TWI750156B - Substrate with film, parts for plasma etching device and manufacturing method thereof - Google Patents

Abstract

The substrate with a coating provided by the present invention is provided with a thermal spray coating on the surface of the substrate with high plasma resistance, not easy to peel off, excellent acid resistance, and high surface resistance.

The film-attached substrate of the present invention is provided with a film on the surface of the substrate; wherein the film has a thickness of 10 to 1000 μm, and contains fluorides and oxides of rare earth elements (Ln) as main components; in the surface of the film , the main component is an oxide of a rare earth element (Ln), a particulate part [α] having a monoclinic structure and a specific diameter, and a fluoride of a rare earth element (Ln) as the main component, having an orthorhombic structure and Particulate parts [β] of a specific diameter are dispersed in an amorphous matrix whose main component is a fluoride of a rare earth element (Ln). Furthermore, the surface of the above-mentioned film is observed with an optical microscope. The white spot-like portion has a low area ratio in the observation field.

Description

Substrate with coating, parts for plasma etching apparatus, and methods for producing the same

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

The thermal spray method is a method of blowing raw material powder heated to a molten state against the surface of a substrate to form a film, and can be used in various fields requiring heat resistance, corrosion resistance, abrasion resistance, and the like. In particular, in the components (parts for plasma etching equipment) provided in plasma processing apparatuses used in the fields of semiconductor and liquid crystal production, in order to prevent loss due to plasma, a thermal spray coating with excellent plasma resistance is required. .

In addition, the thermal spray coating excellent in plasma resistance has been conventionally proposed: a coating formed when at least a part of the raw material powder is not melted at the time of thermal spraying.

For example, a component for a semiconductor manufacturing apparatus described in Patent Document 1 includes a component body and a spray coating formed on the surface of the component body by thermal spraying of oxide particles; wherein the oxide in the spray coating is At least a portion of the particles remain unmelted.

Furthermore, a component for a semiconductor manufacturing apparatus described in Patent Document 2 includes a component body, and a thermal spray coating formed on the surface of the component body by thermal spraying of nitride particles used as raw material powders; wherein, The above-mentioned thermal spray coating is formed by accumulating 90% or more of the powder particles of the nitride in an unmelted state.

In addition, Patent Documents 1 and 2 both describe that the plasma resistance of the components can be improved by applying the above-mentioned oxide spray coating and nitride spray coating to the components for semiconductor manufacturing apparatuses.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-108178

[Patent Document 2] International Publication No. 2010/027073

However, according to the above-mentioned conventional method, it is difficult to obtain a thermal spray coating having sufficiently excellent plasma resistance.

Furthermore, in addition to being excellent in plasma resistance, it is preferable that the film is not easily peeled off. Moreover, it is preferable that the resistance to an acid is high and a surface resistance value is high according to a use. For example, when there is a semiconductor manufacturing apparatus in which a film is formed, the surface of the film may be washed with an acid, and the surface resistance value is expected to be high.

The object of the present invention is to provide a base material with a film attached on the surface of the base material, which is provided with a spray film with high plasma resistance, not easy to peel off, excellent in acid resistance, and high surface resistance value, parts for plasma etching equipment, and the like Production method.

In order to solve the above-mentioned problems, the present inventors have intensively studied and found that specific particle-like parts having a specific crystal structure are dispersed in an amorphous matrix, and the area ratio of the white spot parts is found to be within a specific range by observation with an optical microscope. The film is excellent in plasma resistance and the like, and is not easily peeled off. In addition, in order to form such a film, it has been found that the slurry can be formed by applying gas flame spraying or plasma spraying by dispersing a raw material with very little moisture content in an organic solvent with no moisture content as much as possible.

The present invention is as follows (1) to (6).

(1) A film-attached substrate, which is provided with a film on the surface of the substrate, wherein the film has a thickness of 10 to 1000 μm and contains fluorides and oxides of rare earth elements (Ln) as main components; Oxides of rare earth elements (Ln) with a monoclinic structure and a particle portion [α ₁ ] with a diameter of 10 nm to 1 μm, and fluorides of rare earth elements (Ln) as main components, with an orthorhombic structure _{, Particulate parts [β 1} ] with a diameter of 10 nm to 1 μm are dispersed in an amorphous matrix mainly composed of fluorides of rare earth elements (Ln); When observed at a magnification of 200, a white spot-like portion with a maximum diameter of 50 to 1000 μm was confirmed, and the area ratio of the spot-like portion in the observation field was 0.01 to 2%.

(2) The film-attached substrate according to the above (1), wherein the rare earth element (Ln) is yttrium (Y).

(3) A film-attached base material, which is provided with a film on the surface of the base material, wherein the film has a thickness of 10-1000 μm and contains fluorides and oxides of alkaline earth metals as main components; on the surface of the film, the main components are: Alkaline-earth metal oxide, monoclinic structure, particle-shaped portion [α ₂ ] with diameter of 10 nm to 1 μm, and fluoride of alkaline earth metal as main component, with orthorhombic structure, particle-shaped portion of 10 nm to 1 μm in diameter The part [β ₂ ] is dispersed in an amorphous matrix with fluorides of alkaline earth metals as the main component; and the surface of the above-mentioned film is observed with an optical microscope at a magnification of 200 times, and a maximum diameter of 50~ 1000μm white spot-like part, the area ratio of the spot-like part in the observation field is 0.01~2%.

(4) A component for a plasma etching apparatus, comprising the film-attached substrate according to any one of the above (1) to (3).

(5) A method for producing a base material with a film, comprising: drying a raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal to obtain a dry material having a moisture content of 0.3 mass % or less The drying step of the raw material; the slurry preparation step of dispersing the above-mentioned dried raw material in an organic solvent to obtain a slurry; and using the above-mentioned slurry to perform gas flame spraying or plasma spraying to form a film on the surface of the substrate. Forming step: According to this, the base material with the coating described in any one of the above (1) to (3) is obtained.

(6) A method for manufacturing a part for a plasma etching device, comprising: A drying step of drying raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal to obtain a dry raw material having a moisture content of 0.3% by mass or less; dispersing the above dry raw material in an organic solvent to obtain a slurry The slurry preparation step of the material; and the film forming step of forming a film on the surface of the substrate by performing gas flame spraying or plasma spraying using the above slurry; accordingly, the plasma etching apparatus described in the above (4) is obtained. with parts.

According to the present invention, it is possible to provide a base material with a coating film provided on the surface of the base material with a thermal spray coating with high plasma resistance, resistance to peeling, excellent acid resistance, and high surface resistance, parts for plasma etching apparatus, and the like. manufacturing method.

1: Anode

2: Cathode

3: Gas introduction part

5: Plasma Jet

6: Powder input tube

7: Brittle substrates

8: The first film

9: Plasma spray device

10: Gas flame spray device

12: Combustion chamber

14: Oxygen flow path

16: Fuel flow path

18: Burner

20: Spray gun head

22: Front barrel

24: Slurry supply flow path

26: Auxiliary fuel supply flow path

28: Compressed air supply flow path

31: Matrix (amorphous)

32: Particulate part [α] (monoclinic)

33: Particulate Part [β] (Orthorhombic)

41: Substrate

42: Film

43: Adhesive

44: Box Clamps

45: Base cylindrical fixture

Fig. 1 is a schematic view of the surface of the substrate of the present invention.

FIG. 2 is an exemplary schematic cross-sectional view of the plasma spraying apparatus.

3 is an exemplary schematic cross-sectional view of a gas flame spraying device.

FIG. 4 is a diagram showing the distribution of elements on the surface of the films obtained in Examples.

Fig. 5 is an optical microscope photograph of the surface of the film obtained in the Example.

FIG. 6 is a cross-sectional SEM image of the film obtained in Example.

FIG. 7 is another cross-sectional SEM image of the film obtained in the Example.

FIG. 8 is a schematic diagram for explaining the tensile test of the film performed in the example.

Fig. 9 is a graph showing the results of the drug resistance test carried out in the examples.

FIG. 10 is another cross-sectional SEM image of the film obtained in the Example.

FIG. 11 is another cross-sectional SEM image of the film obtained in the Example.

The present invention will be described.

The film-attached substrate of the present invention is a film-attached substrate provided with a film on the surface of the substrate; wherein the film has a thickness of 10 to 1000 μm and contains fluorides and oxides whose main components are rare earth elements (Ln). ; On the surface of the above-mentioned film, the main component is an oxide of a rare earth element (Ln), a particulate part [α ₁ ] having a monoclinic structure and a diameter of 10 nm to 1 μm , and the main component is a rare earth element (Ln ) fluoride, a particle-like part [β ₁ ] having an orthorhombic structure and a diameter of 10 nm to 1 μm , dispersed in an amorphous matrix whose main component is a fluoride of a rare earth element (Ln); and For the above-mentioned film surface, if an optical microscope is used to observe at 200 times, a white spot-like part with a maximum diameter of 50 to 1000 μm is confirmed, and the area ratio of the spot-like part in the observation field of view is 0.01 to 2%.

Hereinafter, such a film-attached base material is also referred to as "the base material A of the present invention".

In addition, the film with which the base material A of this invention is equipped is also called "film A".

Furthermore, the film-attached substrate of the present invention is a film-attached substrate provided with a film on the surface of the substrate; wherein the film has a thickness of 10 to 1000 μm and contains fluorides and oxides of alkaline earth metals as main components. On the surface of the above-mentioned film, the main component is an oxide of an alkaline earth metal, a particulate part [α ₂ ] having a monoclinic structure and a diameter of 10 nm to 1 μm , and a fluoride of an alkaline earth metal as the main component _2. Particulate parts [β 2 ] having an orthorhombic structure and a diameter of 10 nm to 1 μm are dispersed in an amorphous matrix whose main component is a fluoride of an alkaline earth metal; , if observed with an optical microscope at 200 magnifications, a white spot-like part with a maximum diameter of 50-1000 μm is confirmed, and the spot-like part occupies an area ratio of 0.01-2% in the observation field.

Hereinafter, such a film-attached base material is also referred to as "the base material B of the present invention".

In addition, the film with which the base material B of this invention is equipped is also called "film B".

Hereinafter, the case of simply referring to "the base material of the present invention" includes any meaning of "the base material A of the present invention" and "the base material B of the present invention".

In addition, the case where only the particle-like part [α] is referred to hereinafter includes any meaning of the _{particulate-like part [α 1} ] and the particle-like part [α _{2 ].} Similarly, the case where only the particle-shaped part [β] is referred to shall include any meaning of the _{particle-shaped part [β 1} ] and the particle-shaped part [β _{2 ].}

Furthermore, the method for producing the film-attached substrate of the present invention includes: drying the raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal to obtain a moisture content of 0.3% by mass. The following steps of drying the dried raw material; dispersing the above-mentioned dried raw material in an organic solvent to obtain a slurry; The film forming step of the film; the substrate A of the present invention or the substrate B of the present invention is obtained accordingly.

Hereinafter, the manufacturing method of such a film-attached base material is also called "the manufacturing method of this invention".

The substrate of the present invention is preferably manufactured according to the manufacturing method of the present invention.

<Substrate of the present invention>

The base material A of the present invention will be described.

The substrate A of the present invention is a substrate with a film having a film on the surface of the substrate, wherein the film A has a thickness of 10 to 1000 μm and contains fluorides and oxides whose main components are rare earth elements (Ln).

The coating film A of the base material A of the present invention is obtained by applying gas flame spraying or plasma spraying to the base material using a raw material powder of a fluoride of a rare earth element (Ln) or an oxyfluoride (oxyfluoride). can be formed. Specifically, it may be the same as that of the production method of the present invention, which will be described in detail later.

The thickness of the film A is 10 to 1000 μm, preferably 10 to 200 μm. As described above, since the film A is formed by gas flame spraying or plasma spraying, it has a thickness of 10 to 1000 μm, but other methods such as CVD generally cannot achieve such a thickness.

The thickness of the film A refers to a value measured by an eddy current amplitude induction type, an electromagnetic induction type film thickness meter, or a micrometer.

In addition, the film A contains fluorides and oxides whose main components are rare earth elements (Ln).

Here, the "main component" refers to 50 mass % or more. That is, in the film A, it is preferable that the total content rate of the fluoride and oxide of the rare earth element (Ln) be 50 mass % or more. The total content rate is more preferably 60 mass % or more, particularly preferred is 70 mass % or more, and optimal is 80 mass % or more.

Hereinafter, unless otherwise stated, the term "principal component" adopts this meaning.

In addition, the rare earth element (Ln) refers to scandium (Sc), yttrium (Y), lanthanide element (lantanoid), any of the actinoid elements (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), more The best system is yttrium (Y).

The film A may contain an oxygen-containing fluoride of a rare earth element (Ln).

Oxyfluorides are preferably selected from LnOF, Ln ₃ O ₂ F ₅ , Ln ₂ OF ₄ , LnO _1-X F _1+2X , LnO _0.4 F _2.2 and LnO _1-X F _1+2X (0<X<1 ), select at least one of the groups.

Specific examples of oxyfluorides of rare earth elements (Ln) include, for example, 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)°

The contents of fluorides and oxides of rare earth elements (Ln) in the film A were measured using a microfocusing fluorescent X-ray analyzer (for example, manufactured by Shimadzu Corporation, model: XRF-1700), and the concentrations of elements constituting the film were measured. , and in accordance with the θ-2 θ method using an X-ray diffraction apparatus (such as Shimadzu Corporation, XRD-6000), the X-ray diffraction pattern is measured to confirm the crystal structure, and a comprehensive review of these will be made before deciding .

The content of the element contained in the film was determined using the FP method from the measurement result by the microfocus fluorescent X-ray analyzer. The so-called "FP method" refers to the use of physical constants such as mass absorption coefficient, fluorescence yield, and spectral distribution of the X-ray source [fundamental parameters (FP method)] to obtain the theoretical formula from the theoretical expression of the fluorescence X-ray intensity. The X-ray intensity is compared with the measured X-ray intensity to calculate the concentration of each component.

For the measurement of an X-ray diffraction apparatus (for example, XRD-6000 manufactured by Shimadzu Corporation), the X-ray diffraction pattern is measured by the θ-2θ method under the following conditions, for example. _{The crystal structure of the particle-like portion [α 1} ] and the particle-like portion [β ₁ ] existing on the surface of the coating film and the amorphous matrix can be confirmed by analyzing the X-ray diffraction pattern, which will be described later.

X-ray source: Cu target X-ray source

Tube voltage: 40kV

Tube current: 30mA

Divergence slit: 1°

Scattering slit: 1°

Light receiving slit: 0.3mm

The film A is shown in the schematic diagram of FIG. 1 , and on the surface of the film A, the main component is the particulate part [α ₁ ] of oxides of rare earth elements (Ln) (indicated as the particulate part [α 1 ] in FIG. 1 . _{]), and the particulate part [β 1} ] (indicated as particulate part [β] in FIG. 1 ) of the fluoride whose main component is the rare earth element (Ln), is dispersed in the rare earth element (Ln) ) in an amorphous matrix of fluoride.

Here, the particulate part [α ₁ ] is mainly composed of oxides of rare earth elements (Ln), and the oxides have a monoclinic structure. In addition, the particulate part [β ₁ ] is a fluoride whose main component is a rare earth element (Ln), and the fluoride has an orthorhombic structure. In addition, the part (matrix) other than these is amorphous.

_{In addition, the particle-shaped part [α 1} ] and the particle-shaped part [β ₁ ] dispersed in the matrix on the surface of the film A were obtained by using a transmission electron microscope (TEM), as shown in FIG. 4 described later. The element distribution map can be confirmed.

In addition, the diameters of the particle-shaped part [α ₁ ] and the particle-shaped part [β ₁ ] are both 10 nm to 1 μm, preferably 50 nm to 200 nm.

In addition, the actual particle-shaped part [α ₁ ] and the particle-shaped part [β ₁ ] are not strictly circular, but are often elliptical or polygonal. Here, the diameters of the particle-shaped portion [α ₁ ] and the particle-shaped portion [β ₁ ] mean the average value calculated after obtaining the longest diameter and the shortest diameter.

The area ratio of the particle-like portion [α ₁ ] in the observation field is preferably 1 to 30%.

The area ratio of the particle-like part [β ₁ ] in the observation field is preferably 98-69%.

The total area ratio of the particle-shaped part [α ₁ ] in the observation field and the area ratio of the particle-shaped part [β ₁ ] in the observation field is preferably 90% or more, more preferably 95% or more, especially More than 98% of the best series, more than 99% of the best series, and more than 99.5% of the best series.

The area ratio is measured by obtaining an element distribution map and a lattice image using a transmission electron microscope (TEM), and processing the image using an image processing software such as Image Pro PLUS 3.0, which will be described later.

When the film A included in the base material A of the present invention is observed at 200 magnifications with an optical microscope, a white spot-like portion with a maximum diameter of 50 to 1000 μm is confirmed. Elemental analysis and crystal structure of this spot-like portion were investigated, and the results were not significantly different from other portions. However, as a result of intensive investigation by the present inventors, it was found that the spot-like portion becomes a starting point for forming cracks in the film, and that the film is easily peeled off when the spot-like portion exists more than a certain level. Then, if the maximum diameter of the spot-shaped part is 50~1000μm, when observed with an optical microscope at 200 times, the area ratio in the observation field is 0.01~2%, it is difficult to form cracks on the film, and the film is not easy to be formed. Peel from substrate.

The area ratio of the spot-like portion in the observation field is 0.01-2%, preferably 0.01-1%, and more preferably 0.01-0.5%.

When the area ratio is small, cracks are less likely to occur, and the film is less likely to peel off from the substrate.

The base material B of the present invention will be described.

The base material B of the present invention is a base material with a film having a film on the surface of the base material, wherein the film B has a thickness of 10-1000 μm and contains fluorides and oxides whose main components are alkaline earth metals.

The substrate B of the present invention is similar to the aforementioned substrate A of the present invention, except that the constituent elements of the film are the same.

The following description of the base material B of the present invention is made with respect to the difference from the base material A of the present invention.

The film B is formed by applying gas flame spraying or plasma spraying to the base material using the raw material powder of alkaline earth metal fluoride or oxyfluoride, as in the case of the base material A of the present invention. Specifically, it may be the same as that of the production method of the present invention, which will be 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 base material A of the present invention.

The thickness of the film B refers to a value measured by the same method as in the case of the film A.

In addition, the film B contains fluorides and oxides of alkaline earth metals as main components.

The contents of fluorides and oxides of alkaline earth metals in the film B were carried out in the same manner as in the case of the film A. _{The crystal structure of the particulate portion [α 2} ] and the particulate portion [β ₂ ] existing on the surface of the film, and the matter of the matrix-based amorphousness were also confirmed by the θ-2θ method in the same manner.

The film B included in the base material B of the present invention is as shown in the schematic diagram of FIG. 1 , and on the surface of the film, the main component is the particulate portion [α ₂ ] of an oxide of an alkaline earth metal (indicated as particle in FIG. 1 ). The particle-shaped part [α]), and the particle-shaped part [β ₂ ] (indicated as the particle-shaped part [β] in FIG. 1 ) of the fluoride whose main component is an alkaline earth metal, are dispersed in the main component of the alkaline-earth metal fluoride in an amorphous matrix of fluoride.

Here, the particulate part [α ₂ ] is mainly composed of an oxide of an alkaline earth metal, and the oxide has a monoclinic structure. In addition, the particulate part [β ₂ ] is mainly composed of a fluoride of an alkaline earth metal, and the fluoride has an orthorhombic structure. In addition, the part (matrix) other than these is amorphous.

In addition, the fact that the particulate part [α ₂ ] and the particulate part [β ₂ ] are dispersed in the matrix on the surface of the film can be confirmed using a transmission electron microscope (TEM) as in the case of the film A.

In addition, the diameters of the particle-shaped part [α ₂ ] and the particle-shaped part [β ₂ ] are both 10 nm to 1 μm, preferably 50 nm to 200 nm.

In addition, the actual particle-shaped part [α ₂ ] and the particle-shaped part [β ₂ ] are not strictly circular, but are often elliptical or polygonal. Here, the diameter of the particle-shaped part [α ₂ ] and the particle-shaped part [β ₂ ] refers to an average value calculated after obtaining the longest diameter and the shortest diameter.

The area ratio of the particle-like portion [α ₂ ] in the observation field is preferably 1 to 30%.

The area ratio of the particle-like part [β ₂ ] in the observation field is preferably 98-69%.

The total area ratio of the particle-shaped portion [α ₂ ] in the observation field and the area ratio of the particle-shaped portion [β ₂ ] in the observation field is preferably 90% or more, more preferably 95% or more, especially More than 98% of the best series, more than 99% of the best series, and more than 99.5% of the best series.

This area ratio was measured according to the same method as in the case of the above-mentioned film A.

When the film of the base material B of the present invention is observed at 200 magnifications with an optical microscope, a white spot-like portion with a maximum diameter of 50 to 1000 μm is confirmed. Elemental analysis and crystal structure of this spot-like portion were investigated, and the results were not significantly different from other portions. However, as a result of intensive investigation by the present inventors, it was found that the spot-like portion becomes a starting point for forming cracks in the film, and that the film is easily peeled off when the spot-like portion exists more than a certain level. Then, if the maximum diameter of the spot-shaped part is 50~1000μm, when observed with an optical microscope at 200 times, the area ratio in the observation field is 0.01~2%, it is difficult to form cracks on the film, and the film is not easy to be formed. Peel from substrate.

The area ratio of the spot-like portion in the observation field is 0.01-2%, preferably 0.01-1%, and more preferably 0.01-0.5%.

When the area ratio is small, cracks are less likely to occur, and the film is less likely to peel off from the substrate.

Next, each step included in the manufacturing method of the present invention will be described.

<Drying step>

First, the drying step will be described.

In the drying step of the production method of the present invention, a raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal is dried to obtain a dry raw material having a moisture content of 0.3 mass % or less.

The raw material powder will be explained.

In the production method of the present invention, when a raw material powder containing a fluoride of a rare earth element (Ln) is used, the substrate A of the present invention can be obtained. Moreover, in the production method of the present invention, the base material B of the present invention can be obtained by using a raw material powder containing a fluoride of an alkaline earth metal.

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

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

In addition to the fluorides of rare earth elements (Ln), the raw material powders can also contain rare earth oxyfluorides (compounds containing Ln, O, F, such as YOF), rare earth oxides (such as Y ₂ O ₃ ).

In addition, the fluoride of an alkaline-earth metal is not specifically limited as long as it is a compound which consists of an alkaline-earth metal and fluorine (F).

The raw material powder preferably contains an alkaline earth metal fluoride of 20 mass % or more. The content ratio is 40 mass % or more for the most preferable type, 60 mass % or more for the most preferable type, 70 mass % or more for the optimal type, and 80 mass % or more for the most optimal type.

The raw material powder may contain oxyfluorides of alkaline earth metals and oxides of alkaline earth metals in addition to fluorides of alkaline earth metals.

The particle size of the raw material powder is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm, and particularly preferably 3 to 8 μm.

Furthermore, the average particle diameter (median particle diameter) of the raw material powder is preferably 0.01 to 30 μm, more preferably 0.5 to 3 μm.

Here, the particle size of the raw material powder is a value obtained by performing measurement using a conventionally known laser diffraction/scattering particle size distribution analyzer.

In addition, the average particle diameter of the raw material powder is a value obtained by setting the integral particle size distribution (volume basis) using a conventionally known laser diffraction/scattering particle size distribution measuring apparatus.

The raw material powder system may contain particles composed of a fluoride of a rare earth element (Ln), particles composed of an oxygen-containing fluoride of a rare earth element (Ln), and particles composed of a fluoride of a rare earth element (Ln) and a rare earth element Particles composed of oxyfluorides of element (Ln). Moreover, these particles containing impurities may be contained.

The raw material powder system may contain: particles composed of an alkaline earth metal fluoride, particles composed of an alkaline earth metal oxyfluoride, and particles composed of an alkaline earth metal fluoride and an alkaline earth metal oxyfluoride . Moreover, these particles containing impurities may be contained.

In the drying step, the above-described raw material powder is dried to obtain a dry raw material having a moisture content of 0.3 mass % or less.

The inventors of the present invention have conducted extensive research and found that the specific particle-like part with a specific crystal structure is dispersed in the amorphous matrix, and the part where white spots can be seen when observed with an optical microscope, the area ratio of the film within a specific range is the film. Plasma resistance is excellent, and it is not easy to peel off. In order to form such a film, it was found that a raw material with a very small amount of moisture was dispersed in an organic solvent with no moisture as much as possible. Gas flame spraying or plasma Melting can be formed.

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

The method of setting the moisture content of the raw material powder within the above range is not particularly limited. For example, a method in which the raw material powder is placed in a conventionally known dryer and kept for a certain period of time.

<Slurry preparation step>

The slurry is explained.

In the slurry preparation step, the raw material powder as described above is dispersed in an organic solvent to obtain slurry.

As the organic solvent, known ones can be used, and for example, alcohols can be used. Examples of alcohols include ethanol, methanol, and kerosene. As the organic solvent, ethanol is preferably used.

When alcohol (preferably, cooled alcohol) is used as the organic solvent, when the organic solvent is vaporized by supplying the slurry into the flame, the temperature of the flame can be lowered by utilizing the heat of vaporization. The reason is that it is easier to form a film when at least a part of the raw material powder is kept in an unmelted state, so that higher plasma resistance can be formed on the surface of the base material.

The organic solvent preferably has a low moisture content. As described above, the present inventors have found that it is necessary to set the moisture content of the raw material powder to a certain value or less, and furthermore, if the purity of the organic solvent is high (that is, the moisture content is low), it is possible to reduce the moisture content obtained by the production method of the present invention. The area ratio of the spot-shaped portion of the base film of the invention.

Specifically, the moisture content contained in the organic solvent is preferably 0.5 mass % or less, more preferably 0.2 mass % or less.

A slurry can be obtained by adding the above-mentioned raw material powder to such an organic solvent, and further dispersing by stirring or the like using an ultrasonic transmitter or the like as necessary.

The content of the raw material powder contained in the slurry is preferably 1 to 90% by mass, more preferably 10 to 50% by mass.

<Film formation step>

The film formation step will be described.

In the film forming step of the production method of the present invention, spraying is performed using the above-mentioned slurry, and A film is formed on the surface of the substrate.

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

Plasma spraying will be described.

Plasma spraying is preferably carried out using, for example, the apparatus shown in FIG. 2 .

The plasma spraying device 9 shown in FIG. 2 includes a nozzle-shaped anode 1 and a pair of electrodes in which a cathode 2 is arranged in the center. Plasma is generated by flowing an inert gas (argon, nitrogen, hydrogen, etc.) from the gas introduction part 3 into the doughnut-shaped gap between the anode and the cathode, and ionizing the gas by arc discharge. The plasma gas system is ejected from the nozzle-shaped anode 1 to the outside of the plasma spraying device as a plasma jet 5 .

The raw material powder is supplied to the plasma jet 5 after placing the conveying gas through the slurry feeding pipe 6 connected near the outlet of the nozzle-shaped anode 1 . The slurry containing the raw material powder supplied to the plasma jet is heated to a molten state in the plasma, and then sprayed from the anode 1 on the plasma jet 5 to the outside to form a film 8 on the surface of the substrate 7 .

The slurry supply is preferably 5~100ml/min, more preferably 10~50ml/min.

The solid content concentration in the slurry is preferably 10-60 mass %, more preferably 15-50 mass %, extra-optimal 15-40 mass %, optimum 20-38 mass %, and most optimum 25-35 mass % quality%.

The plasma spraying system can be implemented according to a known method. In addition, it is preferable to perform plasma spraying under the treatment conditions for completely melting the raw material powder, and to form the raw material on the surface of the base material. A film made of powder.

The plasma spraying is preferably carried out at a plasma temperature of 10,000 degrees or more, and more preferably at 15,000 degrees or more. The reason is that a film with more excellent plasma resistance can be formed.

The plasma spraying is preferably carried out under the treatment conditions in which the speed at which the raw material powder is blown against the base material is set to 200 m/s or less, because a film having more excellent plasma resistance can be formed.

Explanation will be given to gas flame spraying.

As the spraying device for performing gas flame spraying, for example, the gas flame spraying device shown in FIG. 3 can be used.

The spraying apparatus 10 shown in FIG. 3 is provided with a combustion chamber 12 inside, and is provided with an oxygen flow path 14 for supplying oxygen-containing gas to the combustion chamber 12, a main fuel flow path 16 for supplying a main fuel, and Burner 18 for igniting the mixture of these oxygen-containing gases and main fuel. In addition, in the combustion chamber 12, a hole (lance head 20) for spraying flame is formed on the opposite side of the burner 18, and a cylindrical front end barrel 22 having a hole in the center is provided outside the lance head 20, The flame is ejected outward from the holes of the lance head 20 and the front end barrel 22 . By adjusting the size of the hole in the front end barrel 22, the speed of the flame can be adjusted.

A slurry supply flow path 24 is formed in the front end cylinder 22, and the slurry is supplied into the flame from there. In addition, an auxiliary fuel supply flow path 26 is further formed in the front end barrel 22, and the auxiliary fuel can be supplied to the flame from there.

A compressed air supply flow path 28 is formed in the lance head 20 from which the supplied The compressed air is supplied in such a manner as to flow along the inner side surface of the hole formed in the front end barrel 22 . Thereby, the slurry supplied from the slurry supply channel 24 is in a state in which it does not adhere to the inner side surface of the hole provided in the front end cylinder 22 .

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

In the spraying apparatus 10 shown in FIG. 3 , the oxygen-containing gas and the main fuel are supplied from the oxygen flow path 14 and the main fuel flow path 16 .

Here, the gas containing oxygen in the oxygen-containing system may be, 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 100~1500L/min, more preferably at 200~1000L/min, and especially at 350~600L/min.

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

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

Here, as the main fuel system, for example, kerosene, acetylene, propylene, propane, ethylene, Natural gas etc. Among these, the main fuel is preferably kerosene.

Furthermore, the mixing ratio of the oxygen-containing gas and the main fuel is not particularly limited, but it is preferably a mixing ratio in which the main fuel is not completely burned. The reason is that if the combustion is incomplete, the flame temperature can be lowered by utilizing the heat of gasification of a part of the unburned main fuel and the organic solvent (alcohols, etc.) in the slurry during gasification, and as a result, it is easy to reduce the flame temperature at least in the raw material powder. Some of them form a film in an unmodified state, and a film-attached substrate with a higher plasma-resistant film on the surface of the substrate can be easily produced.

In addition, the auxiliary fuel described later and the oxygen that can be contained in the slurry and compressed air are not considered here, and it is preferable to adjust only the mixing ratio of the oxygen-containing gas and the main fuel so that the main fuel is not completely burned.

In this way, the oxygen-containing gas and the main fuel are supplied to the combustion chamber and mixed, and the obtained mixture is ignited to generate a flame. Then, the above-mentioned slurry is supplied toward the inside of the flame.

Here, it is preferable to put the slurry into the flame after mixing the slurry with the gas. The gas is preferably air.

The slurry supply amount is preferably 20~100ml/min, and more preferably 30~70ml/min.

The solid content concentration in the slurry is preferably 10-60 mass %, more preferably 15-50 mass %, extra-optimal 15-40 mass %, optimum 20-38 mass %, and most optimum 25-35 mass % quality%.

Although it is not necessary to use compressed air, in some cases, it is preferable to supply the compressed air with a pressure of 0.05 to 1.5 MPa, and more preferably to supply it with a pressure of 0.3 to 0.8 MPa. In addition, the compressed air is preferably supplied at a flow rate of 250 to 2000 L/min, and more preferably supplied at 400 to 800 L/min.

In addition, there are cases in which uncompressed gas (eg, the atmosphere) is used instead of compressed air.

It is preferable to use auxiliary fuel in the film formation step. The temperature of the flame is adjusted using auxiliary fuel.

If auxiliary fuel is supplied to the flame, when the auxiliary fuel is supplied into the flame and vaporized, the temperature of the flame can also be lowered by utilizing the heat of vaporization. This case is preferable because a film can be easily formed while at least a part of the raw material powder is kept in an unmelted state.

As the auxiliary fuel system, 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.

Furthermore, the auxiliary fuel is preferably supplied at a flow rate of 5 to 100 L/min, and more preferably supplied at 10 to 30 L/min.

When using the spraying device 10 shown in FIG. 3 , the distance between the front end of the front end barrel 22 and the main surface of the substrate is preferably 10 to 250 mm, and more preferably 70 to 150 mm.

The base material is explained.

The base material is not particularly limited, and examples thereof include aluminum, stainless steel, glass (quartz glass, alkali-free glass, etc.), ceramics ( _{sintered body composed of Y 2} O ₃ , AlN, Al ₂ O ₃ , etc.), carbon, etc. .

The size and shape of the base material are not particularly limited, but are preferably in a plate shape. In the production method of the present invention, it is preferable to form a film on the main surface of such a plate-shaped base material (also referred to as a "substrate").

In the film forming step, the type and supply amount of organic solvent and auxiliary fuel are preferably adjusted, and gas flame spraying is performed under the processing conditions for forming the film while at least a part of the raw material powder is kept in an unmelted state.

By such a film forming step, a film can be formed on the surface of the above-mentioned substrate.

By such a production method of the present invention, the substrate of the present invention can be obtained.

The film system of the film-attached substrate of the present invention has high plasma resistance, is not easy to peel off, has excellent acid resistance, and has a high surface resistance value.

The type of plasma-resistant plasma here is not particularly limited, for example, atmospheric pressure plasma, inductively coupled plasma, capacitively coupled plasma, magnetized plasma, high-frequency plasma, pyroplasm and the like. In addition, when the porosity of the film is low, the plasma resistance is high.

Specifically, the porosity of the film is preferably 10% or less.

Accordingly, since the substrate with the coating film has high plasma resistance, it can be used for a member exposed to a plasma environment. That is, it can be used as a component for a plasma etching apparatus. For example, components such as semiconductor manufacturing equipment, flat panel display manufacturing equipment, or solar cell panel manufacturing equipment. The film-attached substrate of the present invention is preferably used as a component of a semiconductor manufacturing apparatus. semiconductor The manufacturing device components can be, for example, ion implantation devices, epitaxial growth devices, CVD devices, vacuum evaporation devices, etching devices, sputtering devices, ashing devices and other components exposed to the plasma environment. Such components can be, for example: cavities, bell jars, pedestals, clamp rings, alignment rings, shadow rings, insulating rings, dummy wafers, tubes for plasma generation, Dome chamber for plasma generation, penetration window, infrared penetration window, monitoring window, lift pins for supporting semiconductor wafers, shower plate, baffle, bellows cover, Upper electrode, lower electrode, electrostatic chuck, etc.

[Example]

<Experiment 1>

An aluminum substrate having a thickness of 3 mm was prepared, and a coating film having a thickness of 60 μm was formed _{on the main surface of the substrate by using YF 3 particles as a raw material powder to perform gas flame spraying.}

Here, the average particle diameter (D _{50 ) of the YF 3} particles was 5.3 μm, and as a result of a composition analysis (ICP analysis), it was considered that 99% by mass or more was composed of YF ₃ . In addition, the remainder (less than 1 mass %) can be considered to be YOF, Y ₂ O ₃ or the like.

Moreover, YF ₃ particles performed by using a dryer system 80 deg.] C After 3 hours and dried, dispersed in an alcohol (Japan Alcohol Trading Co., Ltd., moisture content = 0.2 mass% or less) to create a slurry.

In addition, as a result of performing a preliminary experiment, it was found that when dried at 80° C. for 3 hours, almost anhydrous drying state was obtained.

The processing conditions for gas flame spraying are as shown in Table 1 (Conditions 1 to 4) pieces. In addition, the gas flame spraying device was used as shown in FIG. 3 .

Measurements of physical properties and the like were performed on each of the substrates with the coating thus obtained. In addition, the substrate with a film obtained under the condition 1 is also referred to as a "substrate 1 with a film" hereinafter. The substrates with coating obtained under conditions 2, 3, and 4 are also referred to as "substrate 2 with coating", "substrate 3 with coating", and "substrate 4 with coating".

<Composition analysis of film>

For each of the substrates 1 to 4 with the coating, a microfocus X-ray fluorescence analyzer (manufactured by Shimadzu Corporation, model: XRF-1700) was used to measure the concentration of the elements constituting the coating. Then, the content of the element contained in the film was determined using the FP method from the measurement results of the microfocus fluorescent X-ray analyzer. The so-called "FP method" refers to the use of physical constants (basic parameters) such as mass absorption coefficient, fluorescence yield, and X-ray source spectral distribution to obtain the theoretical X-ray intensity from the theoretical formula of the fluorescence X-ray intensity, and then perform and measure it. A method for calculating the concentration of each component by comparing the X-ray intensities.

The results are shown in Table 2.

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

<Analysis of crystal structure of particles constituting the film>

The crystal structure was analyzed using an X-ray diffraction apparatus (manufactured by Shimadzu Corporation, XRD-6000) for each of the films of the film-attached substrates 1 to 4, respectively. The measurement method was carried out under the following conditions using the θ-2θ method. The θ-2θ method is a method in which the X-ray source is fixed, and when the sample stage is just moved by θ, scanning is performed while moving the detector unit by 2θ.

X-ray source: Cu target X-ray source,

Tube voltage: 40kV

Tube current: 30mA

Divergence slit: 1°

Scattering slit: 1°

Light receiving slit: 0.3mm

As a result, _{sharp peaks indicating the existence of Y 2} O ₃ (cubic crystal and monoclinic crystal), YF ₃ , and YOF, respectively, were confirmed. However, there are cases where the peaks are not clear, and it is considered that the film contains 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 the coating film were mechanically polished so that the thickness of the coating film was about 40 μm, and then the final thinning was performed by an ion milling method (2.0 to 5.5 keV). Then, using a TEM (FEI Tecnai Osiris), an acceleration voltage of 200 kV, a Scanning Transmission Electron Microscope (STEM) mode, and EDS, the surface of the film was analyzed. In addition, the electron beam diffraction method was used to confirm the crystal structure, and the size of the particle-shaped portion was confirmed using a bright-field image and a lattice image (not shown) in combination.

The element distribution map on the surface of the obtained film is shown in FIG. 4 .

As shown in FIG. 4 , it was confirmed that the surface of the film was in the YF ₃ amorphous matrix, and the particle-like portion (particulate portion [α]) _{composed of Y 2} O _{3 and the particles composed of YF 3} were dispersed. part (particulate part [β]). In addition, it was confirmed that the particle-shaped part [α] had a monoclinic structure and had a diameter of about 100 nm. In addition, it was confirmed that the particle-shaped portion [β] had an orthorhombic structure and had a diameter of about 100 nm.

<Surface observation with an optical microscope>

Using an optical microscope (manufactured by KEYENCE Co., Ltd., model: VHX-5000), the surface of the film-coated substrate 1 was observed at a magnification of 50 times. Photos are as shown in Figure 5.

As shown in FIG. 5 , white spot-like portions were confirmed. In addition, this spot-shaped part has a substantially circular shape.

The area ratio of the spot-like portion in the observation field was 1.8%.

<Form 1 of the film surface>

With respect to the substrates 1 to 4 with the film, a scanning electron microscope (manufactured by Nippon Electronics Co., Ltd., model: JSM-5600LV) was used to capture SEM images of the film surface. The magnification was set to 100 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

As a result, the surface exhibits extremely smooth properties without unevenness. In addition, depending on the conditions, there are cases in which microaggregates (protrusions of the same quality as the film) are only slightly observed in the order of several tens to several hundreds of μm.

<Form 2 of the film surface>

With respect to the substrates 1 to 4 with the film, a scanning electron microscope (manufactured by Nippon Electronics Co., Ltd., model: JSM-5600LV) was used to capture SEM images of the film surface. The magnification was set to 5000 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

The SEM image of the film surface of the substrate 2 with the film as a representative example is shown in FIG. 6 . There were no cracks on the surface of the film shown in FIG. 6 . In addition, in the case of other conditions, microscopic cracks of about 3 μm may be observed, but cracks exceeding this length do not exist at all.

<The pores of the film section>

The substrates 1 to 4 with the coating film were respectively wrapped in a two-liquid hardening epoxy resin, and polished with an automatic grinder (manufactured by Bühler, models: ECOMET3 and AUTOMET2) to obtain an observation surface, and then a scanning electron microscope was used. (manufactured by Nippon Electronics Co., Ltd., model: JSM-5600LV), an SEM image of the film cross section was taken. The magnification was set to 5000 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

The SEM image of the film cross-section of the substrate 2 with the film as a representative example is shown in FIG. 7 . There are almost no pores in the cross section of the film shown in FIG. 7 . In addition, other conditions are also very few pores in the film.

Next, the SEM images of the film-attached substrate 2 and the film-attached substrate 4 were subjected to binarization processing using Image Pro PLUS 3.0 from MEDIA CYBERNETICS. From the image processed by this image, the void area per visual field area (ie, void area/visual field area×100) was calculated, and this was set as the porosity (%).

As a result, the porosity of the film-attached substrate 2 and the film-attached substrate 4 were extremely low values of 3.9% and 8.7%, respectively.

<Measurement of film strength>

With respect to the substrate 2 with the coating, the surface of the coating is polished so that Ra is less than 1.5.

Next, a cylindrical jig was adhered to the surface of the film using an adhesive, and held in a drying oven set at 150° C. for 60 minutes. Then, as shown in FIG. 8, it was attached to a box-shaped jig, and the cylindrical jig was pulled downward, and the force required to peel off the cylindrical jig was measured.

In addition, for comparison, Y ₂ O ₃ raw material powder was used to prepare a substrate with a film under the same conditions as in Condition 3, and the same test was performed to measure the strength of the film.

As a result, the force required for the film peeling of the film-attached substrate 2 was 71 MPa. On the other hand, _{in the case of the coated substrate using the Y 2} O ₃ raw material powder, it was 43 MPa. From this, it was found that the film strength (tensile strength) of the film-attached substrate of the present invention is extremely high.

<Evaluation of drug resistance>

With respect to the substrate 2 with the coating, the curing was performed so that only the coating was exposed, and the substrate 2 was immersed in an aqueous hydrochloric acid solution of about 10% by volume, and the degree of dissolution of the coating was measured.

In addition, for comparison, Y ₂ O ₃ raw material powder was used to prepare a substrate with a film under the same conditions as in Condition 3, and the same test was performed. The results are shown in Figure 9.

In addition, the same test was also performed using the nitric acid aqueous solution of about 10 volume%, and the same result as FIG. 9 was obtained.

From this, it is found that the film obtained according to the present invention has extremely high resistance to hydrochloric acid and nitric acid.

<Evaluation of Plasma Resistance>

The ICP plasma exposure was performed with respect to the substrate 2 with the coating film, and the evaluation of the plasma resistance was performed. A specific description will be given below.

Plasma exposure was performed using an ICP etching apparatus (ICP etching apparatus EIS-700SI manufactured by ELIONIX Co., Ltd.).

Plasma conditions are as follows:

‧Plasma gas O ₂ , CF ₄ , SF ₆

‧Gas ratio O ₂ 3standard cc/min(sccm), CF ₄ 30sccm, SF ₆ 5sccm

‧Gas pressure 0.6~0.7Pa (there will be some changes according to the actual implementation)

‧Plasma power 800W (reflection system 0W)

‧Bias voltage 55~63V (set to 80% of the maximum value of the device, the value is the actual implementation)

‧Plasma exposure cycle 20min exposure-10min pause meter to implement 16 cycles, a total of 8 hours

Here, the mask for the remaining unexposed part is made of aluminum material, and the surface is treated with black alumite.

The surface shape of the film after the above-mentioned ICP plasma exposure was measured using a laser displacement meter.

In addition, for comparison, Y ₂ O ₃ raw material powder was used to prepare a substrate with a film under the same conditions as in Condition 3, and the same test was performed.

In addition, for comparison, the same test was performed also about the sintered body which consists of YOF.

As a result, the film thickness reduction of the film-attached substrate 2 becomes almost zero. On the other hand, _{when the substrate with the coating film of the Y 2} O ₃ raw material powder was used, the thickness of the coating film was reduced by about 0.7 μm. In addition, in the case of the sintered body made of YOF, the film thickness was reduced by about 0.3 μm.

From this, it turned out that the board|substrate with a film|membrane which belongs to this invention is extremely high in plasma resistance.

<resistance value>

The surface resistance value (two-terminal method) was measured about the board|substrates 1-4 with a film|membrane, respectively. _{In addition, for comparison, a substrate obtained by a general plasma spraying method with a coating made of Y 2} O ₃ not included in the technical scope of the present invention was similarly subjected to the measurement of the surface resistance value.

As a result, in the case of the substrates 1 to 4 with a coating, it was found that the surface resistance value was extremely high _{compared with the case of the coating formed by 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 in Experiment 1 were used.

Further, in accordance with the same in the case of Experiment 1, YF ₃ particles after drying by using a dryer, to form a slurry dispersed in an alcohol purposes.

The plasma spraying system was performed using a plasma spraying apparatus (Sulzer Metco Co., Ltd., plasma spray gun #9MB). The processing conditions were two conditions as shown in Table 3.

Measurements of physical properties and the like were performed on each of the substrates with the coating thus obtained. Hereinafter, the obtained substrate with a coating film is also referred to as "the substrate with a coating film 21" and "the substrate with a coating film 22".

<Composition analysis of film>

For the substrate 21 with a film and the substrate 22 with a film, a microfocus fluorescent X-ray analyzer (manufactured by Shimadzu Corporation, machine tool) was used in the same manner as in Experiment 1. Species: XRF-1700), measure the concentration of elements constituting the film, and then use the FP method to obtain the content of the elements contained in the film from the measurement results of the microfocus fluorescent X-ray analyzer.

As a result, the film-coated substrate 21 and the film-coated substrate 22 are composed of a mixture _{of yttrium fluoride (YF 3} ), oxyfluoride (YOF), and oxide (Y ₂ O _{3 ).}

<Analysis of crystal structure of particles constituting the film>

With respect to the coatings of the coated substrate 21 and the coated substrate 22, in the same manner as in Experiment 1, the crystal structure was analyzed using an X-ray diffraction apparatus (manufactured by Shimadzu Corporation, XRD-6000). The measurement method was also the same as in Experiment 1.

As a result, _{sharp peaks indicating the existence of Y 2} O ₃ (cubic crystal and monoclinic crystal), YF ₃ , and YOF, respectively, were confirmed. However, there are cases where the peaks are not clear, and it is considered that the film contains many amorphous parts.

<TEM observation>

The surfaces of the film-coated substrate 21 and the film-coated substrate 22 were analyzed using a transmission electron microscope (TEM). Specifically, the surfaces of the substrate 21 with a coating film and the substrate 22 with a coating film are first subjected to mechanical polishing to make the thickness of the coating film about 40 μm, and then the final thinning is performed by an ion milling method (2.0-5.5 keV). Then, under the same conditions as in the case of Experiment 1, the surface of the film was analyzed using a TEM.

As a result, it was confirmed that the surface of the coating film was composed of a _{YF 3 amorphous matrix, and that a particle-shaped part (particle-shaped part [α 1 ]) composed of Y 2} O ₃ and a particle-shaped part (particle-shaped part (particle-shaped part) composed of YF _{3 ) were dispersed.} shape part [β ₁ ]). In addition, it was confirmed that the particle-shaped part [α ₁ ] had a monoclinic structure and had a diameter of about 100 nm. In addition, it was confirmed that the particulate part [β ₁ ] had an orthorhombic structure and had 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 film-coated substrate 21 was observed at a magnification of 200 times.

As a result, white speckled portions were observed. In addition, this spot-shaped part has a substantially circular shape.

The area ratio of the spot-like portion in the observation field was 1.5%.

<Form 1 of the film surface>

In the same manner as in the case of Experiment 1, a scanning electron microscope (manufactured by Nippon Electronics Co., Ltd., model: JSM-5600LV) was used for the substrate 21 with the coating, and an SEM image of the surface of the coating was taken. The magnification was set to 100 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

As a result, the surface exhibits extremely smooth properties without unevenness.

<Form 2 of the film surface>

As in the case of Experiment 1, a scanning electron microscope (manufactured by Nippon Electronics Co., Ltd., model: JSM-5600LV) was used for the substrate 21 with a film and the base material 22 with a film to take a SEM image of the surface of the film. The magnification was set to 2000 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

The SEM image of the film surface of the substrate 21 with the film is shown in FIG. 10 , and the SEL image of the film surface of the substrate 22 with the film is shown in FIG. 11 . Membrane surface There are cracks.

<The pores of the film section>

As in the case of Experiment 1, the substrate 21 with the coating film was embedded in a two-liquid curing epoxy resin, and polished with an automatic grinder (manufactured by Bühler, models: ECOMET3 and AUTOMET2) to obtain an observation surface, and then used A scanning electron microscope (manufactured by JEOL Ltd., model: JSM-5600LV) was used to capture an SEM image of the film cross section. The magnification was set to 5000 times, and the automatic adjustment mechanism of the device was used for comparison and brightness adjustment during shooting.

As a result, almost no pores were present in the cross section of the film.

Next, the SEM image of the film-attached substrate 21 was subjected to binarization processing using Image Pro PLUS 3.0 from MEDIA CYBERNETICS. From the image processed by this image, the void area per visual field area (ie, void area/visual field area×100) was calculated, and this was set as the porosity (%).

As a result, the porosity of the film-attached substrate 21 is an extremely low value of about 1 to 5%.

<Measurement of film strength>

The film strength was measured in the same manner as in the case of Experiment 1.

That is, the surface of the film is polished to make Ra less than 1.5 on the substrate 21 with the film, and a cylindrical jig is attached to the surface of the film using an adhesive. After drying, it is mounted on a box-shaped jig as shown in FIG. The force required to peel off the cylindrical jig.

In addition, for comparison, Y ₂ O ₃ raw material powder was used to prepare a substrate with a film under the same conditions as when forming the base material 21 with a film, and the same test was performed to measure the strength of the film.

As a result, the force required for peeling off the film of the film-attached substrate 21 was 71 MPa. On the other hand, _{in the case of the coated substrate using the Y 2} O ₃ raw material powder, it was 43 MPa. From this, it was found that the film strength (tensile strength) of the film-attached substrate of the present invention is extremely high.

<Evaluation of drug resistance>

In the same manner as in the case of Experiment 1, the evaluation of drug resistance was performed. That is, with respect to the substrate 21 with the coating, the curing was performed so that only the coating was exposed, and it was immersed in an aqueous hydrochloric acid solution of about 10% by volume, and the degree of dissolution of the coating was measured. In addition, for comparison, Y ₂ O ₃ raw material powder was used, and a substrate with a film was produced under the same conditions as when the substrate 3 with a film was formed, and the same test was performed.

In addition, the same test was also performed using the nitric acid aqueous solution of about 10 volume%.

As a result, as in the case of Experiment 1, it was found that the film of the film-attached substrate 21 has extremely high resistance to hydrochloric acid and nitric acid.

<Evaluation of Plasma Resistance>

In the same manner as in the case of Experiment 1, ICP plasma exposure was performed on the film-attached substrate 21, and evaluation of plasma resistance was performed. In addition, for comparison, Y ₂ O ₃ raw material powder was used to prepare a substrate with a film under the same conditions as when the substrate 3 with a film was formed, and the same test was performed.

As a result, the film thickness of the film-attached substrate 21 is reduced to almost zero. On the other hand, _{when the substrate with the coating film of the Y 2} O ₃ raw material powder was used, the thickness of the coating film was reduced by about 0.7 μm.

From this, it turned out that the board|substrate with a film|membrane which belongs to this invention is extremely high in plasma resistance.

<resistance value>

The surface resistance value (two-terminal method) was measured similarly to the case of Experiment 1 about the board|substrate 21 with a coating film. _{In addition, for comparison, a substrate obtained by a general plasma spraying method with a coating made of Y 2} O ₃ not included in the technical scope of the present invention was similarly subjected to the measurement of the surface resistance value.

As a result, in the case of the substrate 3 with the coating, it was found that the surface resistance value was extremely high _{compared to the case of the substrate 3 formed of Y 2} O _{3 .}

31: Matrix (amorphous)

32: Particulate part [α] (monoclinic)

33: Particulate Part [β] (Orthorhombic)

Claims (6)

A film-attached base material, which is provided with a film on the surface of the base material, the thickness of the film is 10-1000 μm, and contains fluorides and oxides of rare earth elements (Ln) as main components; on the surface of the film, the main components are: Rare earth element (Ln) oxide, monoclinic structure, particle-shaped portion [ α ₁ ] with diameter of 10 nm to 1 μm, and fluoride whose main component is rare earth element (Ln), orthorhombic structure, diameter Particulate parts [ β ₁ ] of 10 nm to 1 μm are dispersed in an amorphous matrix containing fluorides of rare earth elements (Ln) as the main component; in addition, for the surface of the above-mentioned film, if an optical microscope is used, according to 200 When observed at magnification, white spot-like parts with a maximum diameter of 50 to 1000 μm were confirmed, and the area ratio of the spot-like parts in the observation field was 0.01 to 2%. The film-attached substrate according to claim 1, wherein the rare earth element (Ln) is yttrium (Y). A film-attached base material is provided with a film on the surface of the base material, the thickness of the film is 10-1000 μm, and contains fluorides and oxides of alkaline earth metals as main components; in the surface of the film, the main components are alkaline earth metals Oxide, having a monoclinic structure, a particle-shaped part [ α ₂ ] with a diameter of 10 nm to 1 μm, and a particle-shaped part with an orthorhombic structure and a diameter of 10 nm to 1 μm [ β ₂ ], it is dispersed in an amorphous matrix with fluorides of alkaline earth metals as the main component; and, for the surface of the above-mentioned film, if an optical microscope is used to observe at 200 times, it is confirmed that the maximum diameter of 50 ~ 1000μm white Spot-like part, the area rate of the spot-like part in the observation field is 0.01~2%. A component for a plasma etching device, containing the attachments of any one of claims 1 to 3 The base material of the film. A method for producing a base material with a film, comprising: drying a raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal to obtain a dry raw material with a moisture content of 0.3 mass % or less. step; a slurry preparation step of dispersing the above-mentioned dry raw material in an organic solvent with a moisture content of 0.3% by mass or less to obtain a slurry; and using the above-mentioned slurry to perform gas flame spraying or plasma spraying, and The film forming step of forming a film on the surface of the base material; according to this, the base material with the film attached according to any one of claims 1 to 3 is obtained. A method for producing parts for a plasma etching apparatus, comprising: drying raw material powder containing a fluoride of a rare earth element (Ln) or a fluoride of an alkaline earth metal to obtain a dry raw material with a moisture content of 0.3 mass % or less. a drying step; a slurry preparation step of dispersing the above-mentioned dry raw material in an organic solvent with a moisture content of 0.3 mass % or less to obtain a slurry; and using the above-mentioned slurry to perform gas flame spraying or plasma spraying, And the film forming step of forming a film on the surface of the base material; accordingly, the parts for the plasma etching apparatus of claim 4 are obtained.

Images