CN112647055B - Chemical vapor deposition method for preparing silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon - Google Patents
Chemical vapor deposition method for preparing silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon Download PDFInfo
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- 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
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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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
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- 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
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
Abstract
The invention belongs to the field of coating preparation, and particularly relates to a chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon. Selecting liquid raw materials of Hexamethyldisilane (HMDS) or Hexamethyldisiloxane (HMDSO), H by using a Metal Organic Chemical Vapor Deposition (MOCVD) system2And an Ar gas system, wherein the working pressure is 10-1000 Pa, and the temperature is 900-1350 ℃. Before the coating is deposited, the monocrystalline silicon or polycrystalline silicon substrate is pretreated to form a porous silicon layer, then the coating is deposited on the porous silicon layer, and the composite coating sequentially comprises the porous silicon layer, a buffer layer, an SiOC layer and a pure SiC layer from the Si substrate. The silicon carbide composite coating deposited by the method has the characteristics of compact structure, no obvious crack, good combination with a matrix and the like. The composite coating designed by the invention skillfully coordinates the stress matching problem of the SiC coating and the Si substrate, and the thickness of the composite coating prepared by the method can exceed 1.5 mm.
Description
Technical Field
The invention belongs to the technical field of coating preparation, and particularly relates to a chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon.
Background
Dry etching is the main technical route for chip manufacture, and commonly used etching gas comprises SF6、CF4、C4F8And O2And the like. In the etching process, the fluorine-containing gas mainly has the function of obtaining fluorine ions through ionization, and the fluorine ions and silicon atoms in the silicon carbide substrate are subjected to chemical reaction to generate SiF4Gas and effect etching of silicon atoms. At present, since silicon wafer stages are also mostly made of silicon materials, effective protection needs to be performed on the silicon materials in order to prolong the service life of the stages.
The silicon carbide material has the advantages of large forbidden band width, high breakdown electric field intensity, high inertia, high thermal conductivity and high carrier saturation speed, and is an ideal coating material for the protection field. The chemical vapor deposition method for preparing the silicon carbide coating has incomparable characteristics compared with other methods, such as: high density, high thermal conductivity, high modulus of elasticity, and excellent polishing performance, but it is very difficult to prepare thicker silicon carbide coatings.
The growth of silicon carbide on a silicon substrate produces significant stress, the lattice constants of silicon and silicon carbide being different, the lattice constant of silicon being
Silicon carbide has a lattice constant of
The lattice mismatch rate reaches 19.7 percent. In addition, the stress field will also be generated by the difference of the thermal expansion coefficients of silicon and silicon carbide, which are 2.77 x 10 at room temperature-6K-1And 2.57X 10-6K-1The coefficient of thermal expansion mismatch is about 8% and reaches 20% at growth temperature. Thus, the silicon carbide epitaxial layer may form a large number of defects at the SiC/Si interface for relieving residual stress, such as: stacking Faults (SFs), microtrens, antiphase boundaries (APBs), Protrusions (Protrusions), etc., stress relief can lead to cracking of the coating, and poor bonding of the coating to the substrate.
At present, a common method for preparing a SiC coating on a silicon substrate is to consider adding a buffer layer, namely, before introducing silicon source gas, only carbon source gas is introduced, Si atoms are provided by a Si substrate, so that a very thin SiC buffer layer is arranged on the surface of the Si substrate, and then the SiC coating is deposited. In order to deposit thicker SiC coatings, methods for releasing more stress need to be considered, and millimeter-scale SiC coatings can be deposited by adopting a method of combining a flexible substrate and a buffer layer.
Disclosure of Invention
The invention aims to provide a chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon, which solves the problem of poor bonding between the coating and a substrate caused by mismatched thermal expansion coefficients and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chemical vapor deposition method for preparing silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon adopts HMDSO/HMDS-H2An Ar system, wherein a porous silicon layer, an SiOC buffer layer, an SiOC layer and a pure SiC layer composite coating are sequentially prepared on a silicon substrate; the method comprises the following steps:
(1) preparing porous silicon layer on silicon substrate, and introducing H2And Ar, H2The flow of the gas is 100-1000 sccm, the flow of Ar is 1000-6000 sccm, the etching temperature interval is 900-1350 ℃, the working pressure is 10-1000 Pa, and the etching time is 5 min-1 h;
(2) depositing an SiOC buffer layer on the porous silicon layer, wherein the flow rate of the HMDSO liquid is 0.3-1 g/min, and H2The flow rate of the deposition solution is 100-1000 sccm, the flow rate of Ar is 1000-6000 sccm, the deposition temperature is 1025-1150 ℃, the working pressure is 100-1000 Pa, and the deposition time is 0.5-1 h;
(3) depositing an SiOC layer on the SiOC buffer layer, wherein the flow rate of the HMDSO liquid is 0.3-2 g/min, H2The flow of the deposition solution is 100-1000 sccm, the flow of Ar is 1000-6000 sccm, the deposition temperature is 900-1350 ℃, the working pressure is 10-1000 Pa, and the deposition time is 1-100 h;
(4) depositing a pure SiC coating on the SiOC layer, wherein the flow rate of the HMDS liquid is 0.3-2 g/min, and H2The flow rate of the deposition solution is 100-1000 sccm, the flow rate of Ar is 1000-6000 sccm, the deposition temperature is 900-1350 ℃, the working pressure is 10-1000 Pa, and the deposition time is 3-300 h.
The chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, HMDSO/HMDS-H2In the-Ar system, the purity of each component is 99% or more.
According to the chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, liquid raw materials HMDSO and HMDS are carried into the reaction cavity by Ar after being gasified.
In the chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, in the step (1), preferably, H2The flow rate of the organic silicon compound is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the etching temperature is 1050-1250 ℃, and the working pressure is 200-800 Pa.
In the chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, in the step (2), the preferred HMDSO liquid flow is 0.3-0.8 g/min, and H is2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1150 ℃, and the working pressure is 200-800 Pa.
In the chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, in the step (3), the preferred HMDSO liquid flow is 0.5-1.5 g/min, and H is2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1250 ℃, and the working pressure is 200-800 Pa.
In the chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon, in the step (4), the preferred HMDS liquid flow rate is 0.5-1.5 g/min, and H2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1250 ℃, and the working pressure is 200-800 Pa.
The chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon comprises the steps that the thickness of the porous silicon layer prepared in the step (1) is 10-20 mu m, the thickness of the SiOC buffer layer deposited in the step (2) is smaller than 2 mu m, the thickness of the SiOC layer deposited in the step (3) is controlled to be 50-350 mu m, and the thickness of the pure SiC coating deposited in the step (4) is larger than 1000 mu m.
The chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon has the advantages that the prepared composite coating is obviously layered, the total thickness is more than 1500 mu m, the surface of a pure SiC layer is smooth, the hardness is 25-35 GPa, and the Young modulus is 200-300 GPa.
The chemical vapor deposition method for preparing the silicon carbide composite coating on the monocrystalline silicon or the polycrystalline silicon has the advantages that the prepared composite coating is good in interface bonding, free of crack gaps and 30-35 MPa in bonding force.
The design idea of the invention is as follows:
the invention provides a method for preparing a silicon carbide composite coating on a monocrystalline silicon or polycrystalline silicon substrate by adopting a chemical vapor deposition process. Since the bond energy of Si-C bonds is second only to C-C bonds and B-N bonds, deposition of SiC on Si requires higher energy to form Si-C bonds, typically up to 1050 deg.C. Thus, the biggest difficulty is the interface stress caused by the difference between the crystal lattices and the thermal expansion coefficients of Si and SiC, which greatly limits the thickness of the SiC coating, and thus a buffer layer is required to relieve the stress.
In order to prepare a thicker SiC composite coating, the problem of bonding between the coating and a substrate is firstly considered, the thicker SiC coating and the substrate have higher stress and are easy to fall off. The silicon substrate is pretreated by adopting a flexible substrate method to form a porous silicon layer, the stress can be effectively released by adjusting the thickness of the porous silicon layer, meanwhile, the thicker SiC coating is further ensured to be deposited, a silicon oxycarbide (SiOC) buffer layer is deposited firstly, and the combination is enhanced.
The invention has the advantages and beneficial effects that:
(1) the coating solves the problem of poor interface bonding generated by stress release when SiC grows epitaxially on Si.
(2) The coating has compact structure, no holes, good internal combination and smooth surface.
(3) The invention can deposit the SiC composite coating with a larger thickness range on the Si substrate, the total thickness of the coating can exceed 1.5mm, and the coating has good protective performance.
(4) The coating and the matrix are well combined, no obvious cracks exist, and the binding force can reach 30 MPa.
Drawings
FIG. 1 is a schematic structural view of a porous Si layer.
FIG. 2 is a composite coating texture map.
The specific implementation mode is as follows:
in the concrete implementation process, the inventionThe invention adopts a Metal Organic Chemical Vapor Deposition (MOCVD) system to select liquid raw materials of Hexamethyldisilane (HMDS) and Hexamethyldisiloxane (HMDSO), H2And an Ar gas system, wherein the working pressure is 10-1000 Pa, and the temperature is 900-1350 ℃. Before the chemical vapor deposition coating, firstly, the monocrystalline silicon or polycrystalline silicon substrate is pretreated to form a porous silicon layer, then, the coating is deposited on the porous silicon layer, and the composite coating comprises the porous silicon layer, an SiOC buffer layer, an SiOC layer and a pure SiC layer in sequence from the Si substrate.
The present invention will be explained in further detail below by way of examples and figures.
Example 1:
in this example, the chemical vapor deposition method for preparing the silicon carbide composite coating on the single crystal silicon is as follows:
(1) ultrasonically cleaning a monocrystalline silicon substrate in deionized water and acetone for 5min respectively, then cleaning the monocrystalline silicon substrate in hydrofluoric acid with the concentration of 5 wt% for 10min, and placing the silicon substrate in a reaction cavity;
(2) preparing porous silicon layer on silicon substrate, and introducing H2And Ar, H2The flow rate is 200sccm, the Ar flow rate is 1500sccm, the etching temperature is 1200 ℃, the working pressure is 200Pa, the etching time is 30min, and the thickness of the porous silicon layer is 24.5 mu m, which is shown in figure 1;
(3) depositing a thin SiOC buffer layer on the porous Si layer, the HMDSO liquid flow being 0.3g/min, H2The flow rates of Ar and Ar are respectively 200sccm and 3000sccm, the deposition temperature is 1050 ℃, the working pressure is 300Pa, the deposition time is 30min, and the thickness of the buffer layer is 1.5 mu m;
(4) depositing a SiOC layer on the buffer layer, the liquid flow of HMDSO being 0.5g/min, H2The flow rates of Ar and Ar are respectively 200sccm and 3000sccm, the deposition temperature is 1100 ℃, the working pressure is 200Pa, the deposition time is 10h, and the thickness of the SiOC layer can exceed 250 mu m;
as shown in fig. 2, in the composite coating layer prepared in this example, the thickness of the porous silicon layer and the SiOC buffer layer was 26 μm, and the thickness of the SiOC layer was 83 μm.
(5) Depositing a pure SiC coating on the SiOC layer, the HMDS liquid flow being 0.8g/min, H2At a flow rate of 20The flow rate of Ar is 0sccm, the flow rate of Ar is 3000sccm, the deposition temperature is 1150 ℃, the working pressure is 300Pa, the deposition time is 100h, and the thickness of the pure SiC coating is 1.5 mm.
In the embodiment, the prepared composite coating has obvious layering, the total thickness is more than 1500 mu m, the surface of the pure SiC layer is smooth, the hardness can reach 30GPa, and the Young modulus can reach 280 GPa. The composite coating has good combination at the interface, no crack and no crack gap, and the combination force can reach 35 MPa.
Example 2:
in this embodiment, the chemical vapor deposition method for preparing the silicon carbide composite coating on the polysilicon is as follows:
(1) respectively ultrasonically cleaning a polycrystalline silicon substrate in deionized water and acetone for 10min, then cleaning the polycrystalline silicon substrate in hydrofluoric acid with the concentration of 5 wt% for 15min, and placing the polycrystalline silicon substrate in a reaction cavity;
(2) preparing porous silicon layer on silicon substrate, and introducing H2And Ar, H2The flow rate is 300sccm, the Ar flow rate is 3000sccm, the etching temperature is 1250 ℃, the working pressure is 400Pa, the etching time is 15min, and the thickness of the porous silicon layer is 12.5 mu m;
(3) depositing a thin SiOC buffer layer on the porous Si layer, the HMDSO liquid flow being 0.6g/min, H2The flow rates of Ar and Ar are respectively 500sccm and 5000sccm, the deposition temperature is 1100 ℃, the working pressure is 600Pa, the deposition time is 40min, and the thickness of the buffer layer is 1.8 mu m;
(4) depositing a SiOC layer on the buffer layer, the liquid flow of HMDSO being 0.8g/min, H2The flow rates of Ar and Ar are respectively 400sccm and 4000sccm, the deposition temperature is 1150 ℃, the working pressure is 400Pa, the deposition time is 20h, and the thickness of the SiOC layer is 312 mu m;
(5) depositing a pure SiC coating on the SiOC layer, the HMDS liquid flow being 1.2g/min, H2The flow rate of the pure SiC coating is 200sccm, the flow rate of Ar is 2000sccm, the deposition temperature is 1200 ℃, the working pressure is 600Pa, the deposition time is 150h, and the thickness of the pure SiC coating is 2.1 mm.
In the embodiment, the prepared composite coating has obvious layering, the total thickness is more than 1500 mu m, the surface of the pure SiC layer is smooth, the hardness can reach 25GPa, and the Young modulus can reach 300 GPa. The composite coating has good combination at the interface, no crack and no crack gap, and the combination force can reach 30 MPa.
The results of the examples show that the silicon carbide composite coating deposited by the method has the characteristics of compact structure, no obvious cracks, good combination with the matrix and the like. The composite coating designed by the invention skillfully coordinates the stress matching problem of the SiC coating and the Si substrate, and the thickness of the composite coating prepared by the method can exceed 1.5 mm.
Claims (7)
1. A chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon is characterized in that HMDSO/HMDS-H is adopted2An Ar system, wherein a porous silicon layer, an SiOC buffer layer, an SiOC layer and a pure SiC layer composite coating are sequentially prepared on a silicon substrate; the method comprises the following steps:
(1) preparing porous silicon layer on silicon substrate, and introducing H2And Ar, H2The flow of the gas is 100-1000 sccm, the flow of Ar is 1000-6000 sccm, the etching temperature range is 900-1350 ℃, the working pressure is 10-1000 Pa, and the etching time is 5 min-1 h;
(2) depositing an SiOC buffer layer on the porous silicon layer, wherein the flow rate of the HMDSO liquid is 0.3-1 g/min, and H2The flow rate of the deposition solution is 100-1000 sccm, the flow rate of Ar is 1000-6000 sccm, the deposition temperature is 1025-1150 ℃, the working pressure is 100-1000 Pa, and the deposition time is 0.5-1 h;
(3) depositing an SiOC layer on the SiOC buffer layer, wherein the flow rate of the HMDSO liquid is 0.3-2 g/min, H2The flow of the deposition solution is 100-1000 sccm, the flow of Ar is 1000-6000 sccm, the deposition temperature is 900-1350 ℃, the working pressure is 10-1000 Pa, and the deposition time is 1-100 h;
(4) depositing a pure SiC coating on the SiOC layer, wherein the flow rate of the HMDS liquid is 0.3-2 g/min, and H2The flow of the deposition solution is 100-1000 sccm, the flow of Ar is 1000-6000 sccm, the deposition temperature is 900-1350 ℃, the working pressure is 10-1000 Pa, and the deposition time is 3-300 h;
the thickness of the porous silicon layer prepared in the step (1) is 10-20 microns, the thickness of the SiOC buffer layer deposited in the step (2) is less than 2 microns, the thickness of the SiOC layer deposited in the step (3) is controlled to be 50-350 microns, and the thickness of the pure SiC coating deposited in the step (4) is more than 1000 microns;
the prepared composite coating has obvious layering, the total thickness is more than 1500 mu m, the surface of the pure SiC layer is smooth, the hardness is 25-35 GPa, and the Young modulus is 200-300 GPa;
the prepared composite coating has good bonding at the interface, no crack and no crack gap, and the bonding force is 30-35 MPa.
2. Chemical vapor deposition process for producing silicon carbide composite coatings on monocrystalline or polycrystalline silicon, in accordance with claim 1, characterized in that HMDSO/HMDS-H2In the-Ar system, the purity of each component is 99% or more.
3. A chemical vapor deposition process for producing a silicon carbide composite coating on monocrystalline or polycrystalline silicon as claimed in claim 1, characterized in that the liquid starting materials HMDSO and HMDS are brought into the reaction chamber by Ar after gasification.
4. The chemical vapor deposition method for producing a silicon carbide composite coating on single crystal silicon or polycrystalline silicon according to claim 1, wherein in the step (1), H is2The flow rate of the organic silicon compound is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the etching temperature is 1050-1250 ℃, and the working pressure is 200-800 Pa.
5. The chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon according to claim 1, wherein in the step (2), the flow rate of the HMDSO liquid is 0.3-0.8 g/min, and H is2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1150 ℃, and the working pressure is 200-800 Pa.
6. The chemical vapor deposition method for preparing a silicon carbide composite coating on monocrystalline silicon or polycrystalline silicon according to claim 1, wherein in the step (3), the flow rate of the HMDSO liquid is 0.5-1.5 g/min, and H is2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1250 ℃, and the working pressure is200~800Pa。
7. The chemical vapor deposition method for preparing a silicon carbide composite coating on single crystal silicon or polycrystalline silicon according to claim 1, wherein in the step (4), the liquid flow rate of HMDS is 0.5-1.5 g/min, and H is2The flow rate of the deposition solution is 200-800 sccm, the flow rate of Ar is 2000-5000 sccm, the deposition temperature is 1050-1250 ℃, and the working pressure is 200-800 Pa.
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| CN113684467A (en) * | 2021-07-26 | 2021-11-23 | 中国科学院金属研究所 | Method for preparing amorphous SiOC coating by adopting chemical vapor deposition process |
| CN113564560A (en) * | 2021-07-26 | 2021-10-29 | 中国科学院金属研究所 | Method for depositing amorphous SiOC coating on titanium alloy surface by adopting chemical vapor deposition process |
| CN113716878B (en) * | 2021-09-10 | 2023-06-16 | 湖南倍晶新材料科技有限公司 | Quartz surface composite coating and preparation method thereof |
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