CN118326365B - Silicon carbide coating and preparation method thereof - Google Patents
Silicon carbide coating and preparation method thereof Download PDFInfo
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- CN118326365B CN118326365B CN202410652608.6A CN202410652608A CN118326365B CN 118326365 B CN118326365 B CN 118326365B CN 202410652608 A CN202410652608 A CN 202410652608A CN 118326365 B CN118326365 B CN 118326365B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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Abstract
The invention relates to a silicon carbide coating and a preparation method thereof. The preparation method comprises the following steps of carrying out chemical vapor deposition treatment on a substrate to form a silicon carbide coating, wherein the chemical vapor deposition treatment comprises a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage which are sequentially carried out, a gas source adopted by the chemical vapor deposition treatment comprises diluent gas, hydrogen and organic silicon source gas, the deposition temperature of the low-temperature nucleation stage is 600-800 ℃, the deposition temperature of the medium-temperature growth stage is 1000-1300 ℃, and the deposition temperature of the high-temperature growth stage is 1350-1500 ℃. The stepped heating mode is presented among the stages, and the chemical vapor deposition mode under the stepped heating condition reduces the phenomenon of local overheating or condensation of silicon carbide crystals, effectively inhibits the generation of internal stress of the coating, reduces the formation of microcracks and cavities, improves the compactness of the coating, and further improves the mechanical property of the silicon carbide coating.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a silicon carbide coating and a preparation method thereof.
Background
Silicon carbide (SiC) materials have wide applications in semiconductor devices such as high temperature, high frequency, high voltage, and high power due to their excellent physicochemical properties and thermodynamic stability.
Chemical Vapor Deposition (CVD) is a commonly used surface modification technique for depositing high quality films or coatings, such as silicon carbide coatings, on a variety of substrates. However, the silicon carbide coating prepared by adopting the CVD method still has the problem that stress concentration and microcrack formation are easy to occur, so that the mechanical property of the coating is poor.
Disclosure of Invention
Based on the above, it is necessary to provide a silicon carbide coating with good mechanical properties and a preparation method thereof.
In a first aspect of the present invention, a method for preparing a silicon carbide coating is provided, comprising the steps of:
performing chemical vapor deposition treatment on the substrate to form a silicon carbide coating;
The chemical vapor deposition treatment comprises a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage which are sequentially carried out, wherein an air source adopted by the chemical vapor deposition treatment comprises dilution gas, hydrogen and organic silicon source gas, the deposition temperature of the low-temperature nucleation stage is 600-800 ℃, the deposition temperature of the medium-temperature growth stage is 1000-1300 ℃, and the deposition temperature of the high-temperature growth stage is 1350-1500 ℃.
In the method for preparing the silicon carbide coating by the chemical vapor deposition method, a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage are sequentially carried out in the chemical vapor deposition process, and the temperature of each stage is controlled at a specific temperature. The low-temperature nucleation stage under the lower temperature condition is favorable for providing a good initial growth layer for the silicon carbide, the initial growth layer can form an intermediate transition layer between the substrate and the silicon carbide coating, further is favorable for the nucleation and growth of the silicon carbide, and meanwhile, the smooth transition from the substrate to the thermal expansion coefficient of the silicon carbide coating can be realized, and then the deposition is carried out in the medium-temperature growth stage and the high-temperature growth stage, so that the overall performance of the silicon carbide can be further improved. The stepped heating mode is presented among the stages, and the chemical vapor deposition mode under the stepped heating condition reduces the phenomenon that silicon carbide crystals are locally overheated or condensed, effectively inhibits the generation of internal stress of the coating, reduces the formation of microcracks and cavities, improves the compactness of the coating, further improves the hardness and fracture toughness of the silicon carbide coating, and improves the mechanical property of the silicon carbide coating. Furthermore, the preparation method can improve the interfacial binding force between the coating and the substrate and control the directionality of silicon carbide grains.
In some embodiments, the deposition temperature of the low temperature nucleation stage is 650 ℃ to 750 ℃, and/or,
The deposition temperature of the medium-temperature growth stage is 1150-1250 ℃ and/or,
The deposition temperature of the high-temperature growth stage is 1350-1450 ℃.
In some embodiments, the method of preparation meets at least one of the following conditions:
(1) The temperature is raised to the deposition temperature of the low-temperature nucleation stage at a rate of 0.5-15 ℃ per minute;
(2) Heating to 50-100 ℃ at a rate of 2-10 ℃ per minute and preserving heat for 4-6 min from the deposition temperature of the low-temperature nucleation stage to the deposition temperature of the medium-temperature growth stage;
(3) And heating to 50-100 ℃ at a rate of 2-10 ℃ per minute and keeping the temperature for 4-6 min from the deposition temperature of the medium-temperature growth stage to the deposition temperature of the high-temperature growth stage.
In some embodiments, the hydrogen gas and the organosilicon source gas are not introduced during the heating.
In some embodiments, the method of preparation meets at least one of the following conditions:
(1) The low temperature nucleation stage comprises the following steps:
Heating to the deposition temperature of the low-temperature nucleation stage, firstly preserving heat for 1-2h, and then introducing the air source to perform first chemical vapor deposition, wherein the time of the first chemical vapor deposition is 20-30 min;
(2) The medium temperature growth stage comprises the following steps:
When the temperature reaches the deposition temperature of the medium-temperature growth stage, firstly preserving heat for 1-2 h, then introducing the hydrogen and the silicon source gas for performing second chemical vapor deposition, wherein the time of the second chemical vapor deposition is 20-80 min;
(3) The high temperature growth stage comprises the following steps:
And when the temperature reaches the deposition temperature of the high-temperature growth stage, firstly preserving heat for 1-2h, and then introducing the air source to perform third chemical vapor deposition, wherein the time of the third chemical vapor deposition is 40-100 min.
In some embodiments, the method further comprises, prior to performing the chemical vapor deposition process on the substrate, a step of performing a soak pretreatment on the substrate under vacuum conditions of 400 ℃ to 600 ℃.
In some embodiments, the heat preservation time of the heat preservation pretreatment is 1h to 2h.
In some embodiments, after the high temperature growth phase is completed, the method further comprises the steps of:
Cooling the deposition temperature in the high-temperature growth stage to 700-800 ℃ at a rate of 1-3 ℃ per minute, preserving heat for 2-4 hours, and then cooling to room temperature at a rate of 0.3-1 ℃ per minute.
In some embodiments, the organosilicon source is selected from methyltrichlorosilane, dimethyldichlorosilane, or dimethylsilane, and/or
The diluent gas is selected from argon or helium, and/or
The substrate is selected from graphite, carbon, silicon carbide or ceramic.
In some embodiments, the ratio of the flow rates of the dilution gas, the hydrogen gas, and the organosilicon source gas is (5-20): 1.
In a second aspect of the invention, there is provided a silicon carbide coating prepared according to the method described above.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In one embodiment of the application, a method for preparing a silicon carbide coating is provided, comprising the following steps:
performing chemical vapor deposition treatment on the substrate to form a silicon carbide coating;
The chemical vapor deposition treatment comprises a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage which are sequentially carried out, wherein an air source adopted by the chemical vapor deposition treatment comprises diluent gas, hydrogen and organic silicon source gas, the deposition temperature of the low-temperature nucleation stage is 600-800 ℃, the deposition temperature of the medium-temperature growth stage is 1000-1300 ℃, and the deposition temperature of the high-temperature growth stage is 1350-1500 ℃.
In the method for preparing the silicon carbide coating by the chemical vapor deposition method, a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage are sequentially carried out in the chemical vapor deposition process, and the temperature of each stage is controlled at a specific temperature. The low-temperature nucleation stage under the lower temperature condition is favorable for providing a good initial growth layer for the silicon carbide, the initial growth layer can form an intermediate transition layer between the substrate and the silicon carbide coating, further is favorable for the nucleation and growth of the silicon carbide, and meanwhile, the smooth transition from the substrate to the thermal expansion coefficient of the silicon carbide coating can be realized, and then the deposition is carried out in the medium-temperature growth stage and the high-temperature growth stage, so that the overall performance of the silicon carbide can be further improved. The stepped heating mode is presented among the stages, and the chemical vapor deposition mode under the stepped heating condition reduces the phenomenon that silicon carbide crystals are locally overheated or condensed, effectively inhibits the generation of internal stress of the coating, reduces the formation of microcracks and cavities, improves the compactness of the coating, further improves the hardness and fracture toughness of the silicon carbide coating, and improves the mechanical property of the silicon carbide coating. Furthermore, the method can also improve the interfacial binding force between the coating and the substrate, and can also control the orientation of silicon carbide grains.
The deposition temperature of the low temperature nucleation stage is 600 ℃ to 800 ℃, which is understood as 600 ℃, 620 ℃, 650 ℃, 670 ℃, 700 ℃, 720 ℃, 750 ℃, 770 ℃ or 800 ℃ in the low temperature nucleation stage. Further, the deposition temperature in the low-temperature nucleation stage may be a range of values constituted by any two of the above-mentioned point values as the end values. Preferably, the deposition temperature in the low temperature nucleation stage is 650 ℃ to 750 ℃. In a lower temperature range, the reaction rate is moderate, and the nucleation has smaller thermodynamic barrier, thereby being beneficial to forming uniform, stable and dense SiC crystal nuclei.
The above-mentioned "deposition temperature in the intermediate temperature growth stage is 1000 ℃ to 1300 ℃ may be understood that the deposition temperature in the intermediate temperature growth stage may be 1000 ℃, 1020 ℃, 1050 ℃, 1070 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 1170 ℃, 1200 ℃, 1250 ℃ or 1300 ℃. Further, the deposition temperature in the medium-temperature growth stage may be a range of values constituted by any two of the above-mentioned point values as the end values. Preferably, the deposition temperature in the medium temperature growth stage is 1150-1250 ℃. And in the medium-temperature growth stage under the specific temperature condition, the uniform growth of crystal nucleus is ensured, and the defect generation is reduced.
The deposition temperature in the high temperature growth stage is 1350 ℃ to 1450 ℃, which is understood to be 1350 ℃, 1370 ℃, 1400 ℃, 1420 ℃ or 1450 ℃. Further, the deposition temperature in the high temperature nucleation stage may be a range of values constituted by any two of the above-mentioned point values as the end values. Preferably, the deposition temperature in the high temperature nucleation stage is 1150 ℃ to 1250 ℃. In the high-temperature growth stage with a specific temperature, the reaction rate is accelerated, which is favorable for the rapid thickening of the SiC crystal.
In some embodiments, the preparation method comprises heating to a deposition temperature in the low temperature nucleation stage at a rate of 0.5-15 ℃.
In some embodiments, the preparation method comprises the step of heating the deposition temperature of the low-temperature nucleation stage to the deposition temperature of the medium-temperature growth stage at a rate of 2-10 ℃ per minute at 50-100 ℃ and keeping the temperature for 4-6 minutes.
By way of example, the temperature from the deposition temperature of the low temperature nucleation stage of 750 ℃ to the deposition temperature of the medium temperature growth stage of 1150 ℃ may be raised by raising the temperature from 750 ℃ to 850 ℃ at a rate of 10 ℃ per minute, maintaining the temperature for 5min, then continuing to raise the temperature to 950 ℃ at a rate of 10 ℃ per minute, maintaining the temperature for 5min, then continuing to raise the temperature to 1050 ℃ at 10 ℃ per minute, maintaining the temperature for 5min, and then raising the temperature to 1150 ℃ again at a rate of 10 ℃ per minute, reaching the deposition temperature of the medium temperature growth stage.
In some embodiments, the heating step includes heating at a rate of 2-10 ℃ per minute to 50-100 ℃ and holding for 4-6 min from the deposition temperature of the medium growth stage to the deposition temperature of the high growth stage.
By way of example, the temperature may be raised from a deposition temperature of a medium growth stage of 1150 ℃ to a deposition temperature of a high growth stage of 1350 ℃ by raising the temperature from 1150 ℃ to 1200 ℃ at a rate of 10 ℃ per minute, holding for 5 minutes, then continuing to raise the temperature to 1250 ℃ at a rate of 10 ℃ per minute, holding for 5 minutes, then continuing to raise the temperature to 1300 ℃ at 10 ℃ per minute, holding for 5 minutes, then raising the temperature to 1350 ℃ again at a rate of 10 ℃ per minute, to reach the deposition temperature of the high growth stage.
In some embodiments, no hydrogen and no organosilicon source gas are introduced during the above-described temperature increase.
In some embodiments, the gas source is not vented during the heating to the deposition temperature of the low temperature nucleation stage. That is, the dilution gas, hydrogen gas, and organosilicon source gas are not introduced during the process of raising the temperature to the deposition temperature in the low temperature nucleation stage.
In some embodiments, hydrogen and the organosilicon source gas are not introduced during the temperature ramp from the deposition temperature of the low temperature nucleation stage to the deposition temperature of the medium temperature growth stage. It will be appreciated that no hydrogen and no organosilicon source gases are introduced during the temperature ramp from the deposition temperature of the low temperature nucleation stage to the deposition temperature of the medium temperature growth stage, while the diluent gas is continuously introduced. The stable air pressure value in the deposition chamber can be kept by continuously introducing dilution gas, and the operation safety of equipment is improved.
In some embodiments, hydrogen and the organosilicon source gas are not introduced during the heating from the deposition temperature of the intermediate growth stage to the deposition temperature of the high growth stage. It will be appreciated that no hydrogen and no organosilicon source gases are introduced during the heating from the deposition temperature of the intermediate growth stage to the deposition temperature of the high growth stage, while the diluent gas is continuously introduced. The stable air pressure value in the deposition chamber can be kept by continuously introducing dilution gas, and the operation safety of equipment is improved.
In some embodiments, the low temperature nucleation stage comprises the steps of:
And after the temperature is raised to a low-temperature nucleation stage, firstly preserving heat for 1-2 hours, and then introducing the air source to perform first chemical vapor deposition, wherein the time of the first chemical vapor deposition is 20-30 minutes. It can be understood that in the process of preserving heat for 1-2h at the low-temperature nucleation stage, the gas sources of the diluent gas, the hydrogen and the organosilicon source gas are introduced differently, the chemical vapor deposition treatment is not performed, and after the heat preservation process is completed, the gas sources are introduced again to perform the first chemical vapor deposition.
In some embodiments, the medium temperature growth stage comprises the steps of:
And when the temperature reaches the deposition temperature of the medium-temperature growth stage, firstly preserving heat for 1-2 h, then introducing hydrogen and silicon source gas for performing second chemical vapor deposition, wherein the time of the second chemical vapor deposition is 20-80 min. It can be understood that in the process of preserving heat for 1-2 h at the medium temperature growth stage, hydrogen and organic silicon source gas are not introduced, chemical vapor deposition treatment is not performed, only diluent gas is introduced in the process of preserving heat, the air pressure in the chemical vapor deposition chamber is kept stable, and after the heat preservation process is completed, hydrogen and organic silicon source gas are introduced for performing second chemical vapor deposition.
Further, the second chemical vapor deposition time may be 40min, 50min, 60min, 70min, or 80min. Further, the time of the second chemical vapor deposition may be a range of values formed by any two of the above-mentioned point values as the end values.
In some embodiments, the high temperature growth phase comprises the steps of:
And when the temperature reaches the deposition temperature of the high-temperature growth stage, preserving heat for 1-2 h, and then introducing hydrogen and silicon source gas to perform third chemical vapor deposition, wherein the time of the third chemical vapor deposition is 40-100 min. It can be understood that in the process of preserving heat for 1-2 h at the high-temperature growth stage, hydrogen and organic silicon source gas are not introduced, chemical vapor deposition treatment is not performed, only diluent gas is introduced in the process of preserving heat, the air pressure in the chemical vapor deposition chamber is kept stable, and after the heat preservation process is completed, hydrogen and organic silicon source gas are introduced for performing third chemical vapor deposition.
Further, the time of the third chemical vapor deposition may be 40min, 50min, 60min, 70min, or 80min. Further, the time of the third chemical vapor deposition may be a range of values formed by any two of the above-mentioned point values as the end values.
In some embodiments, the preparation method further comprises a step of performing thermal insulation pretreatment on the substrate under a vacuum condition of 400 ℃ to 600 ℃ before performing chemical vapor deposition treatment on the substrate.
The above-mentioned "400 ℃ to 600 ℃ is understood to mean that the substrate may be subjected to the thermal-insulation pretreatment under the conditions of 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃. Further, the pretreatment temperature of the substrate may be a range of values formed by any two of the above-mentioned point values as the end values. Preferably, the heat preservation pretreatment temperature of the substrate is 450-550 ℃. The substrate is subjected to heat preservation pretreatment at a specific temperature, so that impurities and moisture on the surface of the substrate can be removed, the surface of the substrate has stronger adsorption capacity on SiC crystal nuclei, and the binding force between the silicon carbide coating and the substrate is improved.
In some embodiments, the vacuum level when the substrate is subjected to the soak pretreatment is less than 10Pa.
In some embodiments, the incubation time of the incubation pretreatment is 1h to 2h.
In some embodiments, after the high temperature growth phase is completed, the method further comprises the steps of:
Cooling the deposition temperature in the high-temperature growth stage to 700-800 ℃ at a rate of 1-3 ℃ per minute, preserving heat for 2-4 hours, and then cooling to room temperature at a rate of 0.3-1 ℃ per minute. By adopting the specific gradient cooling, the thermal stress concentration of the silicon carbide coating can be further reduced, and the hardness and fracture toughness of the silicon carbide coating can be further improved.
In some embodiments, hydrogen and the organosilicon source gas are not introduced during the cool down after the high temperature growth phase is completed. It can be understood that the temperature is reduced from the deposition temperature in the high temperature growth stage to 700-800 ℃, the temperature is kept for 2-4 hours, then hydrogen and organosilicon source gas are not introduced in the whole process of reducing the temperature to room temperature, and dilution gas is continuously introduced.
In some embodiments, the organosilicon source is selected from methyltrichlorosilane dimethyldichlorosilane or dimethylsilane.
In some embodiments, the diluent gas is argon or helium.
In some embodiments, substantially may be selected from graphite, carbon, silicon carbide, or ceramic. Further, the ceramic is an oxide ceramic including, but not limited to, an alumina ceramic. But also silicon nitride ceramics.
In some embodiments, the ratio of the flow rates of the diluent gas, the hydrogen gas and the organosilicon source gas is (5-20): 1.
In some embodiments, the flow ratio of the dilution gas, hydrogen, and organosilicon source gas introduced during the low temperature nucleation stage, the medium temperature growth stage, and the high temperature growth stage may be the same.
In some embodiments, the chemical vapor deposition process is performed at a pressure of 9.8KPa to 12 KPa.
In one embodiment of the application, a silicon carbide coating is provided, which is prepared according to the method described above.
In some embodiments, the vickers hardness of the silicon carbide coating is greater than 2500HV, and further, the vickers hardness of the silicon carbide coating is 2500 HV-3000 HV.
In some embodiments, the fracture toughness of the silicon carbide coating is greater than 3 MPa-m 1/2. Further, the fracture toughness of the silicon carbide coating was 3 MPa.m 1/2~8MPa·m1/2.
In order to make the objects, technical solutions and advantages of the present invention more concise, the present invention will be described in the following specific examples, but the present invention is by no means limited to these examples. The following examples are only preferred embodiments of the present invention, which can be used to describe the present invention, and should not be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In order to better illustrate the present invention, the following description of the present invention will be given with reference to examples. The following are specific examples.
Example 1:
(1) And cleaning the graphite substrate, placing the graphite substrate into a chemical vapor deposition cavity, vacuumizing, heating to 500 ℃ within 1h, and preserving heat for 1h.
(2) Then heating to 700 ℃ at the rate of 0.85 ℃ per minute, preserving heat for 1h, then introducing argon, hydrogen and Methyltrichlorosilane (MTS) according to the flow ratio of 10:10:1 for deposition for 25min, controlling the pressure of a chemical vapor deposition chamber to be 10000+/-100 Pa, cutting off the methyltrichlorosilane and the hydrogen after the deposition is finished, retaining the argon, and controlling the pressure of the chemical vapor deposition chamber to be 10000+/-100 Pa all the time.
(3) Gradually heating to 1200 ℃ at a rate of 5 ℃ per minute for 5min, and keeping the temperature for 1h, recovering argon, hydrogen and methyltrichlorosilane for deposition for 25min, cutting off methyltrichlorosilane and hydrogen after the deposition is finished, and keeping the argon, wherein the pressure of a chemical vapor deposition chamber is always controlled to 10000+/-100 Pa;
(4) Gradually heating, heating to 1400 ℃ at a heating rate of 5 ℃ per minute and keeping the temperature for 5min, keeping the temperature for 1h, recovering the gases of argon, hydrogen and methyltrichlorosilane for deposition for 95min, cutting off methyltrichlorosilane and hydrogen after the deposition is finished, and keeping the argon, wherein the pressure of a chemical vapor deposition chamber is always controlled to 10000+/-100 Pa.
(5) The temperature in the chemical vapor deposition chamber is reduced to 700 ℃ at the speed of 1 ℃ per minute, the temperature is kept for 3 hours, then the temperature is reduced to the room temperature at the speed of 0.5 ℃ per minute, and argon is repeatedly replaced for three times before the furnace cover is opened, so that the silicon carbide coating is obtained.
Comparative example 1:
(1) And cleaning the graphite substrate, placing the graphite substrate into a chemical vapor deposition cavity, vacuumizing, heating to 500 ℃ within 1h, and preserving heat for 1h.
(2) Heating to 1200 ℃ at a rate of 2.33 ℃ per hour, preserving heat for 1 hour, then introducing argon, hydrogen and Methyltrichlorosilane (MTS) according to a flow ratio of 10:10:1 for deposition, wherein the deposition time is 145min, controlling the pressure of a chemical vapor deposition chamber to be 10000+/-100 Pa, cutting off the methyltrichlorosilane and the hydrogen after the deposition is finished, retaining the argon, and controlling the pressure of the chemical vapor deposition chamber to be 10000+/-100 Pa all the time.
(3) The temperature in the chemical vapor deposition chamber is reduced to 700 ℃ at the speed of 1 ℃ per minute, the temperature is kept for 3 hours, then the temperature is reduced to the room temperature at the speed of 0.5 ℃ per minute, and argon is repeatedly replaced for three times before the furnace cover is opened, so that the silicon carbide coating is obtained.
Comparative example 2:
(1) And cleaning the graphite substrate, placing the graphite substrate into a chemical vapor deposition cavity, vacuumizing, heating to 500 ℃ within 1h, and preserving heat for 1h.
(2) Heating to 1400 ℃ at the speed of 2.5 ℃ per min, preserving heat for 1h, then introducing argon, hydrogen and Methyltrichlorosilane (MTS) according to the flow ratio of 10:10:1 for deposition, wherein the deposition time is 145min, controlling the pressure of a chemical vapor deposition chamber to be 10000+/-100 Pa, cutting off the methyltrichlorosilane and the hydrogen after the deposition is finished, retaining the argon, and controlling the pressure of the chemical vapor deposition chamber to be 10000+/-100 Pa all the time.
(3) The temperature in the chemical vapor deposition chamber is reduced to 700 ℃ at the speed of 1 ℃ per minute, the temperature is kept for 3 hours, then the temperature is reduced to the room temperature at the speed of 0.5 ℃ per minute, and argon is repeatedly replaced for three times before the furnace cover is opened, so that the silicon carbide coating is obtained.
Comparative example 3
(1) The graphite substrate is cleaned, placed in a chemical vapor deposition cavity, vacuumized, heated to 500 ℃ within 1h, and kept for 1h.
(2) Then heating to 700 ℃ at the rate of 0.85 ℃ per minute, preserving heat for 1h, then introducing argon, hydrogen and Methyltrichlorosilane (MTS) according to the flow ratio of 10:10:1 for deposition for 25min, controlling the pressure of a chemical vapor deposition chamber to be 10000+/-100 Pa, cutting off the methyltrichlorosilane and the hydrogen after the deposition is finished, retaining the argon, and controlling the pressure of the chemical vapor deposition chamber to be 10000+/-100 Pa all the time.
(3) Gradually heating to 1400 ℃ at a heating rate of 5 ℃ per min for 5min, keeping the temperature for 1h, recovering the gases of argon, hydrogen and methyltrichlorosilane for deposition for 25min, cutting off methyltrichlorosilane and hydrogen after the deposition is finished, and keeping the argon, wherein the pressure of a chemical vapor deposition chamber is always controlled to 10000+/-100 Pa in the process.
(4) Then cooling to 1200 ℃ at a temperature rising rate of 5 ℃ per minute, preserving heat for 1h, recovering argon, hydrogen and methyltrichlorosilane for deposition for 95min, cutting off methyltrichlorosilane and hydrogen after the deposition is finished, and retaining the argon, wherein the pressure of a chemical vapor deposition chamber is always controlled to 10000+/-100 Pa;
(5) The temperature in the chemical vapor deposition chamber is reduced to 700 ℃ at the speed of 1 ℃ per minute, the temperature is kept for 3 hours, then the temperature is reduced to the room temperature at the speed of 0.5 ℃ per minute, and argon is repeatedly replaced for three times before the furnace cover is opened, so that the silicon carbide coating is obtained.
And (3) performance detection:
vickers hardness test was carried out according to the method specified in GB/T7997-2014.
Fracture toughness silicon carbide coatings were tested according to the indentation method.
Roughness the silicon carbide surface was tested using a stylus coarseness meter.
Binding force the binding force between the silicon carbide coating and the graphite substrate was tested according to the method specified in GB/T5210-2006.
The performance test of each example with respect to the silicon carbide coating of the comparative example is shown in table 1 below.
TABLE 1
As can be seen from Table 1, the coating prepared in example 1 has a small roughness, a smooth surface, a Vickers hardness of 2824.8HV, a fracture toughness of 6.53 MPa m 1/2, and a silicon carbide coating adhesion to the substrate of 9.26MPa.
When preparing silicon carbide coatings by the methods of comparative example 1 and comparative example 2, chemical vapor deposition was performed only under one temperature condition, and the surface smoothness of the obtained silicon carbide coatings was relatively poor, and the performance in terms of roughness, vickers hardness, fracture toughness and bonding force with a substrate was also inferior to that of example 1.
Comparative example 3 in the preparation of a silicon carbide coating, chemical vapor deposition was performed under relatively low temperature conditions, then chemical vapor deposition was performed under high temperature conditions, and then chemical vapor deposition was performed under medium temperature conditions, so that the obtained silicon carbide coating was poor in uniformity, has a vickers hardness of 2684.1HV, a fracture toughness of 4.23mpa·m 1/2, and a bonding force with a substrate of only 8.48MPa, which is inferior to example 1.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (7)
1. A method for preparing a silicon carbide coating, comprising the steps of:
A step of carrying out heat preservation pretreatment on a substrate under the vacuum condition of 400-600 ℃, wherein the heat preservation time of the heat preservation pretreatment is 1-2 h;
carrying out chemical vapor deposition treatment on the substrate subjected to the heat preservation pretreatment to form a silicon carbide coating;
The chemical vapor deposition treatment comprises a low-temperature nucleation stage, a medium-temperature growth stage and a high-temperature growth stage which are sequentially carried out, wherein an air source adopted by the chemical vapor deposition treatment comprises a dilution gas, hydrogen and an organosilicon source gas, the deposition temperature of the low-temperature nucleation stage is 600-800 ℃, the deposition temperature of the medium-temperature growth stage is 1000-1300 ℃, and the deposition temperature of the high-temperature growth stage is 1350-1500 ℃;
The chemical vapor deposition process includes:
heating to the deposition temperature of the low-temperature nucleation stage at a rate of 0.5-15 ℃ per minute, firstly preserving heat for 1-2 hours after the temperature reaches the deposition temperature of the low-temperature nucleation stage, and then introducing the air source to perform first chemical vapor deposition, wherein the time of the first chemical vapor deposition is 20-30 minutes;
Heating the deposition temperature of the low-temperature nucleation stage to the deposition temperature of the medium-temperature growth stage in a mode of heating the deposition temperature of the low-temperature nucleation stage to the deposition temperature of the medium-temperature growth stage at a rate of 2-10 ℃ per minute to 50-100 ℃ per minute and keeping the temperature for 4-6 minutes, keeping the temperature for 1-2 hours after the temperature reaches the deposition temperature of the medium-temperature growth stage, and then introducing the hydrogen and the silicon source gas to perform second chemical vapor deposition, wherein the time of the second chemical vapor deposition is 20-80 minutes;
Heating the deposition temperature of the medium-temperature growth stage to the deposition temperature of the high-temperature growth stage in a mode of heating the deposition temperature of the medium-temperature growth stage to 50-100 ℃ at a rate of 2-10 ℃ per minute and keeping the temperature for 4-6 minutes, keeping the temperature for 1-2 hours after the temperature reaches the deposition temperature of the high-temperature growth stage, and then introducing the hydrogen and the silicon source gas for performing third chemical vapor deposition, wherein the time of the third chemical vapor deposition is 40-100 minutes;
after the high temperature growth stage is completed, the method further comprises the following steps:
Cooling the deposition temperature in the high-temperature growth stage to 700-800 ℃ at a rate of 1-3 ℃ per minute, preserving heat for 2-4 hours, and then cooling to room temperature at a rate of 0.3-1 ℃ per minute.
2. The method of claim 1, wherein the low temperature nucleation stage has a deposition temperature of 650 ℃ to 750 ℃ and/or,
The deposition temperature of the medium-temperature growth stage is 1150-1250 ℃ and/or,
The deposition temperature of the high-temperature growth stage is 1350-1450 ℃.
3. The method according to any one of claims 1 to 2, wherein the substrate is subjected to a heat-preserving pretreatment under a vacuum condition of 500 ℃.
4. The method according to any one of claims 1 to 2, wherein the heat preservation time of the heat preservation pretreatment is 1h.
5. The method according to claim 1 to 2, wherein the organosilicon source is selected from methyltrichlorosilane, dimethyldichlorosilane or dimethylsilane, and/or
The diluent gas is selected from argon or helium, and/or
The substrate is selected from graphite, carbon, silicon carbide or ceramic.
6. The production method according to any one of claims 1 to 2, wherein the ratio of the flow rates of the diluent gas, the hydrogen gas and the organosilicon source gas is (5 to 20): 1.
7. A silicon carbide coating, characterized in that it is prepared according to the method of any one of claims 1-2.
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