TW201339365A - Formation method of fluoride thermal spray membrane and fluoride thermal spray membrane-coated member - Google Patents

Abstract

An object of this invention is provision of a fluoride thermal spray membrane-coated member formed by coating a carbide cermet on a surface of a substrate and by strongly adhering a fluoride thermal spray membrane through it; and a method for obtaining the same. An under coat or a primer section of a carbide cermet where the front end of a carbide cermet particle is embedded in a substrate and coats as a film form is formed by using a thermal spray gun to high-speed spray a carbide cermet material on a surface of a substrate, and then, a fluoride thermal spray membrane is formed by thermal spraying a fluoride particle on it.

Description

Method for forming fluoride thermal spray coating and fluoride thermal spray coating member

The present invention relates to a method for forming a fluoride thermal spray coating and a fluoride thermal spray coating member. In particular, the present invention provides a method for forming a surface of a member for a semiconductor processing apparatus, which is subjected to plasma etching in a highly corrosive gas environment, a method of forming a fluoride thermal spray coating through a carbide cermet, and by carrying out the method The obtained fluoride thermal spray coating member is coated.

A thermal spray coating is useful as a corrosion-resistant film formed on the surface of a member for a semiconductor processing apparatus. For example, when the above-mentioned member is used for plasma treatment in the presence of a halogen or a halogen compound, or in the field of a semiconductor processing apparatus that needs to clean and remove fine particles generated by plasma treatment, further surface treatment is required, and Several are available to obtain their prior art.

The processing environment of a device such as a dry etching machine, CVD, or PVD used in a semiconductor processing program or a liquid crystal manufacturing program requires high cleaning in order to improve the precision of micro-machining of a circuit formed on a substrate such as tantalum or glass. Sex. However, in various procedures for microfabrication, since a highly corrosive gas or an aqueous solution including fluoride or chloride is used, corrosion loss of components disposed in the above-described apparatus is accelerated, and as a result, corrosion products are caused. The second environmental pollution.

Manufacturing of a semiconductor device ‧ The processing step is a so-called "dry process" in which a compound semiconductor composed of Si, Ga, As, P, or the like is mainly used, and is processed in a vacuum or in a reduced pressure environment. As a device used in such a dry process, there are an oxidizing furnace, a CVD apparatus, a PVD apparatus, an epitaxial growth apparatus, an ion implantation apparatus, a diffusion furnace, a reactive ion etching apparatus, and piping attached thereto. Parts and parts such as exhaust fans, vacuum pumps, valves, etc. Moreover, it is known that these devices use fluorides such as BF ₃ , PF ₃ , PF ₆ , NF ₃ , WF ₃ , HF, BCl ₃ , PCl ₃ , PCl ₅ , POCl ₃ , AsCl ₃ , SnCl ₄ , TiCl ₄ , Chlorides such as SiH ₂ Cl ₂ , SiCl ₄ , HCl, and Cl ₂ , bromides such as HBr, and highly corrosive chemicals and gases such as NH ₃ and CH ₃ F.

Further, in the aforementioned dry process using a halide, in order to achieve activation of the reaction and improve processing accuracy, plasma (low temperature plasma) is often used. In the environment where plasma is used, various halides form highly corrosive atomic or ionized F, Cl, Br, and I, which greatly affects the microfabrication of semiconductor materials. On the other hand, particles of fine SiO ₂ , Si ₃ N ₄ , Si, W, etc., which are stripped by etching, float in the processing environment, and such particles are attached to the surface of the processed or processed device. A problem that causes its quality to be significantly reduced.

As one of the countermeasures for such problems, there has been a method in which a surface treatment is performed on an aluminum anodic oxide (alumite) on the surface of a member for semiconductor manufacturing and processing equipment. Others include oxides of Al ₂ O ₃ , Al ₂ O ₃ ‧Ti ₂ O ₃ , Y ₂ O _{3 ,} and oxides of metals of Group IIIA of the periodic table by thermal spraying or deposition (CVD, PVD) The technique of covering the surface of the member or using the same as a sintered body (Patent Documents 1 to 5).

Moreover, recently, a surface of a thermal spray coating of Y ₂ O ₃ or Y ₂ O ₃ -Al ₂ O ₃ is irradiated with a laser beam or an electron beam to re-melt the surface of the thermal spray coating, thereby improving plasma corrosion resistance. Technology (Patent Documents 6 to 9).

In addition, in the field of high-performance semiconductor processing, as a means for purifying the processing environment, and as a material that exceeds the plasma corrosion resistance of the Y ₂ O ₃ thermal spray coating, YF ₃ (fluorine) is used in a film formation state. Proposal for the method of sputum. For example, a surface of an oxide of a sintered body such as YAG or an oxide of a group IIIA element of the periodic table is coated with a YF ₃ film (Patent Documents 10 to 11) or a mixture of Y ₂ O ₃ or Yb ₂ O ₃ or YF _{3 is} used as a film forming material. The proposal (Patent Documents 12 to 13) or a method in which YF ₃ itself is used as a film forming material and is formed by thermal spraying (Patent Documents 14 to 15) is proposed.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. Hei 6-36583

Patent Document 2 Japanese Patent Publication No. 9-69554

Patent Document 3 Japanese Patent Laid-Open Publication No. 2001-164354

Patent Document 4 Japanese Patent Laid-Open No. Hei 11-80925

Patent Document 5 Japanese Patent Laid-Open Publication No. 2007-107100

Patent Document 6 Japanese Patent Laid-Open Publication No. 2005-256093

Patent Document 7 Japanese Patent Laid-Open Publication No. 2005-256098

Patent Document 8 Japanese Patent Laid-Open Publication No. 2006-118053

Patent Document 9 Japanese Patent Laid-Open Publication No. 2007-217779

Patent Document 10 Japanese Patent Laid-Open Publication No. 2002-293630

Patent Document 11 Japanese Patent Laid-Open Publication No. 2002-252209

Patent Document 12 Japanese Patent Laid-Open Publication No. 2008-98660

Patent Document 13 Japanese Patent Laid-Open Publication No. 2005-243988

Patent Document 14 Japanese Patent Laid-Open Publication No. 2004-197181

Patent Document 15 Japanese Patent Laid-Open Publication No. 2002-037683

Patent Document 16 Japanese Patent Laid-Open Publication No. 2007-115973

Patent Document 17 Japanese Patent Laid-Open Publication No. 2007-138288

Patent Document 18 Japanese Patent Laid-Open Publication No. 2007-308794

Although the fluoride thermal spray coating film has excellent halogen resistance, it has a disadvantage of poor adhesion to a substrate. According to the experience of the inventors and the like, the fluoride thermal spray coating coated on the surface of the substrate can be seen to be cracked or partially peeled off due to lack of ductility and small surface energy. However, in all of the above documents, countermeasures for overcoming this disadvantage have not been discussed. The reason is that fluoride (YF ₃ , AlF _{3 ,} etc.) is not considered to be suitable for thermal spray materials specified by Japanese Industrial Standards (JIS) or International Standardization Organization (ISO), which are the basis of thermal spray processing technology. The standard method of operation for the fluoride thermal spray coating is not specified, and it is considered that the thermal spray processing can be carried out in accordance with the same standards as those for metal (alloy), ceramics, and cermet materials.

Generally, in thermal spraying operations, the surface of the substrate is usually roughened before this operation. In the aforementioned Japanese Industrial Standards (JIS), the following sandblasting and roughening treatment methods are specified for each of the film forming materials:

(1) Metal film system: JIS H8300 "Zinc, aluminum, and alloy thermal spray-thermal spray operation standards", for steel substrates, first used as an oxide (rust) removal and JIS Z0312 After removing oxides such as blast furnace slag and steel slag, the surface to be removed is further subjected to roughening treatment using a cast steel abrasive specified in JIS Z0311 or a fused alumina (Al ₂ O ₃ ) abrasive specified in JIS Z0312.

(2) Ceramic film: After the sandblasting treatment for the oxide removal is carried out in JIS H9302 "Ceramic Thermal Spraying Operation Standard", the surface is roughened by the artificial abrasive (Al ₂ O ₃ , SiC) of JIS R6111. .

(3) Cermet film system: JIS H8306 "Ceramic metal thermal spraying" is defined by using a cast iron abrasive manufactured in accordance with JIS G5903 or an artificial abrasive manufactured in accordance with JIS R6111.

As described above, in the field of thermal spraying, the blasting materials and the roughening state used for the blasting surface treatment of the substrate surface are strictly defined for each film forming material. Further, the substrate roughening treatment described in each of the above-mentioned patent documents relating to the fluoride thermal spray coating does not disclose the treatment conditions or the degree of roughening; or even the disclosed only the sandblasted material, not the disclosure A method of improving the adhesion of a fluoride thermal spray coating (Patent Documents 14 and 16). In Patent Documents 17 and 18, only the roughening treatment using corundum (Al ₂ O ₃ ) is disclosed. In summary, the known literatures related to the patent documents and the fluoride thermal spray coatings do not disclose the roughening treatment as a countermeasure for improving the adhesion of the film and the formation of an intermediate layer such as an undercoat layer, and the surface roughness is not disclosed.

Moreover, in these patent documents, there is no example in which a procedure for directly forming a fluoride thermal spray coating on the surface of a substrate and applying an intermediate layer such as an undercoat layer before application of the fluoride thermal spray coating is employed. Committed to improving the adhesion of fluoride, this is considered to be the cause of frequent film peeling in a practical environment.

Accordingly, an object of the present invention is to provide a fluoride thermal spray coating member in which a thermal spray coating of a fluoride is strongly adhered to a surface of a substrate via a carbide cermet, and an advantageous method for producing the same.

In order to overcome the above problems of the prior art, the present invention has been found to be advantageous in that a novel thermal spray coating forming technique based on the following viewpoints is employed.

(1) In order to improve the adhesion of the fluoride thermal spray coating, it is important to prepare the surface of the substrate. In particular, before the formation of the fluoride thermal spray coating on the surface of the substrate, first, the undercoat layer of the carbide cermet or the carbide cermet is formed on the surface of the substrate to be sparsely dispersed in a state of being inserted as a pile. The intermediate layer (preparation) of the attached primer portion is effective. The intermediate layer of the formed carbide cermet thus prepared is sufficiently compatible with the fluoride (fluorine and carbon), thereby contributing to the improvement of the adhesion strength of the fluoride thermal spray coating of the top coat.

(2) As a preliminary treatment, the surface of the substrate which has been roughened by sand blasting is sprayed with a high speed spray of a carbide cermet to form an undercoat layer. At this time, the first part of the particles sprayed on the surface of the substrate is placed in the state of being inserted and placed on the surface of the substrate, and the spraying process is repeated in this order to form a film, and then the film-formed primer is formed. It is advantageous to form a thermal spray coating of the fluoride obtained by the usual method on the layer.

(3) Further, as the other preliminary treatment method, not only the surface of the base material is roughened by sandblasting, but also particles of carbide cermet are sprayed at a high speed (150 to 600 m/sec.). a non-film-like primer portion (attachment area ratio of about 8 to 50%) in which the particles of the carbide cermet are inserted into the surface of the substrate and are sparsely embedded, and the fluoride is interposed between the primer portions. It is advantageous to attach the thermal spray coating to enhance the adhesion of the fluoride thermal spray coating.

(4) Further, before the surface of the substrate is formed of a part of the undercoat layer or the primer portion made of a carbide cermet, Al ₂ O ₃ or SiC is used in accordance with the ceramic thermal spray coating standard specified in JIS H9302. The blasting and roughening treatment of the particles is advantageous.

(5) Preferably, the surface of the substrate is subjected to roughing by the blasting treatment, and then sprayed at a high speed by using a thermal spray gun for high-speed flame thermal spraying or low-temperature thermal spraying or the like (thermal spraying times) : 5 times or less) a carbide cermet material such as WC-Co or WC-Ni-Cr, and a front end portion of at least a part of the carbide cermet thermal spray particles flying at a high speed is inserted into the surface of the substrate as a pile The non-membranous primer layer which is formed by the sparsely formed structure is basically formed, and by further continuing this state (the number of thermal spraying: 6 times or more), a film formed by depositing carbide cermet thermal spray particles is formed. The undercoat layer is formed and a fluoride thermal spray coating is formed by a common thermal spraying method using a plasma flame or a fossil fuel combustion flame as a heat source via such an intermediate layer (primer portion or undercoat layer).

(6) After further forming an intermediate layer (primer portion, primer layer) formed by spraying the carbide cermet material at a high speed on the surface of the roughened substrate, the substrate is preheated to 80 ° C. It is preferred to thermally spray the fluoride thermal spray material by a method such as atmospheric plasma thermal spraying, vacuum plasma thermal spraying, or high-speed flame thermal spraying at a temperature of 700 ° C.

The present invention developed based on the above viewpoint is a method for forming a fluoride thermal spray coating, characterized in that a carbide cermet material is sprayed on a surface of a roughened substrate by using a spray gun capable of spraying at a high speed. An undercoat layer or a non-membrane form of carbide metal particles in which a tip end portion of the carbide cermet particles is buried in a substrate and coated in a film form is formed. A primer portion, after which a fluoride thermal spray material is sprayed on the primer layer or the primer portion.

Further, the present invention provides a fluoride thermal spray coating member comprising: a substrate comprising a roughened surface; a carbide cermet layer coated on the surface of the substrate; and a layer formed thereon Formed by a fluoride thermal spray coating; the carbide cermet layer is sprayed by using a high speed spray with a thermal spray gun comprising a material selected from the group consisting of Ti, Zr, Hf, V, Nb, Cr, Mn, W, and Si. 1 or more metal carbides, and 5 to 40 mass% of a carbide metal ceramide having a particle diameter of 5 to 80 μm selected from the group consisting of Co, Ni, Cr, Al, and Mo. a film-like undercoat layer in which a part of the carbide cermet particles are buried in a substrate while being thickened, or a non-membrane structure having a structure in which a tip end of the thermally sprayed particles is inserted as a pile and is sparsely structured The primer department is composed of.

Further, in the present invention, (1) the primer layer of the carbide metal particles is buried in the base material at a portion of the surface of the substrate as a part of the carbide cermet particles, and the number of times of thermal spraying is repeated to increase the thickness. a film-like structural layer having a layer thickness of 10 μm to 150 μm; (2) a portion of the primer portion of the carbide cermet having an area ratio of 8 to 50% with respect to the surface of the substrate is a front end of the thermally sprayed particles The portion is formed by a non-membrane structure in a state of being inserted and sparsely piled up; (3) the primer layer of the carbide cermet and the primer layer are selected from the group consisting of Ti, Zr, Hf, V, Nb, One or more metal carbides of Ta, Cr, Mo, W, and Si, and one or more metals and alloys selected from the group consisting of Co, Ni, Cr, Al, and Mo in an amount of 5 to 40% by mass For particles of 5 to 80 μm in size, use a high-speed spray thermal spray gun that can be sprayed at a flight speed of 150 to 600 m/sec., if the primer is used, the number of thermal sprays is 6 or more, if the primer is In the case of the part, the number of thermal spraying is 5 times or less; (4) preheating the substrate to 80-700 ° C before thermal spraying of the fluoride particles; The thermal spraying method of the fluoride is any one selected from the group consisting of an atmospheric plasma thermal spraying method, a vacuum plasma thermal spraying method, and a high-speed flame thermal spraying method; (6) the foregoing substrate is used by spraying Al ₂ O ₃ or SiC and other abrasive materials are sandblasted and roughened, and the surface roughness is adjusted to Ra: 0.05 to 0.74 μm, Rz: 0.09 to 2.0 μm of Al and its alloy, Ti and its alloy, carbon steel, Any of stainless steel, Ni and its alloys, oxides, nitrides, carbides, tellurides, carbon sintered bodies and plastics; (7) The thermal spray coating of the above-mentioned fluorides is selected from the group IIA of the periodic table II, Al of the group IIIB of the periodic table, Y of the group IIIA of the periodic table, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm of the lanthanide metals of the atomic order 57-71, One or more kinds of fluorides of Yb and Lu have a particle diameter of 5 μm to 80 μm, and a film thickness of 20 μm to 500 μm is formed; (8) the fluoride thermal spray coating has a thickness of 20 to 500 μm. A favorable solution.

According to the invention having the above configuration, the following effects are expected:

(1) If a hard carbide cermet is sprayed at a high speed on the surface of the substrate, at least a part of the first part of the carbide cermet thermal spray particles is formed by gradually repeating the spray to form a bottom after being inserted into the surface of the substrate. Coating or the aforementioned primer section. If the fluoride particles are thermally sprayed on the undercoat or primer portion, the fluoride thermal spray particles are attached to the carbide cermet undercoat layer with high adhesion.

(2) In particular, although fluoride is chemically difficult to wet with metals (aluminum, titanium, steel, etc.) and lacks splicability, it has a large chemical affinity with carbide (principal component is carbon) cermet. The surface of the undercoat layer or the primer portion mainly composed of the deposited layer of the carbide cermet thermal spray particles is superimposed with a chemical affinity to form a fluoride thermal spray coating having better adhesion.

(3) Since the aforementioned carbide cermet undercoat layer or primer portion is gradually membranous after forming the state in which the first portion of the thermal sprayed particles are inserted or buried on the surface of the substrate, and the substrate is strongly compressed. Residual stress, so the substrate can exert strong resistance to deformation or strain. In the use environment, the member thus treated can suppress peeling of the fluoride thermal spray coating due to mechanical load or vibration of the member coated with the fluoride film.

(4) By the effect of the undercoat layer or the primer portion of the carbide cermet, and by forming the fluoride thermal spray coating film in the state of preheating the entire substrate, it is possible to obtain a strong adhesion between the respective films. The component of force.

(5) The fluoride thermal spray coating member of the present invention exhibits excellent corrosion resistance (halogen resistance) of the fluoride thermal spray coating body by strongly adhering the substrate to the fluoride thermal spray coating via the carbide cermet Gas-based), halogen-resistant gas plasma corrosiveness, and when used in a member for semiconductor processing, it is possible to obtain a member that is resistant to long-term use.

(6) The fluoride thermal spray coating member of the present invention has a strong carbide cermet layer such as WC-Ni-Cr or Cr ₃ C ₂ -Ni-Cr sprayed by a high-speed flame thermal spraying method or the like on the surface of the substrate. The front end portion of the thermal spray particles is buried in the undercoat layer or the primer portion of the substrate, so that the fluoride thermal spray coating can be formed on the substrate with a stronger adhesive force.

That is, since the fluoride originally has a small surface energy (Al, Ti, Fe, etc.) and is chemically difficult to wet, the cross-linking force of the fluoride particles or the adhesion to the substrate is low and peeling often occurs. nature. Accordingly, according to the present invention, since the fluoride and the carbide cermet (the main component is carbon) have strong chemical affinity and sufficient wettability, if the undercoat or primer portion of the carbide cermet is interposed therebetween. In addition to the surface of the physical attachment mechanism of the fluoride thermal spray particles, the chemical affinity can also be utilized to improve the adhesion of the film.

(7) Further, the undercoat layer of the foregoing carbide cermet is extremely dense (porosity: 0.1% to 0.6%), and the thermal spray particles of the carbide cermet formed by the primer portion of the carbide cermet are inserted as a pile. Since it is sparsely laid out, it has a role of strongly suppressing strain or deformation of the substrate. Therefore, it is possible to effectively prevent the peeling phenomenon in which the fluoride thermal spray coating is easily peeled off due to deformation or vibration of the substrate.

(8) As explained above, the fluoride thermal spray coating formed by the technique of the present invention can sufficiently withstand the thermal shock caused by the repeated severe temperature change, and the physical conditions such as the addition of microvibration and bending stress in a practical environment. The change, while playing the long-term excellent chemical properties of the fluoride thermal spray coating.

Form for implementing the invention

Hereinafter, an embodiment of the present invention will be described based on the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing the flow of steps for carrying out the method of the present invention. Hereinafter, the present invention will be described in this order.

(1) Substrate

The substrate which can be used in the present invention is Al and its alloys, Ti and its alloys, various alloy steels containing stainless steel, carbon steel, Ni and alloys thereof and the like. Others may be ceramic sintered bodies such as oxides or nitrides, carbides, and tellurides, and organic polymer materials such as sintered carbon materials or plastics.

(2) pre-treatment

The surface of the substrate is preferably pretreated according to the ceramic thermal spraying operation standard specified in JIS H9302. For example, after removing rust, grease, or the like on the surface of the substrate, the abrasive particles such as Al ₂ O ₃ or SiC are sprayed and descaled, and then subjected to rough blasting. Further, the roughness after the blasting surface roughening treatment is set to Ra: 0.05 to 0.74 μm, and Rz: 0.09 to 2.0 μm.

(3) Formation of a film-like undercoat layer or a non-film-like primer portion by a carbide cermet a. Film-like undercoat of carbide cermet

On the surface of the roughened substrate after sandblasting, a high-speed flame thermal spraying method or an inert gas thermal spraying method is used to spray a carbide cermet material having a particle diameter of 5 to 80 μm at a high speed by using a thermal spray gun, thereby performing multiple times (6 times). In the above), the tip end portion of at least a part of the thermally sprayed particles is inserted into the surface of the substrate to be buried, and the other portion is attached to the surface of the substrate. Thereby, the undercoat layer in which the carbide cermet is gradually thickened and adhered in a film form is formed. The undercoat layer is a high-speed spray thermal spray gun with a flying speed of 150 to 600 m/sec., preferably 300 to 600 m/sec., and the carbide cermet material is sprayed with a thermal spraying number of 6 times or more and 10 times or less. (Particle size: 5 μm to 80 μm) to form a film. Further, when the flying speed of the sprayed particles is less than 150 μm, the depth of the particles to the surface of the substrate is insufficient to cause the adhesion strength to be weakened. On the other hand, when it is more than 600 m/sec., the effect is saturated when it is a carbide cermet particle. Further, when the number of thermal spraying is 5 or less, it is difficult to uniformly form a film.

Fig. 2 is a view showing an initial stage of application of a primer layer of a carbide cermet, that is, a surface of a substrate immediately after spraying carbide cermet particles at a flying speed of 550 m/sec. by a high-speed flame thermal spraying method. A diagram of the cross-sectional morphology of the part. Figure 2 (b) is a part of the sprayed WC-Co cermet particles attached to the surface of the substrate in a one-by-one manner, while another portion of the WC-Co cermet particles are partially broken by the collision energy with the substrate. The state is dispersed and the coating is attached. In the same manner as in the first stage before the film formation, the distribution of the WC-Co cermet particles sprayed on the surface layer portion of the substrate was observed in a cross-sectional state. The photo is clear, WC-Co metal pottery In the initial stage, the porcelain particles are in a state in which the front end portion is implanted and inserted into the surface of the substrate to be buried, and the other portion is in a state of being simply adhered or buried. The more the number of thermal spraying, the more uniform the film can be formed.

That is, if the surface of the substrate to which the WC-Co cermet thermal spray particles are attached is further sprayed with a WC-Co thermal spray material by a high-speed flame thermal spraying method (≧6 times), the unattached portion on the surface of the substrate ( In the black portion of Fig. 2(a), the particles of WC-Co are also successively deposited, and finally a film-like undercoat layer coated with WC-Co cermet particles is formed on the entire surface. On the other hand, in general metal base coating films such as Ni-Cr and Ni-Al which are widely used in the formation of an oxide ceramic thermal spray coating, it is not seen that the substrate is buried in the substrate as shown in FIG. Particles in.

In the present invention, the undercoat layer of the carbide cermet is applied to the surface of the substrate, and the adhesion to the undercoat layer/substrate can be improved according to the behavior of the hard carbide cermet, while the permeation/primer coating is applied. The adhesion of the film (fluoride thermal spray coating), that is, the adhesion between the roughness of the surface of the undercoat layer and the chemical affinity of carbon and fluoride (top coating film), can achieve the adhesion of the fluoride thermal spray coating. Improvement.

Further, the carbide cermet thermal spray particle system in which the particles of the lowermost layer of the undercoat layer are inserted into the surface of the substrate is strongly bonded to the substrate while imparting a large compressive strain to the surface of the substrate, not only The mechanical deformation of the substrate imparts a large resistance, and the adhesion between the undercoat layer of the carbide cermet and the substrate is also improved, and the adhesion to the thermal spray coating of the fluoride coated thereon is also enhanced.

In the present invention, the undercoat layer of the carbide cermet deposited on the surface of the substrate is attached to the substrate in a state where a part of the thermally sprayed particles is buried, and is soft and Bases such as Al and its alloys, Ti and its alloys, mild steels, and various stainless steels that are easily deformed or strained by the load in the environment are particularly effective, and the types of materials that are stable at all times can be guaranteed. The formation of a thermal spray coating.

That is, the fluoride film is originally lacking ductility, has a small surface energy and is not easily bonded to the metal substrate, and is buried by the carbide cermet particles when the film is easily peeled off due to deformation or strain of the substrate. The suppression of the deformation ability of the substrate generated on the surface of the substrate and the application of the carbide cermet primer layer formed thereon can suppress external stress or strain which the fluoride film is subjected to.

The thickness of the undercoat layer of the above-described carbide cermet formed on the surface of the substrate is preferably in the range of 30 to 200 μm, particularly preferably in the range of 80 to 150 μm. When the thickness of the undercoat layer is less than 30 μm, the film thickness tends to be uneven, and a film thickness of more than 200 μm is formed, and the effect as an undercoat layer is saturated and uneconomical.

b. Formation of a non-film-like primer portion due to carbide cermet

On the surface of the substrate which has been roughened by sand blasting, a high-speed spray thermal spray gun for high-speed flame thermal spraying or inert gas thermal spraying or the like is used to spray carbide cermet particles having a particle diameter of 5 to 80 μm at a high speed. The front end portion of at least a part of the particles of the sprayed hard carbide cermet thermal spray particles is formed in a state of being inserted into the surface of the substrate in an independent state and in a state of being piled up. Further, by such a method, a portion (primer portion) in which the carbide particles of the carbide metal ceramic particles are adhered to and adhered to the surface of the substrate in a sparse form is formed. At this time, if the particle diameter of the carbide cermet particles is less than 5 μm, the supply amount to the thermal spray gun is uneven. It is not possible to spray evenly, and in addition, the amount of insertion is small to fail to form a primer portion in which effective thermal spray particles are scattered and adhered. On the other hand, when the particle diameter is larger than 80 μm, the insertion effect is weakened.

Further, the primer portion is the same as the undercoat layer, and is a heat of a flying speed of 150 to 600 m/sec., preferably 300 to 600 m/sec., for a carbide cermet material (particle size: 5 to 80 μm). The spray gun is set to have a thermal spray number of 5 or less, preferably 3 or less, and the surface of the substrate is 8 to 50% in area ratio, so that the thermal spray particles are attached in a state of sparse and pile-like insertion. section.

The primer portion of the sparsely dispersed carbide cermet thermal spray particles dispersed in the treatment step is not completely film-formed, but has the following structure. That is, as shown in Figs. 2(a) and (b) showing the appearance state of the particles of the carbide cermet material of WC-12mass%Co sprayed on the surface of the SUS310 steel base material, it is known that the sprayed WC-Co A part of the cermet particles adhere to each other in an area of 8 to 50% of the surface of the substrate. In addition, other WC-Co cermet particles are further dispersed and adhered in a partially broken state by collision energy with the substrate, and another portion is completely buried in the substrate, and a carbide metal is formed on the surface layer of the thermal spray coating. The state of the strengthening layer formed by ceramics.

Further, Fig. 2(c) is a view showing a state of distribution of the sprayed WC-Co cermet particles present in the surface layer portion of the substrate in a cross-sectional state. As is clear from the photograph, the WC-Co cermet particles are driven into the surface of the substrate, and the small piles are sparsely popped, while the other portion is simply adhered or buried. In the present invention, in the surface of the substrate in this state, That is, when the fluoride particles are thermally sprayed on the primer portion (which does not form a complete layer) composed of the carbide cermet particles adhered in such a state, it is attempted to utilize the hard WC-Co cermet which is piled. The effect of particles (fluoride thermal spray particles) intertwining each other, that is, the anchoring effect (JIS H8200 thermal spraying term), or the stringing phenomenon (the fluoride particles in the front end of the hard WC-Co cermet particles standing in the pile are stringed A phenomenon of adhesion of a shape) forms a fluoride thermal spray coating having high adhesion on the surface of the substrate.

Further, in the present invention, the SEM photograph of Fig. 2(a) or Fig. 2(b) is applied to the structure of the primer portion of the carbide cermet, and the white portion is used as a carbide by the image analyzing device. The cermet particles and the black portion are the exposed surfaces of the substrate, and are expressed by the area ratio (area occupancy ratio) of the carbide cermet particles. That is, it is preferable that the ratio of the thermal spray particles of the primer portion to the surface area of the substrate, that is, the area ratio is in the range of 8 to 50%. The reason is that, if it is less than 8%, the effect of the fixed wedge generated by the carbide cermet particles is weakened, and when it is more than 50%, the action mechanism is the same as that of the undercoat layer of the carbide cermet described later. The fixed wedge effect of the particles is reduced. In the present invention, the state of the surface of the substrate which is sprayed in the range of the adhesion area ratio of the carbide cermet particles to the surface of the substrate of 8 to 50% is referred to as a "primer portion".

As the carbide cermet thermal spray material which can be used in the present invention, WC-Co, WC-Ni-Cr, WC-Co-Cr, Cr ₃ C ₂ -Ni-Cr or the like can be used. Further, the proportion of the metal component in the carbide cermet is preferably in the range of 5 to 40 mass%, particularly preferably 10 to 30 mass%. The reason is that when the metal component is less than 5 mass%, when the surface of the substrate is strongly sprayed, the proportion of the fine carbide-forming fine powder remaining on the surface of the substrate is reduced, and when the metal component is more than 40 mass%, the metal component is excessively large. The hardness and corrosion resistance are lowered, the effect of interlacing with fluoride particles is lowered, or the corrosive gas invaded by the through pores of the fluoride thermal spray coating causes the substrate to be easily corroded, and the bonding force of the fluoride thermal spray coating is also caused. Disappeared and induced to peel off.

The thermal sprayed carbide cermet material is used in a particle size of 5 to 80 μm, and particularly preferably in the range of 10 to 45 μm. When the particle diameter is less than 5 μm, the supply to the thermal spray gun is discontinuous, and it is difficult to form a uniform film, and when it collides with the substrate, it is finely pulverized and scattered, and it does not easily remain on the substrate surface. On the other hand, when the particle diameter is larger than 80 μm, the effect is saturated and it is not easy to obtain a commercially available product.

(4) Preheating of the substrate

The substrate after the roughening treatment and the primer layer on which the undercoat layer of the carbide cermet or the primer portion of the thermally sprayed particles are dispersed are preheated before the thermal spray treatment of the fluoride. The preheating temperature is preferably controlled according to the base material, and the following temperatures are recommended. In addition, this preheating can be performed as one of the pretreatments.

(i) Al, Ti and alloys of these: 80 ° C ~ 250 ° C

(ii) Steel (low alloy steel): 80 ° C ~ 250 ° C

(iii) Stainless steel: 80 ° C ~ 250 ° C

(iv) Ceramic sintered body such as oxide ‧ carbide: 120 ° C ~ 500 ° C

(v) sintered carbon: 200 ° C ~ 700 ° C

In addition, the preheating may be carried out in the atmosphere, in a vacuum, or in an inert gas, except that the base material is prevented from being oxidized by preheating, and a gas atmosphere such as an oxide film is formed on the surface.

As a method of forming a fluoride thermal spray coating, an atmospheric plasma thermal spraying method, a reduced pressure plasma thermal spraying method, a high-speed flame thermal spraying method, or the like is suitable.

(5) Formation of fluoride thermal spray coating (top coating film) a. Fluoride thermal spray material

As the fluoride thermal spray material used in the present invention, it is Mg of Group IIA of the periodic table, Al of Group IIIB of the periodic table, Y of Group IIIA of the periodic table, and fluoride of the lanthanide of the atomic sequence of 57 to 71. . The metal element names of atomic sequences 57 to 71 may be 镧 (La), 铈 (Ce), 鐠 (Pr), 钕 (Nd), 鉕 (Pm), 钐 (Sm), 铕 (Eu), 釓 (Gd). , 15 kinds of 鋱 (Tb), 镝 (Dy), 鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 镏 (Lu).

Further, as the thermal spray material, the fluoride particles of the above metal are adjusted to have a particle diameter of 5 to 80 μm. The reason is that if the thermal spray material is fine particles of less than 5 μm, there is a disadvantage that the scattering is more than the film formation when colliding with the surface of the substrate, and the particles of more than 80 μm are not easy to supply the thermal spray gun. Equalization, and the tendency of the pores of the film formed by the film to become large is remarkable.

It is preferable that the roughening treatment or the formation of the undercoat layer or the primer portion of the carbide cermet, and further the thermal spraying of the fluoride thermal spray material formed on the surface of the preheated substrate or the like. The thermal spray coating has a thickness of 20 to 500 μm, particularly preferably 50 to 200 μm. The reason for this is that when the film is thinner than 20 μm, a uniform film thickness cannot be obtained, and when it is thicker than 500 μm, the residual stress at the time of formation of the fluoride film is increased, and the adhesion to the substrate is lowered to facilitate peeling. .

(b) Characteristics of fluoride thermal spray coating

As the physicochemical properties of the fluoride itself, the following characteristics can be pointed out. That is, the film of the fluoride is chemically stable to the halogen gas compared to the metal film or the ceramic film, but the surface energy is small, and the mutual binding force of the fluoride particles constituting the film is exemplified. The adhesion strength to the substrate is weak. Further, since a large residual stress is likely to occur during film formation, since the substrate is only slightly deformed after film formation, peeling of the film is likely to occur. Further, since the fluoride exhibits a property of lacking in ductility, the film is liable to be "ruptured", and the acid or alkali cleaning solution penetrates into the inside of the pore portion which is formed during the film formation, and causes corrosion of the substrate. Even if the fluoride itself has good corrosion resistance, there is a problem that it cannot be utilized as an anti-corrosion film.

Accordingly, according to the present invention, the undercoat layer or the particle dispersing portion of the carbide cermet is provided on the surface of the substrate, whereby the adhesion of the film is improved, and the above problems of the fluoride thermal spray coating can be solved. That is, it is possible to prevent the peeling or cracking of the film, and prevent the infiltration of the cleaning liquid accompanying it to prevent the corrosion of the substrate.

In addition, the fluoride thermal spray coating formed by the present invention can be directly used in a film formation state, but can be easily subjected to heat treatment at 250 ° C to 500 ° C after film formation to release residual stress or amorphous. The crystallization is carried out (orthorhombic system), and therefore, in the present invention, the implementation of such treatments is not particularly limited. The reason why the temperature of the heat treatment is limited to the above range is that, if it is 250 ° C or lower, not only the release of the residual stress of the film takes a long time, but also the crystallization is insufficient, and when the temperature is 500 ° C or higher, the fluoride is promoted. The possibility of changes in the physicochemical properties of the thermal spray coating.

Example (Example 1)

In this embodiment, the effect of the treatment on the adhesion of the fluoride thermal spray coating before the surface of the substrate is examined.

(1) Type of pre-treatment

One side of the A13003 alloy ("JIS M4000", size: diameter 25 mm × thickness 5 mm) as a substrate was subjected to the following pretreatment.

(i) After degreasing, gently grind with a wire brush.

(ii) After degreasing, Ni-20mass%Cr was formed into a 50 μm thick metal undercoat layer by atmospheric plasma thermal spraying (flying speed: 250 m/sec.).

(iii) After degreasing, WC-12mass%Co was sprayed into a sparse shape (area ratio: 22%) by high-speed flame thermal spraying (speed of 580 m/sec., number of thermal spraying: 3 times) to form a primer portion. .

(iv) After degreasing, Cr ₃ C ₂ -18 mass% Ni-7 mass% Cr was formed into a 30 μm thick carbide cermet by high-speed flame thermal spraying (flying speed 560 m/sec., number of thermal spraying: 6 times). Undercoat.

(v) After degreasing, the surface of the substrate was subjected to blasting and roughening treatment using an Al ₂ O ₃ abrasive.

(vi) After the above-described sandblasting and graining treatment, a metal undercoat layer containing a Ni-20 mass% Cr film of 50 μm thick was further formed by atmospheric plasma thermal spraying (same as ii).

(vii) After the above-described blasting surface roughening treatment, WC-12mass%Co was further sprayed into a sparse shape (area ratio: 18%) by a high-speed flame thermal spraying method (same as iii) to form a primer portion.

(viii) After the above-described sandblasting surface treatment, Cr ₃ C ₂ -18 mass% Ni-7 mass% Cr is further subjected to a high-speed flame thermal spraying method (same as iv) to form a 30 μm thick undercoat of a carbide cermet.

(2) Formation of fluoride thermal spray coating

On the surface of the pretreated substrate, a 100 μm thick YF ₃ thermal spray coating was formed by atmospheric plasma thermal spraying.

(3) Test method for adhesion of film

The adhesion of the film was measured by the adhesion strength test method specified in JIS H8666 ceramic thermal spray test method.

(4) Test results

The test results are shown in Table 1. From the results, it was revealed that the test piece (No. 1) which forms the fluoride thermal spray coating was almost free from the adhesion after the surface of the substrate was degreased, and the film peeled off at 0.5 to 1.2 MPa. Moreover, the film formed on the metal undercoat layer (No. 2) exhibits an adhesion of about 4 to 5 MPa, but since the surface of the substrate is not subjected to sandblasting, it is visible from the metal undercoat layer and the substrate. Stripped strips of test strips. On the other hand, it was confirmed that the primer portion (No. 3) in which the carbide cermet particles were formed and the primer layer (No. 4) in which the primer layer was formed exhibited high adhesion, and the blasting surface treatment was omitted. The adhesive force required for practical use is obtained.

Next, it is understood that the YF ₃ film (No. 5) formed on the surface of the surface of the substrate to be subjected to the blasting surface treatment has a bonding strength of 4 to 6 MPa, and has a bonding strength higher than that of the film of No. 1, and For the formation of a fluoride thermal spray coating, the blasting roughening treatment is effective. Further, after the blasting surface roughening treatment, the carbide cermet particles are further sprayed thereon to form a primer portion or an undercoat layer is formed, and then the adhesion of the fluoride thermal spray coating film (No. 7, 8) becomes Higher, it can be confirmed that these are suitable as pretreatment methods for forming a fluoride thermal spray coating.

(Example 2)

In this example, the adhesion of the thermally sprayed film when a 100 μm thick YF ₃ thermal spray film was formed by using SS400 steel as a substrate and a vacuum plasma spray method was investigated.

(1) Type of pretreatment (roughening, formation of intermediate layer)

The same kind of pretreatment method as in Example 1 was carried out.

(2) Formation of fluoride thermal spray coating

A 100 μm-thick YF _{3 was} formed by a plasma thermal spraying method (pressure-reduced plasma thermal spraying method) in a reduced pressure atmosphere of Ar gas at 100 to 200 hPa.

(3) Test method for adhesion of film

The same method as in Example 1 was carried out.

(4) Test results

The test results are shown in Table 2. From this result, it is understood that the case where the YF ₃ thermal spray coating is directly formed on the surface of the substrate (No. 1), the adhesion of the formed film after the blasting treatment becomes high, and the Al alloy substrate of the first embodiment can be obtained. Better adhesion. However, even in the case of the SS400 steel substrate, those who sprayed the carbide cermet particles to form the primer portion (No. 3, 7) and those who formed the primer (No. 4, 8) exhibited higher adhesion. That is, it was found that the pretreatment method of applying the undercoat layer or the primer portion by the carbide cermet is not affected by the type of the substrate, and a film having a high adhesion force can be formed.

(Example 3)

In this example, the adhesion of the YF ₃ thermal spray film formed using SS400 steel as a substrate and using a high-speed plasma thermal spray method was investigated.

(1) Type of pretreatment (roughening, formation of intermediate layer)

The same pretreatment method as in Example 1 was carried out.

(2) Formation of fluoride thermal spray coating

A high-frequency plasma thermal spraying method was used to form 100 μm thick YF ₃ .

(3) Test method for adhesion of film

This was carried out in the same manner as in Example 1.

(4) Test results

The test results are shown in Table 3. From the results, it was confirmed that, as in the results of Example 1 and Example 2, it was confirmed that the primer portion or the undercoat layer (No. 3, 4, 7, and 8) of the carbide cermet formed according to the present invention and the substrate were confirmed. Regardless of the presence or absence of blasting, it is possible to form a fluoride thermal spray film which often has a high adhesion.

(Example 4)

In this example, the adhesion of three types of fluoride thermal spray coatings formed by using SUS304 steel as a substrate and using atmospheric plasma thermal spraying was investigated.

(1) Type of pre-treatment

After roughening the substrate with a SiC abrasive, the WC-12mass%Co-5mass%Cr or Cr ₃ C ₂ -17 mass% was sprayed at a high speed under the same conditions as in Example 1 on the roughened surface. Ni-7mass%Cr was sprayed to a thickness of 80 μm.

(2) Formation of fluoride thermal spray coating

120 μm thick CeF ₃ , DyF ₃ , EuF ₃ were applied by atmospheric plasma thermal spraying.

(3) Test method for adhesion of film

This was carried out in the same manner as in Example 1.

(4) Test results

The test results are shown in Table 4. From this result, it was confirmed that even in the case of a fluoride thermal spray coating such as CeF ₃ , DyF ₃ or EuF ₃ , the film of the undercoat layer in which the carbide cermet was formed also had an adhesion improving effect.

(Example 5)

In this embodiment, a surface of an Al alloy substrate (size: width 30 mm × length 50 mm × thickness 3 mm) is formed, and a fluoride thermal spray coating is formed on the surface of the primer portion of the carbide cermet by a method suitable for the present invention, and is evaluated. The plasma etching resistance of the film.

(1) Substrate: After the surface of the Al alloy (A3003 specified in JIS H4000) was subjected to blasting and roughening treatment, the cermet cermet was sprayed at a high speed (550 m/sec.) according to the present invention (thermal spraying times: 2 times). The material was subjected to a pretreatment for forming a sparse-like (area ratio of 12%) primer portion, and then, after preheating to 180 ° C, a fluoride thermal spray coating was formed.

(2) Fluoride for film formation: A film having a film thickness of 180 μm was formed by atmospheric plasma thermal spraying using YF ₃ , DyF ₃ , and CeF ₃ (particle diameter: 5 to 45 μm). Further, as a film of a comparative example, Y ₂ O ₃ , Dy ₂ O ₃ , CeO ₂ and the like and an oxide film were formed to have a thickness of 180 μm by an atmospheric plasma thermal spraying method.

(3) Plasma etching gas ambient gas composition and plasma output power

(i) Gas ambient gas and flow conditions

(a) F-containing gas: CHF ₃ /O ₂ /Ar=80/100/160 (flow rate per minute cm ³ )

(b) CH-containing gas: C ₂ H ₂ /Ar=80/100 (flow rate per minute cm ³ )

(ii) Plasma irradiation output power

High frequency power: 1300W

Pressure: 4Pa

Temperature: 60 ° C

(iii) Gas environment for plasma etching test

(a) Implemented in an environment containing F gas

(b) Implemented in a CH-containing gas environment

(C) Repeating the F-containing gas environment for 1h Implemented in a gas environment containing CH gas for 1 h

(4) Evaluation method

The evaluation of the plasma corrosion resistance test investigated the plasma corrosion resistance and the environmental pollution resistance by counting the number of particles of the film component scattered by the test film by the etching treatment. The number of particles was measured by measuring the time until the number of particles having a particle diameter of 0.2 μm or more adhered to the surface of the tantalum wafer having a diameter of 8 Å disposed in the test vessel reached 30.

(5) Test results

The test results are shown in Table 5. From the results, it is understood that the oxide-based thermal spray coatings of the comparative examples (No. 1, 3, and 5) have the least particles generated in the CH-containing gas, and slightly increase in the F-containing gas, and it is seen that the time until the allowable value is shortened. . However, it has been found that the number of particles generated in a gas atmosphere in which the F-containing gas and the CH-containing gas are alternately repeated is further increased, and the time until the allowable value is extremely short. The reason for this is considered to be that the oxidation of the fluorinated gas in the F-containing gas and the reduction of the CH gas occur repeatedly, and the oxide film on the surface of the oxide ceramic film is constantly unstable and scattered. On the other hand, it is considered that the fluoride thermal spray coatings of No. 2, 4, and 6 are maintained in a chemically stable state in a gas atmosphere containing F gas, CH-containing gas, and the like, and the particles can be suppressed. The production.

(Example 6)

In this example, the corrosion resistance of the fluoride thermal spray coating to the vapor of the hydrohalic acid is evaluated on the surface of the substrate treated in a manner suitable for the method of the present invention.

(1) Substrate: SS400 steel substrate (size: width 30 mm × length 50 mm × thickness 3.2 mm) was used, and the surface was subjected to sandblasting rough surface treatment, and then sprayed at a high speed by high-speed flame thermal spraying (560 m/sec., heat). Number of spraying: 3 times) Carbide cermet particles made of Cr ₂ C ₃ -18 mass% Ni-8 mass% Cr, and sparse form of carbide cermet particles (area ratio 28%) formed on the surface of the substrate The primer portion, after which the substrate was heated to 200 °C.

(2) Fluoride for film formation: It is prepared to form a film having a thickness of 250 μm by a vacuum plasma spray thermal spraying method using MgF ₃ and YF ₃ (particle diameter: 10 to 60 μm). Further, as a film for comparison, MgO and Y ₂ O _{3 were} formed to have a film thickness of 250 μm by a vacuum plasma spray method, and the test was carried out under the same conditions.

(3) Corrosion test method

(a) Corrosion test according to HCl vapor was carried out by charging 100 ml of a 30% aqueous HCl solution at the bottom of a desiccator for chemical experiments, and hanging the test piece on the upper portion thereof to be exposed to HCl. A method of water soluble HCl vapor. The corrosion test temperature was 30 ° C ~ 50 ° C, and the time was 96 hr.

(b) Corrosion test according to HF vapor The corrosion test according to HF vapor was carried out by adding 100 ml of an aqueous HF solution to the bottom of an autoclave made of SUS316 and hanging the test piece on the upper portion thereof. The corrosion test temperature was 30 ° C ~ 50 ° C, and the exposure time was 96 hr.

(6) Test results

The test results are shown in Table 6. From the results, it is understood that in the oxide film (No. 2, 4) of the comparative example, a large amount of red rust reaches the surface of all the film. In other words, it is considered that a large number of through pores are present on the oxide film, and vapors such as HCl and HF pass through the through pores to the inside of the film to corrode the SS400 steel substrate, and the iron component as a corrosion product passes through the pores to reach the surface of the film. It is red rusty. On the other hand, the fluoride thermal spray coatings (No. 1, 3) formed by the method of the present invention can be seen as red rust, but the degree is only about 30 to 40% of the comparative example. As a result, it is considered that there are through-holes in the thermal spray coating of fluoride, but it is less than the oxide-based thermal spray coating, and even the thermal spray coating of fluoride has excellent corrosion resistance, so it can be comprehensive. Good corrosion resistance to vapors resistant to hydrohalic acids.

Industrial availability

The technique of the present invention can be applied to surface treatment of members for semiconductor precision machining apparatuses requiring high halogen corrosion resistance and plasma corrosion resistance. For example, in addition to a deposhield, buffer plate, focusing device disposed on a plasma-treated device using a processing gas containing a halogen and a compound thereof The ring, the insulating ring, the shielding ring, the bellows shroud, the electrode, and the like can also be used as a corrosion-resistant film of a chemical plant device member such as a gas atmosphere gas. Further, the technique for forming a carbide cermet primer layer of the substrate of the present invention can also be applied to a treatment technique for a top coating film of a metal (alloy) film, an oxide ceramic, or a plastic.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing the flow of steps for carrying out the method of the present invention.

Fig. 2 is a cross-sectional SEM image of the first layer and the portion of the surface of the substrate on which the WC-12mass%Co cermet particles are sprayed in a sparse state by a high-speed flame thermal spraying method. (a) a surface in which the surface of the carbide cermet particles is sparsely sprayed, (b) a magnified photograph of the surface of the system, and (c) a section of the substrate which is grown in a state before being sprayed with the undercoat layer of the carbide cermet particles. .

Claims (14)

A method for forming a fluoride thermal spray coating, characterized in that a carbide cermet material is sprayed on a surface of a roughened substrate by using a high-speed spray thermal spray gun to form a front end of the carbide cermet particles An undercoat layer or a non-film-like primer portion of a carbide cermet which is buried in a substrate and coated with a film, and then thermally sprayed with a thermal spray of fluoride on the undercoat layer or the primer portion. material. The method for forming a fluoride thermal spray coating according to the first aspect of the invention, wherein the primer layer of the carbide cermet is formed by burying a front end portion of a part of the carbide cermet particles on the surface side of the substrate. The film-like structural layer having a layer thickness of 10 μm to 150 μm is formed by repeating the number of thermal spraying times in the material. The method for forming a fluoride thermal spray coating according to the first aspect of the invention, wherein the primer portion of the carbide cermet is 8 to 50% in area ratio with respect to the surface of the substrate, and is a front end of the thermally sprayed particles. The part is composed of a non-membranous structure in which the pile is inserted and sparsely laid out. The method for forming a fluoride thermal spray coating according to any one of claims 1 to 3, wherein the primer layer of the carbide cermet and the primer layer are selected from the group consisting of Ti, Zr, Hf, and V. And one or more metal carbides of Nb, Ta, Cr, Mo, W, and Si, and one or more metals and alloys selected from the group consisting of Co, Ni, Cr, Al, and Mo in an amount of 5 to 40% by mass. For particles of 5 to 80 μm in size, use a high-speed spray thermal spray gun that can be sprayed at a flight speed of 150 to 600 m/sec. If the primer is used, the number of thermal sprays is 6 or more. In the case of the primer portion, the number of thermal sprays is 5 or less. A method of forming a fluoride thermal spray coating according to any one of claims 1 to 4, wherein the substrate is preheated to 80 to 700 ° C prior to thermal spraying of the fluoride particles. The method for forming a fluoride thermal spray coating according to any one of claims 1 to 5, wherein the thermal spraying method of the fluoride is selected from the group consisting of atmospheric plasma thermal spraying, vacuum plasma thermal spraying, and high-speed flame. Any of the thermal spray methods of the thermal spray method. The method for forming a fluoride thermal spray coating according to any one of claims 1 to 6, wherein the substrate is subjected to a blasting roughening treatment by spraying an abrasive such as Al ₂ O ₃ or SiC. Surface roughness is adjusted to Ra: 0.05~0.74μm, Rz: 0.09~2.0μm Al and its alloys, Ti and its alloys, carbon steel, stainless steel, Ni and its alloys, oxides, nitrides, carbides, tellurides Any of carbon sintered body and plastic. The method for forming a fluoride thermal spray coating according to any one of claims 1 to 7, wherein the thermal spray coating of the fluoride is selected from the group consisting of Mg of the group IIA of the periodic table, Al of the group IIIB of the periodic table, and the cycle. Fluoride of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu of the lanthanide metal of Group IIIA, atomic order 57~71 The above-mentioned fluoride particles having a particle diameter of 5 μm to 80 μm are formed to have a film thickness of 20 μm to 500 μm. A fluoride thermal spray coating member characterized by: a base material having a roughened surface, a carbide cermet layer coated on the surface of the base material, and a fluoride thermal spray coating formed thereon ; The carbide cermet layer is sprayed with one or more kinds of metal carbides selected from the group consisting of Ti, Zr, Hf, V, Nb, Cr, Mn, W, and Si by using a high-speed spray thermal spray gun. 5 to 40 mass% of a carbide metal ceramic particle having a particle diameter of 5 to 80 μm selected from one or more metal alloys selected from the group consisting of Co, Ni, Cr, Al, and Mo, and the carbide metal ceramic particles are used. A portion of the film-like undercoat layer which is buried in the substrate while being thickened, or a non-membrane structure primer portion having a structure in which the tip end of the thermally sprayed particles is inserted and which is sparsely formed. The fluoride thermal spray coating member according to claim 9, wherein the primer layer of the carbide cermet is formed by burying a front end portion of a part of the carbide cermet particles on the surface of the substrate The film layer having a layer thickness of 10 μm to 150 μm is formed by repeating the number of times of thermal spraying. The fluoride thermal spray coating member according to claim 9, wherein the primer portion of the carbide cermet is 8 to 50% in area ratio with respect to the surface of the substrate by the front end portion of the thermal spray particles. It is composed of a non-membranous structure in a state of being inserted and sparsely stacked. The fluoride thermal spray coating member according to any one of claims 9 to 11, wherein the substrate is roughened by a roughening treatment by spraying an abrasive such as Al ₂ O ₃ or SiC. Degree adjusted to Ra: 0.05~0.74μm, Rz: 0.09~2.0μm Al and its alloys, Ti and its alloys, carbon steel, stainless steel, Ni and its alloys, oxides, nitrides, carbides, tellurides, carbon Any of sintered body and plastic. The fluoride thermal spray coating member according to any one of claims 9 to 12, wherein the fluoride thermal spray coating has a thickness of 20 to 500 μm. The fluoride thermal spray coating member according to any one of claims 9 to 13, wherein the thermal spray coating of the fluoride is selected from the group consisting of Mg of the group IIA of the periodic table, Al of the group IIIB of the periodic table, and the periodic table. One of the fluorides of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu of the lanthanide metal of group IIIA and atomic 57 to 71 The above particles having a particle diameter of 5 μm to 80 μm are formed to have a film thickness of 20 μm to 500 μm.