TWI643978B - Components for semiconductor manufacturing equipment - Google Patents

Abstract

Provided is a member for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recessed portion; and a first layer containing a yttrium compound formed on the corrosion-resistant aluminum substrate, the first layer having: a first region; and A second region between the first region and the anti-corrosion aluminum substrate is located in the recess, and the average particle diameter in the first region is shorter than the average particle diameter in the second region.

Description

Components for semiconductor manufacturing equipment

An aspect of the present invention generally relates to a member for a semiconductor manufacturing apparatus.

In a semiconductor device manufacturing process, a semiconductor manufacturing device that performs processes such as dry etching, sputtering, and CVD (Chemical Vapor Deposition) in a chamber is used. . Particles are often generated in the reaction chamber by a workpiece, an inner wall of the reaction chamber, or the like. Since such fine particles are a factor that reduces the yield of the semiconductor device to be manufactured, it is required to reduce the fine particles.

In order to reduce particles, a member for a semiconductor manufacturing apparatus used in a reaction chamber or its surroundings is required to be resistant to plasma. Therefore, a method of coating the surface of a member for a semiconductor manufacturing device with a coating film (layer) having excellent plasma resistance is used. For example, a member having a yttria thermal spraying film formed on the surface of a substrate is used. However, cracks or peeling often occur in the thermal spray film, and it cannot be said that the durability is sufficient. Since the peeling of the coating film or the peeling from the coating film is a factor in the generation of fine particles, it is required to suppress the peeling of the coating film from the substrate. In this regard, Patent Document 1 discloses that A semiconductor or liquid crystal manufacturing device member using a ceramic film formed by an aerosol deposition method (Patent Document 1).

In recent years, miniaturization of semiconductor devices is progressing, and control of fine particles at a nano level is required.

[Patent Document 1]: Japanese Patent Laid-Open No. 2005-158933

The object is to provide a member for a semiconductor manufacturing device capable of reducing particles.

A first invention is a member for a semiconductor manufacturing device, comprising: an alumite substrate including a recessed portion; and a first layer formed on the anti-corrosion aluminum substrate and containing a yttrium compound, the first layer having: A first region; and a second region located in the recessed portion between the first region and the anti-corrosion aluminum substrate, the mean particle size in the first region is smaller than that in the second region The average particle diameter is short.

According to this member for a semiconductor manufacturing apparatus, the average particle diameter of the first region close to the surface is smaller than the average particle diameter of the second region. That is, the first layer has a dense structure in the first region on the surface side of the member for a semiconductor manufacturing apparatus. Accordingly, the plasma resistance can be improved. The first layer has a structure that is thinner than the first region in the second region in the recess. With the sparse structure of the second region, the stress generated near the interface between the first layer and the corrosion-resistant aluminum substrate in the recess can be relieved. Accordingly, it is possible to suppress the first layer from peeling off from the corrosion-resistant aluminum substrate. With the above, particles can be reduced.

A second invention is a member for a semiconductor manufacturing device, wherein in the first invention, the average particle diameter of the first region is 10 nanometers or more and 19 nanometers or less, and the average value of the second region is the average value. The particle size is 20 nm to 43 nm.

According to this member for a semiconductor manufacturing apparatus, the first layer has a dense structure in the first region on the surface side of the member for a semiconductor manufacturing apparatus. Accordingly, the plasma resistance can be improved. Moreover, the first layer has a sparse structure in a second region within the recess. Accordingly, the stress generated near the interface between the first layer and the anti-corrosion aluminum substrate in the recess can be reduced, and the first layer can be prevented from peeling off from the anti-corrosion aluminum substrate. With the above, particles can be reduced.

A third invention is a member for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recess; and a first layer formed on the corrosion-resistant aluminum substrate and containing yttrium oxide; the first layer has : A first region; and a second region between the first region and the anti-corrosion aluminum substrate provided in the recess, the first region having a monoclinic crystal as a main phase, The aforementioned second region has a cubic crystal as a main phase.

According to this member for a semiconductor manufacturing apparatus, the crystal grains in the first region are skewed compared to the crystal grains in the second region. That is, compared with the grains in the second region, the grains in the first region have a crushed shape. Therefore, the yttrium oxide layer has a dense structure on the surface side of the member for a semiconductor manufacturing device. Accordingly, the plasma resistance can be improved. The first layer has a structure that is thinner than the first region in the second region in the recess. With the sparse structure of the second region, the first layer and the anti- The stress generated near the interface of the etched aluminum substrate can prevent the first layer from peeling off from the etched aluminum substrate. With the above, particles can be reduced.

A fourth invention is a member for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recessed portion; and a first layer containing a yttrium compound formed on the corrosion-resistant aluminum substrate, the first layer having: a first region And a second region provided in the recessed portion between the first region and the anti-corrosion aluminum substrate, the first region being denser than the second region.

According to this member for a semiconductor manufacturing apparatus, the first layer has a dense structure in the first region on the surface side of the member for a semiconductor manufacturing apparatus. Accordingly, the plasma resistance can be improved. Moreover, the first layer has a sparse structure in a second region within the recess. Accordingly, the stress generated near the interface between the first layer and the anti-corrosion aluminum substrate in the recess can be reduced, and the first layer can be prevented from peeling off from the anti-corrosion aluminum substrate. With the above, particles can be reduced.

A fifth invention is a member for a semiconductor manufacturing device, in the fourth invention, a ratio of an area of a sparse region in the cross section of the first region to an area of a cross section of the first region is 0.4% or more 1.7% or less, and the ratio of the area of the sparse region in the cross section of the second region to the area of the cross section of the second region is 2.0% or more.

According to this member for a semiconductor manufacturing apparatus, the first layer has a dense structure in the first region on the surface side of the member for a semiconductor manufacturing apparatus. Accordingly, the plasma resistance can be improved. Moreover, the first layer has a sparse structure in a second region within the recess. Accordingly, the first part in the recess can be alleviated. The stress generated near the interface between the layer and the corrosion-resistant aluminum substrate can suppress the first layer from peeling from the corrosion-resistant aluminum substrate. With the above, particles can be reduced.

A sixth invention is a member for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate having a recessed portion; and a first layer containing a yttrium compound formed on the corrosion-resistant aluminum substrate, the first layer having: a first region And a second region located in the recessed portion between the first region and the anti-corrosion aluminum substrate, the recessed portion having a first portion provided with the first region and a second portion provided with the second region In part, the width of the second portion is narrower than the width of the first portion in a cross section along the lamination direction.

According to this member for a semiconductor manufacturing apparatus, it is possible to suppress a sudden change in the width of the recessed portion, and to suppress the concentration of stress generated near the interface between the first layer in the recessed portion and the anti-corrosion aluminum substrate. Therefore, peeling of the first layer of the self-corrosion-resistant aluminum substrate can be suppressed, and fine particles can be reduced.

A seventh invention is a member for a semiconductor manufacturing device, wherein in the sixth invention, the second portion has a bottom surface along a plane perpendicular to the lamination direction, and in the cross section, an opening width of the first portion is opposite to The ratio of the width of the bottom surface is 1.1 times or more.

According to this member for a semiconductor manufacturing apparatus, it is possible to suppress a sudden change in the width of the recessed portion, and to suppress the concentration of stress generated near the interface between the first layer in the recessed portion and the anti-corrosion aluminum substrate. Therefore, peeling of the first layer of the self-corrosion-resistant aluminum substrate can be suppressed, and fine particles can be reduced.

An eighth invention is a member for a semiconductor manufacturing device, characterized in that in the sixth or eighth invention, the first layer has In the surface on the opposite side to the surface in contact with the anti-corrosion aluminum base material, the width of the recessed portion in the cross section becomes narrower as it is separated from the surface.

According to this member for a semiconductor manufacturing apparatus, it is possible to suppress concentration of stress generated near the interface between the first layer in the recessed portion and the corrosion-resistant aluminum base material. Therefore, peeling of the first layer from the corrosion-resistant aluminum substrate can be suppressed.

A ninth invention is a member for a semiconductor manufacturing device, in the sixth invention, the opening of the recessed portion has a first end portion and a second end portion separated from each other in the cross section, and the second portion has An angle formed by a straight line connecting the first end portion and the second end portion and a straight line connecting the first end portion and the bottom surface with the shortest in the cross section of the bottom surface of the plane perpendicular to the lamination direction is 10 ° above 89 °.

According to this member for a semiconductor manufacturing apparatus, it is possible to suppress a sharp change in the width of the recessed portion, and to suppress the concentration of stress generated near the interface between the first layer in the recessed portion and the corrosion-resistant aluminum substrate. Therefore, peeling of the first layer of the self-corrosion-resistant aluminum substrate can be suppressed, and fine particles can be reduced.

A tenth invention is a member for a semiconductor manufacturing device, wherein in any one of the sixth to ninth inventions, in the cross section, the first layer and the anti-corrosion aluminum substrate in the recessed portion The border is curved.

According to this member for a semiconductor manufacturing apparatus, discontinuous changes in the boundary between the first layer in the recessed portion and the anti-corrosion aluminum substrate are suppressed, and stress generated near the interface between the first layer in the recessed portion and the anti-corrosion aluminum substrate can be suppressed concentrated. Therefore, peeling of the first layer from the corrosion-resistant aluminum substrate can be suppressed.

An eleventh invention is a member for a semiconductor manufacturing device, characterized in that in any one of the seventh to tenth inventions, in the aforementioned cross section, the first layer and the anti-corrosion aluminum base in the recessed portion The boundary of the material has curvature.

According to this member for a semiconductor manufacturing apparatus, discontinuous changes in the boundary between the first layer in the recessed portion and the anti-corrosion aluminum substrate are suppressed, and stress generated near the interface between the first layer in the recessed portion and the anti-corrosion aluminum substrate can be suppressed concentrated. Therefore, peeling of the first layer from the corrosion-resistant aluminum substrate can be suppressed.

A twelfth invention is a member for a semiconductor manufacturing device, wherein in any one of the seventh to eleventh inventions, in the cross section, the first layer and the anti-corrosion aluminum in the recessed portion The radius of curvature of the boundary of the base material is 0.4 micrometer or more.

According to this member for a semiconductor manufacturing apparatus, it is possible to suppress a sudden change in the width of the recessed portion, and to suppress the concentration of stress generated near the interface between the first layer in the recessed portion and the anti-corrosion aluminum substrate. Therefore, peeling of the first layer of the self-corrosion-resistant aluminum substrate can be suppressed, and fine particles can be reduced.

10‧‧‧Anti-corrosion aluminum substrate

10a, 10A ~ 10D, 12A ~ 12D ‧‧‧ recess

10b‧‧‧ convex

11‧‧‧ Components

12‧‧‧Anti-corrosion aluminum layer

20‧‧‧ First floor

41‧‧‧ Part I

42‧‧‧ Part Two

42B‧‧‧ Underside

50, 51‧‧‧circles

53, 54, 55‧‧‧ border

100‧‧‧Semiconductor manufacturing equipment

110‧‧‧Reaction Room

120‧‧‧Semiconductor Manufacturing Device Components

160‧‧‧ electrostatic chuck

191‧‧‧area

201‧‧‧ faces

202‧‧‧ surface

210‧‧‧ wafer

221‧‧‧ Particle

θ 1‧‧‧ angle

A1‧‧‧arrow

E1 ~ E4‧‧‧ first ~ fourth end

OP‧‧‧ opening

R‧‧‧ radius of curvature

R1‧‧‧First Zone

R2‧‧‧Second Zone

WB‧‧‧Width

WO‧‧‧ opening width

FIG. 1 is a cross-sectional view illustrating a semiconductor manufacturing apparatus having a member for a semiconductor manufacturing apparatus according to an embodiment.

2 (a) and 2 (b) are cross-sectional views illustrating members for a semiconductor manufacturing apparatus according to an embodiment.

3 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

Fig. 4 is a photographic view showing a cross section of the first layer.

Fig. 5 is a photographic view showing a cross section of the first layer.

6 (a) and 6 (b) are tables and graphs showing the particle size in the first layer.

7 (a), (b), and (c) are photo diagrams illustrating structural analysis of crystal grains in the first layer.

8 (a), (b), (c), and (d) are photographic diagrams illustrating the structural analysis of the crystal grains in the first layer.

FIG. 9 is a table showing a crystal structure of crystal grains in the first layer.

FIG. 10 is a table showing the crystallite size in the first layer.

11 (a) and 11 (b) are tables and graphs showing the area ratios of the sparse areas in the first layer.

12 (a), (b), (c), and (d) are photographic views showing a cross section of the first layer.

13 (a), (b), (c), and (d) are photographic views showing a cross section of the first layer.

14 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

15 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

16 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

FIG. 17 is a table illustrating the shape of the first layer of a member for a semiconductor manufacturing apparatus according to the embodiment.

18 is a table illustrating a shape of a first layer of a member for a semiconductor manufacturing apparatus according to the embodiment.

FIG. 19 illustrates a semiconductor manufacturing apparatus according to the embodiment; Use the shape of the first layer of the component.

20 (a) and 20 (b) are photographic views illustrating members for a semiconductor manufacturing apparatus according to the embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in the drawings, the same constituent elements are assigned the same reference numerals, and detailed descriptions are appropriately omitted.

FIG. 1 is a cross-sectional view illustrating a semiconductor manufacturing apparatus having a member for a semiconductor manufacturing apparatus according to an embodiment.

The semiconductor manufacturing apparatus 100 shown in FIG. 1 includes a reaction chamber 110, a member 120 for a semiconductor manufacturing apparatus, and an electrostatic chuck 160. The member 120 for a semiconductor manufacturing apparatus is disposed in an upper portion of the inside of the reaction chamber 110 such as a top plate. The electrostatic chuck 160 is disposed in the lower part of the inside of the reaction chamber 110. That is, the member 120 for a semiconductor manufacturing apparatus is disposed on the electrostatic chuck 160 inside the reaction chamber 110. An object to be adsorbed such as a wafer 210 is placed on the electrostatic chuck 160.

In the semiconductor manufacturing apparatus 100, high-frequency power is supplied, and a source gas such as a halogen-based gas such as an arrow A1 shown in FIG. 1 is introduced into the reaction chamber 110. Then, the raw material gas introduced into the inside of the reaction chamber 110 is plasmatized in a region 191 between the electrostatic chuck 160 and the semiconductor manufacturing device member 120.

Here, if fine particles are generated inside the reaction chamber 110 If 221 is attached to the wafer 210, the semiconductor device manufactured may be defective. As a result, the yield and productivity of the semiconductor device may be reduced. Therefore, the member 120 for a semiconductor manufacturing apparatus is required to be resistant to plasma.

In addition, the member for a semiconductor manufacturing apparatus according to the embodiment may be a member arranged at a position other than the upper part of the reaction chamber or around the reaction chamber. The semiconductor manufacturing apparatus using the member for a semiconductor manufacturing apparatus is not limited to the example shown in FIG. 1, and includes any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs processes such as annealing, etching, sputtering, and CVD.

2 (a) and 2 (b) are cross-sectional views illustrating members for a semiconductor manufacturing apparatus according to an embodiment.

As shown in FIG. 2 (a), a member for a semiconductor manufacturing apparatus includes a corrosion-resistant aluminum substrate 10 and a first layer 20.

In the following description, the direction in which the anti-corrosion aluminum substrate 10 and the first layer 20 are laminated is referred to as the Z-axis direction. A direction perpendicular to the Z-axis direction is taken as the X-axis direction. The direction perpendicular to the Z-axis direction and the X-axis direction is taken as the Y-axis direction.

The corrosion-resistant aluminum substrate 10 includes a member 11 and a corrosion-resistant aluminum layer 12 disposed on the member 11. The material of the member 11 is, for example, aluminum or an aluminum alloy. The anti-corrosion aluminum layer 12 includes alumina (Al ₂ O ₃ ). The anti-corrosion aluminum layer 12 is formed by applying an alumite treatment to the member 11. That is, the anti-corrosion aluminum layer 12 is an anodized coating film covering the surface of the member 11. The thickness of the anti-corrosion aluminum layer 12 is, for example, about 0.5 μm (μm) to about 70 μm.

The general anti-corrosion aluminum processing process is composed of the following processes: a process of forming a dense alumina layer (coating film) on the surface of the aluminum substrate; a process of growing the alumina layer; a process of sealing treatment according to need and Dry process. Among these processes, porous alumina is formed in a process of growing an alumina layer, and a form of pores is formed in the recess. In addition, by a sealing treatment or a dry heat treatment, a difference between the thermal expansion coefficient of the aluminum metal and the thermal expansion coefficient of the alumina is formed, and a form of a crack is formed in the alumina layer. When the thickness of the alumina layer formed by the anti-corrosion aluminum treatment is about 0.3 μm, a dense alumina layer without a recess can be obtained. When the thickness of the alumina layer is 0.5 μm or more, porous alumina having a recessed portion is formed. In addition, the thickness of a general anti-corrosion aluminum-treated coating film is 5 μm to 70 μm.

The first layer 20 contains a yttrium compound. For example, the first layer 20 contains at least any one of fluorine and oxygen and yttrium. The first layer 20 is, for example, yttrium oxide (Y ₂ O ₃ ), yttrium fluoride (YF ₃ ), or yttrium oxyfluoride (YOF). In the following example, the first layer 20 is a polycrystal of yttria (Y ₂ O ₃ ). The thickness of the first layer 20 is, for example, about 5 μm.

The first layer 20 includes a surface 201 on the side of the anti-corrosion aluminum base material 10 and a surface 202 on the side opposite to the surface 201. The first layer 20 is in contact with the corrosion-resistant aluminum substrate 10 in the surface 201. The surface 202 becomes the surface of the member 120 for a semiconductor manufacturing device.

The first layer 20 is formed by [aerosol deposition method]. [Aerosol deposition method] is an aerosol that disperses particles containing brittle materials and the like in a gas by spraying nozzles toward a substrate, and the particles collide with gold Substrates such as metals, glass, ceramics, and plastics are deformed and / or broken by particles of brittle materials by the impact of the collision, and the substrates are joined to form a layered structure (also called It is a method of forming a film-like structure directly on a substrate.

In this example, an aerosol containing fine particles containing yttrium oxide is sprayed toward the substrate (the corrosion-resistant aluminum layer 12 of the corrosion-resistant aluminum substrate 10) to form a layered structure (first layer 20).

According to the aerosol deposition method, heating means or cooling means are not particularly required, and a layered structure can be formed at normal temperature, and a layered structure having a mechanical strength equal to or higher than that of a fired body can be obtained. In addition, the density, mechanical strength, and electrical characteristics of the layered structure can be changed in various ways by controlling the conditions under which the particles collide, the shape and composition of the particles.

In the present specification, [polycrystalline] refers to a structure in which crystal grains are bonded and accumulated. Grains are essentially crystals in one composition. The diameter of the crystal grains is usually 5 nanometers (nm) or more. However, when the fine particles are taken into the structure without being broken, the crystal grains are polycrystalline.

In addition, in the description of this case, [microparticles] means that when the primary particles are dense plasmids, the average particle diameter identified by particle size distribution measurement or scanning electron microscope is 5 micrometers (μm) or less. When the primary particles are porous particles that are easily broken by impact, the average particle diameter is 50 μm or less.

[Aerosol] in this specification refers to a solid gas in which helium, nitrogen, argon, oxygen, dry air, and the fine particles are dispersed in a gas including a mixed gas of helium, nitrogen, argon, oxygen, and dry air. The mixed-phase body may include a part of the [aggregate], but the fine particles are essentially dispersed separately. The gas pressure and temperature of the aerosol are arbitrary, but the concentration of the fine particles in the gas is 0.0003 mL when the gas pressure is converted to 1 barometric pressure and the temperature is converted to 20 degrees Celsius. The range of / L ~ 5mL / L is ideal for the formation of layered structures.

The aerosol deposition process is usually carried out at normal temperature, and has a feature at a temperature far below the melting point of the particulate material, that is, the formation of layered structures below several hundred degrees Celsius.

In addition, in this specification, "normal temperature" refers to a temperature at which the sintering temperature of ceramics is significantly low, and is substantially a room temperature environment of 0 to 100 ° C.

The fine particles of the powder constituting the raw material of the layered structure can be composed of fragile materials such as ceramics and semiconductors, and the same fine particles can be mixed with fine particles having different or different particle diameters to use. The fragile material particles are mixed or used in combination. Further, fine particles such as metal materials or organic materials may be mixed with the fine particles of the brittle material, or coated on the surface of the fine particles of the brittle material and used. Even in such cases, the formation of the layered structure is mainly a brittle material.

In addition, in the description of this case, "powder" refers to the aforementioned spontaneous particles. State of aggregation (spontaneous agglutination).

In a composite structure formed by this method, when crystalline fragile material fine particles are used as a raw material, a part of the layered structure of the composite structure is such that its grain size is smaller than that of the raw material fine particles. Polycrystals with small grain sizes often have substantially no crystal orientation. In addition, a grain boundary layer composed of a glass layer does not substantially exist at the interface between the brittle material crystals. Moreover, in many cases, the layered structure part of the composite structure forms an [anchor layer] that invades the surface of the substrate (the corrosion-resistant aluminum substrate 10 in this example). The layered structure on which the anchor layer is formed is formed by being strongly adhered to the substrate with extremely high strength.

The layered structure formed by the aerosol deposition method and the fine particles are obviously packed under pressure with each other. The so-called [green compact], which maintains the state by physical adhesion, is different from the so-called "green compact" Strength of.

In the aerosol deposition method, the fragile particles of flying materials caused fragmentation and deformation on the substrate can be measured by X-ray diffraction method and the like. The crystallite size of the brittle material structure is confirmed. That is, the crystallite size of the layered structure formed by the aerosol deposition method is smaller than the crystallite size of the raw material fine particles. In the [slip plane] or [fracture surface] formed by the particles being broken or deformed, a state in which atoms bonded to other atoms existing in the original particles are exposed is formed [ Fresh noodles surfac)]. It is conceivable that the layered structure is formed by joining the newly-generated surface with high surface energy and activity to the surface of the adjacent fragile material particles or the newly-generated surface of the brittle material and the surface of the substrate.

In addition, when a hydroxyl group exists on the surface of the microparticles in the aerosol, local shear stress generated between the microparticles or between the microparticles and the structure when the microparticles collide can be considered. ), Etc., a mechanochemical acid-base dehydration reaction occurs, and the fine particles are bonded to each other. It is considered that these phenomena continue to occur due to the addition of a continuous mechanical impact force from the outside, and the progress and densification of bonding are repeated by the repetition of deformation and fragmentation of fine particles, and a layered structure made of a brittle material grows.

The first layer 20 containing an yttrium compound (for example, yttria polycrystalline) formed by an aerosol deposition method has a denser structure than that of a yttrium oxide fired body or a yttrium oxide spray film. Accordingly, the plasma resistance of the member 120 for a semiconductor manufacturing device according to the embodiment is higher than the plasma resistance of the fired body or the spray film. Furthermore, the probability that the member 120 for a semiconductor manufacturing device according to the embodiment is a source of generation of particles is lower than the probability of a source of generation of particles such as a fired body or a spray film.

FIG. 2 (b) is an enlarged cross-sectional view showing the vicinity of the boundary B1 between the anti-corrosion aluminum layer 12 and the first layer 20 shown in FIG. 2 (a).

As shown in FIG. 2 (b), the corrosion-resistant aluminum substrate 10 includes a concave portion 10a and a convex portion 10b. As described above, the anti-corrosion aluminum layer 12 is, for example, an anodized coating film formed by an anti-corrosion aluminum process. A crack (recess or hole) is formed in the anti-corrosion aluminum layer 12 during the anti-corrosion aluminum treatment. Therefore, on the surface of the corrosion-resistant aluminum substrate 10 A recessed portion 10a is formed. The convex portion 10 b corresponds to a region where no cracks are formed in the anti-corrosion aluminum layer 12 during the anti-corrosion aluminum treatment.

In addition, in the description of the present case, the [recessed part] refers to those [cracks] or [depressions] and the like existing in the anti-corrosion aluminum layer and not intended to be formed before and after the anti-corrosion aluminum treatment. For example, the [recessed part] in the description of this case does not include a person formed by intentional machining.

The first layer 20 has a first region R1 and a second region R2. The first region R1 is a region on the surface 202 side of the first layer 20. The second region R2 is a region on the anti-corrosion aluminum substrate 10 side of the first layer 20. At least a part of the first region R1 and the second region R2 are juxtaposed in the Z-axis direction. The second region R2 is located between the first region R1 and the corrosion-resistant aluminum substrate 10.

The second region R2 is provided in the recessed portion 10a. That is, the second region R2 is surrounded in the X-Y plane by the surface of the corrosion-resistant aluminum base material 10 on which the recessed portion 10a is formed. For example, the second region R2 is in contact with the surface of the corrosion-resistant aluminum base material 10 forming the recessed portion 10a. The first region R1 is provided above the second region R2 (on the surface 202 side) or above the convex portion 10b. For example, the first region R1 is in contact with the corrosion-resistant aluminum base material 10 in a shallow portion of the convex portion 10b or the concave portion 10a. The surface 202 of the first layer 20 is formed by a first region R1.

In the member for a semiconductor manufacturing apparatus according to the embodiment, the first region R1 is denser than the second region R2. In other words, the second region R2 is thinner than the first region R1. Accordingly, while improving the plasma resistance of the first layer 20, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed.

The structure of the first layer 20 formed on the surface of the corrosion-resistant aluminum substrate 10 (the corrosion-resistant aluminum layer 12) will be described below.

3 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

FIG. 3 is a TEM (Transmission Electron Microscope) image, corresponding to a cross-sectional view shown in FIG. 2 (b).

The structure of the areas A to F in the first layer 20 shown in the photographic diagram will be described below. Regions A and B are included in the aforementioned first region R1. The regions D, E, and F in the first layer 20 are included in the aforementioned second region R2.

In addition, a white region located above the first region R1 is a resin member used to prepare a sample for observation.

4 and 5 are photographic views showing a cross section of the first layer. These figures are photographs taken by TEM. The observation magnification is 250,000 times, and the acceleration voltage is 300kV.

FIG. 4 is an enlarged photographic view of a part of the area A of the first area R1, and FIG. 5 is an enlarged photographic view of a part of the area E of the second area R2. The magnification of the photo map shown in FIG. 4 is the same as the magnification of the photo map shown in FIG. 5. 4 and 5 that the crystal grains in the region A tend to be smaller than the crystal grains in the region E.

6 (a) and 6 (b) are tables and graphs showing the particle size in the first layer.

FIG. 6 (a) shows the average value (mean particle size), the maximum value, the minimum value, and the like of the particle diameters in each of the display areas A to E. Fig. 6 (b) is a graph showing the average particle diameter shown in Fig. 6 (a). The region A-1 indicates a part of the region A, and the region A-2 indicates another part of the region A. Area B-1 represents a part of area B, and area B-2 represents another part of area B. portion.

The particle diameters shown in Figs. 6 (a) and 6 (b) are calculated as follows.

In each of the areas A-1, A-2, B-1, B-2, and C ~ E, two places (two fields of view) were taken, and two photographic pictures similar to those in FIGS. 4 and 5 were obtained. An image processing software (Photoshop (registered trademark) of Adobe Systems, Inc.) was used to read in the photographs taken. The grains whose grain boundaries are clearly observed are selected. As shown in FIGS. 4 and 5, the interface of the grains selected by Photoshop (registered trademark) is scribed. In FIGS. 4 and 5, numbers are added to the selected dies and shown. The number of grains selected here (the number of N shown in Fig. 6 (a)) consists of two photographs in each of the areas A-1, A-2, B-1, B-2, and C ~ E. Figures total about 100.

Next, the image analysis software (LUZEX AP of NIRECO CORPORATION) was used to calculate the diameter (diameter) corresponding to a circle based on the line drawn on the interface for each selected grain. The average particle diameter shown in Fig. 6 (a) is the arithmetic mean (nm) in each region corresponding to the diameter of the circle calculated as described above. The maximum value and the minimum value shown in FIG. 6 (a) are the maximum value (nm) and the minimum value (nm) in each region corresponding to the diameter of the circle calculated as described above.

As shown in FIGS. 6 (a) and 6 (b), the average particle diameter in the regions A and B is shorter than the average particle diameter in the regions D and E. That is, the average particle diameter in the first region R1 is shorter than the average particle diameter in the second region R2. The average particle diameter of the first region R1 is, for example, 10 nm to 19 nm, and preferably 14 nm to 16 nm. The average particle diameter of the second region R2 is, for example, 20 nm to 43 nm, and preferably 39 nm to 43 nm. This means When the first layer 20 is formed by an aerosol deposition method, the grains in the first region R1 are crushed more than the grains in the second region R2. That is, the first layer 20 has a dense structure in the surface side of the member 120 for a semiconductor manufacturing device. Accordingly, the plasma resistance can be improved.

In the aerosol deposition method, a film is formed by the collision of particles, and the film is filled under a high pressure. Therefore, a stress (residual stress) is generated near the interface between the first layer 20 and the anti-corrosion aluminum layer 12. )). It is considered that this stress is particularly likely to be concentrated near the cracks (recesses 10 a) of the corrosion-resistant aluminum layer 12. If stress is generated in the cracks of the anti-corrosion aluminum layer 12, the cracks will progress, and the first layer 20 may peel off from the anti-corrosion aluminum substrate 10, which may cause particles.

On the other hand, in the embodiment, the second region R2 in the recessed portion 10 a has a structure that is thinner than the first region R1 on the surface side. With the sparse structure of the second region R2, the stress generated near the interface between the first layer 20 and the corrosion-resistant aluminum substrate 10 in the recessed portion 10a can be relieved. Accordingly, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed.

As described above, according to the embodiment, the plasma resistance of the surface of the first layer 20 formed on the anti-corrosion aluminum substrate 10 can be improved, and the peeling of the first layer 20 and the anti-corrosion aluminum substrate 10 can be suppressed, and particles can be reduced.

FIGS. 7 (a) to 7 (c) and FIGS. 8 (a) to 8 (d) are photo diagrams illustrating the structural analysis of the crystal grains in the first layer. In this structural analysis, the first layer processed to a thickness of about 70 nm to about 100 nm is used.

7 (a) to 7 (c) are photographic diagrams showing analysis in the area A of the first area R1. FIG. 7 (a) is a TEM image showing the analyzed points. Figure 7 (b) is Diffraction pattern of the electron diffraction at the point P1 shown in FIG. 7 (a). FIG. 7 (c) is a diffraction pattern of the diffraction of the extremely microelectronics at the point P2 shown in FIG. 7 (a).

From the diffraction pattern, the lattice spacing (d) or the plane angle of the lattice plane of the crystals at the analyzed points can be obtained. The lattice interval and the surface angle obtained are compared with the lattice interval and the surface angle (JCPDS (Joint Committee on Powder Diffraction Standards) card of a known structure). Based on this, the crystal structure of the crystal grains at each point is determined.

As shown in FIG. 7 (b), the crystal structure at point P1 is a monoclinic crystal of yttrium oxide. The crystal structure at point P2 as shown in FIG. 7 (c) is also a monoclinic crystal of yttrium oxide.

8 (a) to 8 (d) are photographic views showing analysis in the area E of the second area R2. 8 (a) and 8 (c) are TEM images showing the analyzed points. FIG. 8 (b) is a diffraction pattern of the extremely microelectronic diffraction at the point P3 shown in FIG. 8 (a). FIG. 8 (d) is a diffraction pattern of the diffraction of the extremely microelectrons at the point P4 shown in FIG. 8 (c).

As with the description of points P1 and P2, the crystal structure at points P3 and P4 is determined. As shown in FIG. 8 (b), the crystal structure at point P3 is a cubic crystal of yttrium oxide. The crystal structure at point P4 as shown in FIG. 8 (d) is a cubic crystal of yttrium oxide.

FIG. 9 is a table showing the crystal structure of the crystal grains in the first layer.

In each of the regions A to F, the same analysis as in the description of FIGS. 7 (a) to 7 (c) and FIGS. 8 (a) to 8 (d) was performed. Figure 9 shows 20 in each area The crystal structure of 2 points (2 fields) among the measurement of points. In the analysis of the crystal structure, the results of [rich monoclinic crystal], [rich cubic crystal], [mixed crystal structure], and the like were determined from 20 measurement points.

Regions A and B are [rich monoclinic crystals], and regions D, E, and F are [rich cubic crystals]. Region C has a mixed crystal structure of monoclinic and cubic crystals. That is, for example, the first region R1 is a monoclinic crystal-based phase, and the second region R2 is a cubic crystal-based phase. In addition, the state of a monoclinic main phase refers to a state in which the number of points of a monoclinic crystal is larger than that of a crystal structure other than the monoclinic crystals when the crystal structure is analyzed at a plurality of points (for example, 20 points or more). . Similarly, the state of the cubic phase as the main phase refers to a state in which the number of points of the cubic crystal is larger than the number of points of the crystal structure other than the cubic crystal when the crystal structure analysis of the plurality of points is performed.

Monoclinic crystals have a crystal structure that is skewed from cubic crystals. That is, compared with the grains in the second region R2, the grains in the first region R1 and the grains in the mixed crystal structure region are skewed. This means that when the first layer 20 is formed by an aerosol deposition method, the grains in the first region R1 are crushed more than the grains in the second region R2 and the grains in the mixed crystal structure region. Therefore, the first layer 20 has a dense structure in the surface side of the member 120 for a semiconductor manufacturing device. Accordingly, the plasma resistance can be improved. The first layer 20 has a structure that is thinner than the first region R1 in the second region R2. With the sparse structure of the second region R2, stress generated in the vicinity of the interface between the first layer 20 and the corrosion-resistant aluminum base material 10 in the recessed portion 10a can be reduced, and peeling can be prevented.

FIG. 10 is a table showing the crystallite size in the first layer.

Five samples of the first layer 20 (samples 1 to 5) related to the embodiment Calculate the crystallite size. The crystallite size (nm) of the cubic phase and the crystallite size (nm) of the monoclinic phase in each sample were calculated.

When calculating the crystallite size, the following procedures 1 to 5 are performed.

(Procedure 1): An X-ray diffraction spectrum of a yttrium compound (first layer 20) formed on a corrosion-resistant aluminum substrate is obtained.

(Procedure 2): X-ray diffraction spectrum is read in by X-ray diffraction software (HighScore from PANalytical).

(Procedure 3): The K-α 2 line was removed.

(Procedure 4): Smoothing is performed.

(Procedure 5): An analysis of the crystallite size was performed using the following Scherrer formula.

D = K λ / (β cos θ)

Here, D is the crystallite size, β is the half width of the peak (峰 (rad)), θ is the Bragg angle (rad), and λ is the wavelength of the X-ray used for the measurement.

In the Scherrer formula, β is calculated by β = (β obs-β std). β obs is the half-value width of the X-ray diffraction peak of the measurement sample, and β std is the half-value width of the X-ray diffraction peak of the standard sample. Use 0.94 as the K value. The crystallite size of the cubic phase uses spikes in the (222) plane. The crystallite size of the monoclinic phase uses a spike at the (402) plane. The spikes were separated using the pseudo-Voigt function.

As shown in FIG. 10, the crystallite size (average particle size) of the monoclinic phase obtained by X-ray diffraction is smaller than the crystallite size (average particle size) of the cubic phase obtained by X-ray diffraction. small. In an embodiment, the The crystallite size is 8 nm to 39 nm, preferably 10 nm to 21 nm, and the crystallite size of the monoclinic phase is 5 nm to 19 nm, preferably 5 nm to 12 nm. This means that yttrium oxide, which is a cubic crystal phase, is crushed and changed into a monoclinic phase when the first layer 20 is formed by an aerosol deposition method. That is, the first layer 20 has a dense structure in the surface side of the member 120 for a semiconductor manufacturing device. Accordingly, the plasma resistance can be improved.

11 (a) and 11 (b) are tables and graphs showing the area ratios of the sparse areas in the first layer.

FIG. 11 (a) is a table showing the area ratio (%) of a sparse area in each of the areas A and C to F. FIG. 11 (b) shows the area ratio (%) of the sparse area shown in FIG. 11 (a) in a graph.

Here, [area ratio of sparse area (%)] refers to the ratio of the area of the sparse area in the cross section to the area of a certain cross section. The calculation of the specific [area ratio of the sparse area (%)] will be described with reference to FIGS. 12 (a) to 13 (d).

12 (a) to 13 (d) are photographic views showing a cross section of the first layer.

When calculating the area ratio (%) of a sparse area, the following procedures 1 to 6 are performed.

(Procedure 1): The TEM image of the cross section of the first layer 20 is taken into image analysis software (WINROOF of Mitani Corporation). The observation magnification of this TEM image is 250,000 times. The acquired TEM image is a bright field image.

(Procedure 2): Implement the monochrome of the captured image (TEM image) (Gray scale) and level correction.

(Procedure 3): An ROI (Region of Interest: Attention Area) setting is used to define a region for image analysis, and an unnecessary portion of the analysis is excluded from the acquired TEM image. In this way, the observation range used in the calculation of the area ratio (%) in the sparse area can be selected. The size of one observation range is more than 500nm square. For example, FIG. 12 (a) is a photographic view of an observation range (field of view 1) in a section of the area A, and FIG. 12 (b) is a photographic view of another observation range (field of view 2) in a section of the area A. FIG. 13 (a) is a photographic view of an observation range (field of view 1) in a section of the area E, and FIG. 13 (b) is a photographic view of another observation range (field of view 2) in a section of the area E.

(Procedure 4): The color of the image is expressed in 256 tone. Here, the value of black is 0, and the value of white is 255. The whiter the structure, the thinner the structure, and the darker the structure, the denser the structure. Then, a region having a hue value of 190 or more (a region where the color is white or nearly white) in the video is selected and colored.

FIG. 12 (c) is displayed to emphasize the colored area in the photo map of FIG. 12 (a), and the color of the photo map of FIG. 12 (a) is changed. The area shown in dark black in FIG. 12 (c) corresponds to the area colored by the program 4. Similarly, Fig. 12 (d) shows the area colored by the procedure 4 in the photo map of Fig. 12 (b), and Fig. 13 (c) shows the area colored by the procedure 4 in the photo map of Fig. 13 (a) Fig. 13 (d) shows the area colored by the procedure 4 in the photo graph of Fig. 13 (b).

(Procedure 5): A hole filling process is performed on the colored area, and the holes (uncolored areas) in the colored area are colored.

(Procedure 6): Calculate the number of persons in the observation range on the software The ratio of the area of a colored area to the area of an observation area is regarded as the area ratio of a sparse area. That is, the area ratio (%) of the sparse area = (the area of the colored area in the observation range) / (the area of the observation range) × 100.

With the above procedures 1 to 6, the area ratio of the sparse area in the observation range (field of view 1) shown in FIG. 12 (a) was calculated as 0.4%. The area ratio of the sparse area in the observation range (field of view 2) shown in FIG. 12 (b) was 1.7%. In this way, it is understood that the area ratio of the sparse region in the first region R1 (region A) is low, and the first region R1 has a compact structure.

Similarly, for each of the regions C to F, the area ratio (%) of the sparse region is calculated for each of the two fields of view, and the results are shown in Figs. 11 (a) and 11 (b). The area ratio of the sparse region of the first region R1 (region A) is, for example, 0.4% or more and 1.7% or less. The area ratio of the sparse region of the second region R2 (regions D to F) is, for example, 2.0% or more and 9.3% or less.

As described above, the first layer 20 has a dense structure in the first region R1 on the surface of the member 120 for a semiconductor manufacturing device, and has a sparse structure in the second region R2 on the side of the anti-corrosion aluminum substrate 10.

14 is a photographic view showing a cross section of a member for a semiconductor manufacturing apparatus according to the embodiment.

FIG. 14 is the same as FIG. 3, and shows a cross section of the first layer 20 and the anti-corrosion aluminum layer 12 along the Z-axis direction. The recessed portion 10a includes a first portion 41 provided with a first region R1 and a second portion 42 provided with a second region R2.

The first portion 41 and the second portion 42 are juxtaposed in the Z-axis direction. The first portion 41 is an upper portion of the recessed portion 10a, that is, a shallow portion of the hole. Corrosion-resistant aluminum forming the first portion 41 in the X-Y plane, for example The surface of the base material 10 surrounds a part of the first region R1. In other words, a part of the first region R1 is located in the first part 41. For example, the first portion 41 is a surface of the recessed portion 10 a that is in contact with the first region R1.

The second portion 42 is a portion located below the first portion 41, that is, a deep portion of the hole. For example, the surface of the anti-corrosion aluminum substrate 10 forming the second portion 42 in the X-Y plane surrounds the second region R2. In other words, the second region R2 is located within the second portion 42. For example, the second portion 42 is a surface of the recessed portion 10 a that is in contact with the second region R2.

The width W of the recessed portion 10 a in the cross-section shown in FIG. 14 becomes narrower as it goes away from the surface of the member 120 for a semiconductor manufacturing apparatus. For example, the width W2 of the second portion 42 is narrower than the width W1 of the first portion 41. In addition, the width W1 of the first portion 41 is equal to the distance between the surfaces of the corrosion-resistant aluminum layers 12 side by side in the X-axis direction via the first region R1, for example. The width W2 of the second portion 42 is equal to the distance between the surfaces of the anti-corrosion aluminum layers 12 side by side in the X-axis direction via the second region R2, for example.

If there is a portion where the width W of the recessed portion 10a changes abruptly, stress is concentrated on that portion. On the other hand, in the member 120 for a semiconductor manufacturing apparatus according to the embodiment, the width W of the recessed portion 10 a gradually decreases in the direction from the first layer 20 toward the corrosion-resistant aluminum base material 10. As a result, the width W of the recessed portion 10 a can be suppressed from rapidly changing, and the concentration of stress generated near the interface between the first layer 20 and the corrosion-resistant aluminum base material 10 in the recessed portion 10 a can be suppressed. Therefore, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed, and fine particles can be reduced.

15 and 16 show semiconductors according to the embodiment. Photograph of a cross section of a member for a body manufacturing device.

15 and 16 are cross-sections S of the first layer 20 and the anti-corrosion aluminum layer 12 along the Z-axis direction.

The opening OP of the recessed portion 10a (the first portion 41) has a first end portion E1 and a second end portion E2 separated from each other in a cross section along the Z-axis direction. The first end portion E1 and the second end portion E2 are end portions in the X-axis direction of the recessed portion 10 a and are upper end portions of the opening OP of the recessed portion 10 a.

Each of the first end portion E1 and the second end portion E2 is a tangent point of the first straight line L1 and the corrosion-resistant aluminum layer 12. In addition, the first straight line L1 is a tangent to the anti-corrosion aluminum layer 12 across the recessed portion 10 a in the boundary between the first layer 20 and the anti-corrosion aluminum layer 12.

In a cross section along the Z-axis direction, the recessed portion 10 a has a right-side portion RP and a left-side portion LP side by side in the X-axis direction. The right part RP is located on one side as viewed from the central position Cp shown in FIG. 15, and the left part LP is located on the other side as viewed from the central position Cp. Further, the center position Cp is a position in the center in the X-axis direction of the recessed portion 10a (the second portion 42). The central position Cp is between a position in the X-axis direction of the first end portion E1 and a position in the X-axis direction of the second end portion E2. The first end portion E1 is, for example, a point closest to the surface 202 of the first layer 20 among the right portion RP. The second end portion E2 is, for example, a point closest to the surface 202 of the first layer 20 among the left portion LP.

As shown in FIG. 15, the distance between the first end portion E1 and the second end portion E2 is taken as the opening width WO of the first portion 41.

Alternatively, as shown in FIG. 16, the apex 50t of the circle 50 may be the first end portion E1, and the apex 51t of the circle 51 may be the second end portion E2. circle 50 is an inscribed circle tangent to the boundary 53 between the first layer 20 in the recessed portion 10a and the right portion RP. The circle 51 is an inscribed circle tangent to the boundary 54 between the first layer 20 in the recessed portion 10 a and the left portion LP. The vertex 50t is the point closest to the surface 202 of the first layer 20 in the circle 50, and the vertex 51t is the point closest to the surface 202 of the first layer 20 in the circle 51. Furthermore, in this example, the second portion 42 has a bottom surface 42B extending along the X-Y plane. In this case, the boundary 53 and the boundary 54 do not include the boundary 55 between the first layer 20 and the bottom surface 42B. The boundary 53 and the boundary 54 are respectively curved in a convex direction (toward the surface of the first layer 20).

As shown in FIG. 15, the bottom surface 42B has a third end portion E3 and a fourth end portion E4 in a cross section along the Z-axis direction. The third end portion E3 is located on the same side as the first end portion E1 when viewed from the central position Cp. That is, the third end portion E3 is a point on the right portion RP. The fourth end portion E4 is located on the same side as the second end portion E2 when viewed from the central position Cp. That is, the fourth end portion E4 is a point on the left portion LP. The distance between the first end portion E1 and the third end portion E3 is shorter than the distance between the first end portion E1 and the fourth end portion E4.

For example, the third end portion E3 or the fourth end portion E4 is the point farthest from the surface 202 of the first layer 20 among the second portions 42. The width WB of the bottom surface 42B is defined as the distance between the third end portion E3 and the fourth end portion E4 in a cross section along the Z-axis direction.

Further, as shown in FIG. 15, an angle formed by a straight line (straight line L1) connecting the first end E1 and the second end E2 and a straight line L2 connecting the first end E1 and the bottom surface 42B with the shortest distance is set as an angle θ. 1 (°). The straight line L2 is a straight line connecting the first end portion E1 and the third end portion E3.

In addition, in FIG. 15 and FIG. 16, for example, when the recessed portion 10a is cracked, a cross section perpendicular to the direction in which the crack extends in the X-Y plane is observed. In other words, the direction in which the crack extends corresponds to, for example, the Y-axis direction.

FIG. 17 is a table illustrating the shape of the first layer of a member for a semiconductor manufacturing apparatus according to the embodiment.

The ratio of the opening width WO of the first portion 41 to the width WB of the bottom surface 42B (WO / WB) was calculated from 25 samples of the first layer 20 according to the embodiment.

As shown in FIG. 17, the ratio (WO / WB) is 1.1 or more and 9.7 or less. That is, in the embodiment, the opening width WO is 1.1 times or more and 9.7 times or less the width WB. For example, in the cross section shown in FIG. 15, the opening width WO of the first portion 41 is 14.5 μm, the width WB of the bottom surface 42B is 3.5 μm, and the opening width WO is four times the width WB.

When the ratio (WO / WB) is 1, the width of the first portion 41 is equal to the width of the second portion 42. In this case, there is a possibility that stress is concentrated on the first portion 41 and the first layer 20 is peeled off from the corrosion-resistant aluminum substrate 10. In contrast, the ratio (WO / WB) is 1.1 times or more in the embodiment. Accordingly, it is possible to suppress concentration of stress generated near the interface between the first layer 20 and the corrosion-resistant aluminum base material 10 in the recessed portion 10 a. Therefore, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed, and fine particles can be reduced.

18 is a table illustrating a shape of a first layer of a member for a semiconductor manufacturing apparatus according to the embodiment.

The angle θ 1 was calculated from 25 samples of the first layer 20 according to the embodiment.

As shown in FIG. 18, in the embodiment, the angle θ 1 is 10 ° or more and 89 ° or less, and preferably 17 ° or more and 73 ° or less. This point indicates that the width of the recessed portion 10a is gradually narrowed from the first region R1 toward the second region R2. As a result, the width of the recessed portion 10 a can be suppressed from rapidly changing, and the concentration of stress generated near the interface between the first layer 20 and the corrosion-resistant aluminum substrate 10 in the recessed portion 10 a can be suppressed. Therefore, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed, and fine particles can be reduced.

Further, in the cross section shown in FIG. 14, the boundary between the first layer 20 in the recessed portion 10 a and the corrosion-resistant aluminum base material 10 is curved and has a curvature. For example, imaginary circles C1, C2, and C3 each approximate a part of the boundary between the first layer 20 and the corrosion-resistant aluminum substrate 10 in the recessed portion 10a. The radius of the virtual circle C1 is 16.4 μm, the radius of the virtual circle C2 is 3.7 μm, and the radius of the virtual circle C3 is 16 μm. In addition, each virtual circle shown in FIG. 14 is an example. The curvature radius R of the boundary (boundary 53 or boundary 54) of the 1st layer 20 and the corrosion-resistant aluminum base material 10 in the recessed part 10a is calculated | required by the cross-section observation shown in FIG. The radius of curvature R is the radius of the circle 50 or the circle 51. In a case where the boundary 53 or a portion of the boundary 54 has unevenness, such as when the boundary is not curved, the curvature radius R is determined from an imaginary circle approximately having a curved shape.

FIG. 19 is a table illustrating the shape of the first layer of a member for a semiconductor manufacturing apparatus according to the embodiment.

A curvature radius R was calculated from 25 samples of the first layer 20 according to the embodiment.

As shown in FIG. 19, in the embodiment, the radius of curvature R is 0.4 μm or more and less than 50 μm.

If the first layer 20 in the recessed portion 10a and the anti-corrosion aluminum substrate 10 If there is a discontinuous change in the boundary, the stress is concentrated in that part. On the other hand, in the member 120 for a semiconductor manufacturing device according to the embodiment, the boundary between the first layer 20 in the recessed portion 10 a and the anti-corrosion aluminum base material 10 is curved and has a curvature. Accordingly, discontinuous changes in the boundary between the first layer 20 and the corrosion-resistant aluminum base material 10 in the recessed portion 10 a can be suppressed, and stress concentration can be suppressed. Therefore, peeling of the first layer 20 from the corrosion-resistant aluminum substrate 10 can be suppressed.

The density of the first region R1 and the density of the second region R2 can be adjusted according to the formation conditions of the first layer 20 formed by the aerosol deposition method. For example, the raw material powder of the aerosol sprayed on the corrosion-resistant aluminum base material 10 is adjusted.

For example, a 50% volume-based average particle diameter of 1.0-5.0 μm (hereinafter referred to as a first particle) and a 50% volume-based average particle diameter of less than 1 μm (hereinafter referred to as a first particle) The second fine particles) are mixed as a raw material powder of an aerosol. The mixing ratio is the number of the first fine particles: the number of the second fine particles = 1: 1 to 1: 100. As each of the first fine particles and the second fine particles, for example, yttrium oxide or aluminum oxide can be used.

Since the particle size of the first fine particles is large, the impact caused by the collision of the first fine particles when sprayed on the corrosion-resistant aluminum substrate 10 is large. Accordingly, the crystal grains are distorted, and a dense layer can be formed. In this way, by mixing the first fine particles having a large particle size with the second fine particles having a small particle size, the first region R1 can be made dense.

Furthermore, by using this aerosol deposition method, as described with reference to FIGS. 14 to 19, the boundary between the first layer 20 in the recessed portion 10 a and the anti-corrosion aluminum substrate 10 can be regarded as a curve. For example by the particles contained in the aerosol The sub-collision of the anti-corrosion aluminum substrate 10 deforms the corner of the recessed portion (crack) of the anodized coating film, and the boundary between the first layer 20 in the recessed portion 10 a and the anti-corrosion aluminum substrate 10 is curved.

20 (a) and 20 (b) are photographic views illustrating members for a semiconductor manufacturing apparatus according to the embodiment.

FIG. 20 (a) is a photographic view showing the surface of the corrosion-resistant aluminum substrate 10 (the corrosion-resistant aluminum layer 12) before the first layer 20 is formed. FIG. 20 (b) is a photographic view showing the surface of the first layer 20 after the first layer 20 is formed. The observation range in FIG. 20 (b) is slightly the same as the observation range in FIG. 20 (a). The observation was performed using a laser microscope (LS400 by Olympus).

As shown in FIG. 20 (a), recessed portions 12A to 12D are observed on the surface of the corrosion-resistant aluminum layer 12. Further, as shown in FIG. 20 (b), a plurality of concave portions 10a (concave portions 10A to 10D) were observed on the surface of the first layer 20.

The concave portions 10A to 10D correspond to the concave portions 12A to 12D, respectively. That is, the recessed portions 10A, 10B, 10C, and 10D are formed by forming the first layer 20 on the recessed portions 12A, 12B, 12C, and 12D, respectively.

In plan view, the areas of the concave portions 10A to 10D are larger than the areas of the concave portions 12A to 12D, respectively. For example, it is considered that the corners of the recessed portions of the anti-corrosion aluminum layer 12 are deformed by the collision of fine particles included in the aerosol, and the recessed portions are enlarged. The shape of the recessed portion 10a (recessed portions 10A to 10D) can be adjusted according to the formation conditions of the first layer 20 formed by the aerosol deposition method. For example, the aerosol raw material powder is adjusted as described above.

The embodiment of the present invention has been described above. However, the present invention is not limited to these descriptions. Regarding the aforementioned embodiment, Those skilled in the art will suitably add design changes as long as they have the features of the present invention and are included in the scope of the present invention. For example, the shape, size, material, arrangement, etc. of the anti-corrosion aluminum substrate and the first layer are not limited to those exemplified, and may be appropriately changed.

In addition, each element provided in each of the aforementioned embodiments can be technically combined as much as possible, and those who combine these elements are included in the scope of the present invention as long as they also include the features of the present invention.

According to an aspect of the present invention, there is provided a member for a semiconductor manufacturing apparatus capable of reducing particles.

Claims (18)

A component for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recessed portion; and a first layer containing a yttrium compound formed on the corrosion-resistant aluminum substrate, the first layer having: a first region; and In the recess, a second region between the first region and the anti-corrosion aluminum substrate. The average particle diameter in the first region is shorter than the average particle diameter in the second region. For example, for a member for a semiconductor manufacturing device in the first patent application range, the average particle diameter of the first region is 10 nm to 19 nm, and the average particle diameter of the second region is 20 nm to 43 nm. Meters below. A component for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recess; and a first layer including yttrium oxide formed on the corrosion-resistant aluminum substrate, the first layer having: a first region; and Within the recess, a second region between the first region and the corrosion-resistant aluminum substrate, the first region is dominated by monoclinic crystals, and the second region is dominated by cubic crystals. A component for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate including a recessed portion; and a first layer containing a yttrium compound formed on the corrosion-resistant aluminum substrate, the first layer having: a first region; and A second region between the first region and the anti-corrosion aluminum substrate is in the recess, and the first region is denser than the second region. For example, for a member for a semiconductor manufacturing device according to item 4 of the application, wherein the ratio of the area of the sparse area in the cross section of the first area to the area of the cross section of the first area is 0.4% or more and 1.7% or less. The ratio of the area of the sparse area in the cross section of the two areas to the area of the cross section of the second area is 2.0% or more. A component for a semiconductor manufacturing device, comprising: a corrosion-resistant aluminum substrate having a recess; and a first layer formed on the corrosion-resistant aluminum substrate and containing a yttrium compound, the first layer having: a first region; and Within the recess, a second region between the first region and the anti-corrosion aluminum substrate, the recess has a first portion provided with the first region and a second portion provided with the second region, In the cross-section direction, the width of the second portion is narrower than the width of the first portion. For example, the component for a semiconductor manufacturing device according to item 6 of the patent application, wherein the second portion has a bottom surface along a plane perpendicular to the lamination direction, and in the cross section, a ratio of an opening width of the first portion to a width of the bottom surface. More than 1.1 times. For example, for a member for a semiconductor manufacturing device according to item 6 or item 7, wherein the first layer has a surface on the opposite side to a surface that is in contact with the anti-corrosion aluminum substrate, the width of the recessed portion in the cross section becomes larger. The narrower the surface. For example, the component for a semiconductor manufacturing device according to item 6 of the patent application, wherein the opening of the recess has a first end portion and a second end portion separated from each other in the cross section, and the second portion has a vertical direction along the lamination direction. In the cross section of the plane, an angle formed by a straight line connecting the first end portion and the second end portion and a straight line connecting the first end portion and the bottom surface at the shortest angle is 10 ° or more and 89 ° or less. For example, for a member for a semiconductor manufacturing device according to item 6 or item 7, in the cross section, a boundary between the first layer in the recessed portion and the anti-corrosion aluminum substrate is curved. For example, the component for a semiconductor manufacturing device according to item 6 or item 7, wherein in the cross section, a boundary between the first layer in the recessed portion and the corrosion-resistant aluminum substrate has a curvature. For example, for a member for a semiconductor manufacturing device according to item 6 or item 7, in the cross section, a radius of curvature of a boundary between the first layer in the recess and the corrosion-resistant aluminum substrate is 0.4 μm or more. For example, the component for a semiconductor manufacturing device according to item 8 of the application, wherein in the cross section, a boundary between the first layer in the recess and the anti-corrosion aluminum substrate is curved. For example, the component for a semiconductor manufacturing device according to item 8 of the application, wherein in the cross section, a boundary between the first layer in the recess and the corrosion-resistant aluminum substrate has a curvature. For example, the component for a semiconductor manufacturing device according to item 8 of the patent application, wherein in the cross section, a radius of curvature of a boundary between the first layer and the anti-corrosion aluminum substrate in the recess is 0.4 μm or more. For example, the member for a semiconductor manufacturing device according to item 9 of the application, wherein in the cross section, a boundary between the first layer in the recess and the anti-corrosion aluminum substrate is curved. For example, the component for a semiconductor manufacturing device according to item 9 of the application, wherein in the cross section, a boundary between the first layer and the corrosion-resistant aluminum substrate in the recess has a curvature. For example, the component for a semiconductor manufacturing device according to item 9 of the application, wherein in the cross section, a radius of curvature of a boundary between the first layer and the anti-corrosion aluminum substrate in the recess is 0.4 μm or more.