JP6005314B1 - Film-coated substrate, plasma etching apparatus component, and manufacturing method thereof - Google Patents

Abstract

The present invention provides a coated substrate having a thermal spray coating on the surface of a substrate that has high plasma resistance, is difficult to peel off, has excellent acid resistance, and has a high surface resistance. A substrate with a coating provided with a coating on the surface of the substrate, the coating having a thickness of 10 to 1000 μm, comprising a rare earth element (Ln) fluoride and an oxide as main components. The surface of the film is mainly composed of an oxide of rare earth element (Ln), has a monoclinic structure, and has a particulate portion [α] having a specific diameter and a fluoride of rare earth element (Ln) as the main components. In addition, the particulate portion [β] having an orthorhombic structure and having a specific diameter is dispersed in an amorphous matrix mainly composed of a fluoride of a rare earth element (Ln). When the surface of this is observed using an optical microscope, a white spot-like portion is confirmed, and the area ratio occupied by this spot-like portion in the observation field is low. [Selection] Figure 1

Description

  The present invention relates to a coated substrate, a component for a plasma etching apparatus, and a method for producing the same.

  The thermal spraying method is a method in which a raw material powder heated to a molten state is sprayed on the surface of a substrate to form a film, and is used in various fields that require heat resistance, corrosion resistance, wear resistance, and the like. In particular, members (plasma etching apparatus parts) included in plasma processing apparatuses used in the field of manufacturing semiconductors and liquid crystals are required to have a thermal spray coating excellent in plasma resistance in order to prevent wear due to plasma. .

  As a thermal spray coating excellent in plasma resistance, there has been conventionally proposed a coating formed without melting at least part of the raw material powder during thermal spraying.

  For example, in Patent Document 1, a component for a semiconductor manufacturing apparatus including a component main body and a thermal spray coating formed on the surface of the component main body by thermal spraying of oxide particles, wherein at least oxide particles in the thermal spray coating are included. A part for a semiconductor manufacturing apparatus is described which is partially unmelted.

  Moreover, in patent document 2, it is a component for semiconductor manufacturing apparatuses which comprises a component main body and the thermal spray coating formed in the surface of the said component main body by the thermal spraying of the nitride particle | grains as raw material powder, Comprising: The said thermal spray coating is nitrided. A component for semiconductor manufacturing equipment is described, wherein the powder particles of the product are unmelted and formed by depositing 90% or more.

  Patent Documents 1 and 2 describe that by applying the oxide spray coating or nitride spray coating as described above to a component for a semiconductor manufacturing apparatus, the plasma resistance of the component can be improved. Yes.

JP 2006-108178 A International Publication No. 2010/027073 Pamphlet

  However, it cannot be said that the conventional method as described above can obtain a sprayed coating having sufficiently excellent plasma resistance.

  In addition to being excellent in plasma resistance, it is preferable that the film is difficult to peel off. Moreover, it is preferable that the tolerance with respect to an acid is high depending on a use, and also surface resistance value is high. For example, in the case of a semiconductor manufacturing apparatus in which a film is formed inside, the surface of the film may be cleaned using an acid, and a high surface resistance value is desired.

  The present invention provides a coated substrate having a plasma sprayed coating on the surface of the substrate having a high plasma resistance, hardly peeled off, excellent in acid resistance, and having a high surface resistance value, a component for a plasma etching apparatus, and a method for producing them. For the purpose.

  The present inventor has intensively studied to solve the above problems, and a specific particulate portion having a specific crystal structure is dispersed in an amorphous matrix, and further, white when observed using an optical microscope. It has been found that a film in which the ratio of the area of a spot-like portion that is visible is within a specific range is excellent in plasma resistance and the like and is difficult to peel off. In addition, it has been found that in order to form such a film, it is possible to form a slurry in which a raw material with a very small amount of water is dispersed in an organic solvent containing as little water as possible by gas flame spraying or plasma spraying. .

The present invention includes the following (1) to (6).
(1) A substrate with a coating provided with a coating on the surface of the substrate,
The film has a thickness of 10 to 1000 μm, and includes a rare earth element (Ln) fluoride and an oxide as main components,
On the surface of the film, a particulate portion [α ₁ ] having a monoclinic structure, a diameter of 10 nm to 1 μm, and a rare earth element (Ln) fluoride, mainly composed of an oxide of rare earth element (Ln). The main component, an orthorhombic crystal structure, and a particulate portion [β ₁ ] having a diameter of 10 nm to 1 μm are dispersed in an amorphous matrix mainly containing a rare earth element (Ln) fluoride. And
Further, when the surface of the film is observed at 200 times using an optical microscope, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio of the spot-like part in the observation visual field is 0.00. The base material with a film | membrane which is 01 to 2%.
(2) The film-coated substrate according to (1), wherein the rare earth element (Ln) is yttrium (Y).
(3) A substrate with a coating provided with a coating on the surface of the substrate,
The film has a thickness of 10 to 1000 μm, and contains an alkaline earth metal fluoride and an oxide as main components,
On the surface of the film, the main component is an alkaline earth metal oxide, a monoclinic structure, a particulate portion [α ₂ ] having a diameter of 10 nm to 1 μm, and an alkaline earth metal fluoride. And a particulate portion [β ₂ ] having an orthorhombic structure and having a diameter of 10 nm to 1 μm is dispersed in an amorphous matrix mainly composed of an alkaline earth metal fluoride,
Further, when the surface of the film is observed at 200 times using an optical microscope, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio of the spot-like part in the observation visual field is 0.00. The base material with a film | membrane which is 01 to 2%.
(4) A component for a plasma etching apparatus, comprising the film-coated substrate according to any one of (1) to (3).
(5) a drying step of drying a raw material powder containing a rare earth element (Ln) fluoride or an alkaline earth metal fluoride to obtain a dry raw material having a moisture content of 0.3% by mass or less;
A slurry adjusting step of obtaining a slurry by dispersing the dry raw material in an organic solvent;
Using the slurry, gas flame spraying or plasma spraying, a film forming step of forming a film on the surface of the substrate,
The manufacturing method of the base material with a film by which the base material with a film in any one of said (1)-(3) is obtained.
(6) a drying step of drying a raw material powder containing a rare earth element (Ln) fluoride or an alkaline earth metal fluoride to obtain a dry raw material having a moisture content of 0.3% by mass or less;
A slurry adjusting step of obtaining a slurry by dispersing the dry raw material in an organic solvent;
Using the slurry, gas flame spraying or plasma spraying, a film forming step of forming a film on the surface of the substrate,
A method for manufacturing a component for a plasma etching apparatus, wherein the component for a plasma etching apparatus according to (4) is obtained.

  According to the present invention, there are provided a coated substrate having a plasma sprayed coating on the surface of the substrate having a high plasma resistance, hardly peeled off, excellent in acid resistance, and having a high surface resistance value, a component for a plasma etching apparatus, and a method for producing them. Can be provided.

It is the schematic of the surface of the base material of this invention. It is a schematic sectional drawing which illustrates a plasma spraying apparatus. It is a schematic sectional drawing which illustrates a gas flame spraying apparatus. It is an element distribution map of the surface of the film obtained in the example. It is an optical microscope photograph of the surface of the membrane | film | coat obtained in the Example. It is a cross-sectional SEM image of the film | membrane obtained in the Example. It is another cross-sectional SEM image of the membrane | film | coat obtained in the Example. It is the schematic for demonstrating the tension test to the film | membrane performed in the Example. It is a graph showing the result of the chemical-resistance test performed in the Example. It is another cross-sectional SEM image of the membrane | film | coat obtained in the Example. It is another cross-sectional SEM image of the membrane | film | coat obtained in the Example.

The present invention will be described.
The present invention is a substrate with a coating provided with a coating on the surface of the substrate, the coating having a thickness of 10 to 1000 μm, and containing a rare earth element (Ln) fluoride and an oxide as main components. The surface of the coating is mainly composed of an oxide of rare earth element (Ln), has a monoclinic structure, has a diameter of 10 nm to 1 μm and [α ₁ ], and rare earth element (Ln) fluoride. With a rhombic structure, an orthorhombic structure, and a particulate part [β ₁ ] having a diameter of 10 nm to 1 μm is dispersed in an amorphous matrix mainly containing a rare earth element (Ln) fluoride. Furthermore, when the surface of the film is observed at 200 times using an optical microscope, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area occupied by this spot-like part in the observation field The rate is 0. It is 1-2%, a film with a substrate.
Hereinafter, such a substrate with a film is also referred to as “substrate A of the present invention”.
Moreover, the film | membrane with which the base material A of this invention is provided is also called "the film A."

The present invention is also a substrate with a coating provided with a coating on the surface of the substrate, the coating having a thickness of 10 to 1000 μm, and comprising an alkaline earth metal fluoride and an oxide as main components. And a particulate portion [α ₂ ] having a monoclinic crystal structure, a diameter of 10 nm to 1 μm, and an alkaline earth metal fluoride on the surface of the coating. The main part, an orthorhombic structure, and a particulate part [β ₂ ] having a diameter of 10 nm to 1 μm are dispersed in an amorphous matrix mainly containing an alkaline earth metal fluoride. In addition, when the surface of the film is observed with an optical microscope at 200 times, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio occupied by the spot-like part in the observation field is 0.0 It is 2%, a film with a substrate.
Hereinafter, such a substrate with a film is also referred to as “substrate B of the present invention”.
Moreover, the film | membrane with which the base material B of this invention is provided is also called "film | coat B."

Hereinafter, when simply described as “the substrate of the present invention”, it means both “the substrate A of the present invention” and “the substrate B of the present invention”.
In the following, when the particulate portion [α] is simply described, it means both the particulate portion [α ₁ ] and the particulate portion [α ₂ ]. Similarly, when the particulate part [β] is simply described, it means both the particulate part [β ₁ ] and the particulate part [β ₂ ].

The present invention also includes a drying step of drying a raw material powder containing rare earth element (Ln) fluoride or alkaline earth metal fluoride to obtain a dry raw material having a moisture content of 0.3% by mass or less, A slurry adjusting step of obtaining a slurry by dispersing the dry raw material in an organic solvent, and a film forming step of forming a film on the surface of the substrate by gas flame spraying or plasma spraying using the slurry, and the present invention It is a manufacturing method of the base material with a film | membrane from which the base material A of this invention or the base material B of this invention is obtained.
Hereinafter, such a method for producing a film-coated substrate is also referred to as “the production method of the present invention”.

  The substrate of the present invention is preferably produced by the production method of the present invention.

<Base material of the present invention>
The substrate A of the present invention will be described.
The substrate A of the present invention is a substrate with a coating provided with a coating on the surface of the substrate, and the coating A has a thickness of 10 to 1000 μm and contains a rare earth element (Ln) fluoride and oxide. Contains as the main component.

  The coating A provided in the substrate A of the present invention is formed by gas flame spraying or plasma spraying toward the substrate using a raw material powder of rare earth element (Ln) fluoride or oxyfluoride. Specifically, it may be the same as in the case of the production method of the present invention described in detail later.

The thickness of the film A is 10 to 1000 μm, and preferably 10 to 200 μm. As described above, since the coating A is formed by gas flame spraying or plasma spraying, the thickness is 10 to 1000 μm. However, other methods such as CVD do not usually have such a thickness.
The thickness of the film A means a value measured by an eddy current amplitude sensitive type, an electromagnetic induction type film thickness meter, or a micrometer.

The coating A contains a rare earth element (Ln) fluoride and an oxide as main components.
Here, “main component” means 50% by mass or more. That is, in the coating A, the total content of the rare earth element (Ln) fluoride and the oxide is preferably 50% by mass or more. The total content is more preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more.
In the following description, the term “main component” is used in this sense unless otherwise specified.

The rare earth element (Ln) means scandium (Sc), yttrium (Y), lanthanoid, or actinoid.
The rare earth element (Ln) is preferably at least one selected from the group consisting of samarium (Sm), gadolinium (Gd), dysprosium (Dy), erbium (Er), ytterbium (Yb), and yttrium (Y). Yttrium (Y) is more preferable.

  The film A may contain an oxyfluoride of a rare earth element (Ln).

Oxyfluoride is LnOF, the _{Ln 3 O 2 F 5, Ln} 2 OF 4, LnO 1-X F 1 + 2X, the group consisting of LnO _0.4 F _2.2 and _{LnO 1-X F 1 + 2X} (0 <X <1) It is preferable that at least one selected.

Specific examples of rare earth element (Ln) oxyfluorides include YOF, Y ₃ O ₂ F ₅ , Y ₂ OF ₄ , YO _1-X F _{1 + 2X} , YO _0.4 F _2.2 , YO _1-X F _{1 + 2X} (0 <X <1).

Content of fluoride and oxide of rare earth element (Ln) in coating A is an element constituting the coating using a micro fluorescent X-ray analyzer (for example, Shimadzu Corporation model: XRF-1700). The X-ray diffraction pattern was measured by the θ-2θ method using an X-ray diffractometer (for example, XRD-6000, manufactured by Shimadzu Corporation), and the crystal structure was confirmed. Consider and decide.
From the measurement result by the micro fluorescent X-ray analyzer, the content of the element contained in the film is obtained using the FP method. The FP method uses the physical constants (fundamental parameters) such as mass absorption coefficient, fluorescence yield, and spectrum distribution of the X-ray source to determine the theoretical X-ray intensity from the theoretical formula of the fluorescent X-ray intensity, and the measured X-ray This is a method of calculating the concentration of each component by comparing with the intensity. Measurement with an X-ray diffractometer (for example, XRD-6000 manufactured by Shimadzu Corporation) measures an X-ray diffraction pattern by the θ-2θ method, for example, under the following conditions. It is confirmed by analyzing the X-ray diffraction pattern that the crystal structure and the matrix of the particulate part [α ₁ ] and the particulate part [β ₁ ] existing on the film surface described later are amorphous.
X-ray source: Cu target X-ray source Tube voltage: 40 kV
Tube current: 30 mA
Divergence slit: 1 °
Scattering slit: 1 °
Receiving slit: 0.3mm

As shown in the schematic diagram of FIG. 1, the coating A has a particulate portion [α ₁ ] mainly composed of an oxide of a rare earth element (Ln) on the surface of the coating A (particulate portion [α And a particulate portion [β ₁ ] (indicated in FIG. 1 as a particulate portion [β]) containing a rare earth element (Ln) fluoride as a main component is a rare earth element (Ln) fluoride. It is dispersed in an amorphous matrix containing as a main component.
Here, the particulate portion [α ₁ ] contains a rare earth element (Ln) oxide as a main component, and the oxide has a monoclinic structure. The particulate portion [β ₁ ] contains a rare earth element (Ln) fluoride as a main component, and this fluoride has an orthorhombic structure. Further, the other part (matrix) is amorphous.
Incidentally, the fact that the particulate part [α ₁ ] and the particulate part [β ₁ ] are dispersed in the matrix on the surface of the film A is described later using a transmission electron microscope (TEM). This is confirmed by obtaining an element distribution map as shown in FIG.

Furthermore, the diameters of the particulate part [α ₁ ] and the particulate part [β ₁ ] are both 10 nm to 1 μm, and preferably 50 nm to 200 nm.
Actually, the particulate part [α ₁ ] and the particulate part [β ₁ ] are not strictly circular, but are often elliptical or polygonal. Therefore, the diameters of the particulate portion [α ₁ ] and the particulate portion [β ₁ ] mean an average value calculated after obtaining the longest diameter and the shortest diameter.

The area ratio of the particulate part [α ₁ ] in the observation field is preferably 1 to 30%.
The area ratio of the particulate portion [β ₁ ] in the observation field is preferably 98 to 69%.
The total of the area ratio of the particulate portion [α ₁ ] in the observation field and the area ratio of the particle portion [β ₁ ] in the observation field is preferably 90% or more, and more than 95%. More preferably, it is 98% or more, more preferably 99% or more, and further preferably 99.5% or more.
This area ratio is measured by obtaining an element distribution map and a crystal lattice image using a transmission electron microscope (TEM), processing the image with image processing software such as Image Pro PLUS 3.0 described later. .

  When the film A provided in the substrate A of the present invention is observed at 200 times using an optical microscope, a white spot-like portion having a maximum diameter of 50 to 1000 μm is confirmed. When the elemental analysis and crystal structure of this spot-like part were investigated, there was no significant difference from the other parts. However, as a result of diligent investigations by the inventor, the present inventors have found that a spot-like portion is a starting point of a crack formed in the film, and that if the spot-like part exists more than a certain amount, the film is easily peeled off. When the area ratio in the observation field when the maximum diameter of the spot-like portion is 50 to 1000 μm is observed 200 times using an optical microscope is 0.01 to 2%, It has been found that cracks are hardly formed in the film, and that the film is difficult to peel off from the substrate.

The area ratio occupied by the spot-like portion in the observation visual field is 0.01 to 2%, preferably 0.01 to 1%, and more preferably 0.01 to 0.5%.
If this area ratio is small, cracks are less likely to occur, and the film is more difficult to peel from the substrate.

The base material B of the present invention will be described.
The substrate B of the present invention is a substrate with a coating provided with a coating on the surface of the substrate, and the coating B has a thickness of 10 to 1000 μm, and is mainly composed of an alkaline earth metal fluoride and an oxide. Contains as an ingredient.
The base material B of the present invention is similar to the above-described base material A of the present invention, the difference is the constituent element component of the film, and the rest is the same.
The following description of the base material B of the present invention will be made with respect to differences from the base material A of the present invention.

  As with the base material A of the present invention, the coating B is formed by gas flame spraying or plasma spraying toward the base material using a raw material powder of an alkaline earth metal fluoride or oxyfluoride. . Specifically, it may be the same as in the case of the production method of the present invention described in detail later.

The thickness of the film B is 10 to 1000 μm, preferably 10 to 200 μm, as in the case of the substrate A of the present invention.
The thickness of the film B means a value measured by the same method as that for the film A.

  The coating B contains an alkaline earth metal fluoride and an oxide as main components.

The contents of the alkaline earth metal fluoride and oxide in the film B are the same as in the case of the film A. Similarly, it is confirmed by the θ-2θ method that the crystal structure and the matrix of the particulate part [α ₂ ] and the particulate part [β ₂ ] existing on the film surface are amorphous.

As shown in the schematic diagram of FIG. 1, the coating B provided in the substrate B of the present invention has a particulate portion [α ₂ ] (FIG. 1) containing an alkaline earth metal oxide as a main component on the surface of the coating. In FIG. 1, the particulate portion [α]) and the particulate portion [β ₂ ] (shown as the particulate portion [β] in FIG. 1) containing an alkaline earth metal fluoride as a main component are alkaline earth. It is dispersed in an amorphous matrix mainly composed of a metal fluoride.
Here, the particulate portion [α ₂ ] has an alkaline earth metal oxide as a main component, and the oxide has a monoclinic structure. The particulate portion [β ₂ ] is mainly composed of an alkaline earth metal fluoride, and this fluoride has an orthorhombic structure. Further, the other part (matrix) is amorphous.
Incidentally, the presence of the particulate part [α ₂ ] and the particulate part [β ₂ ] dispersed in the matrix on the surface of the film is the same as in the case of the film A, which is a transmission electron microscope (TEM). Use to confirm.

Furthermore, the diameters of the particulate part [α ₂ ] and the particulate part [β ₂ ] are both 10 nm to 1 μm, and preferably 50 nm to 200 nm.
Actually, the particulate part [α ₂ ] and the particulate part [β ₂ ] are not strictly circular, but are often elliptical or polygonal. Therefore, the diameters of the particulate portion [α ₂ ] and the particulate portion [β ₂ ] mean an average value calculated after obtaining the longest diameter and the shortest diameter.

The area ratio of the particulate part [α ₂ ] in the observation field is preferably 1 to 30%.
The area ratio of the particulate part [β ₂ ] in the observation field is preferably 98 to 69%.
The total of the area ratio of the particulate portion [α ₂ ] in the observation field and the area ratio of the particle portion [β ₂ ] in the observation field is preferably 90% or more, and 95% or more. More preferably, it is 98% or more, more preferably 99% or more, and further preferably 99.5% or more.
This area ratio is measured by the same method as in the case of the coating A described above.

  When the film of the substrate B of the present invention is observed at 200 times using an optical microscope, a white spot-like portion having a maximum diameter of 50 to 1000 μm is confirmed. When the elemental analysis and crystal structure of this spot-like part were investigated, there was no significant difference from the other parts. However, as a result of diligent investigations by the inventor, the present inventors have found that a spot-like portion is a starting point of a crack formed in the film, and that if the spot-like part exists more than a certain amount, the film is easily peeled off. When the area ratio in the observation field when the maximum diameter of the spot-like portion is 50 to 1000 μm is observed 200 times using an optical microscope is 0.01 to 2%, It has been found that cracks are hardly formed in the film, and that the film is difficult to peel off from the substrate.

The area ratio occupied by the spot-like portion in the observation visual field is 0.01 to 2%, preferably 0.01 to 1%, and more preferably 0.01 to 0.5%.
If this area ratio is small, cracks are less likely to occur, and the film is more difficult to peel from the substrate.

  Next, each process with which the manufacturing method of this invention is provided is demonstrated.

<Drying process>
First, the drying process will be described.
In the production method of the present invention, in the drying step, the raw material powder containing the rare earth element (Ln) fluoride or the alkaline earth metal fluoride is dried to obtain a dry raw material having a water content of 0.3% by mass or less. .

The raw material powder will be described.
In the production method of the present invention, when a raw material powder containing a rare earth element (Ln) fluoride is used, the substrate A of the present invention can be obtained. Moreover, in the manufacturing method of this invention, when the raw material powder containing the fluoride of alkaline-earth metal is used, the base material B of this invention can be obtained.

Here, the fluoride of the rare earth element (Ln) is not particularly limited as long as it is a compound composed of the rare earth element (Ln) and fluorine (F). A specific example of the rare earth element (Ln) fluoride is YF ₃ .

  The raw material powder preferably contains 20 mass% or more of a rare earth element (Ln) fluoride. The content is more preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.

In addition to the rare earth element (Ln) fluoride, the raw material powder may contain a rare earth oxyfluoride (a compound containing Ln, O, F, such as YOF) or a rare earth oxide (such as Y ₂ O ₃ ).

  The alkaline earth metal fluoride is not particularly limited as long as it is a compound comprising an alkaline earth metal and fluorine (F).

  The raw material powder preferably contains 20% by mass or more of an alkaline earth metal fluoride. The content is more preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.

  The raw material powder may contain an alkaline earth metal oxyfluoride or an alkaline earth metal oxide in addition to the alkaline earth metal fluoride.

The raw material powder preferably has a particle size of 0.01 to 30 μm, more preferably 0.1 to 15 μm, and further preferably 3 to 8 μm.
The raw material powder preferably has an average particle diameter (median diameter) of 0.01 to 30 μm, and more preferably 0.5 to 3 μm.
Here, the particle diameter of the raw material powder is a value determined by measurement using a conventionally known laser diffraction / scattering particle size distribution measuring apparatus.
The average particle diameter of the raw material powder is a value obtained by measuring an integrated particle size distribution (volume basis) using a conventionally known laser diffraction / scattering particle size distribution measuring apparatus.

  The raw material powder includes particles made of rare earth element (Ln) fluoride, particles made of rare earth element (Ln) oxyfluoride, and particles made of rare earth element (Ln) fluoride and rare earth element (Ln) oxyfluoride. obtain. They may also contain particles that contain impurities.

  The raw material powder may include particles made of an alkaline earth metal fluoride, particles made of an alkaline earth metal oxyfluoride, and particles made of an alkaline earth metal fluoride and an alkaline earth metal oxyfluoride. They may also contain particles that contain impurities.

In the drying step, the raw material powder as described above is dried to obtain a dry raw material having a moisture content of 0.3% by mass or less.
The present inventor has intensively studied, and a specific particulate portion having a specific crystal structure is dispersed in an amorphous matrix, and furthermore, the area of a spot-like portion that appears white when observed using an optical microscope. In order to form such a film, it is found that a film having a specific ratio within a specific range is excellent in plasma resistance and difficult to peel off, and in order to form such a film, an organic solvent containing as little water as possible is used. It has been found that the slurry dispersed in can be formed by gas flame spraying or plasma spraying.

  The moisture content of the raw material powder is preferably 0.2% by mass or less, and more preferably 0.1% by mass or less.

  The method of making the raw material powder have a moisture content in the above range is not particularly limited. For example, the raw material powder is placed in a conventionally known dryer and held for a certain time.

<Slurry adjustment process>
The slurry will be described.
In the slurry adjusting step, the raw material powder as described above is dispersed in an organic solvent to obtain a slurry.

A conventionally well-known thing can be used for an organic solvent, for example, alcohol can be used. Examples of alcohols include ethyl alcohol, methyl alcohol, and kerosene. It is preferable to use ethyl alcohol as the organic solvent.
When an alcohol is used as the organic solvent (preferably a cooled alcohol is used), the temperature of the frame can be lowered by heat of vaporization when the slurry is supplied into the frame and the organic solvent is vaporized. And since it becomes easy to comprise a membrane | film | coat with at least one part of raw material powder being an unmelted state, it can form on the surface of a base material with higher plasma resistance.

The organic solvent preferably has a low water content. As described above, the present inventor has intensively studied, and it is necessary to keep the moisture content of the raw material powder below a certain value. In addition, the purity of the organic solvent is high, that is, the moisture content is low. When it exists, it discovered that the area ratio of the spot-like part in the membrane | film | coat of the base material of this invention obtained by the manufacturing method of this invention became low.
Specifically, the water content contained in the organic solvent is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less.

The raw material powder can be added to such an organic solvent and dispersed by stirring or the like using an ultrasonic transmitter or the like as necessary to obtain a slurry.
It is preferable that the content rate of the raw material powder contained in a slurry is 1-90 mass%, and it is more preferable that it is 10-50 mass%.

<Film formation process>
The film forming process will be described.
In the film forming step of the production method of the present invention, thermal spraying is performed using the slurry to form a film on the surface of the substrate.

  In the film forming step, gas slurry spraying or plasma spraying is performed using the slurry to form a film on the surface of the substrate.

Plasma spraying will be described.
The plasma spraying is preferably performed using, for example, the apparatus shown in FIG.
In FIG. 2, the plasma spraying device 9 has a pair of electrodes of a nozzle-like anode 1 and a cathode 2 arranged at the center thereof. Plasma can be generated by flowing an inert gas (argon, nitrogen, hydrogen, etc.) from the gas introduction part 3 into a donut-shaped gap between the anode and the cathode, and ionizing the gas by arc discharge. The plasma gas is ejected as a plasma jet 5 from the nozzle-like anode 1 to the outside of the plasma spraying apparatus.
The raw material powder is placed on the carrier gas and supplied to the plasma jet 5 through a slurry charging pipe 6 connected in the vicinity of the outlet of the nozzle-like anode 1. The slurry containing the raw material powder supplied to the plasma jet is heated in the plasma to be in a molten state, rides on the plasma jet 5 and is ejected from the anode 1 to the outside, and forms a film 8 on the surface of the substrate 7.

The slurry supply amount is preferably 5 to 100 ml / min, and more preferably 10 to 50 ml / min.
The solid content concentration in the slurry is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, more preferably 15 to 40% by mass, and 20 to 38% by mass. Is more preferable, and it is still more preferable that it is 25-35 mass%.

  Plasma spraying can be performed by a conventionally known method. Moreover, it is preferable to form a film made of the raw material powder on the surface of the base material by plasma spraying under processing conditions for completely melting the raw material powder.

  The plasma spraying is preferably performed at a plasma temperature of 10,000 degrees or higher, and more preferably at 15,000 degrees or higher. This is because a film having better plasma resistance can be formed.

  The plasma spraying is preferably performed under a processing condition in which the speed at which the raw material powder is sprayed onto the substrate is 200 m / s or less. This is because a film having better plasma resistance can be formed.

Gas flame spraying will be described.
As a thermal spraying apparatus that performs gas flame spraying, for example, the gas flame spraying apparatus shown in FIG. 3 can be used.
In FIG. 3, a thermal spraying apparatus 10 has a combustion chamber 12 therein, an oxygen flow path 14 for supplying an oxygen-containing gas to the combustion chamber 12, a main fuel flow path 16 for supplying main fuel, and these And a burner 18 for igniting a mixture of oxygen-containing gas and main fuel. In addition, a hole (gun nozzle 20) for ejecting the frame is formed in the combustion chamber 12 on the side facing the burner 18, and a cylindrical tip tube 22 having a hole in the center on the outside of the gun nozzle 20. Is installed, and the frame can be ejected outward from the holes of the gun nozzle 20 and the tip tube 22. The speed of the frame can be adjusted by adjusting the size of the hole in the tip tube 22.

  A slurry supply channel 24 is formed in the distal end tube 22, and the slurry is supplied from here into the frame. Further, an auxiliary fuel supply channel 26 is further formed in the distal end tube 22, from which auxiliary fuel can be supplied to the frame.

  A compressed air supply passage 28 is formed in the gun nozzle 20, and the compressed air supplied therefrom is supplied so as to flow along the inner side surface of the hole formed in the tip tube 22. As a result, the slurry supplied from the slurry supply channel 24 is configured not to adhere to the inner side surface of the hole of the tip tube 22.

  When the thermal spraying apparatus shown in FIG. 3 is used, the film formation step can be performed by gas flame spraying as follows.

  The oxygen-containing gas and the main fuel are supplied from the oxygen channel 14 and the main fuel channel 16 in the thermal spraying apparatus 10 shown in FIG.

  Here, the oxygen-containing gas may be a gas containing oxygen, for example, air, or a gas in which oxygen and air are mixed. The oxygen-containing gas is preferably oxygen.

  The oxygen-containing gas is preferably supplied at a pressure of 10 to 300 psi.

  The oxygen-containing gas is preferably supplied at a flow rate of 100 to 1500 L / min, more preferably 200 to 1000 L / min, and even more preferably 350 to 600 L / min.

  The main fuel is preferably supplied at a pressure of 10 to 300 psi.

  The main fuel is preferably supplied at a flow rate of 50 to 600 ml / min, more preferably 100 to 300 ml / min, and even more preferably 140 to 220 ml / min.

  Here, kerosene, acetylene, propylene, propane, ethylene, natural gas, or the like can be used as the main fuel. Among these, the main fuel is preferably kerosene.

The mixing ratio of the oxygen-containing gas and the main fuel is not particularly limited, but is preferably a mixing ratio at which the main fuel is incompletely burned. When incompletely combusted, the flame temperature is lowered by the heat of vaporization when some of the main fuel that has not combusted and the organic solvent (alcohols, etc.) in the slurry is vaporized. This is because it becomes easier to form a film with a part of the film unchanged, and it becomes easier to produce a film-coated substrate having a film with higher plasma resistance on the surface of the substrate.
It should be noted that here, only the mixing ratio of the oxygen-containing gas and the main fuel is adjusted so that the main fuel is incompletely burned without considering the auxiliary fuel and oxygen that can be contained in the slurry and compressed air. Is preferred.

In this way, the oxygen-containing gas and the main fuel are supplied to the combustion chamber and mixed, and the resulting mixture is ignited to generate a flame. Then, the slurry is supplied into the frame.
Here, it is preferable that the slurry is mixed with gas and then introduced into the frame. The gas is preferably air.

The slurry supply amount is preferably 20 to 100 ml / min, and more preferably 30 to 70 ml / min.
The solid content concentration in the slurry is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, more preferably 15 to 40% by mass, and 20 to 38% by mass. Is more preferable, and it is still more preferable that it is 25-35 mass%.

Compressed air may not be used, but when used, the compressed air pressure is preferably supplied as 0.05 to 1.5 MPa, more preferably 0.3 to 0.8 MPa. The compressed air is preferably supplied at a flow rate of 250 to 2000 L / min, and more preferably 400 to 800 L / min.
In some cases, uncompressed gas (for example, air) can be used instead of compressed air.

In the film forming step, it is preferable to use an auxiliary fuel. Auxiliary fuel can be used to adjust the temperature of the frame.
When the auxiliary fuel is supplied to the frame, the temperature of the frame can be lowered by the heat of vaporization when the auxiliary fuel is supplied into the frame and vaporized. In this case, it is preferable because at least a part of the raw material powder can easily form a film in an unmelted state.

  As the auxiliary fuel, acetylene, methane, ethane, butane, propane, and propylene can be used.

The auxiliary fuel is preferably supplied at a pressure of 0.05 to 1.0 MPa.
The auxiliary fuel is preferably supplied at a flow rate of 5 to 100 L / min, more preferably 10 to 30 L / min.

  When using the thermal spraying apparatus 10 shown in FIG. 3, it is preferable that the distance from the front-end | tip of the front-end | tip cylinder 22 to the main surface of a base material shall be 10-250 mm, and it is more preferable to set it as 70-150 mm.

The substrate will be described.
The substrate is not particularly limited, and examples thereof include aluminum, stainless steel, glass (such as quartz glass and non-alkali glass), ceramic (such as a sintered body made of Y ₂ O ₃ , AlN, Al ₂ O ₃ , etc.), carbon, and the like. .

  Although the magnitude | size and shape of a base material are not specifically limited, It is preferable that it is a plate-shaped thing. In the manufacturing method of this invention, it is preferable to form a film | membrane on the main surface of such a plate-shaped base material (it is also called a board | substrate).

  In the film formation step, it is preferable to perform gas flame spraying under the processing conditions for adjusting the organic solvent and the auxiliary fuel, adjusting the amount and the like, and forming the film while at least a part of the raw material powder is in an unmelted state.

  A film can be formed on the surface of the substrate by such a film forming process.

  The base material of the present invention can be obtained by such a production method of the present invention.

  The film in the substrate with a film of the present invention has high plasma resistance, is hardly peeled off, has excellent acid resistance, and has a high surface resistance value.

  Here, the plasma resistance is not particularly limited in kind, and examples thereof include atmospheric pressure plasma, inductively coupled plasma, capacitively coupled plasma, magnetic field plasma, high frequency plasma, and thermal plasma. Moreover, when the porosity of the film is low, the plasma resistance is high. Specifically, the porosity of the film is preferably 10% or less.

  Thus, since a base material with a film has high plasma resistance, it can be used for a member exposed to a plasma atmosphere. That is, it can be used as a component for a plasma etching apparatus. For example, members, such as a semiconductor manufacturing apparatus, a flat panel display manufacturing apparatus, or a solar cell panel manufacturing apparatus, are mentioned. The substrate with a film of the present invention is preferably used for a semiconductor manufacturing apparatus member. Examples of the semiconductor manufacturing apparatus member include a member exposed to a plasma atmosphere in an ion implantation apparatus, an epitaxial growth apparatus, a CVD apparatus, a vacuum deposition apparatus, an etching apparatus, a sputtering apparatus, an ashing apparatus, and the like. For example, chamber, bell jar, susceptor, clamp ring, focus ring, shadow ring, insulating ring, dummy wafer, tube for generating plasma, dome for generating plasma, transmission window, infrared transmission window, monitoring Examples thereof include a window, a lift pin for supporting a semiconductor wafer, a shower plate, a baffle plate, a bellows cover, an upper electrode, a lower electrode, and an electrostatic chuck.

<Experiment 1>
An aluminum substrate having a thickness of 3 mm was prepared, and gas flame spraying was performed on the main surface of the substrate using YF ₃ particles as a raw material powder to form a film having a thickness of 60 μm.

Here, the YF ₃ particles had an average particle size (D ₅₀ ) of 5.3 μm, and as a result of composition analysis (ICP analysis), 99% by mass or more was considered to be composed of YF ₃ . The balance (less than 1% by mass) was considered to be YOF, Y ₂ O ₃ or the like.

YF ₃ particles were dried at 80 ° C. for 3 hours using a dryer, and then dispersed in alcohol (manufactured by Nippon Alcohol Sales Co., Ltd., moisture content = 0.2% by mass or less) to form a slurry. .
In addition, as a result of conducting a preliminary experiment, it was found that if it was dried at 80 ° C. for 3 hours, it was almost completely dry.

  There are four processing conditions (conditions 1 to 4) shown in Table 1 in the gas flame spraying. The gas flame spraying apparatus shown in FIG. 3 was used.

  The physical properties and the like of each of the thus-coated substrates were measured. Hereinafter, the substrate with a coating obtained under Condition 1 is also referred to as “substrate 1 with a coating”. The coated substrate obtained under the conditions 2, 3 and 4 is also referred to as “coated substrate 2”, “coated substrate 3”, and “coated substrate 4”.

<Coating composition analysis>
About each of the board | substrates 1-4 with a film | membrane, the density | concentration of the element which comprises a film | membrane was measured using the micro part fluorescence X-ray-analysis apparatus (Shimadzu Corporation make, model: XRF-1700). And the content of the element contained in a membrane | film | coat was calculated | required using the FP method from the measurement result by a micro fluorescence X-ray analyzer. The FP method uses the physical constants (fundamental parameters) such as mass absorption coefficient, fluorescence yield, and spectrum distribution of the X-ray source to determine the theoretical X-ray intensity from the theoretical formula of the fluorescent X-ray intensity, and the measured X-ray This is a method of calculating the concentration of each component by comparing with the intensity.
The results are shown in Table 2.

From the results in Table ₂ , it is estimated that any of the coatings of the coated substrates 1 to 4 is a mixture of yttrium fluoride (YF ₃ ), oxyfluoride (YOF), and oxide (Y ₂ O ₃ ). Is done.

<Crystal structure analysis of particles constituting the film>
About each film | membrane of the board | substrates 1-4 with a film | membrane, the crystal structure was analyzed using the X-ray-diffraction apparatus (The Shimadzu Corporation make, XRD-6000). The measurement method was performed using the θ-2θ method under the following conditions. The θ-2θ method is a method of scanning while moving the detector unit 2θ when the X-ray source is fixed and the sample stage is moved by θ.
X-ray source: Cu target X-ray source Tube voltage: 40 kV
Tube current: 30 mA
Divergence slit: 1 °
Scattering slit: 1 °
Receiving slit: 0.3mm

As a result, peaks indicating the presence of each of Y ₂ O ₃ (cubic and monoclinic), YF ₃ and YOF were confirmed. However, in some cases, the peak was not clear, and the film was thought to contain many amorphous parts.

<TEM observation>
The surfaces of the coated substrates 1 to 4 were analyzed using a transmission electron microscope (TEM). Specifically, first, the surfaces of the substrates 1 to 4 with a film were mechanically polished to a film thickness of about 40 μm, and then the final thin film was formed by an ion milling method (2.0 to 5.5 keV). . Then, the surface of the film was analyzed by TEM (FEI Tecnai Osiris) with an acceleration voltage of 200 kV, a scanning transmission electron microscope (STEM) mode, and EDS. Further, an electron beam diffraction method was used for confirming the crystal structure, and a bright field image and a lattice image (not shown) were also used for confirming the size of the particulate portion.
The element distribution map on the surface of the obtained film is shown in FIG.
As shown in FIG. 4, on the surface of the film, in a YF ₃ amorphous matrix, a particulate portion (particulate portion [α]) composed of Y ₂ O ₃ and a particulate portion composed of YF ₃ ( It was confirmed that the particulate portion [β]) was present in a dispersed state. Further, it was confirmed that the particulate part [α] had a monoclinic structure and had a diameter of about 100 nm. It was also confirmed that the particulate part [β] had an orthorhombic structure and a diameter of about 100 nm.

<Surface observation with an optical microscope>
The surface of the film-coated substrate 1 was observed at a magnification of 50 times using an optical microscope (manufactured by Keyence Corporation, model: VHX-5000). A photograph is shown in FIG.
As shown in FIG. 5, a white spot-like portion was confirmed. Moreover, the spot-like part was substantially circular.
The area ratio occupied by the spot-like portion in the observation visual field was 1.8%.

<Form 1 of coating surface>
About each of the board | substrates 1-4 with a film | membrane, the SEM image of the film | membrane surface was image | photographed using the scanning electron microscope (The JEOL Co., Ltd. make, model: JSM-5600LV). The magnification was set to 100 times, and the automatic adjustment mechanism of the apparatus was used to adjust the contrast and brightness during shooting.
As a result, the surface was smooth and free from irregularities. Depending on the conditions, minute aggregates (projections having the same quality as the film) of about several tens to several hundreds of μm may be slightly observed.

<Form 2 of coating surface>
About each of the board | substrates 1-4 with a film | membrane, the SEM image of the film | membrane surface was image | photographed using the scanning electron microscope (The JEOL Co., Ltd. make, model: JSM-5600LV). The magnification was 5000 times, and the contrast and brightness were adjusted using the automatic adjustment mechanism of the apparatus.
As a representative example, an SEM image of the film surface of the film-coated substrate 2 is shown in FIG. There are no cracks on the surface of the film shown in FIG. In the case of other conditions, a minute crack of about 3 μm was sometimes observed, but no longer crack was present.

<Porosity of film cross section>
Each of the coated substrates 1 to 4 was embedded in a two-component curable epoxy resin, and after obtaining an observation surface by polishing with an automatic polishing machine (Buhler, model: ECOMET3 and AUTOMET2), a scanning electron microscope ( An SEM image of the cross section of the film was taken using JEOL Ltd., model: JSM-5600LV). The magnification was 5000 times, and the contrast and brightness were adjusted using the automatic adjustment mechanism of the apparatus.
As a typical example, an SEM image of a cross section of the film-coated substrate 2 is shown in FIG. There are almost no pores in the cross section of the coating shown in FIG. In addition, the pores of the film were very few under other conditions.

Next, the binarization process was performed about the SEM image of the board | substrate 2 with a film | membrane, and the board | substrate 4 with a film | membrane using MEDIA CYBERNETICS, Image Pro PLUS3.0. From the image after this image processing, the pore area per visual field area, that is, the pore area / visual field area × 100, was calculated and obtained as the porosity (%).
As a result, the porosity of the coated substrate 2 and the coated substrate 4 was extremely low, 3.9% and 8.7%, respectively.

<Measurement of film strength>
About the board | substrate 2 with a film | membrane, the film | membrane surface was grind | polished and Ra was set to less than 1.5.
Next, the cylindrical jig | tool was adhere | attached on the film | membrane surface using the adhesive agent, and it hold | maintained for 60 minutes in the drying furnace set to 150 degreeC. And as shown in FIG. 8, it set to the box-shaped jig | tool, and the force required in order to peel off a cylindrical jig | tool was measured by pulling a cylindrical jig | tool down.
For comparison, a substrate with a film was prepared using the Y ₂ O ₃ raw material powder under the same conditions as Condition 3, and the same test was performed to measure the strength of the film.
As a result, the force required to peel off the film on the substrate 2 with a film was 71 MPa. On the other hand, in the case of the substrate with a film using Y ₂ O ₃ raw material powder, it was 43 MPa. Thus, it turned out that the board | substrate with a film | membrane applicable to this invention has very high intensity | strength (tensile strength) of a film | membrane.

<Evaluation of chemical resistance>
The substrate 2 with a film was cured so that only the film was exposed, and it was immersed in an aqueous hydrochloric acid solution of about 10% by volume, and the degree of dissolution of the film was measured.
For comparison, a substrate with a film was prepared using the Y ₂ O ₃ raw material powder under the same conditions as Condition 3, and the same test was performed. The results are shown in FIG.
Further, a similar test was performed using about 10% by volume of nitric acid aqueous solution, and the same results as in FIG. 9 were obtained.
From this, it was found that the film obtained by the present invention has extremely high resistance to hydrochloric acid and nitric acid.

<Evaluation of plasma resistance>
The coated substrate 2 was exposed to ICP plasma, and the plasma resistance was evaluated. This will be specifically described below.

Plasma exposure was performed using an ICP etching apparatus (EIS-700SI manufactured by Elionix Co., Ltd.).
The plasma conditions are as follows.
・ Plasma gas O ₂ , CF ₄ , SF ₆
・ Gas ratio O _{2 3} standard cc / min (sccm), CF ₄ 30 sccm, SF ₆ 5 sccm
・ Gas pressure 0.6-0.7Pa (Slight fluctuations are observed)
・ Plasma power 800W (reflection is 0W)
・ Bias voltage: 55 to 63V (80% of the maximum value of the device is set)
-Plasma exposure cycle 20 min exposure-10 min rest for 16 cycles for a total of 8 hours Here, a mask for leaving an unexposed portion was made using an aluminum material, and the surface was black anodized.

  About the film | membrane after giving the above ICP plasma exposure, the surface shape was measured using the laser displacement meter.

For comparison, a substrate with a film was prepared using the Y ₂ O ₃ raw material powder under the same conditions as Condition 3, and the same test was performed.
Furthermore, for the sake of comparison, a similar test was performed on a sintered body made of YOF.

As a result, the reduced film thickness of the film-coated substrate 2 was almost zero. On the other hand, in the case of a substrate with a film using Y ₂ O ₃ raw material powder, the reduced film thickness of the film was about 0.7 μm. Further, the reduced film thickness of the sintered body made of YOF was about 0.3 μm.
Thus, it was found that the coated substrate corresponding to the present invention has extremely high plasma resistance.

<Resistance value>
About each of the board | substrates 1-4 with a film | membrane, the surface resistance value (2 terminal method) was measured. For comparison, a substrate with a coating made of Y ₂ O ₃ obtained by a general plasma spraying method and not included in the technical scope of the present invention was obtained, and the surface resistance value was similarly measured. .
As a result, in the case of the substrates 1 to 4 with the film, it was found that the surface resistance value was extremely high as compared with the film made of Y ₂ O ₃ .

<Experiment 2>
An aluminum substrate having a thickness of 3 mm was prepared, and plasma spraying was performed on the main surface of the substrate using YF ₃ particles as a raw material powder to form a film having a thickness of 60 μm.

Here, the same YF ₃ particles as those used in Experiment 1 were used.
Further, as in Experiment 1, YF ₃ particles were dried using a dryer and then dispersed in alcohol to form a slurry.

  Plasma spraying was performed using a plasma spraying apparatus (Sulzer Metco, plasma spray gun # 9MB). There are two processing conditions shown in Table 3.

  The physical properties and the like of each of the thus-coated substrates were measured. Hereinafter, the obtained coated substrate is also referred to as “coated substrate 21” and “coated substrate 22”.

<Coating composition analysis>
For the coated substrate 21 and the coated substrate 22, as in Experiment 1, the concentration of elements constituting the coating was measured using a microscopic fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, model: XRF-1700). Then, the content of the element contained in the film was determined from the measurement result by the micro fluorescent X-ray analyzer using the FP method.
As a result, the coated substrate 21 and the coated substrate 22 are estimated to be a mixture of yttrium fluoride (YF ₃ ), oxyfluoride (YOF), and oxide (Y ₂ O ₃ ).

<Crystal structure analysis of particles constituting the film>
About the film | membrane of the board | substrate 21 with a film | membrane and the board | substrate 22 with a film | membrane, similarly to Experiment 1, the crystal structure was analyzed using the X-ray-diffraction apparatus (The Shimadzu Corporation make, XRD-6000). The measurement method was the same as in Experiment 1.

As a result, peaks indicating the presence of each of Y ₂ O ₃ (cubic and monoclinic), YF ₃ and YOF were confirmed. However, in some cases, the peak was not clear, and the film was estimated to contain many amorphous parts.

<TEM observation>
The surfaces of the coated substrate 21 and the coated substrate 22 were analyzed using a transmission electron microscope (TEM). Specifically, first, the surfaces of the coated substrate 21 and the coated substrate 22 are mechanically polished to a coating thickness of about 40 μm, and then the final thin film is formed by an ion milling method (2.0 to 5.5 keV). Made. And the film | membrane surface was analyzed using TEM on the conditions similar to the case of the experiment 1. FIG.
As a result, on the surface of the film, in the amorphous matrix of YF ₃ , a particulate portion composed of Y ₂ O ₃ (particulate portion [α ₁ ]) and a particulate portion composed of YF ₃ (particulate portion [particulate portion [ It was confirmed that β ₁ ]) was present in a dispersed manner. Further, it was confirmed that the particulate portion [α ₁ ] had a monoclinic structure and had a diameter of about 100 nm. It was also confirmed that the particulate part [β ₁ ] had an orthorhombic structure and a diameter of about 100 nm.

<Surface observation with an optical microscope>
Using the same optical microscope as in Experiment 1, the surface of the coated substrate 21 was observed at a magnification of 200 times.
As a result, a white spot-like portion was confirmed. Moreover, the spot-like part was substantially circular.
The area ratio occupied by the spot-like portion in the observation visual field was 1.5%.

<Form 1 of coating surface>
About the board | substrate 21 with a film | membrane, it carried out similarly to the case of Experiment 1, and image | photographed the SEM image of the film | membrane surface using the scanning electron microscope (The JEOL Co., Ltd. make, model: JSM-5600LV). The magnification was set to 100 times, and the automatic adjustment mechanism of the apparatus was used to adjust the contrast and brightness during shooting.
As a result, the surface was smooth and free from irregularities.

<Form 2 of coating surface>
About the board | substrate 21 with a film | membrane, and the base material 22 with a film | membrane, the case of the experiment 1 WHEREIN: The SEM image of the film | membrane surface was image | photographed using the scanning electron microscope (The JEOL Co., Ltd. make, model: JSM-5600LV). The magnification was set to 2000 times, and the automatic adjustment mechanism of the apparatus was used to adjust the contrast and brightness during shooting.
FIG. 10 shows an SEM image of the film surface of the substrate 21 with film, and FIG. 11 shows an SEM image of the film surface of the substrate 22 with film. In any case, no crack was present on the surface of the film.

<Porosity of film cross section>
About the board | substrate 21 with a film | membrane, after embedding in a 2 liquid-curing type epoxy resin like the case of experiment 1, and obtaining an observation surface by grinding | polishing with an automatic grinder (Buhler company make, ECOMET3 and AUTOMET2), An SEM image of the cross section of the film was taken using a scanning electron microscope (manufactured by JEOL Ltd., model: JSM-5600LV). The magnification was 5000 times, and the contrast and brightness were adjusted using the automatic adjustment mechanism of the apparatus.
As a result, there were almost no pores in the film cross section.

Next, the SEM image of the coated substrate 21 was binarized using MEDIA CYBERNETICS, Image Pro PLUS 3.0. From the image after this image processing, the pore area per visual field area, that is, the pore area / visual field area × 100, was calculated and obtained as the porosity (%).
As a result, the porosity of the coated substrate 21 was extremely low, about 1 to 5%.

<Measurement of film strength>
The film strength was measured in the same manner as in Experiment 1.
That is, for the substrate 21 with a film, the surface of the film is polished, Ra is set to less than 1.5, a cylindrical jig is bonded to the surface of the film using an adhesive, and then dried, as shown in FIG. The force required to set the jig and peel the cylindrical jig was measured.
For comparison, a coated substrate was prepared using the Y ₂ O ₃ raw material powder under the same conditions as when the coated substrate 21 was formed, and the strength of the coating was measured by performing the same test.
As a result, the force required to peel off the coating on the substrate with coating 21 was 71 MPa. On the other hand, in the case of the substrate with a film using Y ₂ O ₃ raw material powder, it was 43 MPa. Thus, it turned out that the board | substrate with a film | membrane applicable to this invention has very high intensity | strength (tensile strength) of a film | membrane.

<Evaluation of chemical resistance>
The chemical resistance was evaluated in the same manner as in Experiment 1. That is, the film-coated substrate 21 was cured so that only the film was exposed, and was immersed in an aqueous hydrochloric acid solution of about 10% by volume, and the degree of dissolution of the film was measured. Further, using the Y ₂ O ₃ raw material powder for comparison, to create a film with the substrate under the same conditions as when forming a film substrate with 30, by performing the same test, a similar test was carried out .
Furthermore, the same test was also performed using about 10 volume% nitric acid aqueous solution.
As a result, similar to the case of Experiment 1, it was found that the film of the substrate with film 21 has extremely high resistance to hydrochloric acid and nitric acid.

<Evaluation of plasma resistance>
About the board | substrate 21 with a film | membrane, similarly to the case of Experiment 1, ICP plasma exposure was performed and the plasma tolerance was evaluated. For comparison, a substrate with a film was prepared using the Y ₂ O ₃ raw material powder under the same conditions as when the substrate 3 with a film was formed, and the same test was performed.

As a result, the reduced film thickness of the coated substrate 21 was almost zero. On the other hand, in the case of a general film-coated substrate using Y ₂ O ₃ raw material powder, the reduced film thickness of the film was about 0.7 μm.
Thus, it was found that the coated substrate corresponding to the present invention has extremely high plasma resistance.

<Resistance value>
About the board | substrate 21 with a film | membrane, it carried out similarly to the case of Experiment 1, and measured the surface resistance value (2 terminal method). For comparison, a substrate with a coating made of Y ₂ O ₃ obtained by a general plasma spraying method and not included in the technical scope of the present invention was obtained, and the surface resistance value was similarly measured. .
As a result, in the case of the substrate 30 with a film, it was found that the surface resistance value was extremely high as compared with the film made of Y ₂ O ₃ .

DESCRIPTION OF SYMBOLS 1 Anode 2 Cathode 3 Gas introduction part 5 Plasma jet 6 Powder injection pipe 7 Brittle base material 8 First coating 9 Plasma spraying device 10 Gas flame spraying device 12 Combustion chamber 14 Oxygen flow channel 16 Fuel flow channel 18 Burner 20 Gun nozzle 22 Tip tube 24 Slurry supply channel 26 Auxiliary fuel supply channel 28 Compressed air supply channel

Claims (6)

A substrate with a coating provided with a coating on the surface of the substrate,
The film has a thickness of 10 to 1000 μm, and includes a rare earth element (Ln) fluoride and an oxide as main components,
On the surface of the film, a particulate portion [α ₁ ] having a monoclinic structure, a diameter of 10 nm to 1 μm, and a rare earth element (Ln) fluoride, mainly composed of an oxide of rare earth element (Ln). The main component, an orthorhombic crystal structure, and a particulate portion [β ₁ ] having a diameter of 10 nm to 1 μm are dispersed in an amorphous matrix mainly containing a rare earth element (Ln) fluoride. The area ratio of the particulate part [α ₁ ] in the observation field is 1 to 30%, and the area ratio of the particulate part [β ₁ ] in the observation field is 98 to 69%. ,
Further, when the surface of the film is observed at 200 times using an optical microscope, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio of the spot-like part in the observation visual field is 0.00. The base material with a film | membrane which is 01 to 2%.   The substrate with a coating according to claim 1, wherein the rare earth element (Ln) is yttrium (Y). A substrate with a coating provided with a coating on the surface of the substrate,
The film has a thickness of 10 to 1000 μm, and contains an alkaline earth metal fluoride and an oxide as main components,
On the surface of the film, the main component is an alkaline earth metal oxide, a monoclinic structure, a particulate portion [α ₂ ] having a diameter of 10 nm to 1 μm, and an alkaline earth metal fluoride. And a particulate portion [β ₂ ] having an orthorhombic structure and having a diameter of 10 nm to 1 μm is dispersed in an amorphous matrix mainly composed of an alkaline earth metal fluoride, The area ratio of the particulate portion [α ₂ ] in the observation field is 1 to 30%, and the area ratio of the particulate portion [β ₂ ] in the observation field is 98 to 69%,
Further, when the surface of the film is observed at 200 times using an optical microscope, a white spot-like part having a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio of the spot-like part in the observation visual field is 0.00. The base material with a film | membrane which is 01 to 2%.   The component for plasma etching apparatuses containing the base material with a film | membrane in any one of Claims 1-3. Drying a raw material powder containing a rare earth element (Ln) fluoride or an alkaline earth metal fluoride to obtain a dry raw material having a moisture content of 0.3% by mass or less;
A slurry adjustment step of obtaining a slurry by dispersing the dry raw material in an organic solvent with a moisture content of 0.3% by mass or less ;
Using the slurry, gas flame spraying or plasma spraying, a film forming step of forming a film on the surface of the substrate,
The manufacturing method of the base material with a film | membrane in which the base material with a film | membrane in any one of Claims 1-3 is obtained. Drying a raw material powder containing a rare earth element (Ln) fluoride or an alkaline earth metal fluoride to obtain a dry raw material having a moisture content of 0.3% by mass or less;
A slurry adjustment step of obtaining a slurry by dispersing the dry raw material in an organic solvent with a moisture content of 0.3% by mass or less ;
Using the slurry, gas flame spraying or plasma spraying, a film forming step of forming a film on the surface of the substrate,
A method for manufacturing a component for a plasma etching apparatus, wherein the component for a plasma etching apparatus according to claim 4 is obtained.