Coating Material for Thermal Spray and Manufacturing Method of Plasma Resistant Coating Layer

Abstract

The present invention relates to a plasma-resistant thermal spray coating material and a method for manufacturing a plasma-resistant coating film, comprising the steps of: mixing 60-80% by weight of Y2O3 powder, 5-25% by weight of Al2O3 powder, and 10-30% by weight of at least one of Si powder or SiO2 powder to form a mixed powder (Step 1); mixing 1-20 parts by weight of a binder and 1-10 parts by weight of a dispersant with 100 parts by weight of the mixed powder to form a mixture (Step 2); spray-drying the mixture to form a spherical powder (Step 3); and heat-treating the spherical powder (Step 4). The technical features include the step (step 5) of spraying the heat-treated powder toward the base material to form a coating film on the base material, and there is an advantage of being able to prevent appearance defects in the form of black spots that occur when high energy is input for a high-quality thermal spray coating film when using an atmospheric plasma spraying (APS) method to manufacture semiconductor or display equipment parts, and an advantage of being able to improve the surface roughness of the coating film.

Description

Technology Field

[0001] The present invention relates to a plasma-resistant thermal spray coating material and a method for manufacturing a plasma-resistant coating film. More specifically, it relates to a plasma-resistant thermal spray coating material and a method for manufacturing a plasma-resistant coating film that can prevent black spot-shaped surface defects that occur when high energy is input to produce a high-quality thermal spray coating film when using an atmospheric plasma spraying (APS) method for manufacturing semiconductors or displays. Background Technology

[0003] Generally, chambers in equipment used in semiconductor manufacturing processes are constructed using anodized aluminum alloys or bulk ceramics such as alumina for insulation. Recently, as the need for corrosion resistance against highly corrosive gases or plasmas used in semiconductor manufacturing processes—such as deposition equipment utilizing chemical vapor deposition (CVD) or etching equipment utilizing plasma etching—has increased, chambers are being fabricated to achieve this high corrosion resistance by applying ceramics such as alumina to the aforementioned aluminum alloys through methods such as plasma spraying, thermal spraying, or sintering following compaction.

[0004] Furthermore, since the semiconductor manufacturing process conducted within the chamber comprises a majority of high-temperature processes such as heat treatment and chemical vapor deposition, the chamber is required to possess heat resistance as well. In other words, components of semiconductor manufacturing equipment such as the chamber require insulation, heat resistance, corrosion resistance, and plasma resistance. Additionally, it is necessary to maintain a strong bond between the coating layer and the substrate to prevent peeling of the coating layer, thereby minimizing particle generation and resulting wafer contamination during the manufacturing process.

[0005] To this end, conventional methods such as chemical vapor deposition, physical vapor deposition, or sputtering have been applied; however, since these are thin film manufacturing processes, there are issues of poor economic efficiency, such as the excessively long processing time required to form a thick film sufficient to satisfy the requirements for corrosion resistance, and there is also a problem in that it is difficult to obtain strong bonding strength between the substrate and the coating layer.

[0006] In addition, plasma spraying or thermal spraying methods, which are mainly used for forming thick films, have the advantage of being able to form thick films. However, since ceramic materials are generally coated onto a metal substrate, the above-mentioned hot process has the problem of reduced bonding strength due to the difference in thermal expansion rates between the metal and the ceramic during the cooling process after coating, and in some cases, there are limitations of the high-temperature process, such as the metal substrate melting and forming an oxide layer.

[0008] Korean Patent Publication No. 10-0454987 (November 6, 2004) discloses a method for manufacturing and regenerating semiconductor manufacturing components using plasma spraying.

[0009] Although the above-described method for manufacturing semiconductor components using plasma spraying has the advantage of preventing film peeling, it has the disadvantage that when a large amount of energy is input to create a high-quality spray coating film, defects in the form of black spots occur on the white background product due to the high energy, resulting in poor appearance quality characteristics. Prior art literature

[0011] (Patent Document 0001) KR 10-0454987 B1 2004.11.06. The problem to be solved

[0012] The objective of the present invention is to provide a plasma-resistant thermal spray coating material and a method for manufacturing a plasma-resistant coating film that can prevent black spot-shaped surface defects that occur when high energy is input for a high-quality thermal spray coating film when manufacturing semiconductors or displays using an atmospheric plasma spraying (APS) method.

[0013] Another objective of the present invention is to provide a plasma-resistant thermal spray coating material and a method for manufacturing a plasma-resistant coating film capable of improving the surface roughness of the coating film. means of solving the problem

[0015] To achieve the above objective, the present invention provides the following means.

[0016] The present invention provides a plasma-resistant thermal spray coating material used on the surface of a component used in semiconductor or display manufacturing equipment, comprising a powder containing 60 to 80 weight% of Y2O3 powder, 5 to 25 weight% of Al2O3 powder, and 10 to 30 weight% of at least one of Si powder or SiO2 powder.

[0017] In addition, the present invention provides a method for manufacturing a plasma-resistant coating film, comprising the steps of: mixing 60 to 80 weight% of Y2O3 powder, 5 to 25 weight% of Al2O3 powder, and 10 to 30 weight% of at least one of Si powder or SiO2 powder to make a mixed powder (Step 1); mixing 1 to 20 weight parts of a binder and 1 to 10 weight parts of a dispersant with 100 weight parts of the mixed powder to make a mixture (Step 2); spray-drying the mixture to make a spherical powder (Step 3); heat-treating the spherical powder (Step 4); and spraying the heat-treated powder toward a substrate to form a coating film on the substrate (Step 5).

[0018] After the above step 4, a step of selecting powders with an average particle size of 5 to 100 µm is added.

[0019] In step 5 above, the thickness of the coating film is 10 to 500 μm.

[0020] In addition, the present invention provides a process component of semiconductor or display manufacturing equipment comprising a plasma-resistant coating film manufactured by the method for manufacturing a plasma-resistant coating film described above. Effects of the invention

[0022] The plasma-resistant thermal spray coating material and the method for manufacturing a plasma-resistant coating film according to the present invention have the advantage of preventing appearance defects in the form of black spots that occur when high energy is input for a high-quality thermal spray coating film when manufacturing semiconductor or display equipment parts using the atmospheric plasma spraying (APS) method.

[0023] In addition, the plasma-resistant thermal spray coating material and the method for manufacturing a plasma-resistant coating film of the present invention have the advantage of being able to improve the surface roughness of the coating film. Brief explanation of the drawing

[0025] Figure 1 is a photograph illustrating the occurrence of black spot appearance defects in Comparative Example 1. Figure 2 is a photograph showing the surface color and color coordinate measurement results of the coating films of Examples 1 and 2 and Comparative Examples 1 and 2. Specific details for implementing the invention

[0026] The present invention will be described in detail below.

[0028] When manufacturing semiconductor or display equipment components using the Advanced Plasma Spray (APS) method, low energy results in lower melting of the coating material, leading to higher porosity and increased roughness, making it difficult to produce high-quality spray coating films.

[0030] Producing high-quality thermal spray coatings requires a significant input of energy; however, this high energy causes defects in the form of black spots on white-based products, resulting in poor appearance quality.

[0032] Although there is a desire to create a coating film with excellent plasma resistance and increased material meltability by coating while maintaining a high energy state, it is currently difficult to apply due to the degradation of appearance quality, such as black spot clusters.

[0034] The present invention is characterized by implementing a black coating film and thereby enabling the use of high coating energy to improve coating quality.

[0036] First, a plasma-resistant thermal spray coating material according to the present invention will be described.

[0038] The plasma-resistant thermal spray coating material of the present invention is,

[0039] As a plasma-resistant thermal spray coating material used on the surface of components used in semiconductor or display manufacturing equipment,

[0040] It is a powder comprising 60~80 wt% of Y2O3 powder, 5~25 wt% of Al2O3 powder, and 10~30 wt% of at least one of Si powder or SiO2 powder.

[0042] The present invention is characterized by solving appearance defects despite the input of high energy by forming a black coating film by mixing one or more of Si powder or SiO2 powder with Y2O3 powder and Al2O3 powder.

[0044] It is preferable that the above Y2O3 powder be included in an amount of 60 to 80 weight percent.

[0045] If the above Y2O3 powder is included in an amount of less than 60% by weight, there is a problem with reduced adhesion of the coating, and if it is included in an amount of more than 80% by weight, there is a problem with difficulty in achieving a color coordinate L of 80% or less.

[0047] It is preferable that the above Al2O3 powder be included in an amount of 5 to 25 weight percent.

[0048] If the above Al2O3 powder is included in an amount of less than 5 wt%, the Y-Al-O intermediate phase may not be properly formed, which leads to an increase in the etching rate when exposed to a plasma environment, and if it is included in an amount of more than 25 wt%, it exists as an Al2O3 phase and reacts with halogen-based corrosive gases or is etched in a plasma atmosphere, which reduces durability and increases the likelihood of generating voids, which may lead to the formation of particles.

[0050] It is preferable that at least one of the above Si powder or SiO2 powder be included in an amount of 10 to 30 weight percent.

[0051] If either or more of the above Si powder or SiO2 powder is included in an amount of less than 10% by weight, it becomes difficult to achieve a color coordinate L of 80% or less, and if it is included in an amount of more than 30% by weight, the adhesion of the coating decreases.

[0053] Next, a method for manufacturing a plasma-resistant coating film according to the present invention is described.

[0055] The method for manufacturing a plasma-resistant coating film according to the present invention is as follows:

[0056] A step of preparing a mixed powder by mixing 60~80 wt% of Y2O3 powder, 5~25 wt% of Al2O3 powder, and 10~30 wt% of at least one of Si powder or SiO2 powder (Step 1);

[0057] A step of preparing a mixture by mixing 1 to 20 parts by weight of a binder and 1 to 10 parts by weight of a dispersant with 100 parts by weight of the above mixed powder (Step 2);

[0058] A step of spray-drying the above mixture to form a spherical powder (Step 3);

[0059] A step of heat-treating the powder of the above-mentioned concept (step 4); and

[0060] A step of spraying the heat-treated powder toward a base material to form a coating film on the base material (Step 5);

[0061] Includes

[0063] Step 2 above is a step of mixing 1 to 20 parts by weight of binder and 1 to 10 parts by weight of dispersant with 100 parts by weight of the mixed powder in a wet manner.

[0065] If the above binder and dispersant are used in excess of the above range, they may act as impurities and degrade the quality of the coating film.

[0067] Step 3 above is a step of spray-drying the mixture to form a spherical powder.

[0069] Step 4 above is a step of improving strength by heat-treating the powder of the above-mentioned sphere at 100 to 1,500°C for 1 to 48 hours in an atmosphere or vacuum.

[0071] After the above step 4, a step of selecting powders with an average particle size of 5 to 100 µm through a classification process may be added.

[0073] Step 5 above is a step of forming a coating film on a base material by spraying the heat-treated powder toward the base material.

[0075] It is preferable that the thickness of the above coating film be 10 to 500 μm.

[0077] The above spraying is performed by atmospheric plasma spraying (APS).

[0078] 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 environment can be cited. Spraying conditions, such as spraying distance, current value, voltage value, argon gas supply amount, and hydrogen gas supply amount, are set according to the application of the spraying material. A predetermined amount of spraying material is loaded into a powder supply device, and the powder is supplied to the tip of the plasma spray gun through a powder hose using a carrier gas (argon). By continuously supplying powder into the plasma flame, the spraying material melts and liquefies, and is formed into a liquid frame by the force of the plasma jet. When the liquid frame comes into contact with the substrate, the molten powder adheres, solidifies, and deposits, thereby forming a coating layer.

[0080] The above base material may be a plasma device component such as an electrostatic chuck, heater, chamber liner, shower head, CVD boat, focus ring, or wall liner applied inside a plasma device, and the material of the coating target may be a metal such as iron, magnesium, aluminum or alloys thereof; a ceramic such as SiO2, MgO, CaCO3, or alumina; or a polymer such as polyethylene terephthalate, polyethylene naphthalate, polypropylene adipate, or polyisocyanate, but is not limited thereto.

[0082] In addition, the present invention provides a process component of semiconductor or display manufacturing equipment comprising a plasma-resistant coating film manufactured by the method for manufacturing a plasma-resistant coating film described above.

[0084] The method for manufacturing a plasma-resistant coating film according to the present invention has the advantage of preventing appearance defects in the form of black spots that occur when high energy is input for a high-quality thermal spray coating film when manufacturing semiconductor or display equipment parts using an atmospheric plasma spraying (APS) method.

[0085] The present invention is not limited to the Atmospheric Plasma Spray (APS) method and has the same advantages in coating methods such as the Suspension Plasma Spray (SPS) method.

[0086] In addition, the method for manufacturing a plasma-resistant coating film according to the present invention has the advantage of being able to improve the surface roughness of the coating film.

[0088] The structure and effects of the present invention will be explained in more detail below through examples. These examples are solely for illustrating the present invention, and the scope of the present invention is not limited by these examples.

[0090] [Comparative Example 1]

[0091] A mixed powder was prepared by mixing 70 wt% of Y2O3 powder, 10 wt% of Al2O3 powder, and 20 wt% of SiO2 powder. A mixture was prepared by mixing 3 wt% of a binder and 2 wt% of a dispersant with 100 wt% of the above mixed powder. The above mixture was spray-dried to form spherical powder. The above spherical powder was heat-treated at 800°C for 5 hours in a vacuum atmosphere. A coating film was formed by performing thermal spray coating using an atmospheric plasma device (Oerlikon Metco). During the thermal spray coating, plasma was generated using 40 psi of argon gas and 40 psi of helium gas, a current of 800 A, a voltage of 35 V, and a separation distance of 140 mm between the coating gun and the substrate to form a coating film with a thickness of 100 μm.

[0093] [Experimental Example 1]

[0094] Figure 1 shows an image of black spot defects occurring in the coating film coated in Comparative Example 1.

[0096] It can be seen that a large number of black spot defects occurred under coating conditions providing high energy, as in Comparative Example 1.

[0098] A mixed powder was prepared by mixing 70 wt% of Y2O3 powder, 10 wt% of Al2O3 powder, 10 wt% of SiO2 powder, and 10 wt% of Si powder. A mixture was prepared by mixing 3 wt% of a binder and 2 wt% of a dispersant with 100 wt% of the above mixed powder. The above mixture was spray-dried to form spherical powder. The above spherical powder was heat-treated at 800°C for 5 hours in a vacuum atmosphere. A coating film was formed by performing thermal spray coating using an atmospheric plasma device (Oerlikon Metco). During the thermal spray coating, plasma was generated using 40 psi of argon gas and 40 psi of helium gas, a current of 800 A, a voltage of 35 V, and a separation distance of 140 mm between the coating gun and the substrate to form a coating film with a thickness of 100 μm.

[0100] A coating film was formed by mixing 70 wt% Y2O3 powder, 10 wt% Al2O3 powder, 10 wt% SiO2 powder, and 10 wt% Si powder instead of mixing 70 wt% Y2O3 powder, 10 wt% Al2O3 powder, and 20 wt% Si powder, while keeping the rest the same.

[0102] [Comparative Example 2]

[0103] A coating film was formed by mixing 70 wt% Y2O3 powder, 10 wt% Al2O3 powder, 10 wt% SiO2 powder, and 10 wt% Si powder instead of mixing 70 wt% Y2O3 powder, 10 wt% Al2O3 powder, 10 wt% SiO2 powder, and 10 wt% SiC powder, except that the rest was the same.

[0105] [Experimental Example 2]

[0106] Color coordinates were measured (Konica Minolta CM2600D) for the coating films of Examples 1 and 2 and Comparative Examples 1 and 2 and are shown in FIG. 2.

[0108] According to Figure 2, while Comparative Example 1 has an ivory color and Comparative Example 2 has a gray color, it can be seen that the coating films of Examples 1 and 2 have a dark coating film formed.

[0110] Therefore, in the case of Examples 1 and 2, there is an advantage in that it can prevent appearance defects in the form of black spots that occur when high energy is input for a high-quality thermal spray coating film.

[0112] [Experimental Example 3]

[0113] The surface roughness (Ra) of the coating films of Examples 1 and 2 and Comparative Example 1 was measured and is shown in Table 1. The measurement speed during surface roughness measurement was 0.75 mm / s.

[0115] 1 2 3 4 5 average Comparative Example 1 4.821㎛ 5.428㎛ 5.168㎛ 5.229㎛ 5.754㎛ 5.280㎛ Example 1 4.258㎛ 4.128㎛ 3.568㎛ 3.779㎛ 4.358㎛ 4.018㎛ Example 2 3.869㎛ 4.158㎛ 4.248㎛ 4.058㎛ 3.967㎛ 4.060㎛

[0117] According to Table 1, it can be seen that the surface roughness of the coating films of Examples 1 and 2 is improved compared to the coating film of Comparative Example 1.

Claims

Claim 1 A plasma-resistant thermal spray coating material used on the surface of a component used in semiconductor or display manufacturing equipment, comprising 60 to 80 weight% of Y2O3 powder, 5 to 25 weight% of Al2O3 powder, and 10 to 30 weight% of at least one of Si powder or SiO2 powder. Claim 2 A method for manufacturing a plasma-resistant coating film, comprising: a step of making a mixed powder by mixing 60-80% by weight of Y2O3 powder, 5-25% by weight of Al2O3 powder, and 10-30% by weight of at least one of Si powder or SiO2 powder (Step 1); a step of making a mixture by mixing 1-20 parts by weight of a binder and 1-10 parts by weight of a dispersant with 100 parts by weight of the mixed powder (Step 2); a step of making a spherical powder by spray-drying the mixture (Step 3); a step of heat-treating the spherical powder (Step 4); and a step of forming a coating film on the substrate by spraying the heat-treated powder toward the substrate (Step 5). Claim 3 A method for manufacturing a plasma-resistant coating film according to claim 2, wherein a step of selecting powders with a particle size of 5 to 100 μm is added after step 4. Claim 4 A method for manufacturing a plasma-resistant coating film according to claim 2, wherein in step 5, the thickness of the coating film is 10 to 500 μm. Claim 5 A process component of semiconductor or display manufacturing equipment comprising a plasma-resistant coating film manufactured by the method for manufacturing a plasma-resistant coating film according to any one of claims 2 to 4.

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