KR102071944B1 - Plasma resistant dense ceramic coating film and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a method of manufacturing a dense ceramic coating film using a melt coating method for ceramics for plasma, and more specifically, to forming a ceramic coating film using a YAS-based (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) frit. A method comprising: melting a glass of Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ or their precursors to produce a glass frit; Coating the prepared YAS-based glass frit on a ceramic base and then melting at a temperature between a softening point temperature of the glass frit and a glass frit manufacturing temperature to form a ceramic coating film; And reheating the ceramic matrix on which the ceramic coating film is formed; and wherein the frit has an average particle diameter (D ₅₀ ) of 20 μm to 60 μm. .

Description

Plasma resistant dense ceramic coating film and manufacturing method thereof

The present invention relates to a method for producing a dense ceramic coating film using a melt coating method for ceramics for plasma resistance, the average particle diameter of the YAS-based (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) frit as a material for the melt coating The present invention provides a method for producing a compact ceramic coating film for controlling plasma by controlling the porosity in the coating film by controlling the coating temperature during melt coating.

As ultrafine wire width is required in the semiconductor manufacturing process, it is very important to reduce the generation of contaminant particles in the chamber in which the plasma process is performed. In general, the plasma process generates chemically active radicals to promote chemical reactions with the material, and the cations dissociated by the plasma enter the surface of the material to facilitate the reaction, and accompanied by physical etching of the material. do.

In order to reduce the generation of contaminant particles in the plasma etching process, a material having low reactivity to the plasma, that is, excellent plasma resistance has been widely adopted.

The component to be developed in the present invention is a core component of the consumable ceramic which forms the inside of the chamber of the semiconductor plasma etching (Asher) process equipment for determining the production yield of the semiconductor chip. Al ₂ O ₃ , SiC, AlN, Y ₂ O _3, etc.), quartz, silicon, etc. are used, and recently, Y ₂ O ₃ , which has excellent plasma resistance, is being adopted.

However, it is obvious that Y ₂ O ₃ is a material showing excellent plasma resistance, but since it is very expensive, a study on Y ₃ Al ₅ O ₁₂ , which is a representative compound between Y ₂ O ₃ and Al ₂ O ₃ , has recently been conducted. In order to reduce the cost to the material, a method of using a plasma-resistant material in a coating rather than bulk has also been derived.

In the case of the spray coating generally applied in relation to the plasma material resistant to coating, there is a problem of generating pores in the base material. In addition, the splat produced by quenching the molten particles is generated with a very weak bonding force, the coating peeling occurs in the plasma etching process and there is also a problem that can cause the process contamination due to particle dropping accordingly.

In addition, the coating method may include aerosol deposition, sputtering, electron beam deposition, thermal deposition, laser deposition, etc. in addition to the spraying method. There is a problem that can act as a factor to increase the production cost required separately.

The present invention has been made to solve the above-described problems, the present invention is applied to the melt coating method away from the coating method having the above problems, the coating method by coating the glass frit for plasma resistant to the base material by the melt coating method In particular, the use of a simple coating method can be minimized, and at the same time, the plasma glass easily penetrates into the base material, and thus, the purpose of securing the compactness of the coating layer for plasma-resistant strengthened bonding strength between the base material and the interface.

In addition, another object of the present invention is to enable a more dense coating film when coated on a ceramic substrate by controlling various process variables such as the particle size, coating temperature of the glass frit.

The present invention, in order to achieve the above object, in the method of forming a ceramic coating film using a YAS-based (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) frit, Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ or Melting their precursors to produce a glass frit; Coating the prepared YAS-based glass frit on a ceramic base and then melting at a temperature between a softening point temperature of the glass frit and a glass frit manufacturing temperature to form a ceramic coating film; And reheating the ceramic matrix on which the ceramic coating film is formed; and wherein the frit has a mean particle diameter (D ₅₀ ) of several μm to 60 μm. .

The temperature between the softening point temperature of the glass frit and the glass frit manufacturing temperature is preferably melted for 30 minutes to 2 hours.

It is preferable that the said ceramic base is sintered alumina.

The content of the Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ is 15 mol% to 40 mol%, 10 mol% to 50 mol%, 30 mol% to 60 mol%, respectively, based on the sum of the three components. desirable.

In order to control the pore amount of the ceramic coating film, it is preferable to maintain the coating temperature in a range of 100 ° C. higher than the coating temperature in the coated state.

The upper limit of the coating temperature is preferably the manufacturing temperature of the glass frit.

In addition, the present invention is prepared by the above-mentioned manufacturing method, the frit-resistant dense ceramic coating film, characterized in that the average particle diameter (D ₅₀ ) of the frit has a porosity of more than 0% and less than 6% To provide.

According to the present invention as described above, it is advantageous in the process part in view of the melting coating method is possible to coating even a ceramic powder having a particle size distribution of irregular shape and wide distribution, unlike the general coating powder having a uniform and spherical particle size The effect is expected.

In addition, unlike the coating method commonly used, by applying the melt coating method, the coating film has high density and strong interfacial bonding force with the base material, and thus a favorable effect as a coating film for plasma is expected.

In addition, an expensive device for coating is not required separately, and the pore size, pore distribution, and porosity of the coating film can be variously controlled only by controlling the size of the frit and controlling the heat treatment conditions, and thus an advantageous effect is expected in an economic aspect.

1 is a microstructure micrograph shown after coating a glass frit having an average particle diameter (D ₅₀ ) of 52.652 μm at 1500 ° C. FIG.
FIG. 2 is a microstructure micrograph showing a glass frit having an average particle diameter (D ₅₀ ) of 20.134 μm after coating at 1500 ° C. FIG.
Figure 3 is a microstructure micrograph shown after coating a glass frit with an average particle diameter (D ₅₀ ) 1.669㎛ at 1500 ℃.
Figure 4 is a microstructure micrograph shown after coating a glass frit with an average particle diameter (D ₅₀ ) 52.652㎛ at 1550 ℃.
Figure 5 is a microstructure micrograph shown after coating a glass frit with an average particle diameter (D ₅₀ ) of 20.134㎛ at 1550 ℃.
6 is a microstructure micrograph showing the glass frit having an average particle diameter (D ₅₀ ) of 1.669 μm after coating at 1550 ° C. FIG.
FIG. 7 is a microstructure micrograph of a glass frit having an average particle diameter (D ₅₀ ) of 52.652 μm after coating at 1600 ° C. FIG.
FIG. 8 is a microstructure micrograph of the glass frit having an average particle diameter (D ₅₀ ) of 20.134 μm after coating at 1600 ° C. FIG.
FIG. 9 is a microstructure micrograph of the glass frit having an average particle diameter (D ₅₀ ) of 1.669 μm after coating at 1600 ° C. FIG.
10 is a photograph showing a comparison of the coating film microstructure according to the coating temperature and the average particle diameter.
11 is a graph showing the average pore size after coating according to the YAS frit average particle diameter.
12 is a microstructure micrograph showing a glass frit having an average particle diameter (D ₅₀ ) of 50.652 μm after coating at 1600 ° C., with a coating thickness of 1327.5 μm.
13 is a photograph showing the analysis of the porosity of the coating film after coating the YAS frit (D ₅₀ = 52.652㎛) 1600 ℃ through image analysis.

Hereinafter, the present invention will be described in detail with reference to the preferred embodiments and the accompanying drawings.

-Starting material

As a starting material in order to achieve the object of the present invention of the _{Y 2 O 3, Al 2 O} 3, SiO 2 , or by melting their precursors was prepared a glass frit, Y ₂ O therefor _{3, Al 2 O 3, SiO} 2 The content is preferably 15 mol% to 40 mol%, 10 mol% to 50 mol%, and 30 mol% to 60 mol%, based on the sum of the three components, respectively. If it is out of this range, the unstable YAS is generated or it is difficult to generate the YAS, so the above range is of critical significance.

-Melt coating method

The prepared YAS-based glass frit is coated on sintered alumina ceramics, and then melted at a temperature between the softening point temperature of the glass frit and the frit manufacturing temperature for 30 minutes to 2 hours to prepare a ceramic coating film. Plasma resistance of the coating film through reheat treatment In addition to improving durability, such as peeling resistance, compactness can be improved. The coating method can be any method such as applying the paste and powder as it is.

Here, when melt coating at a temperature below the softening point of the frit, the frit is not sufficiently melted and the viscosity is high, so that the absorption of the molten glass interface is impossible, and when the frit melt is carried out at a temperature exceeding the frit manufacturing temperature, the frit melt is all inside the base material. As it is absorbed into, it does not form a coating layer on the surface. Therefore, there is a critical significance in the above range. At this time, the absorbed depth is proportional to the initial coating amount, temperature and holding time, and when absorbed for 2 hours or more, excessive absorption into the base material may occur and bending of the base material may occur.

-Dense coating film control

When the coating film is prepared by the melt coating method, the pores are formed as follows. The melt at the time when the frit is completely melted contains many fine bubbles due to the air that enters when the frit melts. Such bubbles are isolated during cooling to form pores, and in order to remove the bubbles, a process design for suppressing bubble generation or removing bubbles is required.

It is also an object of the present invention to manufacture a YAS-based dense coating film to suppress the formation of bubbles and to remove the bubbles generated by improving the filling rate of the YAS frit applied on sintered alumina ceramics or by controlling the viscosity of the melt To prepare a coating layer.

The method of improving the filling rate of the YAS frit is a useful method for controlling the size of the frit, and it is easy for the dense coating film to have an average particle diameter (D ₅₀ ) of 20 μm to 60 μm.

In the case of 20 μm or less, the pore size decreases but the pore distribution area increases, and in the case of 60 μm or more, it is disadvantageous for frit coating. Therefore, there is a critical significance in the above numerical range.

The particle size control through the grinding of the manufactured YAS glass frit can be controlled through various grinding methods such as basket mill, bead mill, tumbling mill, planetary ball mill, etc.In addition to particle size control, all methods including uniaxial pressure molding and cold hydrostatic molding are additionally added. It is possible to improve the filling rate of the frit.

Viscosity control of the melt is preferable and easy to control the coating temperature, in the case of the coating film can form the most dense coating film when melted at 100 ℃ higher than the coating temperature or coating temperature of the frit. Below the coating temperature of the frit, the penetration increases due to the increase in viscosity, which adversely affects the increase in interfacial adhesion. If the coating temperature exceeds 100 ° C, the frit is excessively penetrated into the base material, causing deformation and destruction of the base material. The thickness of the coating film is significantly lowered. Here, the coating temperature is the softening point of the glass frit to the manufacturing temperature of the glass frit, wherein the manufacturing temperature of the glass frit should be equal to or higher than the melting temperature of the glass.

-Property evaluation

Three YAS frits having different average particle diameters (D ₅₀₎ were manufactured as shown in Table 1 below through a grinding process.

Average particle size of YAS frit measured after controlling average particle size through grinding process Sample d (0.1), μm d (0.5), μm d (0.9), μm Example 1 6.828 52.652 104.448 Example 2 1.913 20.134 68.541 Example 3 0.821 1.669 3.28

Here, d (0.1) means D ₁₀ and represents the size at 10% of the total particle size distribution. d (0.5) is the same as D ₅₀ in the notation and shows the size when it is 50% of the total particle size distribution, and is generally expressed as the average particle size. d (0.9) is the same as D ₉₀ in the notation, indicating the size at 90% of the total particle size distribution.

Using the frit prepared according to the above was observed the microstructure of the YAS-based coating film prepared according to the average particle diameter and coating temperature (see FIGS. 1 to 10). As the average particle diameter decreases, the pore size tends to decrease as the filling rate increases (FIG. 11). However, as can be seen in FIG. 10, the frit having the average particle diameter of 1.669 μm of Example 2 has a large pore size. Although the number was reduced, it was confirmed that the micropores of about 10 μm or less were generally distributed. This is judged to be the result of the increase in the number of fine pores formed in the melt as the average particle diameter decreases.

In addition, as the coating temperature increases, the pore size tends to decrease, and the pore distribution also tends to decrease significantly. This is judged to be the result of the viscosity of the melt decreasing as the temperature increases.

As shown in FIG. 12, when the coating layer was coated with a thickness of 1000 μm or more to observe the distribution form of bubbles, it was confirmed that the distribution of pores was located at the upper end of the coating film as the average particle diameter was larger. In addition, in order to form a higher dense coating film, it is necessary to process the coating film to an appropriate thickness after manufacturing the coating film.

As shown in FIG. 13, the porosity of the prepared YAS coating film was measured and analyzed by image analysis on a total of 20 surfaces according to ASTM E2109-01 (Test method B), and as the average particle diameter of the YAS frit was larger, the coating film was obtained. The average porosity of was low. The porosity analysis results of the coating film are summarized in [Table 2].

Analysis of porosity of coating layer prepared under coating condition 1600 ℃ according to average particle diameter (D ₅₀ = 52.652) D ₅₀ = 52.652 μm No.1 2.82% No.2 2.18% No.3 8.81% No.4 4.02% No.5 5.46% No.6 8.43% No.7 8.46% No.8 5.20% No.9 8.19% No.10 4.15% No.11 3.96% No.12 5.36% No.13 3.74% No.14 8.79% No.15 11.12% No.16 11.03% No.17 10.79% No.18 3.32% No.19 2.46% No.20 4.28% AVE 6.13%

According to the present invention, it is possible to produce a coating layer having an average porosity of 6% or less, and in this case, the average particle diameter of the glass frit to be used is in the range of several μm to 60 μm. Here, several micrometers are 1 micrometer or less and 10 micrometers range.

The coating temperature is based on the softening point temperature of the glass frit to the glass frit manufacturing temperature range. The coating temperature for producing a dense coating film is preferably proceeded at a temperature higher than or equal to 100 ℃ than the coating temperature of the frit, if the temperature is out of the following occurs. First, when the melt coating is performed at a temperature below the coating temperature of the frit, the frit is not sufficiently melted and the viscosity is high, so that the surface absorption of the molten glass is impossible. It does not form a coating layer.

In addition, if the average particle size of the frit is less than several μm, the pore size decreases, but the number of pores is present in a large amount, which is disadvantageous in terms of porosity. Decreases, but the pore size becomes too large and may cause a defect of the coating layer itself.

Although the present invention has been described in more detail with reference to examples, the present invention is not necessarily limited to these examples, and various modifications can be made without departing from the spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not stabilized by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (7)

In the method of forming a ceramic coating film using a YAS-based (Y ₂ O ₃ -Al ₂ O ₃ -SiO ₂ ) frit,
Melting glass of Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ or their precursors to produce a glass frit;
Coating the prepared YAS-based glass frit on a ceramic base and then melting at a temperature between a softening point temperature of the glass frit and a glass frit manufacturing temperature to form a ceramic coating film;
Reheating the ceramic base on which the ceramic coating film is formed;
It includes, the average particle diameter of the frit (D ₅₀ ) is a few ㎛ ~ 60㎛,
Forming a ceramic coating film;
Method of manufacturing a dense ceramic coating film for plasma resistance, characterized in that to maintain a range of coating temperature to 100 ℃ higher than the coating temperature in the coated state in order to control the pore amount of the ceramic coating film. The method of claim 1,
In the step of forming the ceramic coating film,
A method for producing a dense ceramic coating film for plasma resistance, characterized in that the glass frit is melted for 30 minutes to 2 hours at a temperature between the softening point temperature of the glass frit and the glass frit manufacturing temperature. The method of claim 1,
The ceramic base is a manufacturing method of the dense ceramic coating film for plasma resistance, characterized in that the sintered alumina. The method of claim 1,
The content of Y ₂ O ₃ , Al ₂ O ₃ , SiO ₂ is 15 mol% to 40 mol%, 10 mol% to 50 mol%, and 30 mol% to 60 mol%, respectively, based on the sum of the three components. The manufacturing method of the dense ceramic coating film for plasma to be made. delete delete It is prepared by the manufacturing method of any one of claims 1 to 4,
A dense ceramic coating film for plasma resistance, characterized in that the average particle diameter (D ₅₀ ) of the frit as starting material is several μm to 60 μm, and has a porosity of more than 0% and 6% or less.

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