Members for semiconductor manufacturing equipment and semiconductor manufacturing equipment

Abstract

To provide a member for a semiconductor manufacturing apparatus that can reduce the generation or influence of particles, and a semiconductor manufacturing apparatus.SOLUTION: A member 120 for a semiconductor manufacturing apparatus that is used in a chamber of a semiconductor manufacturing apparatus includes a base material 10 including a first surface 11, a second surface 12 on the opposite side of the first surface, and at least one hole 13 penetrating the first surface and the second surface, and a ceramic layer 20 provided on the base material. The hole 13 includes a first hole part 13a that continues to the first surface. The ceramic layer includes a first part 21 that is provided on the first surface so as to be exposed, and a second part 22 provided on the first hole part. The arithmetic average height Sa of a surface of the first part is smaller than the arithmetic average height Sa of a surface of the second part.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] Aspects of the present invention generally relate to a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus.

Background Art

[0002] In the manufacturing process of semiconductor devices, semiconductor manufacturing apparatuses that process workpieces such as semiconductor wafers with plasma are used. In such a semiconductor manufacturing apparatus, there may be arranged a member for a semiconductor manufacturing apparatus provided with at least one hole and in contact with plasma. Particles may be generated from such a member for a semiconductor manufacturing apparatus. Since particles cause a reduction in the yield of the manufactured semiconductor devices, reduction of the generation or influence of particles is required.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made based on the recognition of such problems, and an object thereof is to provide a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus capable of reducing the generation or influence of particles.

Means for Solving the Problems

[0005] The first invention is a member for a semiconductor manufacturing apparatus used in a chamber of a semiconductor manufacturing apparatus, including a base material including a first surface, a second surface opposite to the first surface, and at least one hole penetrating the first surface and the second surface, and a ceramic layer provided on the base material. The hole has a first hole portion continuous with the first surface, and the ceramic layer includes a first portion provided so as to be exposed on the first surface and a second portion provided on the first hole portion. The arithmetic mean height Sa of the surface of the first portion is smaller than the arithmetic mean height Sa of the surface of the second portion. It is a member for a semiconductor manufacturing apparatus.

[0006] According to this member for a semiconductor manufacturing apparatus, a ceramic layer is provided on the first surface and the first hole portion of the base material, and the arithmetic mean height Sa of the surface of the first portion on the first surface is smaller than the arithmetic mean height Sa of the surface of the second portion on the first hole portion. Thereby, the generation or influence of particles can be reduced. For example, by making the arithmetic mean height Sa of the surface of the first portion in contact with the corrosive plasma a relatively smooth surface, the generation of particles from the first portion can be effectively suppressed. In addition, since the arithmetic mean height Sa of the surface of the second portion on the first hole portion is relatively large, the generation or influence of particles from the hole can be suppressed. For example, when the first portion provided on the first surface is exposed to plasma, the second portion on the first hole portion is provided near the end of the hole continuous with the first surface, so the electric field is more likely to concentrate than the first portion. On the other hand, since the arithmetic mean height Sa of the surface of the second portion is relatively large, for example, the surface area of the second portion becomes large and the concentration of the electric field can be alleviated. Also, since the arithmetic mean height Sa of the surface of the second portion provided near the end of the hole (near the outlet) is relatively large, for example, particles generated from the hole can be collected by the second portion, and the influence of the particles can be more effectively suppressed.

[0007] The second invention is, in the first invention, the semiconductor manufacturing apparatus member, wherein the hole further has a second hole portion located between the second surface and the first hole portion in a first direction from the first surface toward the second surface, and a third hole portion located between the first hole portion and the second hole portion in the first direction, continuous with the first hole portion, and provided so as to be exposed, and an arithmetic mean height Sa of the third hole portion is larger than an arithmetic mean height Sa of a surface of the first portion and larger than an arithmetic mean height Sa of a surface of the second portion.

[0008] According to this member for a semiconductor manufacturing apparatus, a first portion of a ceramic layer is provided on the first hole portion, and the third hole portion continuous with the first hole portion is in contact with plasma. That is, no ceramic layer is provided on the third hole portion, and the inner wall of the hole is exposed. In other words, in the hole, the third hole portion is an end portion of a base material in contact with plasma. By making the arithmetic mean height Sa of such an end portion of the base material (third hole portion) relatively large, the surface area of the end portion of the base material becomes large, and concentration of an electric field at the end portion of the base material can be suppressed. Thereby, for example, generation of particles from the end portion of the base material can be suppressed.

[0009] The third invention is, in the first or second invention, the semiconductor manufacturing apparatus member, wherein an arithmetic mean height Sa of a surface of the second portion is 10 times or less of an arithmetic mean height Sa of a surface of the first portion.

[0010] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0011] The fourth invention is, in the second invention, the semiconductor manufacturing apparatus member, wherein an arithmetic mean height Sa of the third hole portion is larger than twice an arithmetic mean height Sa of a surface of the first portion.

[0012] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0013] The fifth invention is a member for a semiconductor manufacturing apparatus, which is any one of the first to fourth inventions, wherein the arithmetic mean height Sa of the surface of the second portion is less than 0.5 micrometers.

[0014] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more reliably reduced.

[0015] The sixth invention is a member for a semiconductor manufacturing apparatus, which is any one of the first to fifth inventions, wherein the arithmetic mean height Sa of the surface of the first portion is less than 0.1 micrometers.

[0016] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more reliably reduced.

[0017] The seventh invention is a member for a semiconductor manufacturing apparatus according to the first invention, wherein the hole further has a second hole portion located between the second surface and the first hole portion in a first direction from the first surface toward the second surface, and a third hole portion located between the first hole portion and the second hole portion in the first direction, continuous with the first hole portion and exposed, and the arithmetic mean height Sa of the third hole portion is larger than the arithmetic mean height Sa of the surface of the first portion and smaller than the arithmetic mean height Sa of the surface of the second portion.

[0018] In the third hole portion, the plasma and the base material are in direct contact. Therefore, in the third hole portion, particles may be more likely to be generated from the base material than in the ceramic layer. On the other hand, according to this member for a semiconductor manufacturing apparatus, the third hole portion is disposed at a position farther from the first and second surfaces of the base material than the first and second hole portions. Further, the arithmetic mean height Sa of the third hole portion is smaller than the arithmetic mean height Sa of the surface of the second portion. Thereby, generation of particles from the third hole portion can be reduced.

[0019] The eighth invention is a member for a semiconductor manufacturing apparatus, which is any one of the first to seventh inventions, wherein the ceramic layer contains polycrystalline ceramics.

[0020] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0021] A ninth invention is a member for a semiconductor manufacturing apparatus, in the eighth invention, wherein an average crystallite size of the polycrystalline ceramics, calculated from a TEM image with a magnification of 400,000 times to 2,000,000 times, is 3 nanometers or more and 50 nanometers or less.

[0022] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0023] A tenth invention is a member for a semiconductor manufacturing apparatus, in any one of the first to ninth inventions, wherein the ceramic layer contains at least one selected from the group consisting of oxides of rare earth elements, fluorides of rare earth elements, and oxyfluorides of rare earth elements.

[0024] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0025] An eleventh invention is a member for a semiconductor manufacturing apparatus, in the tenth invention, wherein the rare earth element is at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu.

[0026] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0027] A twelfth invention is a member for a semiconductor manufacturing apparatus, in any one of the first to eleventh inventions, wherein the base material contains ceramics.

[0028] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0029] The 13th invention is the member for a semiconductor manufacturing apparatus according to the 12th invention, wherein the base material contains alumina.

[0030] According to this member for a semiconductor manufacturing apparatus, generation or influence of particles can be more surely reduced.

[0031] The 14th invention is a semiconductor manufacturing apparatus including a chamber and the member for a semiconductor manufacturing apparatus according to any one of the 1st to 13th inventions, wherein the chamber has an inner wall forming a space where plasma is generated, and the ceramic layer of the member for a semiconductor manufacturing apparatus constitutes at least a part of the inner wall.

[0032] According to this semiconductor manufacturing apparatus, generation or influence of particles can be reduced.

Effect of the Invention

[0033] According to an aspect of the present invention, there are provided a member for a semiconductor manufacturing apparatus and a semiconductor manufacturing apparatus capable of reducing generation or influence of particles.

Brief Description of the Drawings

[0034]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Embodiments for Carrying Out the Invention

[0035] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing, the same components are denoted by the same reference numerals, and detailed descriptions thereof will be omitted as appropriate. The drawings are schematic or conceptual, and the relationships between the thickness and width of each part, the ratio of the sizes between parts, etc. are not necessarily the same as those in reality. Even when representing the same part, the dimensions and ratios may be represented differently in the drawings.

[0036] (First Embodiment) FIG. 1 is a cross-sectional view illustrating a semiconductor manufacturing apparatus having a member for a semiconductor manufacturing apparatus according to the first embodiment. The semiconductor manufacturing apparatus 100 shown in FIG. 1 includes a chamber 110, a member 120 for a semiconductor manufacturing apparatus, and an electrostatic chuck 160. The electrostatic chuck 160 is provided at the lower part inside the chamber 110. An object to be adsorbed such as a wafer 210 is placed on the electrostatic chuck 160. In this example, the member 120 for a semiconductor manufacturing apparatus is provided at the upper part inside the chamber 110. For example, the member 120 for a semiconductor manufacturing apparatus is a top plate member of the chamber 110 that is located directly above the electrostatic chuck 160 and the wafer 210 inside the chamber 110.

[0037] Chamber 110 has an inner wall 111 that forms a space (region 191) where plasma is generated. The ceramic layer 20 (see FIG. 2) on the surface of the member 120 for a semiconductor manufacturing apparatus constitutes at least a part of the inner wall 111. In this example, the inner wall 111 has a lower inner wall 111b where the electrostatic chuck 160 is disposed and an upper inner wall 111u disposed above the lower inner wall 111b. The ceramic layer 20 of the member 120 for a semiconductor manufacturing apparatus is provided on at least a part of the upper inner wall 111u.

[0038] In the semiconductor manufacturing apparatus 100, high-frequency power is supplied, and a source gas such as a halogen-based gas is introduced into the chamber 110 as represented by the arrow A1 in FIG. 1. Then, the source gas introduced into the chamber 110 is plasmaized in the region 191 between the electrostatic chuck 160 and the member 120 for a semiconductor manufacturing apparatus.

[0039] Here, when the inner wall of the chamber 110 is corroded by plasma, particles 221 may be generated. If these particles 221 adhere to the wafer 210, defects may occur in the manufactured semiconductor device. Then, the yield and productivity of the semiconductor device may decrease. Therefore, the member 120 for a semiconductor manufacturing apparatus is required to have plasma resistance.

[0040] Note that the member for a semiconductor manufacturing apparatus according to the embodiment may be a member disposed at a position other than the upper part in the chamber. Further, the semiconductor manufacturing apparatus in which the member for a semiconductor manufacturing apparatus is used is not limited to the example of FIG. 1, and includes any semiconductor manufacturing apparatus (semiconductor processing apparatus) that performs processes such as annealing, etching, sputtering, and CVD (Chemical Vapor Deposition).

[0041] The member for a semiconductor manufacturing apparatus according to the embodiment can be suitably used as various members in a semiconductor manufacturing apparatus, particularly as a member used in an environment exposed to a corrosive high-density plasma atmosphere. Specifically, examples include a chamber wall, a shower plate, a liner, a shield, a window, an edge ring, a focus ring, and the like.

[0042] FIG. 2 is a cross-sectional view illustrating a part of a member for a semiconductor manufacturing apparatus according to the first embodiment. FIG. 2 shows an enlarged view of the vicinity of the region R shown in FIG. 1. The member 120 for a semiconductor manufacturing apparatus includes a base material 10 and a ceramic layer 20. The base material 10 has a first surface 11 and a second surface 12 opposite to the first surface 11. The first surface 11 faces the inside of the chamber 110 shown in FIG. 1, and the second surface 12 faces the outside of the chamber 110. At least one hole 13 is provided in the base material 10. The hole 13 penetrates the base material 10 from the first surface 11 to the second surface 12.

[0043] In this example, the base material 10 is, for example, plate-shaped (disk-shaped). The first surface 11 and the second surface 12 are each, for example, a flat surface. However, the first surface 11 and the second surface 12 may be curved surfaces. Also, one hole 13 is provided at the center of the base material 10. For example, a member such as an injector for injecting a raw material gas for plasma is disposed in the hole 13. The raw material gas for plasma is introduced into the chamber 110 through the hole 13. However, the hole 13 does not have to be a hole for supplying a raw material gas for plasma generation into the chamber 110, and may be any hole penetrating the base material 10. Also, the hole 13 does not have to be at the center of the base material 10, and a plurality of holes may be provided.

[0044] The direction from the first surface 11 to the second surface 12 is defined as the Z direction (first direction). One direction perpendicular to the Z direction is defined as the X direction, and a direction perpendicular to the Z direction and the X direction is defined as the Y direction. For example, the first surface 11 and the second surface 12 are perpendicular to the Z direction and extend along the X - Y plane.

[0045] The hole 13 (inner peripheral surface 13s of the hole) has a first hole portion 13a, a second hole portion 13b, and a third hole portion 13c. The hole 13 is, for example, circular when viewed along the Z direction. The inner peripheral surface 13s is the inner peripheral surface of the base material 10 defining the hole 13. The inner peripheral surface 13s faces the inside of the hole 13 and intersects the X - Y plane.

[0046] The first hole portion 13a is located in the vicinity of the first surface 11 on the inner peripheral surface 13s and is a region adjacent to the first surface 11. The first hole portion 13a is continuous with the first surface 11. The first hole portion 13a is located between the first surface 11 and the second surface 12 in the Z direction. The first hole portion 13a is not parallel to the first surface 11 but is an inclined surface that intersects the first surface 11 and the Z direction. The first hole portion 13a may be a surface extending parallel to the Z direction. In this example, in a cross-section parallel to the Z direction as shown in FIG. 2, the first hole portion 13a is linear. However, in a cross-section parallel to the Z direction, the first hole portion 13a does not have to be linear and may be curved, for example. When viewed along the Z direction (i.e., when projected onto the X-Y plane), the first hole portion 13a is, for example, annular surrounded by the first surface 11.

[0047] In this example, in a cross-section parallel to the Z direction, the boundary 14 where the first surface 11 and the first hole portion 13a are in contact is angled. However, the first surface 11 and the first hole portion 13a may be smoothly connected. In other words, in the cross-section of FIG. 2, the boundary 14 may be rounded and curved and have a curvature.

[0048] The second hole portion 13b is located between the first hole portion 13a and the second surface 12 in the Z direction. In other words, the position of the second hole portion 13b in the Z direction is between the position of the first hole portion 13a in the Z direction and the position of the second surface 12 in the Z direction. For example, the second hole portion 13b is located in the vicinity of the second surface 12 on the inner peripheral surface 13s and is a region adjacent to the second surface 12. The second hole portion 13b may be continuous with the second surface 12. The second hole portion 13b extends in the Z direction and is, for example, parallel to the Z direction. The second hole portion 13b constitutes, for example, a vertical surface substantially perpendicular to the second surface 12. When viewed along the Z direction, the second hole portion 13b is, for example, annular and located inside the first hole portion 13a.

[0049] The third hole portion 13c is located between the first hole portion 13a and the second hole portion 13b in the Z direction. In other words, the position of the third hole portion 13c in the Z direction is between the position of the first hole portion 13a in the Z direction and the position of the second hole portion 13b in the Z direction. The third hole portion 13c is a region of the inner peripheral surface 13s that is continuous with the first hole portion 13a. The third hole portion 13c is not parallel to the first surface 11, but is an inclined surface that intersects the first surface 11 and the Z direction. The third hole portion 13c may be a surface that extends in the Z direction. In this example, in a cross-section parallel to the Z direction, the third hole portion 13c is linear. However, in a cross-section parallel to the Z direction, the third hole portion 13c may not be linear and may be curved, for example. When viewed along the Z direction, the third hole portion 13c is, for example, annular, surrounded by the first hole portion 13a and in contact with the first hole portion 13a, and the second hole portion 13b is located inside the third hole portion 13c. The third hole portion 13c and the second hole portion 13b may be continuous.

[0050] In this example, in a cross-section parallel to the Z direction, the direction in which the first hole portion 13a extends and the direction in which the third hole portion 13c extends are on the same straight line. In other words, the angle θ1 formed by the third hole portion 13c and the Z direction is the same as the angle θ2 formed by the first hole portion 13a and the Z direction. However, the angle θ1 and the angle θ2 may be different.

[0051] Also, in this example, in a cross-section parallel to the Z direction, the boundary 17 where the second hole portion 13b and the third hole portion 13c are in contact is angled. However, the second hole portion 13b and the third hole portion 13c may be smoothly connected. In other words, in the cross-section of FIG. 2, the boundary 17 may be rounded and curved and may have a curvature.

[0052] Also, the hole 13 (inner peripheral surface 13s of the hole) has an inclined surface 13ac. The inclined surface 13ac is, for example, a surface including the first hole portion 13a and the third hole portion 13c. The inclined surface 13ac is continuous with the first surface 11 and is inclined with respect to the first surface 11 and the Z direction. The inclined surface 13ac is continuous with the vertical surface (second hole portion 13b) and connects the first surface 11 and the second hole portion 13b. In this example, the inclined surface 13ac formed by the first hole portion 13a and the third hole portion 13c is linear in a cross section parallel to the Z direction. However, the inclined surface 13ac may be curved.

[0053] The angle θα formed between the first surface 11 and the inclined surface 13ac is larger than the angle θβ formed between the second hole portion 13b (vertical surface) and the inclined surface 13ac. For example, the angle θα is the angle formed between the first surface 11 and the first hole portion 13a, and the angle θβ is the angle formed between the second hole portion 13b and the third hole portion 13c.

[0054] The plasma corrosion resistance of the ceramic layer 20 is higher than that of the base material 10. The ceramic layer 20 is provided on the base material 10. More specifically, as shown in FIG. 2, the ceramic layer 20 includes a first portion 21 and a second portion 22. The first portion 21 is provided on the first surface 11 and is in contact with the first surface 11. The first portion 21 is provided substantially over the entire first surface 11. The second portion 22 is provided on the first hole portion 13a and is in contact with the first hole portion 13a. The surface 21s of the first portion 21 and the surface 22s of the second portion are in direct contact with the plasma in the chamber 110. That is, the surface 21s is the surface on the side opposite to the surface in contact with the first surface 11 of the first portion 21, and is provided so as to be exposed in the chamber 110. The surface 22s is the surface on the side opposite to the surface in contact with the first hole portion 13a of the second portion 22, and is provided so as to be exposed in the chamber 110. Since the first surface 11 is covered by the first portion 21, it is not in direct contact with the plasma. Also, since the first hole portion 13a is covered by the second portion 22, it is not in direct contact with the plasma. That is, the first surface 11 and the first hole portion 13a are covered with the ceramic layer 20, and the ceramic layer 20 is configured to be exposed to the plasma. The surface 21s is, for example, a plane parallel to the X-Y plane. The surface 21s may be a curved surface. The surface 22s is an inclined surface that intersects the surface 21s and the Z direction. The surface 21s may be a surface extending in the Z direction.

[0055] The ceramic layer 20 is not provided on the second surface 12, on the second hole portion 13b, and on the third hole portion 13c. In other words, in this example, among the inner peripheral surfaces 13s of the holes 13, the region where the ceramic layer 20 is provided is the first hole portion 13a, and the regions where the ceramic layer 20 is not provided are the second hole portion 13b and the third hole portion 13c. The third hole portion 13c is in contact with the end of the second portion 22. The second hole portion 13b and the third hole portion 13c are exposed to the plasma in the chamber 110 and are in direct contact with the plasma. The second hole portion 13b and the third hole portion 13c are not covered with the ceramic layer 20.

[0056] The arithmetic mean height Sa of the surface 21s of the first part 21 is smaller than the arithmetic mean height Sa of the surface 22s of the second part 22. Note that the arithmetic mean height Sa (surface roughness) can be evaluated by the method described later. For example, the surface roughness of the first part 21 (the roughness of the surface 21s) is smaller than the surface roughness of the second part 22 (the roughness of the surface 22s).

[0057] As described above, in order to reduce particles, members for semiconductor manufacturing equipment that come into contact with plasma are required to have plasma resistance. Therefore, conventionally, a method of coating the surface of a member for a semiconductor manufacturing apparatus with a film (layer) having excellent plasma resistance has been used. However, even when a non-porous portion that occupies most of the member for a semiconductor manufacturing apparatus (for example, a top plate member) is coated with a film having high plasma resistance (for example, Y2O3, etc.), there is a risk that the requirement for particle reduction cannot be sufficiently satisfied these days. Therefore, for example, control of particles from holes is also required. Examples of particles from holes include particles generated by a part of the film provided in the hole detaching, and particles from members (for example, injectors) arranged in the holes.

[0058] On the other hand, in the embodiment, the ceramic layer 20 is provided on the first surface 11 and the first hole portion 13a of the base material 10, and the arithmetic mean height Sa of the surface 21s of the first part 21 on the first surface 11 is smaller than the arithmetic mean height Sa of the surface 22s of the second part 22 on the first hole portion 13a. Thereby, the generation or influence of particles can be reduced.

[0059] For example, since the arithmetic mean height Sa (surface roughness) of the surface 21s of the first part 21 in contact with the corrosive plasma is relatively small, the generation of particles from the first part 21 can be effectively suppressed. That is, for example, the first part has a smooth structure, and the generation of cracks and particles based on the unevenness in the first part 21 can be suppressed. For example, it can be suppressed that the first part 21 is corroded by plasma and a part of it detaches from the ceramic layer 20 to become particles.

[0060] Also, since the arithmetic mean height Sa (surface roughness) of the surface 22s of the second portion 22 on the first hole portion 13a is relatively large, the generation or influence of particles from the hole 13 can be suppressed. For example, since the second portion 22 is provided on the first hole portion 13a, it is considered that in the second portion 22, the influence of the electric field may be greater than that in the first portion 21. That is, when the first portion 21 provided on the first surface 11 is exposed to plasma, the second portion 22 on the first hole portion 13a is near the end of the hole 13, so the electric field may be more likely to concentrate than in the first portion 21. In the portion where the electric field concentrates, the electric field strength is large, and the plasma concentrates, resulting in greater damage by the plasma. There is a risk that the damaged portion may detach from the ceramic layer 20 and generate particles. In contrast, in the embodiment, since the arithmetic mean height Sa of the surface 22s of the second portion 22 is relatively large, the surface area of the second portion 22 becomes large, and the concentration of the electric field can be alleviated.

[0061] Moreover, since the arithmetic mean height Sa of the surface 22s of the second portion 22 provided near the end (near the outlet) of the hole 13 is relatively large, the particles generated from the hole 13 can be collected by the second portion 22, and the influence of the particles can be more effectively suppressed.

[0062] Also, when the plasma generation gas passes through the hole 13, the temperature around the hole changes due to the injection of the gas. Therefore, the thermal stress in the second portion 22 may be higher than the thermal stress in the first portion 21. Due to the thermal stress, there is a risk of cracks and particles occurring in the second portion 22. In contrast, since the arithmetic mean height Sa of the surface 22s of the second portion 22 is relatively large, the surface area of the second portion 22 becomes large, and the heat dissipation effect of the second portion 22 can be enhanced. Thereby, the occurrence of cracks and particles in the second portion 22 can be suppressed.

[0063] For example, it is desirable that the surface roughness of the second part 22 is 2 times or more and 10 times or less, more preferably 5 times or less, that of the first part. It is desirable that the arithmetic mean height Sa of the surface 22s of the second part 22 is 2 times or more and 10 times or less, more preferably 5 times or less, that of the arithmetic mean height Sa of the surface 21s of the first part 21. The arithmetic mean height Sa of the surface 22s of the second part 22 is, for example, less than 0.5 micrometers (μm), and is, for example, 0.005 μm or more. The arithmetic mean height Sa of the surface 21s of the first part 21 is, for example, less than 0.1 μm, and is, for example, 0.001 μm or more. According to such a configuration, generation or influence of particles can be more reliably reduced.

[0064] For example, the surface roughness of the third hole portion 13c is larger than that of the first part 21 and larger than that of the second part 22. For example, the arithmetic mean height Sa of the third hole portion 13c is larger than the arithmetic mean height Sa of the surface 21s of the first part 21 and larger than the arithmetic mean height Sa of the surface 22s of the second part 22.

[0065] As already described, in this example, the ceramic layer 20 is not provided on the third hole portion 13c, and the inner wall of the hole 13 is exposed. That is, the third hole portion 13c is a boundary portion between the ceramic layer 20 and the inner wall of the hole 13, and is a base material end portion in contact with the plasma. By relatively increasing the arithmetic mean height Sa (surface roughness) of such a base material end portion (the third hole portion 13c), the surface area of the base material end portion becomes large, and the concentration of the electric field at the base material end portion can be alleviated. Thereby, for example, damage to the plasma due to electric field concentration at the base material end portion can be suppressed, and generation of particles from the base material end portion can be suppressed.

[0066] For example, it is desirable that the surface roughness of the third hole portion 13c is greater than twice the surface roughness of the first portion 21. It is also preferable that the surface roughness of the third hole portion 13c is not more than ten times the surface roughness of the first portion 21. It is desirable that the arithmetic mean height Sa of the third hole portion 13c is greater than twice the arithmetic mean height Sa of the surface 21s of the first portion 21. It is also preferable that the arithmetic mean height Sa of the third hole portion 13c is not more than ten times the arithmetic mean height Sa of the surface 21s of the first portion 21. According to such a configuration, the generation or influence of particles can be more reliably reduced.

[0067] Also, the surface roughness of the third hole portion 13c may be greater than the surface roughness of the first portion 21 and smaller than the surface roughness of the second portion 22. For example, the arithmetic mean height Sa of the third hole portion 13c may be greater than the arithmetic mean height Sa of the surface 21s of the first portion 21 and smaller than the arithmetic mean height Sa of the surface 22s of the second portion 22.

[0068] In the third hole portion 13c, since the plasma and the base material 10 are in direct contact, particles may easily be generated from the base material 10. In contrast, in the embodiment, the third hole portion 13c is disposed at a position farther from the first surface 11 and the second surface 12 than the first hole portion 13a and the second hole portion 13b. Further, when the arithmetic mean height Sa of the third hole portion 13c is smaller than the arithmetic mean height Sa of the surface of the second portion 22, the generation of particles from the third hole portion 13c can be further reduced. That is, for example, the generation of cracks and particles based on the unevenness in the third hole portion 13c can be suppressed. It is possible to suppress a part of the third hole portion 13c from detaching from the base material 10 and becoming particles.

[0069] As described above, when the base material 10 is corroded by contacting with plasma, fine particles are generated from the base material 10, which may reduce the yield of the manufactured semiconductor device. Therefore, the surface of the base material 10 that contacts the plasma is coated with a ceramic layer having higher plasma corrosion resistance than the base material 10. The hole 13 provided in the base material 10 has, for example, a vertical surface perpendicular to the first and second surfaces of the base material 10. However, a part of the plasma may enter the hole 13 and corrode the inner wall of the hole 13, and particles may be generated from the hole 13. Therefore, a method of providing a ceramic layer with high plasma corrosion resistance on the inner wall (for example, the vertical surface) of the hole 13 can be considered. However, for example, the ceramic layer inside the hole 13 may be relatively fragile, and when the fragile ceramic layer is corroded by plasma, particles are generated. In addition, plasma concentration may easily occur on the inclined surfaces (the first hole portion 13a and the third hole portion 13c) between the first surface 11 and the second hole portion 13b.

[0070] In contrast, in the embodiment, in the inclined surface 13ac formed by the first hole portion 13a and the third hole portion 13c, the second portion 22 of the ceramic layer 20 is provided in the first hole portion 13a relatively close to the first portion 21 that contacts the plasma. Thereby, the generation of particles from the first hole portion 13a can be effectively suppressed. On the other hand, in the inclined surface 13ac, the third hole portion 13c relatively far from the first portion 21 contacts the plasma. That is, the third hole portion 13c, which is farther from the first portion 21 and has a relatively low plasma corrosion risk compared to the first hole portion 13a, is not coated with the ceramic layer 20, and the base material 10 directly contacts the plasma in the third hole portion 13c. Thereby, a ceramic layer with poor properties is formed in the third hole portion 13c, and the generation of particles from the ceramic layer can be effectively suppressed.

[0071] Also, if the inclined surface 13ac is curved in a cross-section parallel to the Z direction, an electric field may concentrate on the inclined surface 13ac or the ceramic layer 20 on the inclined surface 13ac, and particles may be generated. On the other hand, when the inclined surface 13ac is linear in a cross-section parallel to the Z direction, the electric field concentration in the inclined surface 13ac or the ceramic layer 20 on the inclined surface 13ac can be further alleviated.

[0072] Also, for example, in the ceramic layer 20, the second portion 22 is thinner than the first portion 21. That is, the thickness T22 of the second portion 22 is smaller than the thickness T21 of the first portion 21. Since the first portion 21 that is more easily exposed to plasma is thicker than the second portion 22, the generation of particles from the first surface 11 can be more suppressed. On the other hand, since the second portion 22 that is less easily exposed to plasma than the first portion 21 is relatively thin, for example, the collapse of the ceramic layer 20 in the second portion 22 is suppressed, and the generation of particles can be more suppressed. For example, by reducing the film thickness in the second portion, the strain and internal stress in the film are relaxed, and the collapse of the film can be suppressed.

[0073] Note that the thickness of the ceramic layer 20 is the distance from the surface of the base material 10 to the surface of the ceramic layer 20. Specifically, the thicknesses (thicknesses T11 and T22) of the ceramic layer 20 are obtained as follows. As shown in FIG. 2, the member 120 for a semiconductor manufacturing apparatus is cut parallel to the Z direction, and the cross-sectional surface is observed using a scanning electron microscope (SEM: Scanning Electron Microscope) to obtain the thickness of the ceramic layer 20. For example, the thickness T21 of the first portion 21 is the length along the direction perpendicular to the first surface 11 from the first surface 11 to the surface 21s. For example, the thickness T22 of the second portion 22 is the length along the direction perpendicular to the first hole portion 13a from the first hole portion 13a to the surface 22s. For the SEM, for example, S-5500 manufactured by HITACHI may be used, and the SEM observation conditions may be a magnification of 5000 times and an acceleration voltage of 15 kV. When there is variation in thickness in the cross-sectional image, measurements are taken at multiple locations and the average value is calculated. As a method for making the thickness T22 of the second portion 22 smaller than the thickness T21 of the first portion 21, for example, known methods such as varying the film formation time (making the film formation time of the second portion shorter than the film formation time of the first portion) or varying the polishing amount (making the polishing amount of the second portion larger than the polishing amount of the first portion) can be used.

[0074] Also, the edge portion (boundary 14) formed by the first surface 11 and the inclined surface 13ac is located near the plasma irradiation surface (surface 21s). Therefore, plasma may easily concentrate in the vicinity of this edge portion (the ceramic layer 20 on the edge portion). In contrast, in the embodiment, the angle θα formed by the first surface 11 and the inclined surface 13ac is larger than the angle θβ formed by the inclined surface 13ac and the vertical plane (the second hole portion 13b). Due to the relatively large angle θα, the concentration of plasma near the edge portion formed by the first surface 11 and the inclined surface 13ac can be alleviated, and the generation of particles can be suppressed. On the other hand, when the angle θβ is large, plasma is more likely to penetrate into the hole 13. In contrast, due to the relatively small angle θβ, the penetration of plasma into the hole 13 can be effectively suppressed.

[0075] Also, when the angle θα is larger than the angle θβ, it is easier to increase the length of the second hole portion 13b in the Z direction. For example, the length Ln shown in FIG. 6(a) described later is longer than the length Ln shown in FIG. 6(b). Further, for example, in FIG. 2, without changing the thickness of the base material 10 (the positions of the first surface 11 and the second surface 12 in the Z direction) and the diameter of the hole 13 (the positions of the boundary 14 and the boundary 17 in the X direction), if the inclined surface 13ac remains linear and the angle θα is further increased, the position of the boundary 17 moves downward, and the second hole portion 13b becomes longer in the Z direction. Since the flow (directivity) of the raw material gas of the plasma flowing into the chamber from the hole 13 is regulated by, for example, the second hole portion 13b, the longer the second hole portion 13b is, the easier it is to stabilize the flow of the raw material gas. Further, when fixing a unit such as an injector to the second hole portion 13b, the longer the second hole portion 13b is, the easier it is to attach the unit, and it is possible to suppress the unit from being exposed to the plasma.

[0076] The boundaries 14 and 17 are preferably chamfered. Thereby, the ceramic layer 20 on the boundary 14 and the plasma concentration at the boundary 17 can be further alleviated.

[0077] The angle θα is, for example, 150° or more and 180° or less, preferably 160° or more and 180° or less. Thereby, the plasma concentration near the edge portion formed by the first surface 11 and the inclined surface 13ac can be further alleviated, and the generation of particles can be further suppressed.

[0078] The angle θβ is, for example, larger than 90° and 120° or less, preferably larger than 90° and 105° or less. Thereby, it is possible to more effectively suppress the plasma from entering the inside of the hole.

[0079] For example, the density of the second portion 22 is higher than the density of the first portion 21. Further, for example, the hardness of the second portion 22 is higher than the hardness of the first portion 21.

[0080] During the maintenance and handling of the member for a semiconductor manufacturing apparatus, the vicinity of the hole 13 (and the through hole 313 described later) may come into physical contact with another member (for example, a jig such as a pin or a sponge-like cleaning pad). Due to such physical contact, wear, damage, or peeling may occur in the vicinity of the hole 13 (and the through hole 313), and there is a risk of generating particles. For example, during the handling of the member for a semiconductor manufacturing apparatus, a jig such as a positioning pin may be inserted into the hole 13. The second portion 22 provided in the hole 13 is more likely to come into physical contact with such a jig than the first portion 21. Also, for example, during the maintenance of the member for a semiconductor manufacturing apparatus, surface cleaning is performed on the surface side of the first surface 11, and the first portion 21 and the second portion 22 may come into contact with a member such as a cleaning pad. At this time, due to the shape of the hole 13, the force applied from the cleaning pad to the second portion 22 provided in the hole 13 may be greater than the force applied from the cleaning pad to the first portion 21 on the first surface 11. The contact area between the cleaning pad and the member for a semiconductor manufacturing apparatus is generally smaller in the second portion 22 located on the inclined surface than in the first portion 21 located on the flat surface portion. Therefore, when the force applied to the cleaning pad is constant, in the second portion 22, the force received per unit area becomes larger due to the smaller contact area.

[0081] On the other hand, since the density of the second portion 22 is relatively high, it is possible to suppress damage and peeling from occurring in the second portion 22 due to physical contact during the maintenance or handling of the member for a semiconductor manufacturing apparatus. Therefore, it is possible to further suppress the generation of particles. Also, since the hardness of the second portion 22 is relatively high, it is possible to suppress damage and peeling from occurring in the second portion 22 due to physical contact during the maintenance or handling of the member for a semiconductor manufacturing apparatus. Therefore, it is possible to further suppress the generation of particles.

[0082] Figs. 3(a) to 3(c) are cross-sectional views illustrating a part of another member for a semiconductor manufacturing apparatus according to the first embodiment. The members 120a to 120c for semiconductor manufacturing equipment shown in FIGS. 3(a) to 3(c) are different from the member 120 for semiconductor manufacturing equipment described with respect to FIGS. 1 and 2 in the shape of the hole 13. Other than this, the members 120a to 120c for semiconductor manufacturing equipment are the same as the member 120 for semiconductor manufacturing equipment. In the member 120a for semiconductor manufacturing equipment shown in FIG. 3(a), in a cross-section parallel to the Z direction, the first hole portion 13a and the third hole portion 13c are each linear. In FIG. 3(a), in a cross-section parallel to the Z direction, the direction in which the first hole portion 13a extends and the direction in which the third hole portion 13c extends are not on the same straight line and are non-parallel. For example, the angle θ1 formed by the third hole portion 13c and the Z direction is smaller than the angle θ2 formed by the first hole portion 13a and the Z direction.

[0083] In the member 120a for semiconductor manufacturing equipment, in a cross-section parallel to the Z direction, the boundary 15 where the first hole portion 13a and the third hole portion 13c are in contact is angled. However, in the cross-section of FIG. 3(a), the boundary 15 may be rounded and curved and have a curvature.

[0084] In the member 120b for semiconductor manufacturing equipment shown in FIG. 3(b), in a cross-section parallel to the Z direction, the third hole portion 13c is linear and the first hole portion 13a is bent. For example, the first hole portion 13a has a first region 16a in contact with the first surface 11 and a second region 16b in contact with the third hole portion 13c. In the cross-section of FIG. 3(b), the first region 16a and the second region 16b are each linear. The first region 16a and the second region 16b may be curved.

[0085] In the example of FIG. 3(b), the direction in which the first region 16a extends and the direction in which the second region 16b extends are not on the same straight line and are non-parallel. For example, the angle θ3 formed by the second region 16b and the Z direction is smaller than the angle θ4 formed by the first region 16a and the Z direction. Also, in the example of FIG. 3(b), the direction in which the second region 16b extends and the direction in which the third hole portion 13c extends are on the same straight line.

[0086] In the member 120b for a semiconductor manufacturing apparatus, in a cross-section parallel to the Z direction, the boundary 16c where the first region 16a and the second region 16b are in contact is angular. However, in the cross-section of Fig. 3(b), the boundary 16c may be rounded and curved and have a curvature.

[0087] In the member 120c for a semiconductor manufacturing apparatus shown in Fig. 3(c), the first hole 13a has the first region 16a and the second region 16b, and the boundary 16c therebetween is angular. Also, the boundary 15 between the first hole 13a and the third hole 13c is angular. The boundary 15 and the boundary 16c may be rounded and curved and have a curvature. As described above, the cross-sectional shape of the hole 13 may be appropriately bent or curved.

[0088] In the evaluation of the arithmetic mean height Sa, the arithmetic mean height Sa (Arithmetical mean height of the surface) of the surface of the evaluation object is examined using a laser microscope. This arithmetic mean height Sa is defined in the international standard ISO025178 (JISB0681) regarding three-dimensional surface properties.

[0089] As the laser microscope, "VK-X1000 manufactured by KEYENCE" is used. The magnification of the objective lens is set to 1000 times. The S-filter is set to 2.5 μm or 0.8 μm, and the L-filter is set to 0.5 mm.

[0090] The arithmetic mean height is an extension of the two-dimensional arithmetic mean roughness Ra to three dimensions and is a three-dimensional roughness parameter (three-dimensional height direction parameter). Specifically, the arithmetic mean height Sa is the volume of the portion surrounded by the surface shape curved surface and the mean plane divided by the measurement area. Assuming the mean plane is the xy plane, the vertical direction is the z-axis, and the measured surface shape curve is z(x, y), the arithmetic mean height Sa is defined by the following formula. Here, "A" in formula (1) is the measurement area.

Equation

[0091] The density of the ceramic layer 20 indicates the size of the (nanoscale) gaps between the particles constituting the film. The density of the ceramic layer 20 (the density of the first part 21, the second part 22, and the third part 23 to be described later, etc.) can be evaluated by the luminance Sa calculated by the method described in, for example, Japanese Patent No. 6597922. In the embodiment, a high density corresponds to a small luminance Sa.

[0092] Also, in the embodiment, the surface hardness of the ceramic layer 20 and the base material 10 (the hardness of the first part 21, the second part 22, the first hole region 313a and the third hole region 313c to be described later, etc.) can be evaluated by the method defined in ISO14577. Specifically, hardness measurement by a very small indentation hardness test (nanoindentation) is performed on the surface of the evaluation target. The indenter is a Berkovich indenter, the indentation depth is a fixed value of 200 nm, and the indentation hardness (indentation hardness) HIT is measured. A surface excluding scratches and dents is selected as the measurement location of HIT on the surface of the evaluation target. More preferably, the surface of the evaluation target is a polished smooth surface. The number of measurement points is at least 25 or more. The average value of the measured HIT of 25 or more points is taken as the hardness in the embodiment. Regarding other test methods and analysis methods, procedures for verifying the performance of the test apparatus, and conditions required for standard reference samples, compliance with ISO14577 is followed.

[0093] In an embodiment, high plasma corrosion resistance corresponds to a small arithmetic mean height Sa of the surface after a reference plasma resistance test. The reference plasma resistance test is carried out as follows, for example. Plasma is irradiated onto the surface of an object to be evaluated, such as a ceramic layer or a substrate. As a plasma etching apparatus, an inductively coupled plasma reactive ion etching apparatus (Muc-21 Rv-Aps-Se / manufactured by Sumitomo Precision Products Co., Ltd.) is used. The conditions for plasma etching are as follows: the ICP output as the power output is 1500 W, the bias output is 750 W, the process gas is a mixed gas of 100 ccm of CHF3 gas and 10 ccm of O2 gas, the pressure is 0.5 Pa, and the plasma etching time is 1 hour. The state of the surface of the object to be evaluated after plasma irradiation is photographed with a laser microscope. Specifically, a laser microscope "OLS4500 / manufactured by Olympus" is used, and the objective lens is MPLAPON100xLEXT (numerical aperture 0.95, working distance 0.35 mm, condensing spot diameter 0.52 μm, measurement area 128 × 128 μm), and the magnification is 100 times. The λc filter for removing undulation components is set to 25 μm. The measurement is performed at three arbitrary locations, and the average value thereof is taken as the arithmetic mean height Sa. In addition, the three-dimensional surface texture international standard ISO25178 is referred to as appropriate. As one aspect of the present invention, the arithmetic mean height Sa of the surface of the ceramic layer or the substrate after the "reference plasma resistance test" is preferably 0.060 or less, more preferably 0.030 or less.

[0094] With reference to FIGS. 4(a) to 4(c), the method for calculating the angles θα and θβ in the present specification will be described. FIGS. 4(a) to 4(c) are cross-sectional views illustrating a part of the substrate according to the first embodiment.

[0095] The base material 10a shown in Fig. 4(a) is the same as the base material 10 described with respect to Fig. 2. The first surface 11 extends along the X-Y plane. The second hole portion 13b extends along the Z direction. In this example, the inclined surface 13ac connecting the first surface 11 and the second hole portion 13b is linear in a cross-section parallel to the Z direction. In a cross-section parallel to the Z direction, the inclined surface 13ac linearly extends from the end e1 of the first surface 11 to the end e2 of the second hole portion 13b. The end e1 is the point where the first surface 11 contacts the inclined surface 13ac, and the end e2 is the point where the second hole portion 13b contacts the inclined surface 13ac.

[0096] In a cross-section parallel to the Z direction, when the portion P1 of the inclined surface 13ac continuous with the first surface 11 is linear, the angle θα is the angle between the first surface 11 and the portion P1. In a cross-section parallel to the Z direction, when the portion P2 of the inclined surface 13ac continuous with the second hole portion 13b is linear, the angle θβ is the angle between the second hole portion 13b and the portion P2. In the example of Fig. 4(a), the angle θα is the angle formed by the first surface 11 and the line segment connecting the ends e1 and e2, and the angle θβ is the angle formed by the second hole portion 13b and the line segment connecting the ends e1 and e2. Note that the angles θα and θβ are the inner angles of the base material 10 and are 180° or less.

[0097] As shown in Figs. 4(b) and 4(c), when the portions P1 and P2 are curved in a cross-section parallel to the Z direction, the angles θα and θβ are calculated as follows. The base material 10b shown in FIG. 4(b) is different from the base material 10a in the shape of the inclined surface 13ac. In the base material 10b, in a cross-section parallel to the Z direction, among the inclined surface 13ac, the portion P1 continuous with the first surface 11 is curved, and the portion continuous with the portion P1 is linear. In this case, as shown in FIG. 4(b), the angle θα is the angle formed by the first surface 11 and the line segment L1. The line segment L1 is a line segment connecting the end e1 and the end e4, and the end e4 is the end point of the linear portion continuous with the portion P1 of the inclined surface 13ac. Also, in the base material 10b, in a cross-section parallel to the Z direction, among the inclined surface 13ac, the portion P2 continuous with the second hole portion 13b is curved, and the portion continuous with the portion P2 is linear. In this case, as shown in FIG. 4(b), the angle θβ is the angle formed by the second hole portion 13b and the line segment L2. The line segment L2 is a line segment connecting the end e2 and the end e3, and the end e3 is the end point of the linear portion continuous with the portion P2 of the inclined surface 13ac. In this example, among the inclined surface 13ac, the portion between the portion P1 and the portion P2 is a linear portion P3, the end e3 of the portion P3 is the point where the portion P3 contacts the portion P1, and the end e4 of the portion P3 is the point where the portion P3 contacts the portion P2.

[0098] The base material 10c shown in FIG. 4(c) is different from the base material 10a in the shape of the inclined surface 13ac. In the base material 10c, the inclined surface 13ac is curved in a cross-section parallel to the Z direction. In this case, as shown in FIG. 4(c), the angle θα is the angle formed by the first surface 11 and the line segment L3 connecting the end e1 and the end e2. Also, in this case, as shown in FIG. 4(c), the angle θβ is the angle formed by the second hole portion 13b and the line segment L3.

[0099] The base material 10 may be any of metal, ceramics, glass, plastic, and combinations thereof. The base material 10 is preferably metal or ceramics. For the metal, aluminum or an aluminum alloy with an anodic oxidation treatment (alumite treatment) on the surface can be used. For the ceramics, aluminum oxide (alumina), aluminum nitride, etc. can be used.

[0100] The ceramic layer 20 includes, for example, polycrystalline ceramics. The ceramic layer 20 is a layer mainly composed of ceramics. The ceramic layer 20 includes at least one selected from the group consisting of, for example, oxides of rare earth elements, fluorides of rare earth elements, and oxyfluorides of rare earth elements. Examples of the rare earth element include at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. More specifically, the ceramic layer 20 is an oxide of yttrium (Y2O3, Y α O β (non-stoichiometric composition)), yttrium oxyfluoride (YOF, Y5O4F7, Y6O5F8, Y7O6F9, and Y 17 O 14 F 23 ), (YO 0.826 F 0.17 )F 1.174 , YF3, Er2O3, Gd2O3, Nd2O3, Y3Al5O 12 , Y4Al2O9, Y2O3-ZrO2, Er3Al5O 12 , Gd3Al5O 12 , Er4Al2O9, ErAlO3, Gd4Al2O9, GdAlO3, Nd3Al5O 12 , Nd4Al2O9, and NdAlO3. The ceramic layer 20 may include at least one selected from the group consisting of Fe, Cr, Zn, and Cu. For example, the ceramic layer 20 includes at least one of fluorine and oxygen and yttrium. The ceramic layer 20 is mainly composed of, for example, yttrium oxide (Y2O3), yttrium fluoride (YF3), or yttrium oxyfluoride (YOF). As used herein, "main component" means that the component is contained in an amount of more than 50%, preferably 70% or more, more preferably 90% or more, still more preferably 95% or more, and most preferably 100%. The "%" mentioned here is, for example, mass%.

[0101] Alternatively, the ceramic layer 20 may be other than oxides, fluorides, and oxyfluorides. Specifically, compounds containing Cl element or Br element (chlorides, bromides) can be mentioned.

[0102] In the member 120 for a semiconductor manufacturing apparatus, the ceramic layer 20 may be composed only of polycrystalline ceramics, or may include polycrystalline ceramics and amorphous ceramics.

[0103] In the ceramic layer 20, the average crystallite size of the polycrystalline ceramics is 3 nm or more and 50 nm or less. Preferably, the upper limit is 30 nm, more preferably 20 nm, and even more preferably 15 nm. Also, the preferable lower limit is 5 nm.

[0104] The "average crystallite size" can be obtained by the following method. First, a transmission electron microscope (TEM) image is taken at a magnification of 400,000 times or more. The value calculated from the average value of the diameters obtained by circular approximation of 15 crystallites in this image is defined as the average crystallite size. At this time, if the sample thickness during FIB processing is made sufficiently thin to about 30 nm, the crystallites can be discriminated more clearly. The imaging magnification can be appropriately selected within a range of, for example, 400,000 times or more and 2,000,000 times or less.

[0105] In the manufacturing procedure of the member for a semiconductor manufacturing apparatus according to the embodiment, first, a substrate 10 provided with holes 13 is prepared. Then, the shape of the substrate 10 is adjusted by appropriate means. For example, at least any one of blasting, physical polishing, chemical mechanical polishing, lapping, and chemical polishing is performed on the substrate 10. Thereby, the arithmetic mean height Sa (surface roughness) and shape of the first surface 11 and the holes 13 (the first hole portion 13a, the second hole portion 13b, and the third hole portion 13c) can be controlled.

[0106] Thereafter, a ceramic layer 20 is formed on the substrate 10. After forming the ceramic layer 20, finishing polishing is performed. For the polishing, at least any one of blasting, physical polishing, chemical mechanical polishing, lapping, and chemical polishing can be used. Thereby, for example, the arithmetic mean height Sa and the shape of the ceramic layer 20 (the surface 21s of the first portion 21 and the surface 22s of the second portion 22), the second hole portion 13b, and the third hole portion 13c can be controlled.

[0107] Note that, as a method for forming the ceramic layer 20 on the base material 10, for example, methods such as spraying, CVD, ALD (Atomic Layer Deposition), PVD (Physical Vapor Deposition), or aerosol deposition method can be used.

[0108] When forming the ceramic layer 20 on the base material 10, for example, when using the aerosol deposition method, spraying, CVD, or PVD, a mask such as a tape may be provided on the portion that will become the third hole portion 13c, and then a film that will become the ceramic layer 20 may be formed. By removing the mask after film formation, the second hole portion 13b and the third hole portion 13c that are exposed without the ceramic layer 20 being provided are formed. Alternatively, after forming the film without applying a mask, a part of the film may be removed by polishing or the like to form the exposed second hole portion 13b and the third hole portion 13c.

[0109] Depending on the method of forming the ceramic layer 20, in the third hole portion 13c which is the inner peripheral surface 13s of the hole 13, the ceramic layer 20 may be difficult to form compared to the first surface 11. That is, for example, in the case of a method of forming a ceramic layer by supplying (for example, colliding) raw material particles to the base material 10 from the first surface 11 side, such as PVD, thermal spraying, aerosol deposition method, etc., the third hole portion 13c is away from the first surface 11 and inclined with respect to the first surface 11. Therefore, the raw material particles may reach the third hole portion 13c in a state different from a flat surface, such as being difficult to reach the third hole portion 13c. In such a case, if the ceramic layer 20 is formed in the third hole portion 13c, the quality (for example, density, hardness, etc.) of the ceramic layer 20 formed on the third hole portion 13c may be lower than the quality of the ceramic layer 20 formed on the first surface 11. A part of the ceramic layer 20 with low quality and fragility is more likely to detach from the base material and may become a source of particles. By not providing the ceramic layer 20 in the third hole portion 13c, the generation of particles can rather be reduced.

[0110] Similar to the third hole portion 13c, it may be difficult to form a ceramic layer on the inner wall (vertical surface) of the hole 13. When a ceramic layer is provided inside the hole 13, the properties (for example, density and film thickness) of the ceramic layer inside the hole 13 may be inferior to the properties of the ceramic layer provided on the first surface of the base material. When the fragile ceramic layer inside the hole 13 is corroded by plasma, particles are generated. Also, for example, the mechanical properties (for example, strength against external force, hardness or toughness, etc.) of the ceramic layer with inferior properties are inferior to the mechanical properties of the base material. Therefore, there is a risk of particle generation due to physical impact or contact during handling and maintenance of the member for a semiconductor manufacturing apparatus.

[0111] For example, when forming the ceramic layer 20 by PVD, thermal spraying, or aerosol deposition method, etc., since it is difficult to form a film in the vertical second hole portion 13b, by making the second hole portion 13b long, film formation inside the hole can be suppressed.

[0112] In the aerosol deposition method, fine particles serving as a material are made to collide with a substrate, and the fine particles are joined on the substrate by the impact of the collision to form a layered structure. On the other hand, in the aerosol deposition method, if the surface of the substrate with which the fine particles serving as a material collide is rough, it becomes difficult for the fine particles to be joined and accumulated on the substrate, and it becomes difficult to form a layered structure. In the embodiment, since the arithmetic mean height Sa of the third hole portion 13c is relatively large, it is possible to more reliably suppress the formation of a fragile ceramic layer on the third hole portion 13c by the aerosol deposition method. Therefore, the generation of particles can be suppressed.

[0113] As described above, when using the aerosol deposition method, for example, by controlling the arithmetic mean height Sa of the third hole portion 13c, it is possible to suppress the formation of a ceramic layer on the third hole portion 13c. When using the aerosol deposition method, since processes such as masking before film formation may be omitted, it is easy to manufacture a member for a semiconductor manufacturing apparatus.

[0114] The "aerosol deposition method" is a method in which an "aerosol" in which fine particles containing a brittle material are dispersed in a gas is jetted from a nozzle toward a substrate, the fine particles are made to collide with the substrate such as metal, glass, ceramics, plastic, etc., and the brittle material fine particles are deformed and crushed by the impact of this collision and these are joined to directly form a layered structure (also referred to as a film-like structure) composed of the constituent material of the fine particles on the substrate.

[0115] In this example, for example, an aerosol which is a mixture of fine particles of a ceramic material excellent in particle resistance such as yttria and a gas is jetted toward the substrate 10 to form a layered structure (ceramic layer 20).

[0116] According to the aerosol deposition method, it is possible to form a layered structure at room temperature without particularly requiring heating means, cooling means, etc., and to obtain a layered structure having mechanical strength equal to or higher than that of a fired body. Further, by controlling the conditions for colliding fine particles, the shape, composition, etc. of the fine particles, it is possible to variously change the density, microstructure, mechanical strength, electrical properties, etc. of the layered structure.

[0117] In the present specification, "polycrystalline" refers to a structure formed by joining and accumulating crystal particles. The crystal particles substantially constitute a crystal by themselves. The diameter of the crystal particles is usually 5 nanometers (nm) or more. However, when the fine particles are incorporated into the structure without being crushed, the crystal particles are polycrystalline.

[0118] In the present specification, "fine particles" refer to those having an average particle diameter of 5 micrometers (μm) or less identified by particle size distribution measurement, scanning electron microscope, etc. when the primary particles are dense particles. When the primary particles are porous particles that are easily crushed by impact, those having an average particle diameter of 50 μm or less are referred to.

[0119] In the present specification, "aerosol" refers to a solid-gas mixed phase in which the above-mentioned fine particles are dispersed in a gas such as helium, nitrogen, argon, oxygen, dry air, or a mixed gas containing these. Although it may include some "aggregates" in some cases, it substantially refers to a state in which the fine particles are dispersed alone. The gas pressure and temperature of the aerosol are arbitrary, but the concentration of the fine particles in the gas is desirably in the range of 0.0003 mL / L to 5 mL / L at the time of ejection from the discharge port when the gas pressure is converted to 1 atm and the temperature is converted to 20 degrees Celsius for the formation of the layered structure.

[0120] One feature of the aerosol deposition process is that it is usually carried out at room temperature and a layered structure can be formed at a temperature sufficiently lower than the melting point of the fine particle material, that is, 100 degrees Celsius or less. In the specification of this application, "normal temperature" refers to a temperature significantly lower than the sintering temperature of ceramics, substantially an environment of 0 to 100°C, and a room temperature of around 20°C ± 10°C is more common.

[0121] The fine particles constituting the powder as the raw material of the layered structure mainly consist of brittle materials such as ceramics and semiconductors. Fine particles of the same material can be used alone or by mixing fine particles with different particle sizes. In addition, it is possible to use a mixture or composite of fine particles of different brittle materials. Also, it is possible to mix fine particles of metal materials or organic materials with the brittle material fine particles or coat the surface of the brittle material fine particles. Even in these cases, the main component for forming the layered structure is the brittle material.

[0122] In the composite structure formed by this method, when crystalline brittle material fine particles are used as the raw material, the layered structure part of the composite structure is a polycrystal with a crystal grain size much smaller than that of the raw material fine particles, and in many cases, the crystal has substantially no crystal orientation. Also, at the interface between the brittle material crystals, there is substantially no grain boundary layer composed of a glass layer. Also, in many cases, the layered structure part of the composite structure forms an "anchor layer" that bites into the surface of the base material (base material 10 in this example). The layered structure with this anchor layer formed adheres firmly to the base material with extremely high strength.

[0123] The layered structure formed by the aerosol deposition method is clearly different from the so-called "compressed powder" in which the fine particles are packed by pressure and maintain their form by physical adhesion, and has sufficient strength.

[0124] In the aerosol deposition method, the fact that the incoming brittle material fine particles are crushed and deformed on the substrate can be confirmed by measuring the brittle material fine particles used as raw materials and the crystallite (crystalline particle) size of the formed brittle material structure by means of X-ray diffraction method or the like. That is, the crystallite size of the layered structure formed by the aerosol deposition method is smaller than that of the raw material fine particles. On the "slip plane" and "fracture plane" formed by the crushing and deformation of the fine particles, a "newly formed surface" is formed in which atoms that originally existed inside the fine particles and were bonded to other atoms are exposed. It is considered that the layered structure is formed by the bonding of this newly formed surface with high surface energy and high activity to the surface of adjacent brittle material fine particles, the newly formed surface of the adjacent brittle material, or the surface of the substrate.

[0125] In addition, when hydroxyl groups are appropriately present on the surface of the fine particles in the aerosol, a mechanochemical acid-base dehydration reaction occurs due to local shear stress generated between the fine particles or between the fine particles and the structure during the collision of the fine particles, and it is also considered that these are joined together. The application of continuous mechanical impact force from the outside continuously generates these phenomena, and the progress and densification of the joining are carried out by repeated deformation, crushing, etc. of the fine particles, and it is considered that a layered structure made of a brittle material grows.

[0126] For example, when the ceramic layer 20 is formed by the aerosol deposition method, the ceramic layer 20 has a fine structure with a smaller crystallite size and higher density compared to a ceramic fired body, a sprayed film, or the like. Thereby, the particle resistance of the member 120 for a semiconductor manufacturing apparatus according to the embodiment is higher than that of a fired body or a sprayed film. Further, the probability that the member 120 for a semiconductor manufacturing apparatus according to the embodiment becomes a particle generation source is lower than the probability that a fired body, a sprayed film, or the like becomes a particle generation source.

[0127] When manufacturing the member 120 for a semiconductor manufacturing apparatus according to the present invention by, for example, the aerosol deposition method, an example of the apparatus used therefor will be described. The apparatus used for the aerosol deposition method is composed of a chamber, an aerosol supply unit, a gas supply unit, an exhaust unit, and piping. Inside the chamber, for example, a stage for arranging the substrate 10, a driving unit, and a nozzle are arranged. The driving unit can relatively change the positions of the substrate 10 arranged on the stage and the nozzle. At this time, the distance between the nozzle and the substrate 10 may be fixed or variable. In this example, the driving unit shows a mode of driving the stage, but the driving unit may drive the nozzle. The driving direction is, for example, the XYZθ direction.

[0128] The aerosol supply unit is connected to the gas supply unit by piping. In the aerosol supply unit, an aerosol in which raw material fine particles and gas are mixed is supplied to the nozzle through the piping. The apparatus further includes a powder supply unit for supplying the raw material fine particles. The powder supply unit may be arranged inside the aerosol supply unit or may be arranged separately from the aerosol supply unit. Further, separately from the aerosol supply unit, an aerosol formation unit for mixing the raw material fine particles and the gas may be provided. By controlling the supply amount from the aerosol supply unit so that the amount of fine particles ejected from the nozzle becomes constant, a homogeneous structure can be obtained.

[0129] The gas supply unit supplies nitrogen gas, helium gas, argon gas, air, etc. When the supplied gas is air, for example, it is preferable to use compressed air with few impurities such as moisture and oil, or to further provide an air treatment unit for removing impurities from the air.

[0130] Next, an example of the operation of the apparatus used in the aerosol deposition method will be described. With the substrate 10 placed on the stage inside the chamber, the inside of the chamber is evacuated to a pressure below atmospheric pressure, specifically, to about several hundred Pa, by an exhaust section such as a vacuum pump. On the other hand, the internal pressure of the aerosol supply section is set higher than the internal pressure of the chamber. The internal pressure of the aerosol supply section is, for example, several hundred to several tens of thousands of Pa. The powder supply section may be at atmospheric pressure. The fine particles in the aerosol are accelerated so that the injection speed of the raw material particles from the nozzle becomes in the subsonic to supersonic (50 to 500 m / s) region due to the differential pressure between the chamber and the aerosol supply section, etc. The injection speed is controlled by the flow rate of the gas supplied from the gas supply section, the type of gas, the shape of the nozzle, the length and inner diameter of the piping, the exhaust volume of the exhaust section, etc. For example, as the nozzle, a supersonic nozzle such as a Laval nozzle can also be used. The fine particles in the aerosol injected at high speed from the nozzle collide with the substrate 10, are pulverized or deformed, and are deposited as a structure (ceramic layer 20) on the substrate 10. By changing the relative position between the substrate 10 and the nozzle, a composite structure (member 120 for semiconductor manufacturing apparatus) having a structure (ceramic layer 20) with a predetermined area is formed on the substrate 10.

[0131] Further, a disintegration section for dissociating the aggregation of the fine particles may be provided before the injection from the nozzle. As the disintegration method in the disintegration section, any method can be selected. For example, mechanical disintegration such as vibration and collision, electrostatic electricity, plasma irradiation, classification, and other known methods can be mentioned.

[0132] (Second Embodiment) FIGS. 5(a) and 5(b) are cross-sectional views illustrating a part of the member for semiconductor manufacturing apparatus according to the second embodiment.

[0133] The description similar to that of the member 120 for semiconductor manufacturing equipment can be applied to the member 120d for semiconductor manufacturing equipment shown in Fig. 5(a). However, the arithmetic mean height Sa of the surface of the first part 21 may not be smaller than the arithmetic mean height Sa of the surface of the second part 22, or it may be the same as that of the member 120 for semiconductor manufacturing equipment. Also, the arithmetic mean height Sa of the third hole 13c may not be larger than the arithmetic mean height Sa of the surfaces of the first part 21 and the second part 22, or it may be the same as that of the member 120 for semiconductor manufacturing equipment.

[0134] As shown in Fig. 5(a), the member 120d for semiconductor manufacturing equipment has a composite structure 30. The composite structure refers to one having a base material and a structure (such as a layer or a film) provided on the surface of the base material. The composite structure 30 includes a base material 10 and a ceramic layer 20. In this example, the composite structure 30 is a laminate of the base material 10 and the ceramic layer 20. In the embodiment, each of the base material 10 and the ceramic layer 20 may have a laminated structure including a plurality of layers.

[0135] As shown in Fig. 5(a), the composite structure 30 has a first main surface 311 and a second main surface 312 opposite to the first main surface 311. For example, the first main surface 311 is the surface 21s of the first part of the ceramic layer 20, and the second main surface 312 is the second surface 12 of the base material 10. Also, at least one through hole 313 is provided in the composite structure 30. The through hole 313 extends in the Z direction and penetrates the base material 10 and the ceramic layer 20. For example, one through hole 313 is provided at the center of the composite structure 30. However, the through hole 313 may not be at the center of the composite structure 30, or a plurality of through holes may be provided.

[0136] The through-hole 313 is, for example, circular when viewed along the Z direction. The through-hole 313 (the inner peripheral surface 313s of the through-hole) has a first hole region 313a, a second hole region 313b, and a third hole region 313c. The first hole region 313a, the second hole region 313b, and the third hole region 313c are each exposed and provided so as to be in contact with the plasma. The inner peripheral surface 313s is the inner peripheral surface of the composite structure 30 that defines the through-hole 313. The inner peripheral surface 313s faces the inside of the through-hole 313 and intersects the X-Y plane.

[0137] The first hole region 313a is located in the vicinity of the first main surface 311 of the inner peripheral surface 313s and is a region adjacent to the first main surface 311. The first hole region 313a is continuous with the first main surface 311. The first hole region 313a is located between the first main surface 311 and the second main surface 312 in the Z direction. The first hole region 313a is not parallel to the first main surface 311 but is an inclined surface that intersects the first main surface 311 and the Z direction. The first hole region 313a may be a surface that extends parallel to the Z direction. In a cross-section parallel to the Z direction, the first hole region 313a may be linear or curved. When viewed along the Z direction (i.e., when projected onto the X-Y plane), the first hole region 313a is, for example, annular and surrounded by the first main surface 311.

[0138] The second hole region 313b is located between the first hole region 313a and the second main surface 312 in the Z direction. In other words, the position of the second hole region 313b in the Z direction is between the position of the first hole region 313a in the Z direction and the position of the second main surface 312 in the Z direction. For example, the second hole region 313b is located in the vicinity of the second main surface 312 of the inner peripheral surface 313s and is a region adjacent to the second main surface 312. The second hole region 313b may be continuous with the second main surface 312. The second hole region 313b extends in the Z direction and is, for example, parallel to the Z direction. The second hole region 313b is, for example, a vertical surface that is substantially perpendicular to the second main surface 312. When viewed along the Z direction, the second hole region 313b is, for example, annular and located inside the first hole region 313a.

[0139] The third hole region 313c is located between the first hole region 313a and the second hole region 313b in the Z direction. In other words, the position of the third hole region 313c in the Z direction is between the position of the first hole region 313a in the Z direction and the position of the second hole region 313b in the Z direction. The third hole region 313c is a region of the inner peripheral surface 313s that is continuous with the first hole region 313a. The third hole region 313c is not parallel to the first surface 11, but is an inclined surface that intersects the first surface 11 and the Z direction. The third hole region 313c may be a surface that extends in the Z direction. In a cross-section parallel to the Z direction, the third hole region 313c may be linear or curved. When viewed along the Z direction, the third hole region 313c is, for example, annular, surrounded by the first hole region 313a and in contact with the first hole region 313a, and the second hole region 313b is located inside the third hole region 313c. The third hole region 313c and the second hole region 313b may be continuous.

[0140] In the example of FIG. 5(a), the first hole region 313a of the through-hole 313 is the surface 22s of the second portion 22 of the ceramic layer 20, the second hole region 313b is the second hole portion 13b of the hole 13 of the base material 10, and the third hole region 313c is the third hole portion 13c of the hole 13 of the base material 10. A part of the through-hole 313 of the composite structure 30 is at least a part of the hole 13 of the base material 10. Specifically, a part of the through-hole 313 is defined by the second hole portion 13b and the third hole portion 13c that define a part of the hole 13 of the base material 10.

[0141] The hardness of the third hole region 313c is higher than that of the first hole region 313a. For example, the third hole region 313c is more wear-resistant than the first hole region 313a. In the example of Fig. 5(a), the hardness of the third hole portion 13c of the base material 10 is higher than the hardness of the surface 22s of the ceramic layer 20. For example, the hardness of the material of the base material 10 is higher than the hardness of the material of the ceramic layer 20. Thereby, the hardness of the third hole region 313c can be made higher than the hardness of the first hole region 313a. Specifically, for the materials of the first part 21 and the second part 22 of the ceramic layer 20, at least any one of an oxide of a rare earth element, a fluoride of a rare earth element, and an oxyfluoride of a rare earth element can be used. The rare earth element is at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. Also, for the material of the base material 10, at least any one of aluminum oxide (Al2O3), zirconium oxide (ZrO2), and aluminum nitride (AlN) can be used.

[0142] The third hole region 313c is located more inside the through hole 313 than the first hole region 313a. For example, when a jig such as a positioning pin is inserted into the through hole 313 during handling of a member for a semiconductor manufacturing apparatus, the possibility that the third hole region 313c comes into physical contact with the jig is higher than the possibility that the first hole region 313a comes into physical contact with the jig. Also, for example, when the first hole region 313a and the third hole region 313c come into contact with a cleaning pad during maintenance of a member for a semiconductor manufacturing apparatus, if the angle θβ is smaller than the angle θα, the third hole region 313c may be more likely to wear than the first hole region 313a. For example, when the angle θβ is smaller than the angle θα, the corner portion near the boundary between the third hole region 313c and the second hole region 313b is more likely to have force concentrated and be more likely to wear than the corner portion near the boundary between the first hole region 313a and the first main surface 311.

[0143] In contrast, in the embodiment, since the hardness of the third hole region 313c is relatively high, damage to the third hole region 313c can be suppressed by physical contact during maintenance or handling of the member for a semiconductor manufacturing apparatus. Thereby, generation of particles can be suppressed.

[0144] The member 120e for a semiconductor manufacturing apparatus shown in FIG. 5(b) is different from the member 120d for a semiconductor manufacturing apparatus in that the ceramic layer 20 has the third portion 23. In the member 120e for a semiconductor manufacturing apparatus, the third hole region 313c is the surface 23s of the third portion 23. Otherwise, the same description as that of the member 120d for a semiconductor manufacturing apparatus can be applied to the member 120e for a semiconductor manufacturing apparatus.

[0145] The third portion 23 of the ceramic layer 20 is provided on the third hole portion 13c and is in contact with the third hole portion 13c. The third portion 23 is provided continuously from the second portion 22. The surface 23s of the third portion 23 is in direct contact with the plasma. That is, the surface 23s is the surface on the side opposite to the surface of the third portion 23 that contacts the third hole portion 13c, and is provided so as to be exposed in the chamber 110. In this example, the first hole portion 13a and the third hole portion 13c are covered with the ceramic layer 20 so as not to be in direct contact with the plasma. Thereby, generation of particles from the first hole portion 13a and the third hole portion 13c of the holes 13 of the base material can be suppressed. On the other hand, when the ceramic layer 20 is not provided in the third hole portion 13c as in the example of FIG. 5(a), formation of a ceramic layer 20 with inferior properties in the third hole portion 13c can be suppressed, and generation of particles from the ceramic layer 20 can be further suppressed.

[0146] In the example of FIG. 5(b), the first hole region 313a of the through hole 313 is the surface 22s of the second portion 22 of the ceramic layer 20, the second hole region 313b is the second hole portion 13b of the hole 13 of the base material 10, and the third hole region 313c is the surface 23s of the third portion 23 of the ceramic layer 20. Also in this example, a part of the through hole 313 of the composite structure 30 is at least a part of the hole 13 of the base material 10. Specifically, a part of the through hole 313 is defined by the second hole portion 13b that defines a part of the hole 13 of the base material 10.

[0147] Also in the member 120e for a semiconductor manufacturing apparatus, the hardness of the third hole region 313c is higher than the hardness of the first hole region 313a. That is, the hardness of the surface 23s of the third portion 23 of the ceramic layer 20 is higher than the hardness of the surface 22s of the second portion 22 of the ceramic layer 20. Thereby, it is possible to suppress damage to the third hole region 313c due to physical contact during maintenance or handling of the member for a semiconductor manufacturing apparatus. Thereby, it is possible to suppress the generation of particles.

[0148] For example, the material of the third portion 23 is different from the material of the second portion 22, and the hardness of the material of the third portion 23 is higher than the hardness of the material of the second portion 22. Thereby, the hardness of the third hole region 313c can be made higher than the hardness of the first hole region 313a. For example, at least any one of an oxide of a rare earth element, a fluoride of a rare earth element, and an oxyfluoride of a rare earth element can be used as the material of the third portion 23. The rare earth element is at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. By making the composition of the third portion 23 different from the composition of the second portion 22, the hardness of the third portion 23 and the hardness of the second portion 22 can be made different.

[0149] By using masking such as a tape, each of the film that becomes the second portion 22 and the film that becomes the third portion 23 can be provided in a desired range. For example, with a mask provided on the first hole portion 13a or the second portion 22, a film that becomes the third portion 23 is formed on the third hole portion 13c. Also, for example, with a mask provided on the third hole portion 13c or the third portion 23, a film that becomes the second portion 22 is formed on the first hole portion 13a. Thereby, separate films can be formed on the first hole portion 13a and the third hole portion 13c, and the material of the third portion 23 and the material of the second portion 22 can be made different. Thereby, the hardness of the third portion 23 and the hardness of the second portion 22 can be made different. Without using masking, by removing a part of the film by polishing or the like after film formation, separate films may be provided on the first hole portion 13a and the third hole portion 13c.

[0150] For example, the density of the third portion 23 is higher than the density of the second portion 22. Thereby, the hardness of the third hole region 313c can be made higher than the hardness of the first hole region 313a. For example, after forming a single film that becomes the second portion 22 and the third portion 23, the second portion 22 and the third portion 23 can be formed by subjecting a part of the film to a surface modification treatment. As an example of the surface modification treatment, a method of applying energy to a range of a predetermined depth from the surface of the film to melt it and then cooling the range to form a melt-solidified film can be mentioned. The melt-solidified film formed by the surface modification treatment becomes a dense film with fewer voids and a flattened surface compared to the region where the surface modification treatment has not been performed. For the surface modification treatment, a method that can selectively heat-melt the surface may be used. Specifically, the surface modification treatment includes laser annealing treatment or plasma jet treatment. For example, the range where the surface modification treatment is performed becomes the third portion 23, and the range where the surface modification treatment has not been performed becomes the second portion 22.

[0151] The film formation conditions of the third part 23 may be different from those of the second part 22. Thereby, the density of the third part 23 and the density of the second part 22 can be made different, or the hardness of the third part 23 and the hardness of the second part 22 can be made different. Such film formation conditions include, when using the aerosol deposition method, the flow rate, flow velocity, or gas type of the gas supplied from the gas supply unit. The film formation conditions may also be the angle at which the aerosol ejected from the nozzle collides with the substrate. Note that in the present embodiment, the ceramic layer 20 does not necessarily have to be provided on the first hole portion 13a and the third hole portion 13c. The first hole region 313a may be the surface of the substrate 10. The hardness of a part of the substrate surface may be appropriately adjusted by surface treatment (for example, coating or modification treatment).

[0152] FIGS. 6(a) and 6(b) are cross-sectional views illustrating a part of a member for a semiconductor manufacturing apparatus. FIGS. 6(a) and 6(b) each show a substrate 10 of a member for a semiconductor manufacturing apparatus. The configuration of the substrate 10 shown in FIG. 6(a) is the same as the substrate 10 described above with respect to FIG. 2. In the substrate 10 of FIG. 6(a), the angle θα is 150°.

[0153] In the substrate 10 shown in FIG. 6(b), the angle θα is 120°. The substrate 10 of FIG. 6(b) is different from the substrate 10 of FIG. 6(a) in the shape (length and angle) of the inclined surface 13ac and the length of the second hole portion 13b. Otherwise, the configuration of the substrate 10 of FIG. 6(b) is the same as that of the substrate 10 of FIG. 6(a).

[0154] In the substrate 10 shown in FIG. 6(a), the angle θα is larger than the angle θβ. In the substrate 10 shown in FIG. 6(b), the angle θα is smaller than the angle θβ. The length Ln in the Z direction of the second hole portion 13b of the substrate 10 of FIG. 6(a) is longer than the length Ln in the Z direction of the second hole portion 13b of the substrate 10 of FIG. 6(b). Thus, when the thickness of the substrate 10 is constant, when the angle θα is larger than the angle θβ, it is easier to increase the length in the Z direction of the second hole portion 13b.

[0155] Figures 6(a) and 6(b) show the proximity circle PC. The proximity circle PC is close to the edge portion (boundary 14) formed by the first surface 11 and the inclined surface 13ac. The proximity circle PC is a circle that contacts the first surface 11 and the inclined surface 13ac in a cross-section parallel to the Z direction as shown in Figures 6(a) and 6(b). The distance (distance t2) between the position of the center p of the proximity circle PC in the X direction in Figure 6(a) and the position of the boundary 14 in the X direction is the same as the distance (distance t2) between the position of the center p of the proximity circle PC in the X direction in Figure 6(b) and the position of the boundary 14 in the X direction. That is, in Figures 6(a) and 6(b), when the positions of the boundaries 14 in the X direction are made to coincide, the positions of the centers p in the X direction coincide. At this time, the width t of the inclination shown in Figures 6(a) and 6(b) is constant. That is, the width t in Figure 6(a) and the width t in Figure 6(b) are equal to each other. If the radius R of the proximity circle PC shown in Figure 6(a) is r, then the radius R of the proximity circle PC shown in Figure 6(b) is 0.47r.

[0156] Here, the width t of the inclination is the sum of the predetermined distance t1 and the distance t2. In Figure 6(a), the predetermined distance t1 is the distance in the X direction from the boundary 14 to the second hole portion 13b. The predetermined distance t1 is constant. That is, the predetermined distance t1 in Figure 6(a) and the predetermined distance t1 in Figure 6(b) are equal to each other. The width t of the inclination is the distance along the X direction between the center p of the proximity circle PC and the second hole portion 13b in Figure 6(a).

[0157] Figure 7 is a graph showing an example of the stress of a member for a semiconductor manufacturing apparatus. FIG. 7 illustrates the calculation results of the relationship between the radius R of the proximity circle PC and the stress S generated in the member for a semiconductor manufacturing apparatus. That is, FIG. 7 shows the change in the stress S when the radius R of the proximity circle PC of the base material 10 is changed in the member for a semiconductor manufacturing apparatus similar to that in FIG. 2, in the same manner as in FIGS. 6(a) and 6(b). More specifically, in the base material 10, with the distance t2 (the position of the center p of the proximity circle PC in the X direction, the position of the boundary 14 in the X direction) and the thickness of the base material 10 being constant, the angle θα is changed. Thereby, the stress S generated in the ceramic layer 20 formed on the boundary 14 when the radius R, the length of the second hole portion 13b in the Z direction, and the shape (length and angle) of the inclined surface 13ac are changed is calculated. Note that the angle θα is greater than 90°, and at this time, the radius R > 0.27r.

[0158] The stress S is the calculation result of the stress (for example, residual stress) generated at the connection portion between the first portion 21 and the second portion 22 (that is, the ceramic layer 20 formed on the boundary 14). For example, the magnitude of the stress S corresponds to the electric field strength on the surface of the ceramic layer 20 on the boundary 14.

[0159] As the angle θα increases, the radius R of the proximity circle PC increases. As shown in FIG. 7, when the radius R increases, the stress S decreases. For example, let the radius R when the angle θα is 150° as in FIG. 6(a) be r, and the stress S at that time be about s. When the angle θα is 120° as in FIG. 6(b), the radius R is 0.47r, and the stress S at that time is calculated to be about 1.7s. That is, in the example of FIG. 6(a), compared with the example of FIG. 6(b), stress concentration can be suppressed, and the stress is reduced by about 1.7 times. That is, by increasing the angle θα, stress concentration can be alleviated. The angle θα is, for example, 150° or more, more preferably 160° or more.

[0160] For example, make the inclined surface 13ac linear in a cross-section parallel to the Z direction. If the inclined surface 13ac is curved in a cross-section parallel to the Z direction, an electric field may concentrate on the inclined surface 13ac or the ceramic layer 20 on the inclined surface 13ac, and particles may be generated. On the other hand, when the inclined surface 13ac is linear in a cross-section parallel to the Z direction, the electric field concentration in the inclined surface 13ac or the ceramic layer 20 on the inclined surface 13ac can be further alleviated.

[0161] For example, when the radius R is 0.3r, the stress S is about 2.5s, and when the radius R is 0.7r, the stress S is about 1.2s.

[0162] FIG. 8 is a table illustrating the evaluation of particle resistance in a member for a semiconductor manufacturing apparatus. Samples 1 to 5 are each the same as the member 120 for a semiconductor manufacturing apparatus described with reference to FIG. 2. As shown in FIG. 8, in Samples 1 to 5, at least one of the arithmetic mean height Sa of the first portion 21, the arithmetic mean height Sa of the second portion 22, and the arithmetic mean height Sa of the third hole portion 13c is changed. In Samples 1 to 5, except for the arithmetic mean height Sa (for example, the angles θα and θβ, the thickness of the base material 10, etc.), they are constant.

[0163] In Sample 1, the arithmetic mean height Sa of the first portion 21 is 0.03 μm, the arithmetic mean height Sa of the second portion 22 is 0.06 μm, and the arithmetic mean height Sa of the third hole portion 13c is 0.2 μm. In Sample 2, the arithmetic mean height Sa of the first portion 21 is 0.03 μm, the arithmetic mean height Sa of the second portion 22 is 0.12 μm, and the arithmetic mean height Sa of the third hole portion 13c is 0.5 μm. In Sample 3, the arithmetic mean height Sa of the first portion 21 is 0.06 μm, the arithmetic mean height Sa of the second portion 22 is 0.35 μm, and the arithmetic mean height Sa of the third hole portion 13c is 0.3 μm. In Sample 4, the arithmetic mean height Sa of the first portion 21 is 0.08 μm, the arithmetic mean height Sa of the second portion 22 is 0.81 μm, and the arithmetic mean height Sa of the third hole portion 13c is 0.85 μm. In Sample 5, the arithmetic mean height Sa of the first part 21 is 0.15 μm, the arithmetic mean height Sa of the second part 22 is 0.41 μm, and the arithmetic mean height Sa of the third hole portion 13c is 0.2 μm.

[0164] Further, FIG. 8 shows the ratio R21 and the ratio R31 for each sample. The ratio R21 is the ratio of the arithmetic mean height Sa of the second part 22 to the arithmetic mean height Sa of the first part 21. The ratio 31 is the ratio of the arithmetic mean height Sa of the third hole portion 13c to the arithmetic mean height Sa of the first part 21.

[0165] Further, FIG. 8 represents the particle resistance of each sample as "◎", "○", or "×". In the evaluation of the particle resistance, the sample is irradiated with plasma, and the difference between the arithmetic mean height Sa before the plasma irradiation and the arithmetic mean height Sa after the plasma irradiation is evaluated. The conditions for the plasma irradiation are as follows. As the plasma etching apparatus, an inductively coupled plasma reactive ion etching apparatus (Muc-21 Rv-Aps-Se / manufactured by Sumitomo Precision Products Co., Ltd.) is used. The conditions for the plasma etching are such that the output of ICP (Inductively Coupled Plasma) is 1500 W as the power output, the bias output is 750 W, a mixed gas of 100 ccm of CHF3 gas and 10 ccm of O2 gas is used as the process gas, the pressure is 0.5 Pa, and the plasma etching time is 1 hour.

[0166] "◎" indicates that the change in the arithmetic mean height Sa due to plasma irradiation is small in all of the first part 21, the second part 22, and the third hole portion 13c. "○" indicates that the change in the arithmetic mean height Sa due to plasma irradiation is small in two or more of the first part 21, the second part 22, and the third hole portion 13c. "×" represents the particle resistance other than "◎" and "○".

[0167] As already described, for example, the arithmetic mean height Sa of the surface 22s of the second portion 22 is 2 times or more and 10 times or less, more preferably 5 times or less, the arithmetic mean height Sa of the surface 21s of the first portion 21. In other words, the ratio R21 is 2.0 or more and 10 or less, more preferably 5.0 or less. As shown in FIG. 8, the particle resistance of sample 3 with a ratio R21 of 5.8 is higher than the particle resistance of sample 4 with a ratio R21 of 10.1. The particle resistance of sample 1 with a ratio R21 of 2.0 and sample 2 with a ratio R21 of 4.0 is higher than the particle resistance of sample 3.

[0168] Also, as already described, for example, the arithmetic mean height Sa of the third hole portion 13c is greater than 2 times the arithmetic mean height Sa of the surface 21s of the first portion 21. In other words, the ratio R31 is greater than 2.0. As shown in FIG. 8, the particle resistance of sample 1 with a ratio R31 of 6.7, sample 2 with a ratio R31 of 16.7, and sample 3 with a ratio R31 of 5.0 is higher than the particle resistance of sample 5 with a ratio R31 of 1.3.

[0169] Note that each cross-section of the member for a semiconductor manufacturing apparatus described with reference to FIGS. 2 to 6(b) may be a cross-section passing through the center of the hole 13 in the X-Y plane.

[0170] In the present specification, "vertical" and "parallel" include not only strict vertical and strict parallel, but also, for example, variations in the manufacturing process, and may be substantially vertical and substantially parallel.

[0171] The embodiments of the present invention have been described above. However, the present invention is not limited to these descriptions. Regarding the above-described embodiments, those in which those skilled in the art have appropriately made design changes are also included in the scope of the present invention as long as they have the features of the present invention. For example, the shape, dimensions, material, arrangement, installation form, etc. of each element included in the member for a semiconductor manufacturing apparatus, semiconductor manufacturing apparatus, etc. are not limited to those illustrated and can be appropriately changed. Moreover, each element included in each of the above-described embodiments can be combined as far as technically possible, and combinations thereof are also included in the scope of the present invention as long as they include the features of the present invention.

Description of Reference Numerals

[0172] 10, 10a to 10c Substrate, 11 First surface, 12 Second surface, 13 Hole, 13a First hole portion, 13ac Inclined surface, 13b Second hole portion, 13c Third hole portion, 13s Inner peripheral surface, 14, 15 Boundary, 16a First region, 16b Second region, 16c Boundary, 17 Boundary, 20 Ceramic layer, 21 First portion, 21s Surface, 22 Second portion, 22s Surface, 23 Third portion, 23s Surface, 30 Composite structure, θα, θβ, θ1 to θ4 Angles, 100 Semiconductor manufacturing apparatus, 110 Chamber, 111 Inner wall, 111b Lower inner wall, 111u Upper inner wall, 120, 120a to 120e Members for semiconductor manufacturing apparatus, 160 Electrostatic chuck, 191 Region, 210 Wafer, 221 Particle, 311 First main surface, 312 Second main surface, 313 Through hole, 313a First hole region, 313b Second hole region, 313c Third hole region, 313s Inner peripheral surface, L1 to L3 Line segments, T21, T22 Thickness, e1 to e4 Ends, P1 to P3 Portions

Claims

Claim 1 A member for a semiconductor manufacturing apparatus used in a chamber of a semiconductor manufacturing apparatus, comprising: a base material including a first surface, a second surface opposite to the first surface, and at least one hole penetrating the first surface and the second surface; a ceramic layer provided on the base material; and comprising: the hole has a first hole portion continuous with the first surface; the ceramic layer includes a first portion provided so as to be exposed on the first surface and a second portion provided on the first hole portion; a member for a semiconductor manufacturing apparatus, wherein an arithmetic mean height Sa of a surface of the first portion is smaller than an arithmetic mean height Sa of a surface of the second portion. Claim 2 The hole further has: a second hole portion located between the second surface and the first hole portion in a first direction from the first surface toward the second surface; a third hole portion located between the first hole portion and the second hole portion in the first direction, continuous with the first hole portion, and provided so as to be exposed; and further comprising: a member for a semiconductor manufacturing apparatus according to claim 1, wherein an arithmetic mean height Sa of a surface of the third hole portion is larger than an arithmetic mean height Sa of a surface of the first portion and larger than an arithmetic mean height Sa of a surface of the second portion. Claim 3 The member for a semiconductor manufacturing apparatus according to claim 1 or 2, wherein an arithmetic mean height Sa of a surface of the second portion is 10 times or less of an arithmetic mean height Sa of a surface of the first portion. Claim 4 The member for a semiconductor manufacturing apparatus according to claim 2, wherein an arithmetic mean height Sa of a surface of the third hole portion is larger than twice of an arithmetic mean height Sa of a surface of the first portion. Claim 5 The member for a semiconductor manufacturing apparatus according to any one of claims 1 to 4, wherein an arithmetic mean height Sa of a surface of the second portion is less than 0.5 micrometer. Claim 6 The member for a semiconductor manufacturing apparatus according to any one of claims 1 to 5, wherein an arithmetic mean height Sa of a surface of the first portion is less than 0.1 micrometer. Claim 7 The hole further has: a second hole portion located between the second surface and the first hole portion in a first direction from the first surface toward the second surface; a third hole portion located between the first hole portion and the second hole portion in the first direction, continuous with the first hole portion, and exposed; and further comprising: a member for a semiconductor manufacturing apparatus according to claim 1, wherein an arithmetic mean height Sa of a surface of the third hole portion is larger than an arithmetic mean height Sa of a surface of the first portion and smaller than an arithmetic mean height Sa of a surface of the second portion. Claim 8 The ceramic layer is a member for a semiconductor manufacturing apparatus according to any one of claims 1 to 7, including polycrystalline ceramics.

9. The member for a semiconductor manufacturing apparatus according to claim 8, wherein an average crystallite size of the polycrystalline ceramics, calculated from a TEM image with a magnification of 400,000 times to 2,000,000 times, is 3 nanometers or more and 50 nanometers or less.

10. The ceramic layer is a member for a semiconductor manufacturing apparatus according to any one of claims 1 to 9, including at least one selected from the group consisting of oxides of rare earth elements, fluorides of rare earth elements, and oxyfluorides of rare earth elements.

11. The member for a semiconductor manufacturing apparatus according to claim 10, wherein the rare earth element is at least one selected from the group consisting of Y, Sc, Yb, Ce, Pr, Eu, La, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu.

12. The substrate is a member for a semiconductor manufacturing apparatus according to any one of claims 1 to 11, including ceramics.

13. The substrate is a member for a semiconductor manufacturing apparatus according to claim 12, including alumina.

14. A chamber, A member for a semiconductor manufacturing apparatus according to any one of claims 1 to 13, A semiconductor manufacturing apparatus comprising: The chamber has an inner wall that forms a space where plasma is generated, The ceramic layer of the member for a semiconductor manufacturing apparatus constitutes at least a part of the inner wall. A semiconductor manufacturing apparatus.

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