CN117702076A - Graphite base and preparation method thereof - Google Patents
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 20
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- 239000001273 butane Substances 0.000 claims description 2
- -1 ethylene, propylene, acetylene Chemical group 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphite base, which comprises a graphite substrate, a graphene transition layer and a main phase coating, wherein the graphene transition layer and the main phase coating are sequentially attached to the surface of the graphite substrate; the graphene transition layer contains graphene; the main phase coating contains silicon carbide. By the arrangement method, the problem of poor bonding force between the SiC coating and the graphite matrix of the graphite-based product can be solved, the product is prevented from falling off the coating, and the service life of the graphite-based product is prolonged; the preparation method of the graphite base provided by the invention has the advantages of short working procedure, low cost, less risk and investment, no damage to the graphite base body, no influence on the flatness of the silicon carbide coating, no introduction of impurity elements, no interference to the purity of the silicon carbide coating and capability of meeting the requirements of the semiconductor industry.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a graphite base and a method for preparing the graphite base.
Background
The research and application of GaN materials are the leading edge and hot spot of the current global semiconductor research, and are novel semiconductor materials for developing microelectronic devices and optoelectronic devices. The metal organic chemical vapor deposition technology is the mainstream technology of the epitaxial growth of the GaN film at present, wherein graphite is used as a bearing base for the epitaxial growth of the GaN film, has the advantages of high temperature resistance, uniform heat conductivity, good chemical stability, stronger heat shock resistance and the like, and is an important part in a reaction cavity of MOCVD equipment. However, the gas used in the epitaxial growth process is ammonia, graphite is extremely easy to be corroded by ammonia at a high temperature, hydrocarbon is released in the corrosion process, and graphite falling scraps are caused, so that the GaN film is polluted. It is therefore desirable to coat the MOCVD graphite susceptor surface.
Silicon carbide (SiC) is used as one of the third-generation semiconductors, has the advantages of excellent performance of the semiconductor, corrosion resistance, high heat conductivity, thermal shock resistance, high chemical stability and the like, and can work well in GaN epitaxial atmosphere. In addition, siC has a relatively small difference in thermal expansion coefficient from that of graphite, and thus SiC is the preferred material for the surface coating of the graphite susceptor. However, the problems that the graphite substrate is prepared and the bonding force between the SiC coating and the graphite substrate is poor are solved, for example, the graphite-based CVD SiC product often has the problem that the coating is easy to fall off in the epitaxial production process of the client, and the wafer is invalid, so that the service life of the product cannot meet the design requirement.
In the prior art, the bonding force of the SiC coating and the graphite substrate is often improved by changing a CVD deposition process to add a transition layer and roughening the surface of the substrate. However, these two approaches have some drawbacks in the actual process route.
For example, it has been reported in the prior art that the effect of increasing the surface roughness of graphite is achieved by destroying the graphite matrix structure by pre-oxidation, so that the coating material and graphite form a mosaic structure at the coating interface, thereby achieving the effect of improving the bonding force between the two. However, such an operation not only increases a process, but also increases the probability of introducing impurity ions, and the surface modification damages the graphite base itself, so that the surface is uneven, and the flatness of the silicon carbide coating is affected.
Another prior art reports a method for preparing a silicon carbide coating on the surface of graphite, which uses an in situ formed CVR silicon carbide coating to firmly bond to a graphite substrate, improving the bonding strength. However, the method adds one more process, uses a high-temperature graphitization furnace and a chemical vapor deposition furnace, and greatly improves the time and economic cost.
Yet another prior art reports a method for preparing a silicon carbide coating on the surface of graphite in the form of SiC/ZrB 2 SiC is a transition layer, so that mismatching between a graphite matrix and an outer compact coating can be effectively relieved, and the ZrB with loose structure 2 The transition layer can further improve the compressive stress of the SiC coating, avoid the SiC coating from forming cracks, and effectively improve the bonding strength of graphite and the coating. However, the method has the advantages of adding two processes, having different use environments, long time, high cost, more raw materials and difficult control of the interference of impurity elements.
Therefore, there is a need to provide a graphite susceptor which is short in process, low in cost, low in probability of introducing impurity ions, and does not damage the graphite substrate itself, and a method for producing the graphite susceptor.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a graphite susceptor comprising a graphite substrate, and a graphene transition layer and a major phase coating layer sequentially attached to the surface of the graphite substrate; the graphene transition layer contains graphene; the main phase coating contains silicon carbide; the method for preparing the graphite base aims to solve the problem of poor bonding force between the SiC coating and the graphite substrate of the graphite-based CVD SiC product, thereby avoiding the coating falling off of the product in the epitaxial production process of the client, and prolonging the service life of the graphite-based CVD SiC product; the preparation method of the graphite matrix composite coating provided by the invention has the advantages of short process, low cost, less risk and investment, and no damage to the graphite matrix, no influence on the flatness of the silicon carbide coating, no introduction of impurity elements, no interference to the purity of the silicon carbide coating, and more satisfaction of the requirements of the semiconductor industry.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a graphite base, which comprises a graphite substrate, and a graphene transition layer and a main phase coating which are sequentially attached to the surface of the graphite substrate; the graphene transition layer contains graphene; the main phase coating contains silicon carbide.
In a second aspect, the present invention provides a method of preparing a graphite susceptor according to the first aspect of the present invention, said method comprising the steps of:
step 1, pretreating a graphite substrate in a deposition furnace;
step 2, depositing a graphene transition layer on the surface of the graphite matrix by adopting a chemical vapor deposition process;
and 3, adopting a chemical vapor deposition process to deposit a silicon carbide coating outside the graphene transition layer formed in the step 2.
In a third aspect, the invention provides a graphite susceptor prepared by the method of the second aspect of the invention.
Through the technical scheme, compared with the prior art, the invention has at least the following advantages:
(1) According to the invention, the graphene transition layer is arranged between the graphite substrate and the silicon carbide coating, the graphene transition layer is loose in structure, is connected between the graphite substrate and the silicon carbide coating like a spring, and can play a role in buffering in the thermal expansion process of the graphite substrate and the silicon carbide coating, so that the binding force between the silicon carbide coating and the graphite substrate is effectively improved, the coating falling off of a product in the epitaxial production process of a client is avoided, and the service life of the graphite-based CVD SiC product is prolonged.
(2) According to the preparation method, the graphene film is directly generated on the surface of the graphite substrate through the chemical vapor deposition process to serve as the transition layer, the working procedure is short, the cost is low, the preparation of the graphene film transition layer and the preparation of the silicon carbide coating are both carried out through the chemical vapor deposition process, other equipment is not added, the deposition process is carried out continuously through the same furnace body, no manual operation is needed during the reaction, the introduction of element impurities in the transferring process is avoided, the purity of the transition layer and the purity of the coating are guaranteed, and compared with the existing method, the preparation method disclosed by the invention is smaller in risk and investment and more suitable for large-scale production.
(3) According to the preparation method disclosed by the invention, the graphene film is generated on the surface of the graphite substrate by a chemical vapor deposition process to serve as a transition layer, other element impurities are not introduced, the graphite substrate is not damaged, the flatness of the silicon carbide coating is affected, and the quality of a graphite-based CVD SiC product is improved.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Drawings
Fig. 1 is a schematic structural diagram of a graphite base according to an embodiment of the present invention.
Fig. 2 is a schematic flow chart of a preparation method of a graphite base according to an embodiment of the present invention.
Fig. 3 is a raman spectrum of a graphene transition layer of a graphite base according to an embodiment of the present invention.
Fig. 4 is an SEM image of a graphite-based silicon carbide coating according to an embodiment of the present invention.
Reference numerals: 1-graphite matrix, 2-graphene transition layer and 3-main phase coating.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides a graphite base, as shown in fig. 1, comprising a graphite substrate 1, a graphene transition layer 2 and a main phase coating 3, wherein the graphene transition layer 2 and the main phase coating 3 are sequentially attached to the surface of the graphite substrate 1; the graphene transition layer 2 contains graphene; the main phase coating 3 contains silicon carbide.
Although the difference between the thermal expansion coefficients of the graphite matrix and the silicon carbide is small, certain difference still exists, and the silicon carbide coating prepared by the traditional process is easy to crack or fall off, so that the coating can be directly caused to fail, and ammonia gas used in the epitaxial production process corrodes the graphite matrix, thereby influencing the service life of the graphite-based semiconductor material. The inventor of the invention discovers that graphene is used as a material with sp hybridized connection carbon atoms closely stacked into a single-layer two-dimensional honeycomb lattice structure, can be well fixed with a graphite substrate when being adhered to the surface of the graphite substrate as a transition layer, is used as a carbon source material with the graphite substrate, and cannot introduce impurities of other elements into the transition layer, so that the purity of the transition layer is affected, and more importantly, the graphene material has the characteristic of loose structure, is connected between the graphite substrate and a silicon carbide coating like a spring, can play a buffering role in the thermal expansion process of the graphite substrate and the silicon carbide coating, and further improves the bonding strength of the graphite substrate and the silicon carbide coating.
Furthermore, the inventors of the present invention have found that the purity of the graphite susceptor can seriously affect the epitaxial growth of GaN, because metal impurities can affect the purity of the GaN epitaxial film, and can further erode the silicon carbide coating on the graphite substrate to affect the growth of the GaN film, so that the introduction of other element impurities needs to be avoided as much as possible during the deposition of the transition layer. The inventor of the present invention has found through long-term creative research that, in order to improve the purity of the transition layer, one is to reduce the process steps of the coating preparation process as much as possible, because the more the process steps, the more involved deposition materials, and the easier the impurities of other elements are introduced; and secondly, graphene is used as a deposition material of the transition layer, and the graphene and the graphite are allotropes of carbon, so that impurities of other elements cannot be introduced to influence the purity of the transition layer.
In the invention, the thickness of the graphene transition layer is 0.02-50 μm, and the thickness of the main phase coating is 80-120 μm.
Exemplary thicknesses of the graphene transition layers may be 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 3.1 μm, 3.2 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4.4 μm, 5 μm, 50 μm, 30 μm, 50 μm, 25 μm, 50 μm, 4 μm, 3.8 μm, 5 μm, 30 μm, 5 μm, and the like.
The thickness of the primary phase coating may be, for example, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm.
In one example, the graphene transition layer has a thickness of 1 μm to 10 μm and the major phase coating has a thickness of 80 μm to 100 μm.
In one example, the thickness ratio of the graphene transition layer and the major phase coating is 1: (2-500), exemplary, the thickness ratio of the graphene transition layer and the major phase coating may be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, preferably 1: (10-50).
In order to avoid epitaxial growth of the GaN film, in the invention, the purity of graphene in the graphene transition layer is not lower than 99.999%, and the purity of silicon carbide in the main phase coating is not lower than 99.999%.
A second aspect of the present invention provides a method of making a graphite susceptor according to the first aspect of the present invention, said method comprising the steps of:
step 1, pretreating a graphite substrate in a deposition furnace;
step 2, depositing a graphene transition layer on the surface of the graphite matrix by adopting a chemical vapor deposition process;
and 3, adopting a chemical vapor deposition process to deposit a silicon carbide coating outside the graphene transition layer formed in the step 2.
In step 1 of the present invention, it comprises: and under the first pressure environment, carrying out first heating treatment on the graphite substrate, wherein the effect and the effect of the treatment are heating and pressure maintaining transition, and the furnace body damage or product deformation caused by rapid heating is avoided.
In one example, the first pressure environment is 50Pa-500Pa, for example: 50Pa, 100Pa, 150Pa, 200Pa, 250Pa, 300Pa, 350Pa, 400Pa, 450Pa, and 500Pa.
In one example, the first temperature-increasing treatment includes gradually increasing the temperature to 800-1100 ℃ (e.g., 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃) at a temperature-increasing rate of 3 ℃/min-10 ℃/min (e.g., 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min), and incubating for 10min-60min. Proceeding with
In step 2 of the present invention, it comprises: introducing a first deposition auxiliary gas into the deposition furnace, performing second heating treatment under a second pressure environment, and introducing a first mixed gas into the deposition furnace to enable the first mixed gas to perform first chemical vapor deposition on the surface of the graphite substrate so as to form a graphene transition layer; the first mixed gas comprises first carbon source gas, and the first carbon source gas is methane.
In one example, the first deposition assist gas includes argon and hydrogen gas in a gas flow ratio of 1: (0.1-10), the gas flow ratio of the argon to the hydrogen may be, for example, 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10. The first deposition auxiliary gas H 2 The function of (2) is to assist gas, reduce wrinkles of the graphene transition layer, increase the flatness of the graphene transition layer, and the Ar function is to diluteAnd the gas plays a role in dispersing the carbon source, so that the carbon source is distributed more uniformly, and the graphene transition layer with uniform distribution is obtained.
In an example, the argon in the first deposition auxiliary gas has a gas flow rate of 5L/min to 100L/min, for example: 5L/min, 10L/min, 15L/min, 20L/min, 25L/min, 30L/min, 35L/min, 40L/min, 45L/min, 50L/min, 55L/min, 60L/min, 65L/min, 70L/min, 75L/min, 80L/min, 85L/min, 90L/min, 95L/min, 100L/min.
In an example, the hydrogen gas in the first deposition auxiliary gas has a gas flow rate of 5L/min to 100L/min, for example: 5L/min, 10L/min, 15L/min, 20L/min, 25L/min, 30L/min, 35L/min, 40L/min, 45L/min, 50L/min, 55L/min, 60L/min, 65L/min, 70L/min, 75L/min, 80L/min, 85L/min, 90L/min, 95L/min, 100L/min.
In one example, the second pressure environment is 5kPa to 10kPa (e.g., 5kPa, 6kPa, 7kPa, 8kPa, 9kPa, 10 kPa).
In one example, the second elevated temperature treatment includes continuously introducing the first deposition assist gas at a temperature environment of 600 ℃ -1800 ℃ (e.g., 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃) for 10min-300min;
in one example, the deposition time of the first chemical vapor deposition is 150min-600min.
In the invention, the first mixed gas further comprises a second carbon source gas, and the second carbon source gas is one or a combination of a plurality of propane, butane, ethylene, propylene, acetylene or cyclopropane. The inventor of the invention discovers that by using the mixed gas of two hydroxyl gases as a carbon source for depositing the graphene film, the formation speed of the nucleation of the graphene and the 'stitching' (growing) speed between the nucleation and carbon atoms can be better controlled, so that the deposition speed of the graphene film can be better controlled, and the thickness of the transition layer can be further adjusted.
In one example, the gas flow ratio of the first carbon source gas to the second carbon source gas is 1: (0.5-3), the gas flow ratio of the first carbon source gas to the second carbon source gas may be, for example, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, preferably 1: (0.5-2).
In one example, the molar ratio of the first carbon source gas to the second carbon source gas is 1: (0.5-3), the molar ratio of the first carbon source gas to the second carbon source gas may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, preferably 1: (0.5-2).
Specifically, in the present invention, the flow rate of the first carbon source gas may be 20L/min to 60L/min, for example: 20L/min, 21L/min, 22L/min, 23L/min, 24L/min, 25L/min, 26L/min, 27L/min, 28L/min, 29L/min, 30L/min, 31L/min, 32L/min, 33L/min, 34L/min, 35L/min, 36L/min, 37L/min, 38L/min, 39L/min, 40L/min; the flow rate of the second carbon source gas may be 20L/min to 60L/min, for example: 20L/min, 21L/min, 22L/min, 23L/min, 24L/min, 25L/min, 26L/min, 27L/min, 28L/min, 29L/min, 30L/min, 31L/min, 32L/min, 33L/min, 34L/min, 35L/min, 36L/min, 37L/min, 38L/min, 39L/min, 40L/min.
In the step 2 of the invention, the first deposition auxiliary gas introduced when the graphene film is deposited on the surface of the graphite substrate only comprises argon and hydrogen, so that the introduction of other impurity elements can be avoided as much as possible, and the purity of the transition layer is influenced. And the hydrogen is used as auxiliary gas for graphene film deposition, so that the folds of the film can be reduced, the flatness is increased, the deposition of amorphous carbon is reduced, the silicon carbide coating is more uniform and smooth in deposition, the coating quality of a graphite-based product is improved, the argon can be used as diluent gas to play a role in dispersing carbon sources, the carbon sources are distributed more uniformly, and the graphene transition layer with uniform distribution is obtained.
In the step 3 of the invention, a second deposition auxiliary gas is introduced into the deposition furnace, a third heating treatment is performed under a third pressure environment, and a second mixed gas is introduced into the deposition furnace, so that a second chemical vapor deposition is performed on the graphene transition layer to form a silicon carbide transition layer; the second mixed gas comprises a third carbon source gas and a first silicon source gas, wherein the third carbon source gas is methane, and the first silicon source gas is silicon tetrachloride. The third carbon source gas of the second mixed gas is still the same methane as the first carbon source gas in the first mixed gas, so that the introduction of other element impurities can be further avoided, and after the step 2 is finished, the original carbon source gas in the deposition furnace is not required to be pumped out, and the gas source for depositing silicon carbide can be directly pumped in for carrying out the next chemical vapor deposition, so that the process of depositing the silicon carbide coating is further saved.
In an example, the second deposition auxiliary gas also includes argon and hydrogen, and a gas flow ratio of the argon to the hydrogen is 1: (0.8-2). The second deposition auxiliary gas H 2 And Ar acts as a diluent gas to disperse the reactive gas SiCl 4 And CH (CH) 4 The carbon source distribution is more uniform, the silicon carbide coating is more uniformly distributed, and H 2 The SiC coating growth can also be accelerated.
In the step 3 of the invention, when the silicon carbide coating is deposited outside the graphene film, a second deposition auxiliary gas is also introduced into the deposition furnace, wherein the second deposition auxiliary gas has the same components as the first deposition auxiliary gas, and the purity of the graphite base can be prevented from being influenced by the introduction of other element impurities as much as possible.
In an example, the flow rate of the argon in the second deposition auxiliary gas is 40L/min to 60L/min, for example: 40L/min, 45L/min, 50L/min, 55L/min, 60L/min.
In an example, the flow rate of the hydrogen gas in the second deposition auxiliary gas is 60L/min to 100L/min, for example: 60L/min, 65L/min, 70L/min, 75L/min, 80L/min, 85L/min, 90L/min, 95L/min, 100L/min.
In one example, the third pressure environment is 8kPa-12kPa (e.g., 8kPa, 9kPa, 10kPa, 11kPa, 12 kPa).
In one example, the third temperature-increasing treatment includes gradually increasing the temperature to 1100-1400 ℃ at a temperature-increasing rate of 3 ℃/min-10 ℃/min (e.g., 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min) and continuing to introduce the second deposition aid gas for 30min-60min.
In one example, the deposition time of the second chemical vapor deposition is 600min-800min.
In the method of the present invention, further comprising: step 4, carrying out post-treatment on the silicon carbide coating deposited in the step 3; specifically, the step 4 includes continuously introducing the mixed gas of argon and hydrogen into the silicon carbide coating obtained in the step 3 for 30-60 min.
In a third aspect, the invention provides a graphite susceptor prepared by the method of the second aspect of the invention.
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The method is used for preparing the graphite matrix composite coating.
(1) Vacuum heating: the graphite-based product is put in a CVD deposition furnace, the furnace body is closed, the pressure is pumped to 450Pa, the temperature is gradually increased to 1035 ℃ at the heating rate of 10 ℃/min, and the temperature is kept at 1035 ℃ for 30min.
(2) And (3) depositing a graphene transition layer: introducing 60L/min Ar and 40L/min H 2 Continuing for 30min, regulating pressure to 8000Pa, and starting to introduce 40L/min CH 4 And 40L/min C 2 H 2 ，CH 4 And C 2 H 2 Is deposited at 1035℃and 8000Pa at a molar ratio of 1:1300min, then stopping the CH 4 And C 2 H 2 。
(3) Deposition of silicon carbide coating: continuously introducing 60L/min Ar and 100L/min H 2 Gradually heating the temperature to 1200 ℃ at a heating rate of 10 ℃/min, and continuously introducing Ar and H 2 For 60min, maintaining the pressure at 8000Pa, and introducing SiCl 4 80L/min and CH 4 80L/min, continuing the reaction for 800min, and stopping the SiCl feeding 4 And CH (CH) 4 . Continuing to introduce Ar and H 2 60 After the min, the gas is stopped to be introduced, and the furnace is pumped to 450Pa.
(4) Vacuum cooling: gradually cooling to room temperature at a cooling rate of 15 ℃/min, and then introducing N 2 The pressure is regulated to normal pressure at 80L/min, and then the furnace is opened to take out the product. SEM images of the graphite substrate 1/graphene coating 2/major phase coating (silicon carbide coating) 3 were then observed, and as shown in fig. 4, the thicknesses of the graphene transition layer and the major phase silicon carbide coating were measured and calculated and recorded in table 1. The raman spectrum of the graphene transition layer of the above embodiment 1 is shown in fig. 3, and is obviously located at 1582 cm -1 G peak near and at 2700cm -1 The left and right G' peaks prove that a layer of graphene coating is generated on the surface of the graphite matrix.
Example 2 group
Example 2 the procedure of example 1 was followed except that the gas flow rates or molar ratios of the two carbon source gases in the first mixed gas were changed, specifically referring to table 1.
Example 3 group
Example 3 set was conducted with reference to example 1, except that the carbon source gas species of the first mixed gas were changed, specifically with reference to table 1.
Example 4
Example 4 was performed with reference to example 1, except that the second carbon source gas was not included in the first mixed gas, with specific reference to table 1.
Comparative example 1
Comparative example 1 was performed with reference to example 1, except that the graphene transition layer deposition was not performed, and the main phase silicon carbide coating was deposited directly on the graphite substrate, see in particular table 1.
Comparative example 2
Comparative example 2 was conducted with reference to example 1 except that the gas flow rates or molar ratios of the two carbon source gases in the first mixed gas were changed, specifically referring to table 1.
The graphite matrix composite coatings prepared in the above examples and comparative examples were subjected to tests for coating quality and bonding strength, and the test results were recorded in table 1, and the specific operation method is as follows:
(1) The number of cracks in the coating was tested by thermal shock experiments:
and judging through a thermal shock experiment, placing a sample into a muffle furnace at 400 ℃ for standing for 15min, then rapidly placing the sample into water for rapid cooling, repeating for a plurality of times until the silicon carbide coating cracks, and recording the test times when the cracks appear.
(2) Testing the bonding strength by a universal testing machine:
and (3) determining by a universal testing machine, bonding the silicon carbide coating of the outer coating of the graphite product on the universal testing machine by modified acrylic resin, then separating the silicon carbide coating from the graphite substrate by stretching, and recording tensile stress data.
TABLE 1
As can be obtained from table 1, the bonding strength of the graphite substrate and the silicon carbide coating can be greatly improved by introducing the graphene transition layer, and the method is a modification method with both economy and stability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The graphite base is characterized by comprising a graphite substrate, and a graphene transition layer and a main phase coating which are sequentially attached to the surface of the graphite substrate; the graphene transition layer contains graphene; the main phase coating contains silicon carbide.
2. The graphite susceptor of claim 1, wherein the graphene transition layer has a thickness of 0.02 μιη -50 μιη and the major phase coating has a thickness of 80 μιη -120 μιη;
and/or, the thickness ratio of the graphene transition layer to the main phase coating is 1: (2-500).
3. The graphite susceptor of claim 1 or 2, wherein the purity of graphene in the graphene transition layer is not less than 99.999%;
and/or the purity of the silicon carbide in the main phase coating is not lower than 99.999%.
4. A method of making the graphite susceptor of any one of claims 1-3, said method comprising the steps of:
step 1, pretreating a graphite substrate in a deposition furnace;
step 2, depositing a graphene transition layer on the surface of the graphite matrix by adopting a chemical vapor deposition process;
and 3, adopting a chemical vapor deposition process to deposit a silicon carbide coating outside the graphene transition layer formed in the step 2.
5. The method of claim 4, wherein said step 1 comprises: under a first pressure environment, carrying out first heating treatment on the graphite matrix;
preferably, the first pressure environment is 50Pa-500Pa;
preferably, the first temperature-raising treatment includes gradually raising the temperature to 800 ℃ to 1100 ℃ at a temperature-raising rate of 3 ℃/min to 10 ℃/min, and preserving the temperature for 10min to 60min.
6. The method of claim 4, wherein said step 2 comprises: introducing a first deposition auxiliary gas into the deposition furnace, performing second heating treatment under a second pressure environment, and introducing a first mixed gas into the deposition furnace to enable the first mixed gas to perform first chemical vapor deposition on the surface of the graphite substrate so as to form a graphene transition layer; the first mixed gas comprises first carbon source gas, and the first carbon source gas is methane;
preferably, the first deposition auxiliary gas includes argon and hydrogen, and a gas flow ratio of the argon to the hydrogen is 1: (0.1-10);
preferably, the second pressure environment is 5kPa to 10kPa;
preferably, the second heating treatment comprises continuously introducing the first deposition auxiliary gas for 10min-300min in a temperature environment of 600 ℃ to 1800 ℃;
preferably, the deposition time of the first chemical vapor deposition is 150min-600min.
7. The method of claim 6, wherein the first mixed gas further comprises a second carbon source gas that is one or a combination of several of propane, butane, ethylene, propylene, acetylene, or cyclopropane;
and/or, the gas flow ratio of the first carbon source gas to the second carbon source gas is 1: (0.5-3);
and/or the molar ratio of the first carbon source gas to the second carbon source gas is 1: (0.5-3).
8. The method of claim 4, wherein the step 3 comprises: introducing a second deposition auxiliary gas into the deposition furnace, performing third heating treatment under a third pressure environment, and introducing a second mixed gas into the deposition furnace to enable the second mixed gas to perform second chemical vapor deposition on the graphene transition layer to form a silicon carbide transition layer; the second mixed gas comprises a third carbon source gas and a first silicon source gas, wherein the third carbon source gas is methane, and the first silicon source gas is silicon tetrachloride;
preferably, the second deposition auxiliary gas includes argon and hydrogen, and a gas flow ratio of the argon to the hydrogen is 1: (0.8-2);
preferably, the third pressure environment is 8kPa-12kPa;
preferably, the third heating treatment comprises gradually heating to 1100-1400 ℃ at a heating rate of 3-10 ℃/min, and continuously introducing the second deposition auxiliary gas for 30-60 min;
preferably, the deposition time of the second chemical vapor deposition is 600min-800min.
9. The method of claim 4, wherein the method further comprises: step 4, carrying out post-treatment on the silicon carbide coating deposited in the step 3;
preferably, the step 4 includes continuously introducing argon and hydrogen for 30min-60min.
10. A graphite susceptor prepared by the method of any one of claims 4-9.
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| CA2877898A1 (en) * | 2012-06-25 | 2014-01-03 | The Ohio State University | Covalently-bonded graphene coating and its applications thereof |
| CN103570378A (en) * | 2012-08-01 | 2014-02-12 | 苏州宏久航空防热材料科技有限公司 | Method for direct deposition of silicon carbide (SiC) coating on carbon material surface in graphite heat-generating body heating furnace |
| CN105503266A (en) * | 2015-12-25 | 2016-04-20 | 苏州宏久航空防热材料科技有限公司 | Method for preparing SiC coating on graphite thermal field surface |
| CN114368982A (en) * | 2022-01-21 | 2022-04-19 | 巩义市泛锐熠辉复合材料有限公司 | Silicon carbide coating graphite base and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2877898A1 (en) * | 2012-06-25 | 2014-01-03 | The Ohio State University | Covalently-bonded graphene coating and its applications thereof |
| CN103570378A (en) * | 2012-08-01 | 2014-02-12 | 苏州宏久航空防热材料科技有限公司 | Method for direct deposition of silicon carbide (SiC) coating on carbon material surface in graphite heat-generating body heating furnace |
| CN105503266A (en) * | 2015-12-25 | 2016-04-20 | 苏州宏久航空防热材料科技有限公司 | Method for preparing SiC coating on graphite thermal field surface |
| CN114368982A (en) * | 2022-01-21 | 2022-04-19 | 巩义市泛锐熠辉复合材料有限公司 | Silicon carbide coating graphite base and preparation method thereof |
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