CN112126930A - Surface treatment method - Google Patents
Surface treatment method Download PDFInfo
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- CN112126930A CN112126930A CN202010559211.4A CN202010559211A CN112126930A CN 112126930 A CN112126930 A CN 112126930A CN 202010559211 A CN202010559211 A CN 202010559211A CN 112126930 A CN112126930 A CN 112126930A
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- etching
- blasting
- roughened
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- average roughness
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/06—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for producing matt surfaces, e.g. on plastic materials, on glass
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/564—Means for minimising impurities in the coating chamber such as dust, moisture, residual gases
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
- H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
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- Metallurgy (AREA)
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- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Provided is a surface treatment method which can suppress the release of a film-forming material deposited on the surface of a member from the member and can suppress the release of a content. The surface treatment method comprises the following steps: a metal surface (10F) of the member (10) is roughened by sandblasting. Residues caused by the blasting treatment remain on the roughened surface (10F) after the blasting treatment. The method further comprises etching the roughened surface (10F) with an etching liquid. The etching is performed to obtain an arithmetic average roughness (Ra) of the roughened surface (10F) after etching, that is, a roughness measured in accordance with JIS B0601: 2013 is performed so that the arithmetic average roughness (Ra) of the roughened surface (10F) obtained by the blasting is 53% to 100%.
Description
Technical Field
The present invention relates to a surface treatment method.
Background
Various vacuum processing apparatuses such as a sputtering apparatus, an etching apparatus, and an ashing apparatus are composed of a plurality of members having metal surfaces. The members constituting the vacuum processing apparatus include: a member for partitioning a processing space in which a processing object is processed in a vacuum processing apparatus, and other various members disposed in the processing space. The deposition of the film-forming material occurs by the deposition of the film-forming material on these members, which is generated as a result of the processing in the processing space. The film forming material detached from the member becomes fine particles, and may adhere to the processing object or the member to contaminate the processing object. Therefore, for example, sandblasting and thermal spraying are performed on the surface of an adhesion-preventing plate provided in a sputtering apparatus (see, for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012 and 224921
Disclosure of Invention
Problems to be solved by the invention
However, in the surface treatment of the surface of a member applied to a vacuum processing apparatus, there is still room for study in terms of suppressing detachment of a film-forming material deposited on the surface of the member and suppressing discharge of residues (inclusions) caused by the surface treatment.
The invention aims to provide the following surface treatment method: the film forming matter deposited on the surface of the member can be inhibited from coming off the member, and the discharge of the content can be inhibited.
Means for solving the problems
The surface treatment method of one embodiment includes: roughening a metallic surface of a member by blasting, and leaving a residue caused by the blasting on the roughened surface after the blasting; and etching the roughened surface with an etching solution, the etching being performed such that an arithmetic mean roughness of the roughened surface after the etching becomes 53% or more and 100% or less of an arithmetic mean roughness of the roughened surface obtained by the blasting treatment, the arithmetic mean roughness being a value obtained by JIS B0601: 2013.
In the member subjected to the surface treatment method, a part of the dirt, which is the residue caused by the blasting, enters the roughened surface and is encapsulated. For example, when a medium used for blasting is blasted onto a metal surface, the medium may partially enter the member from the surface. In this case, the residue is enclosed in the surface (member) together with the medium. Therefore, the residue contained in the roughened surface is not released. On the other hand, a residue remains on the roughened surface. According to the method, after the blasting, the roughened surface is etched. The surface subjected to etching is in a state where the residue due to the blast treatment is cleaned. Therefore, when this member is used in a vacuum processing apparatus, the film-forming material deposited on the surface of the member is less likely to be detached than a member having a non-roughened surface or a member having a surface which is roughened but not etched to contain residues (dirt) caused by blasting. At the same time, the amount of etching can be minimized, the amount of gas released can be suppressed, and the release of the encapsulated residue as a gas can be suppressed, and it is possible to provide a necessary and sufficient treatment for the surface of a member to be applied to a vacuum processing apparatus.
In the surface treatment method, the etching with the etching solution may include: the roughened surface is etched to remove a thickness of 1 μm or more and 12 μm or less from the surface.
According to this method, the gas emission amount can be made closer to the gas emission amount in the case of a surface containing no residue due to blasting while maintaining the arithmetic average roughness Ra of the roughened surface after etching at 53% or more of the arithmetic average roughness Ra of the roughened surface after blasting, and it is possible to provide necessary and sufficient performance as a surface treatment of a member applied to a vacuum treatment apparatus.
In the surface treatment method, the etching with the etching solution may include: the roughened surface is etched to remove a thickness of 2 μm or more and 8 μm or less from the surface.
According to this method, the arithmetic mean roughness Ra of the roughened surface after etching can be maintained at 53% or more of the arithmetic mean roughness Ra of the roughened surface after blasting, and the gas emission amount can be made closer to the gas emission amount in the case of a surface containing no residue due to blasting, and it is possible to provide sufficient performance required for surface treatment of a member to be applied to a vacuum processing apparatus.
In the surface treatment method, the surface may be formed of any one selected from the group consisting of aluminum, an aluminum alloy, titanium, a titanium alloy, stainless steel, copper, and a copper alloy. According to this configuration, the member can have a surface formed of a metal suitable for a vacuum processing apparatus.
Drawings
Fig. 1 is a process diagram for explaining a step of performing blasting on a surface of a member in one embodiment of a surface treatment method.
Fig. 2 is a process diagram for explaining a step of etching the surface of the member in the above embodiment.
Fig. 3 is a process diagram for explaining a step of cleaning the surface of the member in the above embodiment.
Detailed Description
One embodiment of the surface treatment method is described with reference to fig. 1 to 3. The surface treatment method and examples are described below.
[ surface treatment method ]
The surface treatment method is explained with reference to fig. 1 to 3.
The surface treatment method comprises the following steps: roughening a surface of the component; and etching the roughened surface with an etching liquid. Roughening a surface of a component includes: the metallic surface of the member is roughened by sand blasting. At this time, residues caused by the blasting treatment remain on the roughened surface after the blasting treatment. The residue can include a medium used in the blasting process. The residue may include grease applied to the metal surface and adhering to the medium during the blasting. These media and oils will be described later. Etching of the roughened surface with the etching liquid is carried out as follows: the roughened surface after etching has an arithmetic average roughness Ra of 53% or more and 100% or less of the arithmetic average roughness Ra of the roughened surface obtained by blasting, the arithmetic average roughness Ra being a value obtained by JIS B0601: 2013.
According to such a surface treatment method, in the member subjected to the surface treatment method, a part of the residue caused by the blast treatment enters the roughened surface and is included. For example, when a medium used for blasting is blasted onto a metal surface, a part of the medium may enter the member from the surface. In this case, the residue is enclosed in the surface (member) together with the medium. Therefore, the residue contained in the roughened surface is not released. On the other hand, a residue remains on the roughened surface. According to the method, after the blasting, the roughened surface is etched. The surface subjected to etching is in a state where the residue due to the blast treatment is cleaned. Therefore, when this member is used in a vacuum processing apparatus, the film-forming material deposited on the surface of the member is less likely to be detached than a member having a non-roughened surface or a member having a surface which is roughened but not etched and contains dirt due to blasting.
At the same time, the amount of etching can be minimized, the amount of gas released can be suppressed, and the release of the encapsulated residue as a gas can be suppressed, and it is possible to provide a necessary and sufficient treatment for the surface of a member to be applied to a vacuum processing apparatus.
As shown in fig. 1, in the surface treatment method, first, a member 10 having a metal surface 10F is prepared. In the member 10, at least the surface 10F may be made of metal, but the entire member 10 may be formed of metal. The surface 10F may be formed of any one selected from the group consisting of aluminum, an aluminum alloy, titanium, a titanium alloy, stainless steel, copper, and a copper alloy. Thus, the member 10 can have a surface 10F formed of a metal suitable for use in a vacuum processing apparatus. The member 10 subjected to the surface treatment method may be one-time or not mounted on the vacuum processing apparatus, or may be a member which is mounted on the vacuum processing apparatus and is temporarily detached from the vacuum processing apparatus after being subjected to the treatment in the vacuum processing apparatus.
The vacuum processing apparatus to which the member 10 is applied is an apparatus capable of depositing a film-forming material on the surface 10F of the member 10. The vacuum processing apparatus may be, for example, various film forming apparatuses, etching apparatuses, ashing apparatuses, and the like. The film forming apparatus may be, for example, a sputtering apparatus, a CVD apparatus, a vapor deposition apparatus, or the like.
The member 10 is used in various vacuum processing apparatuses described above. The member 10 may be a member disposed in a processing space partitioned by the vacuum processing apparatus, or may be a member for partitioning the processing space. The member disposed in the processing space may be, for example, an adhesion preventing plate for preventing the film forming material from scattering into the processing space, a tray for supporting a processing object of the vacuum processing apparatus, or the like. The member partitioning the processing space may be, for example, a member forming an inner wall of a vacuum chamber partitioning the processing space. That is, the member 10 may have a flat plate shape or a shape along a predetermined curved surface. The member 10 may be formed of one plate member, or may be a combination of a plurality of plate members.
Next, the surface 10F is roughened by performing blasting treatment on the surface 10F. Can be identified by a method represented by JIS B0601: 2013 the surface roughness in the surface 10F of the member 10 is evaluated by the arithmetic average roughness Ra.
In the blasting process, the medium M ejected from the nozzle N of the blasting apparatus is caused to collide with the surface 10F of the member 10. Thereby, the surface 10F after the blasting is rougher than the surface 10F before the blasting.
The material forming the medium M may be, for example, metal oxide, metal carbide, silicon oxide, silicon carbide, or the like. The material forming the medium M may be, for example, iron, alumina, zirconia, silica, silicon carbide, silica sand, or the like. The medium M is a microparticle formed of each material. The medium M may include two or more kinds of particles made of different materials.
The particle size of the medium M can be 50-300 (japanese particle size standard). In addition, the particle size of the medium M was measured by JIS Z0311: 2004. When blasting surface 10F with medium M, the vapor pressure at 330 ℃ may be 1.33X 10-4Pa or less. Further, the vapor pressure curve of the medium M is preferably lower than that of zinc. In medium M, a medium prepared by JIS Z2244: the vickers hardness defined in 2009 may be 400 or more. This improves the reliability of the surface 10F having the desired arithmetic average roughness Ra.
The medium M used for the blast treatment is often repeatedly used for the purpose of improving the utilization efficiency of the medium M. That is, many blasting apparatuses used for blasting are circulation type blasting apparatuses that circulate the medium M in the blasting apparatus. For the following reason, grease is often adhered to the surface 10F made of metal, which is the object of the blasting process. That is, in order to suppress the surface 10F from being deteriorated, for example, rusted, grease is often applied to the surface 10F after the member 10 is formed. Alternatively, in order to smooth the processing of the metal used to form the member 10, grease is often applied to a portion of the base material of the member 10 corresponding to the surface 10F. Such grease can adhere to the medium M as dirt during the blast treatment.
Therefore, the grease applied to the surface 10F adheres to the medium colliding with the surface 10F, whereby the medium M is contaminated with the grease. Further, the more the number of times the medium M collides with the member 10 increases, the more the amount of grease adhering to the medium M. Therefore, such grease can be contained in the residue caused by the blasting.
In addition, if the grease is applied to the surface 10F before roughening, the grease adhering to the surface 10F can be removed by wiping the grease, washing the surface 10F with water, or the like. However, unlike the grease applied to the surface 10F before roughening, the grease that is driven into the surface 10F together with the medium M by sandblasting is difficult to remove from the surface 10F of the member 10 by wiping or cleaning.
As shown in fig. 2, the roughened surface 10F is etched using an etching solution E. In the present embodiment, the member 10 is immersed in the etching liquid E filled in the 1 st processing tank T1, whereby the surface 10F of the member 10 is etched by the etching liquid E.
In the etching of the surface 10F, the roughened surface is preferably etched to remove a thickness of 1 μm to 12 μm, more preferably 2 μm to 8 μm.
Further, by setting the removal amount by etching to 1 μm or more and 12 μm or less, the emission amount of gas (residue-derived substance) from the surface 10F can be made closer to the emission amount of gas from a surface containing no residue by blasting while maintaining the arithmetic average roughness Ra of the roughened surface after etching at 53% or more of the arithmetic average roughness Ra of the roughened surface after blasting. Further, by setting the removal amount by etching to 2 μm or more and 8 μm or less, the gas release amount from the surface 10F can be made further closer to the gas release amount from the surface containing no residue due to the blast treatment.
As described above, unlike the grease applied to the surface 10F before roughening, the grease that is driven into the surface 10F together with the medium M by the blast treatment is difficult to remove from the surface 10F of the member 10 by wiping or cleaning. In this regard, by etching of the surface 10F using the etching liquid E, a predetermined thickness amount is etched from the surface 10F of the member 10, and therefore the grease is removed from the surface 10F. Further, the medium M is driven into the member 10 together with a part of the member 10 (metal forming the surface 10F) at the time of the blast treatment, and as a result, the grease adhering to the medium M is also driven into the member 10 together with the medium M. Therefore, after the sandblasting treatment, the grease that has entered the surface 10F of the member 10 is not removed, but remains on and in the surface 10F of the member 10 as a residue. However, the grease is removed from the region of the surface 10F into which the medium M is driven and the region exposed to the etching liquid E. That is, the residue remaining on the surface 10F is removed by etching. Even if the medium M remains inside the member 10 after etching, the grease adhering to the medium M is enclosed by the medium M and the member 10 and is enclosed in the member 10. Therefore, after the surface treatment, the grease is not released from the closed environment unless an external force or the like is applied to the medium M, and thus there is no inconvenience.
In addition, when the removal amount by etching is 1 μm to 12 μm, and further 2 μm to 8 μm, the reliability can be improved in that the arithmetic average roughness Ra of the surface 10F is 53% or more of the arithmetic average roughness Ra after the blast treatment. Thus, by maintaining the arithmetic average roughness Ra obtained after the blasting, the effect of preventing the film from being detached can be ensured by the arithmetic average roughness Ra of the surface 10F.
The analysis of the gas emitted from the member 10 is performed by, for example, a quadrupole mass spectrometer attached to a temperature-rising desorption gas analyzer. For the analysis of the gas, for example, after the temperature-rising off-gas analyzer is depressurized, the temperature of the member 10 is raised to a predetermined temperature by using the temperature-rising off-gas analyzer. At this time, the gas released into the temperature-raised desorption gas analyzer was analyzed by a quadrupole mass spectrometer.
The etching solution E may be, for example, an aqueous solution of sodium hydroxide (NaOH), an aqueous solution of potassium hydroxide (KOH), or sulfuric acid (H)2SO4) Hydrochloric acid (HCl), hydrofluoric acid (HF), nitric acid (HNO)3) Or metaphosphoric acid (HPO)3) And the like. The etching solution E may include only one of these solutions, or may include two or more of them.
In the case where the member 10 is formed of an aluminum alloy, the following solutions can be used as the etching solution E. The etching solution E may be an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or sulfuric acid, or may be a mixed solution containing at least two of these solutions. The etching solution E may be an aqueous solution of sodium hydroxide-potassium ferricyanide or a solution obtained by mixing zinc chloride with an aqueous solution of sodium hydroxide. In the case where the surface 10F of the member 10 is etched by electrolytic etching, a solution in which sulfuric acid and phosphoric acid are mixed can be used as the etching liquid E.
When the member 10 is formed of titanium, the following solutions can be used as the etching solution E. The etching solution E may be a solution obtained by mixing an aqueous solution of potassium hydroxide and hydrogen peroxide, a solution obtained by mixing ammonium bifluoride in ethanol, hydrofluoric acid, a mixture of hydrofluoric acid and an aqueous solution of iron (III) nitrate, or hydrochloric acid. In the case where the surface 10F of the member 10 is etched by electrolytic etching, a mixed solution of ethylene glycol and an aqueous solution of sodium chloride may be used as the etching solution E.
In the case where the member 10 is formed of copper, the following solutions can be used as the etching liquid E. The etching solution E may be a mixture of nitric acid, ammonium persulfate, hydrochloric acid, and nitric acid, or a mixture of nitric acid and hydrofluoric acid. When the surface 10F of the member 10 is etched by electrolytic etching, phosphoric acid can be used as the etching liquid E.
In addition, it is preferable to use a solution other than the solution containing hydrofluoric acid and a solution other than the solution containing zinc in the etching solution E. This can suppress the release of zinc in the vacuum processing apparatus to which the member 10 is applied when hydrofluoric acid is released into the vacuum processing apparatus or when the temperature in the vacuum processing apparatus is about 100 ℃.
As shown in fig. 3, the member 10 after etching is cleaned with a cleaning liquid C. In the present embodiment, the member 10 is immersed in the cleaning liquid C filled in the No. 2 treatment tank T2, whereby the surface 10F of the member 10 is cleaned with the cleaning liquid C. The cleaning liquid C may be, for example, pure water or ultrapure water. The temperature of the cleaning liquid C may be, for example, 10 ℃ or higher, or the cleaning liquid C may be boiled. By using pure water or ultrapure water as the cleaning liquid C, when the member 10 is applied to a vacuum processing apparatus, it is possible to suppress the substance that may be discharged into the vacuum processing apparatus from remaining on the surface 10F of the member 10.
[ examples ]
The examples are illustrated with reference to table 1.
Comparative example 1
A film having a diameter of 45mm and a thickness of 3mm was prepared as a film having a thickness defined by JIS H4000: 2014A 5052 made round plate of aluminum alloy. Prepared by JIS Z0311: the surface of the disk was roughened by dry blasting using 100-fold alumina as a medium, as specified in 2004. Next, the disk was immersed in ethanol filled in a beaker, and subjected to ultrasonic cleaning for 5 minutes. Ethanol was replaced every time such ultrasonic cleaning was performed, and 5 times of disk cleaning with ethanol was performed. Thus, a disk of comparative example 1 was obtained.
Comparative example 2
A disc of comparative example 2 was obtained in the same manner as in comparative example 1, except that in comparative example 1, the surface of the disc was machined so that the arithmetic average roughness Ra became 0.3 μm or less by cutting the surface of the disc with a lathe while cooling the disc so that the temperature during cutting did not exceed 40 ℃.
[ example 1]
A film having a diameter of 45mm and a thickness of 3mm was prepared as a film having a thickness defined by JIS H4000: 2014A 5052 made round plate of aluminum alloy. Prepared by JIS Z0311: the surface of the disk was roughened by dry blasting using 100-fold alumina as a medium, as specified in 2004. Subsequently, the disk was immersed in 15 mass% sulfuric acid at 70 ℃ for 1 minute, and the surface of the disk was etched. Thus, the surface of the disk was etched by 1 μm in the thickness direction of the disk. Then, the surface of the disk was washed with water, and the disk was immersed in pure water. Finally, the surface of the disk was rinsed with pure water to obtain a disk of example 1.
[ example 2]
The disk of example 2 was obtained in the same manner as in example 1 except that the disk was immersed in sulfuric acid for 3 minutes, and the surface of the disk was etched by 2 μm in the thickness direction of the disk in this example 1.
[ example 3]
A disk of example 3 was obtained in the same manner as in example 1, except that in example 1, the time for immersing the disk in sulfuric acid was changed to 10 minutes, and thereby the surface of the disk was etched by 8 μm in the thickness direction of the disk.
[ example 4]
A disk of example 4 was obtained in the same manner as in example 1, except that in example 1, the time for immersing the disk in sulfuric acid was changed to 15 minutes, and thereby the surface of the disk was etched by 12 μm in the thickness direction of the disk.
[ example 5]
In example 1, a disk of example 5 was obtained in the same manner as in example 1, except that the disk after roughening was immersed in 50 ℃ and 50g/L aqueous sodium hydroxide solution for 3 minutes, and thereby the surface of the disk was etched by 8 μm in the thickness direction of the disk.
[ evaluation method ]
[ arithmetic average roughness Ra ]
The surface of each disc was measured according to JIS B0601: 2013, and the arithmetic average roughness Ra is measured. The measurement results are shown in table 1 below.
[ gas emission amount ]
The gas released from each disk in vacuum was measured by a temperature rise desorption method. The gas evolution was measured using j.vac.soc.jpn: 58(2015), "the temperature-elevating detached gas analyzer described on page 1 of" die ガス of the bone ため of the vacuum engineering とそ "die (peijiaji 12373, 12363 え). After each disk was placed in the temperature-rising desorbed gas analyzer, the inside of the temperature-rising desorbed gas analyzer was depressurized to vacuum. Subsequently, the temperature in the desorbed gas analyzer was raised to 300 ℃ at a rate of 0.1 ℃/sec. The amount of gas released from the disk during the temperature rise in the desorbed gas analyzer to 300 ℃ was measured. Then, the amount of gas emitted from each disk was normalized by the amount of gas emitted from the disk of comparative example 2. The normalized values are shown in table 1 below.
The gas emitted from each disk was identified by using a quadrupole mass spectrometer attached to a temperature-rising desorption gas analyzer. A gas having a mass ratio m/z of 2 to 100 is mass-analyzed by a quadrupole mass spectrometer. Herein, the mass is measuredThe mass ratio (MH) determined as hydrogen when the ratio m/z was detected as 2, and the mass ratio (MH) determined as water when the mass ratio m/z was detected as 17 or 182O), the mass ratio m/z is detected as 12, 15, 27, 29, 39, 41, 43, 44, 55, 56, 57 and 58, and is determined as the mass ratio of hydrocarbons (MCH). Then, the sum of the mass ratio of hydrocarbon to hydrogen and the mass ratio of water (MH + MH) was calculated2Ratio of O) (MCH/(MH + MH)2O)) are shown in table 1 below.
[ amount of deposit ]
After the measurement of the arithmetic average roughness Ra and the measurement of the amount of gas discharged were completed, an aluminum film having a thickness of 500 μm was formed on the surface of each disk. Then, a tape having a rectangular shape with a transverse length of 1cm and a longitudinal length of 2cm was stuck to the surface of the aluminum film, and when the tape was peeled off from the aluminum film, the amount of aluminum particles adhering to the sticking surface of the tape was visually observed. The amount of aluminum particles was evaluated by the following levels. The evaluation results are shown in table 1 below.
In addition, the inventors assumed that the amount of aluminum adhesion is a result of sharpness (kurtosis, Rku) of the surface. The sharpness of the film due to physical processing is drastically reduced by etching, and the result is considered to be reflected in the amount of the deposit. That is, it can be said that the following can be confirmed: by etching, the dust generation probability of the member is reduced.
Very good aluminum particles could not be visually confirmed
O aluminum particles hardly adhered
The amount of adhered Delta aluminum particles is small
The amount of adhered x aluminum particles is large
[ TABLE 1]
As shown in table 1, the following were confirmed: the arithmetic average roughness Ra of the surface of the disk was 1.5 μm in comparative example 1 and 0.1 μm in comparative example 2. The following were confirmed: the arithmetic average roughness Ra of the surface of the disk was 1.5 μm in example 1, 1.2 μm in example 2, 1.0 μm in example 3, 0.8 μm in example 4, and 1.2 μm in example 5.
The following were confirmed: according to examples 1 to 5, even if the roughened surface is etched, the arithmetic average roughness Ra of the etched surface is maintained to be 53% or more and 100% or less of the arithmetic average roughness Ra of the surface before roughening.
The following were confirmed: the gas evolution rate was 15.0 in comparative example 1 and 1.0 in comparative example 2. The following were confirmed: the gas evolution was 1.8 in example 1, 1.2 in example 2, 1.2 in example 3, 1.1 in example 4 and 1.3 in example 5. Since the arithmetic average roughness Ra of the disc of comparative example 2 was 0.1, which is smaller than the arithmetic average roughness Ra of the discs of examples 1 to 5, it can be estimated that the surface area in the roughened surface of the disc of comparative example 2 is smaller than the surface area in the roughened surface of the disc of examples 1 to 5. However, even when the amount of gas evolution in the disk of comparative example 2 was set to 1.0, the amount of gas evolution in the disks of examples 1 to 5 was limited to 1.8 times or less, and it was confirmed that the above surface treatment method was a necessary and sufficient surface treatment. Particularly, when the thickness of etching was 2 μm or more, the gas release amount was 1.3 times or less the gas release amount in the disk of comparative example 2, and thus it was confirmed that the thickness was more suitable.
The following were confirmed: the ratio of the mass ratio of hydrocarbons to the sum of the mass ratio of hydrogen and the mass ratio of water was 0.35 in comparative example 1 and 0.09 in comparative example 2. The following were confirmed: the ratio of the mass ratio of hydrocarbon to the sum of the mass ratio of hydrogen and the mass ratio of water was 0.21 in example 1, 0.11 in example 2, 0.09 in example 3, 0.08 in example 4, and 0.11 in example 5. In example 4, the amount of gas released was 1.1 times as large as in comparative example 2, and the mass ratio was reduced by approximately 10% compared to comparative example 2, so it can be said that the surface treatment performed in example 4 was a treatment capable of obtaining a disk having a surface equivalent to that of comparative example 2. The surface treatments performed in examples 3 and 5 can be said to be treatments capable of obtaining disks having surfaces equivalent to those in example 4, that is, equivalent to those in comparative example 2. Further, according to examples 3 and 5, the etching amount is small as compared with example 4, and therefore, it is possible to provide necessary and sufficient surface treatment while suppressing an increase in the process time and the environmental load.
The following were confirmed: the ratios of the gas evolution and the mass ratio of hydrocarbons to the sum of the mass ratio of hydrogen and the mass ratio of water in examples 1 to 5 were greatly reduced compared to comparative example 1. From these results, it can be said that it is difficult to sufficiently clean the dirt caused by the blasting treatment by merely cleaning the roughened surface by the blasting treatment, and on the other hand, the dirt caused by the blasting treatment can be cleaned by performing the etching of the surface. Namely, the following were confirmed: by etching the roughened surface to a thickness of 1 μm or more, dirt caused by blasting can be substantially removed by etching.
In addition, the following were confirmed: the ratio of the amount of gas evolved and the mass ratio of hydrocarbons to the sum of the mass ratio of hydrogen and the mass ratio of water in examples 2 to 5 was about the same as the ratio of the amount of gas evolved and the mass ratio of hydrocarbons to the sum of the mass ratio of hydrogen and the mass ratio of water in comparative example 2. From these results, it can be said that by etching the roughened surface to a thickness of 2 μm or more, the dirt caused by the blast treatment can be further removed by etching.
The following were confirmed: the amount of deposit was "x" in comparative example 1 and "Δ" in comparative example 2. The following were confirmed: the amount of the deposits was "o" in example 1 and "excellent" in examples 2 to 5. Thus, according to embodiments 1 to 5, not only the arithmetic average roughness Ra is high, but also a predetermined arithmetic average roughness Ra is provided, and dirt on the surface caused by the blasting treatment is cleaned and the sharpness is reduced. Accordingly, it can be said that the film-forming material adhering to the surface is less likely to come off, and the probability of dust generation can be reduced. That is, it can be said that the member having the surface cleaned by the method can suppress the generation of particles in the vacuum processing apparatus to which the member is applied.
As described above, according to one embodiment of the surface treatment method, the following effects can be obtained.
(1) When the member 10 is used in a vacuum processing apparatus, the film-formed material deposited on the surface 10F of the member 10 is less likely to be detached than a member having a non-roughened surface or a member having a roughened surface but containing dirt due to blasting.
(2) The amount of etching can be minimized, the amount of gas released can be suppressed, and the release of the encapsulated residue as a gas can be suppressed, whereby a necessary and sufficient treatment can be provided as a treatment for the surface 10F of the member 10 applied to the vacuum processing apparatus.
(3) By removing the thickness of 1 μm to 12 μm by etching, the gas emission amount can be made closer to the gas emission amount in the surface containing no residue due to the blasting while maintaining the arithmetic average roughness Ra of the surface 10F after etching at 53% or more with respect to the arithmetic average roughness Ra after blasting.
(4) By removing the thickness of 2 μm or more and 8 μm or less by etching, the gas emission amount can be made closer to the gas emission amount in the surface containing no residue due to the blasting while maintaining the arithmetic average roughness Ra of the surface 10F after etching at 53% or more with respect to the arithmetic average roughness Ra after blasting.
(5) The member 10 can have a surface 10F formed of a metal suitable for use in a vacuum processing apparatus.
The above-described embodiment can be modified as follows.
[ surface ]
The surface 10F may be formed of a metal other than a metal selected from the group consisting of aluminum, an aluminum alloy, titanium, a titanium alloy, stainless steel, copper, and a copper alloy. Even in this case, the effect (1) can be obtained by roughening the surface 10F and etching the surface 10F so that the arithmetic average roughness Ra of the roughened surface 10F is higher than that before roughening.
[ Sand blast treatment ]
The blast treatment of the surface 10F may be a wet blast treatment instead of a dry blast treatment.
[ etching ]
Instead of immersing the member 10 in the etching liquid E, the etching liquid E may be sprayed on the surface 10F of the member 10 by a sprayer to etch the surface 10F.
[ cleaning ]
Instead of immersing the member 10 in the cleaning liquid C, the cleaning liquid C may be sprayed on the surface 10F of the member 10 by a sprayer to clean the surface 10F.
[ maintenance ]
The surface treatment method may include the following steps: the member 10 is maintained after the step of etching the surface 10F. That is, the surface treatment method may include a step of covering the member 10 with a protective member. This can suppress the external force from acting on the etched surface 10F when the member 10 is conveyed. Thus, the destruction of the closed environment containing the residue can be suppressed.
[ description of reference ]
10: a member; 10F: a surface; c: cleaning fluid; e: etching solution; m: a medium; n: a nozzle; t1: a 1 st treatment tank; t2: and (2) a treatment tank.
Claims (4)
1. A surface treatment method comprising:
roughening a metallic surface of a member by blasting, and leaving a residue caused by the blasting on the roughened surface after the blasting; and
etching the roughened surface with an etching liquid,
the etching is performed in such a manner that an arithmetic average roughness of the roughened surface after the etching becomes 53% or more and 100% or less of an arithmetic average roughness of the roughened surface obtained by the blasting, the arithmetic average roughness being a roughness measured by JIS B0601: 2013.
2. The surface treatment method according to claim 1,
the etching with the etching solution includes: the roughened surface is etched to remove a thickness of 1 μm or more and 12 μm or less from the surface.
3. The surface treatment method according to claim 2,
the etching with the etching solution includes: the roughened surface is etched to remove a thickness of 2 μm or more and 8 μm or less from the surface.
4. The surface treatment method according to any one of claims 1 to 3,
the metal surface is formed of any one selected from the group consisting of aluminum, an aluminum alloy, titanium, a titanium alloy, stainless steel, copper, and a copper alloy.
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