阅读说明：本技术 等离子体处理装置用构件及等离子体处理装置 (Member for plasma processing apparatus and plasma processing apparatus ) 是由 石川和洋 日野高志 斋藤秀一 于 2020-04-20 设计创作，主要内容包括：提供一种耐等离子体性优异、耐久性高的等离子体处理装置用构件及等离子体处理装置。所述等离子体处理装置用构件具备包含作为金属元素或半金属元素的第一元素的基材(2)、以及位于该基材上的以氧化钇为主成分的膜(3),在膜(3)中,在氧化钇的晶格面偏离{111}方向的偏离角度为±10°以内的范围内取向的氧化钇的晶粒的面积率为45％以上。(Provided are a member for a plasma processing apparatus, which has excellent plasma resistance and high durability, and a plasma processing apparatus. The member for a plasma processing apparatus comprises a base material (2) containing a first element which is a metal element or a semimetal element, and a film (3) which is located on the base material and contains yttrium oxide as a main component, wherein in the film (3), the area ratio of crystal grains of yttrium oxide which are oriented in a range in which the lattice plane of yttrium oxide deviates from the {111} direction by within + -10 DEG is 45% or more.)

1. A member for a plasma processing apparatus, comprising a base material containing a first element which is a metal element or a semimetal element, and a film containing yttrium oxide as a main component on the base material, wherein the area ratio of crystal grains of yttrium oxide oriented in a range in which a deviation angle of a crystal lattice plane of yttrium oxide from a {111} direction is within + -10 DEG is 45% or more.

2. The member for a plasma processing apparatus according to claim 1, wherein an area ratio of crystal grains of yttrium oxide oriented in a range in which a deviation angle of a crystal lattice plane of yttrium oxide from a {111} direction is ± 5 ° or less is 20% or more in the film.

3. The member for a plasma processing apparatus according to claim 1 or 2, wherein the intensity of the peak attributed to the (222) plane of yttrium oxide is represented by I₂₂₂The intensity of the (310) plane peak of yttrium oxide is represented by I₃₁₀When, I₃₁₀/I₂₂₂Is 0.12 or less.

4. The member for a plasma processing apparatus according to any one of claims 1 to 3, wherein an amorphous portion containing the first element, yttrium, and oxygen is provided between the substrate and the film.

5. The member for a plasma processing apparatus according to claim 4, wherein a content of yttrium in the amorphous portion is the largest in a mass ratio.

6. The member for a plasma processing apparatus according to any one of claims 1 to 5, wherein a coefficient of variation of a thickness of the film is 0.04 or less.

7. The member for a plasma processing apparatus according to any one of claims 1 to 6, wherein an absolute value of a skewness of a thickness of the film is 1 or less.

8. The member for a plasma processing apparatus according to any one of claims 1 to 7, wherein an arithmetic average roughness Ra of a surface of the film exposed to plasma is 0.01 μm or more and 0.1 μm or less, a plurality of pores are provided on the surface, and a value obtained by subtracting an average value of equivalent circle diameters of the pores from an average value of distances between centers of gravity of adjacent pores is 28 μm or more and 48 μm or less.

9. The member for a plasma processing apparatus according to any one of claims 1 to 8, wherein the mean grain size of the crystal grains of yttrium oxide is 0.01 to 2.5 μm.

10. The member for a plasma processing apparatus according to any one of claims 1 to 9, wherein a first peak of yttrium oxide measured by a cathodoluminescence method is located in a visible light region.

11. A plasma processing apparatus comprising the member for a plasma processing apparatus according to any one of claims 1 to 10.

Technical Field

The present invention relates to a member for a plasma processing apparatus and a plasma processing apparatus.

Background

Conventionally, as a member for a plasma processing apparatus which requires high plasma resistance, a member for a plasma processing apparatus which includes a base material and a film made of yttria which is coated by a thermal spraying method has been used.

As such a member for a plasma processing apparatus, for example, patent document 1 proposes a ceramic article including a base material made of alumina and a corrosion-resistant coating layer having an adhesion strength of about 15MPa or more provided directly on the base material.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 4532489

Disclosure of Invention

Problems to be solved by the invention

As shown in patent document 1, the corrosion-resistant coating has a maximum adhesion strength of only 46MPa, and in recent years, a higher adhesion is required to a substrate, and the corrosion-resistant coating cannot cope with this.

Further, if the ceramic article is used in an environment where temperature rise and fall are repeated, the corrosion-resistant coating is formed by a thermal spraying method, and therefore, a large amount of pores and microcracks remain, and there is a case where the reduction of fine particles is not possible.

Means for solving the problems

The member for a plasma processing apparatus of the present invention includes: a base material containing a first element which is a metal element or a semimetal element; and a film containing yttrium oxide as a main component on the substrate, wherein the film is configured such that an area ratio of crystal grains of yttrium oxide oriented in a range in which a deviation angle of a crystal lattice plane of yttrium oxide from a {111} direction is 10 DEG or less is 45% or more.

The plasma processing apparatus of the present invention includes the member for a plasma processing apparatus.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the member for a plasma processing apparatus of the present invention, a member for a plasma processing apparatus having excellent plasma resistance and high durability can be provided.

According to the plasma processing apparatus of the present invention, a plasma processing apparatus having high durability and reliability can be provided.

Drawings

The objects, features and advantages of the present invention will become more apparent from the detailed description and the accompanying drawings.

FIG. 1 is a schematic view showing an example of a cross section of a member for a plasma processing apparatus according to the present invention.

FIG. 2 is a polar diagram showing the film properties of the member for a plasma processing apparatus according to the present invention.

FIG. 3 is a polar diagram showing the film properties of the member for a plasma processing apparatus according to the present invention.

FIG. 4 is a polar diagram showing the film properties of the member for a plasma processing apparatus according to the present invention.

FIG. 5 is a polar diagram showing the film properties of the member for a plasma processing apparatus according to the comparative example.

FIG. 6 is a polar diagram showing the film properties of the member for a plasma processing apparatus according to the comparative example.

FIG. 7 is a schematic view showing a sputtering apparatus for obtaining a member for a plasma processing apparatus according to the present invention.

FIG. 8 shows that the film and composition formula of the member for a plasma processing apparatus of the present invention measured by a cathodoluminescence method are in a stoichiometric ratio (Y)₂O₃) A graph of the emission spectrum of each of the yttria ceramics (sintered bodies).

Detailed Description

Hereinafter, the member for a plasma processing apparatus according to the present invention will be described in detail with reference to the accompanying drawings.

As shown in fig. 1, a member 1 for a plasma processing apparatus according to the present invention includes: a substrate 2 containing a first element which is a metal element or a semimetal element; and a film 3 containing yttrium oxide as a main component on the base material 2. An amorphous portion 4 containing the first element, yttrium, and oxygen may be provided between the substrate 2 and the film 3. The amorphous portion 4 contains the first element and yttrium, and thus has high covalent bonding properties to the substrate 2 and the film 3, and thus can improve the adhesion strength of the film 3 to the substrate 2. Since the amorphous portion 4 is amorphous, structural relaxation is facilitated even when the temperature is increased and decreased repeatedly, and thus the adhesion strength can be sufficiently maintained. For example, when the thickness of the film 3 is 5 μm or more and 200 μm or less and the thickness of the amorphous portion 4 is 2nm or more and 4nm or less, the adhesion strength can be 60MPa or more. The adhesion strength may be measured by fixing a pin (stud pin) for peeling the film 3 to the surface of the film 3 with an epoxy resin, and then using a thin film adhesion strength tester (manufactured by Quad Group, Sebastian V-a).

Here, the semimetal element means an element showing a property intermediate between the metal element and the nonmetal element, and means 6 elements of boron, silicon, germanium, arsenic, antimony, and tellurium.

Examples of the substrate 2 include quartz, aluminum having a purity of 99.999% (5N) or more, aluminum alloys such as aluminum 6061 alloy, aluminum nitride ceramics, alumina ceramics, silicon carbide ceramics, and the like. The aluminum nitride ceramic and the alumina ceramic mean, for example, if they are alumina ceramics, the aluminum in terms of Al is contained in 100 mass% of the total of the components constituting the substrate 2₂O₃The obtained value, i.e., the alumina content, is 90 mass% or more. Alumina ceramics may include magnesium oxide, calcium oxide, silicon oxide, and the like in addition to alumina. Silicon carbide ceramics may contain boron, carbon, and the like in addition to silicon carbide.

Here, aluminum alloys such as aluminum having a purity of 99.999% (5N) or more, aluminum 6061 alloys, and aluminum nitride ceramics each contain iron, copper, and silicon as inevitable impurities.

The main component in the present invention means a component that accounts for 90 mass% or more of 100 mass% of the components constituting the film 3.

Fig. 1 is described for clarifying the presence of the film 3 and the amorphous portion 4, and does not faithfully show the correlation between the thicknesses of the substrate 2, the film 3, and the amorphous portion 4.

The compositional formula of yttrium oxide is, for example, Y₂O_3-x(0≤x≤1)。

The film 3 does not contain a substance other than yttria, and may contain fluorine (F), sodium (Na), magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), sulfur (S), chlorine (Cl), potassium (K), calcium (Ca), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), strontium (Sr), or the like, in addition to yttria, depending on the purity of a target used in forming the film 3, the device configuration, or the like. The components constituting the film 3 may be identified by using a thin film X-ray diffraction apparatus.

In order to identify the amorphous portion 4 as amorphous, first, a sample is produced from the member 1 for a plasma processing apparatus of the present invention by using a Focused Ion Beam (FIB) method. A part of the sample may be identified as amorphous from an electron diffraction pattern obtained at an acceleration voltage of 200kv and using a Fast Fourier Transform (FFT) as an object to be observed with an atomic resolution analysis electron microscope (for example, JEM-ARM200F, manufactured by JEOL Ltd., or a model following it).

The content of yttrium in the amorphous portion 4 may be the largest in terms of mass ratio. With such a configuration, the silicon substrate is stable even when exposed to a high-temperature environment, and the possibility of reaction with conductive silicon contained in the substrate 2 is low, so that the possibility of occurrence of leakage current is low. In the amorphous portion 4, yttrium may be 42 mass% or more, for example, in total 100 mass% of the components constituting the amorphous portion 4. Plasma resistance can be determined by measuring the amount of weight loss after plasma treatment. If the plasma resistance is good, the weight loss is small. The mass ratio of the components constituting the amorphous portion 4 may be converted into a mass ratio from an atomic ratio of the elements constituting the amorphous portion 4 obtained by energy dispersive X-ray analysis (EDX) with respect to the amorphous portion 4.

Fig. 2 to 4 are polar views showing the characteristics of the film of the member for a plasma processing apparatus according to the present invention, and show the results of measurement of the film 3 on the substrate 2 by an EBSD (Electron Back Scattered Diffraction) method using a sputtering apparatus described later. Fig. 2 shows characteristics of a film formed in a central portion of a chamber of a sputtering apparatus, fig. 4 shows characteristics of a film formed in a peripheral portion of the chamber of the sputtering apparatus, and fig. 3 shows characteristics of a film formed in an intermediate portion of the chamber of the sputtering apparatus between the central portion and the peripheral portion. Fig. 5 and 6 are polar views showing the film properties of the plasma processing apparatus member of the comparative example. Fig. 5 shows the characteristics of the film of comparative example 1 produced on a substrate using an atmospheric pressure plasma spraying method (APS), and fig. 6 shows the characteristics of the film of comparative example 2 produced on a substrate using a suspension plasma spraying method (SPS).

Patterns of pole point diagrams in EBSD measurement of the crystal lattice plane in the {111} direction appear in the central portion and the peripheral portion. The film 3 is a polycrystalline film containing yttrium oxide as a main component, and the central pattern appears more intensively as the lattice planes constituting the polycrystalline film are aligned in the {111} direction. Therefore, it can be said that the directions of the respective crystals constituting the film 3 are more aligned in the {111} direction in the example than in the comparative example.

[ Table 1]

Table 1 shows the area ratios, which are the ratios of crystal grains in the observation plane, in the ranges where the deviation angles of the lattice planes from the {111} directions are within. + -. 5 ℃ and within. + -. 10 ℃. In the examples, the ratio of crystals present in the range in which the deviation angle of the crystal lattice plane from the {111} direction is within ± 5 ° and within ± 10 ° is large, and the crystal orientation of the film 3 is more uniform than in comparative examples 1 and 2, and it can be said that the orientation is high.

The adhesion strength of the film 3 is about 50MPa or more in the examples and about 20MPa in the comparative examples, and the adhesion strength of the film 3 of the examples having high orientation is improved. The adhesion strength of the film can be measured by the Sebastian method. The adhesion strength of the film 3 is sufficient when the area ratio of crystal grains oriented in a range in which the deviation angle of the crystal lattice plane from the {111} direction is within ± 10 ° is 45% or more. As described above, by forming the yttrium oxide film 3 having high orientation on the upper surface 2a of the substrate 2 of the member 1 for a plasma processing apparatus, the adhesion strength between the film 3 and the substrate 2 is improved, and the member 1 for a plasma processing apparatus having high plasma resistance for a long period of time can be realized.

When the area ratio of crystal grains oriented in a range in which the deviation angle of the crystal lattice plane from the {111} direction is within ± 10 ° is 80% or more, the adhesion strength is further improved. In particular, when the area ratio of crystal grains oriented in a range in which the deviation angle of the crystal lattice plane from the {111} direction is within ± 5 ° is 20% or more, the adhesion strength is further improved.

By further improving the orientation of the film 3 in this way, the adhesion strength between the film 3 and the substrate 2 is further improved, and the member 1 for a plasma processing apparatus having high plasma resistance for a long period of time can be realized. The area fraction of crystal grains oriented in a range in which the deviation angle of the crystal lattice plane from the {111} direction is within ± 5 ° may be 54% or more.

In the examples, the intensity of the peak ascribed to the (222) plane of yttria was represented by I₂₂₂The intensity of the peak ascribed to the (310) plane of yttria was represented by I₃₁₀When, I₃₁₀/I₂₂₂Is 0.12 or less. This indicates that the number of lattice defects existing in the film 3 is extremely small, and that thermal stress generated on the surface can be relaxed even when exposed to plasma of an etching gas, and therefore, the member 1 for a plasma processing apparatus having high plasma resistance for a long period of time can be realized without generating cracks and particles. Here, the intensity of the peak of (222) plane is represented by the intensity I₂₂₂And intensity of peak belonging to (310) plane I₃₁₀Is a value measured by an X-ray diffraction apparatus.

The coefficient of variation of the thickness of the film 3 may be 0.04 or less. The member 1 for a plasma processing apparatus according to the present invention satisfying such a configuration can be used for a long period of time as compared with a member for a plasma processing apparatus having a coefficient of variation in thickness exceeding this range.

Here, if the description is given using the reference symbols shown in fig. 1, the coefficient of variation is: the thickness from the upper surface 2a to the surface of the film 3 is measured at a plurality of points in a cross section perpendicular to the upper surface 2a of the substrate 2 on which the film 3 is formed, and the standard deviation of the obtained values is divided by the average value to obtain the value.

The absolute value of the skewness of the thickness of the film 3 may be 1 or less. If the absolute value of the deviation of the thickness is 1 or less, the distribution of the thickness becomes a normal distribution or a distribution close to a normal distribution, and high stress is not likely to locally remain, so that the possibility of peeling of the film 3 can be reduced even if the plasma is repeatedly exposed for a long period of time. In particular, the thickness of the film 3 may have a deviation of 0 to 1.

Here, skewness is an index (statistic) indicating how much a distribution deviates from a normal distribution, that is, the bilateral symmetry of the distribution, and when the skewness Sk > 0, the tail of the distribution is oriented to the right, when the skewness Sk equals 0, the distribution is bilaterally symmetric, and when the skewness Sk < 0, the tail of the distribution is oriented to the left.

The thickness skewness can be determined by using a function SKEW provided by Excel (registered trademark, Microsoft Corporation).

More specifically, the measurement was performed using a spectroscopic interferometer with a refractive index of 1.92. At least 20 or more observation regions as objects, for example, regions in a range of 50mm in both the lateral and longitudinal directions, are measured without any deviation.

In the member 1 for a plasma processing apparatus according to the present invention, in which the coefficient of variation in thickness is 0.04 or less, the maximum height Rz of the roughness curve of the surface of the film 3 is 6 μm or less. The maximum height Rz of the roughness curve of the surface of the film 3 can be measured by a laser microscope (ultra-deep color 3D shape measuring microscope (VK-9500 or its succeeding model) manufactured by KEYENCE) in accordance with JIS B0601-2001. As the measurement conditions, the magnification was 1000 times (eyepiece: 20 times, objective: 50 times), the measurement mode was the color super depth, the measurement resolution (pitch) in the height direction was 0.05 μm, the optical zoom was 1.0 times, the gain was 953, the ND filter was 0, the measurement range was 278. mu. m.times.210. mu.m, the cutoff λ s was 2.5 μm, and the cutoff λ c was 0.08 mm. In the calculation of the numerical value, the number n is set to 5 or more, and the average value of the obtained values is defined as the maximum height Rz of the roughness curve of the surface of the film 3.

The thickness of the film 3 in the member 1 for a plasma processing apparatus of the present invention is 5 μm or more and 200 μm or less. The film 3 has a micro vickers hardness Hmv of 7.5GPa or more. The method for measuring the micro Vickers hardness Hmv is carried out according to JIS R1610 (2003). The measurement was performed using AMT-X7FS, an automatic micro hardness testing system manufactured by MATSUZAWA, with a test load of 0.4903N (50gf) and a holding force of 15 seconds. A sample in which the film 3 is provided on the upper surface 2a of the mirror-finished substrate 2 is preferably used.

In the film 3, particularly if the coefficient of variation of the thickness is 0.025 or less, the member 1 for a plasma processing apparatus has a high cost-efficiency ratio because the lifetime is extended at the same average thickness.

Also, the membrane 3 may be: the surface exposed to plasma has an arithmetic average roughness Ra of 0.01-0.1 [ mu ] m, has a plurality of pores, and has a value A obtained by subtracting the average value of the equivalent circle diameters of the pores from the average value of the distance between the centers of gravity of adjacent pores, the value A being 28-48 [ mu ] m.

The value A of 28 μm to 48 μm indicates that the number of pores is small, the pores are small, and the pores are dispersed. Therefore, the member 1 for a plasma processing apparatus satisfying the above configuration has a small number of particles generated from the inside of the gas hole. Even if microcracks starting from the pores occur, the microcracks are dispersed to such an extent that the propagation of the microcracks can be blocked by the pores in the vicinity, and therefore the number of particles generated along with the propagation of the microcracks is small.

The arithmetic average roughness Ra may be measured in accordance with JIS B0601-2013. Specifically, a surface roughness measuring instrument (Surfcorder) SE500 manufactured by Okagaku K.K. was used, and the radius of a stylus was set to 5 μm, the measurement length was set to 2.5mm, and the cutoff value was set to 0.8 mm.

In the member 1 for a plasma processing apparatus of the present invention, the area occupancy of the plurality of pores in the film 3 may be 1.5 area% or more and 6 area% or less. When the area occupancy of the pores is 1.5 area% or more and 6 area% or less, even if micro-cracks occur on the surface exposed to plasma (including the surface newly exposed by the plasma exposure to reduce the thickness of the film), the expansion of the micro-cracks can be blocked by the pores, and therefore the number of particles associated with the micro-cracks is small. Since the area ratio of the pores on the surface exposed to the plasma is low, the number of particles generated from the inside of the pores is further reduced.

In the member 1 for a plasma processing apparatus of the present invention, the average value of the spheroidization ratios of the pores in the film 3 may be 60% or more. When the spheroidization ratio of the pores is within this range, residual stress is less likely to accumulate in the peripheral portion of the pores, and therefore, particles are less likely to be generated from the peripheral portion of the pores when exposed to plasma.

Here, the spheroidization ratio of the pores is determined by the following equation (1) by using the ratio determined by the graphite area method.

Spheroidization ratio (%) of pores (actual area of pores)/(area of minimum circumscribed circle of pores) × 100 … (1)

In particular, the average spheroidization rate of pores may be 62% or more.

The average value of the distance between centers of gravity of the pores, the average value of the equivalent circle diameter of the pores, the area occupancy, and the spheroidization ratio can be obtained by the following methods.

First, the surface of the film 3 is observed at a magnification of 100 times using a digital microscope, and an image of an area of 7.68mm is taken by a CCD camera, for example²The observation image obtained in the range of (3.2 mm in the lateral direction and 2.4mm in the longitudinal direction) was used as an object, and the average value of the distance between the centers of gravity of the pores was obtained by a method such as the center-of-gravity distance method for measuring the degree of dispersion, using image analysis software "a-man (ver 2.52)" (registered trademark, manufactured by Asahi Kasei Engineering co., ltd., which will be described later as image analysis software "a-man").

By performing analysis by a method such as particle analysis using the image analysis software "a as you" using the same observation image as the above observation image, the average value of the equivalent circle diameters of pores, the area occupancy rate, and the spheroidization rate can be obtained.

The average grain size of the crystal grains of yttrium oxide may be 0.01 to 2.5 μm. If the average particle size is 0.01 μm or more, the grain boundary triple point per unit area decreases, and even if a high voltage is applied in the plasma processing apparatus, chipping (chipping) from the grain boundary triple point decreases, and therefore, abnormal discharge is less likely to occur. On the other hand, if the average particle size is 0.01 μm or more and 2.5 μm or less, the fracture toughness of the film 3 becomes high, and even if a defect exists on the surface of the film 3 exposed to plasma, the generation and propagation of a micro crack from the defect can be suppressed.

The average grain size of the crystal grains of yttrium oxide can be determined by using a band contrast map obtained by an EBSD (Electron Back Scattered Diffraction Pattern: Electron Back Scattering Diffraction) method. Specifically, a band contrast chart having a magnification of 10000 times, a length in the lateral direction of 12 μm, and a length in the longitudinal direction of 9 μm was obtained by observing the surface of the film 3. The average particle diameter can be determined by radially drawing 6 straight lines of the same length, for example, 6 μm, around an arbitrary point on the band contrast chart, and dividing the total of the lengths of the 6 straight lines by the total of the numbers of crystals present on the straight lines.

In particular, the mean grain size of the crystal grains of yttrium oxide may be 0.07 to 2 μm.

The first peak of yttrium oxide may be in the visible region according to a measurement using a cathodoluminescence method.

FIG. 8 shows that the film and composition formula of the member for a plasma processing apparatus of the present invention measured by a cathodoluminescence method are in a stoichiometric ratio (Y)₂O₃) A graph of the emission spectrum of each of the yttria ceramics (sintered bodies).

According to fig. 8, the first peak of the sintered body is located in the ultraviolet region, whereas the first peak of the film is located in the visible region. The first peak is the peak with the highest intensity of yttria.In this way, the fact that the first peak of yttria as the main component of the film is located on the higher wavelength side than the first peak of yttria as the main component of the sintered body means that the compositional formula of yttria is a non-stoichiometric ratio, for example, Y₂O_3-x(0＜x≤1)。

If the first peak of yttrium oxide is located in the visible light region, oxygen defects are generated as shown in the above composition formula, and electrons are easily moved in the oxygen defects, so that the effect of removing static electricity is improved.

In particular, the first peak of yttria can be located between 400nm and 600 nm.

Next, a method for manufacturing the member 1 for a plasma processing apparatus of the present invention will be described. First, a method for producing the substrate 2 will be described in which the substrate 2 is formed of alumina ceramic.

Preparing alumina (Al) having an average particle diameter of 0.4 to 0.6 μm₂O₃) A powder and alumina B powder having an average particle diameter of about 1.2 to 1.8 μm. Preparation of silicon oxide (SiO)₂) The powder was used as a Si source to prepare calcium carbonate (CaCO)₃) The powder served as Ca source. A fine powder having an average particle diameter of 0.5 μm or less is prepared as the silica powder. To obtain an alumina ceramic containing Mg, magnesium hydroxide powder was used. In the following description, the powders other than the alumina a powder and the alumina B powder are collectively referred to as first subcomponent powders.

Then, a predetermined amount of the first subcomponent powder was weighed. Next, the alumina a powder and the alumina B powder were weighed so that the mass ratio was 40: 60-60: 40, and converting Al into Al in 100 mass% of the constituent components of the obtained alumina ceramic₂O₃The content of (b) is 99.4 mass% or more, and an alumina mixed powder is prepared. In the first subcomponent powder, it is preferable to first grasp the Na content in the alumina blend powder and convert the Na content in the case of producing alumina ceramics into Na₂O is weighed so that the ratio of the converted value to the value obtained by converting the component (Si, Ca, etc. in this example) constituting the first subcomponent powder to an oxide is 1.1 or less.

Then, 1 to 1.5 parts by mass of a binder such as PVA (polyvinyl alcohol), 100 parts by mass of a solvent, and 0.1 to 0.55 part by mass of a dispersant are added to 100 parts by mass of the total of the alumina mixed powder, the first subcomponent powder, the alumina mixed powder, and the first subcomponent powder, and mixed and stirred in a stirring device to obtain a slurry.

Then, the slurry is spray-granulated to obtain granules, and the granules are molded into a predetermined shape by a powder press molding apparatus, an isostatic press molding apparatus, or the like, and cut as necessary to obtain a substrate-shaped molded body.

Next, the surface on the side where the film 3 is to be formed may be polished using diamond abrasive grains having an average grain size of 1 μm or more and 5 μm or less and a polishing disk made of tin after firing at a firing temperature of 1500 or more and 1700 or less and a holding time of 4 hours or more and 6 hours or less to obtain a base material.

Next, a method of forming the film 3 will be described with reference to fig. 7. Fig. 7 is a schematic diagram showing a sputtering apparatus 20, and the sputtering apparatus 20 includes a chamber 15, a gas supply source 13 connected to the inside of the chamber 15, an anode 14 and a cathode 12 positioned in the chamber 15, and a target 11 connected to the cathode 12 side.

As a method for forming the film 3, the substrate 2 obtained by the above method is provided on the anode 14 side in the chamber 15. On the opposite side in the chamber 15, a target 11 of metal yttrium having a purity of 4N or more is provided on the cathode 12 side. In this state, the inside of the chamber 15 is reduced in pressure by the exhaust pump, and argon and oxygen are supplied as the gas G from the gas supply source 13.

Here, by controlling the partial pressure of argon, the area ratio of the crystal grains of yttrium oxide oriented in the range in which the deviation angle of the crystal lattice plane of yttrium oxide from the {111} direction is within ± 10 ° or within ± 5 °. In order to make the area ratio of the crystal grains of yttrium oxide oriented in the range of deviation angle of the crystal lattice plane of yttrium oxide from {111} direction within + -10 DEG be 45% or more, the partial pressure of argon is set to be 1.4Pa or less. In order to make the area ratio of the crystal grains of yttrium oxide oriented in the range of the deviation angle of the crystal lattice plane of yttrium oxide from the {111} direction within + -5 DEG 20% or more, the partial pressure of argon is set to 0.005Pa to 1.2 Pa.

Then, an electric field is applied between the anode 14 and the cathode 12 by a power supply, plasma P is generated, and sputtering is performed, thereby forming a metal yttrium film on the surface of the base material 2. The thickness in 1 formation was sub-nm. Next, an oxidation process of the metal yttrium film is performed. Then, the member 1 for a plasma processing apparatus according to the present invention can be obtained by alternately performing the steps of forming a metal yttrium film and oxidizing the metal yttrium film so that the total thickness of the films 3 becomes 10 μm to 200 μm, and laminating the films, the member 1 for a plasma processing apparatus including: a substrate 2 containing aluminum as a first element, a film 3 containing yttrium oxide as a main component on the substrate 2, and an amorphous portion 4 interposed between the substrate 2 and the film 3 and containing the first element, yttrium, and oxygen.

In order to obtain the member 1 for a plasma processing apparatus having the largest yttrium content in the amorphous portion 4 in terms of mass ratio, the time of the primary oxidation step may be shortened to, for example, 1 hour or less.

In order to obtain the member 1 for a plasma processing apparatus in which the amorphous portion 4 is in a layered form and the thickness of the amorphous portion 4 is 0.0001 to 0.0008 times the thickness of the film, the time of the primary oxidation step may be 30 minutes or less.

In order to obtain the member 1 for a plasma processing apparatus in which the amorphous portion 4 is layered and the thickness of the amorphous portion 4 is 1nm to 9nm, the time of the primary oxidation step may be set to 3 minutes or less.

In order to obtain the member 1 for a plasma processing apparatus in which the mean grain size of the crystal grains of yttrium oxide is 0.01 to 2.5 μm, the step of forming a metal yttrium film and the oxidation step of the metal yttrium film may be adjusted so that the film thickness is 5 to 500 μm.

In order to obtain the member 1 for a plasma processing apparatus in which the 1 st peak of yttria measured by the cathodoluminescence method is located in the visible light region, the pressure of oxygen used in the oxidation step may be, for example, 0.5Pa to 5 Pa.

The power supplied from the power supply may be either high-frequency power or direct-current power.

The member 1 for a plasma processing apparatus according to the present invention obtained by the above-described manufacturing method can reduce the number of particles generated from the inside of the gas hole and the number of particles generated along with the expansion of the microcracks.

The member 1 for a plasma processing apparatus according to the present invention is applicable to, for example, a high-frequency wave transmission window member through which a high-frequency wave for generating plasma is transmitted, an orifice plate (shower plate) for distributing a plasma generating gas, a susceptor (susceptor) for mounting a semiconductor wafer, and the like in a plasma processing apparatus such as a sputtering apparatus 20, and can realize a plasma processing apparatus having high durability and reliability.

The present invention can be embodied in other various forms without departing from the spirit or essential characteristics thereof. Therefore, the foregoing embodiments are merely exemplary in all aspects, and the scope of the present invention is defined by the appended claims and is not limited by the text of the specification in any way. Further, all of the modifications and changes belonging to the claims are within the scope of the present invention. For example, inventions resulting from combinations of embodiments of the present invention are also within the scope of the present invention.

Description of the reference numerals

1: member for plasma processing apparatus

2: base material

3: film

4: amorphous part

20: sputtering device