Next, the oxidized tantalum substrate (with a tantalum oxide layer on its surface) is embedded in a graphite crucible filled with carbon powder (purchased from SEC-Carbon, average particle size 20 μm). Using the carbon powder as the carbon-containing material, the carbonization reaction listed in Table 1 is carried out under atmospheric pressure. The inert gas for the carbonization reaction is argon or helium. Finally, decarburization is performed at 800 °C, yielding the samples from Experiments 1–29.
[0037] <Comparative Examples 1-2>
[0038] Apart from oxidation treatment, carbonization was carried out using the same process as in the above experimental examples. Please refer to Table 1 for the carbonization conditions.
[0039] Scanning electron microscopy (SEM) analysis:
[0040] The thickness of the tantalum oxide layer formed after oxidation treatment in Experiments 1-29 was observed using a SEM scale bar, and the measurement results are recorded in Table 1 below.
[0041] The cross sections of the specimens in Experimental Examples 1-29 and Comparative Examples 1-2 were observed using SEM, and the thickness of the tantalum carbide layer was obtained according to the SEM scale bar. The measurement results are recorded in Table 1 below.
[0042] Table 1
[0043]
[0044]
[0045] In Table 1, "O" below "Whether water vapor is introduced" indicates that water vapor is introduced; "X" indicates that water vapor is not introduced.
[0046] In Table 1, "O" under "Peel Resistance" indicates good peel resistance; "X" indicates poor peel resistance.
[0047] Based on SEM images, the difference between the thickest and thinnest microstructures of the same film layer was used as the evaluation data for uniformity. Measurements showed that Examples 1-4 and Examples 26-27 exhibited the best uniformity (thickness difference within 3 μm); Examples 9, 14-17, and Examples 28-29 also showed good uniformity (thickness difference between 5 μm and 10 μm). Comparative Example 1 essentially did not form a tantalum carbide layer, while Comparative Example 2 showed a thickness difference of 10 μm.
[0048] Density: The density of the tantalum carbide layer is measured using the specific surface area, and is obtained as a relative value. The lower the specific surface area value, the better the density.
[0049] The measured data show that the specific surface area of the tantalum carbide layers in Experiments 6–17 is approximately 0.13 cm². 2 / g~1.60cm 2 / g, with excellent density and resistance to peeling, making it a preferred choice for thermal conductivity and application in high-temperature downstream processes; the specific surface area of the tantalum carbide layers in Examples 1-5 is approximately 3.74 cm². 2 / g~6.94cm 2 / g, with a specific surface area of approximately 3.45 cm² compared to the tantalum carbide layer in Comparative Example 2. 2 The density is low, resulting in poor compactness, which is detrimental to downstream applications. In particular, Comparative Example 2 has poor compactness and a long formation time, resulting in poor thermal conductivity.
[0050] Analysis of high temperature resistance: Tantalum carbide has a melting point of 3880℃, while the general crystal growth process temperature is between 2000℃ and 2300℃. This material itself is higher than the process temperature, so regardless of thickness, uniformity or density, it can withstand high temperature processes without peeling, cracking or damage.
[0051] Peel resistance analysis: The test specimens were fixed, and the surface layer of tantalum carbide was peeled off using a strong-tear adhesive polymer film. The results showed that tantalum carbide layers treated at 600°C were quite unstable and brittle, and completely peeled off at 1100°C. Comparative examples 1-2, which did not undergo oxidation treatment, exhibited poor peel resistance.
[0052] Figure 3 and Figure 4 The images are SEM images of the samples from Experimental Example 3 and Experimental Example 27, respectively. (From Table 1 above...) Figure 3 and Figure 4 It can be seen that by increasing the oxidation temperature from 120℃ to 1100℃, the thickness of the tantalum oxide layer can be increased from 8μm to 50μm. Figure 5 and Figure 6 These are SEM images of the samples from Experimental Example 4 and Experimental Example 14. (From Table 1 above...) Figure 5 and Figure 6 It can be seen that the difference between Example 4 and Example 14 is only in the oxidation treatment time, so the length of the oxidation treatment time will also affect the thickness of the tantalum carbide layer.
[0053] Furthermore, comparing Experiment 4 and Experiment 9, the introduction of water vapor increased the thickness of the tantalum oxide layer from 8 μm to 68 μm. Therefore, it can be verified that the thickness of the tantalum oxide layer is affected by oxidation temperature, oxidation time, and water vapor; increasing the oxidation temperature, oxidation time, or the introduction of water vapor all increase the thickness of the tantalum oxide layer.
[0054] Comparing Experiment 15 and Experiment 16, increasing the carbonization temperature from 1500℃ to 2100℃ increases the tantalum carbide layer thickness from 75μm to 80μm. Comparing Experiment 28 and Experiment 29, increasing the carbonization time from 60 minutes to 120 minutes increases the tantalum carbide layer thickness from 94μm to 100μm. Therefore, when the tantalum oxide layer thickness is the same, the tantalum carbide layer thickness is mainly affected by the carbonization temperature, but the degree of change is not significant. On the other hand, comparing Experiment 3 and Experiment 17, at the same carbonization temperature of 2100℃ and a carbonization time of 60 minutes, the tantalum carbide layer thickness increases from 8μm to 88μm, while the original tantalum oxide thicknesses are 4μm and 75μm respectively. This verifies that the thickness of the tantalum carbide layer is more easily affected by the thickness of the tantalum oxide layer.
[0055] Figure 7 and Figure 8 The images shown are SEM images of the samples from Comparative Example 1 and Comparative Example 2, respectively. (From Table 1 above...) Figure 7 and Figure 8 It can be seen that Comparative Example 1 hardly formed tantalum carbide, while the tantalum carbide layer in Comparative Example 2 had poor density.
[0056] In summary, this invention first generates tantalum oxide on the surface of a tantalum substrate through oxidation treatment, and then performs a carbonization reaction to transform the aforementioned tantalum oxide into tantalum carbide. Therefore, compared with the method of directly carbonizing tantalum at higher temperatures and for longer periods, it can generate TaC from carbon in situ at lower temperatures and for shorter periods of time. Thus, it not only has advantages such as simple process, environmental protection and non-toxicity, adjustable film thickness and high uniformity, high film density, and high reusability, but also solves the coating peeling problem caused by the existing method of forming TaC coating on the surface of graphite crucible.
[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for manufacturing a high-temperature resistant device, characterized in that, include: Provide a tantalum substrate as the device body; The tantalum substrate is oxidized in an oxygen-containing environment to form a tantalum oxide layer on its surface, wherein the oxidation temperature is between 100°C and 1100°C; and The oxidized tantalum substrate is embedded in a carbon-containing material and subjected to a carbonization reaction in an inert gas to transform the tantalum oxide layer into a tantalum carbide layer.
2. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The oxygen-containing environment includes oxygen, water vapor, inert gas, or a combination thereof.
3. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The oxidation process is performed at atmospheric pressure.
4. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The oxidation treatment time is between 15 minutes and 120 minutes.
5. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The tantalum carbide layer is in the form of the chemical formula Ta. x O y This indicates that y / x is between 0.5 and 2.
5.
6. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The inert gas includes argon, helium, or a combination thereof.
7. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The carbonization reaction is carried out at atmospheric pressure, the reaction temperature is between 1500℃ and 2100℃, and the reaction time is between 15 minutes and 2 hours.
8. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, The carbon-containing material includes carbon powder, graphite powder, activated carbon, polyvinyl alcohol, polyvinyl butyral, sucrose, glucose, or a combination thereof.
9. The method for manufacturing the high-temperature resistant device according to claim 1, characterized in that, Following the carbonization reaction, decarbonization is also included.
10. A high-temperature resistant device, characterized in that, include: Tantalum substrate; as well as The tantalum carbide layer is a layer formed on the surface of the tantalum substrate, wherein... The thickness of the tantalum carbide layer is between 2 μm and 100 μm.
11. The high-temperature resistant device according to claim 10, characterized in that, The specific surface area of the tantalum carbide layer is between 0.1 cm². 2 / g to 2cm 2 / g.
12. The high-temperature resistant device according to claim 10, characterized in that, The high-temperature resistant device includes crucibles, aerospace mechanism accessories, high-temperature reaction vessel accessories, or crystal growth accessories.