WO2019182306A1 - Procédé de revêtement de matériau de base en graphite à l'aide d'un procédé de revêtement hybride - Google Patents

Procédé de revêtement de matériau de base en graphite à l'aide d'un procédé de revêtement hybride Download PDF

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WO2019182306A1
WO2019182306A1 PCT/KR2019/003103 KR2019003103W WO2019182306A1 WO 2019182306 A1 WO2019182306 A1 WO 2019182306A1 KR 2019003103 W KR2019003103 W KR 2019003103W WO 2019182306 A1 WO2019182306 A1 WO 2019182306A1
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silicon carbide
silicon
base material
coating
graphite
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PCT/KR2019/003103
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English (en)
Korean (ko)
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김석진
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주식회사 카보넥스
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Publication of WO2019182306A1 publication Critical patent/WO2019182306A1/fr

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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
    • C23C16/02—Pretreatment of the material to be coated
    • 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
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising

Definitions

  • the present invention relates to a graphite substrate coating method using a hybrid coating method, when forming a silicon carbide coating layer on the surface of the graphite substrate, to a graphite substrate coating method using a hybrid coating method for preventing cracking, peeling, etc. will be.
  • quartz-based components or graphite-based components are used in LED organometallic chemical vapor deposition equipment.
  • quartz or graphite materials may cause foreign matters at the deposition temperature of organometallic chemical vapor deposition equipment, causing a decrease in yield, or because the deposition of GaN on the surface requires frequent cleaning, so that the process is frequently interrupted. There was a problem of deterioration.
  • Examples of such techniques may be exemplified by Korean Patent Registration No. 10-0951633 and Korean Patent Application Publication No. 10-2011-0041920.
  • a method of depositing and coating SiC over a material such as graphite is known, and there are many advantages such as increasing chemical resistance, heat resistance, and increasing strength.
  • the present invention when a single silicon carbide (SiC) layer is formed on the graphite surface by a CVD process, the present invention is devised to prevent cracking due to thermal shock, and a hybrid coating method is used to double the inside and the outside of the graphite substrate.
  • the present invention provides a method of coating high quality silicon carbide on a graphite substrate by forming a silicon carbide (SiC) layer.
  • the present invention is to be applied to a semiconductor process for manufacturing a component having a silicon carbide coating layer.
  • the present invention provides a graphite substrate coating method using a novel hybrid coating method that can economically form a high-quality silicon carbide coating layer by a simplified process using a simpler equipment and a safe raw material on the graphite substrate material It is in a ship.
  • the coating method of the graphite base material using a hybrid coating method comprises the steps of: a) supporting a solid silicon on a porous carrier; b) preparing a first silicon carbide coating layer by loading a graphite base material for coating in a vacuum chamber and a porous carrier on which the solid silicon is loaded, and then performing heat treatment at 1,400 to 2,000 ° C .; And c) depositing a second silicon carbide coating layer on the first silicon carbide coating layer through chemical vapor deposition.
  • the step a) may be performed by loading the solid silicon on top of the porous carrier and then performing heat treatment.
  • the solid silicon may be loaded in the form of powder, particles, flakes or chunks.
  • the porous carrier may be any one or two or more selected from graphite, aluminum nitride, and silicon carbide.
  • the pore diameter of the porous carrier may be from 0.001 to 1 mm.
  • the porosity of the porous carrier may be 10 to 60%.
  • the first silicon carbide coating layer may have a thickness of 10 to 200 ⁇ m.
  • step b) the silicon gas discharged from the porous carrier, the gas distribution mounted between the porous carrier and the graphite base material In contact with the plate, it may be to spread evenly into the vacuum chamber.
  • the graphite substrate coating method using the hybrid coating method according to the present invention can prevent cracks due to thermal shock when a single silicon carbide (SiC) layer is formed on the graphite surface using a conventional CVD process.
  • SiC silicon carbide
  • the present invention can coat the silicon carbide on the graphite base material by simply placing the substrate and silicon in the vacuum chamber and simply heat-treating, there is little coating parameter using the equipment of simple structure, and the silicon carbide coating layer economically with excellent reproducibility by a simple process. Can be formed.
  • FIG. 1 is a schematic diagram showing a coating method of a graphite base material using a hybrid coating method according to an embodiment of the present invention
  • Figure 2 is a photograph of the equipment used in the graphite substrate coating method using a hybrid coating method according to an embodiment of the present invention
  • FIG 3 is a schematic view of forming a second silicon carbide layer through a CVD process after forming a first silicon carbide layer on the surface of the graphite base material using a silicon powder, without supporting the silicon on the porous carrier,
  • FIG 4 is an XRD graph of a first silicon carbide coating layer according to an embodiment of the present invention.
  • FIG. 5 is an SEM cross-sectional image of a graphite matrix base material on which a first silicon carbide coating layer is formed according to an embodiment of the present invention
  • FIG. 6 is an SEM cross-sectional image and an EDS spectrum of a graphite matrix base material on which a first silicon carbide coating layer and a second silicon carbide coating layer are formed according to an embodiment of the present invention
  • FIG. 7 is an SEM cross-sectional image and an EDS spectrum of the second silicon carbide coating layer of FIG. 6.
  • FIG. 8 is a photograph after applying a graphite base material having a silicon carbide layer formed only on a surface of the graphite base material through a CVD process to a semiconductor process as a silicon wafer carrier,
  • FIG. 9 is a photograph after applying a graphite base material on which a first and a second silicon carbide layer is formed using silicon powder as a silicon wafer carrier in a semiconductor process without supporting silicon on a porous carrier.
  • the term "hybrid coating method” means to form a coating layer using two or more coating methods when coating on the coating material.
  • the hybrid coating method includes a chemical vapor infiltration reaction (CVIR) in which a silicon source penetrates into pores of the graphite surface to form a buffer layer inside the graphite surface, and the silicon and the coating material on which the buffer layer is formed.
  • CVIR chemical vapor infiltration reaction
  • One example is the use of chemical vapor deposition, which supplies a source of carbon in a gaseous state to form a silicon carbide layer on the surface of the material to be coated.
  • the silicon source when performing the chemical vapor deposition method, may be a silicon metal, that is, a solid silicon (hereinafter referred to as solid silicon), and when performing the chemical vapor deposition method, as a source of silicon and carbon CH 3 SiCl 3 , (CH 3 ) 2 SiCl 2 , (CH 3 ) 3 SiCl, SiCl 4 and the like can be used.
  • the solid silicon has a melting point of about 1400 ° C. and a boiling point of about 3200 ° C. at room temperature, but the melting point and the boiling point of the solid silicon are lowered.
  • the solid silicon when heat-treated at about 1400 °C to 2000 °C in a vacuum atmosphere lower than atmospheric pressure, the solid silicon is evaporated to the silicon gas through the liquid state.
  • the silicon gas may react with the porous graphite material to form a coating layer inside the surface of the graphite base material.
  • the coating layer may have an ⁇ -SiC, ⁇ -SiC crystal structure, but the present invention is not limited to the crystal structure.
  • the method of coating a graphite base material using a hybrid coating method includes the steps of: a) supporting solid silicon on a porous carrier; b) preparing a first silicon carbide coating layer by loading a graphite base material for coating in a vacuum chamber and a porous carrier on which the solid silicon is loaded, and then performing heat treatment at 1,400 to 2,000 ° C .; And c) depositing a second silicon carbide coating layer on the first silicon carbide coating layer through chemical vapor deposition.
  • the heat treatment temperature is less than 1,400 ° C., the amount of silicon gas generated from the porous carrier is insignificant. 1 Silicon carbide coating layer is difficult to manufacture.
  • the heat treatment temperature is greater than 2,000 ° C., the silicon component may be evaporated from the first silicon carbide coating layer, so that it is difficult to form a silicon carbide (SiC) layer having a uniform thickness inside the graphite matrix.
  • the heat treatment temperature is preferably 1,400 to 2,000 ° C to achieve the desired effect of the present invention.
  • step c) it is possible to deposit the second silicon carbide coating layer at 500 to 1,400 °C.
  • step c) when the temperature is less than 500 ° C., it is difficult to deposit a second silicon carbide coating layer on the first silicon carbide coating layer, and when the temperature is higher than 1400 ° C., silicon remaining in the first silicon carbide coating layer may be formed. Evaporation may occur, so that interlayer separation may occur on the surface of the graphite by the evaporated silicon during the step c).
  • FIGS. 1 and 2 a coating method of a graphite base material using a hybrid coating method according to an embodiment of the present invention will be described in detail.
  • FIG. 1 is a schematic diagram showing a method for coating a graphite base material using a hybrid coating method according to an embodiment of the present invention
  • Figure 2 is used in the method for coating a graphite base material using a hybrid coating method according to an embodiment of the present invention Of the equipment being photographed.
  • the silicon carbide generated inside the graphite matrix through the chemical vapor deposition method.
  • Forming a new second silicon carbide coating layer on the layer is characterized in that the silicon carbide layer is formed in both directions based on the graphite surface of the base material as shown in FIG.
  • the silicon carbide coating is a silicon carbide raw material to supply a silicon source and a carbon source together to form a silicon carbide coating layer on the surface of the base material, in which case the interface properties between the base material and the coating layer is not easy to bond to the coating layer, or If the surface roughness is not uniform, there is a problem that the roughness of the surface of the base material after coating.
  • the present invention deposits silicon on the inner surface of the graphite substrate to form a first silicon carbide coating layer by reacting carbon and silicon on an outer surface layer of the graphite substrate to form a second silicon carbide coating layer through an additional process.
  • the coating method of the graphite base material using a hybrid coating method the first step of supporting the solid silicon on the porous carrier; A second step of loading a graphite base material on a jig provided in the vacuum chamber and loading a porous carrier on which the solid silicon is loaded in a container provided on the bottom of the jig; A third step of heating the inside of the vacuum chamber to 1,400 ° C. to 2,000 ° C.
  • the silicon carbide coating layer is formed on the graphite base material by controlling only the vacuum degree and the heat treatment temperature of the vacuum chamber using a simple equipment of a vacuum chamber capable of heat treatment. It is possible to do
  • the vacuum degree of the vacuum chamber is 10 -2 to 10 -7 Torr to achieve the effect aimed at in the present invention.
  • a vacuum chamber provided with a heater (heating element) so as to heat the inside of the vacuum chamber.
  • the first step of supporting the solid silicon on the porous carrier described above, after loading the solid silicon on top of the porous carrier The heat treatment may be performed in a vacuum atmosphere.
  • the vacuum atmosphere may be an atmosphere in which the internal pressure is controlled to 10 -2 to 10 -7 Torr, the heat treatment temperature may be 1200 to 1400 °C.
  • the solid silicon may be uniformly loaded into the micropores of 0.01 mm or less as well as the macropores of 0.1 mm or more of the porous carrier. Accordingly, in the fourth and fifth steps, since the silicon gas is finely supplied in a predetermined amount, the first silicon carbide coating layer may be uniformly formed into the graphite base material.
  • the solid silicon may not melt and may not penetrate into the above-described porous carrier. Accordingly, in the fourth and fifth steps, the silicon gas is excessively supplied to form a non-uniform first silicon carbide coating layer, or there is a problem in that the coating is not performed because the amount of raw material for forming the coating layer is insufficient.
  • the solid silicon is preferably in the form of powder, particles, or chunks having a large surface area so that melting and evaporation of the solid silicon can occur efficiently.
  • the particle size of the solid silicon may be about 0.1 to 100 ⁇ m.
  • the solid silicon when the solid silicon is heated in the vacuum chamber while being loaded in the porous carrier, the solid silicon is melted and evaporated to provide a silicon source gas for forming a silicon carbide coating layer. do.
  • the silicon gas is very non-uniform in the space in the chamber when adsorbed to the above-mentioned graphite matrix, and forms a cluster in the vapor state to form a surface of the matrix.
  • the coating layer adsorbed on the non-uniform is very non-uniform.
  • the solid silicon is supported on a carrier of a porous material which is stable at the heat treatment temperature.
  • the support of the solid silicon on the porous carrier may be achieved by immersing the porous carrier in hot liquid silicon to absorb the silicon into the voids.
  • the silicon supported in the carrier is present as solid silicon in the pores, but when the temperature rises in the vacuum chamber, it is present as microdroplets of the same size as the pores and then evaporates. Therefore, even though the silicon supported in the carrier is melted, the surface area is evaporated to the maximum state, so the supply of silicon gas is made efficiently, and since the supply of gas is also diverged through the pores, the silicon is dispersed in a dispersed state rather than a cluster. It is effective to be evenly adsorbed on the graphite base material.
  • the solid silicon loaded on the porous carrier has a porous structure at the bottom of the silicon as the silicon dissolves when the temperature rises in the vacuum chamber during the coating of the silicon carbide for the silicon carbide coating. It fills the pores of the carrier.
  • the silicon gas is diverged through the pores of the porous carrier, so that uniform silicon carbide coating is possible.
  • the carrier may be made of graphite, aluminum nitride or silicon carbide stable at the coating temperature.
  • the diameter of the pores of the carrier having a porous structure is preferably 0.001 to 1 mm. If the pore size is too small, less than 0.001 mm, it is difficult to form the first silicon carbide coating layer due to inefficiency of silicon gas dissipation in the step 4, and if the pore size is greater than 1 mm, the pore size is too large. There is a problem in that the excessive supply of silicon gas to form a non-uniform first silicon carbide coating layer.
  • the first silicon carbide layer is formed on the graphite matrix through melting and dissipation using silicon powder, and then an additional process is performed.
  • the second silicon carbide layer is formed through the silicon carbide layer, the thickness of the silicon carbide layer is not constant within the graphite matrix, so that a tensile force is generated due to a difference in thermal expansion rate between the silicon carbide and the graphite on the graphite surface when the semiconductor process is applied at high temperature and low pressure. This can happen.
  • the porosity of the carrier is 10 to 60%. If the porosity is too small, less than 10%, the amount of silicon that can be supported on the carrier decreases, so that the divergence during the third step is not sufficient. If the porosity is too large, more than 60%, there is a problem that the durability of the carrier is lowered.
  • the first silicon carbide coating layer and the second silicon carbide coating layer may have the same crystal structure independently of each other.
  • the thickness of the first silicon carbide coating layer preferably has a thickness of 10 to 200 ⁇ m, if less than 10 ⁇ m thickness it is difficult to prevent the cracks of the surface of the base material due to the difference in thermal expansion coefficient, if the thickness exceeds 200 ⁇ m The use of excess silicon is not economical and is undesirable since the coating process time is greatly increased to form the thickness.
  • the thickness of the second silicon carbide coating layer is not necessarily limited, but is formed to a thickness of about 10 to 30 ⁇ m is good for improving the surface strength of the above-mentioned graphite base material, excessive thickness is a problem of dimensional defects, thickness nonuniformity, etc. May cause.
  • the above-described chemical vapor deposition method for depositing the second silicon carbide coating layer is preferable to use the above-described chemical vapor deposition method for depositing the second silicon carbide coating layer.
  • Chemical vapor deposition is sufficient if the method commonly used in this field, the working temperature when performing the chemical vapor deposition, that is, the temperature inside the chamber may be 500 to 1,400 °C.
  • the second silicon carbide coating layer may be deposited by injecting a mixed gas including a source of silicon and carbon, an inert gas, and a reducing gas into the reaction chamber when performing the chemical vapor deposition method.
  • the source of silicon and carbon CH 3 SiCl 3 , (CH 3 ) 2 SiCl 2 , (CH 3 ) 3 SiCl, SiCl 4 and the like may be used, but is not limited thereto.
  • the inert gas may be, for example, argon (Ar), neon (Ne), helium (He) or nitrogen (N 2 ), and the reducing gas may be, for example, hydrogen (H 2 ) or ammonia (NH 3 ), or the like. have.
  • the flow rate ratio of the mixed gas may inject 5 to 15 sccm of inert gas and 10 to 30 sccm of reducing gas with respect to 1 sccm of the source of silicon and carbon.
  • the flow rate of the mixed gas needs to be selected to an appropriate value according to the volume of the CVD furnace used and the thickness of the second silicon carbide coating layer to be deposited.
  • the present invention when performing the fourth step, it is possible to use a gas distributor (distributer) provided in the vacuum chamber separately.
  • the silicon gas discharged from the porous carrier may be brought into contact with a gas distribution plate mounted between the porous carrier and the graphite base material to uniformly spread the inside of the vacuum chamber.
  • the gas distribution plate may be disposed between the porous carrier and the graphite base material, and may have a structure capable of covering the solid silicon and the porous carrier.
  • the gas distribution plate may be installed below the jig.
  • the gas distribution plate serves to spread the silicon gas derived from the solid silicon uniformly in the chamber by forming small holes artificially or naturally.
  • the silicon carbide coating can be made quickly and uniformly by inducing dispersion of the silicon gas in the chamber, and in this case, it may partially replace the function of the carrier of the porous material.
  • the hole size and shape of the gas distribution plate and the distance between the holes can be variously designed in consideration of the shape and distance of the base material to be coated, the distance from the solid silicon, the distance from the carrier, and the size of the chamber. The size can be adjusted between 0.05 and 10 mm.
  • the first silicon carbide coating layer was formed inside the graphite base material at 10 ⁇ 6 Torr and 1800 ° C. while the silicon flakes, which were solid silicon, were supported on the carrier.
  • the gas of any one of SiCl 2 , SiH 2 , tetramethyldisiloxane (TMDSO), and hexamethyldisiloxane (HMDSO) and CH 4 was deposited at 900 ° C. using a gas of any one of C 3 H 4 , and CCl 4 .
  • FIG. 4 is an XRD graph of the first silicon carbide coating layer
  • FIG. 5 is an SEM cross-sectional image of a graphite base material on which the first silicon carbide coating layer is formed
  • FIG. 6 is formed of the first silicon carbide coating layer and the second silicon carbide coating layer.
  • Figure 7 is a SEM cross-sectional image and the EDS spectrum of the second silicon carbide coating layer of FIG.
  • the first silicon carbide coating layer having an ⁇ -SiC crystal structure is formed inside the surface of the graphite base material.
  • the first silicon carbide coating layer penetrates into the graphite base material to form a uniform layer.
  • the thickness of the first silicon carbide coating layer is about 100 ⁇ m.
  • the first silicon carbide coating layer penetrates up to about 200 ⁇ m into the surface of the graphite base material, and a second silicon carbide coating layer having a thickness of about 20 ⁇ m is formed outside the surface of the graphite base material. It can be seen that.
  • the second silicon carbide coating layer does not show fine cracks and layer separation, and may be formed outside the surface of the graphite base material with a uniform thickness.
  • FIG. 8 is a photograph after applying a graphite base material having a silicon carbide layer formed on the surface of the graphite base material only through a CVD process to a semiconductor process as a silicon wafer carrier.
  • the product coated with silicon carbide only by the CVD process when a micro crack occurs during the semiconductor process, as shown in Figure 8 (a), the graphite component of the lower part of the silicon carbide layer through the hole is the upper part of the graphite substrate
  • the fine cracks continue to be discharged into the fine particles, resulting in large holes in which the microcracks are expanded as shown in FIG. If the hole is formed on the back surface of the product made of the graphite base material or on the hard-to-find part during the semiconductor process, there is a problem that the yield of unknown cause and quality problems are continuously generated.
  • the method of coating a graphite base material using the hybrid coating method according to the present invention has a first silicon carbide layer under the second silicon carbide layer made by the CVD process, even though the second silicon carbide on the surface of the product due to excessive use Even if micro cracks occur in the layer, the above-mentioned problems are fundamentally solved, and thus, an amazing effect of stabilizing the product quality and extending the lifespan can be expected.
  • FIG. 9 is a photograph after applying a graphite base material on which a first and a second silicon carbide layer is formed using silicon powder without a silicon on a porous carrier to a semiconductor process as a silicon wafer carrier.
  • a tensile force is generated due to a difference in silicon carbide and thermal expansion coefficient of the graphite substrate graphite surface in that it undergoes harsh semiconductor processes such as high temperature / high pressure or high temperature / low pressure.
  • defects such as layer separation (FIG. 9 (a) red dotted circle) or fine cracks (FIG. 9 (b) red dotted circle) of the silicon carbide of the graphite matrix were confirmed.
  • the graphite base material having the silicon carbide layer of the present invention prepared by forming the first silicon carbide on the inner surface layer of the graphite base material by using the porous carrier on which the silicon of the present invention is formed, and then forming the second silicon carbide layer Since the graphite base material and the silicon carbide layer are integrated, it was confirmed that there is almost no defect rate even when applied to the semiconductor process.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un procédé de revêtement de carbure de silicium pouvant former de manière économique une couche de revêtement de carbure de silicium de haute qualité sur un matériau de base en graphite par un procédé simple utilisant un équipement ayant une structure plus simple et des matières premières plus sûres. Plus spécifiquement, le procédé de revêtement de carbure de silicium comprend : a) une étape de support de silicium solide sur un support poreux; b) une étape de préparation d'une première couche de revêtement de carbure de silicium par chargement, dans une chambre à vide, d'un matériau de base en graphite pour le revêtement et le support poreux sur lequel du silicium solide est supporté, puis par traitement à chaud de ceux-ci à une température de 1 400 °C à 2 000 °C; et c) une étape de dépôt d'une seconde couche de revêtement de carbure de silicium sur le dessus de la première couche de revêtement de carbure de silicium par l'intermédiaire d'un procédé de dépôt chimique en phase vapeur.
PCT/KR2019/003103 2018-03-19 2019-03-18 Procédé de revêtement de matériau de base en graphite à l'aide d'un procédé de revêtement hybride WO2019182306A1 (fr)

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Application Number Priority Date Filing Date Title
KR1020180031595A KR102103573B1 (ko) 2018-03-19 2018-03-19 하이브리드 코팅법을 이용한 그라파이트 모재의 코팅방법
KR10-2018-0031595 2018-03-19

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WO2019182306A1 true WO2019182306A1 (fr) 2019-09-26

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