Yttrium protective film, method for manufacturing the same, and components.

Abstract

The purpose of the present invention is to provide an yttrium-based protective film having excellent plasma resistance. The present invention relates to: an yttrium-based protective film having a porosity of less than 1.5 vol%, a Young's modulus of at least 100.00 GPa, and a Vicker's hardness of at least 8.50 GPa; and a member having the yttrium-based protective film.

Description

[Technical Field]

[0001] The present invention relates to a yttrium-based protective film, a method for producing the same, and a member. [Background Art]

[0002] When manufacturing semiconductor devices, for example, the surface of a semiconductor substrate (silicon wafer) is microfabricated by dry etching using halogen-based gas plasma in a chamber, and the interior of the chamber from which the semiconductor substrate is taken out after dry etching is cleaned using oxygen gas plasma.

[0003] At this time, members exposed to plasma in the chamber corrode, and corroded portions may fall off in particulate form from the corroded member. The fallen particles can adhere to the semiconductor substrate and become foreign matter that causes defects in circuits.

[0004] Accordingly, conventionally, a protective film containing yttrium oxide or yttrium oxyfluoride (yttrium-based protective film) is known as a protective film for protecting members exposed to plasma. Patent Document 1 discloses a thermal sprayed coating containing yttrium oxide or yttrium oxyfluoride formed by thermal spraying. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Unexamined Patent Publication No. 2018-76546 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] Studies by the present inventors have revealed that conventional yttrium-based protective films may have insufficient plasma resistance (corrosion resistance against plasma) in some cases.

[0007] This invention has been made in view of the above points, and aims to provide a yttrium protective film with excellent plasma resistance. [Means for solving the problem]

[0008] As a result of diligent research, the inventors of this invention discovered that the above objective can be achieved by adopting the following configuration, and thus completed the present invention. In other words, the present invention provides the following [1] to

[30] . [1] A yttrium protective film having a porosity of less than 1.5 volume%, a Young's modulus of 100.00 GPa or higher, and a Vickers hardness of 8.50 GPa or higher. [2] The yttrium protective film described in [1] above, having a Young's modulus / Vickers hardness of 16.5 or less. [3] The yttrium protective film described in [1] or [2] above, containing 0.10 to 3.00 atomic percent of argon. [4] A yttrium protective film according to any one of [1] to [3] above, containing 5 atomic percent or more of yttrium. [5] A yttrium protective film according to any one of [1] to [4] above, containing 25 to 65 atomic percent of fluorine. [6] A yttrium protective film as described in any one of [1] to [5] above, wherein the F / O ratio, which is the ratio of fluorine content to oxygen content, is less than 2.80. [7] A yttrium protective film according to any one of [1] to [6] above, wherein the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is 60% or more. [8] A yttrium protective film according to any one of [1] to [7] above, having a crystallite size of 5 to 30 nm. [9] A yttrium protective film according to any one of [1] to [8] above, having a thickness of 0.01 to 30.0 μm.

[0009]

[10] A component comprising a base material and a yttrium protective film as described in any one of [1] to [9] above.

[11] The member according to

[10] above, wherein the base material has at least a first film-forming surface and a second film-forming surface different from the first film-forming surface as film-forming surfaces, a first film that is the yttrium-based protective film is formed on the first film-forming surface, and a second film that is a yttrium-based protective film different from the first film is formed on the second film-forming surface.

[12] The Vickers hardness HV2 of the second membrane is y of the Vickers hardness HV1 of the first membrane A times, within the range of ±40%, the member according to

[11] above, provided that y A is, when the angle formed between the first film-forming surface and the second film-forming surface is taken as x within 0 to 90° A , when x A is 0 to 60°, it is calculated by the following formula (1), and when x A is more than 60° and 90° or less, it is calculated by the following formula (2). (1)y A =-0.00034751x A 2 +0.01538782x A +1.00625521 (2)y A =-0.00197743x A +0.75229358

[13] The thickness t2 of the second film is y of the thickness t1 of the first film B times, within the range of ±40%, the member according to

[11] or

[12] above, provided that y B is, when the angle formed between the first film-forming surface and the second film-forming surface is taken as x within 0 to 170° B , when x B is 0 to 90°, it is calculated by the following formula (3), and when x B is more than 90° and 170° or less, it is calculated by the following formula (4). (3)y B =-0.00012389x B 2 +0.00659698x B +0.99721254 (4)y B =-0.00005913x B 2 +0.01099778xB -0.26784922

[14] The crystallite size S2 of the second film is equal to the y of the crystallite size S1 of the first film. C The component described in any one of the above

[11] to

[13] , which is within ±40% of double. C The angle between the first film deposition surface and the second film deposition surface is set to x from 0 to 170°. C In this case, it is calculated by the following formula (5). (5)y C =0.00009729x C 2 -0.00273425x C +0.99976959

[15] The member according to any one of

[11] to

[14] above, wherein the angle between the first film-forming surface and the second film-forming surface is 10° to 160°.

[16] The member according to any one of

[11] to

[15] above, wherein the angle between the first film-forming surface and the second film-forming surface is 90°, and the HV1 / HV2 ratio, which is the ratio of the Vickers hardness HV1 of the first film to the Vickers hardness HV2 of the second film, is 1.05 to 2.50.

[17] The component according to any one of

[11] to

[16] above, wherein the angle between the first film-forming surface and the second film-forming surface is 90°, and the t1 / t2 ratio, which is the ratio of the thickness t1 of the first film to the thickness t2 of the second film, is 1.5 to 3.5. However, the unit of thickness is μm.

[18] The member according to any one of

[11] to

[17] above, wherein the angle between the first film-forming surface and the second film-forming surface is 90°, and the t1 / t2 ratio, which is the ratio of the thickness t1 of the first film to the thickness t2 of the second film, is 2.0 to 6.0. However, the unit of thickness is μm.

[19] The component according to any one of

[11] to

[18] above, wherein the angle between the first film deposition surface and the second film deposition surface is 90°, and the S1 / S2 ratio, which is the ratio of the crystallite size S1 of the first film to the crystallite size S2 of the second film, is 0.35 to 0.90. However, the unit of crystallite size is nm.

[20] The component according to

[19] above, wherein the crystallite size S1 of the first film is less than 20 nm.

[21] The component according to

[19] or

[20] above, wherein the crystallite size S2 of the second film is 15 nm or more.

[22] The component according to any one of

[10] to

[21] above, wherein the surface roughness of the film-forming surface of the substrate is 0.001 to 3.00 μm in terms of arithmetic mean roughness Ra.

[23] The component according to any one of

[10] to

[22] above, wherein the porosity of the base material is 2.0 volume% or less.

[24] The component according to any one of

[10] to

[23] above, wherein the base material is composed of at least one selected from the group consisting of carbon, ceramics, and metal.

[25] The member according to

[24] , wherein the ceramic is at least one selected from the group consisting of glass, quartz, aluminum oxide, aluminum nitride, Si-impregnated silicon carbide, and aluminum oxynitride, and the metal is at least one selected from the group consisting of aluminum and aluminum-containing alloys.

[26] The component according to any one of

[10] to

[25] above, wherein the maximum length of the film-forming surface of the substrate is 30 mm or more.

[27] The member according to any one of

[10] to

[26] above, wherein one or more underlayers are provided between the substrate and the yttrium protective film, and the underlayer contains at least one oxide selected from the group consisting of Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3 and Gd2O3.

[28] A component according to any one of the above

[10] to

[27] , used inside a plasma etching apparatus or a plasma CVD apparatus.

[0010]

[29] A method for producing a yttrium protective film according to any one of [1] to [9] above, wherein, in a vacuum, an evaporation source is evaporated and deposited on a substrate while irradiating with ions of at least one element selected from the group consisting of oxygen, argon, neon, krypton, and xenon from an ion gun, and the evaporation source is Y2O3, or Y2O3 and YF3.

[30] A method for producing a yttrium protective film according to

[29] , wherein at least argon ions are irradiated from the ion gun toward the substrate. [Effects of the Invention]

[0011] According to the present invention, a yttrium-based protective film with excellent plasma resistance can be provided. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is a schematic diagram showing an example of a component. [Figure 2] Figure 2 is a schematic diagram showing a ring-shaped substrate with half of it cut out. [Figure 3] Figure 3 is a schematic diagram showing a portion of the cross-section of another ring-shaped substrate. [Figure 4] Figure 4 is a schematic diagram showing a portion of the cross-section of yet another ring-shaped substrate. [Figure 5] Figure 5 is a schematic diagram showing the apparatus used in the manufacture of yttrium protective films. [Figure 6] Figure 6 is a schematic diagram showing a substrate having a first film-forming surface and a second film-forming surface. [Modes for carrying out the invention]

[0013] The meanings of the terms used in this invention are as follows: A numerical range represented using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0014] [Yttrium protective film] The yttrium protective film of this embodiment has excellent plasma resistance because it has a porosity of less than 1.5 volume%, a Young's modulus of 100.00 GPa or higher, and a Vickers hardness of 8.50 GPa or higher. The yttrium protective film of this embodiment will be described in more detail below.

[0015] <Porosity> Due to the excellent plasma resistance of the yttrium protective film, the porosity of the yttrium protective film is less than 1.5 volume%, preferably 1.0 volume% or less, more preferably 0.5 volume% or less, even more preferably 0.3 volume% or less, particularly preferably 0.2 volume% or less, and most preferably 0.1 volume% or less.

[0016] In order to achieve the above porosity range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0017] The porosity of the yttrium protective film is determined as follows: First, using a focused ion beam (FIB), a slope is applied to the yttrium protective film and a portion of the substrate (described later) at a 52° angle in the thickness direction from the surface of the yttrium protective film toward the substrate, exposing the cross-section. The exposed cross-section is observed at a magnification of 20,000x using a field emission scanning electron microscope (FE-SEM), and a cross-sectional image is captured. Cross-sectional images are taken at multiple locations. Specifically, for example, if the yttrium protective film is circular, images are taken at a total of five points: one point in the center of the surface of the yttrium protective film and four points located 10 mm away from the outer edge. The size of the cross-sectional image is 6 μm × 5 μm. If the thickness of the yttrium protective film is 5 μm or more, cross-sectional images are taken at multiple locations so that the entire cross-section of the yttrium protective film can be observed in the thickness direction. Next, the obtained cross-sectional images are analyzed using image analysis software (ImageJ, manufactured by National Institutes of Health) to identify the area of ​​pores in the cross-sectional images. The ratio of the area of ​​pores to the total cross-sectional area of ​​the yttrium protective film is calculated and considered to be the porosity (unit: volume %) of the yttrium protective film. Note that pores that are too fine to be detected by the image analysis software (pores with a diameter of 20 nm or less) are considered to have an area of ​​0.

[0018] <Young's modulus> Due to the excellent plasma resistance of the yttrium protective film, the Young's modulus of the yttrium protective film is 100.00 GPa or higher, preferably 110.00 GPa or higher, more preferably 120.00 GPa or higher, and even more preferably 130.00 GPa or higher. On the other hand, the Young's modulus of the yttrium protective film is, for example, 250.00 GPa or less, and preferably 200.00 GPa or less. The Young's modulus of the yttrium protective film is measured at 20°C using the dynamic modulus test method (ultrasonic pulse method) described in the Japanese Industrial Standard (JIS R1602:1995).

[0019] <Vickers hardness> Due to the excellent plasma resistance of the yttrium protective film, the Vickers hardness of the yttrium protective film is 8.50 GPa or higher, preferably 9.50 GPa or higher, more preferably 10.50 GPa or higher, even more preferably 11.50 GPa or higher, and particularly preferably 12.50 GPa or higher. On the other hand, the Vickers hardness of the yttrium protective film is, for example, 20.00 GPa or less, and preferably 18.00 GPa or less.

[0020] In order to achieve the Vickers hardness within the above range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0021] The Vickers hardness of the yttrium protective film is measured using a nanoindentation tester (iMicro, KLA). More specifically, the nanoindentation hardness (unit: GPa) is measured by varying the load between 0 and 50 mN. Measurements are taken at 20 locations, and the average value is considered to be the Vickers hardness. Other test conditions are as follows: For the nanoindentation testing machine, we used the "iMicro" manufactured by KLA, and fixed the sample (a yttrium protective film placed on the surface of the substrate) to its sample stage. For sample fixation, we use Alemco's thermoplastic temporary adhesive "Crystalbond 555" (fluidization temperature: 48°C). For the actuator, we selected the "inForce50," which can handle loads up to 50mN. A Berkovich indenter with a triangular pyramidal tip (tip radius of curvature: 20 nm) is used as the indenter.

[0022] <Young's modulus / Vickers stiffness> For the reason that the yttrium protective film has excellent plasma resistance, in the yttrium protective film of this embodiment, the ratio of Young's modulus (unit: GPa) to Vickers hardness (unit: GPa) (Young's modulus / Vickers hardness) is preferably 16.5 or less, more preferably 15.5 or less, even more preferably 14.5 or less, and particularly preferably 13.5 or less. On the other hand, this ratio (Young's modulus / Vickers hardness) is preferably 8.0 or higher, and more preferably 9.0 or higher, because it prevents the yttrium protective film from becoming brittle.

[0023] <Ar content> In this embodiment, the yttrium protective film contains a certain amount of argon (Ar). This increases the Vickers hardness of the yttrium protective film.

[0024] First, in this embodiment, the yttrium protective film is formed by ion-assisted deposition (IAD). The IAD method is, in general terms, a method in which an evaporation source is evaporated and deposited onto a substrate while irradiating it with ions in a vacuum. In this case, for example, irradiating with argon (Ar), which has higher kinetic energy, in addition to oxygen (O) ions results in a greater intensity of the evaporated evaporation source being embedded in the substrate compared to irradiating with oxygen (O) ions alone. This is expected to result in the formation of an Ar-containing yttrium protective film, which will have a high Vickers hardness.

[0025] Specifically, because it increases the Vickers hardness of the yttrium protective film, the argon content (Ar content) in the yttrium protective film is preferably 0.10 atomic% or more, more preferably 0.15 atomic% or more, and even more preferably 0.20 atomic% or more.

[0026] However, if the Ar content of the yttrium protective film becomes too high, the Vickers hardness of the yttrium protective film tends to decrease. Therefore, the Ar content of the yttrium protective film is preferably 3.00 atomic% or less, more preferably 2.00 atomic% or less, even more preferably 1.50 atomic% or less, particularly preferably 1.00 atomic% or less, and most preferably 0.50 atomic% or less. In other words, the Ar content in the yttrium protective film is preferably 0.10 to 3.00 atomic percent.

[0027] The method for measuring the Ar content of the yttrium protective film will be described later.

[0028] <composition> In this embodiment, for the reason that the yttrium protective film has excellent plasma resistance, the yttrium content of the yttrium protective film is preferably 5 atomic% or more, more preferably 10 atomic% or more, and even more preferably 20 atomic% or more. From the viewpoint of improving electrical insulation, the yttrium content of the yttrium protective film is preferably 70 atomic% or less, more preferably 60 atomic% or less, and even more preferably 50 atomic% or less. In this embodiment, the yttrium protective film preferably contains, for example, yttrium oxide or yttrium fluoride.

[0029] The following describes the cases in which the yttrium protective film contains either yttrium oxide or yttrium fluoride.

[0030] Yttrium oxide First, let's explain the case where the yttrium protective film contains yttrium oxide (Y2O3). In this case, the Y2O3 content of the yttrium protective film is preferably 95% by mass or more, and more preferably 98% by mass or more. The Y2O3 content of the yttrium protective film produced using only Y2O3 as the evaporation source by the manufacturing method described later shall satisfy the above range.

[0031] (Orientation degree) When applying a large-area yttrium protective film, a higher degree of orientation of the (222) plane of the Y2O3 in the yttrium protective film (hereinafter also simply referred to as "degree of orientation") is preferable from the viewpoint of suppressing the occurrence of cracks (including wrinkles; the same applies hereinafter) in the yttrium protective film. Therefore, the degree of orientation of the yttrium protective film is preferably 50% or more, more preferably 65% ​​or more, even more preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, even more preferably 95% or more, very preferably 98% or more, and most preferably 99% or more. In order to achieve the above-mentioned degree of orientation, it is preferable to manufacture the yttrium protective film using the manufacturing method described later. The degree of orientation is the percentage (in %) of the peak intensity of the (222) plane in the XRD pattern of the yttrium protective film, where the sum of the peak intensities of all planes of Y2O3 is set to 100.

[0032] The XRD patterns of the yttrium protective film (and the underlying layer described later) are obtained by performing XRD measurements in micro-area 2D (two-dimensional) mode using an X-ray diffractometer (D8 DISCOVER Plus, Bruker) under the following conditions. ·X-ray source: CuKα ray (output: 45kV, current: 120mA) • Scanning range: 2θ = 10° to 80° • Step time: 0.2s / step • Scan speed: 10° / min Step width: 0.02° • Detector: Multimode detector EIGER (2D mode) • Entrance optical system: Multilayer mirror + 1.0 mmφ microslit + 1.0 mmφ collimator • Light-receiving optical system: OPEN

[0033] Yttrium fluoride Next, we will explain the case where the yttrium protective film contains yttrium hydroxyfluoride. Chemical formulas representing yttrium oxyfluoride include YOF and Y5O4F7. YOF is an orthorhombic crystal with low hardness, while Y5O4F7 has a special rhombohedral crystal structure and is highly hard. In this embodiment, it is preferable that the yttrium protective film has a high proportion of Y5O4F7 having a rhombohedral crystal structure. That is, it is preferable that the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is above a certain value. As a result, the yttrium protective film is hard and exhibits a Vickers hardness above a certain value.

[0034] (Peak intensity ratio) The peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern of the yttrium protective film (hereinafter also referred to as the "Y5O4F7 peak intensity ratio" or simply the "peak intensity ratio") is preferably 60% or more, more preferably 80% or more, even more preferably 90% or more, and particularly preferably 95% or more.

[0035] In order to achieve the Y5O4F7 peak intensity ratio within the above range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0036] The Y5O4F7 peak intensity ratio is the percentage (in %) of the main peak intensity of Y5O4F7 in the X-ray diffraction (XRD) pattern of the yttrium protective film, where the sum of the main peak intensities of the crystalline phases shown below is set to 100. The main peaks for each crystalline phase appear around 2θ=28.1° for Y5O4F7, around 2θ=29.2° for Y2O3, and around 2θ=29.2° for YOF. The main peak of Y5O4F7 appears superimposed on the peaks of the Y6O5F8 crystal and the Y7O6F9 crystal. Furthermore, the main peak of YF3 also appears superimposed on the main peak of Y5O4F7. All peaks located at the main peak position of Y5O4F7 are treated as peaks of Y5O4F7. If a YF3 crystal is present, the intensity of the second main peak of the YF3 crystal, located around 2θ = 24.5°, is multiplied by 1.3 to represent the main peak, and this is taken as the main peak intensity of YF3. At the same time, the intensity of the second main peak of the YF3 crystal, which has been multiplied by 1.3, is subtracted from the intensity of the peak of Y5O4F7 (the peak located at the main peak position of Y5O4F7). For example, if the intensity (relative intensity) of the second main peak of the YF3 crystal is "2.0" and the intensity (relative intensity) of the peak located at the main peak position of Y5O4F7 is "6.0", then the intensity of the second main peak of the YF3 crystal is converted to "2.6" (= 2.0 × 1.3). Therefore, the intensity of the peak located at the main peak position of Y5O4F7 is subtracted by the converted intensity of the second main peak of the YF3 crystal, resulting in "3.4" (= 6.0 - 2.6).

[0037] The XRD pattern of the yttrium protective film is obtained by performing XRD measurements in micro-region 2D (two-dimensional) mode using an X-ray diffractometer (D8 DISCOVER Plus, Bruker) under the conditions described above.

[0038] (Content of each element) If the yttrium protective film contains yttrium oxyfluoride, it contains yttrium (Y), oxygen (O), and fluorine (F).

[0039] The Y content of the yttrium protective film is preferably 20 atomic% or more, more preferably 25 atomic% or more, even more preferably 26 atomic% or more, particularly preferably 27 atomic% or more, and most preferably 27.5 atomic% or more. On the other hand, the Y content of the yttrium protective film is preferably 35 atomic% or less, more preferably 30 atomic% or less, even more preferably 29 atomic% or less, and particularly preferably 28 atomic% or less.

[0040] The oxygen content of the yttrium protective film is preferably 20 atomic% or more, more preferably 21 atomic% or more, even more preferably 22 atomic% or more, particularly preferably 23 atomic% or more, and most preferably 24 atomic% or more. On the other hand, the oxygen content of the yttrium protective film is preferably 35 atomic% or less, more preferably 30 atomic% or less, even more preferably 28 atomic% or less, particularly preferably 26 atomic% or less, and most preferably 25 atomic% or less.

[0041] The F content of the yttrium protective film is, for example, 25 atomic percent or more, preferably 35 atomic percent or more, more preferably 40 atomic percent or more, even more preferably 44 atomic percent or more, particularly preferably 47 atomic percent or more, and most preferably 48 atomic percent or more. On the other hand, the F content of the yttrium protective film is, for example, 65 atomic percent or less, preferably 60 atomic percent or less, more preferably 55 atomic percent or less, even more preferably 52 atomic percent or less, even more preferably 50 atomic percent or less, particularly preferably 49.5 atomic percent or less, and most preferably 49 atomic percent or less.

[0042] In order to bring the content of each element within the above range, for example, the manufacturing conditions, such as the amount of evaporation source, are appropriately adjusted in the manufacturing method described later.

[0043] The content of each element (in atomic percent) in the yttrium protective film is measured using an energy-dispersive X-ray analyzer (EX-250SE, Horiba, Ltd.).

[0044] (F / O ratio) The F / O ratio, which is the ratio of F content (unit: atomic%) to O content (unit: atomic%) in the yttrium protective film, is preferably less than 2.80, more preferably less than 2.50, and even more preferably less than 2.15. On the other hand, the F / O ratio of the yttrium protective film is preferably greater than 1.50, more preferably greater than 1.70, and even more preferably greater than 1.90.

[0045] (Degree of orientation: width at half maximum of the rocking curve) From the viewpoint of suppressing the occurrence of cracks in the yttrium protective film, a higher degree of orientation of the (151) plane of Y5O4F7 in the yttrium protective film (hereinafter also simply referred to as "degree of orientation") is preferable. As an indicator of orientation, the full width at half maximum (FWHM) of the rocking curve of the (151) plane of Y5O4F7 is used. Specifically, the rocking curve of the peak of the (151) plane of Y5O4F7 obtained using a two-dimensional mode detector is integrated in the 2θ direction, and the FWHM is used to evaluate the orientation. The smaller this FWHM (unit: °), the higher the degree of orientation. The full width at half maximum of the rocking curve of the (151) plane of Y5O4F7 is preferably 40° or less, more preferably 30° or less, even more preferably 25° or less, even more preferably 20° or less, particularly preferably 15° or less, and most preferably 10° or less. In order to achieve the above-mentioned degree of orientation, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0046] <Crystallite size> As mentioned above, for example, particles that detach from a component exposed to plasma can adhere to a semiconductor substrate and become foreign matter that causes defects in the circuit. In this case, the smaller the particle size, the more effectively defects can be suppressed. Therefore, the crystallite size of the yttrium protective film is preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less.

[0047] On the other hand, the larger the crystallite size of the yttrium protective film, the smaller and more stable the change in crystallite size when heated, resulting in improved heat resistance. Therefore, the crystallite size of the yttrium protective film is preferably 5 nm or larger, more preferably 7 nm or larger, and even more preferably 10 nm or larger. Therefore, the crystallite size of the yttrium protective film is preferably 5 to 30 nm.

[0048] In order to achieve the crystallite size within the above range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0049] The crystallite size in the yttrium protective film is determined using Scherrer's formula based on XRD pattern data obtained by XRD measurement of a mirror-polished yttrium protective film.

[0050] <Thickness> The thickness of the yttrium protective film is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.5 μm or more, particularly preferably 1.0 μm or more, and most preferably 2.0 μm or more.

[0051] On the other hand, the thickness of the yttrium protective film is preferably 30.0 μm or less, more preferably 25.0 μm or less, even more preferably 20.0 μm or less, particularly preferably 15.0 μm or less, and most preferably 10.0 μm or less. Therefore, the thickness of the yttrium protective film is preferably 0.01 to 30.0 μm.

[0052] The thickness of the yttrium protective film is measured as follows: Using a scanning electron microscope (SEM), the cross-section of the yttrium protective film is observed, and the thickness of the yttrium protective film is measured at five arbitrary points. The average value of these five measurements is then considered to be the thickness of the yttrium protective film (in μm).

[0053] <Compressive stress> The stress (internal stress, residual stress) in the yttrium protective film is preferably compressive stress rather than tensile stress. The compressive stress of the yttrium protective film is preferably 100 MPa or more, more preferably 300 MPa or more, even more preferably 500 MPa or more, and particularly preferably 700 MPa or more. On the other hand, the compressive stress of the yttrium protective film is preferably 1700 MPa or less, more preferably 1600 MPa or less, and even more preferably 1500 MPa or less.

[0054] The compressive stress of the yttrium protective film is determined as follows: A yttrium protective film is formed on a quartz glass substrate. The surface shape of the formed yttrium protective film is measured using a surface shape measuring device (Surfcom NEX 241 SD2-13, manufactured by Tokyo Seimitsu Co., Ltd.), and the compressive stress (film stress σ) of the yttrium protective film is determined from Stoney's formula (see below). σ=Yd 2 / (6c(1-ν)t) In the above formula, σ is the film stress, Y is the Young's modulus of the substrate, d is the thickness of the substrate, ν is the Poisson's ratio of the substrate, t is the thickness of the yttrium protective film, and c is the radius of curvature.

[0055] [Components] Next, I will explain the components. First, the components will be explained in general terms based on Figure 1.

[0056] Figure 1 is a schematic diagram showing an example of member 6. Component 6 comprises at least a base material 5 and a yttrium protective film 4, in this order. For example, the yttrium protective film of this embodiment described above is used as the yttrium protective film 4. As shown in Figure 1, a base layer (base layer 1, base layer 2, and base layer 3) may be placed between the substrate 5 and the yttrium protective film 4. However, the underlying layers are not limited to three layers.

[0057] The following provides a detailed explanation of each component.

[0058] <Base material> The substrate has a surface on which at least a yttrium protective film (or underlayer) is formed. This surface may hereafter be referred to as the "film-forming surface" for convenience.

[0059] 《Material》 The material of the base material is selected appropriately according to the intended use of the component. The substrate is composed of at least one material selected from the group consisting of, for example, carbon (C), ceramics, and metals. Here, the ceramic is at least one selected from the group consisting of, for example, glass (such as soda-lime glass), quartz, aluminum oxide (Al2O3), aluminum nitride (AlN), silicon carbide impregnated with Si, and aluminum oxynitride (AlON). Si-impregnated silicon carbide is obtained by heating and melting elemental Si and impregnating it with silicon carbide (SiC). The metal is, for example, at least one selected from the group consisting of aluminum (Al) and alloys containing aluminum (Al). Al is preferred as the metal.

[0060] "shape" The shape of the base material is not particularly limited and can be, for example, flat, ring-shaped, dome-shaped, concave, or convex, and can be appropriately selected depending on the application of the component.

[0061] Surface roughness of the deposited film The surface roughness of the film-forming surface of the substrate is preferably 3.00 μm or less, more preferably 2.50 μm or less, even more preferably 1.50 μm or less, even more preferably 1.00 μm or less, particularly preferably 0.60 μm or less, even more preferably 0.40 μm or less, very preferably 0.20 μm or less, and most preferably 0.08 μm or less, as an arithmetic mean roughness Ra. On the other hand, the surface roughness of the film-forming surface of the substrate is preferably 0.001 μm or more, and more preferably 0.01 μm or more, as an arithmetic mean roughness Ra. The surface roughness (arithmetic mean roughness Ra) of the film-deposited surface is measured in accordance with JIS B 0601:2001.

[0062] 《Maximum length of the film-forming surface》 The maximum length of the film-forming surface of the substrate is preferably 30 mm or more, more preferably 70 mm or more, even more preferably 100 mm or more, and particularly preferably 150 mm or more. Note that "maximum length" refers to the maximum length of the film-deposited surface. Specifically, for example, if the film-deposited surface is a circle in plan view, it is its diameter; if it is a ring in plan view, it is its outer diameter; and if it is a square in plan view, it is the length of the longest diagonal. On the other hand, the maximum length of the film-forming surface is, for example, 2000 mm or less, preferably 1500 mm or less, more preferably 1000 mm or less, even more preferably 700 mm or less, and most preferably 500 mm or less.

[0063] Figure 2 is a schematic diagram showing half of the ring-shaped substrate 5 cut out. For example, if the base material 5 shown in Figure 2 has an outer diameter D1 of 100 mm, an inner diameter D2 of 90 mm, and a thickness t of 5 mm, its maximum length is 100 mm. The substrate 5 has a film-forming surface 7, but as shown in Figure 2, it may have a first film-forming surface 7a and a second film-forming surface 7b that is different from the first film-forming surface 7a. The first film-forming surface 7a defines, for example, the maximum length (outer diameter D1) of the film-forming surface 7. The ratio of the area of ​​the second film deposition surface 7b to the total area of ​​the film deposition surface 7 is, for example, 60% or less.

[0064] Figure 3 is a schematic diagram showing a portion of the cross-section of another ring-shaped substrate 5. As shown in Figure 3, the substrate 5 may have a plurality of second film-forming surfaces 7b. Figure 4 is a schematic diagram showing a portion of the cross-section of yet another ring-shaped substrate 5.

[0065] <Base layer> As described above, one or more underlayers may be placed between the substrate and the yttrium protective film. Forming an underlayer relieves the tensile stress in the yttrium protective film, generating compressive stress, and also increases the adhesion of the yttrium protective film to the substrate.

[0066] 《Number of layers》 The number of layers in the underlayment is not particularly limited to an upper limit, but it is preferably 5 layers or less, more preferably 4 layers or less, even more preferably 3 layers or less, especially preferably 2 layers or less, and most preferably 1 layer.

[0067] 《Layer State》 The underlying layer is preferably an amorphous layer or a microcrystalline layer (an amorphous layer containing crystals).

[0068] "composition" The base layer preferably contains at least one oxide selected from the group consisting of Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

[0069] When two or more underlayers are placed between the substrate and the yttrium protective film, it is preferable that the oxides of the underlayers are different from those of adjacent underlayers. A specific example of a case where adjacent substrate layers have different oxides is when, for instance, the oxide in substrate layer 1 is "SiO2", the oxide in substrate layer 2 is "Al2O3 + SiO2", and the oxide in substrate layer 3 is "Al2O3".

[0070] Thickness The thickness of the underlayer is preferably 0.05 μm or more, more preferably 0.1 μm or more, even more preferably 0.2 μm or more, even more preferably 0.5 μm or more, particularly preferably 0.8 μm or more, and most preferably 1.1 μm or more. On the other hand, the thickness of the underlayer is, for example, 15.0 μm or less, preferably 10.0 μm or less, more preferably 7.0 μm or less, even more preferably 5.0 μm or less, and particularly preferably 3.0 μm or less. The thickness of the underlying layer is measured in the same way as the thickness of the yttrium protective film.

[0071] <Uses of the components> The component of this embodiment can be used, for example, as a top plate or other component inside semiconductor device manufacturing equipment (such as plasma etching equipment or plasma CVD equipment). However, the uses are not limited to these.

[0072] [Method for manufacturing yttrium protective film and components] Next, a method for manufacturing the yttrium protective film of this embodiment will be described. The following description also serves as a description of the method for manufacturing the components of this embodiment.

[0073] In this embodiment, ion-assisted deposition (IAD) is used. In general terms, a yttrium protective film is formed by evaporating an evaporation source (such as Y2O3 or YF3) in a vacuum while irradiating it with ions, and then depositing it onto the substrate.

[0074] By using the IAD method, a very dense yttrium protective film can be formed. In other words, the resulting yttrium protective film has low porosity. In contrast, yttrium protective films obtained by methods such as thermal spraying, aerosol deposition (AD), and ion plating (IP) tend to retain many pores.

[0075] <Device configuration> Figure 5 is a schematic diagram showing the apparatus used in the manufacture of yttrium protective films. The apparatus shown in Figure 5 has a chamber 11. The inside of the chamber 11 can be evacuated by driving a vacuum pump (not shown). Inside the chamber 11 are crucibles 12 and 13 and an ion gun 14, with a holder 17 positioned above them. The holder 17 is integrated with the support shaft 16 and rotates in conjunction with the rotation of the support shaft 16. A heater 15 is positioned around the holder 17. The holder 17 holds the substrate 5 described above with its film-forming surface facing downwards. The substrate 5 held in the holder 17 is heated by the heater 15 and rotates as the holder 17 rotates. Furthermore, quartz-type film thickness monitors 18 and 19 are mounted in the chamber 11.

[0076] <Formation of a yttrium protective film (Part 1)> In the apparatus shown in Figure 5, we will now describe the case in which a yttrium-based protective film containing yttrium oxide (Y2O3) (not shown in Figure 5) is formed on the substrate 5. First, one or both of the crucibles 12 and 13 are filled with the evaporation source Y2O3. After the holder 17 holds the substrate 5, the inside of the chamber 11 is evacuated to create a vacuum. Next, the holder 17 is rotated while the heater 15 is driven. This rotates the base material 5 while heating it. In this state, ion-assisted deposition is performed to form a film on the substrate 5. In other words, the evaporation source Y2O3 packed in one or both of the crucibles 12 and 13 is evaporated while irradiating with ions (ion beam) from the ion gun 14. The evaporation source is melted and evaporated by irradiation with an electron beam (not shown). In this way, the evaporated evaporation source adheres to the film-forming surface of the substrate 5 (or the surface of the underlying layer if one exists), forming a yttrium-based protective film containing yttrium oxide (Y2O3).

[0077] The ions irradiated by the ion gun 14 are preferably ions of at least one element selected from the group consisting of oxygen, argon, neon, krypton, and xenon, with argon ions being more preferred. It is more preferable to use ions of at least two elements selected from the group consisting of oxygen, argon, neon, krypton, and xenon as the ions irradiated by the ion gun 14, and it is even more preferable to use oxygen and argon ions in combination. This suggests that the yttrium protective film formed will contain a certain amount of argon (Ar).

[0078] Chamber pressure The film deposition is carried out in a vacuum. Specifically, the pressure inside chamber 11 is set to 6 × 10⁻¹⁰ to reduce the porosity of the yttrium protective film that is formed. -2 Preferably Pa or less, 5 × 10 -2 Less than Pa is more preferable, 3 × 10 -2 Pa or lower is even more preferable. On the other hand, the pressure inside chamber 11 is 1 × 10⁻⁶ -6 Pa is preferable, 1 × 10 -5 Pa or higher is preferable, 1 × 10 -4 Pa or higher is preferable.

[0079] 《Temperature of the base material》 During film formation, the temperature of the substrate 5 heated by the heater 15 is preferably 200°C or higher, more preferably 270°C or higher, even more preferably 320°C or higher, particularly preferably 370°C or higher, and most preferably 400°C or higher. On the other hand, this temperature is preferably 600°C or lower, preferably 500°C or lower, and more preferably 450°C or lower.

[0080] 《Film formation speed》 Prior to the start of film formation, the rate at which the evaporation sources in crucibles 12 and 13 evaporate (film formation rate) is monitored using crystal film thickness monitors 18 and 19, respectively. The film deposition rate is adjusted by controlling the conditions of the electron beam irradiated onto the evaporation source and the conditions of the ion beam of the ion gun 14 (current value, current density, etc.). During the deposition of the yttrium protective film, the deposition rate (in nm / min) of each evaporation source is adjusted to the desired value.

[0081] The film deposition rate of the evaporation source Y2O3 is preferably 1 nm / min or higher, more preferably 1.5 nm / min or higher, and even more preferably 2 nm / min or higher. The deposition rate of the evaporation source Y2O3 is preferably 20 nm / min or less, more preferably 15 nm / min or less, even more preferably 10 nm / min or less, even more preferably 5 nm / min or less, particularly preferably 3.5 nm / min or less, and most preferably 2.1 nm / min or less.

[0082] Conditions for ion irradiation The distance between the ion gun 14 and the substrate 5 is preferably 700 mm or more, and more preferably 900 mm or more. On the other hand, this distance is preferably 1500 mm or less, and more preferably 1300 mm or less. The ion beam current value is preferably 1000mA or more, and more preferably 1500mA or more. On the other hand, the ion beam current value is preferably 3000mA or less, and more preferably 2500mA or less. The ion beam current density is 40 μA / cm². 2 The above is preferable, and 65 μA / cm². 2 The above is more preferable: 75 μA / cm 2 The above is even more preferable, 77 μA / cm 2 The above is particularly preferable. On the other hand, the ion beam current density is 140 μA / cm². 2 The following is preferred: 120 μA / cm 2 The following is more preferable: 100 μA / cm 2 The following is even more preferable.

[0083] Ar / O ratio As described above, it is preferable to use both argon ions and oxygen ions as the ions irradiated from the ion gun 14. In this case, the Ar / O ratio, which is the ratio of the amount of argon (Ar) ions to the amount of oxygen (O) ions, is preferably greater than 2 / 50, more preferably 4 / 50 or greater, even more preferably greater than 4 / 50, even more preferably 5 / 50 or greater, particularly preferably 6 / 50 or greater, even more preferably 7 / 50 or greater, very preferably 8 / 50 or greater, and most preferably 10 / 50 or greater. On the other hand, the Ar / O ratio is, for example, 25 / 50 or less, preferably 20 / 50 or less, more preferably 15 / 50 or less, and even more preferably 12 / 50 or less.

[0084] The Ar / O ratio is the amount of argon (Ar) ions irradiated from the ion gun 14 toward the substrate 5 (unit: W / m²). 2 ) and the amount of oxygen (O) ions (unit: W / m³) irradiated from the ion gun 14 toward the substrate 5. 2 This is the ratio to ). Here, "W / m 2 " is a unit that represents the kinetic energy (ion energy flux) across a unit area in a unit time.

[0085] <Formation of a yttrium protective film (Part 2)> Next, we will describe the case in which a yttrium protective film containing yttrium oxyfluoride (not shown in Figure 5) is formed on the substrate 5. First, one crucible 12 is filled with evaporation source Y2O3, and the other crucible 13 is filled with evaporation source YF3. After the holder 17 holds the substrate 5, the inside of the chamber 11 is evacuated to create a vacuum. Next, the holder 17 is rotated while the heater 15 is driven. This rotates the base material 5 while heating it. In this state, ion-assisted deposition is performed to form a film on the substrate 5. In other words, while ions (ion beam) are irradiated from the ion gun 14, the evaporation source Y2O3 in crucible 12 and the evaporation source YF3 in crucible 13 are evaporated in parallel. The evaporation source is melted and evaporated by irradiation with an electron beam (not shown). In this way, the evaporated evaporation source adheres to the film-forming surface of the substrate 5 (or the surface of the underlying layer if one exists), forming a yttrium protective film containing yttrium oxyfluoride.

[0086] The ions irradiated by the ion gun 14 are the same as those used to form a yttrium protective film containing yttrium oxide (Y2O3).

[0087] 《Film formation speed》 The film deposition rate ratio (Y2O3 / YF3) between the film deposition rate of evaporation source Y2O3 (unit: nm / min) and the film deposition rate of evaporation source YF3 (unit: nm / min) is preferably 1 / 9.5 or higher, more preferably 1 / 8.0 or higher, even more preferably 1 / 6.0 or higher, and particularly preferably 1 / 4.5 or higher. On the other hand, the deposition rate ratio (Y2O3 / YF3) is preferably 1 / 1.1 or less, more preferably 1 / 1.3 or less, even more preferably 1 / 1.8 or less, and particularly preferably 1 / 2.5 or less.

[0088] The combined rate of film deposition from evaporation source Y2O3 and evaporation source YF3 is preferably 5 nm / min or higher, more preferably 8 nm / min or higher, and even more preferably 10 nm / min or higher. On the other hand, this combined rate is preferably 50 nm / min or lower, more preferably 35 nm / min or lower, and even more preferably 20 nm / min or lower.

[0089] Chamber pressure, substrate temperature, ion irradiation conditions, and Ar / O ratio The chamber pressure, substrate temperature, ion irradiation conditions, and Ar / O ratio when forming a yttrium protective film containing yttrium oxyfluoride are the same as those when forming a yttrium protective film containing yttrium oxide (Y2O3).

[0090] <Formation of the underlying layer> It is preferable to form the above-described underlayers (for example, underlayer 1, underlayer 2, and underlayer 3) on the film-forming surface of the substrate 5 before forming the yttrium protective film. The underlayer is formed by ion-assisted deposition, similar to the yttrium protective film. For example, when forming a base layer made of Al2O3, Al2O3 is packed into one or both of the crucibles 12 and 13 as an evaporation source, and the evaporation source is evaporated while irradiating with ions (ion beam) from the ion gun 14, and then attached to the film-forming surface of the substrate 5. The conditions for forming the underlayer are the same as those for forming the yttrium protective film.

[0091] By the way, the base material may contain water of crystallization. For example, when an aluminum oxide (Al2O3) substrate is heated from room temperature, the generation of crystal water, which is caused by the hydrate (e.g., boehmite γ-alumina), a low-temperature stable phase of aluminum oxide, can be observed at around 520°C. When moisture originating from the crystalline water of the substrate is contained in the formed yttrium protective film, the number of hydrogen atoms in the yttrium protective film tends to increase.

[0092] Therefore, before depositing the evaporation source Y2O3 onto the film-forming surface of the substrate (i.e., forming a yttrium protective film), a base layer is formed on the film-forming surface of the substrate. This is preferable because, as a result, at least the film-forming surface of the substrate is covered, making it less likely for the crystalline water of the substrate to be included in the formed yttrium protective film, and consequently, the number of hydrogen atoms in the yttrium protective film decreases.

[0093] <Preheating of the base material> It is preferable to heat the substrate at a high temperature (preheat) before forming the yttrium protective film, because this makes it less likely for the crystalline water of the substrate to be incorporated into the yttrium protective film. The preheating temperature is preferably 300°C or higher, more preferably 400°C or higher, even more preferably 450°C or higher, and particularly preferably 500°C or higher. On the other hand, the preheating temperature is, for example, 800°C or lower, preferably 750°C or lower, and more preferably 700°C or lower.

[0094] The preheating time is preferably 60 minutes or more, more preferably 120 minutes or more, even more preferably 240 minutes or more, and particularly preferably 480 minutes or more. On the other hand, the preheating time is preferably 1200 minutes or less, more preferably 1000 minutes or less, even more preferably 800 minutes or less, and particularly preferably 600 minutes or less.

[0095] The atmosphere for preheating is, for example, an atmospheric environment.

[0096] <Angle dependence> Figure 6 is a schematic diagram showing a substrate 5 having a first film-forming surface 7a and a second film-forming surface 7b. The substrate 5 shown in Figure 6 is held in a holder 17 within a chamber 11 (not shown in Figure 6) with the first film-forming surface 7a facing downwards. The other components are the same as those of the apparatus described based on Figure 5, so their description is omitted. The angle θ between the first film deposition surface 7a and the second film deposition surface 7b is, for example, 0° or more, preferably 10° or more. On the other hand, the angle θ is, for example, 180° or less, preferably 170° or less, and more preferably 160° or less. The angle θ may also be 90°.

[0097] As a result of the manufacturing method described above, a yttrium protective film is formed on the film-forming surfaces (first and second film-forming surfaces) of the substrate. The yttrium protective film formed on the first deposition surface is called the "first layer," and the yttrium protective film formed on the second deposition surface is called the "second layer." The first layer is, for example, the yttrium protective layer of this embodiment described above. The second layer is, for example, a yttrium-based protective layer that is different from the first layer. The substrate has at least a first film-forming surface and a second film-forming surface as film-forming surfaces, but may also have another film-forming surface.

[0098] Vickers hardness of yttrium protective coatings The Vickers hardness HV2 of the second layer is equal to the Vickers hardness HV1 of the first layer. A It is preferable that the value be within ±40% of double, more preferably within ±30%, and even more preferably within ±20%. However, y A The angle θ between the first and second deposition surfaces is set to x from 0 to 90°. A When x A When x is between 0 and 60°, it is calculated using the following formula (1), and x A When the angle is greater than 60° and less than or equal to 90°, it is calculated using the following formula (2). (1) y A =-0.00034751x A 2 +0.01538782x A +1.00625521 (2)y A =-0.00197743x A +0.75229358

[0099] When the angle θ between the first and second film deposition surfaces is 90°, the HV1 / HV2 ratio, which is the ratio of the Vickers hardness HV1 of the first film to the Vickers hardness HV2 of the second film, is preferably 1.05 or higher, more preferably 1.20 or higher, and even more preferably 1.35 or higher. On the other hand, in this case, the HV1 / HV2 ratio is preferably 2.50 or lower, more preferably 2.30 or lower, and even more preferably 2.10 or lower.

[0100] Thickness of the yttrium protective film The thickness t2 of the second layer is equal to the thickness t1 of the first layer. B It is preferable that the value be within ±40% of double, more preferably within ±30%, and even more preferably within ±20%. However, y B The angle θ between the first and second deposition surfaces is set to x from 0 to 170°. B When x B When x is between 0 and 90°, it is calculated using the following formula (3), and x BWhen the angle is greater than 90° and less than or equal to 170°, it is calculated using the following formula (4). (3)y B =-0.00012389x B 2 +0.00659698x B +0.99721254 (4)y B =-0.00005913x B 2 +0.01099778x B -0.26784922

[0101] The thickness t1 of the first layer tends to be greater than the thickness t2 of the second layer. Specifically, when the angle θ between the first film deposition surface and the second film deposition surface is 90°, the t1 / t2 ratio, which is the ratio of the thickness t1 (unit: μm) of the first film to the thickness t2 (unit: μm) of the second film, is preferably 1.5 or greater, and more preferably 1.6 or greater. On the other hand, in this case, the t1 / t2 ratio is, for example, 3.5 or less, and preferably 3.0 or less.

[0102] Incidentally, if the angle θ between the first and second film-forming surfaces is 90°, the surface of the substrate opposite to the second film-forming surface (surface 7c in Figure 6) may also become a second film-forming surface, and a second film (yttrium protective film) may be formed. In this case, the t1 / t2 ratio becomes larger, specifically, preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 4.0 or higher. On the other hand, in this case, the t1 / t2 ratio is, for example, 6.0 or less, and preferably 5.5 or less.

[0103] Crystallite size of yttrium protective film The crystallite size S2 of the second film is equal to the crystallite size S1 of the first film. C It is preferable that the value be within ±40% of double, more preferably within ±30%, and even more preferably within ±20%. However, y C The angle θ between the first and second deposition surfaces is set to x from 0 to 170°. C In this case, it is calculated by the following formula (5). (5)y C =0.00009729x C 2 -0.00273425x C +0.99976959

[0104] The crystallite size S1 of the first film tends to be smaller than the crystallite size S2 of the second film. Specifically, when the angle θ between the first and second film deposition surfaces is 90°, the S1 / S2 ratio, which is the ratio of the crystallite size S1 (unit: nm) of the first film to the crystallite size S2 (unit: nm) of the second film, is preferably 0.90 or less, more preferably 0.80 or less, and even more preferably 0.70 or less. On the other hand, in this case, the S1 / S2 ratio is, for example, 0.35 or higher, and preferably 0.45 or higher. In this case, the crystallite size S1 of the first film is preferably less than 20 nm, more preferably less than 18 nm, and even more preferably less than 15 nm. The crystallite size S2 of the second film is preferably 15 nm or more, more preferably 17 nm or more, and even more preferably 18 nm or more. [Examples]

[0105] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples described below. Examples 1 to 21 below are examples, and Examples 22 to 24 are comparative examples.

[0106] <Examples 1-24> Using the apparatus described in Figure 5, components equipped with a yttrium protective film were manufactured under the conditions shown in Tables 1 to 3 below.

[0107] As the substrate, a plate-shaped substrate having film-forming surfaces (first film-forming surface and second film-forming surface) with values ​​shown in Tables 1 to 3 below was used. More specifically, the substrate used was bent midway along its longitudinal direction, thereby forming the first film-forming surface (length: 100 mm) and the second film-forming surface (length: 100 mm). The angle θ between the first film-forming surface and the second film-forming surface (unit: °) is shown in Tables 1 to 3 below.

[0108] The substrate was held in a holder inside the chamber and preheated in an atmospheric environment. The preheating temperature was 550°C and the preheating time was 600 minutes.

[0109] Next, using the IAD method under the manufacturing conditions shown in Tables 1 to 3 below, the underlayer and yttrium protective film (first and second film) shown in Tables 1 to 3 below were formed on the film-forming surface (first and second film-forming surface) of the substrate.

[0110] Note that in Example 5, the second film refers to the yttrium protective film (second film) formed on the surface opposite to the second film-forming surface that connects to the first film-forming surface (corresponding to surface 7c in Figure 6). For this reason, "back surface" is written in the "angle" column of "film-forming surface" in Tables 1-3 below.

[0111] If no underlayer was formed, a "-" was entered in the corresponding column in Tables 1-3 below.

[0112] When forming the yttrium protective film, argon (Ar) ions and oxygen (O) ions were irradiated onto the substrate from an ion gun at the Ar / O ratios shown in Tables 1-3 below. When forming the base layer, only oxygen (O) ions were irradiated from the ion gun.

[0113] Manufacturing conditions not listed in Tables 1-3 below included a distance of 1100 mm between the ion gun and the substrate, and an ion beam current of 2000 mA.

[0114] The composition of the underlayer and the yttrium protective film is shown in Tables 1-3 below. When a yttrium protective film containing yttrium oxide is formed, its composition is listed as "Y2O3" in Tables 1-3 below. When a yttrium protective film containing yttrium oxyfluoride is formed, Tables 1-3 below show the composition determined from the content of each element (Y, O, F, etc.).

[0115] In Example 13, one side of an aluminum (Al) substrate was anodized to create a base layer made of Al2O3. This base layer is referred to as "anodized" in Tables 1-3 below.

[0116] In addition, the following items (such as Ar content) for the substrate and yttrium protective film were determined using the method described above. The results are shown in Tables 1-3 below. Note that compressive stress is indicated by a negative value.

[0117] Regarding the yttrium protective film (first and second layers), the values ​​shown in Tables 1-3 below refer to the first layer unless otherwise specified. The composition of the second film was the same as that of the first film.

[0118] <Etching amount> The plasma resistance of each yttrium protective film was evaluated by ion etching. Specifically, a 10mm x 5mm surface of the yttrium protective film was first polished to a mirror finish, and a portion of the polished surface (referred to as the "test surface") was masked with Kapton tape. Next, using a CCP-type plasma etching apparatus, a plasma was generated by discharging electricity in a gas under conditions of a pressure of 10 Pa and an RF power of 600 W. An exposure test was then conducted in which the test surface was exposed to the generated plasma. More specifically, discharge (plasma generation) was performed using CF4 gas (flow rate: 100 sccm) and O2 gas (flow rate: 100 sccm), and CF4 ions were generated in the plasma. A 15-minute discharge (plasma generation) was repeated 10 times, resulting in a total exposure test of 150 minutes. This etched the unmasked areas of the test surface. Subsequently, the amount of etching was determined by measuring the step difference between the masked and unmasked areas of the test surface using a stylus-type surface shape measuring instrument (ULVAC, Inc., Decak150). The results are shown in Tables 1-3 below. The smaller the etching amount (in nm), the better the plasma resistance can be evaluated.

[0119] [Table 1]

[0120] [Table 2]

[0121] [Table 3]

[0122] <Summary of Evaluation Results> As shown in Tables 1-3 above, Examples 1-21 showed less etching of the yttrium protective film (first layer) and better plasma resistance compared to Examples 22-24.

[0123] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2023-184119 filed on 26 October 2023, the contents of which are incorporated herein by reference. [Explanation of Symbols]

[0124] 1, 2, 3: Base layer 4: Yttrium protective film 5: Base material 6: Components 7: Film forming surface 7a: First film formation surface 7b: Second film formation surface 7c: Face 11: Chamber 12, 13: Crucible 14: Ion gun 15: Heater 16: Support shaft 17: Holder 18, 19: Crystal-type film thickness monitor

Claims

1. Porosity is less than 1.5% by volume. The Young's modulus is 100.00 GPa or higher. A yttrium-based protective film with a Vickers hardness of 8.50 GPa or higher.

2. The yttrium protective film according to claim 1, wherein the Young's modulus / Vickers hardness is 16.5 or less.

3. The yttrium protective film according to claim 1, containing 0.10 to 3.00 atomic percent of argon.

4. The yttrium protective film according to claim 1, which contains 5 atomic percent or more of yttrium.

5. The yttrium protective film according to claim 1, containing 25 to 65 atomic percent of fluorine.

6. The yttrium protective film according to claim 1, wherein the F / O ratio, which is the ratio of fluorine content to oxygen content, is less than 2.

80. However, the units for both fluorine content and oxygen content are atomic percent.

7. Y in X-ray diffraction pattern ５ O ４ F ７ The yttrium protective film according to claim 1, wherein the peak intensity ratio is 60% or more.

8. The yttrium protective film according to claim 1, wherein the crystallite size is 5 to 30 nm.

9. The yttrium protective film according to claim 1, having a thickness of 0.01 to 30.0 μm.

10. A component comprising a base material and a yttrium protective film according to any one of claims 1 to 9.

11. The substrate has, as a film-forming surface, at least a first film-forming surface and a second film-forming surface different from the first film-forming surface, On the first film-forming surface, the first film, which is the yttrium protective film, is formed. The member according to claim 10, wherein a second film, which is a yttrium protective film different from the first film, is formed on the second film-forming surface.

12. The Vickers hardness HV of the second film ２ The Vickers hardness HV of the first film is １ y Ａ The member according to claim 11, which is within the range of ±40% of double. provided that y Ａ is x where the angle formed between the first film-forming surface and the second film-forming surface is between 0° and 90° Ａ and when x Ａ is 0° to 60°, it is calculated by the following formula (1); when x Ａ is more than 60° and 90° or less, it is calculated by the following formula (2). (1)y Ａ =-0.00034751x Ａ ２ +0.01538782x Ａ +1.00625521 (2)y Ａ =-0.00197743x Ａ +0.75229358

13. The thickness of the second film ２ The thickness t of the first film is １ y Ｂ The member according to claim 11, which is within the range of ±40% of double. However, y Ｂ The angle between the first film-forming surface and the second film-forming surface is set to x from 0 to 170°. Ｂ When x Ｂ When x is between 0 and 90°, it is calculated using the following formula (3): Ｂ When the angle is greater than 90° and less than or equal to 170°, it is calculated using the following formula (4). (3)y Ｂ =-0.00012389x Ｂ ２ +0.00659698x Ｂ +0.99721254 (4) Ｂ =-0.00005913x Ｂ ２ +0.01099778x Ｂ -00.26784922

14. Crystallite size S of the second film ２ The crystallite size S of the first film is １ y Ｃ The member according to claim 11, which is within the range of ±40% of double. However, y Ｃ The angle between the first film-forming surface and the second film-forming surface is set to x from 0 to 170°. Ｃ In this case, it is calculated by the following formula (5). (5)y Ｃ =0.00009729x Ｃ ２ -0.00273425x Ｃ +0.99976959

15. The member according to claim 11, wherein the angle between the first film-forming surface and the second film-forming surface is 10° to 160°.

16. The angle between the first film-forming surface and the second film-forming surface is 90°. The Vickers hardness HV of the first film １ The Vickers hardness HV of the second film ２ HV is the ratio of １ / HV ２ The member according to claim 11, wherein the ratio is 1.05 to 2.

50.

17. The angle between the first film-forming surface and the second film-forming surface is 90°. The thickness t of the first film １ And the thickness t of the second film ２ The ratio is t １ / t ２ The component according to claim 11, wherein the ratio is 1.5 to 3.

5. However, the unit of thickness is μm.

18. The angle between the first film-forming surface and the second film-forming surface is 90°. The thickness t of the first film １ And the thickness t of the second film ２ The ratio is t １ / t ２ The member according to claim 11, wherein the ratio is 2.0 to 6.

0. However, the unit of thickness is μm.

19. The angle between the first film-forming surface and the second film-forming surface is 90°. Crystallite size S of the first film １ And the crystallite size S of the second film. ２ S is the ratio of １ / S ２ The member according to claim 11, wherein the ratio is 0.35 to 0.

90. However, the unit of crystallite size is nm.

20. Crystallite size S of the first film １ The member according to claim 19, wherein the n is less than 20 nm.

21. Crystallite size S of the second film ２ The member according to claim 19, wherein the n is 15 nm or more.

22. The member according to claim 10, wherein the surface roughness of the film-forming surface of the substrate is 0.001 to 3.00 μm in terms of arithmetic mean roughness Ra.

23. The member according to claim 10, wherein the porosity of the substrate is 2.0 volume% or less.

24. The member according to claim 10, wherein the base material is composed of at least one selected from the group consisting of carbon, ceramics, and metal.

25. The ceramic is at least one selected from the group consisting of glass, quartz, aluminum oxide, aluminum nitride, Si-impregnated silicon carbide, and aluminum oxynitride. The member according to claim 24, wherein the metal is at least one selected from the group consisting of aluminum and aluminum-containing alloys.

26. The member according to claim 10, wherein the maximum length of the film-forming surface of the substrate is 30 mm or more.

27. Between the substrate and the yttrium protective film, there is one or more underlayers, The aforementioned underlayer is Al ２ O ３ SiO ２ , Y ２ O ３ , MgO, CaO, SrO, BaO, B ２ O ３ , SnO ２ , P ２ O ５ Li ２ O, Na ２ O, K ２ O, ZrO ２ La ２ O ３ , Nd ２ O ３ Yb ２ O ３ , Eu ２ O ３ and Gd ２ O ３ The component according to claim 10, comprising at least one oxide selected from the group consisting of the following.

28. The component according to claim 10, used inside a plasma etching apparatus or a plasma CVD apparatus.

29. A method for producing a yttrium protective film according to any one of claims 1 to 9, In a vacuum, an evaporation source is evaporated and deposited onto a substrate while irradiating it with ions of at least one element selected from the group consisting of oxygen, argon, neon, krypton, and xenon from an ion gun. As the evaporation source, Y ２ O ３ , or Y ２ O ３ and YF ３ A method for producing a yttrium protective film using the following method.

30. A method for producing a yttrium protective film according to claim 29, wherein at least argon ions are irradiated from the ion gun toward the substrate.

Images