Plasma resistant composite laminate

Abstract

To provide a plasma resistant composite laminate which has good performance with respect to adhesion, reduces the occurrence of delamination during plasma processing, and thus extends the life of a plasma reaction chamber.SOLUTION: The plasma resistant composite stack includes a substrate 10, a first adhesive layer 11, and a first plasma resistant layer 12. The substrate has a top surface, and the first adhesion layer is disposed between the top surface 101 of the substrate and the first plasma resistant layer. An arithmetic mean roughness (Ra) of the upper surface of the substrate is 2 μm to 10 μ m, a porosity of the first bonding layer is 0.05% to 10%, a porosity of the first plasma resistant layer is 0.03% to 6%, and a ratio of the porosity of the first bonding layer to the porosity of the first plasma resistant layer is in a range of 1.6 to 333.33.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to composite laminates, and more particularly to composite laminates that are plasma bombardment and corrosion resistant. [Background technology]

[0002] Plasma processing is an important technology widely used in the preparation of small semiconductor devices. Typically, materials are placed in a plasma reaction chamber where specific gases are excited to a plasma state, and then the materials are treated with the plasma. However, in addition to the material to be treated, the gas in the plasma state also simultaneously impinges on and damages the inner walls or components of the plasma reaction chamber (such as gas distribution components, substrate support components, and gas exhaust components). When the plasma reaction chamber contains a halogen gas, such as fluorine or chlorine, the halogen gas is easily decomposed into chemically active free radicals by the gas in the plasma state, which causes corrosion of the inner walls or components of the plasma reaction chamber.

[0003] To solve the aforementioned problems in plasma processing, wear-resistant and corrosion-resistant coatings are applied to the interior of the chamber, including the inner walls and components, to protect against damage and corrosion caused by gases in the plasma state, thereby maintaining the standard performance and long life of the plasma reaction chamber. In addition, it is well known that yttrium oxide, yttrium fluoride, or aluminum oxide exhibits good resistance to plasma corrosion, and therefore, plasma-resistant coating layers can be manufactured from these materials by methods such as air plasma spraying (APS), suspension plasma spraying (SPS), physical vapor deposition (PVD), or atomic layer deposition (ALD).

[0004] However, single-layer plasma-resistant coatings made of the above materials usually have poor adhesion to the inner walls or components of the plasma reaction chamber, which causes the plasma-resistant coating to easily peel off under continuous bombardment by plasma-state gases, resulting in the inability to provide continuous and sufficient protection for the interior of the plasma reaction chamber. Therefore, further development and research into plasma-resistant coatings is still needed, with the aim of improving their adhesion ability to prevent the problem of easy peeling and detachment and extend the life of the plasma reaction chamber. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] United States Patent Application Publication No. 2005 / 0037193A1 Summary of the Invention

[0006] In view of the problems of the prior art, the object of the present invention is to provide a plasma-resistant composite laminate which can exhibit better adhesion ability than traditional plasma-resistant coatings, so that the plasma-resistant composite laminate can be applied inside a plasma reaction chamber, thereby efficiently solving the problem of fast delamination and prolonging the life of the plasma reaction chamber.

[0007] To achieve the above object, the present invention provides a plasma-resistant composite laminate, the laminate comprising a substrate, a first adhesive layer, and a first plasma-resistant layer. The substrate has an upper surface, and the first adhesive layer is disposed between the upper surface of the substrate and the first plasma-resistant layer. The upper surface has an arithmetic mean roughness (Ra) in the range of 2 micrometers (μm) to 10 μm. The first adhesive layer has a porosity of 0.05% to 10%, and the first plasma-resistant layer has a porosity of 0.03% to 6%, with the ratio of the porosity of the first adhesive layer to the porosity of the first plasma-resistant layer being in the range of 1.6 to 333.33.

[0008] By disposing a first adhesive layer between the substrate and the first plasma-resistant layer, and simultaneously controlling the roughness of the upper surface of the substrate, the porosity of the first adhesive layer and the first plasma-resistant layer, and the ratio thereof within a specific range, the plasma-resistant composite laminate has a good adhesive strength (e.g., 6000 kN / mm 2 This makes the plasma-resistant composite laminate effective in resisting plasma corrosion (i.e., collision with gas in plasma state) and does not peel off during the process. In other words, the plasma-resistant composite laminate can constantly and thoroughly protect the inside of a plasma reaction chamber and extend its lifespan.

[0009] In some embodiments, the ratio of the porosity of the first adhesive layer to the first plasma-resistant layer may be, but is not limited to, 10 to 333.33. In other embodiments, the ratio of the porosity of the first adhesive layer to the first plasma-resistant layer may be 25 to 333.33. In yet other embodiments, the ratio of the porosity of the first adhesive layer to the first plasma-resistant layer may be 50 to 333.33. In yet still other embodiments, the ratio of the porosity of the first adhesive layer to the first plasma-resistant layer may be 80 to 333.33.

[0010] In some embodiments, the material of the first adhesive layer is selected from the group consisting of yttrium oxide (YO), yttrium fluoride (YF), yttrium oxyfluoride (YOF), aluminum oxide (AlO), yttrium aluminum oxide (YAlO), and the like. 12 In other embodiments, the first adhesive layer material may include yttrium oxide, yttrium aluminum oxide, or any combination thereof.

[0011] In some embodiments, the thickness of the first adhesive layer may be, but is not limited to, 2 μm to 200 μm. In other embodiments, the thickness of the first adhesive layer may be 2 μm to 150 μm. In yet other embodiments, the thickness of the first adhesive layer may be 2 μm to 100 μm. In yet still other embodiments, the thickness of the first adhesive layer may be 10 μm to 100 μm.

[0012] In some embodiments, the surface of the first adhesive layer may have an Ra of 2 μm to 10 μm. Specifically, the surface of the first adhesive layer refers to the surface facing the substrate.

[0013] In some embodiments, the plasma-resistant composite laminate can also include a second adhesive layer disposed between the first adhesive layer and the upper surface of the substrate. The porosity of the second adhesive layer can be between 0.05% and 10% and is different from the porosity of the first adhesive layer. In other embodiments, the porosity of the first adhesive layer is greater than the porosity of the second adhesive layer.

[0014] In some embodiments, the ratio of the porosity of the second adhesive layer to the first plasma-resistant layer may be, but is not limited to, 1.6 to 333.33. In other embodiments, the ratio of the porosity of the second adhesive layer to the first plasma-resistant layer may be 10 to 333.33. In yet another embodiment, the ratio of the porosity of the second adhesive layer to the first plasma-resistant layer may be 25 to 333.33. In yet another embodiment, the ratio of the porosity of the second adhesive layer to the first plasma-resistant layer may be 50 to 333.33. In yet another embodiment, the ratio of the porosity of the second adhesive layer to the first plasma-resistant layer may be 80 to 333.33.

[0015] In some embodiments, the second adhesive layer material can contain yttrium oxide, yttrium fluoride, yttrium oxyfluoride, aluminum oxide, yttrium aluminum oxide, or any combination thereof. In other embodiments, the second adhesive layer material can also contain yttrium oxide, yttrium aluminum oxide, or any combination thereof.

[0016] In some embodiments, the thickness of the second adhesive layer may be, but is not limited to, 2 μm to 200 μm. In other embodiments, the thickness of the second adhesive layer may be 2 μm to 150 μm. In yet other embodiments, the thickness of the second adhesive layer may be 2 μm to 100 μm. In yet still other embodiments, the thickness of the second adhesive layer may be 2 μm to 80 μm. In yet still yet still other embodiments, the thickness of the second adhesive layer may be 2 μm to 45 μm.

[0017] In some embodiments, the Ra of the surface of the second adhesive layer may be, but is not limited to, 2 μm to 10 μm. Specifically, the surface of the second adhesive layer refers to the surface facing the substrate.

[0018] In some embodiments, multiple adhesive layers, such as a third adhesive layer and a fourth adhesive layer, may be disposed between the second adhesive layer and the upper surface. The porosity range, material, thickness range, and surface Ra of the multiple adhesive layers may be the same as that of the second adhesive layer. However, these adhesive layers differ from each other and from the second adhesive layer in at least one of the porosity, material, thickness, and surface Ra, i.e., the adhesive layers themselves and the second adhesive layer are separate and independent layers.

[0019] In some embodiments, the porosity of the first plasma-resistant layer may be, but is not limited to, 0.03% to 3%. In other embodiments, the porosity of the first plasma-resistant layer may be 0.03% to 2%. In yet other embodiments, the porosity of the first plasma-resistant layer may be 0.03% to 1%.

[0020] In some embodiments, the material of the first plasma-resistant layer may include yttrium oxide, yttrium fluoride, yttrium oxyfluoride, aluminum oxide, yttrium aluminum oxide, or any combination thereof. In other embodiments, the material of the first plasma-resistant layer may also include yttrium oxide, yttrium aluminum oxide, or any combination thereof.

[0021] In some embodiments, the thickness of the first plasma-resistant layer may be, but is not limited to, 15 μm to 300 μm. In other embodiments, the thickness of the first plasma-resistant layer may be 50 μm to 300 μm. In yet other embodiments, the thickness of the first plasma-resistant layer may be 50 μm to 200 μm. In yet still other embodiments, the thickness of the first plasma-resistant layer may be 50 μm to 150 μm.

[0022] In some embodiments, the Ra of the surface of the first plasma-resistant layer may be, but is not limited to, 1 μm to 10 μm. In other embodiments, the Ra of the surface of the first plasma-resistant layer may be 2 μm to 10 μm. Specifically, the surface of the first plasma-resistant layer refers to the surface facing the substrate.

[0023] According to the present invention, multiple plasma-resistant layers, such as a second plasma-resistant layer and a third plasma-resistant layer, can be disposed on the surface of the first plasma-resistant layer. The porosity range, material, thickness range, and surface Ra of the multiple plasma-resistant layers can be the same as those of the first plasma-resistant layer. However, these plasma-resistant layers differ from each other and from the first plasma-resistant layer in at least one of the porosity, material, thickness, and surface Ra, i.e., these plasma-resistant layers and the first plasma-resistant layer are separate and independent layers.

[0024] According to the present invention, the material of the substrate is not particularly limited. Those skilled in the art can select the substrate material as needed, provided that it does not affect the effects achieved by the present invention. For example, the substrate material may be selected from, but is not limited to, aluminum alloy, stainless steel, quartz, or aluminum oxide.

[0025] In some embodiments, the thickness of the substrate can be, but is not limited to, 2 millimeters (mm) to 50 mm.

[0026] In some embodiments, the Ra of the upper surface of the substrate can be, but is not limited to, 1 μm to 10 μm.

[0027] In this specification, the Ra of a surface is analyzed by a surface roughness measuring instrument in accordance with the ISO1997 standard method.

[0028] In this specification, unless otherwise specified, a range expressed as "from a small value to a large value" indicates a range equal to or greater than the small value and equal to or less than the large value. For example, an Ra range of 2 μm to 10 μm indicates "equal to or greater than 2 μm and equal to or less than 10 μm." [Brief explanation of the drawings]

[0029] [Figure 1] 1 is a schematic vertical cross-sectional view showing a plasma-resistant composite laminate of Example 1. FIG. [Figure 2] FIG. 10 is a schematic vertical cross-sectional view showing a plasma-resistant composite laminate of Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0030] From now on, the implementation form of the plasma-resistant composite laminate and comparative examples will be described below. Those skilled in the art will easily understand the advantages and effects of the present invention from the following examples and comparative examples. Various modifications and variations can be made to implement or apply the present invention without departing from the spirit of this application. Example 1: Plasma-resistant composite laminate

[0031] 1 is a schematic longitudinal cross-sectional view showing a plasma-resistant composite laminate of Example 1. Specifically, the plasma-resistant composite laminate 1 of Example 1 includes a substrate 10, a first adhesive layer 11, and a first plasma-resistant layer 12. Furthermore, the first adhesive layer 11 is formed on an upper surface 101 of the substrate 10, and the first plasma-resistant layer 12 is formed on the surface of the first adhesive layer 11.

[0032] The plasma-resistant composite laminate 1 of Example 1 was prepared primarily by the method described below. First, a substrate 10 made of stainless steel was provided, and the upper surface 101 of the substrate 10 was treated with a cyclone sandblaster to achieve an Ra of approximately 4.5 μm. Next, yttrium aluminum oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the upper surface 101 of the substrate 10 under high-power conditions of 46 kW to 48 kW to form a first adhesive layer 11 with a thickness of approximately 50 μm. The first adhesive layer 11 had a porosity of approximately 0.05% and a surface Ra of approximately 4.5 μm. Next, yttrium aluminum oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the surface of the first adhesive layer 11 under high-power conditions of more than approximately 48 kW to form a first plasma-resistant layer 12. The first plasma-resistant layer 12 had a porosity of approximately 0.03%, a thickness of approximately 100 μm, and a surface Ra of approximately 4.3 μm. Furthermore, the ratio of the porosity of first adhesive layer 11 to the porosity of first plasma-resistant layer 12 was approximately 1.67. Finally, the surface of first plasma-resistant layer 12 was washed successively with carbon dioxide gas and high-pressure water, and then dried in an oven to obtain plasma-resistant composite laminate 1 of Example 1. Examples 2 to 4: Plasma-resistant composite laminate

[0033] The plasma-resistant composite laminates of Examples 2 to 4 had the same structure as the plasma-resistant composite laminate of Example 1, and were prepared using the same process. The main differences were as follows: In Example 2, atmospheric plasma spraying was performed under medium-power conditions of 42 kW to 44 kW to form yttrium aluminum oxide on the upper surface of the substrate, resulting in a first adhesive layer with a thickness of approximately 50 μm, a porosity of approximately 2.5%, and a surface Ra of approximately 4.4 μm. The porosity ratio of the first adhesive layer to the porosity of the first plasma-resistant layer was approximately 83.33. In Example 3, atmospheric plasma spraying was performed under low-power conditions of 40 kW or more and less than 42 kW to form yttrium aluminum oxide on the upper surface of the substrate, resulting in a first adhesive layer with a thickness of approximately 50 μm, a porosity of approximately 5%, and a surface Ra of approximately 5 μm. The porosity ratio of the first adhesive layer to the porosity of the first plasma-resistant layer was approximately 166.67. In Example 4, atmospheric pressure plasma spraying was performed under ultra-low power conditions of less than 40 kW to form yttrium aluminum oxide on the upper surface of the substrate, resulting in a first adhesive layer having a thickness of approximately 50 μm, a porosity of approximately 10%, and a surface Ra of approximately 6.2 μm, with the porosity ratio of the first adhesive layer to the porosity of the first plasma-resistant layer being approximately 333.33. Except for the aforementioned differences in the first adhesive layer, Examples 2 to 4 were prepared according to the same preparation process as Example 1, and plasma-resistant composite laminates of Examples 2 to 4 were produced. Example 5: Plasma-resistant composite laminate

[0034] 2 is a schematic longitudinal cross-sectional view showing the plasma-resistant composite laminate of Example 5. Specifically, the plasma-resistant composite laminate 2 of Example 5 includes a substrate 20, a second adhesive layer 21A, a first adhesive layer 21B, and a first plasma-resistant layer 22. Furthermore, the second adhesive layer 21A is formed on the upper surface 201 of the substrate 20, the first adhesive layer 21B is formed on the surface of the second adhesive layer 21A, and the first plasma-resistant layer 22 is formed on the surface of the first adhesive layer 21B.

[0035] The plasma-resistant composite laminate 2 of Example 5 was prepared primarily by the following method. First, a substrate 20 made of stainless steel was prepared, and the upper surface 201 of the substrate 20 was treated with a cyclone sandblaster to achieve an Ra of approximately 4.5 μm. Next, yttrium oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the upper surface 201 of the substrate 20 under medium-power conditions of 42 kW to 44 kW to form a second adhesive layer 21A with a thickness of approximately 20 μm. The second adhesive layer 21A had a porosity of approximately 0.5% and a surface Ra of approximately 4.5 μm. Next, yttrium aluminum oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the surface of the second adhesive layer 21A under ultra-low-power conditions of less than 40 kW to form a first adhesive layer 21B. The first adhesive layer 21B had a porosity of approximately 10%, a thickness of approximately 70 μm, and a surface Ra of approximately 7.5 μm. Next, yttrium aluminum oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the surface of first adhesive layer 21B under high-power conditions of over 48 kW to form first plasma-resistant layer 22. First plasma-resistant layer 22 had a porosity of approximately 0.03%, a thickness of approximately 70 μm, and a surface Ra of approximately 4.3 μm. Furthermore, the ratio of the porosity of first adhesive layer 21B to the porosity of first plasma-resistant layer 22 was approximately 333.33. Finally, the surface of first plasma-resistant layer 22 was washed successively with carbon dioxide gas and high-pressure water, and then dried in an oven to obtain plasma-resistant composite laminate 2 of Example 5. Comparative Example 1: Single-layer plasma-resistant coating

[0036] Comparative Example 1 represents a prior art plasma-resistant coating and was prepared primarily by the method described below. First, a substrate made of stainless steel was provided, and its upper surface was treated with a cyclone sandblaster to achieve an Ra of approximately 4.5 μm. Next, yttrium aluminum oxide was selected as the material, and atmospheric pressure plasma spraying was performed on the upper surface of the substrate under high-power conditions exceeding 48 kW to form an yttrium aluminum oxide layer. Finally, the yttrium aluminum oxide layer was washed sequentially with carbon dioxide gas and high-pressure water, and then dried in an oven to obtain the single-layer plasma-resistant coating of Comparative Example 1. The yttrium aluminum oxide layer had a porosity of approximately 0.03%, a thickness of approximately 150 μm, and a surface Ra of approximately 4.3 μm. Test Example 1: Determination of Porosity

[0037] In Test Example 1, the plasma-resistant composite laminates of Examples 1 to 5 were used as samples to be tested. Specifically, images of the plasma-resistant composite laminates of Examples 1 to 5 were taken using a scanning electron microscope (SEM), and then imported into ImageJ software for analysis. The area to be calculated was selected, and the ratio of the pore area to the area of ​​the entire material, which was determined as the porosity, was calculated using the software. The porosity of each of the laminates of Examples 1 to 5 was measured using the above method, and the results are shown in Table 1 below. The ratio of the porosity of the first adhesive layer to the porosity of the first plasma-resistant layer of each of the laminates of Examples 1 to 5 was also calculated, and the results are shown in Table 1 below.

[0038] [Table 1]

[0039] The results in Table 1 above show that in the plasma-resistant composite laminates of Examples 1 to 5, the porosity of the first adhesive layer is greater than the porosity of the first plasma-resistant layer, and further, the ratio of the porosity of the first adhesive layer to the porosity of the first plasma-resistant layer falls within a specific range of 1.67 to approximately 333.33. Test Example 2: Determination of Adhesion Force

[0040] The adhesion strength of the plasma-resistant composite laminates of Examples 1 to 5 and the single-layer plasma-resistant coating of Comparative Example 1 was measured according to the procedures and conditions set forth in ASTM C633-13(2021), which is the standard test method for adhesion or cohesive strength of thermal spray coatings, and the results are shown in Table 2 below. Generally, the adhesion strength of the plasma-resistant coating in the plasma reaction chamber should be 6000 kN / mm to effectively avoid the problem of peeling and thus extend the life of the plasma reaction chamber. 2 The adhesive strength was evaluated four times for each group, and the results shown in Table 2 are the average of the four test results.

[0041] [Table 2]

[0042] From the results in Table 2 above, the single-layer plasma-resistant coating of Comparative Example 1 had a 4500kN / mm 2 It was shown that this adhesive strength cannot meet industry-accepted standards, resulting in the prior art problem of easily peeling from the interior of the plasma reaction chamber, including the inner walls and components. The plasma-resistant composite laminate of Example 1 had an adhesive strength of 6323 kN / mm 2 The adhesive strength of Examples 3 to 5 was approximately 2.5 times the industry standard. Therefore, the plasma-resistant composite laminates of Examples 1 to 5 can solve the problem of the prior art, which is the tendency for peeling to occur due to insufficient adhesive strength.

[0043] In view of this, by disposing at least one adhesive layer between the substrate and the plasma-resistant layer, and simultaneously controlling the surface roughness of the substrate, the porosity of the plasma-resistant layer and adhesive layer, and the ratio between the porosities of these layers, this plasma-resistant composite laminate can be manufactured to meet industry-accepted standards (e.g., 6000 kN / mm 2Therefore, the plasma-resistant composite laminate can withstand plasma corrosion (i.e., collision with gas in a plasma state) and is less likely to peel off. In other words, the plasma-resistant composite laminate can constantly provide thorough protection for the inside of a plasma reaction chamber and extend its lifespan.

Claims

1. A plasma-resistant composite laminate comprising: a substrate; a first adhesive layer; and a first plasma-resistant layer, the substrate having an upper surface, the first adhesive layer being disposed between the upper surface of the substrate and the first plasma-resistant layer; a plasma-resistant composite laminate, wherein the upper surface of the substrate has an arithmetic mean roughness (Ra) of 2 μm to 10 μm, the first adhesive layer has a porosity of 0.05% to 10%, the first plasma-resistant layer has a porosity of 0.03% to 6%, and the ratio of the porosity of the first adhesive layer to the porosity of the first plasma-resistant layer is in the range of 1.6 to 333.

33.

2. 10. The plasma-resistant composite laminate of claim 1, wherein the first adhesive layer material comprises yttrium oxide, yttrium fluoride, yttrium oxyfluoride, aluminum oxide, yttrium aluminum oxide, or any combination thereof.

3. 2. The plasma-resistant composite laminate according to claim 1, wherein the first adhesive layer has a thickness of 2 μm to 200 μm.

4. 2. The plasma-resistant composite laminate according to claim 1, wherein the arithmetic mean roughness (Ra) of the surface of the first adhesive layer is 2 μm to 10 μm.

5. 5. The plasma-resistant composite laminate of claim 1, further comprising a second adhesive layer disposed between the first adhesive layer and the upper surface of the substrate, the second adhesive layer having a porosity of 0.05% to 10%, the porosity of the second adhesive layer being different from the porosity of the first adhesive layer.

6. 6. The plasma-resistant composite laminate of claim 5, wherein the second adhesive layer material comprises yttrium oxide, yttrium fluoride, yttrium oxyfluoride, aluminum oxide, yttrium aluminum oxide, or any combination thereof.

7. 6. The plasma-resistant composite laminate according to claim 5, wherein the second adhesive layer has a thickness of 2 μm to 200 μm.

8. 5. The plasma-resistant composite laminate of claim 1, wherein the material of the first plasma-resistant layer comprises yttrium oxide, yttrium fluoride, yttrium oxyfluoride, aluminum oxide, yttrium aluminum oxide, or any combination thereof.

9. 5. The plasma-resistant composite laminate according to claim 1, wherein the first plasma-resistant layer has a thickness of 15 μm to 300 μm.

10. The plasma-resistant composite laminate according to any one of claims 1 to 4, wherein the material of the substrate comprises an aluminum alloy, stainless steel, quartz, or aluminum oxide.

Images