JP2013181238A - Method of blackening white thermally sprayed fluoride film, and member coated with thermally sprayed fluoride film having black layer on surface thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of reforming a surface of a thermally sprayed fluoride film excellent in corrosion resistance and plasma erosion resistance, and to provide a member coated with a thermally sprayed film having a blackened layer where an industrial design, letters, numerals, a trademark and the like are drawn on the surface of a white thermally sprayed film by applying a blackening technique.SOLUTION: A white thermally sprayed fluoride film is formed on a surface of a substrate by an atmospheric plasma thermal spray method, a vacuum plasma thermal spray method, or high speed flame thermal spray, and thereafter plasma of a F gas or an inert gas comprising F, such as N, Ar, He, and Ne, is generated on the surface of the thermally sprayed film to generate at least one of gas ions selected from ionized F, N, (F+N), (F+Ar), (F+He), (F+Ne)and the like to inject thereinto, whereby a F component is added to the surface of the film, and at the same time the surface of the white thermally sprayed fluoride film is blackened.

Description

  The present invention relates to a method for blackening a white fluoride sprayed coating and a fluoride sprayed coating coated member having a black layer on the surface, and in particular, it is not only exposed to an atmosphere of highly corrosive halogen gas or its compound, but sometimes Regarding a member used in an environment affected by the plasma etching action of a halogen gas, a fluoride sprayed coating member having a black layer having excellent corrosion resistance and plasma etching resistance on the surface thereof, and a blackening method It is a proposal.

  Various surface treatment technologies have been developed and used in many industrial fields for the purpose of supplementing the corrosion resistance, heat resistance, and wear resistance of the substrate surface and improving the appearance of the film appearance (surface). Yes. One of them is a thermal spraying method.

The thermal spraying method uses a gas plasma flame such as Ar or H ₂ or a hydrocarbon combustion flame to soften or melt particles of metal (hereinafter referred to as “metal” including “alloy”), ceramics, cermet, etc. This is a surface treatment technique for forming a film by spraying and depositing on the surface of the substrate to be treated. In this method, as long as the material is softened or melted by heat, not only glass and plastic but also metals such as tungsten (melting point 3,387 ° C.) and tantalum (melting point 2,996 ° C.) having a high melting point, A1 It is also possible to form a film with oxide ceramics such as ₂ O ₃ (melting point: 2,015 ° C.) and MgO (melting point: 2,800 ° C.), and the feature is that the degree of freedom in selecting the type of coating material is very high. . For this reason, the thermal spray coating is adopted in many industrial fields as one of the surface treatment techniques.

  By the way, the above-mentioned sprayed coating covering member is a semiconductor processing device member, particularly a semiconductor in which it is necessary to clean and remove fine particles generated by the plasma processing in an environment where halogen or a halogen compound exists. When used in the field of processing equipment, surface treatment as described below is preferable, and there are some proposals for the prior art for that purpose.

  In other words, in processing equipment such as dry etcher, CVD, PVD, etc. used in semiconductor processing and liquid crystal manufacturing processes, it is necessary to perform microfabrication and increase accuracy with high integration of substrate circuits such as silicon and glass. As a processing environment, higher cleanliness has been demanded. On the other hand, since various corrosive harmful gases such as fluoride and chloride or aqueous solutions are used in various processes for microfabrication, the components used in these processes are subject to corrosion wear. As a result, there is a concern about an increase in the defective rate of semiconductor processed products and a decrease in production efficiency due to secondary environmental pollution caused by generation and scattering of corrosion products.

In particular, the semiconductor device is mainly composed of a compound semiconductor composed of Si, Ga, As, P, etc., and many of the manufacturing processes are dry processes that are processed in a vacuum or a reduced pressure. Various processes such as film formation, impurity implantation, etching, ashing, and cleaning are repeated. As an apparatus belonging to such a dry process, an oxidation furnace, a CVD apparatus, a PVD apparatus, an epitaxial growth apparatus, an ion implantation apparatus, a diffusion furnace, a reactive ion etching apparatus, piping attached to these apparatuses, a supply / exhaust fan, There are members and parts such as vacuum pumps and valves. In these devices, fluorides such as BF ₃ , PF ₃ , PF ₆ , NF ₃ , WF ₃ and HF, BC1 ₃ , PC1 ₃ , PC1 ₅ , POC1 ₃ , AsC1 ₃ , SnC1 ₃ , SnCl ₄ , TiC1 ₄ , chlorides such as SiH ₂ C1 ₂ , SiC1 ₄ , HCl, C1 ₂ , bromides and other halides such as HBr, and also NH ₃ , CH ₃ F, etc. Corrosive chemicals and gases may be used.

In the dry process, plasma (low temperature plasma) is often used to activate the reaction and improve processing accuracy. This is because in an environment where plasma is used, the halide becomes a highly corrosive atomic or ionized F, Cl, Br, or I, and exerts a great effect on fine processing of a semiconductor material. On the other hand, fine particles of SiO ₂ , Si ₃ N ₄ , Si, W, and the like that are removed by the etching process float from the surface of the semiconductor material subjected to the plasma process (particularly plasma etching process) in the environment. There is a problem that these materials adhere to the surface of the device during or after processing and the quality thereof is significantly reduced.

As one of these countermeasures, surface treatment with aluminum anodic oxide (alumite) has been proposed. In addition, oxides such as A1 ₂ O ₃ , A1 ₂ O ₃ .TiO ₂ , Y ₂ O _3, etc., and oxides of Group IIIa metals of the periodic table are sprayed or deposited (CVD, PVD). Techniques for coating the surface of a device member or using it as a sintered material are known (Patent Documents 1 to 5).

More recently, plasma erosion resistance has been improved by irradiating the surface of the Y ₂ O ₃ , Y ₂ O ₃ -A1 ₂ O ₃ sprayed coating with a laser beam or electron beam to remelt the surface of the sprayed coating. The technique to make is also known (patent documents 6 to 9). On the other hand, in order to improve the cleanliness of high-performance semiconductor processing / manufacturing environment, plasma erosion resistance is improved by applying YF ₃ (yttrium fluoride) in the form of film instead of Y ₂ O ₃ sprayed coating. There is also technology to make it. For example, the surface of an oxide of a group IIIa element in the periodic table including a sintered body such as YAG is coated with a YF ₃ film (Patent Documents 10 to 11), Y ₂ O ₃ , Yb ₂ O ₃ , YF ₃ The proposals include a method using a mixture such as the above (Patent Documents 12 to 13), or a method of forming a coating by a thermal spraying method using YF ₃ itself as a film forming material (Patent Documents 14 to 15).

Japanese Patent Publication No. 6-36583 Japanese Patent Laid-Open No. 9-69554 JP 2001-164354 A Japanese Patent Laid-Open No. 11-80925 JP 2007-107100 A Japanese Patent Laid-Open No. 2005-256093 JP 2005-256098 A JP 2006-118053 A JP 2007-217779 A JP 2002-293630 A JP 2002-252209 A JP 2008-98660 A Japanese Patent Laid-Open No. 2005-243988 JP 2004-197181 A JP 2002-037683 A JP 2007-115973 A

Journal of Japan Thermal Spray Association, “Spraying technology vol.26 No.2 / 3, published on January 31, 2007, pages 18-25, overview of cold spray and trends in research and development”

  In the present invention, in particular, the disadvantages of the white fluoride film formed by the conventional thermal spraying method are improved, without disturbing the excellent halogen corrosion resistance and plasma erosion resistance characteristic of the fluoride spray coating, It is an object of the present invention to provide a method for realizing blackening of the surface of the sprayed coating and such a member.

  On the other hand, when a film is formed by a thermal spraying method using a combustion flame of a fossil fuel such as an inert gas plasma jet, hydrocarbon gas, kerosene or the like disclosed in Patent Document 14, the following phenomenon occurs. Occur.

(1) In the thermal spraying method using a plasma jet as a heat source, fluoride particles flying in a high temperature jet are exposed to a high temperature environment of 5000 ° C. to 7000 ° C., and 2000 ° C. to 2800 ° C. even in a combustion flame. Therefore, in any heat source, some of the fluoride particles induce a thermal decomposition reaction and an oxidation reaction to release F ₂ gas.

Then, with the release of the F ₂ gas, components of the fluoride particles is changed, fluoride sprayed coating has been formed becomes those that vary stoichiometrically. For example, when plasma spraying is performed using YF ₃ particles, it is presumed that F ₂ gas is released in the heat source and changes to a fluoride represented by YF _3-X .

(2) It is presumed that the halogen resistance of the yttrium fluoride sprayed coating expressed by YF _3-X is chemically unstable as compared with fluoride particles (YF ₃ ). This has been found in the paragraph (0010) of Patent Document 14 that “the color of the yttrium fluoride film changes due to the corrosive halogen gas if only yttrium fluoride is used. Also, yttrium fluoride is used. It was found that the corrosion resistance was not sufficient by itself, and the yttrium fluoride film was depleted. ”

  That is, in this patent document 14, as a countermeasure against a change in the color of the film and a decrease in corrosion resistance, the amorphous fluoride sprayed film immediately after film formation is heat-treated at a temperature of 200 ° C. to 500 ° C. A technology to change to orthorhombic is proposed. However, even if this method is applied, as described in paragraph (0014) of this document, the change in the color of the film is only reduced and is not a drastic measure.

(3) Further, in Patent Document 16, in paragraph (0021), it is described that a cold spray method or an aerosol deposition method is desirable as a method for forming a fluoride film. Argon gas or helium gas is used as the plasma gas, and further, by mixing hydrogen gas with these inert gases, the plasma temperature increases and the plasma gas velocity increases, enabling more precise film formation. It is described that a dense and low-reactive film can be formed by mixing 1 to 40% by volume of hydrogen gas.

However, according to Non-Patent Document 1, in the cold spray method, an inert gas such as Ar, N ₂ , and He used in the cold spray method is heated to 500 ° C., and the film formation particles are 300 to 1200 m / S. It is a method of spraying at high speed. In this method, there is a disclosure that a gas at 500 ° C. is lowered to room temperature due to the adiabatic expansion phenomenon at the sprayed portion of the nozzle. Under these conditions, this method is not a suitable method for forming a fluoride film.

Further, Patent Document 16 does not disclose technical information necessary for the cold spray method to form a fluoride film. On the other hand, compared with the cold spray method, in order to further increase the plasma heat source temperature in the plasma spraying method at a significantly higher temperature, H ₂ gas is mixed in an inert gas such as Ar, He and the plasma temperature. The reason for this is explained in spite of technical contradiction, such as the possibility of film formation at a low gas temperature by the cold spray method. Absent.

(4) Although there is a method of heat-treating the fluoride sprayed coating, this method has the disadvantages of lowering the production efficiency and increasing the cost in addition to the increase of the manufacturing process.

(5) Furthermore, there are processes in which a fluoride spray coating is formed by atmospheric plasma spraying or high-speed flame spraying. However, in these methods, the film-forming fluoride particles are thermally decomposed in a high-temperature heat source, resulting in a strange odor. Since harmful F ₂ gas accompanied with gas is released, the working environment is deteriorated, and there is a problem in the health and safety of the work.

  The object of the present invention is to change the color of the surface of the white fluoride spray coating to black without impairing the basic properties (chemical / physical properties) of the white fluoride spray coating. It is to propose a technique for improving quality assurance and design as an industrial product by displaying numbers, figures, patterns, or identification symbols such as company names and production numbers.

  As a result of intensive studies in order to solve the above-described problems of the prior art, the inventors have obtained the following knowledge. That is, when an ion of fluorine gas or an inert gas containing fluorine gas (hereinafter referred to as F-containing gas ion) is injected into the surface of the white fluoride spray coating formed on the substrate surface, only the injection portion changes to black. In particular, the white portion of the non-ion-implanted portion can be clearly distinguished. The situation is so discriminating as to write letters or draw pictures on a blank sheet with a pencil or black ink.

  The present invention developed on the basis of such knowledge is that fluorine gas or an inert gas containing fluorine gas is formed on the surface of the base material directly or on the surface of the white fluoride sprayed coating formed through the undercoat. In other words, the surface of the white sprayed coating is blackened by injecting F ions, that is, F-containing gas ions.

  In addition, the present invention sprays a base material and a white fluoride spraying material formed on the surface of the base material for a group IIIa group Y, a group IIIb Al, and a metal element having an atomic number of 57 to 71. The member formed of a white fluoride sprayed coating having a thickness of 20 to 500 μm is formed on the surface by the blackening method (Claims 1 to 7). To a fluoride sprayed coating-coated member having a black layer on the surface, characterized by having a black F-containing gas ion-implanted layer formed by blackening a range from 1 to less than 10 μm.

In the present invention, the following configuration is a more preferable solution.
(1) The F-containing gas ions are F gas or one or more inert gases selected from N ₂ , Ar, He and Ne containing F.
(2) The blackening is performed by applying high-frequency power to a substrate in an atmosphere of one or more F-containing gas ions selected from F ₂ under reduced pressure or N ₂ , Ar, He and Ne containing F. An ion implantation concentration of one or more inert gases selected from F-containing N ₂ , Ar, He, and Ne containing F gas or F containing a negatively charged fluoride spray film and exhibiting a positive charge behavior It is realized by forming a black F-containing gas ion-implanted layer on at least a part of the surface of the thermal spray coating by performing ion implantation so that it falls within the range of 1 × 10 ¹⁰ to 1 × 10 ²⁰ / cm ^2. ,
(3) The blackening is performed from the surface of the white fluoride spray coating to a depth of less than 10 μm,
(4) The blackening is such that only the F-containing gas ion implantation part is partially changed to black,
(5) The white fluoride sprayed coating is a coating having a thickness of 20 to 500 μm formed by spraying white powder for powder spraying with a particle size of 5 to 80 μm.
(6) The white fluoride sprayed coating is composed of Y of the periodic table group IIIa, Al of group IIIb of the periodic table, La, Pr, Nd, Pm, Eu, lanthanoid metal elements having atomic numbers 57 to 71, Composed of one or more fluorides selected from Gd, Tb, Dy, Ha, Er, Tm, Yb, and Lu;
(7) A metal / alloy undercoat selected from Al, Al—Ni, Al—Zn, Ni—Cr, and Ni—Cr—Al between the substrate and the white fluoride sprayed coating is 50 to 150 μm. Constructing with film thickness,
(8) The white fluoride sprayed coating and the undercoat are formed by any one of spraying methods selected from an air plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, and a low temperature spraying method,
(9) The base material for forming the white fluoride sprayed coating is Al and alloys thereof, Ti and alloys thereof, Ni and alloys thereof, various stainless steels, alloy steels, carbon steels, oxides, nitrides and carbides. Selected from metallic materials and non-metallic materials selected from sintered bodies such as silicides and carbon,

The technology for blackening the surface of the white fluoride spray coating according to the method of the present invention can be expected to have the following effects.
(1) Fluoride spray coating with addition of F component restores the corrosion resistance of fluoride spray coating caused by degradation of F component lost by decomposition reaction or oxidation reaction by spraying heat source, and demonstrates the original mechanism of action of fluoride be able to.
(2) Only a part or all of the appearance color of the surface of the white fluoride spray coating can be changed to black by ion implantation of F gas or F-containing gas containing F.
(3) By blackening the white fluoride sprayed coating, it is possible to impart thermal radiation characteristics or add a heat receiving action to the sprayed coating.
(4) By blackening the white fluoride sprayed coating, it becomes possible to visually determine the adhesion of fine particles generated in the semiconductor processing apparatus to the coating surface and the amount of the particles. Therefore, it is possible to accurately determine the cleaning time of the apparatus and contribute to the improvement of the productivity of semiconductor processed products.
(5) The fluoride sprayed coating formed by blackening the surface according to the method of the present invention not only has the basic corrosion resistance and plasma erosion resistance of the base coating, but also has the same characteristics as the white fluoride sprayed coating. It can be used as an ordinary fluoride spray coating.
(6) In the covering member in which the entire surface of the film is blackened, the black portion is limited to less than 10 μm from the surface. Therefore, when used in an actual semiconductor processing apparatus, corrosive action by halogen gas, plasma erosion, etc. There is an advantage that a non-uniform film consumption state generated by a physical action (the early consumption part changes from black to white) can be visualized. Therefore, it becomes easy to take measures such as changing the shape of the member and correcting the thickness of the film to correct the unevenness of wear.
(7) Even if the black layer portion on the surface of the fluoride film is consumed due to corrosion or erosion action and the white portion is exposed, the original physicochemical performance of fluoride other than the thermal radiation characteristics can be exhibited.
(8) When injecting inert gas ions, a polymer tape or the like from which figures, letters, numbers, company names, trademarks, product numbers, other identification symbols, etc. are cut in advance is applied to the surface of the substrate. When ions are implanted, only letters and numbers can be changed to black, and this can be used to display various identification symbols on the member to improve the product and industrial design characteristics.

It is process drawing for demonstrating the blackening method which concerns on this invention. It is a basic diagram of the ion implantation apparatus for inject | pouring F containing gas ion into the surface of a white fluoride sprayed coating. It is a photograph which shows the grade of the color of the film | membrane surface which injected the ion of F or various F containing inert gas, and was blackened. (A) Appearance of YF fluoride spray coating (white) (b) Appearance of fluoride (YF ₃ ) spray coating with F ions (black) (c) Fluoride spray coating with F and N ions injected Appearance (black) (d) Appearance of fluoride sprayed coating implanted with F and Ar ions (black) (e) Appearance of fluoride sprayed coating implanted with F and He ions (black) The surface of the fluoride spray coating, after patch a switching disconnect polymer tape English name is a photograph showing the appearance of the ion-implanted YF ₃ spray coating F and Ar.

Hereinafter, preferred embodiments of the present invention will be described. FIG. 1 shows a process flow for carrying out the method of the present invention. In the following, details of the configuration of the present invention will be described in the order of the steps.
(1) Selection of base material The base material applied to the present invention is preferably Al and its alloys, Ti and its alloys, various alloy steels including stainless steel, carbon steel, Ni and its alloy steels, and the like. In addition, a sintered body such as an oxide, nitride, carbide, or silicide, or a carbon material is used.

(2) Pretreatment It is preferable that the surface of the base material is treated in accordance with a ceramic spraying work standard defined in JIS H9302. For example, after removing the rust and oils and fats on the surface of the base material, the surface is roughened by spraying abrasive particles such as A1 ₂ O ₃ and SiC, and pretreated so that fluoride spray particles are likely to adhere. The roughness after roughening is preferably about Ra: 0.05 to 0.74 μm and Rz: about 0.09 to 2.0 μm.

(3) Preheating of base material The base material after pretreatment (blast roughening treatment) and a base material on which a metal undercoat has been applied are preferably preheated prior to the spraying treatment of fluoride. The preheating temperature is preferably controlled according to the base material, and the following temperatures can be recommended. This preheating can be applied in the air, in a vacuum, or in an inert gas, but it is necessary to avoid an atmosphere in which the base material is oxidized by preheating and an oxide film is formed on the surface.

a. Al, Ti and their alloys: 80 ° C to 250 ° C
b. Steel (low alloy steel): 80 ° C to 250 ° C
c. Various stainless steels: 80 ° C to 250 ° C
d. Sintered bodies such as oxides and carbides: 120 ° C to 500 ° C
e. Sintered carbon: 200 ° C to 700 ° C

  When the substrate is preheated during spraying, the spray particles of fluoride adhering to the surface of the substrate are crushed to form a flat disk shape and adhere to the substrate surface and exhibit high adhesion. . However, when sprayed on the surface of the base material with low temperature without preheating, the sprayed particles will show a splash shape. There is a risk of lowering.

(4) Formation of fluoride spray coating a. Fluoride spray material Fluoride spray material powder that can be used in the present invention is made of elemental periodic group IIIb group Al, periodic table group IIIa group Y, and lanthanoid metal fluorides having atomic numbers 57-71. Use. The metal elements having atomic numbers 57 to 71 are lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd). , Terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).

  As these metal fluoride particles, particles adjusted to a particle size of 5 to 80 μm are used. The reason is that for fine particles of 5 μm or less, when they collide with the surface of the substrate, they are more scattered than when they are formed, whereas for particles larger than 80 μm, the feed rate to the spray gun is difficult to equalize. On the other hand, it is because the tendency for the pores of the formed film to become large becomes remarkable.

  The thermal spray coating obtained by spraying a powder of a fluoride spray material should have a thickness of 20 to 500 μm, and particularly preferably in the range of 50 to 200 μm. The reason is that with a film thinner than 20 μm, a uniform film thickness cannot be obtained. On the other hand, when it is formed thicker than 500 μm, the residual stress in the film at the time of forming the fluoride sprayed coating increases, and it is easy to peel off from the substrate. Because it becomes.

b. Method of forming a fluoride sprayed coating After applying an undercoat directly on the surface of the substrate, a fluoride sprayed coating is formed thereon as a top coat. As a method for forming the fluoride spray coating, an atmospheric plasma spraying method, a low pressure plasma spraying method, a high-speed flame spraying method, a low temperature spraying method, or the like is preferably used.

  In the present invention, as the undercoat, a metal (alloy) such as Al, Al—Ni, Al—Zn, Ni—Cr, or Ni—Cr—Al is applied to a thickness in the range of 30 to 150 μm. Good. These undercoats are applied by flame spraying, electric arc spraying, high-speed flame spraying, and various plasma spraying methods.

(5) Ion implantation method diagram 2 for blackening the fluoride sprayed coating surface, the surface of the thermal spray coating to blackening, F-containing gas ions, i.e., N ₂ containing F gases or F, An example of an ion implantation apparatus used for injecting F-containing gas ions such as Ar, He, Ne and the like to blacken only the surface layer of a white fluoride spray coating is shown. This ion implantation apparatus includes a high voltage pulse generating power source 24 for applying a high voltage pulse to a grounded reaction vessel 21 and a plasma generating power source 25 for generating gas plasma around a member 22 to be processed. In addition, a superimposing device 26 for simultaneously applying both a high voltage pulse and a high frequency voltage to the conductor 23 and the member to be processed 22 is interposed between the high voltage pulse generation power source 24 and the plasma generation power source 25. Is placed. The conductor 23 and the member to be processed 22 are connected to the superimposing device 26 via the high voltage introduction unit 29. Further, in this apparatus, a gas introducing device (not shown) for introducing a gas for ion implantation into the reaction vessel 21 and a vacuum device (not shown) for evacuating the reaction vessel 21 are respectively provided with a valve 27a and a valve 27a. It is connected to the reaction vessel 21 through 27b.

Next, a method for implanting the F-containing gas ions into the surface of the processing target member 22 using the ion implantation apparatus will be described.
First, the member 22 to be treated is placed at a predetermined position in the reaction vessel 21, the vacuum device is operated, the air in the reaction vessel 21 is exhausted and degassed, and then F gas or F-containing non-contained gas is introduced by the gas introduction device. Introduce active gas.

Next, high frequency power from the plasma generating power supply 25 is applied to the member 22 to be processed. In addition, since the reaction container 21 is in an electrically neutral state by the ground wire 28, the member 22 to be processed has a relatively negative potential. Therefore, the positive ions in the inert gas plasma generated by the application: F ⁺ , (F−N) ⁺ , (F−Ar) ⁺ , (F−He) ⁺ , and (F−Ne) ⁺ are relative to each other. Will occur around the member 22 to be negatively charged.

  Further, when a high voltage pulse (negative high voltage pulse) from the high voltage pulse generator 24 is applied to the member 22 to be processed, the positive ions in the implanted gas are relatively negatively charged. The surface of the member 22 is shockedly attracted and ion implantation is performed.

In the present invention, the operation of the above ion implantation apparatus is performed by performing ion implantation of F-containing gas under the following conditions, adding an F component to the surface of the thermal spray coating, and a blackening layer on the surface of the white fluoride thermal spray coating, That is, an F-containing gas ion implantation layer is formed.
(A) Ion implantation gas
(i) F ion _{implantation: F 2, HF, CHF 3} , CF 4 , etc.
(ii) For F-containing inert gas ion implantation: NF ₃ , (i) + N ₂ , (i) + Ar, (i) + He, (i) + Ne, NF ₃ + Ar, NF ₃ + He
The ratio of F / inert gas for F-containing / inert gas ion implantation (ii) is preferably 20 to 80/80 to 20 by volume ratio.
(I) Appearance color of fluoride sprayed film implanted with F ions is gray black to black
Although the sprayed coating in which the inert gas ions of (ii) are implanted is blackened, the chemical characteristics of the fluoride, particularly the corrosion resistance, is improved by increasing the F component in both coatings.
(B) Gas pressure: Gas pressure flowing into the reaction vessel after evacuation: 0.5 to 1.0 Pa
(C) Gas flow rate: 80 to 100 ml / min
(D) High voltage pulse applied voltage: 10 to 40 kV
(E) Injection time: 0.5-5 hours

The implantation depth of the F-containing gas ions implanted into the surface of the fluoride sprayed coating under the above conditions is less than 10 μm from the surface, and the concentration is in the range of 1 × 10 ¹⁰ to 1 × 10 ²⁰ / cm ² . As for the appearance color of the film, all of the F-containing gas ion implanted portions are in a black state.

(6) variations in the appearance color after ion implantation into the white thermal sprayed surface Figure 3 shows the appearance color change in YF ₃ thermal spray coating before and after injection of various F-containing gas ions.
FIG. 3 (a) shows the appearance of the YF ₃ sprayed coating immediately after the spray coating, and is white (milky white).
FIG. 3 (b) shows the appearance of the coating obtained by injecting only the F gas on the surface of the YF ₃ sprayed coating. (Black)
FIG. 3 (c), the surface of the sprayed coating of the same, a film appearance was injected to (F + N) gas ions using NF ₃ gas. (Black)
FIG. 3 (d), the surface of the sprayed coating of the same, a film appearance was injected with _NF 3 + Ar to (F + N + Ar) gas ions. (Black)
FIG. 3 (e) is an appearance of a coating obtained by implanting (F + Ne) gas ions using a mixed gas of F + He on the surface of the thermal spray coating. (Black)

FIG. 4 shows an example in which (N + F) gas ions are injected using NF ₃ gas after a commercially available polymer film having a company name cut out is applied to the surface of a white YF ₃ sprayed coating. Since only the company name is blackened by ion implantation, various letters, numbers, serial numbers, designs, trademarks, etc. can be freely drawn using this technology.

  The above-described F-containing gas ion implantation method and apparatus are not limited to the exemplified method and apparatus, but include commercially available large / medium current ion implantation apparatuses, ion implantation apparatuses for modifying semiconductor and metal surfaces. Etc. are also available. The detailed reason why the surface of the thermal spray coating changes to black by injecting various F-containing gas ions is not yet clear in tests and analyzes using a general-purpose optical microscope, electron microscope, X-ray diffractometer, etc. In the future, we plan to elucidate the mechanism of blackening by conducting tests using an analyzer that uses synchrotron radiation.

Example 1
In this example, the plasma erosion resistance of a thermal spray coating blackened by ion implantation of F gas and F-containing inert gas in accordance with the present invention on the surface of a white fluoride spray coating is compared with the conventional technology (gas ion Comparison was made with an atmospheric plasma sprayed coating (comparative example).
(1) Specimen coating YF ₃ , DyF ₃ , CeF ₃ fluoride spray coating is formed on the surface of an Al base (dimensions: width 20 mm × length 30 mm × thickness 3 mm) to a film thickness of 100 μm by atmospheric plasma spraying. After that, the surface of the coating was subjected to an ion implantation treatment in a gas atmosphere of F, FN, F-Ar, and F-He for 2 hours to change the implantation surface to black. As comparative examples, YF ₃ , DyF ₃ , and CeF ₃ atmospheric plasma sprayed coatings without gas ion implantation treatment were prepared and tested under the same conditions.

The plasma etching atmosphere gas composition and conditions are shown below.
(2) Atmospheric gas and flow rate conditions (a) F-containing gas: CHF ₃ / O ₂ / Ar = 80/100/160 (flow rate cm ³ per minute)
(B) CH-containing gas: C ₂ H ₂ / Ar = 80/100 (flow rate cm ³ per minute)

(3) Plasma irradiation output:
High frequency power: 1300W
Pressure: 4Pa
Temperature: 60 ° C

(4) Plasma etching test atmosphere (a) Implementation in an F-containing gas atmosphere (b) Implementation in a CH-containing gas atmosphere (c) In an atmosphere in which the F-containing gas atmosphere 1h and the CH-containing gas atmosphere 1h are alternately repeated Conducted in

(5) Evaluation method In the evaluation of the plasma erosion resistance test, the plasma erosion resistance and the environmental pollution resistance were investigated by measuring the number of particles of the film component scattered from the test film by the etching treatment. The number of particles was evaluated by measuring the time until the number of particles having a particle size of 0.2 μm or more attached to the surface of a silicon querier having a diameter of 8 inches placed in a test container reached 30.

(6) Test results The test results are shown in Table 1. As is clear from the results shown in Table 1, the comparative example fluoride spray coating (No. 5, 10, 15) has a large amount of particles generated in the F-containing gas, and the amount of particles generated in the CH-containing gas. It can be seen that the plasma erosion action in the former gas atmosphere is intense. Furthermore, the amount of particles generated in an atmosphere in which F-containing gas and CH-containing gas are alternately repeated is further increased. This is because the surface of the fluoride sprayed coating becomes unstable due to the repetition of the oxidizing action of the fluorinated gas in the F-containing gas and the reducing action of the CH gas, and the film is easily scraped by the plasma. Presumed.

  On the other hand, the fluoride sprayed coating (No. 1, 6, 11) subjected to the F-containing gas ion implantation treatment and the sprayed coating (No. 2-4, 7˜) in which F-containing gas ions and inert gas ions were simultaneously implanted. 9, 12-14) It was found that the amount of particles generated by the plasma was reduced, and the time to reach the amount of particles was extended by 10-20%. That is, in these cases, it can be seen that the F component is replenished on the surface of the fluoride sprayed coating that has disappeared in the thermal spraying heat source, so that it is effective in restoring the plasma erosion resistance of the coating.

(Example 2)
In this example, the plasma erosion resistance of the ion-implanted fluoride sprayed coating according to the present invention was compared with that of a conventional Y ₂ O ₃ or A1 ₂ O ₃ sprayed coating.
(1) Specimen coating A JIS H4000-regulated A3003 (dimensions: width 30 mm x length 50 mm x thickness 5 mm) was used as the base material, and an Ni-20 mass% Cr undercoat was applied to the surface by atmospheric plasma spraying. On top of that, YF ₃ is formed to a thickness of 120 μm by atmospheric plasma spraying, and EuF ₃ is formed to a thickness of 120 μm by low pressure plasma spraying. Further, various kinds of materials are formed on the surface of the fluoride sprayed coating in the same manner as in Example 1. F-containing gas ions were implanted.
Moreover, as a fluoride sprayed coating of the comparative example, Y ₂ O ₃ and A1 ₂ O ₃ sprayed coatings which are used as a plasma sprayed erosion resistant coating and a gas sprayed coating without gas ion implantation were used.

(2) Plasma erosion resistance test method The plasma erosion resistance test was performed under the same conditions in the F gas of Example 1 and in an F-containing inert gas atmosphere. The evaluation was performed by measuring the thickness of the test film before and after the test with a surface roughness meter.

(3) Test results The test results are summarized in Table 2. As is clear from the results shown in this table, the fluoride sprayed coating (Nos. 5 and 11) of the comparative example has less erosion loss than the oxide sprayed coating (Nos. 6 and 12), and has excellent plasma resistance. It is recognized that it has erosion properties. On the other hand, the test films (Nos. 1 to 4, 7 to 10) into which ions of F and F-containing inert gas were implanted showed even higher plasma erosion resistance, and were more resistant to erosion by F-containing gas ion implantation. Improvement was confirmed.

(Example 3)
In this example, the corrosivity of the fluoride sprayed coating subjected to the ion implantation treatment according to the method of the present invention to the halogen acid vapor was investigated.
(1) subjected試皮film substrate as SUS304 Steel by atmospheric plasma spraying directly on the surface of the [dimension horizontal 30 mm × vertical 50 mm × thickness 3.2mm], after forming the YF ₃ fluoride film to a thickness of 250μm , F, and (F—N), (F—Ar), (F—He), and the like were each subjected to ion implantation treatment in an atmosphere. Further, as a comparative fluoride film, an air plasma sprayed film (YF ₃ ) and (Y ₂ O ₃ ) formed to a thickness of 250 μm were tested under the same conditions.

(2) Corrosion test method (a) Corrosion test with HCl vapor is carried out by placing 100 ml of 30% HCl aqueous solution at the bottom of a desiccator for chemical experiments and suspending a test piece on the top to expose to HCl vapor generated from the HCl aqueous solution. The method to do was adopted. The corrosion test temperature is 30 ° C. to 50 ° C., and the time is 96 hours.
(B) In the corrosion test with HF vapor, 100 ml of HF aqueous solution was placed in the bottom of an autoclave made of SUS316L, and a test piece was hung on the top to carry out a corrosion test with HF vapor. The corrosion test temperature is 30 ° C. to 50 ° C., and the time is 96 hours.

(3) Test results The test results are summarized in Table 3. As is clear from the results shown in Table 3, the YF ₃ (No. 5) film of the comparative example changed from white to gray before the test and tended to change with the halogen-based acid vapor. In addition, the Y ₂ O ₃ film (No. 6) also exhibits a color change from white to light brown before the test, and the presence of a chemical change due to acid vapor is estimated. The cause of these discoloration may be the influence of the corrosion reaction of the base material by the halogen-based acid vapor that has entered through the through pores of the test film, but the details are not clear.
On the other hand, in YF ₃ (No. 1) implanted with F-containing gas ions, almost no change was observed in the appearance color, and a thermal spray coating (No. 2 to 2) in which F and inert gas ions were simultaneously implanted. In 4), since the appearance color itself has changed to black before the test, it is insensitive to changes in the corrosive action caused by this type of halogen acid vapor. However, from the result of the test film (No. 1) in which only the F-containing gas ion implantation is performed, it is expected that the YF ₃ film changed in black also exhibits excellent corrosion resistance.

  The product according to the present invention can be used for a semiconductor precision processing apparatus member that requires high halogen corrosion resistance and plasma erosion resistance. For example, in addition to the deposition shield, baffle plate, focus ring, insulator ring, shield ring, bellows cover, electrode, etc., which are disposed in the plasma processing apparatus using a processing gas containing halogen and its compound, It can be used as a corrosion-resistant film for chemical plant equipment members in similar gas atmospheres.

21 Reaction vessel 22 Material to be treated (with fluoride spray coating)
23 conductor 24 high voltage pulse generating power supply 25 plasma generating power supply 26 superimposing device 27a valve 27b valve 28 ground wire 29 high voltage introducing device for simultaneous application of high voltage pulse and high frequency voltage

Claims (10)

  The surface of the white sprayed coating is blackened by injecting F-containing gas ions directly onto the surface of the base material or the surface of the white fluoride sprayed coating formed through the undercoat. A method for blackening a white fluoride sprayed coating. _2. The white fluoride spray-coated film according to claim 1, wherein the F-containing gas ions are F gas or one or more inert gases selected from N ₂ , Ar, He, and Ne containing F. 3. Blackening method. In the blackening, high-frequency power is applied to the substrate in an atmosphere of one or more F-containing gas ions selected from F ₂ under reduced pressure or N ₂ , Ar, He and Ne containing F, and white fluoride spraying is performed. The ion implantation concentration of one or more inert gases selected from F-containing N ₂ , Ar, He and Ne containing F gas or F containing a negatively charged film and exhibiting positive charge behavior is 1 ×. It is realized by forming a black F-containing gas ion-implanted layer on at least a part of the surface of the thermal spray coating by performing ion implantation so as to be within a range of 10 ¹⁰ to 1 × 10 ²⁰ / cm ^2. The blackening method of the white fluoride sprayed coating of Claim 1 or 2.   The method for blackening a white fluoride sprayed coating according to any one of claims 1 to 3, wherein the blackening is performed from the surface of the white fluoride sprayed coating to a depth of less than 10 µm.   5. The blackening method for a white fluoride sprayed coating according to claim 1, wherein the blackening is such that only the F-containing gas ion implantation portion is partially changed to black.   The said white fluoride sprayed coating is a film | membrane with a film thickness of 20-500 micrometers formed by spraying the powder for white fluoride spraying with a particle size of 5-80 micrometers, The any one of Claims 1-5 characterized by the above-mentioned. The blackening method of the white fluoride sprayed coating of 1 characterized by the above-mentioned.   The white fluoride sprayed coating is composed of Y of Group IIIa, Al of Group IIIb, La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, lanthanoid metal elements having atomic numbers of 57 to 71. The method for blackening a white fluoride sprayed coating according to any one of claims 1 to 6, comprising at least one fluoride selected from Ha, Er, Tm, Yb, and Lu. .   A metal / alloy undercoat selected from Al, Al—Ni, Al—Zn, Ni—Cr, and Ni—Cr—Al is formed between the substrate and the white fluoride sprayed coating with a thickness of 50 to 150 μm. The blackening method for a white fluoride sprayed coating according to any one of claims 1 to 7, wherein the method is applied.   A film formed by spraying a base material and a white fluoride spraying material of the elemental periodic table IIIa group Y, group IIIb group Al, metal element of atomic number 57-71 formed on the surface of the base material A member comprising a white fluoride sprayed coating having a thickness of 20 to 500 µm, the white fluoride sprayed coating is formed on the surface from the surface by the blackening method according to any one of claims 1 to 7. A fluoride sprayed coating-coated member having a black layer on the surface, characterized by having a black F-containing gas ion-implanted layer obtained by blackening a range of less than 10 μm.   A metal / alloy underlayer selected from Al, Al—Ni, Al—Zn, Ni—Cr, and Ni—Cr—Al having a thickness of 50 to 150 μm between the substrate and the white fluoride sprayed coating. The fluoride sprayed coating-coated member having a black layer on the surface according to claim 9, further comprising a coat.