CN117230427A - Si with double interface layers 3 N 4 Preparation method of-SiC composite coating graphite base - Google Patents
Si with double interface layers 3 N 4 Preparation method of-SiC composite coating graphite base Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 102
- 239000010439 graphite Substances 0.000 title claims abstract description 102
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 238000000576 coating method Methods 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000007789 gas Substances 0.000 claims abstract description 69
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 238000000151 deposition Methods 0.000 claims abstract description 57
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 56
- 230000008021 deposition Effects 0.000 claims abstract description 54
- 239000005055 methyl trichlorosilane Substances 0.000 claims abstract description 48
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims abstract description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004321 preservation Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 32
- 238000001704 evaporation Methods 0.000 description 31
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 31
- 230000008020 evaporation Effects 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 9
- 238000005382 thermal cycling Methods 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The application discloses a Si with double interface layers 3 N 4 -a method for preparing a graphite susceptor with a SiC composite coating, comprising the steps of: pretreating the surface of a graphite substrate, placing the graphite substrate in a chemical vapor deposition furnace, performing vacuumizing treatment in the chemical vapor deposition furnace, and then introducing silicon tetrachloride gas, ammonia gas and diluent gas argon; heating to 1400-1600 ℃, performing CVD deposition, maintaining the furnace pressure at 2kPa, performing heat preservation reaction for 3-5h, and closing silicon tetrachloride gas and ammonia gas; reducing the temperature to 1050-1150 ℃, introducing methyltrichlorosilane gas and hydrogen, performing CVD deposition, maintaining the furnace pressure at 2kPa, preserving heat for reaction for 5-10h, and closing methyltrichlorosilane gasA body and hydrogen gas; after the reaction is completed, cooling to room temperature in an atmosphere filled with argon, and taking out the product; si with double interfacial layer prepared by the method of the application 3 N 4 The SiC composite coating has high connection strength with a graphite matrix, good compactness, strong oxidation resistance, high heat conductivity and strong heat stability.
Description
Technical Field
The application belongs to the technical field of semiconductors, and in particular relates to Si 3 N 4 Preparation method of SiC composite coating and Si prepared by preparation method 3 N 4 -SiC composite coating and deposited with the Si 3 N 4 -graphite susceptor with double interfacial layer of SiC composite coating.
Background
With the rapid development of third generation semiconductors, gallium nitride (GaN) plays an important role in the field of LED lighting, and currently, metal Organic Chemical Vapor Deposition (MOCVD) is mainly used for GaN-based LED epitaxial growth. The graphite base plate for the semiconductor is used as a substrate for epitaxial growth of a single crystal SiC, inP, gaN, alN semiconductor in MOCVD equipment, and the thermal stability, the thermal uniformity and other performance parameters play a decisive role in the growth quality of an epitaxial material, so that the graphite base plate is a core key component of the MOCVD equipment. Graphite has excellent performances of high temperature resistance, high heat conduction, high temperature strength and the like, is used as a first choice material of a base plate base body of an epitaxial single crystal substrate, but graphite materials can fail due to powder falling by corrosion in the service process, meanwhile, fallen powder can pollute a chip, and the surface coating technology is an effective means for solving the problem, so that the preparation of the graphite coating with high temperature resistance, corrosion resistance and chemical stability is particularly important.
Silicon carbide (SiC) has a series of excellent characteristics of good thermodynamic stability, excellent thermal conductivity, oxidation resistance, corrosion resistance, gas flow scouring resistance, low gas permeability and the like, and combines good coverage and controllability of Chemical Vapor Deposition (CVD) technology, so that the SiC coating becomes the first choice material of the protective coating for the surface of the graphite base. However, due to the relatively large thermal expansion coefficient of SiC coating (about 4.5×10 -6 and/K), has larger thermal expansion difference with the graphite base plate matrix, so that residual stress of the SiC coating is overlarge in the preparation and use processes, and when the shear stress peak value at the interface of the coating is larger than the bonding strength of the coating, the coating can crack and even fall off, thereby affecting the growth quality of epitaxial materials, reducing the service life of the graphite base and increasing the economic cost.
Disclosure of Invention
Based on the above technical problems in the prior art, one of the objects of the present application is to provide Si with a dual interfacial layer 3 N 4 Preparation of SiC-coated graphite susceptors by addition of silicon nitride (Si 3 N 4 ) The interface between the graphite matrix and the coating is changed from the original C-SiC interface layer to C-Si 3 N 4 SiC double interfacial layer due to Si 3 N 4 Meanwhile, the silicon-containing modified graphite has a thermal expansion coefficient smaller than that of graphite and SiC, and nitrogen-containing functional groups are added and Si is improved by carrying out nitrogen plasma modification on the surface of the graphite 3 N 4 Affinity of the matrix to Si 3 N 4 Is a nucleation core for promoting Si 3 N 4 Growth of film while preparing Si under the temperature conditions of the present application 3 N 4 The coating has higher surface roughness, and Si can be improved when the SiC coating is deposited on the coating 3 N 4 The mechanical engagement strength between SiC interface layers can effectively solve the problem of poor bonding capability of a graphite substrate and a coating caused by overlarge residual stress of a graphite base in the preparation and use processes, and Si 3 N 4 Has excellent heat resistance, oxidation resistance, corrosion resistance, high thermal conductivity and the like similar to SiC, has the condition of serving as a monocrystal semiconductor epitaxial growth substrate in MOCVD equipment, and avoids the introduction of Si 3 N 4 The transition layer may cause a decrease in thermal performance of the substrate.
In order to achieve the above purpose, the present application adopts the following technical scheme:
si with double interface layers 3 N 4 The preparation method of the SiC composite coating graphite base comprises the following steps:
s1, pretreating the surface of a graphite substrate, and placing the graphite substrate into a chemical vapor deposition furnace;
s2, performing vacuumizing treatment in a chemical vapor deposition furnace, and then introducing silicon tetrachloride gas, ammonia gas and diluent gas argon, wherein the molar ratio of the ammonia gas to the silicon tetrachloride gas is 5-8:1;
s3, heating to 1400-1600 ℃, performing CVD deposition, maintaining the furnace pressure at 2kPa, and performing heat preservation reaction for 3-5 hours;
s4, after the step S3 is completed, closing silicon tetrachloride gas and ammonia gas, reducing the temperature to 1050-1150 ℃, then introducing methyl trichlorosilane gas and hydrogen gas, performing CVD deposition, keeping the furnace pressure to be 2kPa, and performing heat preservation reaction for 10-15 hours, wherein the flow ratio of the methyl trichlorosilane gas to the hydrogen gas is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
In some embodiments, in the step S2, the flow rates of the ammonia gas and the silicon tetrachloride gas are 800ml/min and 100ml/min, respectively, where the ammonia gas is used as a nitrogen source for depositing the silicon nitride coating layer, and the silicon chloride gas is used as a silicon source for depositing the silicon nitride coating layer.
In some embodiments, in the step S1, the surface of the graphite substrate is pretreated by: and (3) firstly polishing the surface of the graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate into alcohol, cleaning for 1h by using ultrasonic waves, drying for 20min at 70 ℃ in an oven, and finally placing the graphite into a plasma cleaner and cleaning for 30min by using nitrogen plasma.
In some embodiments, in step S3, the temperature is increased to 1400-1600 ℃ at a heating rate of 10 ℃/min.
In some embodiments, the silicon tetrachloride gas is generated by gasification of a silicon tetrachloride liquid at a temperature above 70 ℃; the methyltrichlorosilane gas is generated by gasifying methyltrichlorosilane liquid at the temperature of more than 90 ℃.
In some embodiments, in the step S4, cooling water is introduced to cool to 1050-1150 ℃.
The second object of the present application is to provide a composite coating layer, which is prepared by the preparation method of any one of the above embodiments.
It is a further object of the present application to provide a graphite susceptor having a dual interface coating comprising a graphite substrate and a coating deposited on said graphite susceptor, said coating being a composite coating as described above.
Compared with the prior art, the application has the following beneficial effects:
(1) Silicon nitride (Si) 3 N 4 ) At the same time, has a thermal expansion coefficient which is smaller than that of graphite and silicon carbide (SiC), and the application introduces Si between the substrate and the SiC coating 3 N 4 As an excessive coating, the method effectively reduces the tendency of cracking of the substrate and the coating caused by excessive residual stress in the preparation and use processes of the graphite base, and improves the bonding strength of the substrate and the coating and the service life of the base.
(2)Si 3 N 4 Has the characteristics of excellent heat resistance, oxidation resistance, corrosion resistance and the like, can effectively improve a series of performances of matrix surface hardness, wear resistance, corrosion resistance, oxidation resistance, ablation resistance and the like, and is Si 3 N 4 The coating not only relies on itself to isolate the diffusion of oxygen to the substrate material, but also can effectively inhibit the diffusion of oxygen by the silicon dioxide which is an oxidation product of the silicon nitride coating, thereby greatly improving the oxidation resistance of the material.
(3)Si 3 N 4 Like SiC, it has excellent thermal stability and high thermal conductivity, and can ensure the quality of epitaxial material growth when used as a substrate for single crystal semiconductor epitaxial growth in MOCVD equipment.
(4) The continuous high-temperature deposition furnace reaction equipment is adopted, and the two CVD depositions are not required to be carried out in the two equipment, so that the surface pollution of the product is reduced, the production cost and time are saved, and the production efficiency is improved.
Drawings
FIG. 1 is a process flow diagram of the present application.
FIG. 2 is a schematic diagram showing the connection of a silicon tetrachloride evaporation tank, a methyltrichlorosilane evaporation tank, a gas mixing tank, a water bath heating tank, a deposition furnace and a vacuum pump of a chemical vapor deposition furnace used in the embodiment of the application.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the application, which is therefore not limited to the specific embodiments disclosed below.
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 application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The chemical vapor deposition furnace used in the following examples of the present application, as shown in FIG. 2, comprises a silicon tetrachloride evaporation tank 1, a methyltrichlorosilane evaporation tank 2, a gas mixing tank 3, a water bath heating tank 4, a deposition furnace 5 and a vacuum pump 6; the silicon tetrachloride evaporation tank 1 and the methyltrichlorosilane evaporation tank 2 are respectively connected with a mixed gas tank 3, the mixed gas tank 3 is connected with a deposition furnace 5, the silicon tetrachloride evaporation tank 1 and the methyltrichlorosilane evaporation tank 2 are respectively arranged in a water bath heating tank 4, the silicon tetrachloride evaporation tank 1 and the mixed gas tank 3 are respectively connected with an argon gas source, the mixed gas tank 3 is also connected with an ammonia gas source and a hydrogen source, and the deposition furnace 5 is connected with a vacuum pump 6; the water bath heating tank 4 is used for heating and gasifying silicon tetrachloride liquid in the silicon tetrachloride evaporating tank 1 and methyltrichlorosilane liquid in the methyltrichlorosilane evaporating tank 2, the deposition furnace 5 is used for reacting, a graphite flow distribution disc (not shown in the figure) is arranged in the deposition furnace 5, and condensed water channels (not shown in the figure) are arranged around the furnace chamber so as to reduce the temperature in the furnace. The chemical vapor deposition furnace is a device conventionally used in the art, and is not described in detail herein.
Example 1
As shown in FIG. 1, the Si provided by the application 3 N 4 -a method for preparing a SiC composite coating, comprising the steps of:
s1, pretreatment is carried out on the surface of a graphite matrix: firstly polishing the surface of the graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate in alcohol, cleaning for 1h by using ultrasonic waves, drying for 20min at 70 ℃ in an oven, and placing the graphite substrate on a graphite shunt plate;
s2, placing a proper amount of silicon tetrachloride liquid and methyltrichlorosilane liquid in a silicon tetrachloride evaporation tank and a methyltrichlorosilane evaporation tank respectively for standby, opening a vacuumizing device to vacuumize vapor deposition furnace equipment, then introducing argon to enable the equipment to be filled with the argon, heating the silicon tetrachloride evaporation tank in a water bath to introduce silicon tetrachloride gas into the deposition furnace, and simultaneously introducing ammonia into the deposition furnace; wherein the flow rates of the ammonia gas and the silicon tetrachloride gas are respectively 800mL/min and 100mL/min, the molar ratio of the ammonia gas to the silicon tetrachloride gas is 5:1,
s3, heating the deposition furnace to 1400-1600 ℃ at a heating rate of 10 ℃/min, performing CVD deposition, maintaining the furnace pressure of 2kPa, performing heat preservation reaction for 2-5h, and forming Si on the surface of the graphite substrate 3 N 4 A coating;
s4, after the reaction in the step S3 is completed, closing ammonia gas and silicon tetrachloride gas, introducing cooling water to reduce the temperature in the deposition furnace to 1050-1150 ℃, heating the methyl trichlorosilane evaporation tank in a water bath to introduce the methyl trichlorosilane gas into the deposition furnace, simultaneously introducing hydrogen into the deposition furnace, performing CVD deposition, maintaining the furnace pressure to be 2kPa, performing heat preservation reaction for 10-15 hours, and coating Si on the silicon 3 N 4 Forming a SiC coating on the surface of the graphite base of the coating; wherein the flow ratio of the methyltrichlorosilane gas to the hydrogen is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
To verify the thermal stability of the coating without nitrogen plasma cleaning, a vacuum thermal cycling experiment was performed: and (3) placing the coating into a high-temperature resistance furnace, vacuumizing, heating to 1500 ℃, preserving heat for 20min, and cooling to room temperature along with the furnace. The SiC coating was found to drop off after 206 cycles of thermal cycling, si 3 N 4 And falls off after undergoing 217 cycles of thermal cycling.
Example 2
Si provided by the application 3 N 4 -a method for preparing a SiC composite coating, comprising the steps of:
s1, pretreatment is carried out on the surface of a graphite matrix: firstly polishing the surface of a graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate in alcohol, cleaning the graphite substrate for 1h by using ultrasonic waves, drying the graphite substrate in an oven at 70 ℃ for 20min, finally placing the graphite substrate in a plasma cleaning machine, cleaning the graphite substrate by using nitrogen plasma for 30min, and placing the graphite substrate on a graphite shunt plate;
s2, placing a proper amount of silicon tetrachloride liquid and methyltrichlorosilane liquid in a silicon tetrachloride evaporation tank and a methyltrichlorosilane evaporation tank respectively for standby, opening a vacuumizing device to vacuumize vapor deposition furnace equipment, then introducing argon to enable the equipment to be filled with the argon, heating the silicon tetrachloride evaporation tank in a water bath to introduce silicon tetrachloride gas into the deposition furnace, and simultaneously introducing ammonia into the deposition furnace; wherein the flow rates of the ammonia gas and the silicon tetrachloride gas are respectively 800mL/min and 100mL/min, the molar ratio of the ammonia gas to the silicon tetrachloride gas is 5:1,
s3, heating the deposition furnace to 1400-1600 ℃ at a heating rate of 10 ℃/min, performing CVD deposition, maintaining the furnace pressure of 2kPa, performing heat preservation reaction for 2-5h, and forming Si on the surface of the graphite substrate 3 N 4 A coating;
s4, after the reaction in the step S3 is completed, closing ammonia gas and silicon tetrachloride gas, introducing cooling water to reduce the temperature in the deposition furnace to 1050-1150 ℃, heating the methyl trichlorosilane evaporation tank in a water bath to introduce the methyl trichlorosilane gas into the deposition furnace, simultaneously introducing hydrogen into the deposition furnace, performing CVD deposition, maintaining the furnace pressure to be 2kPa, performing heat preservation reaction for 10-15 hours, and coating Si on the silicon 3 N 4 Forming a SiC coating on the surface of the graphite base of the coating; wherein the flow ratio of the methyltrichlorosilane gas to the hydrogen is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
To verify the thermal stability of the coating, a vacuum thermal cycling experiment was performed: and (3) placing the coating into a high-temperature resistance furnace, vacuumizing, heating to 1500 ℃, preserving heat for 20min, and cooling to room temperature along with the furnace. SiC coating was found to drop after 262 cycles of thermal cycling, si 3 N 4 And falls off after undergoing 303 cycles of thermal cycling.
Example 3
Si provided by the application 3 N 4 Of SiC composite coatingThe preparation method comprises the following steps:
s1, pretreatment is carried out on the surface of a graphite matrix: firstly polishing the surface of a graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate in alcohol, cleaning the graphite substrate for 1h by using ultrasonic waves, drying the graphite substrate in an oven at 70 ℃ for 20min, finally placing the graphite substrate in a plasma cleaning machine, cleaning the graphite substrate by using nitrogen plasma for 30min, and placing the graphite substrate on a graphite shunt plate;
s2, placing a proper amount of silicon tetrachloride liquid and methyltrichlorosilane liquid in a silicon tetrachloride evaporation tank and a methyltrichlorosilane evaporation tank respectively for standby, opening a vacuumizing device to vacuumize vapor deposition furnace equipment, then introducing argon to enable the equipment to be filled with the argon, heating the silicon tetrachloride evaporation tank in a water bath to introduce silicon tetrachloride gas into the deposition furnace, and simultaneously introducing ammonia into the deposition furnace; wherein the flow rates of the ammonia gas and the silicon tetrachloride gas are respectively 800mL/min and 100mL/min, the molar ratio of the ammonia gas to the silicon tetrachloride gas is 6:1,
s3, heating the deposition furnace to 1400-1600 ℃ at a heating rate of 10 ℃/min, performing CVD deposition, maintaining the furnace pressure of 2kPa, performing heat preservation reaction for 2-5h, and forming Si on the surface of the graphite substrate 3 N 4 A coating;
s4, after the reaction in the step S3 is completed, closing ammonia gas and silicon tetrachloride gas, introducing cooling water to reduce the temperature in the deposition furnace to 1050-1150 ℃, heating the methyl trichlorosilane evaporation tank in a water bath to introduce the methyl trichlorosilane gas into the deposition furnace, simultaneously introducing hydrogen into the deposition furnace, performing CVD deposition, maintaining the furnace pressure to be 2kPa, performing heat preservation reaction for 10-15 hours, and coating Si on the silicon 3 N 4 Forming a SiC coating on the surface of the graphite base of the coating; wherein the flow ratio of the methyltrichlorosilane gas to the hydrogen is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
To verify the thermal stability of the coating, a vacuum thermal cycling experiment was performed: and (3) placing the coating into a high-temperature resistance furnace, vacuumizing, heating to 1500 ℃, preserving heat for 20min, and cooling to room temperature along with the furnace. The SiC coating was found to undergo 271 cyclesFalling off after thermal cycling, si 3 N 4 And falls off after undergoing 334 cycles of thermal cycling. By the Si with double interface layer of the application 3 N 4 The graphite base formed by depositing the SiC composite coating on the surface of the graphite matrix has good thermal stability and can be used in high-temperature and corrosive atmosphere for a long time.
Example 4
Si provided by the application 3 N 4 -a method for preparing a SiC composite coating, comprising the steps of:
s1, pretreatment is carried out on the surface of a graphite matrix: firstly polishing the surface of a graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate in alcohol, cleaning the graphite substrate for 1h by using ultrasonic waves, drying the graphite substrate in an oven at 70 ℃ for 20min, finally placing the graphite substrate in a plasma cleaning machine, cleaning the graphite substrate by using nitrogen plasma for 30min, and placing the graphite substrate on a graphite shunt plate;
s2, placing a proper amount of silicon tetrachloride liquid and methyltrichlorosilane liquid in a silicon tetrachloride evaporation tank and a methyltrichlorosilane evaporation tank respectively for standby, opening a vacuumizing device to vacuumize vapor deposition furnace equipment, then introducing argon to enable the equipment to be filled with the argon, heating the silicon tetrachloride evaporation tank in a water bath to introduce silicon tetrachloride gas into the deposition furnace, and simultaneously introducing ammonia into the deposition furnace; wherein the flow rates of the ammonia gas and the silicon tetrachloride gas are respectively 800mL/min and 100mL/min, the molar ratio of the ammonia gas to the silicon tetrachloride gas is 7:1,
s3, heating the deposition furnace to 1400-1600 ℃ at a heating rate of 10 ℃/min, performing CVD deposition, maintaining the furnace pressure of 2kPa, performing heat preservation reaction for 2-5h, and forming Si on the surface of the graphite substrate 3 N 4 A coating;
s4, after the reaction in the step S3 is completed, closing ammonia gas and silicon tetrachloride gas, introducing cooling water to reduce the temperature in the deposition furnace to 1050-1150 ℃, heating the methyl trichlorosilane evaporation tank in a water bath to introduce the methyl trichlorosilane gas into the deposition furnace, simultaneously introducing hydrogen into the deposition furnace, performing CVD deposition, maintaining the furnace pressure to be 2kPa, performing heat preservation reaction for 10-15 hours, and coating Si on the silicon 3 N 4 Forming a SiC coating on the surface of the graphite base of the coating; wherein the flow ratio of the methyltrichlorosilane gas to the hydrogen is1:20；
And S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
Example 5
Si provided by the application 3 N 4 -a method for preparing a SiC composite coating, comprising the steps of:
s1, pretreatment is carried out on the surface of a graphite matrix: firstly polishing the surface of a graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate in alcohol, cleaning the graphite substrate for 1h by using ultrasonic waves, drying the graphite substrate in an oven at 70 ℃ for 20min, finally placing the graphite substrate in a plasma cleaning machine, cleaning the graphite substrate by using nitrogen plasma for 30min, and placing the graphite substrate on a graphite shunt plate;
s2, placing a proper amount of silicon tetrachloride liquid and methyltrichlorosilane liquid in a silicon tetrachloride evaporation tank and a methyltrichlorosilane evaporation tank respectively for standby, opening a vacuumizing device to vacuumize vapor deposition furnace equipment, then introducing argon to enable the equipment to be filled with the argon, heating the silicon tetrachloride evaporation tank in a water bath to introduce silicon tetrachloride gas into the deposition furnace, and simultaneously introducing ammonia into the deposition furnace; wherein the flow rates of the ammonia gas and the silicon tetrachloride gas are respectively 800mL/min and 100mL/min, the molar ratio of the ammonia gas to the silicon tetrachloride gas is 8:1,
s3, heating the deposition furnace to 1400-1600 ℃ at a heating rate of 10 ℃/min, performing CVD deposition, maintaining the furnace pressure of 2kPa, performing heat preservation reaction for 2-5h, and forming Si on the surface of the graphite substrate 3 N 4 A coating;
s4, after the reaction in the step S3 is completed, closing ammonia gas and silicon tetrachloride gas, introducing cooling water to reduce the temperature in the deposition furnace to 1050-1150 ℃, heating the methyl trichlorosilane evaporation tank in a water bath to introduce the methyl trichlorosilane gas into the deposition furnace, simultaneously introducing hydrogen into the deposition furnace, performing CVD deposition, maintaining the furnace pressure to be 2kPa, performing heat preservation reaction for 10-15 hours, and coating Si on the silicon 3 N 4 Forming a SiC coating on the surface of the graphite base of the coating; wherein the flow ratio of the methyltrichlorosilane gas to the hydrogen is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
The technical features of the above embodiments may be arbitrarily combined, and for brevity, all of the possible combinations of the technical features of the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, it should be considered as the scope described in the present specification.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. 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 application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (8)
1. Si with double interface layers 3 N 4 The preparation method of the SiC composite coating graphite base is characterized by comprising the following steps:
s1, pretreating the surface of a graphite substrate, and placing the graphite substrate into a chemical vapor deposition furnace;
s2, performing vacuumizing treatment in a chemical vapor deposition furnace, and then introducing silicon tetrachloride gas, ammonia gas and diluent gas argon, wherein the molar ratio of the ammonia gas to the silicon tetrachloride gas is 5-8:1;
s3, heating to 1400-1600 ℃, performing CVD deposition, maintaining the furnace pressure at 2kPa, and performing heat preservation reaction for 3-5 hours;
s4, after the step S3 is completed, closing silicon tetrachloride gas and ammonia gas, reducing the temperature to 1050-1150 ℃, then introducing methyl trichlorosilane gas and hydrogen gas, performing CVD deposition, keeping the furnace pressure to be 2kPa, and performing heat preservation reaction for 10-15 hours, wherein the flow ratio of the methyl trichlorosilane gas to the hydrogen gas is 1:20;
and S5, after the reaction in the step S4 is completed, closing the methyltrichlorosilane gas and the hydrogen, cooling to room temperature in an atmosphere filled with argon, and taking out the product.
2. Si with double interfacial layer according to claim 1 3 N 4 The preparation method of the SiC composite coating graphite base is characterized in that in the step S2, the flow rates of the ammonia gas and the silicon tetrachloride gas are 800mL/min and 100mL/min respectively.
3. Si with double interfacial layer according to claim 1 3 N 4 The preparation method of the SiC composite coating graphite base is characterized in that in the step S1, the surface pretreatment mode of the graphite base is as follows: and (3) firstly polishing the surface of the graphite substrate by using 1500-mesh sand paper, then placing the graphite substrate into alcohol, cleaning for 1h by using ultrasonic waves, drying for 20min at 70 ℃ in an oven, and finally placing the graphite into a plasma cleaner and cleaning for 30min by using nitrogen plasma.
4. Si with double interfacial layer according to claim 1 3 N 4 The preparation method of the SiC composite coating graphite base is characterized in that in the step S3, the temperature is increased to 1400-1600 ℃ at the heating rate of 10 ℃/min.
5. Si with double interfacial layer according to claim 1 3 N 4 The preparation method of the SiC composite coating graphite base is characterized in that the silicon tetrachloride gas is generated by gasifying silicon tetrachloride liquid at the temperature of more than 70 ℃; the methyltrichlorosilane gas is generated by gasifying methyltrichlorosilane liquid at the temperature of more than 90 ℃.
6. Si with double interfacial layer according to claim 1 3 N 4 The preparation method of the SiC composite coating graphite base is characterized in that cooling water is introduced in the step S4 to cool the graphite base to 1050-1150 ℃.
7. A coating having a bi-interfacial layer, characterized in that it is prepared by the preparation method according to any one of claims 1-6.
8. A graphite susceptor comprising a graphite substrate and a coating deposited on said graphite substrate, said coating being a coating having a bi-interfacial layer according to claim 7.
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