Preparation method of anti-etching ceramic coating material

Abstract

The invention discloses a preparation method of an anti-etching ceramic coating material, which comprises the following steps: introducing elements such as Al, Sc, Yb and La, forming an entropy stabilizing material with yttrium oxide, and optimizing the chemical composition and crystalline phase structure of the entropy stabilizing material, thereby preparing a coating with high compactness, high bonding strength and excellent anti-etching performance. The powder with controllable granularity and narrow distribution range is prepared by adopting an improved spray granulation process, and the uniformity, compactness and low surface roughness of a coating are realized by combining a suspension plasma spraying technology. The coating material disclosed by the invention has high-temperature stability, chemical inertness and excellent etching resistance in an extreme working environment, can meet the long-term stable operation requirements of semiconductor manufacturing, photoetching equipment and other high-end precision equipment, and provides a reliable protection solution for the equipment. Therefore, not only is the application progress of the yttrium oxide material in the field of anti-etching coatings promoted, but also the performance and reliability of the coatings in the related fields are effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of material surface engineering, and particularly to a preparation method of an anti-etching ceramic coating material. Background Art

[0002] In the fields of semiconductor manufacturing and lithography equipment, components are often exposed to extremely harsh operating environments, such as high temperature, vacuum, high-energy particle bombardment, and strong corrosive gas environments. These complex working conditions pose severe requirements on the performance of materials. The most prominent problems are the combined effects of chemical corrosion, thermal stress, and plasma erosion. This not only leads to the rapid failure of precision components of the equipment but also directly affects the manufacturing quality of semiconductor chips and the working life of lithography equipment. Currently, the key materials for anti-etching mainly include oxides such as alumina, zirconia, and yttrium oxide (Y 2 O 3 ). Among them, yttrium oxide has become a research hotspot due to its unique physical and chemical properties. This material has a high melting point (about 2430 °C), a low vapor pressure, extremely strong chemical stability, and excellent anti-plasma impact performance. During the semiconductor manufacturing process, especially in the etching, cleaning, and deposition processes, the surface of components often comes into direct contact with high-energy plasma. At this time, the yttrium oxide coating can effectively block the corrosive effect of plasma, thus significantly improving the reliability and durability of the equipment.

[0003] However, traditional yttrium oxide coating preparation technologies (such as thermal spraying) still face many challenges in practical applications. First of all, the thermal spraying technology uses powder as the raw material, and the prepared coating often has a high porosity, which makes its corrosion resistance in corrosive media limited. In addition, the bonding method between the coating and the substrate in thermal spraying is mostly mechanical bonding, and the bonding strength is low, which is easy to fail due to peeling during long-term use. With the continuous development of semiconductor processes towards higher precision and more severe working conditions, traditional thermal spraying coatings can no longer meet the requirements for denseness, bonding force, and long-term high stability.

[0004] To overcome the limitations of traditional coating technologies, in recent years, Suspension Plasma Spraying (SPS) has gradually attracted attention. By combining spray granulation and using a suspension as the coating raw material, this technology can effectively solve the problems of large powder particle size and poor fluidity in traditional thermal spraying. The uniform dispersion of micron-sized spherical powders in the suspension makes the coating deposition process more precise and can significantly improve the density and uniformity of the coating. In addition, the SPS technology can also achieve a coating structure with a lower porosity, enhance the corrosion resistance, and further optimize the suspension characteristics and the bonding strength between the coating and the substrate by adjusting the granulation parameters and plasma spraying parameters. Although the application prospect of suspension plasma spraying technology in the preparation of yttrium oxide coatings is broad, there are still some technical bottlenecks at present. For example, the stability of the suspension has a great influence on the final performance of the coating. How to improve the dispersion and fluidity of the powder by optimizing the powder granulation process is an urgent problem to be solved. In addition, during the plasma spraying process, if the separation particle size distribution range is wide and the fluidity is poor, agglomeration and nozzle blockage are likely to occur, thus affecting the uniformity and corrosion resistance of the coating. At the same time, the existing pure yttrium oxide coating materials have poor oxygen barrier ability, which has a negative impact on the substrate during the re-service process. Therefore, it is urgent to develop a coating material that can make the coating dense, have a small surface roughness, and be resistant to etching and oxidation to meet the usage requirements of high-performance equipment. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of the present application, to avoid obscuring the purpose of this section, the abstract, and the title, and such simplifications or omissions shall not be used to limit the scope of the present invention.

[0006] Therefore, the purpose of the present invention is to provide a preparation method for an anti-etching ceramic coating material. By over-doping rare earth elements, the microstructure of the coating is optimized, and the corrosion resistance of the coating is improved. In particular, the incorporation of rare earth elements (such as Yb, Sc, etc.) can significantly improve the oxidation resistance of the coating and effectively delay the diffusion of oxygen ions.

[0007] To solve the above technical problems, according to one aspect of the present invention, the following technical solutions are provided:

[0008] A preparation method for an anti-etching ceramic coating material, the steps are as follows:

[0009] S1. Mix high-purity yttrium oxide Y 2 O 3 with scandium oxide Sc 2 O 3 or ytterbium oxide Yb 2 O3 Or aluminum oxide Al 2 O 3 Lanthanum oxide La 2 O 3 Mixing in molar ratio according to stoichiometric ratio to form a multi-stable body composition;

[0010] S2. Adding ZrO to the multi-stabilizer composition 2 Ball milling beads: use ethanol or deionized water as the dispersion medium to fully ball mill for 1-8 hours to form a slurry;

[0011] S3, drying the ball-milled slurry to constant weight, and sieving with a 200-mesh sieve;

[0012] S4, prepare a slurry with a solid content of 20-40wt%, and adjust the slurry viscosity to 10-50mPa·s;

[0013] S5, granulating the slurry treated in step S4 using a spray drying device to obtain a granular powder with a particle size distribution of 0.5 μm-50 μm;

[0014] S6. Disperse the powder after spray granulation in an ethanol-water mixed solution, add a dispersant, and use an ultrasonic dispersion device for 15-60 minutes, and use magnetic stirring to ensure that the suspension is evenly dispersed;

[0015] S7. Select the base material and improve the surface roughness by sandblasting or chemical cleaning;

[0016] S8. Use suspension plasma spraying equipment to spray the suspension obtained in step S6 onto the base material. During the spraying process, the coating thickness is controlled to be 30-200 μm and the spraying rate is 5-30 μm / min. After spraying, high-temperature sintering treatment is performed, and the heat is kept for 1-8 hours, and then cooled to room temperature at a rate of 5-10°C / min to form a ceramic coating material.

[0017] As a preferred embodiment of the method for preparing an anti-etching ceramic coating material according to the present invention, in step S1, the multi-stabilizer composition is Y 1-x Sc x O 1.5 , 0.1≤x≤0.5 or Y 1-x Yb x O 1.5 , 0.1≤x≤0.5 or Y 1-x La x O 1.5 , 0.1≤x≤0.5 or Y 1-x (Sc 1-y Yb y ) x O1.5 where 0.1 ≤ x ≤ 0.5 and 0.1 ≤ y ≤ 0.5), or Y 1-x (Al 1- y Yb y ) x O 1.5 where 0.1 ≤ x ≤ 0.5 and 0.1 ≤ y ≤ 0.5.

[0018] As a preferred embodiment of the preparation method of the anti-etching ceramic coating material described in the present invention, in step S5, the inlet temperature of the spray drying equipment is set to 150 - 200 °C, the outlet temperature is 80 - 120 °C, the rotation speed of the atomizer is 12,500 - 21,000 r / min, and the atomization air pressure is 0.2 - 0.5 MPa.

[0019] As a preferred embodiment of the preparation method of the anti-etching ceramic coating material described in the present invention, in the ethanol-water mixed solution of step S6, the volume fraction of ethanol is 70 - 90%.

[0020] As a preferred embodiment of the preparation method of the anti-etching ceramic coating material described in the present invention, in step S6, the dispersants are polyvinylpyrrolidone PVP and polyvinyl alcohol PVA, and the concentration is 0.1 - 0.5 wt%.

[0021] As a preferred embodiment of the preparation method of the anti-etching ceramic coating material described in the present invention, in step S8, the spraying parameters of the suspension plasma spraying equipment are as follows: plasma gas flow rate: 40 - 80 slpm of argon as the main gas and 5 - 20 slpm of hydrogen as the auxiliary gas; current and voltage: current 300 - 600 A, voltage 40 - 90 V; spraying distance: 50 - 100 mm; feeding speed: 2 - 50 mL / min.

[0022] As a preferred embodiment of the preparation method of the anti-etching ceramic coating material described in the present invention, in step S8, the heating rate of the high-temperature sintering is 5 - 10 °C / min, and it is raised from room temperature to 1100 - 1500 °C.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] 1. The present invention prepares a coating with high density, high bonding strength, and excellent etching resistance by introducing elements such as Al, Sc, Yb, La, etc., and forming an entropy-stabilized material with yttrium oxide to optimize its chemical composition and crystal phase structure. By adopting an improved spray granulation process, powders with controllable particle size and narrow particle size distribution are prepared, and combined with suspension plasma spraying (SPS) technology, the uniformity, density, and low surface roughness of the coating are achieved. The coating material of the present invention has high-temperature stability, chemical inertness, and excellent etching resistance in extreme working environments, can meet the long-term stable operation requirements of high-end precision equipment such as semiconductor manufacturing and lithography equipment, and provides a reliable protection solution for these equipment. Therefore, the present invention not only promotes the application progress of yttrium oxide materials in the field of anti-etching coatings, but also effectively improves the performance and reliability of coatings in related fields.

[0025] 2. By optimizing the doping ratio and combination of rare earth elements (such as the ratio of Yb, Sc, La), the present invention can improve the plasma erosion resistance and chemical corrosion resistance of the coating while ensuring the density of the coating and the bonding force with the substrate. Therefore, the coating material of the present invention not only has excellent etching resistance, but also can provide long-term stable protection in high-precision industrial equipment such as semiconductor manufacturing and lithography equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail below in conjunction with the drawings and detailed embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts. Among them:

[0027] Figure 1 XRD pattern of the ceramic coating prepared in Example 1 of the present invention;

[0028] Figure 2 Cross-sectional SEM image of the ceramic coating prepared in Example 1 of the present invention;

[0029] Figure 3 Schematic diagram for characterizing the surface roughness of the ceramic coating prepared in Example 1 of the present invention;

[0030] Figure 4 Schematic diagram for characterizing the surface roughness of the ceramic coating prepared in Example 2 of the present invention;

[0031] Figure 5 Schematic diagram for characterizing the surface roughness of the ceramic coating prepared in Example 5 of the present invention;

[0032] Figure 6Schematic diagram of the surface morphology of the ceramic coating prepared in Example 7 of the present invention;

[0033] Figure 7 Schematic diagram for characterizing the surface roughness of the ceramic coating prepared in Example 7 of the present invention;

[0034] Figure 8 Schematic diagram for characterizing the surface roughness of the ceramic coating prepared in Example 8 of the present invention. Detailed implementation manners

[0035] To make the above objects, features, and advantages of the present invention more obvious and understandable, the following provides a detailed description of the specific implementation manners of the present invention in conjunction with the accompanying drawings.

[0036] The present invention provides a preparation method of an anti-etching ceramic coating material, which over-dopes rare earth elements, optimizes the microstructure of the coating, and improves the corrosion resistance of the coating. In particular, the incorporation of rare earth elements (such as Yb, Sc, etc.) can significantly improve the oxidation resistance of the coating and effectively delay the diffusion of oxygen ions. The specific embodiments are as follows:

[0037] Example 1

[0038] S1. Using Y 2 O 3 and Yb 2 O 3 as raw materials, mix them according to the molar ratio in the chemical formula of Y 0.8 Yb 0.2 O 1.5 .

[0039] S2. Using the above raw materials, with a planetary high-energy ball mill and ethanol as the dispersion medium, add ZrO 2 ball milling beads, and carry out ball milling for 4 hours to ensure uniform mixing of the slurry.

[0040] S3. Prepare a slurry with a solid content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature to 180 °C, the outlet temperature to 100 °C, the atomizer rotation speed to 18000 r / min, and the atomization air pressure to 0.3 MPa to obtain powder with a particle size distribution in the range of D10 = 12 μm and D90 = 20 μm.

[0041] S4. Disperse the powder after spray drying in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0042] S5. Spray on a single-crystalline silicon substrate using a suspension plasma spraying (SPS) device with the following spraying parameters: argon gas flow rate of 60 slpm, hydrogen auxiliary gas flow rate of 10 slpm, current of 500 A, voltage of 60 V, spraying distance of 80 mm, feed rate of 3 mL / min, and control the coating thickness to be 100 μm.

[0043] S6. After spraying, perform a sintering treatment with a heating rate of 5 °C / min, raise the temperature from room temperature to 1300 °C, hold for 3 hours, then cool to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 2.2172 μm.

[0044] Example 2

[0045] S1. Use Y 2 O 3 and La 2 O 3 as raw materials and mix them according to the molar ratio in the chemical formula of Y 0.7 La 0.3 O 1.5 .

[0046] S2. Pass the above raw materials through a planetary high-energy ball mill with ethanol as the dispersion medium, add ZrO 2 ball milling beads, and perform ball milling for 4 hours to ensure uniform mixing of the slurry.

[0047] S3. Pass the ball-milled slurry through a sieve (200-mesh sieve) and dry it at 120 °C to constant weight.

[0048] S4. Prepare a slurry with a solid content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature to 180 °C, the outlet temperature to 100 °C, the atomizer rotation speed to 18000 r / min, and the atomization air pressure to 0.3 MPa to obtain a powder with a particle size distribution in the range of D10 = 10 μm and D90 = 18 μm.

[0049] S5. Disperse the spray-dried powder in an ethanol-water mixed solution (ethanol volume fraction of 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure uniform suspension.

[0050] S6. Spray on a single-crystalline silicon substrate using a suspension plasma spraying (SPS) device with the following spraying parameters: argon gas flow rate of 60 slpm, hydrogen auxiliary gas flow rate of 10 slpm, current of 500 A, voltage of 60 V, spraying distance of 80 mm, feed rate of 3 mL / min, and control the coating thickness to be 50 μm.

[0051] S7. After spraying, sintering treatment is carried out. The heating rate is 5 °C / min, rising from room temperature to 1300 °C, holding for 3 hours, and then cooling to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 1.7575 μm.

[0052] Example 3

[0053] S1. Using Y 2 O 3 and Sc 2 O 3 as raw materials, and mixing them according to the molar ratio in the chemical formula of Y 0.8 Sc 0.2 O 1.5 for mixing.

[0054] S2. Pass the above raw materials through a planetary high-energy ball mill with ethanol as the dispersion medium, add ZrO 2 ball milling beads, and carry out ball milling for 4 hours to ensure uniform mixing of the slurry.

[0055] S3. Prepare a slurry with a solid content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature to 180 °C, the outlet temperature to 100 °C, the atomizer rotation speed to 18000 r / min, and the atomization air pressure to 0.3 MPa to obtain a powder with a particle size distribution in the range of D10 = 12 μm and D90 = 20 μm.

[0056] S4. Disperse the powder after spray drying in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0057] S5. Use a suspension plasma spraying (SPS) device to spray on a single-crystalline silicon substrate. The spraying parameters are as follows: argon gas flow rate 60 slpm, hydrogen auxiliary gas flow rate 10 slpm, current 500 A, voltage 60 V, spraying distance 80 mm, feed rate 3 mL / min, and control the coating thickness to 100 μm.

[0058] S6. After spraying, carry out sintering treatment. The heating rate is 5 °C / min, rising from room temperature to 1300 °C, holding for 3 hours, and then cooling to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 2.2172 μm.

[0059] Example 4

[0060] S1. Using Y 2 O 3 and Yb 2 O 3 as raw materials, and mixing them according to the molar ratio in the chemical formula of Y0.8 Ytterbium 0.2 Oxygen 1.5 Mix them.

[0061] S2. Use a planetary high-energy ball mill to mix the above raw materials with ethanol as the dispersion medium, add ZrO 2 grinding beads and conduct ball milling for 4 hours to ensure uniform mixing of the slurry.

[0062] S3. Prepare a slurry with a solids content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature at 180 °C, the outlet temperature at 100 °C, the atomizer rotation speed at 18000 r / min, and the atomization air pressure at 0.3 MPa to obtain a powder with a particle size distribution in the range of D10 = 12 μm and D90 = 20 μm.

[0063] S4. Disperse the powder after spray drying in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure a uniform suspension.

[0064] S5. Use a suspension plasma spraying (SPS) device to spray on a single-crystalline silicon substrate. The spraying parameters are as follows: argon gas flow rate 60 slpm, hydrogen auxiliary gas flow rate 10 slpm, current 500 A, voltage 60 V, spraying distance 50 mm, feeding speed 3 mL / min, and control the coating thickness to be 100 μm.

[0065] S6. After spraying, perform sintering treatment. The heating rate is 5 °C / min, raise the temperature from room temperature to 1300 °C, hold for 3 hours, and then cool down to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 2.2172 μm

[0066] Example 5

[0067] S1. Use Y 2 O 3 and ytterbium 2 O 3 as raw materials and mix them according to the molar ratio in the chemical formula of Y 0.8 Ytterbium 0.2 O 1.5 Mix them.

[0068] S2. Use a planetary high-energy ball mill to mix the above raw materials with ethanol as the dispersion medium, add ZrO 2 grinding beads and conduct ball milling for 4 hours to ensure uniform mixing of the slurry.

[0069] S3. Prepare a slurry with a solids content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature at 180 °C, the outlet temperature at 100 °C, the atomizer rotation speed at 15000 r / min, and the atomization air pressure at 0.3 MPa to obtain a powder with a particle size distribution in the range of D10 = 12 μm and D90 = 20 μm.

[0070] S4. Disperse the powder after spray drying in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0071] S5. Use a suspension plasma spraying (SPS) device to spray on a single-crystalline silicon substrate. The spraying parameters are as follows: argon gas flow rate 60 slpm, hydrogen auxiliary gas flow rate 10 slpm, current 500 A, voltage 60 V, spraying distance 80 mm, feed rate 3 mL / min, and control the coating thickness to be 100 μm.

[0072] S6. After spraying, perform sintering treatment. The heating rate is 5 °C / min, raise the temperature from room temperature to 1300 °C, hold for 3 hours, and then cool down to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 2.2172 μm.

[0073] Example 6

[0074] S1. Use Y 2 O 3 and Yb 2 O 3 as raw materials, and mix them according to the molar ratio in the chemical formula of Y 0.8 Yb 0.2 O 1.5 .

[0075] S2. Pass the above raw materials through a planetary high-energy ball mill with ethanol as a dispersion medium, add ZrO 2 ball milling beads, and perform ball milling for 4 hours to ensure uniform mixing of the slurry.

[0076] S3. Prepare a slurry with a solids content of 30 wt%, adjust the viscosity to 45 mPa·s, and then pass it through a spray drying device. Set the inlet temperature at 180 °C, the outlet temperature at 100 °C, the atomizer rotation speed at 18000 r / min, and the atomization air pressure at 0.3 MPa to obtain a powder with a particle size distribution in the range of D10 = 12 μm and D90 = 20 μm.

[0077] S4. Disperse the powder after spray drying in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% sodium polyacrylate as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0078] S5. Spray on a single-crystalline silicon substrate using a suspension plasma spraying (SPS) device with the following spraying parameters: argon gas flow rate of 60 slpm, hydrogen auxiliary gas flow rate of 10 slpm, current of 500 A, voltage of 60 V, spraying distance of 80 mm, feed rate of 3 mL / min, and control the coating thickness to be 100 μm.

[0079] S6. After spraying, perform a sintering treatment with a heating rate of 5 °C / min, raise the temperature from room temperature to 1300 °C, hold for 3 hours, then cool down to room temperature at a rate of 3 °C / min. The finally obtained coating is dense and uniform, and the surface roughness Sq = 2.2172 μm.

[0080] Example 7

[0081] S1. Use Y 2 O 3 and La 2 O 3 as raw materials and mix them according to the molar ratio in the chemical formula of Y 0.7 La 0.3 O 1.5 .

[0082] S2. Pass the above raw materials through a planetary high-energy ball mill with ethanol as the dispersion medium, add ZrO 2 ball milling beads, and perform ball milling for 0.5 hours to ensure uniform mixing of the slurry.

[0083] S3. Screen the ball-milled slurry (through a 200-mesh sieve) and dry it at 120 °C to constant weight.

[0084] S4. Disperse the dried powder in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0085] S5. Spray on a single-crystalline silicon substrate using a suspension plasma spraying (SPS) device with the following spraying parameters: argon gas flow rate of 60 slpm, hydrogen auxiliary gas flow rate of 10 slpm, current of 500 A, voltage of 60 V, spraying distance of 80 mm, feed rate of 3 mL / min, and control the coating thickness to be 50 μm.

[0086] S6. After spraying, perform a sintering treatment with a heating rate of 5 °C / min, raise the temperature from room temperature to 1300 °C, hold for 3 hours, then cool down to room temperature at a rate of 3 °C / min.

[0087] S7. The finally obtained coating has a relatively poor density, and the surface roughness Sq = 11.1672 μm.

[0088] Example 8

[0089] S1. Using Y 2 O 3 and Yb 2 O 3 as raw materials, mix them according to the molar ratio in the chemical formula of Y 0.8 Yb 0.2 O 1.5 for mixing.

[0090] S2. Pass the above raw materials through a planetary high-energy ball mill with ethanol as the dispersion medium, add ZrO 2 ball milling beads, and carry out ball milling for 4 hours to ensure uniform mixing of the slurry.

[0091] S3. Disperse the dried powder in an ethanol-water mixed solution (ethanol volume fraction is 80%), add 0.3 wt% polyvinylpyrrolidone PVP as a dispersant, and perform ultrasonic treatment for 30 minutes to ensure the uniformity of the suspension.

[0092] S4. Use a suspension plasma spraying (SPS) device to spray on a single-crystalline silicon substrate. The spraying parameters are as follows: argon gas flow rate 60 slpm, hydrogen auxiliary gas flow rate 10 slpm, current 500 A, voltage 60 V, spraying distance 80 mm, feeding speed 3 mL / min, and control the coating thickness to be 100 μm.

[0093] S5. After spraying, carry out sintering treatment. The heating rate is 5 °C / min, rise from room temperature to 1300 °C, keep warm for 3 hours, and then cool down to room temperature at 3 °C / min. The finally obtained coating has a poor density, and the surface roughness Ra = 10.9 μm.

[0094] Perform performance tests on the coatings prepared in the above Examples 1 - 8 as follows:

[0095] 1. Carry out X-ray diffraction test on the coating prepared in Example 1. The results are as Figure 1 shown. It can be obtained from Figure 1 that the ceramic coating prepared by the present invention has good crystallinity.

[0096] 2. Carry out scanning electron microscope analysis on the interface of the ceramic coating prepared in Example 1. As Figure 2 shown, the results show that the interior of the coating is dense, with a density of 97% and no obvious pores.

[0097] 3. Characterize the surface roughness of the ceramic coating prepared in Example 1. As Figure 3 shown, it is found that the surface roughness is low, only Sq = 2.2172 μm.

[0098] 4. The cross-section of the ceramic coating prepared in Example 2 was analyzed by scanning electron microscopy. As Figure 4 shown, it was found that the inside of the coating was also dense, without obvious pores, and the density reached 99%. It was found that the surface roughness was relatively low, only Sq = 1.7575 μm

[0099] 5. The cross-section of the ceramic coating prepared in Example 3 was analyzed by scanning electron microscopy. It was found that the inside of the coating was also dense, without obvious pores, and it could also reach 99%.

[0100] 6. The cross-section of the ceramic coating prepared in Example 4 was analyzed by scanning electron microscopy. It was found that the surface roughness of the coating increased slightly.

[0101] 7. The cross-section of the ceramic coating prepared in Example 5 was analyzed by scanning electron microscopy. As Figure 5 shown, it was found that the density inside the coating decreased to 90%, and the surface roughness Sq = 5.1213 μm.

[0102] 8. The cross-section of the ceramic coating prepared in Example 6 was analyzed by scanning electron microscopy. It was found that the density inside the coating was slightly 97%.

[0103] 9. The cross-section of the ceramic coating prepared in Example 7 was analyzed by scanning electron microscopy. As Figure 7 and Figure 8 shown, due to insufficient fluidity of the slurry, the surface of the coating had large undulations, and the surface roughness Ra = 16.8 μm.

[0104] 10. The cross-section of the ceramic coating prepared in Example 8 was analyzed by scanning electron microscopy. As Figure 8 shown, similarly due to insufficient fluidity of the slurry, the surface of the coating had large undulations, and the surface roughness Ra = 10.9 μm.

[0105] Although the present invention has been described above with reference to the embodiments, various improvements can be made to it and components therein can be replaced with equivalents without departing from the scope of the present invention. In particular, as long as there is no structural conflict, the various features in the embodiments disclosed in the present invention can be combined with each other in any way. The cases of these combinations are not exhaustively described in this specification only for the sake of saving space and resources. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A method for preparing an anti-etching ceramic coating material, characterized in that: Here are the steps: S1. Mixing high-purity yttrium oxide Y2O3 with scandium oxide Sc2O3 or ytterbium oxide Yb2O3 or aluminum oxide Al2O3 or lanthanum oxide La2O3 in a molar ratio according to a stoichiometric ratio to form a multi-stabilizer composition; S2, adding ZrO2 ball milling beads to the multi-stabilizer composition, and fully ball milling for 1-8 hours with ethanol or deionized water as a dispersion medium to form a slurry; S3, drying the ball-milled slurry to constant weight, and sieving with a 200-mesh sieve; S4, prepare a slurry with a solid content of 20-40wt%, and adjust the slurry viscosity to 10-50mPa·s; S5, granulating the slurry treated in step S4 using a spray drying device to obtain a granular powder with a particle size distribution of 0.5 μm-50 μm; S6. Disperse the powder after spray granulation in an ethanol-water mixed solution, add a dispersant, and use an ultrasonic dispersion device for 15-60 minutes, and use magnetic stirring to ensure that the suspension is evenly dispersed; S7. Select the base material and improve the surface roughness by sandblasting or chemical cleaning; S8. Use suspension plasma spraying equipment to spray the suspension obtained in step S6 onto the base material. During the spraying process, the coating thickness is controlled to be 30-200 μm and the spraying rate is 5-30 μm / min. After spraying, high-temperature sintering treatment is performed, and the heat is kept for 1-8 hours, and then cooled to room temperature at a rate of 5-10°C / min to form a ceramic coating material.

2. The method for preparing an anti-etching ceramic coating material according to claim 1, characterized in that: In step S1, the multi-stable body composition is Y 1-x Sc x O 1.5 , 0.1≤x≤0.5 or Y 1-x Yb x O 1.5 , 0.1≤x≤0.5 or Y 1- x La x O 1.5 , 0.1≤x≤0.5 or Y 1-x (Sc 1-y Yb y ) x O 1.5 , 0.1≤x≤0.5, 0.1≤y≤0.5) or Y 1-x (Al 1- y Yb y ) x O 1.5 , 0.1≤x≤0.5, 0.1≤y≤0.

5.

3. The method for preparing an anti-etching ceramic coating material according to claim 1, characterized in that: In step S5, the inlet temperature of the spray drying equipment is set to 150-200°C, the outlet temperature is 80-120°C, the atomizer speed is 12500r / min-21000r / min, and the atomization air pressure is 0.2-0.5MPa.

4. The method for preparing an anti-etching ceramic coating material according to claim 1, characterized in that: In the ethanol-water mixed solution of step S6, the volume fraction of ethanol is 70-90%.

5. The method for preparing an anti-etching ceramic coating material according to claim 1, characterized in that: In step S6, the dispersant is polyvinyl pyrrolidone PVP or polyvinyl alcohol PVA, and the concentration is 0.1-0.5 wt%.

6. The method for preparing an anti-etching ceramic coating material according to claim 1, characterized in that: In step S7, the substrate material is single crystal silicon, ceramic or metal alloy.

7. The method for preparing an anti-etching ceramic coating material according to claim 2, characterized in that: In step S8, the spraying parameters of the suspension plasma spraying equipment are: plasma gas flow: argon main gas 40-80slpm, hydrogen auxiliary gas 5-20slpm; current and voltage: current 300-600A, voltage 40-90V; spraying distance: 50-100mm; feed rate: 2-50mL / min.

8. The method for preparing an anti-etching ceramic coating material according to claim 2, characterized in that: In step S8, the high temperature sintering heating rate is 5-10°C / min, from room temperature to 1100-1500°C.

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