KR20210103937A - Alloy sprayed film and film deposition apparatus - Google Patents

Abstract

The present invention provides an alloy spray coating whose exfoliation is suppressed from a film deposition treating component, and a film deposition apparatus having the alloy spray coating. For example, a spray coating is used in a film deposition apparatus comprising: a film deposition source; a board support unit facing the film deposition source; a film deposition treating component which surrounds the film deposition source or a film deposition treating atmosphere between the film deposition source and the board support unit; and a vacuum container containing the film deposition source, the board support unit, and the film deposition treating component. The present invention provides the spray coating where an alloy spray coating having at least one of a first element between aluminum, scandium, and hafnium is installed toward the film deposition treating atmosphere.

Description

ALLOY SPRAYED FILM AND FILM DEPOSITION APPARATUS

The present invention relates to an alloy sprayed coating and an apparatus for forming a film.

There is a technique for forming a film on a substrate in a vacuum container by sputtering, CVD, or the like. At this time, a film|membrane may adhere to components for film formation (for example, an adhesion prevention plate etc.) other than the board|substrate provided in the vacuum container. When such a film|membrane peels as a particle from the component for film|membrane formation, a particle may enter into a film|membrane, and the yield fall of a film|membrane product may occur.

For this reason, there is a method of forming a thermal sprayed film having the surface roughness of the body on the surface of the component for film formation treatment (for example, refer to Patent Document 1). By forming such a thermal sprayed film on the surface of the component for a film-forming process, unnecessary film|membrane peeling from the component for a film-forming process is suppressed effectively.

Japanese Patent Laid-Open No. 2008-291299

However, when a material having a relatively high film stress is selected as the material for the film to be formed on the substrate, or when film formation is carried out for a long time and the film formed on the film forming process component becomes relatively thick, the thermal sprayed film is deposited on the thermal sprayed film. When subjected to the stress of the film, there is a possibility that the thermal sprayed film will be peeled off from the film forming process part together with the film. Therefore, it is calculated|required that it is further excellent in peeling resistance in the thermal sprayed film formed in such the component for film formation processing.

In view of the above circumstances, it is an object of the present invention to provide an alloy sprayed coating in which peeling from a component for a film forming process is further suppressed, and a film forming apparatus provided with the alloy sprayed coating.

In order to achieve the above object, an alloy thermal sprayed coating according to one aspect of the present invention is a thermal sprayed coating provided on the surface of a film-forming part exposed to a film-forming processing atmosphere, and is made of aluminum, at least one of scandium and hafnium. has 1 element.

In such an alloy sprayed coating, even if a high-stress coating is deposited on the alloy sprayed coating, the alloy sprayed coating is less likely to be peeled off from the component for film formation processing.

In the alloy sprayed coating, the sprayed coating may include at least one second element of zirconium, titanium, and silicon in addition to the first element.

If it is such an alloy sprayed coating, since it contains the 2nd element of at least any one of zirconium, titanium, and silicon other than a 1st element, it becomes difficult to peel off an alloy sprayed coating from the component for a film formation process.

In the alloy thermal sprayed coating, the first element may be included in the thermal sprayed coating in an amount of 0.05 wt% or more and 1.5 wt% or less.

If it is such an alloy sprayed coating, since 0.05 wt% or more and 1.5 wt% or less of a 1st element are contained in the sprayed coating, the alloy sprayed coating becomes difficult to peel off from the component for film formation processing.

In the alloy sprayed coating, the second element may include 0.1 wt% or more and 0.5 wt% or less of zirconium in the sprayed coating, or 0.1 wt% or more and 3.0 wt% or less of titanium.

If it is such an alloy thermal sprayed coating, since the 2nd element is contained in the thermal sprayed film at the said density|concentration, it becomes difficult to peel off an alloy thermal spraying film from the component for film formation processing.

In the above-mentioned alloy sprayed coating, the film-forming process component may be an anti-adhesive plate surrounding the film-forming process atmosphere or a shielding member surrounding the sputtering target.

Such an alloy thermal sprayed coating becomes difficult to peel off from the anti-adhesion plate surrounding the film formation treatment atmosphere or the shield member surrounding the sputtering target.

In the alloy sprayed film, a high-melting-point metal film may be formed on the substrate exposed to the film-forming process atmosphere.

If it is such an alloy sprayed coating, even if a high-melting-point metal film is formed in the component for a film formation process, it becomes difficult to peel off an alloy sprayed film from the component for a film formation process.

In order to achieve the above object, a film forming apparatus according to one aspect of the present invention is provided with a film forming source, a substrate support, a component for film forming processing, and a vacuum container.

The substrate support faces the film formation source.

The component for the film formation treatment includes a film forming treatment atmosphere between the film forming source and the substrate support, or an alloy sprayed coating surrounding the film forming source and having at least one first element of aluminum, scandium, and hafnium. It is provided toward the said film-forming process atmosphere.

The vacuum vessel houses the film forming source, the substrate support, and the components for the film forming process.

With such a film forming apparatus, even if a high-stress film is deposited on the alloy sprayed coating, the alloy sprayed coating is less likely to be peeled off from the component for film formation processing.

In the film forming apparatus, the alloy sprayed film may include at least one second element of zirconium, titanium, and silicon in addition to the first element.

If it is such a film forming apparatus, since it contains the 2nd element of at least any one of zirconium, titanium, and silicon other than a 1st element, it becomes difficult to peel off an alloy sprayed film from the component for film forming processing.

As described above, according to the present invention, there is provided an alloy sprayed coating in which peeling from a component for a film forming process is further suppressed, and a film forming apparatus provided with the alloy sprayed coating.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of a film forming apparatus.
It is a schematic diagram which shows the partial cross section of the component for film formation processing to which the alloy sprayed coating was irradiated.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings. XYZ coordinates may be introduced in each drawing. Moreover, the same code|symbol may be attached|subjected to the same member or the member which has the same function, and after demonstrating the member, description may be abbreviate|omitted suitably.

An example of the film forming apparatus in which the alloy sprayed coating of this embodiment is used is demonstrated. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of a film forming apparatus.

The film forming apparatus 1 includes a vacuum vessel 10 , a support 20 , a sputtering target 30 , film forming processing components 40 , 41 , 42 , a magnetic circuit portion 50 , and an alloy Deserts 60 , 61 , 62 , an exhaust mechanism 70 , a gas supply mechanism 75 , and a power source 80 are provided. The support 20 is provided with a substrate 21 that is an object of the film forming process.

The vacuum container 10 is a container capable of maintaining a reduced pressure state. The vacuum vessel 10 accommodates the support 20, the sputtering target 30, and the components 40, 41, 42 and the like for film formation processing. An exhaust mechanism 70 such as a vacuum pump or a valve is connected to the vacuum container 10 through a pipe 71 . The atmosphere in the vacuum container 10 is maintained at a predetermined pressure by the exhaust mechanism 70 . A gas supply mechanism 75 such as a flow meter and a valve is installed in the vacuum vessel 10 through an introduction pipe 76 . The gas supply mechanism 75 supplies the discharge gas into the vacuum vessel 10 . The discharge gas is, for example, an inert gas (Ar, Ne, He, etc.). In addition, a pressure gauge for measuring the pressure in the vacuum container 10 may be installed in the vacuum container 10 .

The support 20 is a substrate support member of the film forming apparatus 1 . The support 20 is installed in the vacuum vessel 10 . The support 20 faces the sputtering target 30 . The support 20 supports the substrate 21 . In the support 20, the mounting surface on which the substrate 21 is mounted may be a conductor or an insulator. For example, an electrostatic chuck may be installed on the mount surface. A temperature control mechanism for maintaining the substrate 21 at a predetermined temperature may be built in the support 20 . The substrate 21 is appropriately changed depending on the applied device, and for example, an insulating substrate such as a glass substrate or a quartz substrate, a semiconductor substrate such as a silicon wafer, or a metal substrate.

The sputtering target 30 (hereinafter, the target 30 ) is installed in the vacuum vessel 10 through the insulating spacer 11 . The target 30 is disposed opposite to the support 20 . The target 30 has the target material 31 which is a target main body, the base material 32, and the bonding member 33. As shown in FIG. The target 30 is a film forming source of the film forming apparatus 1 .

The target material 31 has the sputtering surface 31s sputtered by plasma. The target material 31 is suitably changed according to the composition of the film|membrane formed in the board|substrate 21. As shown in FIG. The target material 31 is a metal, a semi-metal, or a ceramic. For example, the target material 31 is a high melting point metal such as tungsten (W), molybdenum (Mo), titanium (Ti), tungsten silicide (WSi), or titanium nitride (TiN), silicon (Si), silicon carbide ( a semiconductor material such as SiC). The target material is not limited to these metals and semimetals, and may be silicon nitride (SiN) or the like. The planar shape of the target material is appropriately adjusted corresponding to the planar shape of the substrate 21 .

The base material 32 is a backing plate, and is provided on the back surface of the target material 31. As shown in FIG. The substrate 32 has portions 321 and 322 of different diameters. The substrate 32 is a convex body in which a portion 322 protrudes from the portion 321 . In other words, in the substrate 32 , a step is formed by the portions 321 and 322 . The outer diameter of the part 322 is substantially the same as the diameter of the target material 31, for example. A flow path through which a refrigerant flows may be installed inside the substrate 32 .

The bonding member 33 is provided between the target material 31 and the base material 32 . The bonding member 33 densely bonds the target material 31 and the base material 32 . The joining member 33 is, for example, a brazing material such as indium.

The magnetic circuit unit 50 is disposed on the back surface of the target 30 opposite to the support 20 . The magnetic circuit part 50 has a yoke 51 arranged parallel to the target 30 and a magnet 52 provided on the yoke 51 . The magnet 52 is arrange|positioned in contact with the back surface of the target 30 on the opposite side to 31 s of sputtering surfaces.

In the vicinity of the sputtering surface 31s, the magnetic field emitted from the magnet 52 leaks, and electrons in the plasma are captured by the leaked magnetic field. Thereby, a high-density plasma is formed in the vicinity of the sputtering surface 31s, and so-called magnetron sputtering is performed. The shape and number of magnets 52 are appropriately adjusted from the viewpoint of stability of discharge, in-plane distribution of the film-forming layer of the substrate 21, or improvement of the use efficiency of the target 30.

The component 40 for a film-forming process is an annular shielding member. The component 40 for a film formation process is made of metal. For example, it is a grounding shield whose potential is the ground potential. When the film forming apparatus 1 is viewed from the top, the film forming process component 40 surrounds the outer periphery of the target 30 . The component 40 for a film-forming process opens the sputtering surface 31s of the target 30, and is arrange|positioned in the vacuum container 10 along the outer periphery of the target 30. As shown in FIG. The component 40 for a film-forming process is being fixed to the upper part of the vacuum container 10, for example. The shape of the component 40 for a film-forming process is an example, and is not restrict|limited to the shape shown in figure.

The material of the component 40 for a film-forming process is stainless steel, aluminum, etc., for example. Between the component 40 for a film-forming process and the target 30, the space|interval of about 0.1 mm - several mm is provided, for example. As a result, during film formation, from the so-called Paschen's law, discharge is less likely to occur in the gap between the component 40 for film formation and the target 30, and plasma accumulates in the vicinity of the sputtering surface 31s to sustain stable plasma discharge. do.

The alloy thermal sprayed film 60 is thermally sprayed onto the component 40 for film formation processing. For example, the alloy sprayed coating 60 is formed in the surface of the component 40 for film formation processing in which the component 40 for a film formation process faces the film formation processing atmosphere 12 .

The alloy sprayed film 60 includes at least one first element of aluminum (Al) and, in addition to aluminum, scandium (Sc) and hafnium (Hf). In addition, the alloy sprayed coating 60 may include at least one second element of zirconium (Zr) and titanium (Ti). Alternatively, silicon (Si) may be selected as the second element.

Here, the sum of at least one of the first elements of Sc and Hf is included in the alloy sprayed coating 60 by 0.05 wt% or more and 1.5 wt% or less. In this case, the alloy sprayed coating 60 is any one of an Al-Sc alloy sprayed coating, an Al-Hf alloy sprayed coating, and an Al-Sc-Hf alloy sprayed coating.

In addition, when a second element is contained, in the Al-Sc-Zr alloy thermal sprayed coating or Al-Hf-Zr alloy thermal sprayed coating, 0.1 wt% or more and 0.5 wt% or less of Zr may be contained, or an Al-Sc-Ti alloy In the thermal sprayed film or Al-Hf-Ti alloy thermal sprayed film, Ti may be contained in 0.1 wt% or more and 3 wt% or less, or in the Al-Sc-Si alloy thermal sprayed film or Al-Hf-Si alloy thermal sprayed film, Si is 0.5 wt% More than 5 wt% may be included.

Here, when the weight % of the first element is less than 0.05 wt%, recrystallization tends to occur in the alloy sprayed coating, and the thermal history tends to make the Western alloy sprayed coating soft. As a result, the alloy sprayed coating is subjected to the stress of the coating deposited thereon, and there is a possibility that the coating may be peeled off together with the coating. On the other hand, if the weight % of the first element is greater than 1.5 wt %, the material hardness increases, making it difficult to process the material used for thermal spraying, which is not preferable.

Here, when Ti as the second element is smaller than 0.1 wt%, the recrystallization inhibitory effect is reduced, and when Ti is larger than 3 wt%, the influence of intermetallic compounds is increased, and the thermal sprayed film strength is lowered, which is undesirable. Alternatively, when Zr becomes smaller than 0.1 wt%, the recrystallization inhibitory effect becomes small, and when Zr becomes larger than 0.5 wt%, the hardness of the thermal spray material increases, making it unsuitable for thermal spray material processing.

The component 41 for the film-forming process is an anti-adhesive plate which surrounds the film-forming process atmosphere 12 . The component 41 for a film forming process is provided along the inner wall of the vacuum container 10 from the upper part to the lower part of the vacuum container 10, for example. Moreover, the component 41 for a film-forming process is arrange|positioned toward the support 20 from the center part of the vacuum container 10. As shown in FIG. The shape of the component 41 for a film-forming process is an example and is not restrict|limited to the shape shown in figure. The component 41 for a film-forming process is made of metal. For example, the potential is the ground potential. The material of the component 41 for a film-forming process is stainless steel, aluminum, etc., for example.

The alloy sprayed coating 61 is sprayed onto the component 41 for a film forming process. For example, the alloy sprayed coating 61 is formed on the surface of the component 41 for a film formation process in which the component 41 for a film formation process faces the film formation process atmosphere 12 . The composition of the alloy sprayed coating 61 is the same as that of the alloy sprayed coating 60 .

The component 42 for a film-forming process is a shutter which opens the target 30 toward the board|substrate 21, or shields 31 s of sputtering surfaces. The component 42 for a film-forming process is provided substantially parallel to 31 s of sputtering surfaces, for example. The shape of the component 42 for a film-forming process is an example, and is not restrict|limited to the shape shown in figure. The component 42 for a film-forming process is made of metal. For example, the potential is the ground potential. The material of the component 42 for a film-forming process is stainless steel, aluminum, etc., for example.

The alloy thermal sprayed coating 62 is thermally sprayed on the main surface facing the substrate 21 of the component 42 for film formation processing and the main surface facing the target 30 . The composition of the alloy sprayed coating 62 is the same as that of the alloy sprayed coating 60 .

The power source 80 is connected to the target 30 through a line 81 . The power source 80 supplies power to the target 30 . The power supply 80 may be a DC power supply, a VHF power supply, or an RF power supply. When the power source 80 is a high frequency power source such as a VHF power source or an RF power source, a matching circuit may be installed on the line 81 between the power source 80 and the target 30 .

When a discharge gas is introduced into the vacuum container 10 and electric power is applied to the target 30 , discharge by capacitive coupling is performed between the target 30 and the vacuum container 10 or the film forming process component 41 . happens Thereby, plasma is formed in the vicinity of the sputtering surface 31s. And from the sputtering surface 31s exposed to plasma, sputtering particle|grains scatter toward the film-forming process atmosphere 12. As shown in FIG.

As a result, the film which uses the target material 31 as a material is formed in the board|substrate 21. As shown in FIG. At the same time, since the film-forming components 40, 41, and 42 are also exposed to the film-forming process atmosphere 12, a film is also deposited on the alloy sprayed coatings 60, 61, and 62.

It is a schematic diagram which shows the partial cross section of the component for film formation processing to which the alloy sprayed coating was irradiated. Here, the component 4 for film-forming processing represents any one of the components 40, 41, and 42 for film-forming processing, and the alloy sprayed coating 6 is any one of the alloy sprayed coatings 60, 61, and 62 here. indicates During film formation, the surface 6s of the alloy sprayed coating 6 is exposed to the film formation treatment atmosphere 12 .

The thermal spraying surface 4s of the component 4 for film-forming processing is blast-processed by the insulating particle before the alloy thermal sprayed film 6 is thermally sprayed. For example, the sprayed surface 4s has an arithmetic mean roughness Ra of 3 µm or more. For example, when the arithmetic mean roughness Ra of the sprayed surface 4s becomes smaller than 3 micrometers, the adhesiveness of the component 4 for film formation and the alloy sprayed coating 6 worsens, and it is unpreferable.

The alloy sprayed coating 6 is formed on the sprayed surface 4s by any one of arc spraying, frame spraying, plasma spraying, and cold spray spraying. The alloy thermal sprayed film 6 is, for example, an amorphous film immediately after thermal spraying. The thickness of the alloy thermal sprayed coating 6 is 100 micrometers or more and 400 micrometers or less, for example. The surface 6s of the alloy sprayed coating 6 has an arithmetic mean roughness Ra of 8 µm or more and 40 µm or less.

The component 4 for film-forming processing (a shield member, an adhesion prevention plate, a shutter, etc.) is not provided with a water cooling mechanism generally. Therefore, the temperature of the component 4 for a film-forming process may become 350 degreeC or more by being exposed to the film-forming process atmosphere 12. In this embodiment, the temperature at which the component 4 for a film-forming process is heated to 350 degreeC or more by the thermal history in which the component 4 for film-forming process is exposed to the film-forming process atmosphere 12 is "process temperature" ” is called.

Under these conditions, as a thermal sprayed film to be formed on the component 4 for film formation treatment, a thermal sprayed film composed of pure Al (containing 99.00 wt% or more of Al) or a thermal sprayed film composed of an Al-Cu alloy (hereinafter referred to as an Al thermal sprayed film) ), recrystallization tends to occur in the thermal sprayed coating. As a result, the Al sprayed coating becomes soft by the thermal history, and eventually, a phenomenon occurs in which the Al sprayed coating is peeled off from the component 4 for film formation processing together with the coating.

In addition, when the film deposited on the Al thermal sprayed film is a film with high stress, the adhesive force of the Al thermal sprayed film to the film forming process component 4 is lost to the stress, and the film is formed together with the Al thermal sprayed film forming process component ( 4) may come off.

In this way, when an Al thermal sprayed film is selected as the thermal sprayed film for the component 4 for film formation processing, the Al thermally sprayed film peels off together with the film and generates particles due to the thermal history.

On the other hand, the alloy sprayed coating 6 of this embodiment has aluminum (Al), and at least any one of 1st element of scandium (Sc) and hafnium (Hf). In addition, the alloy sprayed film 6 may contain at least one second element of zirconium (Zr), titanium (Ti), and silicon (Si).

With such an alloy sprayed coating 6 , recrystallization is difficult to occur in the alloy sprayed coating 6 even if the alloy sprayed coating 6 receives a thermal history and reaches a process temperature. As a result, even if the alloy sprayed coating 6 receives a thermal history and reaches the process temperature, it maintains a desired hardness and becomes difficult to peel off from the component 4 for film formation processing.

For example, when the alloy sprayed coating 6 made of Al-0.2wt% Sc is used, the Vickers hardness increases from 20HV to 30HV to 70HV along with the thermal history when the process temperature is in the range of 260°C to 370°C. there is an example Alternatively, when the alloy sprayed coating 6 in which Al and 0.1 wt% to 0.7% of Sc are mixed is used, there is an example in which the recrystallization completion temperature is about 570°C while the recrystallization start temperature is about 350°C. That is, by adding Sc to Al, recrystallization of the alloy thermal sprayed film 6 is suppressed at the process temperature level, and the alloy thermal sprayed film 6 maintains a desired hardness.

Table 1 is a table showing the thermal sprayed shield life when the WSi film and the SiN film are deposited on each of the Al thermal sprayed film as a comparative example and the alloy thermal sprayed film 6 of this embodiment. Here, the shield life (kW/h) refers to the electric power ( kW) multiplied by the film formation time (h). That is, the shield life is an index showing the peeling resistance of the thermal sprayed coating to the stress of the coating. The larger the shield life, the higher the peel resistance of the thermal sprayed coating with respect to the stress of the coating. Moreover, the SUS304 board was used as a board|substrate.

As shown in Table 1, when the film is a WSi film, the shield life is increased to 600 kW·h in the alloy thermal sprayed film 6 while 500 kW·h is in the Al thermal sprayed film. When the coating film is a SiN film, the shield life is increased to 400 kW·h in the alloy thermal sprayed film 6 compared to 250 kW·h in the Al thermal sprayed film.

In this way, when the alloy thermal sprayed film 6 is formed on the component 6 for film formation, compared with the case where the Al thermal spray film is formed on the component 4 for film formation processing, the peel resistance to the film is greatly increased. found out For example, an AlSc film formed by sputtering instead of thermal spraying is not preferable because an appropriate surface roughness cannot be obtained and a thickness sufficient to withstand the stress of the deposited film is not obtained.

As mentioned above, although embodiment of this invention was described, this invention is not limited only to embodiment mentioned above, It goes without saying that various changes can be added. Each embodiment is not limited to an independent form, and may be combined as much as technically possible.

1: Film forming apparatus
4, 40, 41, 42: parts for film forming processing
4s: brave face
6, 60, 61, 62: alloy thermal spray coating
6s: surface
10: vacuum vessel
11: Insulation spacer
12: film formation treatment atmosphere
20: support
21: substrate
30: sputtering target (target)
31: target material
31s: sputtering surface
32: description
33: joint member
50: magnetic circuit part
51: York
52: magnet
70: exhaust mechanism
71: plumbing
75: gas supply mechanism
76: introduction tube
80: power
81: track
321, 322: part

Claims (8)

A thermal sprayed coating provided on a surface of a component for a film formation treatment exposed to a film formation treatment atmosphere, comprising:
An alloy thermal sprayed coating comprising aluminum and at least one first element of scandium and hafnium. According to claim 1,
The thermal sprayed coating is an alloy sprayed coating further comprising at least one second element of zirconium and titanium in addition to the first element. 3. The method according to claim 1 or 2,
The first element is an alloy sprayed coating in which 0.05 wt% or more and 1.5 wt% or less are included in the sprayed coating. 3. The method according to claim 1 or 2,
As the second element, the thermal sprayed coating includes 0.1 wt% or more and 0.5 wt% or less of zirconium, or 0.1 wt% or more and 3.0 wt% or less of titanium. 3. The method according to claim 1 or 2,
The component for the film formation treatment is an alloy sprayed coating which is an anti-adhesion plate surrounding the atmosphere for the film formation treatment or a shield member surrounding the sputtering target. 3. The method according to claim 1 or 2,
An alloy sprayed coating in which a high-melting-point metal film is formed on the above-mentioned film-forming components. a film-forming source;
a substrate support facing the film formation source;
A film formation treatment atmosphere between the film formation source and the substrate support, or an alloy thermal sprayed film surrounding the film formation source and having at least one first element of aluminum, scandium, and hafnium toward the film formation processing atmosphere The installed film forming process parts, and
A film forming apparatus comprising: a vacuum container for accommodating the film forming source, the substrate support, and the film forming process component. 8. The method of claim 7,
In addition to the first element, the alloy sprayed coating further includes at least one second element of zirconium, titanium, and silicon.

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