JP7129581B1 - Materials for deposition equipment - Google Patents

Abstract

Kind Code: A1 A film-forming apparatus member is provided which can be easily removed without leaving deposits and which is excellent in retention of deposits during use. A member for a film forming apparatus comprising a base material and a plating film formed on the surface of the base material, wherein the arithmetic mean roughness Ra (μm) on the surface of the base material is equal to the plating film A member for a film forming apparatus, which is smaller than the value r1 calculated by the following formula (1) using the film thickness t (μm) of . r1=0.4578t-0.5027 (1) [Selection diagram] Fig. 1

Description

TECHNICAL FIELD The present invention relates to a member for a film forming apparatus. The present invention also relates to a method for manufacturing the member for a film forming apparatus, a method for removing deposits, a method for recovering valuable metals, and a method for regenerating the member for a film forming apparatus.

Vacuum deposition methods such as vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD) are widely used as methods for forming a coating of metal or the like on the surface of an object to be processed. Also, in recent years, film formation methods that do not require a reduced pressure atmosphere, such as a method of applying ink containing metal nanoparticles and firing at a low temperature, have been developed.

In these film forming methods, it is usually difficult to selectively form a coating only on the surface of the object to be processed. pile up. If film formation is continued with deposits attached, the deposits fall off from the surface of the member and contaminate the inside of the film forming apparatus. In particular, if the fallen deposit adheres to the surface of the object to be processed, it causes film formation failure.

Therefore, the various members used in the film forming apparatus are required to be resistant to the sediment deposited on the surface during use, in other words, to be excellent in sediment retention.

Further, generally, a member to which a certain amount of deposit has adhered is removed from the film forming apparatus and subjected to a deposit removal process for removing the deposit.

As a method for removing deposits, it is conceivable to use a physical method such as blasting, for example.

Physical methods such as blasting have the advantage of being able to remove deposits regardless of their material. However, the working efficiency is poor, and a considerable amount of working time is required particularly for removing deposits from the surfaces of film forming apparatus members having various shapes and sizes. Moreover, when valuable metals such as precious metals are contained in the sediments, it is desirable not only to remove them but also to recover and reuse them. However, when removal is performed by blasting, the removed deposits and the abrasive material (media) used for blasting are mixed, making it difficult to separate and recover valuable metals from them. .

Therefore, instead of the physical method, it is conceivable to use a chemical method of dissolving and removing the deposits using an acid or the like.

The chemical method has the advantage that deposits can be dissolved and removed simply by immersing the film-forming device member in a chemical solution such as acid, regardless of the shape and size of the film-forming device member. . However, in order to dissolve the deposits, it is necessary to use different chemicals depending on the material of the deposits, and it is particularly difficult to dissolve deposits containing chemically stable metals such as precious metals. . If an acid with extremely high oxidizing power such as aqua regia is used, it is possible to dissolve precious metals, but in that case, the film-forming apparatus members themselves, which should not be originally dissolved, may also be dissolved.

Furthermore, in chemical removal, the components contained in the sediment are dissolved in the chemical solution, resulting in a state of very low concentration. Therefore, in order to separate and recover valuable metals such as precious metals contained in the sediment, further chemical treatment is required, which is inefficient.

Therefore, Patent Document 1 proposes forming a metal surface layer made of zinc, nickel, or the like in advance on the surface of a jig for forming a thin film. When the jig for forming a thin film is used, a deposit adheres on the metal surface layer. Therefore, by dissolving the metal surface layer with an acid or an alkali after use, the deposit adhering thereon can be peeled off from the jig. With this method, since the deposit itself does not need to be dissolved, valuable metals such as noble metals can be easily recovered after peeling.

JP-A-11-106918

However, as a result of investigation by the present inventors, even when a metal surface layer is provided as proposed in Patent Document 1, the deposit cannot be peeled off well, and even if dissolution treatment is performed, It has been found that deposits may remain on the substrate surface. It has also been found that the member provided with the metal surface layer does not retain the deposits sufficiently, and the deposited deposits sometimes fall off during use.

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and provides a member for a film forming apparatus that can be easily removed without leaving any deposits and is excellent in retaining the deposits during use. for the purpose. Another object of the present invention is to provide a method for removing deposits from used film forming apparatus members, and a valuable metal recovery method for recovering valuable metals from used film forming apparatus members.

As a result of extensive research, the present inventors have found that, in a member for a film forming apparatus comprising a substrate and a plating film formed on the surface of the substrate, the surface roughness of the substrate and the film of the plating film It has been found that the above problem can be solved by controlling the thickness so as to satisfy a predetermined relationship.

The present invention has been made based on the above findings, and the gist and configuration thereof are as follows.

1. A member for a film forming apparatus comprising a base material and a plating film formed on the surface of the base material,
A member for a film forming apparatus, wherein the arithmetic mean roughness Ra (μm) on the surface of the base material is smaller than the value r ₁ calculated by the following formula (1) using the film thickness t (μm) of the plating film .
r ₁ =0.4578t−0.5027 (1)

2. 2. The member for a film forming apparatus according to 1 above, wherein the film thickness t of the plating film is 3.1 μm or more.

3. 3. The member for a film forming apparatus according to 1 or 2 above, wherein the arithmetic mean roughness Ra (μm) is 0.10 μm or more.

4. 3. The member for a film forming apparatus according to 1 or 2 above, wherein the material of the base material is at least one selected from the group consisting of stainless steel, valve metals, and valve metal alloys.

5. 1 or 2 above, wherein the plated film consists of at least one selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Pd, Ag, Cd, In, Sn, and Sb The member for a film forming apparatus according to 1.

6. A method for manufacturing a member for a film forming apparatus,
A roughening treatment step of roughening the surface of the base material;
a plating step of plating the surface of the substrate after the roughening treatment step to form a plating film,
The arithmetic mean roughness Ra (μm) on the surface of the base material after the roughening treatment step is more than the value r ₁ calculated by the following formula (1) using the film thickness t (μm) of the plating film A method for manufacturing a small member for a film forming apparatus.
r ₁ =0.4578t−0.5027 (1)

7. A deposit removal method for removing deposits adhering to a surface of a film forming apparatus member after being used in the film forming apparatus, comprising:
The member for a film forming apparatus is the member for a film forming apparatus according to 1 or 2 above,
A deposit removing method, comprising a deposit removing step of removing the deposit from the film forming apparatus member by dissolving a plating film of the film forming apparatus member.

8. A valuable metal recovery method for recovering valuable metals contained in deposits adhering to the surface of a film forming apparatus member after being used in the film forming apparatus, comprising:
The member for a film forming apparatus is the member for a film forming apparatus according to 1 or 2 above,
a deposit removing step of removing the deposit from the film forming apparatus member by dissolving the plating film of the film forming apparatus member;
and a recovering step of recovering valuable metals from the deposits removed in the deposit removing step.

9. A method for regenerating a film forming apparatus member after being used in a film forming apparatus, comprising:
The member for a film forming apparatus is the member for a film forming apparatus according to 1 or 2 above,
a deposit removing step of removing deposits adhering to the surface of the film forming apparatus member from the film forming apparatus member by dissolving the plating film of the film forming apparatus member;
a plating step of plating the surface of the base material after the deposit has been removed to form a plating film,
The arithmetic mean roughness Ra (μm) on the surface of the base material before forming the plating film is more than the value r ₁ calculated by the following formula (1) using the film thickness t (μm) of the plating film A method for regenerating a small film forming apparatus member.
r ₁ =0.4578t−0.5027 (1)

The film-forming apparatus member of the present invention can be easily removed without leaving deposits, and is excellent in retention of deposits during use. Moreover, according to the deposit removing method of the present invention, the deposit can be efficiently removed from the used film-forming apparatus member. Furthermore, according to the valuable metal recovery method of the present invention, valuable metals such as noble metals can be efficiently recovered from used film forming apparatus members.

It is a schematic diagram which shows the evaluation method of adhesiveness of a deposit.

Hereinafter, embodiments of the present invention will be specifically described. In addition, this invention is not limited to embodiment described below.

(Members for film deposition equipment)
A member for a film forming apparatus according to one embodiment of the present invention is a member for a film forming apparatus including a base material and a plating film formed on the surface of the base material.

The film-forming apparatus member of the present invention can be used in any film-forming apparatus without particular limitation. The film forming apparatus may be a so-called vacuum film forming apparatus that forms a film in a reduced pressure atmosphere, or may be a film forming apparatus that forms a film in a non-reduced pressure atmosphere such as atmospheric pressure. . Examples of the vacuum film forming apparatus include a vacuum deposition apparatus, a sputtering apparatus, an ion plating apparatus, and a chemical vapor deposition (CVD) apparatus. Examples of a film forming apparatus that forms a film in a non-depressurized atmosphere include a film forming apparatus using ink containing metal nanoparticles.

The deposition apparatus member may be a deposition-inhibiting member. Here, the deposition-inhibiting member is defined as a member used for the main purpose of preventing deposits from adhering to the constituent members of the film-forming apparatus member.

[Base material]
Any base material can be used as the base material of the film-forming apparatus member without any particular limitation. Although the material of the base material is not particularly limited, it is preferable to use a metal base material in terms of ease of control of surface roughness, strength, corrosion resistance, cost, and the like. In particular, from the viewpoint of corrosion resistance and cost, the material of the substrate is preferably at least one selected from the group consisting of stainless steel, valve metals, and valve metal alloys, such as stainless steel, aluminum, aluminum alloys, and titanium. , and titanium alloys, and more preferably at least one selected from the group consisting of stainless steel, titanium, and titanium alloys. Since stainless steel, titanium, and titanium alloys have particularly excellent corrosion resistance, various plating solutions can be used without restrictions as plating solutions for forming plating films and chemical solutions for dissolving plating films. can be done.

The size of the base material is not particularly limited, and any size can be used. However, if the thickness is excessively thin, the strength may decrease and handling may become difficult. Therefore, the thickness of the substrate is preferably 200 μm or more, more preferably 500 μm or more. On the other hand, the upper limit of the thickness is also not particularly limited, but may be 100 mm or less, 50 mm or less, or 5 mm or less.

[Plating film]
Any plated film can be used as the plated film of the film forming apparatus member without any particular limitation. For example, a plating film made of at least one selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Pd, Ag, Cd, In, Sn, and Sb can be used. Among them, it is preferable to use a Ni plating film or a Cu plating film from the viewpoint of ease of handling and ease of dissolution.

A method for forming the plated film is not particularly limited, and the plated film can be formed by any method. The plating film may be a wet plating film, a hot dip plating film, or a dry plating film. Examples of the wet plating film include electrolytic plating film and electroless plating film. Examples of the dry plating coating include vacuum deposition coating, sputtering coating, ion plating coating, chemical vapor deposition (CVD) coating, and the like. Among them, it is preferable to use an electroplating film from the viewpoint of ease of film formation, cost, productivity, and the like.

In the film forming apparatus member of the present invention, the arithmetic mean roughness Ra (μm) on the surface of the base material is a value calculated by the following formula (1) using the film thickness t (μm) of the plating film It is important that r be less than ₁ .
r ₁ =0.4578t−0.5027 (1)

If the surface roughness of the substrate does not satisfy the above conditions, the plated film will not be sufficiently dissolved even if the dissolution treatment is performed after use, and as a result, the deposit will remain without being peeled off. The reason for this is considered as follows. That is, in order to reliably remove the adhered deposits, the plating film present between the substrate and the deposits is completely dissolved with a chemical solution such as acid or alkali, and the deposits are removed from the substrate. need to be stripped. However, when the surface roughness of the base material is large compared to the film thickness of the plating film, in other words, when the film thickness of the plating film is thinner than the surface roughness of the base material, the unevenness of the base material surface causes the plating film to become uneven. continuity is lost. Therefore, even if the film-forming apparatus member is immersed in the chemical solution, the dissolution does not progress to the inside, and as a result, the deposit cannot be removed.

In addition, if the surface roughness of the base material does not satisfy the above conditions, deposits adhering to the surface of the film-forming apparatus member are likely to come off during use. An example of experimental results for confirming the reason will be described below.

(Experiment 1)
In order to evaluate the influence of the surface roughness of the substrate on the adhesion of the deposit, the following experiment was conducted. The structure of the test piece used and the test method will be described with reference to FIG. Here, the adhesion of deposits refers to the adhesion of deposits adhering to the surface of the film forming apparatus member and the film forming apparatus member.

First, a test piece 10 having a plating film on the surface of the substrate 11 was prepared. As the base material 11, a substrate of 50 mm×20 mm×1 mm thickness made of stainless steel (SUS304) was used. As the plating film, a Ni plating film 12 having a film thickness of about 10 μm was formed on one surface of the substrate 11 . The Ni-plated film 12 was formed by electroplating nickel using a Watt bath after subjecting the substrate 11 to pretreatment. The composition of the Watt bath was NiSO ₄ : 300 g/L, NiCl ₂ : 70 g/L, H ₃ BO ₃ : 45 g/L. As the pretreatment, ultrasonic cleaning, ultrasonic degreasing, water washing, sulfuric acid treatment, and water washing were sequentially performed. The conditions for the ultrasonic degreasing were as follows: degreasing liquid: Etrex 11 (manufactured by Nippon Electroplating Engineers Co., Ltd.), temperature: 55° C., time: 1 minute. The conditions for the sulfuric acid treatment were sulfuric acid concentration: 0.5 mol/L, temperature: room temperature, and time: 30 seconds.

An Au sputtered film 13 was deposited as a deposit on the surface of the obtained test piece 10 . The sputtered Au film 13 was formed by sputtering for about 100 minutes, and the thickness of the sputtered Au film 13 was set to about 2 μm.

Next, in order to evaluate the adhesion of the Au sputtered film 13 to the test piece 10, a tensile test was performed. Specifically, a SnPbAg wire 15 was fixed to the surface of the Au sputtered film 13 as a deposit using SnPbAg solder 14 . The surface of the sputtered Au film 13 other than the portion where the SnPbAg wire 15 was fixed was masked with masking tape 16 .

With the test piece 10 fixed, the SnPbAg wire 15 was pulled in the direction (arrow A) perpendicular to the surface of the test piece 10, and the tensile load at the time when peeling or breakage occurred was measured as the breaking strength. The measurement was performed twice for each condition, and Table 1 shows the average values of the obtained breaking strengths.

Table 1 shows the results of the above tests conducted under four conditions in which the surface roughness of the base material is different. In order to adjust the surface roughness of the substrate, No. In tests 2 to 4, the surface of the substrate was blasted prior to the pretreatment described above, and the surface roughness was adjusted by changing the blasting conditions as shown in Table 1. On the other hand, No. In test 1, polished stainless steel was directly subjected to pretreatment without blasting. Each blasting condition in Table 1 indicates that the following abrasives were used.
・ WA #30: White alumina abrasive #30 (average particle size: 500 to 710 μm)
・ WA #60: White alumina abrasive #60 (average particle size: 212 to 300 μm)
・ WA #80: White alumina abrasive #80 (average particle size: 150 to 212 μm)

As can be seen from the results shown in Table ₁ , no. In No. 1 to 3, the breaking strength was 6.0 N/mm ³ or more, while Ra was r ₁ or more. In No. 4, the breaking strength was less than 6.0 N/mm ³ and adhesion of deposits was poor.

In addition, No. In No. 1, 3 and 4, peeling was observed at the interface between the Ni plated film 12 and the Au sputtered film 13 when the tensile test was performed. In No. 2, the SnPbAg wire was cut without peeling at the interface.

As described above, by making the arithmetic mean roughness Ra (μm) on the surface of the substrate smaller than the value r ₁ calculated by the following formula (1) using the film thickness t (μm) of the plating film In addition, it is possible to easily remove the deposit without leaving it, and it is possible to prevent the deposit from falling off during use.

In the present invention, the desired effects can be obtained if the arithmetic mean roughness Ra of the substrate and the film thickness t of the plating film satisfy the above relationship. Therefore, individual values of Ra and t are not particularly limited.

However, when the plated film is extremely thin, the surface of the substrate must be made extremely smooth in order to satisfy the above conditions. In addition, when the plated film is extremely thin, the effect of film thickness variations becomes obvious, and as a result, there is a possibility that the stability of deposit removal may be lowered. Therefore, from the viewpoint of productivity and further stabilization of deposit removal, the film thickness of the plating film is preferably 1.0 μm or more, more preferably 2.5 μm or more, and more preferably 3.1 μm or more. and most preferably 3.5 μm or more.

On the other hand, if the plated film is excessively thick, it takes time to form the film, which reduces productivity. Moreover, since it is necessary to dissolve the thick plating film, it takes a long time to remove the deposits. Therefore, the film thickness of the plating film is preferably 100 μm or less, more preferably 60 μm or less, even more preferably 48 μm or less, and most preferably 35 μm or less.

Further, if the arithmetic mean roughness Ra of the base material is to be excessively reduced, it will be necessary to perform very precise polishing, resulting in a decrease in productivity and an increase in cost. Therefore, the arithmetic mean roughness Ra of the substrate is preferably 0.01 μm or more, more preferably 0.03 μm or more. Further, as shown in Table 1, from the viewpoint of further improving the breaking strength, that is, further improving the effect of preventing the sediment from falling off, Ra is preferably 0.1 μm or more, and 0.71 μm or more. more preferably 0.91 μm or more, and most preferably 1.5 μm or more.

On the other hand, if Ra is excessively large, the film thickness of the plated film must be considerably increased in order to satisfy the above conditions. Therefore, the arithmetic mean roughness Ra of the substrate is preferably 10 μm or less, more preferably 6 μm or less. Further, as shown in Table 1, from the viewpoint of further improving the breaking strength, that is, further improving the effect of preventing the sediment from falling off, Ra is preferably 4.5 μm or less, and 4.0 μm or less. and more preferably 3.0 μm or less.

The plated coating can be provided on any portion of the base material surface. However, from the viewpoint of removing without leaving deposits when the plating film is dissolved, the coverage area ratio of the plating film to the entire surface of the substrate is preferably 50% or more, and 70% or more. more preferably 90% or more, most preferably 95% or more. The coverage area rate may be 100%. In other words, the plating film may be provided on the entire surface of the substrate.

When the film-forming apparatus member of the present invention is actually used in a film-forming apparatus, deposits generally do not adhere to the entire surface of the film-forming apparatus member, and the film-forming material is supplied exclusively. Adheres to side surfaces only. For example, when it is used in a sputtering apparatus, deposits are deposited on the side facing the sputtering target, and hardly adhere to the opposite side of the film forming apparatus member. At this time, if a plated film is also formed on a portion where no deposit has adhered, the plated film is dissolved from that portion, so that the deposit can be easily removed. Therefore, it is effective to set the coverage area ratio to 50% or more as described above.

For the same reason, in the film-forming apparatus member according to one embodiment of the present invention, it is preferable that the one surface, the other surface, and the side surface of the substrate have a plating film.

(Manufacturing method for film forming apparatus member)
Next, a method for manufacturing the film forming apparatus member will be described. Note that points that are not particularly mentioned can be the same as those of the above-described film forming apparatus member.

In one embodiment of the present invention, the method for manufacturing a member for a film forming apparatus includes a roughening treatment step of roughening the surface of a base material, and plating the surface of the base material after the roughening treatment step. and a plating step of forming a plating film. Then, the arithmetic mean roughness Ra (μm) on the surface of the substrate after the roughening treatment step is calculated by the following formula ( ₁ ) using the film thickness t (μm) of the plating film. be smaller than
r ₁ =0.4578t−0.5027 (1)

[Roughening treatment step]
In this embodiment, in order to adjust the surface roughness of the base material, the surface of the base material is roughened prior to the formation of the plating film (roughening treatment step). The method of the roughening treatment is not particularly limited, and any method can be used as long as it can adjust the surface roughness. For example, the roughening can be performed by blasting. At that time, the surface roughness of the substrate can be adjusted by changing the particle size of the media used for blasting and the projection conditions.

[Plating process]
Next, plating is applied to the surface of the substrate after the roughening treatment step to form a plating film (plating step). The plating method is not particularly limited, and any method can be adopted. The plating may be wet plating, hot dip plating, or dry plating. Examples of the wet plating include electrolytic plating and electroless plating. Examples of dry plating include vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD). Among them, it is preferable to use electroplating from the viewpoint of ease of film formation, cost, productivity, and the like.

In addition, when performing the said plating, pretreatment can be performed arbitrarily. As the pretreatment, it is preferable to perform an arbitrary combination of treatments such as degreasing, pickling, and water washing depending on the material of the base material to be used.

Moreover, the plating film does not need to be provided on the entire surface of the base material, and may be provided on at least a portion thereof, in particular, on the surface to which deposits adhere when the base material is installed in a film forming apparatus. Therefore, it is also preferable to perform plating after providing a mask on the portion of the surface that does not need to be plated.

(Deposit removal method)
Next, a method for removing deposits from used film forming apparatus members will be described. Note that the points that are not particularly mentioned can be the same as the description of the film-forming apparatus member described above.

A deposit removal method according to an embodiment of the present invention is a deposit removal method for removing deposits adhering to the surface of a film forming apparatus member after being used in the film forming apparatus. and a deposit removing step of removing the deposit from the film forming apparatus member by dissolving the plating film of the film forming apparatus member. Here, as the film forming apparatus member, the above film forming apparatus member can be used.

[Deposit removal step]
In the deposit removing step, the deposit is removed from the film forming apparatus member by dissolving the plating film of the film forming apparatus member. By dissolving the plating film, the deposit can be removed from the substrate surface without dissolving it. In the deposit removal step, it is permissible for some or all of the components that make up the deposit to be dissolved, but as described later, when recovering the valuable metal contained in the deposit, it is easy to recover. From this point of view, it is preferable that the deposits are not substantially dissolved in the deposit removal step.

The method of dissolving the plated film is not particularly limited, but usually the plated film may be dissolved using a chemical solution such as an acid or an alkali. The method of applying the chemical solution is also not particularly limited, and any method such as a method of immersing the film forming apparatus member in the chemical solution, a method of spraying the chemical solution onto the film forming apparatus member, or the like can be used. A method of immersing the film-forming apparatus member in the chemical solution is preferable from the viewpoint of ensuring that the plated film is dissolved. Moreover, in that case, it is preferable to stir the chemical solution in order to increase the dissolution rate.

The chemical solution is not particularly limited, and any chemical solution can be used as long as it can dissolve the plating film and does not dissolve the base material. Examples of the acid that can be used include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, and mixtures of two or more thereof. As a mixture of a plurality of acids, for example, aqua regia or reverse aqua regia can be used. Moreover, as said alkali, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and cyanide aqueous solution can be used, for example. A cyanide salt is preferably used as the cyanide. Examples of the cyanide salt include sodium cyanide and potassium cyanide. Also, the chemical solution may further contain an oxidizing agent. Examples of the oxidizing agent include hydrogen peroxide and hypochlorous acid. Examples of the chemical solution containing an oxidizing agent include a mixed solution of sulfuric acid and hydrogen peroxide, a mixed solution of hydrochloric acid and hydrogen peroxide, and the like.

Although the concentration of the chemical solution is not particularly limited, it is preferably adjusted according to the material and film thickness of the plating film to be dissolved. For example, when nitric acid is used to dissolve the Ni plating film, the concentration of the nitric acid is preferably 2 mol/L or more, more preferably 3 mol/L or more in terms of molarity.

The temperature of the chemical solution is not particularly limited, but from the viewpoint of enhancing the solubility of the plating film, it is preferable to use the chemical solution after heating to a temperature higher than room temperature. The temperature may be, for example, 40° C. or higher, 50° C. or higher, or 60° C. or higher. On the other hand, if the temperature is too high, handling becomes difficult, so the temperature of the chemical solution is preferably 90° C. or lower, more preferably 80° C. or lower.

The chemical solution used in the deposit removal process can be disposed of as a waste solution after being used for a certain period of time, but from the viewpoint of reducing the environmental load, it is preferable to adjust the components before reuse.

Further, the film-forming apparatus member after removing the deposits as described above is in a state of only the base material without the plating film. Therefore, it is preferable to re-plat the surface of the film forming apparatus member (substrate) from which the deposits have been removed to form a plated film and reuse the film forming apparatus member. In other words, in another embodiment of the present invention, the deposit removing step and the surface of the base material from which the plating film and the deposit have been removed in the deposit removing step are plated again and plated. It may be a method for regenerating a member for a film forming apparatus, including a re-plating step for forming a film.

By regenerating the film-forming apparatus member in this way, the substrate can be used repeatedly while removing and recovering the deposits.

(Valuable metal recovery method)
Next, a valuable metal recovery method for recovering valuable metals contained in deposits adhering to the surface of the film forming apparatus member from the used film forming apparatus member will be described. Note that points that are not particularly mentioned can be the same as the description of the film forming apparatus member and the deposit removing method described above.

A valuable metal recovery method according to an embodiment of the present invention recovers valuable metals contained in deposits adhering to the surface of a film forming apparatus member from a film forming apparatus member after being used in the film forming apparatus. A valuable metal recovery method comprising: a deposit removing step of removing the deposit from the film forming apparatus member by dissolving the plated coating of the film forming apparatus member; and a recovery step of recovering valuable metals from the sediments. Here, as the film forming apparatus member, the above film forming apparatus member can be used.

[Deposit removal step]
The deposit removing step is as described in the description of the deposit removing method.

[Recovery process]
After the deposit is removed from the film forming apparatus member in the deposit removing step, the valuable metal is recovered from the deposit. The recovery method is not particularly limited, but for example, the solid content present in the chemical solution used in the deposit removal step is separated from the chemical solution by a method such as filtration, and if necessary, dissolved, purified, or the like. Just do it. In the present invention, since the valuable metal can be recovered as a solid matter in this manner, recovery can be performed extremely efficiently compared to the case where the valuable metal itself is dissolved and recovered.

For example, when the deposit is a noble metal, the solid deposit (noble metal) can be separated from the chemical solution and then dissolved in aqua regia or the like to be liquefied and recovered. It can also be recovered as an ingot or the like by once melting by a method such as high-frequency melting and then solidifying. It is preferable to recycle the recovered valuable metals.

Valuable metals are not limited to noble metals, and any metals can be recovered. Examples of valuable metals used for film formation include Au, Ag, Pt, Pd, Rh, Ir, Ru, Os, Mo, Ta, W, Al, Co, Cu, Fe, Mg, Mn, Sn, Cr , Nb, Ti, V, Ni, Bi, Ga, Ge, Si, Sr, Ba and the like.

In addition, in the deposit removing step, if the valuable metal in the deposit is dissolved in the chemical solution, it can be recovered by a method such as electrolytic winning, for example.

(Method for Regenerating Film Deposition Apparatus Members)
Next, a method for regenerating used film forming apparatus members will be described. Points that are not particularly mentioned can be the same as those of the film forming apparatus member, the method for manufacturing the film forming apparatus member, and the deposit removing method described above.

A method for recycling a film-forming apparatus member according to an embodiment of the present invention is intended for the above-described film-forming apparatus member. The regeneration method includes the following steps.
(1) a deposit removal step of removing deposits adhering to the surface of the film-forming apparatus member from the film-forming apparatus member by dissolving the plating film of the film-forming apparatus member; A plating step of plating the surface of the base material after the material has been removed to form a plating film

Then, in the regeneration method, the arithmetic mean roughness Ra (μm) on the surface of the base material before forming the plating film is calculated by the following equation (1) using the film thickness t (μm) of the plating film. _A value smaller than the calculated value r1.
r ₁ =0.4578t−0.5027 (1)

In this recycling method, deposits are removed from the used film-forming apparatus member, and then the plating film is formed again. It can be used for membranes. In addition, since the surface roughness of the base material and the film thickness of the plated film satisfy the conditions described above in the recycled film-forming apparatus member, deposits can be easily removed even after reuse. . Therefore, according to this method, the film forming apparatus member can be used repeatedly.

Incidentally, at the time of removing the deposits in the deposit removing step, the arithmetic mean roughness Ra (μm) on the surface of the base material is the film thickness t (μm) of the plating film to be formed in the next plating step. If the value r calculated by the above formula ( ₁ ) is ₁ or more using good.

In other words, the regeneration method in another embodiment of the present invention further includes a surface roughening process after the deposit removing process and before the plating process, and the surface roughening process reduces Ra ( μm) can be adjusted to be _less than r1.

Further, the regeneration method in another embodiment of the present invention further includes a judgment step of judging whether or not a surface roughening treatment step is necessary after the deposit removal step and before the surface roughening treatment step. can be done. In the determination step, for example, it is determined whether Ra (μm) is smaller _than r1, and if Ra (μm) is already smaller _than r1, the next step is performed without performing the roughening treatment step. When the plating step is performed and Ra (μm) is r1 or _more , the surface roughening treatment step can be performed.

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples and comparative examples of the present invention, but the present invention is not limited thereto.

First, in the same manner as in Experiment 1, a test piece having a Ni plating film on the surface of the base material was prepared. However, in this example, the Ni plating film was formed on the entire surface of the substrate, that is, all of the front surface, back surface, and side surface. Conditions such as the dimensions and material of the test piece were the same as in Experiment 1 above. The blasting conditions were as shown in Table 2. Each blasting condition indicates that the following abrasives were used.
・ WA #30: White alumina abrasive #30 (average particle size: 500 to 710 μm)
・ WA #60: White alumina abrasive #60 (average particle size: 212 to 300 μm)
・ WA #80: White alumina abrasive #80 (average particle size: 150 to 212 μm)
・WA #220: White alumina abrasive #220 (average particle size: 45 to 75 μm)
・ WA #400: White alumina abrasive #80 (average particle size: 20 to 58 μm)
・GC #1000: green silicon carbide #80 (average particle size: 7 to 27 μm)

The arithmetic mean roughness Ra of the substrate surface before forming the Ni plating film and the thickness t of the Ni plating film were measured by the following methods. Table 2 shows the measurement results.

(Arithmetic mean roughness Ra)
The arithmetic mean roughness Ra of the base material surface before forming the Ni plating film was measured using a stylus-type surface roughness measuring instrument "Small Surface Roughness Measuring Instrument Surftest SJ-210" (manufactured by Mitutoyo Co., Ltd.). measured by The measurement conditions were as follows.
・Roughness curve cutoff value λc: 0.8 mm
・Cutoff value λs for cross-sectional curve: 2.5 μm
・Number of sections: 5
・Measurement length: 4mm

(Thickness t of plating film)
The film thickness t of the plating film was calculated from the weight difference before and after forming the plating film. Specifically, first, the weight _w0 of the substrate before forming the plating film was measured. Next, the weight _w1 of the test piece after forming the plating film was measured. From the obtained values, the plating film thickness t was determined by the following formula.
t (μm) = (w ₁ -w ₀ )/(d x S) x 10000
here,
w ₀ : Weight (g) of substrate before forming plating film
w ₁ : Weight (g) of the test piece after forming the plating film
d: Density of Ni: 8.90 g/cm ³
S: Surface area of substrate (cm ² )

Table 2 also shows the value of r1 calculated by the formula (1) using the obtained film thickness t and whether or not the condition that Ra is less than r1 is satisfied.

(Peeling test)
Next, in order to evaluate the easiness of removing deposits from each test piece, a peeling test was conducted according to the following procedure.

First, an Au sputtered film was formed as a deposit on the surface of the Ni-plated film of the test piece by sputtering. The film thickness of the Au sputtered film was about 0.7 μm.

Next, the test piece on which the Au sputtered film was formed was immersed in nitric acid to dissolve the Ni plating film. As the nitric acid, nitric acid having a concentration of 7 mol/L and a temperature of 60° C. was used, and the immersion time was 240 minutes. However, invention example No. Since only No. 9 had a very thick plating film, the immersion time was set to 480 minutes. During immersion, continuous stirring was performed using a stirrer placed at the bottom of the vessel.

After the immersion time had passed, the test piece was pulled out of the nitric acid and washed with water. After that, the Au peeling rate on the surface of the test piece was measured. The Au peeling rate is determined by the amount w _Au,0 (g) of Au adhered to the test piece by the sputtering, and the amount w _Au,1 of Au remaining on the test piece after the Ni plating film was removed by the nitric acid immersion. (g), it was calculated by the following formula.
Au peeling rate (%) = {1-w _{Au, 1} /w _{Au, 0} } × 100

Here, the amount of Au attached to the test piece by sputtering w _Au,0 is obtained by measuring the weight of the test piece before sputtering and the weight of the test piece after sputtering when performing the sputtering, and from the difference between the two. asked.

The amount of _{Au wAu,1} remaining on the test piece after the Ni plating film was removed by immersion in nitric acid was measured by the following procedure. First, the Au remaining on the surface of the test piece after the Ni plating film was removed by immersion in nitric acid was dissolved in an aqueous potassium cyanide solution. Next, the potassium cyanide aqueous solution in which Au was dissolved was adjusted to 100 mL, and the Au concentration (g/L) was measured by ICP emission spectrometry. w _Au,1 (g) was obtained from the Au concentration. Here, when the Au peeling rate is 100%, it means that the Au sputtered film adhering to the surface of the test piece has been completely removed. Therefore, the higher the Au peeling rate, the better. Table 2 also shows the evaluation results in which the case where the Au peeling rate is 98% or more is accepted (○), and the case where the Au peeling rate is less than 98% is rejected (x).

As can be seen from the results shown in Table 2, the test pieces satisfying the conditions of the present invention were able to achieve an extremely high Au peeling rate of 98% or more. Moreover, since the peeled Au sputtered film was separated as a solid without being dissolved, it could be easily recovered by a method such as filtration.

10 Specimen 11 Base material 12 Ni plating film 13 Au sputter film 14 SnPbAg solder 15 SnPbAg wire

Claims (3)

A member for a film forming apparatus comprising a base material and a plating film formed on the surface of the base material,
The plated film consists of at least one selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Ag, Cd, and Sb,
The arithmetic mean roughness Ra (μm) on the surface of the base material is 0.71 μm or more, and the value r calculated by the following formula (1) using the film thickness t (μm) of the plating film is larger than ₁ A small film forming device member.
r ₁ =0.4578t−0.5027 (1) 2. The member for a film forming apparatus according to claim 1, wherein the plating film has a film thickness t of 3.1 [mu]m or more. 3. The film-forming apparatus member according to claim 1, wherein the material of said base material is at least one selected from the group consisting of stainless steel, valve metals, and valve metal alloys.

Images