Yttrium-based coating

Abstract

The invention provides a yttrium-based coating. The yttrium-based coating comprises an atmospheric plasma spraying bottom layer, the atmosphere plasma spraying coating is formed by spraying a spherical yttrium-based material to the surface of a base material through an atmosphere plasma spraying method. The preparation method of the spherical yttrium-based material comprises the following steps: (1) mixing yttrium-based composite powder, a solvent, a binder and a dispersant to obtain yttrium-based composite slurry; (2) granulating the yttrium-based composite slurry to obtain yttrium-based composite particles; (3) sintering the yttrium-based composite particles to obtain yttrium-based agglomerated particles; and (4) spheroidizing the yttrium-based agglomerated particles obtained in the step (3) to obtain the spherical yttrium-based material. According to the method, the spraying raw materials of the yttrium-based coating are optimized, and the spherical yttrium-based material which has a spherical shape with a smooth surface, good fluidity and concentrated powder size distribution is taken as the raw material, so that the yttrium-based coating has high density, hardness and uniformity.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor device preparation, and specifically relates to the preparation of semiconductor device coating, and in particular to an yttrium-based coating. Background Art

[0002] In the semiconductor manufacturing process, in order to perform high-integration micro-machining on substrate circuits such as silicon wafers, the plasma dry etching process has become increasingly important. It is necessary to use materials with excellent plasma resistance as chamber components, or to use materials with excellent plasma resistance to form a coating on the surface of the components to extend the life of the components. Therefore, the semiconductor etching equipment etching components must use ceramic materials with high hardness, high wear resistance, high dielectric strength, high corrosion resistance and good chemical stability to cover the inner wall of the chamber. This coating is particularly important for corrosion resistance to a wide variety of halogen-containing plasmas.

[0003] CN107946163A discloses a chamber component for a plasma processing chamber device. The chamber component includes a main body having an outer layer containing yttrium oxide, and a coating formed on the main body, wherein the coating contains a material containing yttrium fluoride, and discloses a method for manufacturing a chamber component used in a plasma processing environment, comprising: immersing the main body of the chamber component having an outer layer formed of yttrium oxide in a wet coating solution, wherein the wet coating solution contains at least one ammonium salt and HF; reacting fluoride ions from the wet coating solution with yttrium oxide from the chamber component; and forming a coating containing a fluorine-containing yttrium oxide material.

[0004] CN113913783A discloses a deposited coating containing both fluorinated yttrium oxide and a metal oxide. The coating can be prepared by placing a non-fluorinated yttrium oxide precursor coating onto a surface using an atomic layer deposition technique, followed by a step of fluorinating the precursor to produce fluorinated yttrium oxide by a fluorine annealing step. The precursor coating contains yttrium oxide and a metal oxide. The fluorine annealing step converts a substantial portion of the yttrium oxide into fluorinated yttrium oxide, fluorinated yttrium oxide, or a combination of these to form a resulting coating containing a combination of a metal oxide (that is not fluorinated) and fluorinated yttrium oxide.

[0005] CN116695048A discloses a yttrium-based spray coating and a manufacturing method of the present invention. Yttrium oxide, yttrium fluoride or yttrium oxyfluoride is thermally sprayed onto a substrate to form a coating with a thickness of 10-500 μm, and the coating is chemically cleaned with a cleaning solution of an organic acid, an inorganic acid or a mixture thereof until the number of particles with a size of less than 300 nm on the surface of the coating becomes no more than 5 particles / mm 2, thereby obtaining a yttrium-based spray coating. The yttrium-based spray coating exhibits high corrosion resistance even in a halogen gas plasma atmosphere and prevents yttrium-based particles from peeling off during etching treatment.

[0006] Due to the strict requirement that yttrium-based coatings exhibit corrosion resistance to a wide variety of halogen-containing plasmas, it is particularly important to develop a yttrium-based material that can form a yttrium-based coating with high density, hardness and uniformity. Summary of the invention

[0007] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a yttrium-based coating. The present invention optimizes the spraying raw materials of the yttrium-based coating, first granulates the submicron-level ultrafine yttrium-based composite powder composed of submicron-level yttrium oxyfluoride and submicron-level yttrium fluoride, and then spheroidizes and densifies the obtained yttrium-based aggregate particles. The prepared spherical yttrium-based material has a smooth spherical morphology, good fluidity, and concentrated powder particle size distribution. The yttrium-based coating using the raw material has high density, hardness and uniformity.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a yttrium-based coating, the yttrium-based coating comprising an atmospheric plasma sprayed bottom layer; the atmospheric plasma sprayed coating is sprayed onto a substrate surface by an atmospheric plasma spraying method with a spherical yttrium-based material; the mass percentage of fluorine element in the spherical yttrium-based material is 15%-20%, and the D50 particle size of the spherical yttrium-based material is 10μm-50μm; the spherical yttrium-based material is prepared by the following preparation method, the preparation method comprising: (1) mixing a yttrium-based composite powder, a solvent, a binder and a dispersant to obtain a yttrium-based composite slurry; the yttrium-based composite powder comprises submicron yttrium oxyfluoride and submicron yttrium fluoride; (2) treating the step (1) with a spherical yttrium-based composite powder; and (3) preparing a yttrium-based composite slurry. ) granulating the yttrium-based composite slurry to obtain yttrium-based composite particles; (3) sintering the yttrium-based composite particles in step (2) to obtain yttrium-based aggregated particles; (4) spheroidizing the yttrium-based aggregated particles in step (3) to obtain the spherical yttrium-based material; in the yttrium-based composite powder in step (1), the D50 particle size of submicron yttrium oxyfluoride and submicron yttrium fluoride is independently 0.1 μm-1 μm; the spheroidization method in step (4) includes plasma spheroidization, and the process of plasma spheroidization includes: adding the yttrium-based aggregated particles in step (3) into a plasma jet for melting to obtain yttrium-based droplets, and the yttrium-based droplets are sprayed into a cooling medium to obtain the spherical yttrium-based material.

[0009] The present invention optimizes the spraying raw materials of the yttrium-based coating and uses spherical yttrium-based materials with a smooth spherical morphology, good fluidity, and concentrated powder particle size distribution as the raw material, so that the yttrium-based coating has high density, hardness and uniformity, high electrical insulation and corrosion resistance, and the dense coating reduces the generation and transfer of tiny particles, which is conducive to resisting etching exposed by plasma.

[0010] In the present invention, the chemical formula of the spherical yttrium-based material can be expressed as Y a O b F c , wherein a≥b, c≥b; in the spherical yttrium-based material, the mass percentage of fluorine element is 15%-20%, for example, it can be 15%, 16%, 17%, 18%, 19% or 20%, including but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; the D50 particle size of the spherical yttrium-based material is 10μm-50μm, for example, it can be 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm or 50μm, including but not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0011] The present invention uses submicron yttrium oxyfluoride and submicron yttrium fluoride to prepare spherical yttrium-based materials. The submicron particle size can effectively improve the density of the prepared yttrium-based coating. The addition of yttrium fluoride is conducive to reducing the combination of YO group and F group under F atmosphere, which can make the prepared coating particles more compact and firm, not easy to transfer, and reduce the possibility of degradation. Therefore, the addition of yttrium fluoride is conducive to the improvement of mechanical properties and strength of the prepared yttrium-based coating, and the coating shows excellent plasma resistance. The submicron ultra-fine yttrium-based composite powder is agglomerated to a suitable size to ensure that the spherical yttrium-based material can be normally transported during the coating processing, and the flight in the plasma jet can be fully accelerated. The spheroidization and densification treatment avoids the situation that the specific surface area of ​​the spherical yttrium-based material is too large during the coating processing, resulting in the heat not being evenly transferred to the internal primary powder, so that the internal primary powder cannot be melted and the surface primary powder is melted again, thereby causing the coating structure to be loose.

[0012] The present invention performs plasma spheroidization treatment on yttrium-based aggregate particles to prepare a spherical yttrium-based material with a smooth spherical morphology, good fluidity, and concentrated powder particle size distribution, which is conducive to forming a yttrium-based coating with high density, hardness and uniformity during the spraying process.

[0013] In the yttrium-based composite powder of step (1), the D50 particle size of the submicron yttrium oxyfluoride is 0.1 μm-1 μm, for example, it can be 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 0.3 μm-0.7 μm.

[0014] In the yttrium-based composite powder of step (1), the D50 particle size of submicron yttrium fluoride is 0.1μm-1μm, for example, it can be 0.1μm, 0.2μm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.7μm, 0.8μm, 0.9μm or 1μm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 0.3μm-0.7μm.

[0015] Preferably, in the method for preparing the spherical yttrium-based material, the yttrium-based composite slurry in step (1) comprises, by parts by weight: 100 parts of yttrium-based composite powder; 3-10 parts of solvent; 100-200 parts of adhesive; Dispersant 3 parts - 11 parts.

[0016] The yttrium-based composite slurry in step (1) of the present invention includes, by weight, 3 to 10 parts of solvent, for example, 3, 4, 5, 6, 7, 8, 9 or 10 parts, 100 to 200 parts of binder, for example, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 parts, and 3 to 11 parts of dispersant, for example, 3, 4, 5, 6, 7, 8, 9, 10 or 11 parts. The contents of the above components in the yttrium-based composite slurry of the present invention include but are not limited to the listed values, and other values ​​not listed within the numerical range are equally applicable.

[0017] Preferably, in the method for preparing the spherical yttrium-based material, in the yttrium-based composite powder in step (1), the mass percentage of submicron yttrium oxyfluoride is 80%-90%, for example, it can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0018] Preferably, in the method for preparing the spherical yttrium-based material, the mass percentage of submicron yttrium fluoride in the yttrium-based composite powder in step (1) is 10%-20%, for example, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0019] Preferably, in the preparation method of the spherical yttrium-based material, in the yttrium-based composite slurry in step (1), the binder includes any one of polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, starch or phenolic resin, or a combination of at least two thereof. Typical but non-limiting combinations include polyvinyl alcohol and polyvinyl pyrrolidone, methyl cellulose and ethyl cellulose, sodium carboxymethyl cellulose and hydroxypropyl cellulose, hydroxypropyl cellulose and starch, or starch and phenolic resin.

[0020] Preferably, in the method for preparing the spherical yttrium-based material, in the yttrium-based composite slurry in step (1), the dispersant includes any one of sodium stearate, fatty alcohol polyoxyethylene ether, sodium polyacrylate, polyacrylamide, polyethylene glycol or ethanol, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of sodium stearate and fatty alcohol polyoxyethylene ether, a combination of sodium polyacrylate and polyacrylamide, or a combination of polyethylene glycol and ethanol.

[0021] Preferably, in the method for preparing the spherical yttrium-based material, in the yttrium-based composite slurry in step (1), the solvent includes deionized water.

[0022] Preferably, in the method for preparing the spherical yttrium-based material, the preparation method of the yttrium-based composite powder in step (1) includes mechanical mixing.

[0023] In the present invention, the yttrium-based composite powder is prepared by conventional mechanical mixing, such as mechanical stirring or ball milling, which is not specifically limited.

[0024] Preferably, in the method for preparing the spherical yttrium-based material, the preparation method of the yttrium-based composite slurry in step (1) includes high-energy ball milling.

[0025] In the present invention, a yttrium-based composite slurry is prepared by high-energy ball milling, wherein the ball milling medium is an yttrium oxide ceramic ball of Φ=8 mm, the ball-to-material ratio is 2:(3-8), for example, it can be 2:3, 2:4, 2:5, 2:6, 2:7 or 2:8, the ball milling time is 6h-12h, for example, it can be 6h, 7h, 8h, 9h, 10h, 11h or 12h, the ball milling speed is 200rpm-600rpm, for example, it can be 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm or 600rpm, and the process parameters of the above-mentioned high-energy ball milling include but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0026] Preferably, in the method for preparing the spherical yttrium-based material, the granulation method in step (2) includes spray drying.

[0027] The present invention granulates the yttrium-based composite slurry by spray drying, the feeding speed of the spray drying granulation is 80 mL / min-160 mL / min, for example, it can be 80 mL / min, 90 mL / min, 100 mL / min, 110 mL / min, 120 mL / min, 130 mL / min, 140 mL / min, 150 mL / min or 160 mL / min, and the air inlet temperature is 160°C-300°C, for example, it can be 16 0℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃ or 300℃, the outlet temperature is 120℃-180℃, for example, it can be 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃. The above-mentioned spray drying process parameters include but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0028] Preferably, in the method for preparing the spherical yttrium-based material, after the granulation in step (2) is completed, the method further comprises screening the yttrium-based composite particles to D 50 The particle size is 10 μm-50 μm, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] Preferably, in the preparation method of the spherical yttrium-based material, the sintering temperature in step (3) is 800°C-1200°C, for example, it can be 800°C, 820°C, 840°C, 860°C, 880°C, 900°C, 920°C, 940°C, 960°C, 980°C, 1000°C, 1020°C, 1040°C, 1050°C, 1080°C, 1090°C, 1100°C, 1120°C, 1140°C, 1160°C, 1180°C or 1200°C, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, in the method for preparing the spherical yttrium-based material, the sintering in step (3) is performed in a vacuum environment, and the vacuum degree of the vacuum environment is 10 -2 -10 -3 Pa, for example, can be 10 -3 Pa, 20 -3 Pa, 30 -3 Pa, 40 -3 Pa, 50 -3 Pa, 60 -3 Pa, 70 -3 Pa, 80 -3 Pa, 90 -3 Pa or 10 -2 Pa, including but not limited to the listed values, other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, in the preparation method of the spherical yttrium-based material, the sintering time in step (3) is 0.2h-2h, for example, it can be 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, including but not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0032] Preferably, in the method for preparing the spherical yttrium-based material, after the sintering in step (3) is completed, the method further comprises screening the yttrium-based aggregate particles to D 50 The particle size is 10 μm-50 μm, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] Preferably, in the method for preparing the spherical yttrium-based material, after the spheroidization treatment in step (4) is completed, the method further comprises screening the spherical yttrium-based material to D 50The particle size is 10 μm-50 μm, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In the present invention, in the preparation method of the spherical yttrium-based material, the yttrium-based polymer particles described in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by an external powder feeding method, and the powder feeding amount is 80g / min-160g / min, for example, it can be 80g / min, 90g / min, 100g / min, 110g / min, 120g / min, 130g / min, 140g / min, 150g / min or 160g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare the spherical yttrium-based material.

[0035] Preferably, in the preparation method of the spherical yttrium-based material, during the plasma spheroidization treatment, the distance between the emission position of the plasma jet and the cooling medium is 500mm-800mm, for example, it can be 500mm, 520mm, 540mm, 560mm, 580mm, 600mm, 610mm, 620mm, 630mm, 640mm, 650mm, 660mm, 670mm, 680mm, 690mm, 700mm, 720mm, 740mm, 760mm, 780mm or 800mm, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 600mm to 700mm.

[0036] The distance between the emission position of the plasma jet and the cooling medium in the present invention refers to the distance between the ejection outlet of the plasma spray gun and the surface of the cooling medium, and the distance is set to 500 mm to 800 mm, so that the molten YOF-based droplets can be sprayed onto the cooling medium without loss, so as to improve the yield and make it have a rapid cooling effect. When the distance is too small, the loss of solvent and powder caused by the injection pressure increases, and when the distance is too large, the yield on the cooling medium surface decreases due to the influence of the injection angle, and it is difficult to achieve a sufficient rapid cooling effect.

[0037] Preferably, in the preparation method of the spherical yttrium-based material, during the plasma spheroidization treatment, the emission power of the plasma jet is 60kW-80kW, for example, it can be 60kW, 62kW, 64kW, 66kW, 68kW, 70kW, 72kW, 74kW, 76kW, 78kW or 80kW, including but not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] Preferably, in the method for preparing the spherical yttrium-based material, during the plasma spheroidization treatment, the cooling medium includes nitrogen and / or argon.

[0039] In the present invention, the cooling medium may be nitrogen and / or argon. When nitrogen is selected as the cooling medium, argon can also be used as the protective atmosphere gas for the powder.

[0040] In the present invention, an atmospheric plasma spraying method is used to prepare a yttrium-based coating. During the spraying process, part of YF will decompose at high temperature, and Y will combine with O to form YOF, thereby preparing a yttrium-based coating with excellent plasma resistance. The preparation steps specifically include: (a) cleaning the substrate with alcohol, drying it, and then roughening and activating the surface by sandblasting; (b) applying the spherical yttrium-based material to the surface of the substrate treated in step (a) by atmospheric plasma spraying (APS) to obtain a yttrium-based coating.

[0041] The drying temperature in step (a) is 60°C-100°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C. The sandblasting pressure in step (a) is 0.1MPa-0.4MPa, for example, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa or 0.4MPa. The sandblasting distance in step (a) is 3 0mm-150mm, for example, it can be 30mm, 40mm, 50mm, 60mm, 70mm, 80mm, 90mm, 100mm, 110mm, 120mm, 130mm, 140mm or 150mm, the angle of the sandblasting in step (a) is 70°-90°, for example, it can be 70°, 75°, 80°, 85° or 90°, and the material of the sandblasting in step (a) is 120# alumina white corundum sand. The process parameters for pre-treating the substrate in the above step (a) include but are not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0042] The current of the plasma spraying in step (b) is 300A-500A, for example, 300A, 350A, 400A, 450A or 500A. The voltage of the plasma spraying in step (b) is 40V-65V, for example, 40V, 45V, 50V, 55V, 60V or 65V. The auxiliary gas flow rate of the plasma spraying in step (b) is 1L / min-10L / min, for example, 1L / min, 2L / min, 3L / min, 4L / min, 5L / min, 6L / min, 7L / min, 8L / min, 9L / min or 10L / min. 0L / min, the scanning speed of the plasma spraying in step (b) is 150m / min, the energy of the plasma flame flow is adjusted by adjusting the current and the auxiliary gas, the powder feeding amount is 20L / min-100g / min, for example, it can be 20L / min, 30L / min, 40L / min, 50L / min, 60L / min, 70L / min, 80L / min, 90L / min or 100L / min, the powder feeding carrier gas flow rate of the plasma spraying in step (b) is 2.0L / min-12.0L / min, for example, it can be 2, 3, 4, 5, 6, 7, 8, 9 , 10, 11L / min or 12L / min, the main gas flow rate of the plasma spraying in step (b) is 25L / min-70L / min, for example, it can be 20L / min, 30L / min, 35L / min, 40L / min, 45L / min, 50L / min, 55L / min, 60L / min, 65L / min or 70L / min, and the spraying distance of the plasma spraying in step (b) is 100mm-200mm, for example, it can be 100mm, 110mm, 120mm, 130mm, 140mm, 150mm, 160mm , 170mm, 180mm, 190mm or 200mm, the spraying angle of the plasma spraying in step (b) is 80°-90°, for example, it can be 80°, 81°, 82°, 83°, 84°, 85°, 86°, 87°, 88°, 89° or 90°, during the plasma spraying process in step (b), the temperature of the surface of the substrate is 50°C-120°C, for example, it can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, and the above process parameters include but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] The present invention adjusts the power of plasma spraying by regulating the current and voltage of the plasma spraying in step (b). During the spraying process, YF will decompose at high temperature, and Y will combine with O, further regulating the composition ratio of the spherical yttrium-based material to improve the density, hardness and plasma resistance of the prepared coating. However, if the power of plasma spraying is too high, the powder particles will be excessively melted into a molten droplet particle state, splashing and impacting on the surface of the substrate, and rapidly depositing, cooling and shrinking to form a stress-bearing structure, resulting in shrinkage cracks.

[0044] Preferably, the yttrium-based coating further comprises a suspension plasma spray coating; the suspension plasma spray coating is prepared by spraying the yttrium-based composite powder of step (1) onto the surface of the atmospheric ion spray coating by a suspension plasma spraying method.

[0045] The present invention selects an atmospheric plasma spray coating with low preparation cost as a bottom layer, and a suspension plasma spray coating with higher density as a top layer, and uses a submicron extremely fine yttrium-based composite powder including submicron yttrium oxyfluoride and submicron yttrium fluoride as a raw material for suspension plasma spraying, thereby reducing costs while significantly improving the performance of the yttrium-based coating, making it more dense, more resistant to plasma etching gas corrosion, and further increasing its service life.

[0046] The specific process parameters of the suspension plasma spraying in the present invention are well known in the art and are not particularly limited. For example, the suspension slurry preparation method for suspension plasma spraying in the present invention includes mixing the yttrium-based composite powder with deionized water, anhydrous ethanol, dispersant polyvinyl pyrrolidone and ammonium citrate, wherein the mass fraction of the solid powder accounts for 10%-40% of the total mass of the slurry, for example, it can be 10%, 15%, 20%, 25%, 30%, 35% or 40%, the dispersant polyvinyl pyrrolidone is 1%-1.5%, the suspension is stabilized by steric hindrance, the volume ratio of water to ethanol is 1:1, and the ammonium citrate is 0.25%-0.5%.

[0047] The suspension plasma spraying of the present invention uses an Axial III spray gun, and the process parameters of the suspension plasma spraying include: The flow rate of the main gas Ar of the suspension plasma spraying is 40L / min-75L / min, for example, it can be 40L / min, 45L / min, 50L / min, 55L / min, 60L / min, 65L / min, 70L / min or 75L / min; the flow rate of the auxiliary gas H2 of the suspension plasma spraying is 6L / min-20L / min, for example, it can be 6L / min, 8L / min, 10L / min, 12L / min, 14L / min, 16L / min, 18L / min. L / min or 20L / min; the voltage of the suspension plasma spraying is 65V-80V, for example, it can be 65V, 67V, 69V, 70V, 72V, 74V, 76V, 78V or 80V; the current of the suspension plasma spraying is 400A-550A, for example, it can be 400A, 420A, 440A, 460A, 480A, 500A, 510A, 520A, 530A, 540A or 550A; the slurry amount of the suspension plasma spraying is 25mL / min-65mL / min , for example, it can be 25mL / min, 30mL / min, 35mL / min, 40mL / min, 45mL / min, 50mL / min, 55mL / min, 60mL / min or 65mL / min, the spraying distance of the suspension plasma spraying is 60mm-150mm, for example, it can be 60mm, 70mm, 80mm, 90mm, 100mm, 110mm, 120mm, 130mm, 140mm or 150mm, and the process of the suspension plasma spraying also includes The substrate is cooled from the back with nitrogen or compressed air, and the pressure of the cooling gas is 0.3MPa-0.5MPa, for example, 0.3MPa, 0.32MPa, 0.34MPa, 0.36MPa, 0.38MPa, 0.4MPa, 0.42MPa, 0.44MPa, 0.46MPa, 0.48MPa or 0.5MPa to ensure that the surface temperature of the coating and the substrate is lower than 150°C. The above process parameters include but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0048] Compared with the prior art, the present invention has the following beneficial effects: (1) The yttrium-based coating provided by the present invention has high density, hardness and uniformity, and also has high electrical insulation and corrosion resistance. The dense coating reduces the generation and transfer of tiny particles, which is beneficial for resisting etching exposed by plasma; (2) The present invention optimizes the spraying raw materials of the yttrium-based coating and uses a spherical yttrium-based material with a smooth spherical morphology, good fluidity, moderate particle size and concentrated powder particle size distribution as the raw material, thereby ensuring that the spherical yttrium-based material can be normally transported during the coating processing and can be fully accelerated in the plasma jet, thereby avoiding the situation in the coating processing where the specific surface area of ​​the spherical yttrium-based material is too large, resulting in the heat not being evenly transferred to the primary powder inside, making the primary powder inside unable to melt and the primary powder on the surface melt again, thereby causing the coating structure to be loose; (3) The present invention uses submicron yttrium oxyfluoride and submicron yttrium fluoride as raw materials for preparing spherical yttrium-based materials. The submicron particle size can effectively improve the density of the prepared yttrium-based coating. The addition of yttrium fluoride is beneficial to reducing the combination of YO group and F group under F atmosphere, which can make the prepared coating particles more compact and firm, not easy to transfer, and reduce the possibility of degradation. Therefore, the addition of yttrium fluoride is beneficial to improving the mechanical properties and strength of the prepared yttrium-based coating, and the coating exhibits excellent plasma resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 1 is a SEM image of the yttrium-based aggregate particles that have not been spheroidized in Preparation Example 1.

[0050] Figure 2 This is a SEM image of the spherical yttrium-based material after spheroidization treatment in Preparation Example 1.

[0051] Figure 3 This is a SEM image of the surface of the yttrium-based coating prepared in Example 1.

[0052] Figure 4 This is a SEM image of the cross section of the yttrium-based coating prepared in Example 1.

[0053] Figure 5 This is a SEM image of the surface of the yttrium-based coating prepared in Example 16. DETAILED DESCRIPTION

[0054] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0055] Preparation Example 1: This preparation example provides a method for preparing a spherical yttrium-based material, and the preparation method is as follows: (1) According to the mass percentage, 100 parts of yttrium-based composite powder, 7 parts of water, 150 parts of polyvinyl alcohol and 8 parts of ethanol are mixed, and 100 parts of yttrium oxide ceramic balls with a diameter of Φ=8 mm are added, and high-energy ball milling is performed for 8 hours at a ball milling speed of 400 rpm to obtain a yttrium-based composite slurry; in the yttrium-based composite powder, the mass percentage of yttrium oxyfluoride is 85%, the D50 particle size is 0.45 μm, and the mass percentage of yttrium fluoride is 15%, and the D50 particle size is 0.55 μm; (2) granulating the yttrium-based composite slurry prepared in step (1) by spray drying, wherein the feed rate of the spray drying granulation is 120 mL / min, the air inlet temperature is 200° C., and the air outlet temperature is 150° C., to obtain yttrium-based composite particles; sieving the prepared yttrium-based composite particles to a D50 particle size of 37 μm; (3) sintering the yttrium-based composite particles obtained in step (2) at 1050° C. for 0.65 h to obtain yttrium-based aggregate particles; sieving the prepared yttrium-based aggregate particles to a D50 particle size of 37 μm; (4) The yttrium-based polymer particles obtained in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by using an external powder delivery method. The powder delivery rate is 120 g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare a spherical yttrium-based material. The distance between the emission position of the plasma jet and the cooling medium is 650 mm, the emission power of the plasma jet is 70 kW, and the cooling medium is nitrogen. The prepared spherical yttrium-based material is sieved to a D50 particle size of 37 μm.

[0056] The spherical yttrium-based material prepared in this preparation example has a D50 particle size of 37 μm and a mass fraction of fluorine element of 17.5%.

[0057] The SEM image of the yttrium-based polymer particles prepared in step (3) of this preparation example is as follows: Figure 1 As shown, the SEM image of the spherical yttrium-based material after spheroidization treatment in step (4) is as follows Figure 2 shown.

[0058] Preparation Example 2: This preparation example provides a method for preparing a spherical yttrium-based material, and the preparation method is as follows: (1) According to the mass percentage, 100 parts of yttrium-based composite powder, 3 parts of water, 100 parts of polyvinyl alcohol and 3 parts of ethanol are mixed, 80 parts of yttrium oxide ceramic balls with a diameter of Φ=8 mm are added, and high-energy ball milling is performed for 10 hours at a ball milling speed of 500 rpm to obtain a yttrium-based composite slurry; in the yttrium-based composite powder, the mass percentage of yttrium oxyfluoride is 80%, the D50 particle size is 0.3 μm, and the mass percentage of yttrium fluoride is 20%, and the D50 particle size is 0.7 μm; (2) granulating the yttrium-based composite slurry prepared in step (1) by spray drying, wherein the feed rate of the spray drying granulation is 80 mL / min, the air inlet temperature is 280° C., and the air outlet temperature is 160° C., to obtain yttrium-based composite particles; sieving the prepared yttrium-based composite particles to a D50 particle size of 11 μm; (3) sintering the yttrium-based composite particles obtained in step (2) at 800° C. for 2 h to obtain yttrium-based aggregate particles; sieving the prepared yttrium-based aggregate particles to a D50 particle size of 11 μm; (4) The yttrium-based polymer particles obtained in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by using an external powder delivery method, the powder delivery rate is 90 g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare a spherical yttrium-based material. The distance between the emission position of the plasma jet and the cooling medium is 600 mm, the emission power of the plasma jet is 60 kW, and the cooling medium is nitrogen. The prepared spherical yttrium-based material is sieved to a D50 particle size of 11 μm.

[0059] The spherical yttrium-based material prepared in this preparation example has a D50 particle size of 11 μm and a mass percentage of fluorine element of 20%.

[0060] Preparation Example 3: This preparation example provides a method for preparing a spherical yttrium-based material, and the preparation method is as follows: (1) According to the mass percentage, 100 parts of yttrium-based composite powder, 10 parts of water, 200 parts of polyvinyl alcohol and 11 parts of ethanol are mixed, and 110 parts of yttrium oxide ceramic balls with a diameter of Φ=8 mm are added, and high-energy ball milling is performed for 6 hours at a ball milling speed of 600 rpm to obtain a yttrium-based composite slurry; in the yttrium-based composite powder, the mass percentage of yttrium oxyfluoride is 90%, and the D50 particle size is 0.7 μm, and the mass percentage of yttrium fluoride is 10%, and the D50 particle size is 0.3 μm; (2) granulating the yttrium-based composite slurry prepared in step (1) by spray drying, wherein the feed rate of the spray drying granulation is 160 mL / min, the air inlet temperature is 300° C., and the air outlet temperature is 180° C., to obtain yttrium-based composite particles; sieving the prepared yttrium-based composite particles to a D50 particle size of 49 μm; (3) sintering the yttrium-based composite particles obtained in step (2) at 1200° C. for 0.2 h to obtain yttrium-based aggregate particles; sieving the prepared yttrium-based aggregate particles to a D50 particle size of 49 μm; (4) The yttrium-based polymer particles obtained in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by using an external powder delivery method, the powder delivery rate is 150 g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare a spherical yttrium-based material. The distance between the emission position of the plasma jet and the cooling medium is 700 mm, the emission power of the plasma jet is 79 kW, and the cooling medium is nitrogen. The prepared spherical yttrium-based material is sieved to a D50 particle size of 49 μm.

[0061] The spherical yttrium-based material prepared in this preparation example has a D50 particle size of 49 μm and a mass fraction percentage of fluorine element of 15%.

[0062] Preparation Example 4: This preparation example provides a method for preparing a spherical yttrium-based material, and the preparation method is as follows: (1) According to the mass percentage, 100 parts of yttrium-based composite powder, 7 parts of water, 150 parts of polyvinyl pyrrolidone and 8 parts of ethanol are mixed, and 100 parts of yttrium oxide ceramic balls with a diameter of 8 mm are added, and high-energy ball milling is performed for 8 hours at a ball milling speed of 400 rpm to obtain a yttrium-based composite slurry; in the yttrium-based composite powder, the mass percentage of yttrium fluoride is 85%, and the D50 particle size is 0.1 μm, and the mass percentage of yttrium fluoride is 15%, and the D50 particle size is 0.1 μm; (2) granulating the yttrium-based composite slurry prepared in step (1) by spray drying, wherein the feed rate of the spray drying granulation is 120 mL / min, the air inlet temperature is 200° C., and the air outlet temperature is 150° C., to obtain yttrium-based composite particles; sieving the prepared yttrium-based composite particles to a D50 particle size of 37 μm; (3) sintering the yttrium-based composite particles obtained in step (2) at 1050° C. for 0.65 h to obtain yttrium-based aggregate particles; sieving the prepared yttrium-based aggregate particles to a D50 particle size of 37 μm; (4) The yttrium-based polymer particles obtained in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by using an external powder delivery method. The powder delivery rate is 120 g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare a spherical yttrium-based material. The distance between the emission position of the plasma jet and the cooling medium is 500 mm, the emission power of the plasma jet is 70 kW, and the cooling medium is nitrogen. The prepared spherical yttrium-based material is sieved to a D50 particle size of 37 μm.

[0063] The spherical yttrium-based material prepared in this preparation example has a D50 particle size of 37 μm and a mass fraction percentage of fluorine element of 16%.

[0064] Preparation Example 5: This preparation example provides a method for preparing a spherical yttrium-based material, and the preparation method is as follows: (1) According to the mass percentage, 100 parts of yttrium-based composite powder, 7 parts of water, 150 parts of starch and 8 parts of ethanol are mixed, and 100 parts of yttrium oxide ceramic balls with a diameter of 8 mm are added, and high-energy ball milling is performed for 8 hours at a ball milling speed of 400 rpm to obtain a yttrium-based composite slurry; in the yttrium-based composite powder, the mass percentage of yttrium oxyfluoride is 85%, and the D50 particle size is 1 μm, and the mass percentage of yttrium fluoride is 15%, and the D50 particle size is 1 μm; (2) granulating the yttrium-based composite slurry prepared in step (1) by spray drying, wherein the feed rate of the spray drying granulation is 120 mL / min, the air inlet temperature is 200° C., and the air outlet temperature is 150° C., to obtain yttrium-based composite particles; sieving the prepared yttrium-based composite particles to a D50 particle size of 37 μm; (3) sintering the yttrium-based composite particles obtained in step (2) at 1050° C. for 0.65 h to obtain yttrium-based aggregate particles; sieving the prepared yttrium-based aggregate particles to a D50 particle size of 37 μm; (4) The yttrium-based polymer particles obtained in step (3) are injected into the plasma jet generated by the Axial III high-power plasma spray gun for melting by using an external powder delivery method, the powder delivery rate is 120 g / min, and the molten droplets are sprayed into the cooling medium until the powder is cooled to room temperature to prepare a spherical yttrium-based material. The distance between the emission position of the plasma jet and the cooling medium is 800 mm, the emission power of the plasma jet is 70 kW, and the cooling medium is nitrogen. The prepared spherical yttrium-based material is sieved to a D50 particle size of 37 μm.

[0065] The spherical yttrium-based material prepared in this preparation example has a D50 particle size of 37 μm and a mass fraction percentage of fluorine element of 19%.

[0066] Preparation Example 6: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that the D50 particle size of yttrium fluoride is 1.5 μm.

[0067] Preparation Example 7: This preparation example provides a preparation method for a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that the D50 particle size of yttrium oxyfluoride is 1.5 μm.

[0068] Preparation Example 8: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that the D50 particle size of yttrium fluoride and yttrium oxyfluoride are both 1.5 μm.

[0069] Preparation Example 9: This preparation example provides a preparation method for a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that 60 parts by mass of a binder is added to the yttrium-based composite slurry.

[0070] Preparation Example 10: This preparation example provides a preparation method for a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that 250 parts by mass of a binder is added to the yttrium-based composite slurry.

[0071] Preparation Example 11: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as that of Preparation Example 1 except that the emission power of the plasma jet in step (4) is 45 kW.

[0072] Preparation Example 12: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as that of Preparation Example 1 except that the emission power of the plasma jet in step (4) is 90 kW.

[0073] Preparation Example 13: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as that of Preparation Example 1, except that the distance between the emission position of the plasma jet and the cooling medium in step (4) is 400 mm.

[0074] Preparation Example 14: This preparation example provides a method for preparing a spherical yttrium-based material. The preparation method is the same as that of Preparation Example 1, except that the distance between the emission position of the plasma jet and the cooling medium in step (4) is 900 mm.

[0075] Comparative Preparation Example 1: This comparative preparation example provides a method for preparing yttrium-based polymer particles. The preparation method is the same as Preparation Example 1 except that step (4), that is, spheroidization treatment, is not performed.

[0076] Comparative Preparation Example 2: This comparative preparation example provides a preparation method for a spherical yttrium-based material. The preparation method is the same as Preparation Example 1 except that in step (1), yttrium oxyfluoride powder is used to completely replace the yttrium-based composite powder.

[0077] Embodiment 1: This embodiment provides a yttrium-based coating, which uses the spherical yttrium-based material prepared in Preparation Example 1 as a raw material, prepares a yttrium base layer by an atmospheric plasma spraying method, and prepares a yttrium-based top layer by a suspension plasma spraying method.

[0078] The method for preparing the yttrium substrate layer by atmospheric plasma spraying comprises: (a) The substrate is cleaned with alcohol, dried, and then the surface is roughened and activated by sandblasting. The drying temperature is 85°C, the sandblasting pressure is 0.25MPa, the sandblasting distance is 90mm, the sandblasting angle is 80°, and the sandblasting material is 120# alumina white corundum sand. The above-mentioned process parameters for pretreatment of the substrate include but are not limited to the listed values, and other values ​​not listed in the numerical range are also applicable; (b) The spherical yttrium-based material is applied to the substrate surface treated in step (a) by atmospheric plasma spraying (APS) to obtain a yttrium-based coating. The current of the plasma spraying is 400A, the voltage is 50V, the auxiliary gas flow rate is 5L / min, the scanning speed is 150m / min, the energy of the plasma flame flow is adjusted by adjusting the current and the auxiliary gas, the powder feeding amount is 60L / min, the powder feeding carrier gas flow rate is 8L / min, the main gas flow rate is 45L / min, the spraying distance is 150mm, the spraying angle is 85°, and the temperature of the substrate surface is 80°C during the spraying process.

[0079] The method for preparing the yttrium-based top layer by suspension plasma spraying comprises: (a) mixing the yttrium-based composite powder described in step (1) of Preparation Example 1 with deionized water, ethanol, dispersant polyvinyl pyrrolidone and ammonium citrate, wherein the mass fraction of the yttrium-based composite powder accounts for 25% of the total mass of the slurry, the mass fraction of the dispersant polyvinyl pyrrolidone accounts for 1%-1.5% of the total mass of the slurry, the mass fraction of ammonium citrate accounts for 0.25%-0.5% of the total mass of the slurry, and the volume ratio of water to ethanol is 1:1; (b) Use Axial III spray gun for suspension plasma spraying, with main gas Ar flow rate of 55 L / min, secondary gas H2 flow rate of 15 L / min, voltage of 70 V, current of 450 A, slurry volume of 45 mL / min, spraying distance of 90 mm, and compressed air for cooling from the back of the substrate. The cooling gas pressure is 0.4 MPa-0.5 MPa to ensure that the surface temperature of the coating and the substrate is lower than 150 °C.

[0080] The SEM image of the surface of the yttrium-based coating provided in this embodiment is as follows: Figure 3 The SEM image of the cross section is shown in Figure 4 shown.

[0081] Embodiment 2: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 2 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 2 as a raw material.

[0082] Embodiment 3: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 3 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 3 as a raw material.

[0083] Embodiment 4: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 4 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 4 as a raw material.

[0084] Embodiment 5: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 5 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 5 as a raw material.

[0085] Embodiment 6: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 6 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 6 as a raw material.

[0086] Embodiment 7: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 7 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 7 as a raw material.

[0087] Embodiment 8: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 8 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 8 as a raw material.

[0088] Embodiment 9: This embodiment is the same as Embodiment 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 9 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 9 as a raw material.

[0089] Embodiment 10: This embodiment is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 10 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 10 as a raw material.

[0090] Embodiment 11: This embodiment is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 11 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 11 as a raw material.

[0091] Embodiment 12: This embodiment is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 12 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 12 as a raw material.

[0092] Embodiment 13: This embodiment is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 13 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 13 as a raw material.

[0093] Embodiment 14: This embodiment is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Preparation Example 14 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Preparation Example 14 as a raw material.

[0094] Embodiment 15: This embodiment provides a yttrium-based coating, which is the same as that of Embodiment 1 except that the yttrium-based coating is only formed by atmospheric plasma spraying and does not include a top layer obtained by suspension plasma spraying.

[0095] Embodiment 16: In this embodiment, except that the current of plasma spraying of the yttrium base layer is 650A and the voltage is 70V during the preparation process, the other conditions are the same as those in Example 1. The coating structure obtained is as follows: Figure 5 shown.

[0096] Comparative Example 1: This comparative example is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Comparative Example 1 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Comparative Preparation Example 1 as a raw material.

[0097] Comparative Example 2: This comparative example is the same as Example 1 except that the yttrium base layer uses the spherical yttrium-based material prepared in Comparative Example 2 as a raw material, and the yttrium-based top layer uses the yttrium-based composite powder in Comparative Preparation Example 2 as a raw material.

[0098] Performance Test: The hardness of the coating surface layer was measured by Vickers microhardness method, the porosity of the bottom layer and the surface layer cross section was measured by metallographic microscopy, the coated test piece was exposed to a 100-200°C glow plasma chamber and filled with CF4 gas for 100 hours, and the coating surface state and the coating and substrate bonding state were observed to test the corrosion resistance of the coating, the surface profiler was used to test the roughness of the surface coating, and the porosity of the yttrium-based coating prepared in all the above examples and comparative examples was tested. The test results are shown in Table 1.

[0099] Table 1

[0100] According to the test results of the above-mentioned Example 15, the present invention optimizes the spraying raw materials of the yttrium-based coating and uses spherical yttrium-based materials with a smooth spherical morphology, good fluidity, moderate particle size and concentrated powder particle size distribution as raw materials. The yttrium-based coating has high density, hardness and uniformity, high electrical insulation and corrosion resistance, and the dense coating reduces the generation and transfer of tiny particles, which is beneficial for resisting etching exposed to plasma.

[0101] According to the test results of Examples 1 to 5, the present invention prepares a yttrium-based top layer by spraying submicron-level ultra-fine yttrium-based composite powder on the surface of a yttrium-based coating based on a spherical yttrium-based material through suspension plasma spraying, thereby further improving the performance of the yttrium-based coating, making it more compact, more resistant to plasma etching gas corrosion, and further increasing its service life.

[0102] According to the test results of Examples 6 to 8, when the D50 particle size of yttrium fluoride and / or yttrium oxyfluoride used to prepare the spherical yttrium-based material is 1.5 μm, that is, when the D50 particle sizes of yttrium fluoride and yttrium oxyfluoride do not meet the submicron size at the same time, the quality of the prepared coating is significantly reduced, the porosity is increased, the hardness is reduced, the roughness is increased, and even powdery shedding of the coating occurs during the plasma etching process.

[0103] According to the test results of Examples 9 and 10, when the mass ratio of the binder is not within the range defined by the present invention during the preparation of the spherical yttrium-based material, the spherical yttrium material cannot be obtained and the bottom coating cannot be prepared.

[0104] In Example 16, when the power of plasma spraying is too high during the preparation of the spherical yttrium-based material, the powder particles are excessively melted into a molten droplet particle state, splashing and impacting the surface of the substrate, and rapidly depositing, cooling and shrinking to form a stress-bearing structure, such as Figure 5 As shown, shrinkage cracks occur on the coating surface, and during the plasma etching process, the coating falls off in chunks.

[0105] According to the test results of Comparative Example 1, if spheroidization treatment is not performed during the preparation of the spherical yttrium-based material, the prepared yttrium-based aggregate particles do not have a smooth spherical morphology, have poor fluidity, and have an unconcentrated powder particle size distribution. Compared with Example 1, the quality of the yttrium-based coating prepared therefrom deteriorates, and during the plasma etching process, local powder shedding of the coating occurs.

[0106] In Comparative Example 2, if the spherical yttrium-based material only contains yttrium oxyfluoride powder but does not contain yttrium fluoride, the combination of the YO group and the F group in the F atmosphere cannot be reduced during the plasma spraying process, so that the prepared Y2O3 coating particles are not tight and firm enough and are easily transferred, increasing the risk of coating degradation. Therefore, the mechanical properties and strength of the prepared yttrium-based coating are reduced, and the plasma resistance becomes worse.

[0107] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A yttrium-based coating, characterized in that The yttrium-based coating comprises an atmospheric plasma sprayed bottom layer; the atmospheric plasma sprayed coating is sprayed with a spherical yttrium-based material onto the surface of the substrate by an atmospheric plasma spraying method; The mass percentage of fluorine in the spherical yttrium-based material is 15%-20%, and the D50 particle size of the spherical yttrium-based material is 10μm-50μm; The spherical yttrium-based material is prepared by the following preparation method, which comprises: (1) mixing yttrium-based composite powder, solvent, binder and dispersant to obtain yttrium-based composite slurry; The yttrium-based composite powder comprises submicron yttrium oxyfluoride and submicron yttrium fluoride; (2) granulating the yttrium-based composite slurry described in step (1) to obtain yttrium-based composite particles; (3) sintering the yttrium-based composite particles of step (2) to obtain yttrium-based aggregate particles; (4) spheroidizing the yttrium-based particles in step (3) to obtain the spherical yttrium-based material; In the yttrium-based composite powder of step (1), the D50 particle size of the submicron yttrium oxyfluoride and the submicron yttrium fluoride is independently 0.1 μm-1 μm; The spheroidization treatment in step (4) includes plasma spheroidization treatment, and the process of the plasma spheroidization treatment includes: The yttrium-based polymer particles in step (3) are added into a plasma jet for melting to obtain yttrium-based droplets, and the yttrium-based droplets are sprayed into a cooling medium to obtain the spherical yttrium-based material.

2. The yttrium-based coating according to claim 1, characterized in that In the method for preparing the spherical yttrium-based material, the yttrium-based composite slurry in step (1) comprises, by parts by weight: 100 parts of yttrium-based composite powder; 3-10 parts of solvent; 100-200 parts of adhesive; Dispersant 3 parts - 11 parts.

3. The yttrium-based coating according to claim 1, characterized in that In the preparation method of the spherical yttrium-based material, in the yttrium-based composite powder of step (1), the mass percentage of submicron yttrium oxyfluoride is 80%-90%, and the mass percentage of submicron yttrium fluoride is 10%-20%.

4. The yttrium-based coating according to claim 1, characterized in that In the method for preparing the spherical yttrium-based material, the preparation method of the yttrium-based composite slurry in step (1) includes high-energy ball milling.

5. The yttrium-based coating according to claim 1, characterized in that In the method for preparing the spherical yttrium-based material, the granulation method in step (2) includes spray drying.

6. The yttrium-based coating according to claim 1, characterized in that In the preparation method of the spherical yttrium-based material, the sintering temperature in step (3) is 800° C.-1200° C., and the sintering time in step (3) is 0.2 h-2 h.

7. The yttrium-based coating according to claim 1, characterized in that In the method for preparing the spherical yttrium-based material, the sintering in step (3) is performed in a vacuum environment, and the vacuum degree of the vacuum environment is 10 -2 -10 -3 Pa.

8. The preparation method according to claim 1, characterized in that: In the method for preparing the spherical yttrium-based material, during the plasma spheroidization treatment, the distance between the emission position of the plasma jet and the cooling medium is 500mm-800mm.

9. The yttrium-based coating according to claim 1, characterized in that In the method for preparing the spherical yttrium-based material, during the plasma spheroidization process, the emission power of the plasma jet is 60kW-80kW.

10. The yttrium-based coating according to claim 1, characterized in that The yttrium-based coating also includes a suspension plasma spray coating; the suspension plasma spray coating is prepared by spraying the yttrium-based composite powder in step (1) onto the surface of the atmospheric ion spray coating by a suspension plasma spraying method.

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