Mixed thermally sprayed film, component for film deposition apparatus, method for manufacturing component for film deposition apparatus, and method for manufacturing mixed thermally sprayed film

Abstract

To provide a mixed thermally sprayed film that absorbs a stress difference to a deposition film that is deposited on a thermally sprayed film of a film deposition processing component and can prevent breakage or detachment of the deposition film itself, and to provide a component for a film deposition apparatus using a thermally sprayed film and a method for manufacturing a component for a film deposition apparatus.SOLUTION: A mixed thermally sprayed film provided on a surface of a film deposition processing component exposed to a film deposition treatment atmosphere of depositing a film comprises a mixture of Al and an AlSi alloy and has a surface roughness Ra of 9-60 μm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a mixed sprayed film provided on the surface of a film-forming processing part exposed to a film-forming processing atmosphere in which a film is formed, a film-forming apparatus part, a manufacturing method for the film-forming apparatus part, and a manufacturing method for the mixed sprayed film. [Background technology]

[0002] There are techniques for forming a film on a substrate in a vacuum chamber using methods such as sputtering and CVD. In this case, the film may adhere to film-forming processing parts (e.g., anti-adhesion plates) other than the substrate that are placed in the vacuum chamber. If such a film peels off from the film-forming processing parts as particles, the particles may get into the film and cause a decrease in the yield of the film product.

[0003] For these reasons, a thermal sprayed film having a predetermined surface roughness is formed on the surface of the film-forming processing part (see, for example, Patent Document 1). By forming such a thermal sprayed film on the surface of the film-forming processing part, unwanted peeling of the film from the film-forming processing part is effectively suppressed.

[0004] However, if a material with a relatively high film stress is selected as the material for the film formed on the substrate, or if film formation is carried out for a long period of time so that the thickness of the film formed on the film formation processing part becomes relatively thick, if the sprayed film overcomes the stress of the film deposited on it, the sprayed film may peel off from the film formation processing part together with the film.

[0005] In addition, there are high-melting-point materials (W, Ta, Ti and their alloys) used as film-forming materials in semiconductor manufacturing. These high-melting-point metals have high (thermal) stress, so there is a demand for further improvement in peeling resistance.

[0006] Therefore, in the past, the sprayed coating material was changed to match the coating material. For example, there have been cases where soft materials such as pure aluminum have been sprayed to absorb stress. However, soft materials such as pure aluminum have low material strength and cannot withstand the stress itself, which can cause the sprayed coating to break. As a result, there was a tendency for particles to increase as the coating progressed.

[0007] On the other hand, attempts have been made to use high-strength materials such as Al alloys, Ni, and Ti, which have the property of being resistant to the stress of the deposited film. In this case, no increase in particles is observed during deposition, but there is a problem that when deposition is completed, the difference in stress due to the difference in thermal expansion coefficient between the base material of the deposition processing parts (e.g. SUS304) and the deposited film cannot be absorbed. As a result, stress is concentrated in the deposited film itself, causing the deposition film to break and peel off, which is a problem. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2008-291299 A Summary of the Invention [Problem to be solved by the invention]

[0009] In view of the above-mentioned circumstances, an object of the present invention is to provide a mixed sprayed film, for example, when using a sputtering target of a high melting point metal, which can absorb the stress difference with the deposited film deposited on the sprayed film of a film-forming processing part and prevent the deposited film itself from being destroyed or peeled off, even when the film is formed to the end of the sputtering target, and a part for a film-forming apparatus using the mixed sprayed film, a manufacturing method for a part for a film-forming apparatus, and a manufacturing method for a mixed sprayed film. [Means for solving the problem]

[0010] The first aspect of the present invention, which solves the above-mentioned problems, is a mixed sprayed coating provided on a surface of a coating process part exposed to a coating process atmosphere in which a coating is formed, the mixed sprayed coating being made of a mixture of Al and an AlSi alloy and having a surface roughness Ra of 9 to 60 μm. A second aspect of the present invention is the mixed sprayed coating of the first aspect, which has a thickness of 300 to 500 μm. A third aspect of the present invention is the mixed sprayed coating according to the first or second aspect, wherein the AlSi has a Si content of 0.5 to 12 mass %. A fourth aspect of the present invention is a coating apparatus part having a thermal sprayed film formed on a surface of a component substrate exposed to a coating treatment atmosphere in which a coating is formed, the thermal sprayed film being a mixed thermal sprayed film made of a mixture of Al and an AlSi alloy and having a surface roughness Ra of 9 to 60 μm. A fifth aspect of the present invention is the part for a film formation apparatus according to the fourth aspect, which is an adhesion prevention plate surrounding the film formation processing atmosphere, or a shielding member surrounding a sputtering target serving as a film formation source for the film formation. A sixth aspect of the present invention is the part for a film forming apparatus according to the fourth or fifth aspect, wherein the surface roughness Ra of the surface of the part substrate on which the mixed sprayed film is formed is 3 to 5 μm. A seventh aspect of the present invention is a method for manufacturing a film-forming device component having a thermal spray coating formed on a surface of a component substrate exposed to a film-forming treatment atmosphere, comprising: The method for manufacturing a part for a film-forming apparatus includes a step of forming, on the surface of the part substrate, a mixed sprayed coating made of a mixture of Al and an AlSi alloy and having a surface roughness Ra of 9 to 60 μm. An eighth aspect of the present invention resides in the method for manufacturing a film forming apparatus part of the seventh aspect, in which the film forming apparatus part is an adhesion prevention plate that surrounds the film forming process atmosphere, or a shielding member that surrounds a sputtering target that serves as a film forming source. A ninth aspect of the present invention resides in the method for producing a part for a film forming apparatus according to the seventh or eighth aspect, wherein the surface of the part substrate on which the mixed sprayed film is formed has a surface roughness Ra of 3 to 5 μm. A tenth aspect of the present invention is a method for producing a mixed sprayed coating, in which two spray wires, one made of an Al spray wire and the other made of an AlSi alloy, are fed at a constant speed while an arc is generated at the intersection of the two spray wires, and the molten materials of each are sprayed to form a mixed sprayed coating.

[0011] The mixed sprayed film of the present invention has the effect of absorbing the stress difference with the deposited film deposited on the sprayed film of the film-forming processing part, even when a film is formed to the end of the sputtering target using, for example, a high-melting point metal sputtering target, thereby preventing damage or peeling of the deposited film itself, and by using this mixed sprayed film, it is possible to realize a film-forming apparatus part and a method for manufacturing a film-forming apparatus part that have the above-mentioned effects. [Brief description of the drawings]

[0012] [Figure 1] 1 is a schematic diagram showing an example of a sputtering apparatus equipped with a film forming processing part for providing a mixed sprayed film of the present invention. [Diagram 2] FIG. 1 is a schematic diagram illustrating an arc spraying method. [Diagram 3] 1 is a micrograph of a cross section of the mixed sprayed coating of Example 1. [Figure 4] 2 is a micrograph of a cross section of the thermal sprayed coating of Comparative Example 1. [Diagram 5] 1 is a micrograph of a cross section of the thermal sprayed coating of Comparative Example 2. [Figure 6] FIG. 1 is a diagram showing the results of tensile strength measurement. [Figure 7] FIG. 1 is a diagram showing the results of tensile strength measurement. [Figure 8] FIG. 1 is a diagram showing the results of tensile strength measurement. [Figure 9] FIG. 13 is a diagram showing the results of measurement of particles on the surface of a thermal sprayed film. [Figure 10] FIG. 13 is a diagram showing the results of measurement of particles on the surface of a thermal sprayed film. [Figure 11] FIG. 13 is a diagram showing how hardness is measured. [Figure 12] FIG. 13 is a diagram showing the results of hardness measurements. [Figure 13]FIG. 13 is a diagram showing the results of hardness measurements. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. The mixed sprayed coating of the present invention is a mixed sprayed coating provided on the surface of a coating treatment part that is exposed to a coating treatment atmosphere in which a coating is formed, and is made of a mixture of Al and an AlSi alloy. Al is preferably aluminum (4NAl) having a purity of 99.99% or higher.

[0014] The AlSi alloy is an alloy of aluminum and silicon, and the Si content is 0.5 to 12 mass%, preferably 1 to 5 mass%, because if the Si content is high, the hardness of the AlSi alloy becomes too high, and the stress relaxation ability decreases.

[0015] The mixed sprayed coating of the present invention is formed by arc spraying or plasma spraying using Al and an AlSi alloy, and is more preferably formed by arc spraying. In plasma spraying, it is necessary to mix powders, and since the melting method changes depending on the difference in the melting point of the powder, it is difficult to adjust, and since it is not possible to control the surface roughness in plasma spraying, a blasting process is required at the end. Therefore, arc spraying is preferable.

[0016] The mixture ratio of Al to the AlSi alloy is approximately 1:1 by volume, but a range of 90:100 to 100:90 is acceptable.

[0017] Specifically, the mixed sprayed film of the present invention is formed by, for example, using an arc spraying device capable of simultaneously spraying and forming a film using two types of spray wires, feeding two spray wires consisting of an Al spray wire and an AlSi alloy spray wire at a constant speed, generating an arc at the intersection of the two spray wires, and spraying the molten materials of each wire with gas to form a mixed sprayed film. In arc spraying, a desired mixed sprayed film can be obtained by adjusting the current, voltage, air cap, gas type, and gas pressure, and the surface roughness can also be adjusted.

[0018] The mixed sprayed coating is a mixture of Al and an AlSi alloy, and although it is not an alloy, it is also called a pseudo-alloy sprayed coating. The thickness of the mixed sprayed film is preferably 300 to 500 nm.

[0019] The mixed sprayed coating of the present invention has a surface roughness Ra, which is an arithmetic mean roughness, of 9 to 60 μm, preferably 20 to 40 μm, and more preferably 25 to 35 μm. The surface roughness of the mixed sprayed coating formed by spraying can be adjusted to a desired surface roughness by appropriately adjusting the spraying conditions, but the surface roughness Ra may also be adjusted by performing a blasting treatment after spraying.

[0020] The mixed sprayed film of the present invention is suitable for application to the surface of a film-forming processing part of a sputtering device. For example, even if a high-melting point metal sputtering target is used and a film is formed to the end of the sputtering target, the stress difference with the deposited film deposited on the mixed sprayed film of the film-forming processing part is absorbed, preventing damage or peeling of the deposited film itself.

[0021] Fig. 1 is a schematic diagram of an example of a sputtering apparatus equipped with a film forming part for forming a mixed sprayed film of the present invention. In Fig. 1, a device for forming a vacuum space and various devices for film formation are omitted.

[0022] As shown in FIG. 1, a sputtering target 12 mounted on a backing plate 11 and a film-forming substrate 14 fixed by an electrostatic chuck (ESC) 13 are provided in a vacuum film-forming chamber 10 so as to face each other, and the space between the sputtering target 12 and the film-forming substrate 14 is surrounded by film-forming processing parts. Specifically, in this example, the film-forming processing device includes a cylindrical first shield member 21, a doughnut-shaped second shield member 22 surrounding the film-forming substrate 14, and a third shield member 23 connecting them. These film-forming processing parts are members that prevent the diffusion of the film-forming material emitted from the sputtering target 12, and the film-forming material adheres to the film. Thus, the mixed sprayed film of the present invention is formed on the surfaces of the first shield member 21, the second shield member 22, and the third shield member 23.

[0023] Films of the film-forming materials are formed on the mixed sprayed film on the surfaces of the first shield member 21, the second shield member 22, and the third shield member 23, and are successively deposited to form a deposited film, but when a deposited film is formed on the mixed sprayed film of the present invention, the stress difference between the newly formed film on this deposited film and the deposited film is absorbed, and it is possible to prevent the deposition film itself from being destroyed or peeled off. It is possible to prevent the generation of particles due to destruction or peeling of the deposited film, and it is possible to prevent poor deposition due to particles even if the sputtering target 12 is used to the end.

[0024] In particular, in recent years, sputtering targets 12 made of high melting point materials (W, Ta, Ti and alloys thereof) used in semiconductor manufacturing are used, and the size of the targets has also increased to 12 inches or more, so that if the film formation process is continued until the sputtering target 12 is used up, the amount of deposition of the high melting point material deposited on the sprayed film of the shielding member increases, the area and thickness of the deposited film increase, and the stress on the sprayed film increases, so that the sprayed film on the surface of the shielding member is required to have even greater stress resistance, but even in this case, it is possible to prevent the generation of particles and the like until the large sputtering target 12 is used up. Specific examples of high melting point film formation materials include W, WN, WSi, SiN, TiW, Ta / TaN, Ti / TiN, etc.

[0025] Furthermore, for example, when the sputtering target 12 is 12 inches in size, the first shield member 21 has an outer diameter of about 600 mm and a height of, for example, about 60 mm to 250 mm. The second shield member 22 and the third shield member 23 have dimensions equivalent thereto.

[0026] As described above, the mixed sprayed coating of the present invention is formed on the surfaces of the components for a coating apparatus, such as the first shield member 21, the second shield member 22, and the third shield member 23, by a spraying method.

[0027] As the thermal spraying method, an arc thermal spraying method, a flame thermal spraying method, a plasma thermal spraying method, etc. can be used, but in order to realize the present invention, an arc thermal spraying method is preferable. According to the arc thermal spraying method, it is relatively easy to adjust the surface roughness, it is relatively easy to form a mixed sprayed film having the above-mentioned desired characteristics, and even if a high melting point coating material is deposited on the mixed sprayed film, it is possible to suppress the generation of particles until the end.

[0028] 2 is a schematic diagram illustrating the arc spraying method. Arc spraying is a technique in which a predetermined voltage / current 33 is applied between two spray materials 31, 32 that are continuously fed in the direction of the arrow to generate arcing 34 near the tips of the two spray materials, and at the same time, the metal melted by the arcing 34 is atomized into spray particles 36 using a blowing gas 35. The atomized spray particles 36 are blown through an opening 37a provided in an air cap 37 onto a target substrate 38, whereby the desired sprayed film 39 is formed by depositing the sprayed particles 36 on the target substrate 38.

[0029] In the present invention, the two spray materials are one made of Al and the other made of an AlSi alloy, and the spray gas is preferably air, nitrogen gas, argon gas, or the like.

[0030] <Example 1> In Example 1, a SUS304 substrate with a planar dimension of 80 mm x 100 mm and a thickness of 2 mm was used, and a mixed sprayed film consisting of a mixture of aluminum (4NAl) with a purity of 99.99% or more and an AlSi alloy was formed on the surface by arc spraying. The thickness was 350 μm and the surface roughness Ra was 29 μm. The AlSi alloy used was an AlSi alloy with a Si content of 5 mass %. The surface roughness was measured using a surface roughness measuring device based on JIS B0601 (1994), and the arithmetic mean roughness, ie, surface roughness Ra, was calculated. A detailed observation of the surface and cross section of the produced mixed sprayed coating revealed no cracks or peeling.

[0031] Figure 3 shows a micrograph of the cross section of the mixed sprayed coating. As a result, no large pores were found in the cross section of the mixed sprayed coating, and the adhesion to the substrate was good. As shown in the enlarged photograph of Figure 3(b), it was found that the mixed state of 4NAl and AlSi was almost uniform. In the enlarged photograph, the light-colored parts are 4N-Al, and the dark parts are Al-5%Si.

[0032] <Comparative Example 1> In Comparative Example 1, a sprayed film made of 4NAl alone was formed by arc spraying on the surface of the same substrate as in Example 1, so as to have the same thickness as in Example 1. The thickness was 320 μm. FIG. 4 shows a micrograph of a cross section of the sprayed coating.

[0033] <Comparative Example 2> In Comparative Example 2, a thermal sprayed film made of an AlSi alloy alone was formed by arc spraying on the surface of the same substrate as in Example 1 to the same thickness as in Example 1. The thickness was 300 μm. FIG. 5 shows a micrograph of a cross section of the sprayed coating.

[0034] <Comparative Example 3> In Comparative Example 3, a mixed sprayed film consisting of 4NAl and a CuAl alloy (Cu-3.5% Al) was formed to the same thickness on the surface of the same substrate as in Example 1 by arc spraying.

[0035] <Comparative Example 4> In Comparative Example 4, a mixed sprayed film of 4NAl and Ti was formed by arc spraying on the surface of the same substrate as in Example 1 to the same thickness.

[0036] <Comparative Example 5> In Comparative Example 5, a mixed sprayed film consisting of Ti (two types) and a CuAl alloy (Cu-3.5% Al) was formed to the same thickness on the surface of the same substrate as in Example 1 by arc spraying.

[0037] <Film forming equipment parts> The mixed sprayed film of Example 1 and the sprayed films of Comparative Examples 1 and 2 were formed on a component for a film-forming apparatus, which was an adhesion prevention plate corresponding to the second shield member 22 in FIG. 1, to prepare a component for a film-forming apparatus. Using this film-forming apparatus part, a WSi film was formed on a substrate to a thickness of 1.5 mm using a WSi sputtering target, and the chamber was cooled and then the film-forming apparatus part was observed.

[0038] In the case of the Al / AlSi mixed sprayed coating of Example 1, peeling of the WSi deposited film on the mixed sprayed coating was not observed. On the other hand, in the case of the sample having the Al sprayed film of Comparative Example 1, peeling was observed in the WSi deposited film, and cracks were generated on the deposition surface. Furthermore, in the case of the sample having the AlSi sprayed film of Comparative Example 2, peeling was observed in the WSi deposited film, and fractures occurred within the deposited film.

[0039] <Tensile strength measurement> For the thermal sprayed films of Example 1 and Comparative Examples 1 to 5, the tensile strength was measured by a tensile tester according to the 5-7 pull-off method of JIS K5600. The results are shown in Figures 6 and 7. As a result, the 4NAl / AlSi mixed sprayed coating of Example 1 had the highest tensile strength, equivalent to that of the AlSi alloy sprayed coating. Moreover, as shown in FIG. 8, it was found that the mixed sprayed coating of Example 1 had a tensile strength that was increased by 23% compared to the 4NAl sprayed coating of Comparative Example 1.

[0040] <Surface particle measurement> Using an air born particle counter, a 0.4 MPa particle counter equipped with a 0.1 μm filter was used to blow clean air at 28.3 L / min for 30 seconds onto the sprayed coating surfaces of the mixed sprayed coatings of Example 1 and Comparative Examples 1, 3, 4, and 5, and the generated particles were measured. The measurement was performed three times, and the results are shown in Figures 9 and 10. As a result, it was found that the mixed sprayed coating of Example 1 had fewer surface particles than the comparative example. The Al / CuAl mixed sprayed coating of Comparative Example 3 also had few surface particles, but as described above, it had low tensile strength and low adhesion, making it difficult to use.

[0041] <Hardness measurement> For the mixed sprayed films of Example 1, Comparative Example 1 (FIG. 12), and Comparative Examples 3 to 5 (FIG. 13), the hardness of the cross section of the sprayed film was measured by a micro Vickers hardness tester. Fig. 11 shows the state of hardness measurement of the cross section of the thermal sprayed coating. As shown in Fig. 11, the hardness was measured at 10 points, and the results are shown in Figs. 12 and 13. As a result, it was found that the mixed sprayed coating of Example 1 had an average strength that was increased by 51% compared to Comparative Example 1. In addition, the hardness range expanded from 15.1 in Comparative Example 1 to 36.7 in Example 1. From this, it was found that the mixed sprayed coating of Example 1 has a form that combines hardness and flexibility, with a mixture of the hardness range from the soft Al sprayed material to the relatively high hardness range of the Al-Si sprayed material, since Al and AlSi are uniformly mixed and present. In addition, the mixed sprayed coatings of Al / CuAl in Comparative Example 3, Al / Ti in Comparative Example 4, and CuAl / Ti in Comparative Example 5 had high average hardness, but did not have a low hardness region and, as mentioned above, had many surface particles and were difficult to use.

[0042] In the present invention, a mixed sprayed film of Al and an AlSi alloy is used, which absorbs the stress difference with the deposited film deposited on the sprayed film of the coating processing part, and prevents the deposition film itself from being broken or peeled off. The reason why an AlSi alloy is used as the Al alloy to be mixed and sprayed with Al is that it is possible to select a practical and optimal combination of mechanical properties in controlling mechanical properties such as hardness and tensile strength by the added elements while avoiding problems such as impurity contamination in the coating process, but it is considered that if there is an Al alloy such as other Al-based binary or ternary Al alloy that can have mechanical properties equivalent to the above-mentioned AlSi sprayed film, it will be possible to obtain a mixed sprayed film having the same effect as the present invention. [Explanation of symbols]

[0043] 10 Vacuum deposition chamber 11 Backing Plate 12 Sputtering Target 13 Electrostatic Chuck (ESC) 14 Film deposition substrate 21 First shield member 22 Second shield member 23 Third shield member 31 Thermal spray materials 33 Current 34 Arcing 35 Gas 36 Spray particles 37 Air Cap 37a opening 38 Target Substrate 39 Thermal spray coating

Claims

1. A mixed sprayed film provided on the surface of a film-forming processing part that is exposed to a film-forming processing atmosphere in which film is formed, the mixed sprayed film being made of a mixture of Al and an AlSi alloy and having a surface roughness Ra of 9 to 60 μm.

2. The mixed thermal spray coating according to claim 1, having a thickness of 300 to 500 μm.

3. The mixed sprayed coating according to claim 1 or 2, wherein the Si content of the AlSi alloy is 0.5 to 12 mass %.

4. A film-forming device component having a thermal spray coating formed on a surface of a component substrate exposed to a film-forming treatment atmosphere, The part for a coating device, wherein the sprayed coating is a mixed sprayed coating made of a mixture of Al and an AlSi alloy and has a surface roughness Ra of 9 to 60 μm.

5. 5. The part for a film forming apparatus according to claim 4, which is an adhesion prevention plate surrounding the film forming atmosphere, or a shielding member surrounding a sputtering target serving as a film forming source for the film formation.

6. 6. The part for a film forming apparatus according to claim 4, wherein the surface of the part substrate on which the mixed sprayed film is formed has a surface roughness Ra of 3 to 5 μm.

7. A method for manufacturing a film-forming device part having a thermal spray coating formed on a surface of a component substrate exposed to a film-forming treatment atmosphere, comprising: The method for manufacturing a part for a film-forming apparatus includes a step of forming a mixed spray coating made of a mixture of Al and an AlSi alloy and having a surface roughness Ra of 9 to 60 μm on the surface of the part substrate.

8. 8. The method for producing a film forming apparatus part according to claim 7, wherein the film forming apparatus part is an adhesion prevention plate surrounding the film forming processing atmosphere, or a shielding member surrounding a sputtering target serving as a film forming source.

9. 9. The method for manufacturing a film-forming device part according to claim 7, wherein the surface of the part substrate on which the mixed sprayed film is formed has a surface roughness Ra of 3 to 5 μm.

10. A method for manufacturing a mixed sprayed film in which two spray wires, one made of an Al spray wire and the other made of an AlSi alloy, are fed at a constant speed while an arc is generated at the intersection of the two spray wires, and the molten material of each is sprayed to form a mixed sprayed film.

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