A method for detecting corrosion resistance of SiC-C base and its application

Abstract

The present invention provides a method for detecting the corrosion resistance of a SiC-C base and its application, which belongs to the field of chemical detection technology. The method for detecting the corrosion resistance of a SiC-C base provided by the present invention comprises the following steps: (1) depositing a dot-shaped transition metal film with a dot matrix distribution on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample; (2) corroding the pretreated SiC-C base sample obtained in step (1) in a mixed gas flow of HCl and H2 to obtain a corroded sample; (3) measuring the corrosion depth of the corroded sample obtained in step (2). The detection method provided by the present invention can effectively improve the detection efficiency. The results of the embodiment show that the corrosion rate of the detection method provided by the present invention can reach 0.146×10 ‑2 ~0.302×10 ‑2 μm / min.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical detection, and in particular to a method for detecting the corrosion resistance of a SiC-C base and an application thereof. Background Art

[0002] Si-based chips are integrated circuit chips manufactured from silicon materials. The silicon substrate is obtained through epitaxial growth on a wafer. Currently, metal-organic chemical vapor deposition (MOCVD) is the most commonly used method for epitaxial growth of silicon substrates. The SiC-coated graphite susceptor is a core component of MOCVD equipment. It is in direct contact with the substrate, supporting and heating the silicon substrate. It exhibits excellent chemical stability and high mechanical properties at high temperatures.

[0003] When epitaxial growth is carried out on a silicon substrate, the silicon substrate is placed in the supporting groove of the SiC-C base. Silicon is deposited on the surface of the silicon substrate and other areas of the base. After the epitaxial growth is completed, the silicon wafers after epitaxial growth in the supporting groove are removed; the deposited silicon on the surface of the base is then cleaned with HCl gas flow to ensure the recycling of the base. However, during the cleaning process using the HCl gas flow, the base surface where no silicon is deposited and the supporting groove after the wafer is removed are completely exposed to the large flow of HCl, resulting in direct contact between the surface SiC and HCl, which is very easy to corrode the exposed parts, resulting in failure phenomena such as coating shedding, perforation and black spots during use, affecting the quality of the silicon wafer. Therefore, it is necessary to judge the corrosion resistance of the SiC-C base and select a SiC-C base with better corrosion resistance to avoid affecting the quality of the silicon wafer.

[0004] Currently, the commonly used methods for judging the corrosion resistance of SiC-C bases are hydrothermal corrosion and Cl2 corrosion. The hydrothermal corrosion judgment method takes 7 to 60 days to have a significant corrosion effect. The corrosion cycle is long and the detection efficiency cannot meet the needs of practical applications. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for detecting the corrosion resistance of a SiC-C base and its application. The detection method provided by the present invention can accurately and effectively detect the corrosion resistance of a SiC-C base with high detection efficiency.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for detecting the corrosion resistance of a SiC-C base, comprising the following steps:

[0008] (1) depositing a dot-shaped transition metal film distributed in a lattice on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample;

[0009] (2) corroding the pretreated SiC-C base sample obtained in step (1) in a mixed gas flow of HCl and H2 to obtain a corroded sample;

[0010] (3) Measuring the corrosion depth of the corrosion sample obtained in step (2).

[0011] Preferably, the material of the dot-shaped transition metal film in step (1) is Pt, Cr or Ni.

[0012] Preferably, in step (1), the diameter of the dot-shaped transition metal film is 1 to 2 mm, and the thickness of the dot-shaped transition metal film is 30 to 60 nm.

[0013] Preferably, the deposition time in step (1) is 20 to 40 seconds, and the target-substrate distance of the deposition is 11 to 12 cm.

[0014] Preferably, in step (2), the flow rates of HCl and H2 are independently 5 to 20 L / min, and the flow ratio of HCl to H2 is 1:(0.5 to 1.5).

[0015] Preferably, the corrosion temperature in step (2) is 1000-1400° C., and the corrosion time is 40-80 h.

[0016] Preferably, the process of heating to the corrosion temperature is programmed temperature heating, comprising:

[0017] The first stage is a first heating from room temperature to 500°C, wherein the heating rate of the first heating is 1-3°C / min;

[0018] In the second stage, the temperature is raised from 500° C. to 1000-1400° C., and the second heating rate is 5-8° C. / min.

[0019] Preferably, corrosion pretreatment is performed after the programmed temperature rise is completed; the time of the corrosion pretreatment is 100 to 200 minutes, the atmosphere of the corrosion pretreatment is an inert atmosphere or nitrogen, and the pressure of the corrosion pretreatment is 60,000 to 90,000 Pa.

[0020] Preferably, cooling is performed after the corrosion, and the cooling rate is 3-5°C / min.

[0021] The present invention also provides an application of the detection method described in the above technical solution, wherein the corrosion depth is used to characterize the corrosion resistance of the SiC-C base sample; or the corrosion rate is calculated using the corrosion time and the obtained corrosion depth of the detection method, and the corrosion resistance of the SiC-C base sample is characterized by the corrosion rate.

[0022] The present invention provides a method for detecting the corrosion resistance of a SiC-C base, comprising the following steps: (1) depositing a dot-shaped transition metal film with a dot matrix distribution on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample; (2) corroding the pretreated SiC-C base sample obtained in step (1) in a mixed gas flow of HCl and H2 to obtain a corroded sample; and (3) measuring the corrosion depth of the corroded sample obtained in step (2). The detection method provided by the present invention utilizes a mixed flow of HCl and H2 to corrode the SiC-C base, simulating the actual use environment of the SiC-C base, so that the morphology after corrosion is consistent with the morphology of the SiC-C base after failure due to use at the application end, which is convenient for detection; a transition metal is deposited on the surface of the SiC-C base to catalyze the corrosion of the SiC-C base by HCl, greatly improving the corrosion efficiency and effectively improving the detection rate; at the same time, a mixed flow of HCl and H2 is used to corrode the SiC-C base, and H2 is used as a carrier gas for HCl, which can uniformly transport HCl to the corrosion area, ensuring uniform corrosion of the SiC-C base, effectively increasing the corrosion rate, and further improving the detection efficiency; at the same time, H2 can combine with the intermediate byproducts of the HCl corrosion reaction of the SiC-C base, promoting the forward reaction and further improving the corrosion efficiency. The results of the embodiment show that the corrosion rate of the detection method provided by the present invention can reach 0.146×10 -2 ~0.302×10 -2 μm / min, and the corrosion depth or corrosion rate is used to accurately reflect the corrosion resistance of the SiC-C base in the service environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A detection device for the detection method of Example 1;

[0024] Figure 2 This is a macroscopic photograph of a SiC-C base sample after being tested using the testing method of Example 1;

[0025] Figure 3 The corrosion depth of the SiC-C base sample block of Example 1 that has not been corroded is measured using the white light detection method, and the corrosion depth of the SiC-C base sample block that has been corroded using the detection method of Example 1 is shown;

[0026] Figure 4 The corrosion depth of the SiC-C base sample block of Example 2 that has not been corroded is measured using the white light detection method, and the corrosion depth of the SiC-C base sample block that has been corroded using the detection method of Example 2 is shown;

[0027] Figure 5 The corrosion depth of the SiC-C base sample block of Example 3 that has not been corroded using the white light detection method and the corrosion depth of the SiC-C base sample block after being corroded using the detection method of Example 3 are shown. DETAILED DESCRIPTION

[0028] The present invention provides a method for detecting the corrosion resistance of a SiC-C base, comprising the following steps:

[0029] (1) depositing a dot-shaped transition metal film distributed in a lattice on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample;

[0030] (2) corroding the pretreated SiC-C base sample obtained in step (1) in a mixed gas flow of HCl and H2 to obtain a corroded sample;

[0031] (3) Measuring the corrosion depth of the corrosion sample obtained in step (2).

[0032] The present invention deposits a dot-shaped transition metal film with lattice distribution on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample.

[0033] As an embodiment of the present invention, the source of the SiC-C base sample can be a sample cut from an unused base; the size of the SiC-C base sample can be 20mm×20mm~40mm×40mm, or 25mm×25mm~30mm×30mm; the thickness of the SiC-C base sample can be 2~5mm, or 3~4mm; the thickness of the SiC coating in the SiC-C base sample can be 100~150μm, or 120~140μm, or 130~135μm.

[0034] As an embodiment of the present invention, the deposition method may be a magnetron sputtering method; the deposition device may be a high vacuum coating apparatus; the deposition power may be 50 to 100 W, or 60 to 80 W; the deposition time may be 20 to 40 s, or 25 to 30 s; the target-substrate distance of the deposition may be 11 to 12 cm, or 11 cm. In an embodiment of the present invention, the deposition device may specifically be a Leica-ace600. In the present invention, by limiting the deposition process parameters, uniform deposition of the transition metal film is achieved, over-catalysis or incomplete catalysis of the corrosion site is avoided, and the detection efficiency is further improved.

[0035] As an embodiment of the present invention, the material of the dot-shaped transition metal film can be Pt, Cr or Ni, or can also be Pt. In the present invention, by limiting the type of transition metal, the catalytic effect of the transition metal is enhanced, the corrosion efficiency is further improved, the corrosion cycle is shortened, and the detection efficiency is improved.

[0036] As one embodiment of the present invention, the diameter of the dot-shaped transition metal film can be 1-2 mm, or 1 mm; the thickness of the dot-shaped transition metal film can be 30-60 nm, or 40-55 nm, or 45-50 nm; and the spacing between the dot-shaped transition metal films can be 5-10 mm, or 6-9 mm, or 7-8 mm. In the present invention, by limiting the size of the transition metal film, the catalytic effect of the transition metal is fully utilized, further improving the catalytic efficiency.

[0037] As one embodiment of the present invention, the method for depositing a dot-shaped transition metal film with a lattice distribution can include laminating a ceramic cover plate with small holes to the surface of the SiC-C substrate sample, and then depositing a transition metal on the surface of the ceramic cover plate to form a lattice transition metal film. The apertures on the ceramic cover plate can have a diameter of 1-2 mm, or even 1 mm. In the present invention, the ceramic cover plate with uniform small holes defines the position of the transition metal film, ensuring a uniform distribution of the transition metal on the SiC-C substrate surface, fully utilizing the transition metal's catalytic effect on HCl corrosion and further improving catalytic efficiency.

[0038] After obtaining the pretreated SiC-C base sample, the present invention corrodes the pretreated SiC-C base sample in a mixed gas flow of HCl and H2 to obtain a corroded sample.

[0039] As one embodiment of the present invention, the flow rates of the HCl and H2 can independently be 5 to 20 L / min, 8 to 15 L / min, or 10 to 12 L / min; the flow ratio of the HCl to H2 can be 1:(0.5 to 1.5) or 1:1. In the present invention, by limiting the flow rates and flow ratio of HCl and H2, the corrosive effect of HCl is fully utilized, further increasing the corrosion rate. At the same time, using H2 as the carrier gas for HCl allows the HCl to be evenly delivered to the corrosion area, ensuring uniform corrosion of the SiC-C base and further improving detection efficiency.

[0040] As an embodiment of the present invention, the temperature of the corrosion process can be 1000-1400°C, or 1100-1300°C, or 1200-1250°C; the time of the corrosion process can be 40-80h, or 50-70h, or 60-65h. In the present invention, by limiting the process parameters of the corrosion process, the corrosion process is promoted.

[0041] As an embodiment of the present invention, the process of heating to the corrosion temperature may be a programmed temperature heating process, comprising:

[0042] In the first stage, the temperature is first increased from room temperature to 500°C, and the heating rate of the first heating can be 1-3°C / min, or 2-2.5°C / min;

[0043] The second stage is a second heating from 500°C to 1000-1400°C. The second heating rate can be 5-8°C / min, or even 6-7°C / min. In the present invention, by limiting the heating program of the corrosion temperature, it is avoided that rapid heating causes large thermal stress between the SiC coating and the graphite substrate due to the different degrees of thermal expansion, which can cause cracks or even detachment of the coating, thereby affecting the detection efficiency.

[0044] As one embodiment of the present invention, the temperature programming can be performed under a protective atmosphere; the protective atmosphere can be an inert atmosphere or nitrogen; the flow rate of the gas in the protective atmosphere can be 20 to 80 L / min, or 40 to 60 L / min. In the present invention, by introducing the protective atmosphere, air is removed from the reaction system, thereby preventing oxidation side reactions from occurring during the temperature increase process and affecting detection efficiency.

[0045] As an embodiment of the present invention, the pressure of the programmed temperature increase can be 60,000 to 90,000 Pa, or 70,000 to 80,000 Pa. In the present invention, by applying pressure during the temperature increase process, which serves as the basis for the subsequent corrosion reaction, the stability of the reaction system can still be ensured after the corrosive gas is introduced, thereby further improving the detection efficiency.

[0046] As an embodiment of the present invention, a vacuum treatment may be performed before the programmed temperature increase; the pressure of the vacuum treatment may be 100 to 300 Pa, 150 to 250 Pa, or 180 to 200 Pa. In the present invention, by limiting the process parameters of the vacuum treatment, air in the reaction system is effectively removed, the influence of air on the corrosion reaction is avoided, and the detection efficiency is further improved.

[0047] As an embodiment of the present invention, corrosion pretreatment can be performed after the programmed temperature is completed; the atmosphere and pressure of the corrosion pretreatment can be the same as the atmosphere and pressure of the programmed temperature, which will not be repeated here; the time of the corrosion pretreatment can be 100 to 200 minutes, or 120 to 180 minutes, or 150 to 160 minutes. In the present invention, thermal stress exists inside the silicon carbide coating during the programmed temperature rise process. By limiting the process parameters of the corrosion pretreatment process, the coating structure is stabilized, and the temperature of the entire reaction system is made more uniform, thereby increasing the corrosion rate and further improving the detection efficiency.

[0048] The present invention has no special limitation on the etching device, as long as it can achieve the mixed gas flow of HCl and H2 entering at the upper end and exiting at the lower end.

[0049] As an embodiment of the present invention, cooling can be performed after the etching is completed; the atmosphere and pressure of the cooling can be the same as the atmosphere and pressure of the programmed temperature increase, which will not be described in detail here; the cooling rate can be 3-5°C / min, 3.5-4.5°C / min, or even 4°C / min. In the present invention, by limiting the process parameters of the cooling process, the coating is prevented from shedding due to a large temperature difference between the inside and outside, thereby affecting the test results.

[0050] After the corrosion sample is obtained, the corrosion depth of the corrosion sample is measured.

[0051] As an embodiment of the present invention, the measurement may be performed by detecting the corrosion depths of 2 to 6 randomly selected corrosion areas of the point-shaped transition metal film and then taking an average value to obtain the corrosion depth of the corrosion sample.

[0052] The present invention deposits transition metals on the surface of a SiC-C base to catalyze the corrosion of the SiC-C base by HCl, thereby greatly improving the corrosion efficiency. Simultaneously, a mixed gas flow of HCl and H2 is used to corrode the SiC-C base. H2 serves as a carrier gas for HCl, enabling the HCl to be uniformly transported to the corrosion area, thereby ensuring uniform corrosion of the SiC-C base and further improving the detection efficiency. Simultaneously, H2 can combine with intermediate byproducts of the HCl corrosion reaction of the SiC-C base, thereby promoting the forward reaction and further improving the corrosion efficiency.

[0053] The present invention also provides an application of the detection method described in the above technical solution, wherein the corrosion depth is used to characterize the corrosion resistance of the SiC-C base sample; or the corrosion rate is calculated using the corrosion time and the obtained corrosion depth of the detection method, and the corrosion resistance of the SiC-C base sample is characterized by the corrosion rate.

[0054] To further illustrate the present invention, the method for detecting the corrosion resistance of the SiC-C base provided by the present invention and its application are described in detail below in conjunction with the examples, but they should not be understood as limiting the scope of protection of the present invention.

[0055] Example 1

[0056] A method for detecting the corrosion resistance of a SiC-C base comprises the following steps:

[0057] (1) A ceramic cover plate with 1 mm uniform pores was attached to the surface of a 20 × 20 mm, 3 mm thick SiC-C substrate sample (the grain size of the SiC coating was 70% 1-5 μm and 30% 5-10 μm). A dot-shaped transition metal film with a dotted distribution was deposited by magnetron sputtering at a target-substrate distance of 3 cm and 80 W for 40 s to obtain a pretreated SiC-C substrate sample. The dot-shaped transition metal film had a diameter of 1 mm and a thickness of 60 nm.

[0058] (2) Place the pre-treated SiC-C base sample obtained in step (1) into the Figure 1 In the etching furnace shown, a vacuum treatment is performed to ensure air inlet at the upper end and air outlet at the lower end, and the pressure is 200 Pa. Then, argon gas is introduced at 60 L / min and the pressure is maintained at 80,000 Pa for programmed temperature increase. The temperature is first increased to 500° C. at a heating rate of 2° C. / min, and then increased to 1000° C. at a second heating rate of 5° C. / min. The argon atmosphere and pressure are maintained for 100 min of corrosion pretreatment. A mixed gas flow of HCl and H2 is introduced at a flow rate of 10 L / min independently and the corrosion is carried out at 1000° C. and 80,000 Pa for 75 h. After the corrosion is completed, the sample is cooled at a cooling rate of 5° C. / min under the conditions of argon gas at 60 L / min and the pressure is maintained at 80,000 Pa to obtain a corrosion sample.

[0059] (3) Using a white light detection method, the corrosion depths of four randomly selected point-shaped corrosion areas of the transition metal film are detected, and the average value is taken to obtain the corrosion depth of the corrosion sample obtained in step (2).

[0060] The SiC-C base sample after being corroded by the detection method of Example 1 was photographed, and the macroscopic photograph obtained was as follows: Figure 2 As shown. Figure 2 It can be seen that the surface of the SiC-C base sample with dotted transition metal film is obviously corroded, indicating that transition metal can effectively increase the corrosion rate of SiC coating on the surface of SiC-C base sample.

[0061] Example 2

[0062] The only difference between Example 2 and Example 1 is that the grain size of the SiC coating in the SiC-C base sample is 50% 5-10 μm and 50% 20-30 μm, and the rest is the same as Example 1.

[0063] Example 3

[0064] The only difference between Example 3 and Example 1 is that the grain size of the SiC coating in the SiC-C base sample is 80% 10-20 μm and 20% 50-60 μm, and the rest is the same as Example 1.

[0065] The test results of the test method for the corrosion resistance of the SiC-C base in Examples 1 to 3 are as follows: Figures 3-5 and as shown in Table 1; Figures 3-5 The left side of the figure represents the corrosion depth of the SiC-C base sample block that has not been corroded by the detection method of Examples 1 to 3, Figures 3-5 The figures on the right side of the figure represent the corrosion depth of the SiC-C base sample after being corroded by the detection methods of Examples 1 to 3.

[0066] from Figures 3-5 It can be seen from the test method for the corrosion resistance of the SiC-C base in Examples 1 to 3 that the corrosion depth of the corroded sample after testing, the corrosion depth of any four corroded areas, and the average corrosion depth results are shown in Table 1.

[0067] Table 1 Test results of the test method for the corrosion resistance of SiC-C base in Examples 1 to 3

[0068] Example 1 Example 2 Example 3 Corrosion depth (μm) 8.3172 13.5960 6.5698 Corrosion rate (μm / min) <![CDATA[0.185×10 -2 ]]> <![CDATA[0.302×10 -2 ]]> <![CDATA[0.146×10 -2 ]]>

[0069] As can be seen from Table 1, the detection method provided by the present invention can make the corrosion rate of the SiC coating in the SiC-C base reach 0.146×10 -2 ~0.302×10 -2 μm / min, the corrosion rate is high, which can effectively improve the detection efficiency; at the same time, through comparison, it can be seen that the corrosion resistance of the SiC-C base sample of Example 3 is the best, the corrosion resistance of Example 1 is second, and the corrosion resistance of Example 2 is the worst.

[0070] The standard for judging the corrosion resistance of SiC-C pedestals is: when the thickness of the transition metal film layer is between 30 and 60 nm, the corrosion rate of a qualified pedestal does not exceed 0.4 μm / min after 40 to 50 hours of corrosion. Therefore, the detection method provided by the present invention can determine whether the pedestal's corrosion resistance meets the requirements and is suitable for normal use.

[0071] Comparative Example 1

[0072] A high-temperature hydrothermal corrosion test was performed on the SiC-C base sample in Example 2 using a static autoclave. The water medium used in the test was deionized water. The test temperature was 360±6°C and the pressure was 18.2±1.4 MPa. After 60 days of corrosion, the corrosion depth of the corroded SiC-C base sample was detected.

[0073] The test shows that the corrosion depth of the sample after hydrothermal corrosion in Comparative Example 1 is 10 μm, and the corrosion rate is 0.012×10 -2 μm / min.

[0074] By comparing Examples 1 to 3 with Comparative Example 1, it can be clearly seen that the detection method provided by the present invention takes a shorter time to achieve similar technical effects and has a higher corrosion rate. Therefore, it can be seen that the detection method provided by the present invention effectively improves the detection rate.

[0075] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for detecting the corrosion resistance of a SiC-C base, comprising the following steps: (1) depositing a dot-shaped transition metal film distributed in a lattice on the surface of a SiC-C base sample to obtain a pretreated SiC-C base sample; (2) corroding the pretreated SiC-C base sample obtained in step (1) in a mixed gas flow of HCl and H2 to obtain a corroded sample; (3) measuring the corrosion depth of the corroded area of ​​the point-shaped transition metal film of the corrosion sample obtained in step (2); The material of the dot-shaped transition metal film in step (1) is Pt, Cr or Ni; In step (2), the flow rates of HCl and H2 are independently 5-20 L / min, and the flow ratio of HCl to H2 is 1:(0.5-1.5); The corrosion temperature in step (2) is 1000-1400° C., and the corrosion time is 40-80 hours.

2. The detection method according to claim 1, wherein In the step (1), the diameter of the dot-shaped transition metal film is 1-2 mm, and the thickness of the dot-shaped transition metal film is 30-60 nm.

3. The detection method according to claim 2, characterized in that The deposition time in step (1) is 20-40 seconds, and the target-substrate distance of the deposition is 11-12 cm.

4. The detection method according to claim 1, wherein The process of heating to the corrosion temperature is programmed temperature heating, which includes: The first stage is a first heating from room temperature to 500°C, and the heating rate of the first heating is 1-3°C / min; In the second stage, the temperature is raised from 500° C. to 1000-1400° C., and the heating rate of the second heating is 5-8° C. / min.

5. The detection method according to claim 4, characterized in that After the programmed temperature rise is completed, corrosion pretreatment is performed; the time of the corrosion pretreatment is 100-200 minutes, the atmosphere of the corrosion pretreatment is an inert atmosphere or nitrogen, and the pressure of the corrosion pretreatment is 60000-90000Pa.

6. The detection method according to claim 1, characterized in that The corrosion is followed by cooling, with a cooling rate of 3-5°C / min.

7. An application of the detection method according to any one of claims 1 to 6, characterized in that: The corrosion depth is used to characterize the corrosion resistance of the SiC-C base sample; or the corrosion rate is calculated using the corrosion time of the detection method and the obtained corrosion depth, and the corrosion resistance of the SiC-C base sample is characterized by the corrosion rate.

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