KR102356172B1 - Method for Producing Plasma-Resistant Coating Layer - Google Patents

Abstract

According to the present invention, a method for manufacturing a plasma-resistant coating layer comprises the steps of: (1) forming a lower coating layer by spraying, onto an object to be coated, first rare earth metal compound powder including 90 to 99.9 wt% of first rare earth metal compound particles and 0.1 to 10 wt% of silica (SiO_2) particles, through a thermal spray process; (2) processing the surface of the first rare earth metal compound coating layer formed in step (1) so that the same has an average surface roughness of 1 to 6 μm; and (3) forming an upper coating layer by spraying second rare earth metal compound particles on the first rare earth metal compound coating layer, subjected to the processing of step (2), through a suspension plasma spray process. Therefore, plasma resistance and withstand voltage characteristics can be improved.

Description

Method for producing a plasma-resistant coating film {Method for Producing Plasma-Resistant Coating Layer}

The present invention relates to a method for manufacturing a plasma-resistant coating film, and more particularly, to a method for manufacturing a plasma-resistant coating film applied to a semiconductor manufacturing process including semiconductor etching equipment.

In general, a chamber of equipment used in a semiconductor manufacturing process is made using anodized aluminum alloy or ceramic bulk such as alumina for insulation.

In recent years, chambers used in semiconductor manufacturing processes, such as deposition equipment using chemical vapor deposition (CVD) or etching equipment using plasma etching, etc., have such high corrosion resistance as the need for corrosion resistance to highly corrosive gases or plasmas increases. In order to have a , a ceramic coating layer such as alumina on the aluminum alloy is manufactured through a method such as plasma spraying or thermal spraying.

In addition, since a high-temperature process, such as a heat treatment process and chemical vapor deposition, occupies a large number of semiconductor manufacturing processes performed in the chamber, the chamber is required to have heat resistance as well. In addition, a member of a semiconductor manufacturing facility such as a chamber requires insulation, heat resistance, corrosion resistance, and plasma resistance, and the coating layer and the substrate maintain a strong bonding force to prevent peeling of the coating layer, thereby generating particles during the manufacturing process and thus It is necessary to minimize wafer contamination by

For this purpose, there are cases where chemical vapor deposition, physical vapor deposition, or sputtering, which are generally used in the past, have been applied. There is a problem in that economical efficiency is lowered, such as taking, and there is a problem in that it is difficult to obtain a strong bonding force between the substrate and the coating layer.

In addition, although a method of coating a thick film through plasma spraying is suggested in Korean Patent No. 10-0454987 to coat a thick film of 100 μm or more, it is difficult to manufacture a dense coating film when the thick film is coated through plasma spraying. There is this.

On the other hand, aerosol deposition can overcome the above problems and produce a dense thick film, but in the case of a rare earth metal compound, there is a problem in that it is difficult to make a dense thick film of 100 μm or more. In the case of aerosol deposition, which is being researched recently, it is technically possible to form a 10㎛ level film, but problems such as peeling may occur during long-term use due to the low adhesion formed by simple mechanical engagement between the film and the surface, and dry etching process The film is etched by the CF ₄ plasma ions and radicals used in the process, and particles are generated, which can contaminate the wafer.

In addition, as a prior art, Korean Patent Application Laid-Open No. 10-2017-0080123 (2017.07.10.) discloses an open channel of the coating layer by double sealing through aerosol deposition and hydration treatment after thermal spray coating of the first rare earth metal compound. channel) and open pores are minimized to secure chemical resistance and to manufacture a dense rare-earth metal compound coating film.

In addition, Korea Patent Application Publication No. 10-2013-0123821 (2013.11.13.) is formed by plasma spray coating of a thermal spray coating powder mixed with 30 to 50 wt% of aluminum oxide and 50 to 70 wt% of yttrium oxide on a coating object. After preparing the amorphous first coating film, a multi-layer plasma coating film technology in which a second coating film having higher density and plasma resistance than the first coating film is formed by aerosol deposition is described.

However, in the prior literature, the coating layer prepared by atmospheric plasma spray (Atmospheric Plasma Spray) generates tensile stress due to volume contraction accompanying the melt-solidification process, and the coating layer formed by aerosol deposition is subjected to mechanical collision. As the compressive stress is generated by the multi-layer coating layer, when atmospheric plasma spraying and aerosol deposition are applied at the same time when manufacturing a multi-layer coating layer, peeling and destruction of the coating layer may be induced due to the stress difference between the coating layers.

Therefore, in the plasma-resistant coating film formed of the multi-layer coating layer, peeling and particle generation problems that may occur due to a decrease in the bonding force between the coating layers still remain, and the manufacturing technology of the plasma-resistant coating film having durability and long life characteristics is required. .

On the other hand, Suspension Plasma Spray (SPS) has emerged as a means for depositing finer particles, which is sprayed in a plasma flame after preparing a suspension by mixing a few micro-level thermal spray powder with a liquid such as water or ethanol. It is an advanced technology of plasma spraying technology that provides powder stably.

However, since suspension plasma spraying supplies high enough plasma energy to volatilize water or ethanol, it is difficult to form a thick coating layer of 150 μm or more due to thermal shock, and particles may occur due to peeling of the coating layer. In addition, the concentration of the thermal spray powder in the suspension is limited to a level of 50% or less, so the film formation rate is slow, and this film formation rate causes fatal problems in reducing the manufacturing speed and increasing the manufacturing cost.

In addition, as shown in FIG. 1 below, the suspension plasma spray does not cover all the surface roughness because the size of the spray powder used is small, and a shadow effect that generates some defects occurs, resulting in high surface roughness, low It may cause problems such as adhesion and low density.

Therefore, in order to improve the suspension plasma spraying method, the inventor has repeatedly studied a method for manufacturing a high-density plasma-resistant coating film having excellent withstand voltage characteristics while optimizing the bonding force between the coating layers, resulting in the present invention.

Korean Patent No. 10-0454987 Korean Patent Publication No. 10-2017-0080123 Korean Patent Publication No. 10-2013-0123821

The main object of the present invention is to provide a method for producing a plasma-resistant coating film having excellent bonding strength of the coating film, forming a high-density dense thin film, and having improved withstand voltage characteristics.

The present invention also provides a plasma-resistant member formed with a plasma-resistant coating film with improved plasma resistance and withstand voltage characteristics by using the method for producing the plasma-resistant coating film.

In order to achieve the above object, one embodiment of the present invention provides (1) a second composition comprising 90 to 99.9 wt % of the first rare earth metal compound particles and 0.1 to 10 wt % of silica (SiO 2 ) particles on an object to be coated 1 forming a lower coating layer using a rare earth metal compound powder through a thermal spray process; (2) surface processing the surface of the first rare earth metal compound coating layer formed in step (1) to have an average surface roughness of 1 to 6 μm; and (3) forming an upper coating layer on the first rare earth metal compound coating layer on which the processing of step (2) has been performed through a suspension plasma spraying process of the second rare earth metal compound particles; Provided is a method for manufacturing a plasma coating film.

In a preferred embodiment of the present invention, the first rare earth metal compound powder may include 95 to 99.9 wt% rare earth metal compound particles and 0.1 to 5 wt% silica (SiO2) particles.

In a preferred embodiment of the present invention, the size of the first rare earth metal compound powder may be 10 to 60 μm, and the thickness of the lower coating layer may be 50 to 500 μm.

In a preferred embodiment of the present invention, the size of the second rare earth metal compound particles may be 0.1 to 10 μm, and the thickness of the upper coating layer may be 50 to 150 μm.

In a preferred embodiment of the present invention, the porosity of the lower coating layer may be less than 2 vol%, and the porosity of the upper coating layer may be less than 1 vol%.

In a preferred embodiment of the present invention, the first rare earth metal compound and the second rare earth metal compound are each selected from the group comprising yttria (Y2O3), yttrium fluoride (YF), and yttrium oxyfluoride (YOF). can

In a preferred embodiment of the present invention, the first rare earth metal compound may be yttria (Y 2 O 3 ).

In a preferred embodiment of the present invention, the thermal spraying process in step (1) may be atmospheric plasma spraying.

In a preferred embodiment of the present invention, the surface treatment in step (2) may be performed by polishing using a diamond pad.

In another preferred embodiment of the present invention, the present invention provides a plasma-resistant member manufactured by the above manufacturing method.

In another preferred embodiment of the present invention, the present invention relates to a first rare earth metal compound powder comprising 90 to 99.9 wt % of the first rare earth metal compound particles and 0.1 to 10 wt % silica (SiO 2 ) particles by a thermal spraying process for adhesive strength. 20 (MPa) or more of the lower coating layer coated on the object to be coated; It provides a plasma-resistant coating film comprising a; an upper coating layer coated on the lower coating layer by a suspension plasma spraying process of second rare earth metal compound particles, and having a porosity of 1 vol% or less.

In a preferred embodiment of the present invention, the first rare earth metal compound and the second rare earth metal compound are each selected from the group comprising yttria (Y2O3), yttrium fluoride (YF), and yttrium oxyfluoride (YOF). can

In a preferred embodiment of the present invention, the first rare earth metal compound may be yttria (Y 2 O 3 ).

In a preferred embodiment of the present invention, the porosity of the lower coating layer may be less than 2 vol%, and the porosity of the upper coating layer may be less than 1 vol%.

In a preferred embodiment of the present invention, the thickness of the lower coating layer may be 50 to 500 μm, and the thickness of the upper coating layer may be 50 to 150 μm.

In the method for manufacturing a plasma-resistant coating film according to the present invention, the annealing effect of the lower coating layer containing the first rare earth metal compound is applied by applying the suspension plasma spray having high thermal stress when the upper coating layer containing the second rare earth metal compound is manufactured. A dense and chemically stable coating thin film can be formed through the thermal diffusion process, and in addition, plasma resistance and withstand voltage characteristics are improved due to the dense second rare earth metal compound coating layer (upper coating layer) manufactured by suspension plasma spraying. provides an effect.

In addition, the upper coating layer prepared by the suspension plasma spraying and the lower coating layer made by thermal spraying have similar tensile stresses, and thus provide stable adhesion to reduce peeling and particle generation of the coating layer.

In addition, the present invention can provide a reasonable process time by supplementing the problem of the slow film formation rate of the suspension plasma spraying by applying thermal spraying to prepare the lower coating layer.

1 is a schematic diagram for explaining a shadow effect that occurs during thermal spray coating.
2 is a schematic diagram for explaining the structure of a plasma-resistant coating film including a first rare earth metal compound coating layer and a second rare earth metal compound coating layer of the present invention.
3 is (A) Comparative Example 1, (B) the coating film prepared by Comparative Example 4 and the lower coating film in the plasma-resistant coating film according to the present invention and (D) the side of the plasma-resistant coating film prepared by Example 1 is a scanning electron microscope (SEM) picture of
Figure 4 is (A) Comparative Example 1, (B) the surface of the coating film prepared by Comparative Example 4 and the lower coating film in the plasma-resistant coating film according to the present invention and (D) the surface of the plasma-resistant coating film prepared by Example 1 is a scanning electron microscope (SEM) picture of

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In one aspect of the present invention, (1) a thermal spraying process with a first rare earth metal compound powder comprising 90 to 99.9 wt% of first rare earth metal compound particles and 0.1 to 10 wt% silica (SiO2) particles on an object to be coated forming a lower coating layer through; (2) surface processing the surface of the lower coating layer formed in step (1) to have an average surface roughness of 1 to 6 μm; and (3) forming an upper coating layer through a suspension plasma spraying process of second rare earth metal compound particles on the surface-treated lower coating layer on which the processing of step (2) has been performed. Provided is a method for manufacturing a plasma coating film.

More specifically, the method for producing a plasma-resistant coating film according to the present invention is a first rare earth metal compound powder containing 0.1 to 10 wt% silica (SiO2) particles in the coating object (A) as shown in FIG. After forming the lower coating layer (B) through a thermal spraying process, the surface is processed so that the average surface roughness of the lower coating layer (B) is 1 to 6 μm, and then suspension plasma spraying with a high coating density (SPS: Suspension Plasma Spray) Through the process, the upper coating layer (C) containing the second rare earth metal compound is formed on the surface-processed lower coating layer (B) to form a high-density plasma-resistant coating film with excellent bonding strength, plasma resistance and voltage resistance between the coating layers. can

In the method for manufacturing a plasma-resistant coating film according to the present invention, first, a first rare earth metal compound powder containing 90 to 99.9 wt% of the first rare earth metal compound particles and 0.1 to 10 wt% silica (SiO2) particles is heated to a coating object. A lower coating layer is formed by thermal spray coating [step (1)].

The coating object is an electrostatic chuck, a heater, a chamber liner, a shower head, a CVD boat, a focus ring, and a wall liner applied inside the plasma apparatus. It may be a plasma device component such as, as a material of the coating object, metal such as iron, magnesium, aluminum or alloys thereof; ceramics such as SiO2, MgO, CaCO3, and alumina; It may be a polymer such as polyethylene terephthalate, polyethylene naphthalate, polypropylene adipate, polyisocyanate, etc., but is not limited thereto.

In addition, by sanding the surface of the object to be coated to give a certain surface roughness, adhesion properties between the object to be coated and the lower coating layer including the first rare earth metal compound to be formed thereafter may be improved.

In this embodiment, the coating object may be sanded to have a surface roughness having an average center roughness value of about 1 to 6 μm. When the surface roughness of the object to be coated is less than 1 μm, the adhesive properties of the lower coating layer containing the first rare earth metal compound and the silica component formed thereafter and the object to be coated are lowered. This can happen. On the contrary, when the surface roughness of the coated object due to the sanding process exceeds 6 μm, the upper coating layer including the second rare earth metal compound formed on the lower coating layer is uniform by affecting the surface roughness of the lower coating layer to be formed thereafter. There may be a problem in that it is not formed in one thickness.

On the other hand, as shown in Table 1 below, when the coating film is prepared by using a rare earth metal compound powder containing a small amount of silica component in addition to the rare earth metal compound particles as a thermal spraying material, there is an effect of improving the adhesion of the coating layer.

division coating method Coating film type Adhesion (MPa) One APS YF3 10.0 2 APS YOF 8.0 3 APS Y2O3
(+ SiO2 0.1~10wt.%) 20.0

Therefore, in manufacturing the plasma-resistant coating film according to the present invention, in order to improve the adhesion of the lower coating layer, the first rare earth metal compound powder contains 90 to 99.9 wt % of the first rare earth metal compound particles and 0.1 to 10 wt % silica ( SiO2) particles may further improve the adhesive properties of the lower coating layer, and more preferably 95 to 99.9 wt% of the first rare earth metal compound particles and 0.1 to 5 wt% silica (SiO2) particles.

In this case, the first rare earth metal compound may be selected from the group including yttria (Y ₂ O ₃ ), yttrium fluoride (YF), and yttrium oxyfluoride (YOF), and specifically yttria (Y ₂ O ₃ ) It is preferable to be

In step (1), the lower coating layer is a layer formed by thermal spray coating of a first rare earth metal compound powder including a first rare earth metal compound and silica on an object to be coated, and a first rare earth metal compound having a particle size of 10 to 60 μm. It is preferable to use a powder, and more preferably, it can be prepared by using the first rare earth metal compound powder having a particle size of 20 to 40 μm. When the first rare earth metal compound powder is less than 10 μm, the granular powders agglomerate with each other due to the electrostatic attraction between the granular powders, making it difficult to transport in the atmosphere, or thermal spraying due to the low mass after transporting the granular powder There is a high possibility that it cannot be transferred to the central frame of the gun and deviate from the target position, and when it exceeds 60 μm, the size of the droplet increases and the size of the defect is formed relatively large in the process of solidification of the droplet, resulting in a high density. is reduced, and thus the surface roughness of the first rare earth metal compound coating layer increases, so that the second rare earth metal compound coating layer cannot form a uniform thin film.

In addition, the thickness of the first rare earth metal compound coating layer is preferably 50 to 500 μm, more preferably 100 to 200 μm. When the thickness of the first rare-earth metal compound coating layer is less than 50 μm, the effect of improving the overall film formation rate is reduced, and when it exceeds 500 μm, the process time increases, thereby reducing productivity.

In addition, the porosity of the lower coating layer formed by thermal spray coating with the first rare earth metal compound powder is preferably less than 2 vol%.

The thermal spraying of step (1) can be applied without limitation as long as it is a thermal spray coating capable of forming a coating layer that satisfies the requirements such as strong bonding strength and corrosion resistance between the coating object and the lower coating layer, preferably high hardness and Plasma spray coating can be applied in terms of high electrical resistance.

Specifically, the thermal spraying in step (1) may be performed by plasma spraying, and the plasma spraying method is atmospheric plasma spraying (APS) performed in the atmosphere, reduced pressure plasma spraying that is sprayed at an atmospheric pressure lower than atmospheric pressure ( It may be in the form of low pressure plasma spraying (LPS) or high pressure plasma spraying in which plasma spraying is performed in a pressure vessel higher than atmospheric pressure.

According to such plasma spraying, for example, the coating layer can be manufactured by generating plasma under the conditions of a voltage of 80.0V and a current of 600A using 40 NLPM of argon gas and 8 NLPM of hydrogen gas.

Moreover, the thermal spraying of this invention can be performed by atmospheric pressure plasma spraying. In this case, the plasma gas is not particularly limited and can be appropriately selected. For example, nitrogen/hydrogen, argon/hydrogen, argon/helium, argon/nitrogen, etc. can be used, and in the present invention, argon/hydrogen is thermally sprayed. it is preferable

In addition, as a specific example of plasma spraying, in the case of argon/hydrogen plasma spraying, atmospheric pressure plasma spraying using a mixed gas of argon and hydrogen in an atmospheric atmosphere may be used. Thermal spraying conditions, such as a spraying distance, a current value, a voltage value, argon gas supply amount, and hydrogen gas supply amount, condition setting according to the use of a thermal spraying member, etc. A predetermined amount of a thermal spray material is filled in the powder supply device, and the powder is supplied to the tip of the plasma thermal spray by a carrier gas (argon) through a powder hose. By continuously feeding the powder into the plasma flame, the thermal spray material is melted and liquefied, and the plasma jet is used to form a liquid frame. When the liquid frame is brought into contact with the substrate, the molten powder is adhered, solidified, and deposited, thereby forming the first rare earth metal compound coating layer.

Subsequently, step (2) is a step of surface processing the surface of the lower coating layer including the first rare earth metal compound and the silica component to have an average surface roughness of 1 to 6 μm.

In the method for producing a plasma-resistant coating film according to the present invention, the step (2) is a step of processing the surface of the lower coating layer formed in the step (1) to have an average surface roughness of 1 to 6 μm, wherein (1) After grinding is performed so that the lower coating layer formed in the step has a uniform thickness, the surface is roughened so that the surface of the lower coating layer has an average surface roughness of 1 to 6 μm.

In this case, the surface processing may be performed by polishing using a diamond pad, but is not limited thereto. In addition to polishing using a diamond pad, it may be polished using chemical mechanical polishing (CMP) or other polishing procedures.

Through the surface processing, the surface of the lower coating layer formed in step (1) may be roughened to have an average surface roughness of 1 to 6 μm, thereby improving adhesion between the lower coating layer and the upper coating layer. When the average surface roughness of the surface of the lower coating layer is 6 μm or more, the surface roughness becomes excessively high and the coating is not performed properly on the lower coating layer, which may cause peeling of the upper coaching layer.

Subsequently, step (3) is a step of forming an upper coating layer by depositing a second rare earth metal compound by suspension plasma spraying to form a denser coating layer on the lower coating layer.

On the other hand, in forming the double coating layer, the upper coating layer may be formed by aerosol deposition on the lower coating layer prepared by atmospheric plasma spraying as disclosed in the prior literature. In addition, after forming the lower coating layer by atmospheric plasma spraying as in the present invention, the upper coating layer can be formed by aerosol suspension plasma spray deposition.

In this case, as shown in Table 2 below, the coating layer prepared by atmospheric plasma spraying generates tensile stress, and as the coating layer formed by aerosol deposition generates compressive stress due to mechanical collision, atmospheric plasma spraying When applying and aerosol deposition at the same time, peeling and breaking of the coating layer may be induced due to the stress difference between the coating layers. , delamination between the coating layers due to the stress difference is not induced.

APS SPS Aerosol Deposition Coating Stress (MPa) -3.0 ± 6.0 -3.0 ± 6.0 -195.9 ± 49.9 Base stress (MPa) -26.9 ± 13.9 -30 ± 15.8 -63.9 ± 17.1 base metal stress
- Coating stress (MPa) -10 to -43.8 -10 to -55.8 99.2 ~ 199 stress tensile stress tensile stress compressive stress

Therefore, in forming the plasma-resistant coating film of the present invention, in order to improve the adhesion between the lower coating layer and the upper coating layer prepared by atmospheric plasma spraying, the second rare earth compound is prepared by using a suspension plasma spraying method to form the upper coating layer. An upper coating layer containing

As an embodiment, a second rare earth metal compound suspension composition for forming an upper coating layer including the second rare earth metal compound will be described.

As an embodiment, the second rare earth metal compound powder is ball milled at a revolutions per minute (RPM) range of 100 to 140 for 3 hours or more to prepare solid contents, and then distilled water is mixed do. A slurry composition is prepared by adding a dispersant or the like as an additive. In this case, the content of the second rare earth metal compound powder may be included in an amount of 10 to 50 parts by weight based on 100 parts by weight of distilled water.

In this case, as the second rare earth metal compound, it is preferable to use a powder having a particle size of 0.1 to 10 μm, and more preferably, a powder of the second rare earth metal compound having a particle size of 1 to 5 μm may be used. If the powder of the second rare earth metal compound is less than 0.1 μm, it is difficult for the powder of the second rare earth metal compound in the solvent to agglomerate and disperse. Therefore, it is difficult to achieve the object of the present invention.

According to this suspension plasma spraying, for example, the plasma generation conditions are argon gas 340SCFH, nitrogen gas 100SCFH, hydrogen gas 80SCFH supply at a flow rate of 285.0V voltage and current 380A to generate plasma under the conditions of 380A to form a coating layer. .

In this case, the upper coating layer including the second rare earth metal compound may be formed by repeatedly laminating the second rare earth metal compound twice or more using the above-described suspension plasma spraying method.

In addition, the thickness of the upper coating layer including the second rare earth metal compound is preferably 50 to 150 ㎛. If the thickness of the second rare earth metal compound coating layer is less than 50 μm, it is difficult to secure plasma resistance because the thickness of the chemically stable and dense second rare earth metal compound coating layer is not sufficient. When it exceeds 150 μm, the residual stress of the coating layer Due to this, not only peeling may occur, but also a phenomenon that the withstand voltage characteristic is deteriorated occurs.

As shown in Table 3 below, the coating layer formed by the suspension plasma spraying of yttria (Y ₂ O ₃ ) solution exhibits an effect of improving the withstand voltage characteristics as the thickness of the coating layer increases in the range of 150 μm or less, whereas the coating layer When the thickness of the layer exceeds 150 μm, as the thickness of the coating layer increases, the withstand voltage characteristic is rather deteriorated.

division coating method Coating film type coating film thickness Withstand voltage (V) One SPS Y2O3 coating film 50 2,384 2 SPS Y2O3 coating film 100 2,453 3 SPS Y2O3 coating film 150 2,173 4 SPS Y2O3 coating film 200 1987

In this case, it is preferable that the upper coating layer including the second rare earth metal compound has a low porosity and dense in order to secure the mechanical strength and electrical properties of the plasma-resistant coating film.

Therefore, the porosity of the upper coating layer including the second rare earth metal compound formed by the suspension plasma spray coating is less than 1 vol%, and the porosity of the lower coating layer including the first rare earth metal compound and the silica component is 2 vol%. It is preferable to indicate a numerical value.

In one embodiment, the porosity of the upper coating layer containing the second rare earth metal compound is 40% or less of the porosity of the lower coating layer containing the first rare earth metal compound and the silica component to form a chemically stable coating film with improved plasma resistance It is more preferable in terms of

In addition, the second rare earth metal compound may be selected from the group including yttria (Y ₂ O ₃ ), yttrium fluoride (YF), and yttrium oxyfluoride (YOF), and specifically, yttria (Y ₂ O). ₃ ), more preferably, the first rare earth metal compound and the second rare earth metal compound are the same component between the first rare earth metal compound coating layer (lower coating layer) and the second rare earth metal compound coating layer (upper coating layer) Since the bonding strength is improved, it is possible to minimize the generation of particles and contamination of the wafer due to the peeling of the coating film and the manufacturing process.

In another aspect of the present invention, (1) a first rare earth metal compound powder comprising 90 to 99.9 wt% of first rare earth metal compound particles and 0.1 to 10 wt% silica (SiO2) particles on an object to be coated is subjected to a thermal spraying process forming a lower coating layer through; (2) surface processing the surface of the first rare earth metal compound coating layer formed in step (1) to have an average surface roughness of 1 to 6 μm; and (3) forming an upper coating layer on the first rare earth metal compound coating layer on which the processing of step (2) has been performed through a suspension plasma spraying process of the second rare earth metal compound particles; It provides a plasma-resistant member manufactured by a method of manufacturing a plasma coating film.

In another aspect of the present invention, the present invention provides an adhesive strength of 20 ( MPa) or more, comprising an upper coating layer coated on the lower coating layer by a suspension plasma spraying process of the lower coating layer and the second rare earth metal compound particles coated on the object to be coated, and having a porosity of 1 vol% or less It provides a plasma-resistant coating film .

In this case, the first rare earth metal compound and the second rare earth metal compound may be selected from the group comprising yttria (Y ₂ O ₃ ), yttrium fluoride (YF), and yttrium oxyfluoride (YOF), respectively, and preferably Preferably, the first rare earth metal compound may be yttria (Y ₂ O ₃ ).

In addition, the porosity of the lower coating layer may be less than 2 vol%, the porosity of the upper coating layer may be less than 1 vol%, the thickness of the lower coating layer is 50 to 500 μm, and the thickness of the upper coating layer is 50 to 150 μm. can

Hereinafter, the present invention will be described in more detail through examples. However, the following examples only illustrate the present invention, and the present invention is not limited by the following examples.

Comparative Examples 1-3

It was performed using an atmospheric plasma spraying device (Oerlikon Metco, F4MB), and plasma was generated at a voltage of 80.0V and a current of 600A using 40 NLPM of argon gas and 8 NLPM of hydrogen gas, Y ₂ O ₃ , YF ₃ or YOF A coating layer was formed on the thermal spray coating powder to a thickness of 150 μm.

Comparative Examples 4 to 6

It was performed using a suspension plasma thermal spraying device (Progressive, 100HE), and using a flow rate of argon gas 340SCFH, nitrogen gas 100SCFH, and hydrogen gas 80SCFH, plasma was generated at a voltage of 285.0V and a current of 380A, and Y ₂ to a thickness of 100㎛ O ₃ , YF ₃ or YOF coating layer was formed.

division material coating method Hardness
(Hv) porosity
(%) surface
asperity adhesion Comparative Example 1 Y2O3 APS 415 4.5 4.5±0.4 10.0 Comparative Example 2 YF3 APS 272 1.7 5.1±0.8 10.0 Comparative Example 3 YOF APS 377 4.4 4.6±0.5 8.0 Comparative Example 4 Y2O3 SPS 524 0.6 2.0±0.5 15.0 Comparative Example 5 YF3 SPS 466 0.8 2.2±0.4 13.0 Comparative Example 6 YOF SPS 497 0.8 1.7±0.2 10.0

Examples 1-3

1-1: lower coating layer formation

It was carried out using an atmospheric plasma spraying device (Oerlikon Metco, F4MB), and plasma was generated at a voltage of 80.0V and a current of 600A using 40 NLPM of argon gas and 8 NLPM of hydrogen gas to form a coating layer with an average thickness of 200 μm. Thereafter, surface processing was performed so that the surface roughness of the coating layer was 1 to 3 μm and the thickness of the coating layer was 150 μm by surface polishing.

1-2: upper coating layer formation

It was performed using a suspension plasma thermal spraying device (Progressive, 100HE), and using a flow rate of argon gas 340SCFH, nitrogen gas 100SCFH, and hydrogen gas 80SCFH, plasma was generated at a voltage of 285.0V and a current of 380A to create a 50㎛ thickness Y ₂ O ₃ , YF ₃ or YOF coating layer was formed.

division lower coating layer top coating layer Hardness
(Hv) porosity
(%) surface
asperity adhesion
(MPa) material coating method material coating method Example 1 Y2O3 +
1wt% SiO2 APS Y2O3 SPS 542,
531 0.8 1.8±0.2 20.0 Example 2 Y2O3 +
1wt% SiO2 APS YF3 SPS 554,
458 0.9 1.9±0.3 20.0 Example 3 Y2O3 +
1wt% SiO2 APS YOF SPS 548,
487 0.9 1.8±0.3 20.0

As shown in Table 4, the plasma-resistant coating film according to Examples 1 to 3 not only had better adhesion than the coating film according to Comparative Examples 1 to 6, but also had excellent mechanical properties, and it was confirmed that a dense thin film was formed. .

In addition, as shown in FIGS. 3 (D) and 4 (D), the high-density upper coating layer in the plasma-resistant coating film prepared by Example 1 forms a coating layer having a very dense structure compared to the lower coating layer. confirmed that.

A: Coating object
B: first rare earth metal compound coating layer (lower coating layer)
C: Second rare earth metal compound coating layer (upper coating layer)

Claims (15)

(1) forming a lower coating layer on the object to be coated through a thermal spray process of first rare earth metal compound powder including 90 to 99.9 wt % of first rare earth metal compound particles and 0.1 to 10 wt % silica (SiO 2 ) particles ;
(2) surface processing the surface of the first rare earth metal compound coating layer formed in step (1) to have an average surface roughness of 1 to 6 μm; and
(3) forming an upper coating layer on the first rare-earth metal compound coating layer on which the processing of step (2) has been performed through a suspension plasma spraying process of the second rare-earth metal compound particles; Plasma-resistant, comprising: Method for manufacturing a cast coating film.
According to claim 1,
The first rare earth metal compound powder is a method of manufacturing a plasma-resistant coating film, characterized in that it comprises 95 to 99.9 wt% of the rare earth metal compound particles and 0.1 to 5 wt% silica (SiO2) particles.
The method of claim 1,
The size of the first rare earth metal compound powder is 10 to 60 μm,
The thickness of the lower coating layer is a method for producing a plasma-resistant coating film, characterized in that 50 to 500 μm.
According to claim 1,
The size of the second rare earth metal compound particles is 0.1 to 10 μm,
The thickness of the upper coating layer is a method for producing a plasma-resistant coating film, characterized in that 50 to 150 μm.
The method of claim 1,
The porosity of the lower coating layer is less than 2 vol%,
The porosity of the upper coating layer is a method for producing a plasma-resistant coating film, characterized in that less than 1 vol%.
The method of claim 1,
The first rare earth metal compound and the second rare earth metal compound are each selected from the group comprising yttria (Y ₂ O ₃ ), yttrium fluoride (YF), and yttrium oxyfluoride (YOF). Plasma resistant, characterized in that Method for manufacturing a cast coating film.
According to claim 1,
The first rare earth metal compound is yttria (Y ₂ O ₃ ) Method for producing a plasma-resistant coating film, characterized in that.
According to claim 1,
The thermal spraying process of step (1) is a method for producing a plasma-resistant coating film, characterized in that atmospheric plasma spraying.
The method of claim 1,
The surface processing of step (2) is a method for producing a plasma-resistant coating film, characterized in that performed by polishing (polishing) using a diamond pad.
The plasma-resistant member manufactured by any one of the manufacturing methods of any one of Claims 1-9.
The first rare earth metal compound powder comprising 90 to 99.9 wt% of the first rare earth metal compound particles and 0.1 to 10 wt% silica (SiO2) particles is coated on the object to be coated with an adhesive strength of 20 (MPa) or more through a thermal spray process. coating layer;
A plasma-resistant coating film comprising a; an upper coating layer coated on the lower coating layer by a suspension plasma spraying process of second rare earth metal compound particles, and having a porosity of 1 vol% or less.
12. The method of claim 11,
The first rare earth metal compound and the second rare earth metal compound are each selected from the group comprising yttria (Y ₂ O ₃ ), yttrium fluoride (YF), and yttrium oxyfluoride (YOF). Plasma resistant, characterized in that castle coating film.
12. The method of claim 11,
The first rare earth metal compound is yttria (Y ₂ O ₃ ) Plasma-resistant coating film, characterized in that.
12. The method of claim 11,
The porosity of the lower coating layer is less than 2 vol%,
Plasma-resistant coating film, characterized in that the porosity of the upper coating layer is less than 1 vol%.
12. The method of claim 11,
The thickness of the lower coating layer is 50 to 500 µm, and the thickness of the upper coating layer is 50 to 150 µm.

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