CN113265631B

CN113265631B - Alloy melt-blown film and film forming apparatus

Info

Publication number: CN113265631B
Application number: CN202011627743.3A
Authority: CN
Inventors: 门胁豊; 吉田敏伸; 赤濑仁荣
Original assignee: Ulvac Techno Ltd
Current assignee: Ulvac Techno Ltd
Priority date: 2020-02-14
Filing date: 2020-12-31
Publication date: 2023-05-02
Anticipated expiration: 2040-12-31
Also published as: JP7424854B2; KR102468589B1; KR20210103937A; CN113265631A; JP2021127499A

Abstract

Provided are an alloy melt-blown film which can further suppress peeling from a member for film formation treatment, and a film forming apparatus having the alloy melt-blown film. For example, there is provided a melt-blown film for a film forming apparatus, the film forming apparatus comprising: a film forming source; a substrate support unit facing the film forming source; a film forming process member that surrounds a film forming process ambient gas or the film forming source between the film forming source and the substrate support portion; and a vacuum container for accommodating the film forming source, the substrate supporting portion, and the film forming processing member; an alloy-blown film is provided to the film-forming process atmosphere, the alloy-blown film having aluminum and a first element, the first element being at least one element of scandium and hafnium.

Description

Alloy melt-blown film and film forming apparatus

Technical Field

The present invention relates to an alloy melt-blown film and a film forming apparatus.

Background

There is a technique of forming a film on a substrate in a vacuum container by sputtering, CVD (Chemical Vapor Deposition: chemical vapor deposition) or the like. In this case, a film may be attached to a member for film formation processing (e.g., an anti-adhesion plate) other than the substrate provided in the vacuum chamber. If such a film is peeled as particles from the film-forming processing member, the particles may enter the film, and the yield of the film product may be lowered.

For this reason, there is a method of forming a melt-blown film having a uniform surface roughness on the surface of a film-forming processing member (for example, refer to patent document 1). By forming such a melt-blown film on the surface of the film-forming processing member, unnecessary peeling of the film from the film-forming processing member is effectively suppressed.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2008-29299

Disclosure of Invention

Problems to be solved by the invention

However, when a material having a relatively high film stress is selected as a material of the film formed on the substrate or when a film formed on the film forming member is formed for a long period of time and the thickness of the film formed on the film forming member is relatively thick, if the film deposited on the film to be fused cannot be overcome, the film to be fused may be peeled off from the film forming member together with the film. Therefore, in the melt-blown film formed on such a film-forming processing member, more excellent peeling resistance is required.

In view of the above, an object of the present invention is to provide an alloy melt-blown film that further suppresses peeling from a film-forming processing member, and a film forming apparatus having the alloy melt-blown film.

Means for solving the problems

In order to achieve the above object, an alloy cast film according to an aspect of the present invention is a cast film provided on a surface of a film forming member exposed to a film forming process ambient gas, and includes aluminum and a first element, wherein the first element is at least one element of scandium and hafnium.

In such an alloy-blown film, even if a film with high stress is deposited on the alloy-blown film, the alloy-blown film becomes difficult to peel from the film-forming processing member.

In the alloy cast film, the cast film may contain a second element in addition to the first element, and the second element may be at least one element selected from zirconium, titanium, and silicon.

In such an alloy-blown film, since the second element is at least one element selected from zirconium, titanium and silicon in addition to the first element, the alloy-blown film becomes difficult to be peeled from the film-forming processing member.

The alloy melt film may contain the first element in an amount of 0.05wt% to 1.5wt% in the melt film.

In such an alloy melt-blown film, the first element is contained in the melt-blown film in an amount of 0.05 to 1.5wt% inclusive, so that the alloy melt-blown film is less likely to be peeled from the film-forming processing member.

In the alloy cast film, as the second element, the cast film may contain 0.1wt% or more and 0.5wt% or less of zirconium, or 0.1wt% or more and 3.0wt% or less of titanium.

In such an alloy melt-blown film, the second element is contained in the melt-blown film at the concentration described above, so that the alloy melt-blown film is less likely to be peeled from the film-forming processing member.

In the alloy-blown film, the film-forming processing member may be an anti-adhesion plate surrounding the film-forming processing ambient gas or a shielding member surrounding the periphery of the sputtering target.

Such an alloy-blown film becomes difficult to peel off from the adhesion-preventing plate surrounding the film-forming process ambient gas or the shielding member surrounding the periphery of the sputtering target.

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

In such an alloy-blown film, even if a high-melting-point metal film is formed on the film-forming-process member, the alloy-blown film becomes difficult to peel from the film-forming-process member.

In order to achieve the above object, a film forming apparatus according to an aspect of the present invention includes a film forming source, a substrate supporting portion, a film forming processing member, and a vacuum chamber.

The substrate support portion faces the film forming source.

The film forming process member surrounds a film forming process ambient gas between the film forming source and the substrate support portion or the film forming source, and an alloy melt film is provided toward the film forming process ambient gas, the alloy melt film having aluminum and a first element, the first element being at least one element of scandium and hafnium.

The vacuum container accommodates the film forming source, the substrate supporting portion, and the film forming processing member.

In such a film forming apparatus, even if a film with high stress is deposited on the alloy melt film, the alloy melt film becomes difficult to peel off from the film forming processing member.

In the film forming apparatus, the alloy melt film contains a second element in addition to the first element, and the second element is at least one element selected from zirconium, titanium and silicon.

In such a film forming apparatus, since the second element is at least one element selected from zirconium, titanium and silicon in addition to the first element, the alloy melt-blown film becomes difficult to be peeled from the film forming processing member.

ADVANTAGEOUS EFFECTS OF INVENTION

As described above, according to the present invention, there are provided an alloy melt-blown film which further suppresses peeling from a film-forming processing member, and a film-forming apparatus having the alloy melt-blown film.

Drawings

Fig. 1 is a schematic cross-sectional view showing one example of a film forming apparatus.

Fig. 2 is a schematic diagram showing a partial cross section of a member for film formation treatment irradiated with an alloy melt film.

Description of the reference numerals

1: a film forming device,

4. 40, 41, 42: a film forming treatment member,

4s: a melt-shot surface,

6. 60, 61, 62: alloy melt-injection film,

6s: a surface(s),

10: a vacuum container,

11: an insulating spacer,

12: a film forming process atmosphere,

20: a supporting table,

21: a substrate (substrate),

30: a sputtering target (target),

31: a target material,

31s: a sputtering surface,

32: a base material,

33: a joint member,

50: a magnetic circuit part,

51: a magnetic yoke,

52: a magnet,

70: an exhaust mechanism,

71: piping(s),

75: a gas supply mechanism,

76: an ingress pipe,

80: a power supply,

81: a circuit (line),

321. 322: part(s).

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing, XYZ axis coordinates are sometimes introduced. In addition, the same members or members having the same functions may be denoted by the same reference numerals, and appropriate description thereof will be omitted after description thereof.

An example of a film forming apparatus using the alloy melt-blown film of the present embodiment will be described. Fig. 1 is a schematic cross-sectional view showing one example of a film forming apparatus.

The film forming apparatus 1 includes a vacuum chamber 10, a support 20, a sputtering target 30,

film forming members

40, 41, and 42, a magnetic circuit 50, alloy-

cast films

60, 61, and 62, an exhaust mechanism 70, a gas supply mechanism 75, and a power supply 80. The support 20 is provided with a substrate 21 as a target of film formation processing.

The vacuum vessel 10 is a vessel capable of maintaining a depressurized state. The vacuum chamber 10 accommodates a support table 20, a sputtering target 30, film

formation processing members

40, 41, 42, and the like. The vacuum container 10 is connected to an exhaust mechanism 70 such as a vacuum pump or a valve through a pipe 71. The exhaust mechanism 70 maintains the ambient gas in the vacuum chamber 10 at a predetermined pressure. The vacuum vessel 10 is provided with a gas supply mechanism 75 such as a flowmeter and a valve through an introduction pipe 76. The gas supply mechanism 75 supplies a discharge gas into the vacuum chamber 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 vessel 10 may be provided in the vacuum vessel 10.

The support table 20 is a substrate support portion of the film forming apparatus 1. The support table 20 is disposed in the vacuum vessel 10. The support table 20 faces the sputtering target 30. The support table 20 supports a substrate 21. In the support base 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 provided on the mounting surface. A temperature adjusting mechanism for maintaining the substrate 21 at a predetermined temperature may be incorporated in the support base 20. The substrate 21 is appropriately changed according to the applicable equipment, and examples thereof include an insulating substrate such as a glass substrate or a quartz substrate, a semiconductor substrate such as a silicon wafer, and a metal substrate.

A sputtering target 30 (hereinafter referred to as target 30) is provided in the vacuum chamber 10 via an insulating spacer 11. The target 30 is disposed so as to face the support table 20. The target 30 includes a target body, i.e., a target 31, a base material 32, and a joining member 33. The target 30 is a film forming source of the film forming apparatus 1.

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

The base material 32 is a back plate, and is disposed on the inside of the target 31. The substrate 32 has

portions

321, 322 of different diameters. Portion 322 of substrate 32 is a convex body protruding from portion 321. In other words, in the base material 32, steps are formed by the

portions

321, 322. The outer diameter of the portion 322 is, for example, substantially the same as the diameter of the target 31. A flow path for flowing the refrigerant may be provided in the base material 32.

The bonding member 33 is provided between the target 31 and the base material 32. The bonding member 33 is tightly bonded to the target 31 and the base material 32. The bonding member 33 is, for example, a solder such as indium.

The magnetic circuit portion 50 is disposed on the rear side of the target 30 opposite to the support base 20. The magnetic circuit portion 50 includes a yoke 51 disposed parallel to the target 30 and a magnet 52 provided on the yoke 51. The magnet 52 is disposed so as to face the rear surface of the target 30 on the side opposite to the sputtering surface 31s.

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

The film formation processing member 40 is an annular shielding member. The film formation processing member 40 is made of metal, for example, a ground shield having a potential of a ground potential. When the film forming apparatus 1 is viewed in plan, the film forming processing member 40 surrounds the outer periphery of the target 30. The film formation processing member 40 opens the sputtering surface 31s of the target 30 and is disposed along the outer periphery of the target 30 in the vacuum chamber 10. The film formation processing member 40 is fixed to, for example, the upper portion of the vacuum chamber 10. The shape of the film formation processing member 40 is only one example, and is not limited to the shape shown in the drawing.

The material of the film formation processing member 40 is, for example, stainless steel, aluminum, or the like. A gap of, for example, about 0.1mm to several mm is provided between the film formation processing member 40 and the target 30. As a result, during film formation, it becomes difficult to generate discharge in the gap between the film formation processing member 40 and the target 30 according to the so-called bar Shen Dinglv, and plasma is accumulated in the vicinity of the sputtering surface 31s, and stable plasma discharge is continued.

The alloy melt-blown film 60 is melt-blown onto the film-forming processing member 40. For example, an alloy melt film 60 is formed on the surface of the film forming process member 40 facing the film forming process ambient gas 12.

The alloy melt-blown film 60 has aluminum (Al) and at least one first element of scandium (Sc) and hafnium (Hf) other than aluminum. The alloy cast film 60 may contain at least one second element selected from zirconium (Zr) and titanium (Ti). Alternatively, silicon (Si) may be selected as the second element.

Wherein, in the alloy melt film 60, the total content of at least one first element of Sc and Hf is 0.05wt% or more and 1.5wt% or less. In this case, the alloy melt-blown film 60 is any one of an Al-Sc alloy melt-blown film, an Al-Hf alloy melt-blown film, and an Al-Sc-Hf alloy melt-blown film.

In addition, in the case of containing the second element, the content of Zr in the Al-Sc-Zr alloy melt-blown film or the Al-Hf-Zr alloy melt-blown film may be 0.1wt% or more and 0.5wt% or less, or the content of Ti in the Al-Sc-Ti alloy melt-blown film or the Al-Hf-Ti alloy melt-blown film may be 0.1wt% or more and 3wt% or less, or the content of Si in the Al-Sc-Si alloy melt-blown film or the Al-Hf-Si alloy melt-blown film may be 0.5wt% or more and 5wt% or less.

If the weight% of the first element is less than 0.05wt%, recrystallization tends to occur in the alloy melt film, and the alloy melt film tends to be soft due to the thermal history. As a result, the alloy melt-blown film cannot overcome the stress of the film deposited thereon, and may be peeled off from the film-forming processing member together with the film. On the other hand, if the weight% of the first element is more than 1.5wt%, the hardness of the material becomes high, and the processing of the material used for the melt-injection becomes difficult, which is not preferable.

Here, if Ti is less than 0.1wt%, the recrystallization inhibition effect becomes small, and if Ti is more than 3wt%, the influence of intermetallic compounds becomes large, and the strength of the melt film is lowered, which is not preferable. Alternatively, if Zr is less than 0.1wt%, the recrystallization inhibition effect becomes small, and if Zr is more than 0.5wt%, the hardness of the melt-blown material becomes high, and the melt-blown material is unsuitable for processing.

The film formation processing member 41 is an adhesion preventing plate surrounding the film formation processing ambient gas 12. For example, the film formation processing member 41 is provided along the inner wall of the vacuum chamber 10 from the upper portion toward the lower portion of the vacuum chamber 10. The film formation processing member 41 is disposed from the middle of the vacuum chamber 10 toward the support base 20. The shape of the film formation processing member 41 is only one example, and is not limited to the shape shown in the figure. The film formation processing member 41 is made of metal, and its potential is, for example, a ground potential. The material of the film formation processing member 41 is, for example, stainless steel, aluminum, or the like.

The alloy melt film 61 is melt-shot on the film forming process member 41. For example, the alloy melt film 61 is formed on the surface of the film forming process member 41 facing the film forming process ambient gas 12. The alloy melt film 61 has the same composition as the alloy melt film 60.

The film formation processing member 42 is a shutter plate that opens the target 30 to the substrate 21 or shields the sputtering surface 31s. The film formation processing member 42 is provided substantially parallel to the sputtering surface 31s, for example. The shape of the film formation processing member 42 is only one example, and is not limited to the shape shown in the drawing. The film formation processing member 42 is made of metal, and its potential is, for example, a ground potential. The material of the film formation processing member 42 is, for example, stainless steel, aluminum, or the like.

The alloy-blown film 62 is blown onto a main surface of the film-forming processing member 42 facing the substrate 21 and a main surface facing the target 30. The composition of the alloy melt film 62 is the same as that of the alloy melt film 60.

The power supply 80 is connected to the target 30 via a line 81. The power supply 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 supply 80 is a high-frequency power supply such as VHF power supply or RF power supply, a matching circuit may be provided in the line 81 between the power supply 80 and the target 30.

When a discharge gas is introduced into the vacuum chamber 10 and electric power is supplied to the target 30, electric discharge occurs between the target 30 and the vacuum chamber 10 or the film formation processing member 41 due to capacitive coupling. Thereby, plasma is formed near the sputtering surface 31s. Then, the sputtered particles are scattered from the sputtering surface 31s exposed to the plasma toward the film formation processing ambient gas 12.

As a result, a coating film made of the target 31 is formed on the substrate 21. At the same time, the film forming

process members

40, 41, 42 are also exposed to the film forming process ambient gas 12, so that the films are deposited on the alloy melt-blown

films

60, 61, 62.

Fig. 2 is a schematic diagram showing a partial cross section of a member for film formation treatment irradiated with an alloy melt film. The film forming process member 4 is any one of the film forming

process members

40, 41, 42, and the alloy melt film 6 is any one of the

alloy melt films

60, 61, 62. During the film formation, the surface 6s of the alloy melt-blown film 6 is exposed to the film formation processing ambient gas 12.

Before the alloy is sprayed to the film 6, the sprayed surface 4s of the film-forming member 4 is subjected to blasting treatment with insulating particles. For example, the fused surface 4s has an arithmetic average roughness Ra of 3 μm or more. For example, if the arithmetic average roughness Ra of the melt-blown surface 4s is less than 3 μm, the adhesion between the film-forming treatment member 4 and the alloy melt-blown film 6 is poor, which is not preferable.

An alloy shot film 6 is formed on the shot surface 4s by any one of arc shot, flame shot, plasma shot, cold spray shot, and the like. The alloy melt film 6 is, for example, an amorphous film immediately after the end of the melt. The thickness of the alloy melt film 6 is, for example, 100 μm or more and 400 μm or less. The surface 6s of the alloy melt-blown film 6 has an arithmetic average roughness Ra of 8 μm or more and 40 μm or less.

The film formation processing member 4 (shielding member, adhesion preventing plate, barrier, etc.) generally has no water cooling mechanism. Therefore, the film formation processing member 4 may be exposed to the film formation processing ambient gas 12, and thus the temperature thereof may be 350 ℃ or higher. In the present embodiment, the film formation processing member 4 is heated to, for example, 350 ℃ or higher by the thermal history of the film formation processing member 4 being exposed to the film formation processing ambient gas 12, and this temperature is referred to as "processing temperature".

Under such conditions, when a film made of pure Al (containing 99.00wt% or more of Al) or a film made of al—cu alloy (hereinafter referred to as Al film) is used as the film to be formed on the film-forming member 4, recrystallization tends to occur in the film to be formed. As a result, the Al-melt film becomes soft by the thermal history, and eventually, the Al-melt film is peeled off from the film forming processing member 4 together with the film.

If the film deposited on the Al-melt film is a film having a high stress, the adhesion force of the Al-melt film to the film-forming member 4 cannot overcome the stress, and the film Al may be peeled off from the film-forming member 4 together with the melt film.

In this way, when an Al-melt film is selected as the melt film on the film formation processing member 4, the Al-melt film is peeled off together with the coating film by the thermal history, and particles are generated.

In contrast, the alloy cast film 6 of the present embodiment has aluminum (Al) and at least one first element of scandium (Sc) and hafnium (Hf). Further, the alloy-blown film 6 may have at least one second element selected from zirconium (Zr), titanium (Ti) and silicon (Si).

In such an alloy-blown film 6, even if the alloy-blown film 6 receives a thermal history and reaches a processing temperature, recrystallization is less likely to occur in the alloy-blown film 6. As a result, even if the alloy melt film 6 receives the thermal history and reaches the processing temperature, the desired hardness is maintained, and the film formation processing member 4 is hard to peel off.

For example, when an alloy melt film 6 composed of Al-0.2wt% Sc is used, there is an example in which the Vickers hardness increases from 20HV to 30HV to 70HV with the heat history in the range of 260 ℃ to 370 ℃. Alternatively, in the case of using an alloy melt film 6 in which Al and 0.1wt% to 0.7% of Sc are mixed, there is an example in which the recrystallization start temperature is about 350 ℃, and the recrystallization finish temperature is about 570 ℃. That is, by adding Sc to Al, recrystallization of the alloy cast film 6 is suppressed at the processing temperature, and the alloy cast film 6 maintains a desired hardness.

[ Table 1 ]

Table 1 shows the shielding lives of the melt-blown films in the case where the WSi film and the SiN film were deposited on the Al melt-blown film as a comparative example and the alloy melt-blown film 6 of the present embodiment, respectively. The mask life (kW/h) is a value obtained by multiplying the power (kW) input to the target 30 until the film deposited on the film can be peeled off from the film formation processing member 4 when film formation is continued at the processing temperature, by the film formation time (h). That is, the shielding life is an index indicating the peeling resistance of the fuse film against the stress of the film. The longer the shielding life, the higher the peel resistance of the film to the stress of the film. Further, SUS304 plate was used as the substrate.

As shown in table 1, when the film was a WSi film, the shielding life of the Al-melt film was 500kw×h, and the shielding life of the alloy-melt film 6 was increased to 600kw×h. When the film is a SiN film, the shielding life of the Al-melt film is 250kw×h, and the shielding life of the alloy-melt film 6 is raised to 400kw×h.

When the alloy cast film 6 was formed on the film formation processing member 6 in this manner, it was found that the peeling resistance with respect to the film was significantly improved as compared with the case where the Al cast film was formed on the film formation processing member 4. For example, in an AlSc film formed not by meltallizing but by sputtering, an appropriate surface roughness cannot be obtained, and a thickness capable of overcoming the stress of a film deposited thereon cannot be obtained, which is not preferable.

While the embodiments of the present invention have been described above, it goes without saying that the present invention is not limited to the above embodiments and various modifications are possible. The embodiments are not limited to the independent modes, and can be combined within the scope of the technology.

Claims

1. An alloy melt-blown film which is provided on a surface of a member for film formation treatment exposed to a film formation treatment atmosphere, characterized in that,

comprises aluminum and a first element, wherein the first element is at least one element of scandium and hafnium,

the first element is contained in the melt-blown film in an amount of 0.05wt% or more and 1.5wt% or less.

2. The alloy melt-blown film according to claim 1, wherein,

the film contains a second element in addition to the first element, wherein the second element is at least one element selected from zirconium and titanium.

3. The alloy melt-blown film according to claim 2, wherein,

the second element is 0.1wt% or more and 0.5wt% or less of zirconium or 0.1wt% or more and 3.0wt% or less of titanium in the melt-blown film.

4. Alloy melt-blown film according to claim 1 or 2, characterized in that,

the film forming process member is an anti-adhesion plate surrounding the film forming process ambient gas or a shielding member surrounding the periphery of the sputtering target.

5. Alloy melt-blown film according to claim 1 or 2, characterized in that,

a high-melting-point metal film is formed on the film-forming processing member.

6. A film forming apparatus is characterized by comprising:

a film forming source;

a substrate support portion facing the film forming source;

a film forming process member that surrounds a film forming process ambient gas or the film forming source between the film forming source and the substrate support, and that is provided with an alloy melt film having aluminum and a first element, wherein the first element is at least one element of scandium and hafnium, and wherein the alloy melt film contains 0.05wt% or more and 1.5wt% or less of the first element; and

and a vacuum container for accommodating the film forming source, the substrate supporting portion, and the film forming processing member.

7. The film forming apparatus according to claim 6, wherein,

the alloy melt-blown film contains a second element in addition to the first element, wherein the second element is at least one element selected from zirconium, titanium and silicon.