TWI733815B - Method of aerosol deposition coating for plasma resistant coating - Google Patents

Abstract

The present invention is related to the aerosol deposition coating method of plasma resistant coating. More specifically, during plasma etching, the inside of the equipment is protected in the plasma environment, so that the roughness of the metal base material coating layer is reduced , Reduce the occurrence of particles, and improve the bonding force of the coating layer and the metal base material. The aerosol deposition coating method of plasma resistant coating is related to this.

Description

Aerosol deposition coating method for plasma resistant coating

The aerosol deposition coating method of the plasma resistant coating of the present invention is related to the aerosol deposition coating method, so that when the plasma is etched, the inside of the equipment is not affected by the plasma, and the roughness of the metal base material coating layer is reduced, so that The aerosol deposition coating method that generates fewer particles and improves the bonding force between the coating layer and the metal base material.

Semiconductor components, display screen components, and other integrated circuit components are manufactured by etching or chemical vapor deposition (Chemical Vapour Deposition, CVD) coating methods in a high-density plasma environment. Therefore, it is necessary to use plasma-resistant accessories to assemble the etching device in a high-density plasma environment.

In the etching of the high-density plasma environment, ceramic materials such as rare earth oxide, aluminum nitride, silicon oxide, and metal materials of anodized coating are used as plasma resistant accessories.

However, recently manufactured integrated circuit components with a line width of less than 20 nm require etching and other processes in a higher-density plasma environment. Therefore, compared with the mentioned single aerosol deposition coating film or anodic oxidation coating of semiconductor equipment accessories, plasma resistant accessories have higher requirements for plasma resistance and electrical insulation properties.

In order to solve the above-mentioned problem, the Korean Laid-open Patent Publication No. 10-2013-0123821 (2013.11.13) included an amorphous first coating film formed by an aerosol deposition coating and an aerosol deposition method. For the second coating film, the plasma resistant parts of the two coating films are technically recorded.

The problem is that despite the continuous development of the above-mentioned plasma resistant parts, in the semiconductor manufacturing process, corrosive gas or plasma process, the bonding force between the coating layer and the base material is insufficient, and the corrosion of the base material causes the generation of particles. In the field of technology, continuous development is still required.

<Patent Literature>

(Patent Document 0001) Korean Patent Publication No. 10-2013-0123821 (2013.11.13)

<Invention Purpose>

The purpose of the present invention is to protect the inside of equipment from plasma damage during plasma etching, and to reduce the roughness of the base material coating layer and the generation of particles. In order to improve the bonding force between the coating layer and the metal base material, the aerosol deposition coating method required for the plasma resistant coating is also provided.

<Invention plan>

In order to achieve the above objective, the present invention provides a plasma-resistant coating aerosol deposition coating method, wherein the aerosol deposition coating method includes the following steps (a) after removing impurities from the metal base material, the metal base material The value of the surface roughness Ra of the metal base material is within 10μm, and the surface of the metal base material is mirror-finished; (b) the metal base material is fixed against the coating nozzle And (c) using a coating nozzle to take in air, enter the coating powder, and spray it on the metal base material to form a coating layer.

The metal base material of the present invention may be selected from aluminum (Al), stainless steel (SUS) or a combination thereof. In the step (a), a step of washing the metal base material whose surface is mirror-finished is added. The step (b) also includes adjusting the inside of the surge chamber of the aerogel deposition equipment to a vacuum state.

In addition, the spray powder of the present invention may be one or more selected from the group consisting of _{oxides, fluorides, nitrides, yttrium oxide (Y 2} O ₃ ), and aluminum oxides (Al ₂ O _{3 ).} The thickness of the coating layer formed in the above step (c) is about 0.1 to 200 μm, and the step (c) includes the step of washing the surface of the coated metal base material.

Another aspect of the present invention is to provide a plasma resistant coating layer formed according to the method described above.

According to the aerosol deposition coating method of the plasma resistant coating of the present invention, the plasma resistant material forms a coating layer on the metal base material, which can protect the inside of the equipment in the plasma environment where plasma etching occurs. As the roughness of the coating layer on the metal base material decreases, the generation of particles is also reduced. Moreover, the bonding force between the coating layer and the metal base material caused by thermal shock is also improved.

10: Metal base material

20: surface

30: Coating layer

40: Coating powder

50: coating nozzle

Figure 1 shows the outline of aerosol deposition coating.

2 is an image of the adhesion of the coating layers of Example 1 and Comparative Example 1 to Comparative Example 4. FIG.

Figure 3 is the SEM picture of the coating layer of the aluminum base material with different roughness.

4 is a graph of thermal shock measurement conditions of Example 1 and Comparative Example 1. FIG.

FIG. 5 is an image of the thermal shock measurement results of Example 1 and Comparative Example 1. FIG.

Unless otherwise defined, all technical and scientific terms used in this specification are consistent with the content understood by those with ordinary knowledge in the technical field to which the present invention belongs. Generally, the nomenclature used in this specification uses common names that are widely known in this technical field.

Throughout the specification, unless otherwise stated to the contrary, when a certain part is described, "including" a certain component does not mean that other component elements are excluded, but it means that other component elements are also included.

The present invention relates to the aerosol deposition coating method for providing the plasma resistant coating of the present invention, wherein the aerosol deposition coating method includes the following steps (a) after removing impurities from the metal base material, the metal base material The surface roughness Ra value of the metal base material reaches within 10μm, the step of mirror finishing the surface of the metal base material; (b) the step of fixing the metal base material against the coating nozzle; and (c) using the coating nozzle The step of spraying the coating powder into the air and spraying on the metal base material to form a coating layer.

Hereinafter, the present invention uses FIG. 1 to specifically describe the content of each step. Figure 1 shows the outline of aerosol deposition coating.

According to the present invention, the aerosol deposition coating method related to plasma resistant coating includes (a) after removing impurities from the metal base material, making the surface roughness Ra of the metal base material (10) reach within 10 μm. The surface (20) is subjected to a mirror finishing step.

Moreover, the metal base material (10) can be selected from aluminum (Al), stainless steel (SUS), or a combination thereof, and is not limited thereto.

At this time, when non-metallic nonmetal is used as the base material, the coating layer thickness is limited, so it is difficult to form the coating layer, the bonding force between the coating layer and the base material is also reduced, and the coating is caused by thermal shock. The cloth layer and the base material are separated.

In addition, when the surface roughness of the metal base material is high, when the aerosol deposition coating layer is formed, the surface roughness of the coating layer (30) formed becomes high, and there is a problem of particle generation during plasma etching. Therefore, the surface of the metal base material (10) needs to be subjected to the above-mentioned mirror finishing.

At this time, the Ra value, which is one of the surface roughness values of the surface (20), is most preferably within 10 μm.

If the Ra value is less than 10μm, the surface roughness (Ra) of the aerosol-deposited coating becomes larger, and the relative adhesion becomes lower. That is, the thickness of the formed coating layer is not uniform enough, which will cause the peeling phenomenon caused by the thickness deviation. As a result, the peeling phenomenon occurs in the process using corrosive gas or plasma, which causes the problem of product damage or shortened equipment life.

In addition, the above-mentioned mirror finishing is to smooth the surface (20) of the metal base material (10). The mirror finishing methods include lapping, polishing, chemical mechanical polishing (CMP), and polishing. There are no restrictions on cutting, grinding, cutting, machining, etc.

In addition, the metal base material whose surface is mirror-finished in step (a) above needs to include a washing step. The washing can use air, water, solvents, etc. to remove pollutants, impurities, dust, etc. from the metal base material. , Wash in the usual way.

Next, the step (b) above is a step in which the metal base material is fixed against the coating nozzle (50) of the aerosol deposition coating equipment, and the mirror-finished surface (20) is fixed facing the coating nozzle (50). , In order to facilitate the implementation of aerosol deposition coating.

Moreover, as described above, the metal base material is fixed on the aerosol deposition coating equipment, and the pressure regulating chamber of the aerosol deposition coating equipment can also be adjusted to a vacuum state. A pressure difference is generated between the aerosol pressure regulating chamber and the coating pressure regulating chamber, and the temperature inside the pressure regulating chamber at this time can also reach normal temperature.

In the above-mentioned spray regulator chamber, gas and coating powder are injected to complete the preparation of aerosol deposition of the metal base material. The above-mentioned transport gas can be an inert gas, which can be selected from _{one or more of the group consisting of He, Ne, Ar, and N 2} ; but it is not limited to this.

In addition, the above-mentioned coating powder is one or more selected from the group consisting of _{oxides, fluorides, nitrides, yttrium oxide (Y 2} O ₃ ), and aluminum oxides (Al ₂ O _{3 ); but it is not limited thereto.}

In addition, the step (c) is a step of spraying the conveying gas and the coating powder (40) on the metal base material using a coating nozzle (50) to form a coating layer (30).

At this time, the thickness of the coating layer (30) is about 1-200μm. When the thickness of the coating layer is within 1μm, the equipment will have a protective effect against plasma. reduce. In the case where the thickness of the above-mentioned coating layer is 200 μm or more, the economic efficiency is reduced. In addition, the thickness of the coating layer (30) is most preferably about 1-100 μm.

In addition, the metal base material coated after step (c) needs to be washed. The washing method can be the same as the washing method performed after the mirror finish in step (a).

Therefore, the plasma resistant coating according to the aerosol deposition coating method of the present invention is a coating layer (30) formed on the upper part of the metal base material (10), which forms a lower surface roughness, and there is less electrical resistance. The particles caused by the slurry can achieve the protective effect inside the equipment.

In addition, the present invention can also provide a plasma-resistant coating layer formed according to the method described above.

Hereinafter, the present invention will be described in more detail based on examples. However, the examples implemented below are only examples of the invention, and the content of the present invention is not limited by the following embodiments.

"Example 1"

First, in the surge chamber of the aerosol deposition coating equipment in a vacuum environment at room temperature, a vibrator for powder vibration is used to gelatinize yttrium oxide gas with an average particle size of about 30 μm. Then use the pressure difference between the aerosol surge chamber and the coating surge chamber, the aerosolized yttrium oxide powder, together with the conveying gas (N ₂ ), at a speed of 300-350m/s, the surface roughness (Ra ) Is about 10μm on the mirror-finished aluminum base material, which produces physical impact and forms a high-density yttrium oxide coating layer.

"Comparative Example 1-4"

The base material in comparative example 1 is aluminum oxide (Al ₂ O ₃ ), comparative example 2 is silicon wafer (Si wafer), comparative example 3 is aluminum anodizing layer, and comparative example 4 is quartz (quartz), except that, the coating layer is formed in the same way.

"Test Example 1" Measurement of coating layer thickness, coating deposition amount, roughness, and uniformity

The thickness of the coating layer formed in Example 1 and Comparative Examples 1-4 was measured with the roughness (Ra) measuring instrument (series) of Mitutoyo Company; about the coating deposition amount, coating uniformity, and roughness (Ra), use Contact and non-contact tester (mitutoyo roughness tester) are used for measurement; the hardness (Hardness) is measured with a hardness tester (Vickers hardness tester), the above test is performed more than 5 times, and the results are shown in Table 1 below .

In the above table 1, the so-called coating layer that can be formed refers to the thickness of the coating layer that can be peeled off during coating after several times of aerosol deposition coating on the base material. The uniformity of coating refers to the thickness of the coating layer after coating. , On the coated surface, the thickness deviation varies with the position.

The above Table 1 shows that in Example 1 with aluminum as the base material, when aerosol coating is used, the coating deposition amount for one pass is at least a thickness of 0.5μm to 1μm; the cumulative repeated aerosol coating As a result, the thickness of the coating layer that can be formed will be shown to be 100 μm or more.

In contrast, in Comparative Examples 1 to 4 using non-metallic base materials, the coating deposition amount of one pass of aerosol coating is at least 0.1μm and the maximum thickness is 1μm. As a result of repeated coating accumulation, the coating layer that can be formed has a thickness within about 10 to 30 μm. Compared with the coating layer example 1, it is obviously difficult to form a coating layer.

Therefore, the aerosol deposition coating is physically deposited, and the non-metallic base material peels off the coating layer, and it can be seen that the formation of the coating layer is difficult. In particular, for ceramic base materials whose hardness or strength is stronger, the coating powder (powder) is relatively difficult to form a coating layer.

In addition, the surface roughness of the coating layer, which is consistent with the surface roughness of the base material, is shown to be within 10 μm, and the hardness of the coating layer is also shown to exceed 300 Hv regardless of the type of base material. In terms of coating uniformity, it is confirmed that the thickness deviation is within 90~110% depending on the surface position, which is relatively uniform.

In addition, regarding the above-mentioned Example 1 and Comparative Examples 1 to 4, the adhesiveness is related as shown in FIG. 2.

FIG. 2 is a film formation rate of about 1 μm/pass, showing the implementation patterns of Example 1 and Comparative Examples 1 to 4 with a thickness of 10 to 20 μm. As shown in Figure 2, it can be confirmed that the aerosol deposition coating on the metal base material has excellent adhesion. In addition, in the case of the non-metal base material, peeling occurs between the coating layer and the base material.

"Experimental Example 2" Determination of the thickness change of the coating layer divided by Ra in Example 1

The roughness of the aluminum base material was applied with different roughness aerosol coatings according to Table 2, and the thickness of the coating layer formed by different Ra was measured in the same method as the above experiment 1. The results are shown in Table 2 and Figure 3. .

As shown in Table 2 above, when the roughness of the metal base material is within 10μm, the thickness of the coating layer that can be formed is more than 100μm, and the coating is formed more uniformly. If the roughness of the metal base material is greater than 10μm, the coating The layer will peel off, so the coating layer is not completely formed, so that the thickness of the coating layer cannot be measured. Here, when the above-mentioned peeling phenomenon occurs in the initial stage of coating, an uneven coating layer will be formed; when the above-mentioned peeling phenomenon occurs during the coating process, a peeling phenomenon will occur.

Moreover, as shown in FIG. 3, when the roughness is less than 10 μm, the coating thickness is about 20 μm, and the coating layer is formed more uniformly. When the roughness is greater than 10 μm, the surface of the base material is not smooth enough, and an uneven coating layer can be confirmed from the initial stage of coating.

"Test Example 3" Measurement of Thermal Shock

Related to Example 1 and Comparative Example 1, the thickness of the coating layer is within 20μm, and then the thermal shock is measured. As shown in Figure 4, it is adjusted from 0°C to 200°C or 300°C, and then maintained at each temperature. After hours of quick freezing, the result of thermal shock was measured, and the result is shown in Fig. 5.

Fig. 5 is a graph showing the thermal shock measurement results of Example 1 (metal, Al) and Comparative Example 3 (non-metal, anodized layer). As shown in FIG. 5, in the case of Example 1, the thermal shock measurement cycle was performed 54 times, and no peeling of the coating layer occurred. In the case of Comparative Example 3, when the thermal shock measurement cycle was performed twice, the coating layer peeled off partly, and when it was cycled 8 times, it was confirmed that most of the coating layer peeled off.

Above, the specific part of the content of the present invention has been described in detail, which does not mean that the present invention is limited to the examples in the pictures, but for those with general knowledge in the relevant field, these specific descriptions are intended to illustrate more ideal In terms of implementation, those with ordinary knowledge in the relevant field can understand that this is not intended to limit the scope of the present invention. Therefore, the actual scope of the present invention should be defined in accordance with the scope of additional patent applications and their equivalents.

10: Metal base material

20: surface

30: Coating layer

40: Coating powder

50: coating nozzle

Claims (4)

An aerosol deposition coating method for plasma resistant coating, which includes the following steps: (a) After removing impurities from an aluminum base material, make the surface roughness Ra of the aluminum base material reach within 10 μm, and the aluminum base material Perform a mirror finishing step on the surface; (b) the step of fixing the aluminum base material against a coating nozzle; (c) use the coating nozzle to take in air, and yttrium oxide (Y ₂ O ₃ ) powder , Spraying on the aluminum base material to form a coating layer; wherein, in step (a), it further includes a step of washing the surface of the aluminum base material after the mirror finish. The aerosol deposition coating method as described in the first item of the scope of patent application, wherein in step (b), the step of adjusting the inside of the surge chamber of an aerosol deposition coating equipment to a vacuum state is further included. The aerosol deposition coating method as described in item 1 of the scope of the patent application, wherein in step (c), further includes a step of washing the surface of the coated aluminum base material. A plasma resistant coating layer is formed by the aerosol deposition coating method as described in any one of items 1 to 3 in the scope of the patent application.

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