Component and method for manufacturing same

Abstract

The present invention provides a member (6) having an yttrium-based protective film (4). The member (6) has, in this order, a base material (5), one or more stress relaxation layers (8, 9), and an yttrium protective film (4), and the yttrium protective film (4) has a Vickers hardness of 800 HV or more.

Description

Technical Field

[0001] The present invention relates to a component and a method for manufacturing the same. Background Art

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

[0003] At this time, the components exposed to the plasma in the chamber are corroded, and there is a case where the corroded portion falls off from the corroded component in the form of particles. The fallen particles (granules) adhere to the semiconductor substrate and may become foreign matters that cause defects in the circuit.

[0004] Therefore, conventionally, as a protective film for protecting components exposed to the plasma, a protective film containing yttrium oxide or yttrium oxyfluoride (yttrium-based protective film) is known.

[0005] Patent Document 1 discloses a thermal spray coating containing yttrium oxide or yttrium oxyfluoride formed by thermal spraying.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018 - 76546 Summary of the Invention

[0009] The inventors of the present invention conducted research and found that the conventional yttrium-based protective film has insufficient heat resistance and plasma resistance (corrosion resistance to plasma).

[0010] The present invention has been completed in view of the above aspects, and an object thereof is to provide a component having a yttrium-based protective film with excellent heat resistance and plasma resistance.

[0011] The inventors of the present invention conducted in-depth research and found that the above object can be achieved by adopting the following configuration, and thus the present invention has been completed.

[0012] That is, the present invention provides the following [1] to

[25] .

[0013] [1] A component having, in order, a substrate, one or more stress relaxation layers, and a yttrium-based protective film, wherein the Vickers hardness of the yttrium-based protective film is 800 HV or more.

[0014] [2] The component according to the above [1], wherein the heat-resistant temperature of the yttrium-based protective film is 300°C or more.

[0015] [3]The component according to [1] or [2] above, wherein the thickness of the stress relaxation layer is 0.05 to 9.0 μm.

[0016] [4]The component according to any one of [1] to [3] above, wherein the surface roughness of the film-forming surface of the substrate is 0.001 μm or more and less than 4.5 μm in terms of arithmetic mean roughness Ra.

[0017] [5]The component according to any one of [1] to [4] above, wherein the stress relaxation layer 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.

[0018] [6]The component according to [5] above, wherein the stress relaxation layer contains at least two oxides selected from the above group.

[0019] [7]The component according to [5] above, wherein the stress relaxation layer contains at least one of Al2O3, SiO2, and Y2O3, the content of Al2O3 is 0 to 70 mol%, the content of SiO2 is 0 to 90 mol%, the content of Y2O3 is 0 to 60 mol%, and the content of the above oxides other than Al2O3, SiO2, and Y2O3 is 20 mol% or less.

[0020] [8]The component according to [5] above, wherein the stress relaxation layer contains SiO2 and Y2O3, the mol ratio of SiO2 / Y2O3 is 90 / 10 to 20 / 80, and the content of the above oxides other than SiO2 and Y2O3 is 10 mol% or less.

[0021] [9]The component according to [5] above, wherein the stress relaxation layer contains Al2O3, and the content of Al2O3 is 10 to 70 mol%.

[0022]

[10] The component according to any one of [1] to [9] above, wherein there is at least one base layer between the substrate and the stress relaxation layer, and the base layer contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

[0023]

[11] The component according to

[10] above, wherein there are two or more of the above base layers, and the oxides are different from each other between the adjacent base layers.

[0024]

[12] The component according to

[10] or

[11] above, wherein the base layer contains SiO2 or contains at least two oxides selected from Al2O3, SiO2, and Y2O3.

[0025]

[13] The component according to any one of [1] to

[12] above, wherein the porosity of the yttrium-based protective film is less than 2.0% by volume.

[0026]

[14] The component according to any one of [1] to

[13] above, wherein the thickness of the yttrium-based protective film is 0.3 μm to 15 μm.

[0027]

[15] The component according to any one of [1] to

[14] above, wherein the crystallite size of the yttrium-based protective film is 6 nm to 40 nm.

[0028]

[16] The component according to any one of [1] to

[15] above, wherein the yttrium-based protective film contains yttrium oxide.

[0029]

[17] The component according to

[16] above, wherein the degree of orientation of the (222) crystal plane of Y2O3 in the yttrium-based protective film is 50% or more.

[0030]

[18] The component according to any one of [1] to

[15] above, wherein the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern of the yttrium-based protective film is 60% or more.

[0031]

[19] The component according to any one of [1] to

[18] above, wherein the substrate is composed of at least one selected from carbon, ceramic, and metal.

[0032]

[20] The component according to

[19] above, wherein the ceramic is alumina or quartz.

[0033]

[21] The component according to any one of [1] to

[20] above, wherein the maximum length of the film-forming surface of the substrate is 30 mm or more, the substrate has a first film-forming surface with a specified maximum length and a second film-forming surface different from the first film-forming surface as the film-forming surface, the angle formed by the first film-forming surface and the second film-forming surface is 20° to 120°, and the proportion of the area of the second film-forming surface relative to the total area of the film-forming surface is 60% or less.

[0034]

[22] The component according to any one of [1] to

[21] above is used inside a plasma etching device or a plasma CVD device.

[0035]

[23] A method for manufacturing a component, which is a method for manufacturing the component described in any one of [1] to

[22] above. The yttrium-based protective film is formed by irradiating ions of at least one element selected from oxygen, argon, neon, krypton, and xenon in a vacuum while evaporating an evaporation source and attaching it to the surface of the stress relaxation layer. Y2O3 or Y2O3 and YF3 are used as the evaporation source.

[0036]

[24] According to the method for manufacturing a component described in

[23] above, in the formation of the yttrium-based protective film, the temperature of the substrate is 320 °C or higher.

[0037]

[25] According to the method for manufacturing a component described in

[23] or

[24] above, before forming the yttrium-based protective film, one or more layers of the stress relaxation layer are formed on the surface of the substrate.

[0038] According to the present invention, it is possible to provide a component having a yttrium-based protective film with excellent heat resistance and plasma resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic diagram showing an example of a component.

[0040] Figure 2 It is a schematic diagram showing a half of the annular substrate cut away.

[0041] Figure 3 It is a schematic diagram showing a part of the cross section of another annular substrate.

[0042] Figure 4 It is a schematic diagram showing a part of the cross section of yet another annular substrate.

[0043] Figure 5 It is a schematic diagram showing a device used in the manufacture of the yttrium-based protective film. DETAILED DESCRIPTION

[0044] The meanings of the terms in the present invention are as follows.

[0045] The numerical range expressed using "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0046] [Component]

[0047] Figure 1 It is a schematic diagram showing an example of the component 6.

[0048] The component 6 at least sequentially has a substrate 5, a stress relaxation layer (stress relaxation layers 8 and 9), and a yttrium-based protective film 4. However, the stress relaxation layer is not limited to two layers.

[0049] AsFigure 1 As shown, a base layer (base layers 1, 2, and 3) can be disposed between the base material 5 and the stress relaxation layer (stress relaxation layer 8). However, the base layer is not limited to three layers.

[0050] The component of the present embodiment (hereinafter also referred to as "the present component") has the following-described present protective film as a yttrium-based protective film.

[0051] Since the surface of the present component is covered by the present protective film, like the present protective film, it has excellent plasma resistance.

[0052] Hereinafter, each part included in the present component will be described in detail.

[0053] 〈Yttrium-based protective film〉

[0054] Hereinafter, the yttrium-based protective film will also be simply referred to as "protective film", and the yttrium-based protective film (protective film) included in the component of the present embodiment (the present component) will also be referred to as "the present protective film".

[0055] The present protective film has excellent heat resistance and plasma resistance.

[0056] Hereinafter, the present protective film will be described in more detail.

[0057] 《Vickers hardness》

[0058] For the reason that the present protective film has excellent heat resistance and plasma resistance, the Vickers hardness of the present protective film is 800 HV or more, preferably 1000 HV or more, more preferably 1100 HV or more, further preferably 1200 HV or more, still further preferably 1250 HV or more, particularly preferably 1300 HV or more, very preferably 1350 HV or more, and most preferably 1400 HV or more.

[0059] On the other hand, the Vickers hardness of the present protective film is preferably 1800 HV or less, and more preferably 1600 HV or less.

[0060] In order to make the Vickers hardness within the above range, it is preferable to manufacture the protective film by the following-described method (the present manufacturing method).

[0061] The Vickers hardness of the protective film is determined according to JIS Z 2244 (2009).

[0062] More specifically, it is the Vickers hardness (HV0.005) determined using a micro Vickers hardness tester (HM-220, manufactured by Mitutoyo Corporation) with a diamond indenter having an opposite surface angle of 136° when applying a test force of 4.9 mN (0.049 N).

[0063] 《Heat resistance temperature》

[0064] The heat resistance temperature of this protective film is preferably 300 °C or higher, more preferably 350 °C or higher, further preferably 450 °C or higher, still further preferably 550 °C or higher, particularly preferably 650 °C or higher, and most preferably 750 °C or higher.

[0065] In order to make the heat resistance temperature within the above range, it is preferred to manufacture the protective film by the following method (this manufacturing method).

[0066] The heat resistance temperature of the protective film is obtained by conducting the following test (heat resistance test).

[0067] First, use an atmospheric calcination furnace to heat a sample of the component with the protective film at a heating rate of 300 °C / hr, heat it at an arbitrary temperature T1 for 1 hour, and cool it at 50 °C / hr to take out the sample. Then, use an optical microscope to confirm whether cracks occur in the protective film.

[0068] Conduct such a heat resistance test at a temperature T1 of 100 °C to 800 °C (every 50 °C), and take the maximum temperature T1 at which no cracks occur as the heat resistance temperature of the protective film.

[0069] 《Porosity》

[0070] Due to the excellent heat resistance and plasma resistance of this protective film, the porosity of this protective film is preferably less than 2.0% by volume, more preferably 1.5% by volume or less, further preferably 1.0% by volume or less, still further preferably 0.5% by volume or less, particularly preferably 0.3% by volume or less, very preferably 0.2% by volume or less, and most preferably 0.1% by volume or less.

[0071] In order to make the porosity within the above range, it is preferred to manufacture the protective film by the following method (this manufacturing method).

[0072] The porosity of the protective film is obtained as follows.

[0073] First, use a focused ion beam (FIB) to perform a ramp process on a part of the component with the protective film from the surface of the protective film towards the substrate at an angle of 52° in the thickness direction to expose the cross-section. Observe the exposed cross-section with a field emission scanning electron microscope (FE-SEM) at a magnification of 20,000 times and take a cross-sectional image thereof.

[0074] The cross-sectional image is taken at multiple locations. Specifically, for example, when the protective film is circular, it is taken at a total of 5 points, namely 1 point at the center of the surface of the protective film (or the surface of the substrate) and 4 points located at a position 10 mm from the outer periphery. The size of the cross-sectional image is 6 μm × 5 μm. When the thickness of the protective film is 5 μm or more, cross-sectional images are taken at multiple shooting locations in such a way that the entire cross-section of the protective film can be observed in the thickness direction.

[0075] Next, the obtained cross-sectional image was analyzed using image analysis software (ImageJ, manufactured by the National Institute of Health) to determine the area of the pore portion in the cross-sectional image. The ratio of the area of the pore portion to the area of the entire cross-section of the protective film was calculated and regarded as the porosity (unit: volume %) of the protective film. It should be noted that for micro pores that cannot be detected by the image analysis software (pores with a pore diameter of 20 nm or less), their area was regarded as 0.

[0076] 《Composition》

[0077] This protective film preferably contains yttrium oxide or yttrium oxyfluoride.

[0078] Hereinafter, this protective film in each case will be described.

[0079] (Yttrium oxide)

[0080] First, the case where this protective film contains yttrium oxide (Y2O3) will be described.

[0081] In this case, the content of Y2O3 in this protective film is preferably 95% by mass or more, more preferably 98% by mass or more, and further preferably 100% by mass.

[0082] The protective film manufactured by using only Y2O3 as an evaporation source by the method described later (this manufacturing method) consists essentially of Y2O3, and its Y2O3 content satisfies the above range.

[0083] ((Degree of orientation))

[0084] In the case of making the protective film large in area, from the viewpoint of suppressing the generation of cracks (including wrinkles, the same applies hereinafter) in the protective film, the higher the degree of orientation of the (222) crystal plane of Y2O3 in the protective film (hereinafter, also simply referred to as "degree of orientation"), the better.

[0085] In addition, the higher the degree of orientation of the protective film, the less stress will be generated randomly during heating, and the heat resistance is improved.

[0086] Therefore, the degree of orientation of this protective film is preferably 50% or more, more preferably 65% or more, further preferably 80% or more, still further preferably 85% or more, particularly preferably 90% or more, more particularly preferably 95% or more, very preferably 98% or more, and most preferably 99% or more.

[0087] In order to make the degree of orientation within the above range, it is preferable to manufacture the protective film by the method described later (this manufacturing method).

[0088] The degree of orientation is the ratio (unit: %) of the peak intensity of the (222) crystal plane when the sum of the peak intensities of the respective planes of Y2O3 is set to 100 in the XRD pattern of the protective film.

[0089] The XRD pattern of the protective film (and the stress relaxation layer and the base layer described later) is obtained by performing XRD measurement in a micro-detail 2D (two-dimensional) mode using an X-ray diffractometer (D8 DISCOVER Plus, manufactured by Bruker Corporation) under the following conditions.

[0090] · X-ray source: CuKα ray (output: 45 kV, current: 120 mA)

[0091] · Scanning range: 2θ = 10° to 80°

[0092] · Step time: 0.2 s / step

[0093] · Scanning speed: 10° / min

[0094] · Step size: 0.02°

[0095] · Detector: Multi-mode detector EIGER (2D mode)

[0096] · Incident-side optical system: Multilayer mirror + 1.0 mmφ micro-slit + 1.0 mmφ collimator

[0097] · Light-receiving-side optical system: OPEN

[0098] (yttrium oxyfluoride)

[0099] Next, the case where the protective film contains yttrium oxyfluoride will be described.

[0100] As chemical formulas representing yttrium oxyfluoride, YOF, Y5O4F7, etc. can be cited. YOF is an orthorhombic crystal with low hardness, while Y5O4F7 has a special crystal structure of rhombohedron and has higher hardness.

[0101] The protective film preferably has a larger proportion of Y5O4F7 having a rhombohedral crystal structure. That is, the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is preferably a certain value or more. Thereby, the protective film is harder and the Vickers hardness shows a certain value or more.

[0102] In addition, the protective film is formed by using the method (this manufacturing method) described later, and thus is dense and has a small porosity.

[0103] ((peak intensity ratio))

[0104] The peak intensity ratio of Y5O4F7 (hereinafter also referred to as "Y5O4F7 peak intensity ratio" or simply "peak intensity ratio") in the X-ray diffraction pattern of this protective film is 60% or more, preferably 80% or more, more preferably 90% or more, further preferably 95% or more, still further preferably 98% or more, particularly preferably 99% or more, and most preferably 100%.

[0105] In order to make the Y5O4F7 peak intensity ratio within the above range, it is preferred to manufacture the protective film by the method described below (this manufacturing method).

[0106] The Y5O4F7 peak intensity ratio is the ratio (unit: %) of the main peak intensity of Y5O4F7 when the total of the main peak intensities of the crystal phases shown below is set to 100 in the X-ray diffraction (XRD) pattern of the protective film.

[0107] For the main peak of each crystal phase, Y5O4F7 appears near 2θ = 28.1°, Y2O3 appears near 2θ = 29.2°, and YOF appears near 2θ = 29.2°.

[0108] At the main peak position of Y5O4F7, the peaks of Y6O5F8 crystals and Y7O6F9 crystals overlap and appear. In addition, the main peak of YF3 also overlaps and appears at the main peak position of Y5O4F7.

[0109] All the peaks at the main peak position of Y5O4F7 are treated as the peaks of Y5O4F7.

[0110] When there is a YF3 crystal, the intensity of the second main peak of the YF3 crystal, that is, the peak near 2θ = 24.5°, is multiplied by 1.3 times to convert it into the main peak equivalent value, and this is used as the main peak intensity of YF3. At this time, the intensity of the second main peak of the YF3 crystal converted to 1.3 times is subtracted from the intensity of the peak of Y5O4F7 (the peak located at the main peak position of Y5O4F7). Suppose 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), so the intensity of the peak located at the main peak position of Y5O4F7 minus the intensity of the converted second main peak of the YF3 crystal is calculated as "3.4" (= 6.0 - 2.6).

[0111] The XRD pattern of the protective film is obtained by performing XRD measurement in the micro-detail 2D (two-dimensional) mode using an X-ray diffractometer (D8 DISCOVER Plus, manufactured by Bruker Corporation) under the above conditions.

[0112] ((Contents of each element))

[0113] This protective film contains yttrium (Y), oxygen (O), and fluorine (F) in the presence of yttrium oxyfluoride.

[0114] The Y content of this protective film is preferably 20 atomic % or more, more preferably 25 atomic % or more, further preferably 26 atomic % or more, particularly preferably 27 atomic % or more, and most preferably 27.5 atomic % or more.

[0115] On the other hand, the Y content of this protective film is preferably 35 atomic % or less, more preferably 30 atomic % or less, further preferably 29 atomic % or less, particularly preferably 28 atomic % or less.

[0116] The O content of this protective film is preferably 20 atomic % or more, more preferably 21 atomic % or more, further preferably 22 atomic % or more, particularly preferably 23 atomic % or more, and most preferably 24 atomic % or more.

[0117] On the other hand, the O content of this protective film is preferably 35 atomic % or less, more preferably 30 atomic % or less, further preferably 28 atomic % or less, particularly preferably 26 atomic % or less, and most preferably 25 atomic % or less.

[0118] The F content of this protective film is preferably 35 atomic % or more, more preferably 40 atomic % or more, further preferably 44 atomic % or more, particularly preferably 47 atomic % or more, and most preferably 48 atomic % or more.

[0119] On the other hand, the F content of this protective film is preferably 60 atomic % or less, more preferably 55 atomic % or less, further preferably 52 atomic % or less, still further preferably 50 atomic % or less, particularly preferably 49.5 atomic % or less, and most preferably 49 atomic % or less.

[0120] In order to make the content of each element within the above range, for example, in the method (this manufacturing method) described later, the manufacturing conditions such as the amount of the evaporation source are appropriately adjusted.

[0121] The content of each element in the protective film (unit: atomic %) is measured using an energy dispersive X-ray analyzer (EX-250SE, manufactured by Horiba, Ltd.).

[0122] ((Degree of orientation))

[0123] When making the protective film larger in area, from the viewpoint of suppressing cracks from occurring in the protective film, the higher the degree of orientation of the (151) crystal plane of Y5O4F7 in the protective film (hereinafter, also simply referred to as "degree of orientation"), the better.

[0124] In addition, the higher the degree of orientation of the protective film, the less stress is generated randomly during heating, and the heat resistance is improved.

[0125] As an index of the degree of orientation, the full width at half maximum (FWHM) of the rocking curve of the (151) crystal plane of Y5O4F7 is used. Specifically, the rocking curve of the peak of the (151) crystal plane of Y5O4F7 obtained using a two-dimensional pattern detector is integrated in the 2θ direction, and the FWHM is used to evaluate the degree of orientation. The smaller the FWHM (unit: °), the higher the degree of orientation can be said to be.

[0126] The full width at half maximum of the rocking curve of the (151) crystal plane of Y5O4F7 is preferably 40° or less, more preferably 30° or less, further preferably 25° or less, still further preferably 20° or less, particularly preferably 15° or less, and most preferably 10° or less.

[0127] In order to make the degree of orientation within the above range, it is preferable to manufacture the protective film by the method described later (this manufacturing method).

[0128] 《Crystallite size》

[0129] As described above, for example, particles (granules) detached from components exposed to plasma adhere to the semiconductor substrate, and may become foreign substances that cause defects in the circuit.

[0130] At this time, the smaller the size of the particles, the more the generation of defects can be suppressed.

[0131] Therefore, the crystallite size of this protective film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, still further preferably 15 nm or less, particularly preferably 11 nm or less, more particularly preferably 10 nm or less, very preferably 9 nm or less, and most preferably 8 nm or less.

[0132] On the other hand, the larger the crystallite size of the protective film, the smaller the change in the crystallite size during heating and the more stable it is, and the heat resistance is improved.

[0133] Therefore, for the reason that the heat resistance of this protective film is more excellent, the crystallite size of this protective film is preferably 2 nm or more, more preferably 6 nm or more, further preferably 7 nm or more, and particularly preferably 10 nm or more.

[0134] In order to make the crystallite size within the above range, it is preferable to manufacture the protective film by the method described later (this manufacturing method).

[0135] The crystallite size in the protective film is obtained using the Scherrer formula based on the data of the XRD pattern obtained by XRD measurement of the protective film polished by mirror polishing.

[0136] 《Thickness》

[0137] The thickness of the present protective film is preferably 0.3 μm or more, more preferably 1.0 μm or more, further preferably 1.5 μm or more, still further preferably 5 μm or more, and particularly preferably 10 μm or more. The thickness of the present protective film may also be 15 μm or more.

[0138] On the other hand, the thickness of the present protective film is preferably 300 μm or less, more preferably 200 μm or less, further preferably 100 μm or less, still further preferably 50 μm or less, particularly preferably 30 μm or less, and most preferably 15 μm or less. The thickness of the present protective film may be 10 μm or less.

[0139] The thickness of the protective film is measured as follows.

[0140] Using a scanning electron microscope (SEM), observe the cross-section of the protective film, measure the thickness of the protective film at any 5 points, and regard the average value of the 5 measured points as the thickness of the protective film (unit: μm).

[0141] 《Number of Hydrogen Atoms》

[0142] The fewer the number of hydrogen atoms in the present protective film, the better. Thus, the plasma resistance of the present protective film is more excellent.

[0143] The reason is presumably as follows. That is, if there is a large amount of hydrogen in the protective film, the hydrogen easily reacts with fluorine contained in the plasma (or the gas used to generate the plasma). As a result, the protective film is easily damaged. On the other hand, if there is less hydrogen in the protective film, the reaction with fluorine is relatively reduced, and the damage to the protective film is suppressed.

[0144] Specifically, the number of hydrogen atoms (the number of hydrogen atoms in the film) in the present protective film is preferably 5.0×10 21 per cm 3 or less, more preferably 4.5×10 21 per cm 3 or less, further preferably 3.5×10 21 per cm 3 or less, still further preferably 3.0×10 21 per cm 3 or less, particularly preferably 2.5×10 21 per cm 3 or less, and most preferably 2.3×10 21 per cm 3 or less.

[0145] It should be noted that the hydrogen in the protective film is highly likely to be affected by the moisture contained in the substrate described later.

[0146] In particular, when the base material is made of ceramics, by heating the base material (preheating) before forming the protective film, the number of hydrogen atoms in the formed protective film can be reduced.

[0147] In addition, the method of reducing the number of hydrogen atoms in the protective film will be described later.

[0148] On the other hand, the number of hydrogen atoms in this protective film is preferably 0.1×10 21 atoms / cm 3 or more, and more preferably 0.5×10 21 atoms / cm 3 or more.

[0149] The number of hydrogen atoms in the protective film is determined using a secondary ion mass spectrometer (model IMS-6f, manufactured by AMETEK, Inc.) under the conditions of primary ion Cs + , primary acceleration voltage of 15.0 kV, detection area of φ8 μm, and measurement depth of 500 nm.

[0150] 《Compressive Stress》

[0151] The stress (film internal stress, residual stress) of this protective film is preferably not tensile stress but compressive stress.

[0152] The compressive stress of this protective film is preferably 700 MPa or more, more preferably 1000 MPa or more, and further preferably 1200 MPa or more.

[0153] On the other hand, the compressive stress of this protective film is preferably 1700 MPa or less, more preferably 1600 MPa or less, and further preferably 1500 MPa or less.

[0154] The compressive stress of the protective film is determined as follows.

[0155] A protective film is formed on a quartz glass substrate, and the surface shape of the formed protective film is measured using a surface shape measuring device (Surfcom NEX241SD2-13, manufactured by Tokyo Seimitsu Co., Ltd.), and the compressive stress (film stress σ) of the protective film is determined according to the Stoney formula (the following formula).

[0156] The Stoney formula is expressed as follows.

[0157] σ = Yd 2 / (6c(1 - ν)t)

[0158] In the above formula, σ: film stress, Y: Young's modulus of the substrate, d: thickness of the substrate, ν: Poisson's ratio of the substrate, t: thickness of the protective film, c: radius of curvature.

[0159] 〈Base Material〉

[0160] The substrate has at least a surface on which a stress relaxation layer (or the base layer described later) can be formed. Hereinafter, for convenience, this surface is sometimes referred to as the "film-forming surface".

[0161] 《Material》

[0162] The material of the substrate is appropriately selected according to the use of the component, etc.

[0163] The substrate is composed of, for example, at least one selected from carbon (C), ceramics, and metals.

[0164] Here, the ceramics are preferably, for example, at least one selected from glass (such as soda-lime glass), quartz, alumina (Al2O3), aluminum nitride (AlN), cordierite, yttrium oxide, silicon carbide (SiC), silicon-impregnated silicon carbide, silicon nitride (SiN), sialon, and aluminum oxynitride (AlON). As the ceramics, alumina or quartz is more preferred.

[0165] Silicon-impregnated silicon carbide is obtained by heating and melting elemental silicon and impregnating it into silicon carbide (SiC).

[0166] The metal is preferably, for example, at least one selected from aluminum (Al) and alloys containing aluminum (Al).

[0167] 《Shape》

[0168] The shape of the substrate is not particularly limited. For example, a flat plate shape, a ring shape, a dome shape, a concave shape, or a convex shape can be cited, and it can be appropriately selected according to the use of the component, etc.

[0169] 《Surface roughness of the film-forming surface》

[0170] The smaller the surface roughness of the film-forming surface of the substrate, the denser and harder the yttrium-based protective film formed on the film-forming surface, and cracks are less likely to occur during heating (especially repeated heating), and the heat resistance is more excellent.

[0171] Therefore, the surface roughness of the film-forming surface of the substrate is preferably less than 4.5 μm, more preferably 2.0 μm or less, further preferably 1.0 μm or less, still further preferably 0.5 μm or less, particularly preferably 0.20 μm or less, and most preferably 0.12 μm or less, in terms of arithmetic mean roughness Ra.

[0172] On the other hand, the surface roughness of the film-forming surface of the substrate is preferably 0.001 μm or more, more preferably 0.01 μm or more, and further preferably 0.08 μm or more, in terms of arithmetic mean roughness Ra.

[0173] The surface roughness (arithmetic mean roughness Ra) of the film-forming surface is measured in accordance with JIS B 0601:2001.

[0174] 《Maximum Length of Film-Forming Surface》

[0175] The maximum length of the film-forming surface of the substrate is preferably 30 mm or more, more preferably 100 mm or more, further preferably 200 mm or more, still further preferably 300 mm or more, particularly preferably 500 mm or more, very preferably 800 mm or more, and most preferably 1000 mm or more.

[0176] It should be noted that the "maximum length" refers to the maximum length of the film-forming surface. Specifically, for example, when the film-forming surface is circular in plan view, it is the diameter; when it is annular in plan view, it is the outer diameter; and when it is quadrilateral in plan view, it is the maximum length of the diagonal.

[0177] On the other hand, the maximum length of the film-forming surface is preferably 2000 mm or less, more preferably 1500 mm or less.

[0178] Figure 2 It is a schematic view showing half of the annular substrate 5 cut away.

[0179] For Figure 2 the substrate 5 shown, for example, when the outer diameter D1 is 100 mm, the inner diameter D2 is 90 mm, and the thickness t is 5 mm, its maximum length is 100 mm.

[0180] The substrate 5 has a film-forming surface 7, and as Figure 2 shown, it can have a first film-forming surface 7a with a specified maximum length (outer diameter D1) and a second film-forming surface 7b different from the first film-forming surface 7a.

[0181] The ratio of the area of the second film-forming surface 7b to the total area of the film-forming surface 7 is preferably 60% or less.

[0182] Figure 3 It is a schematic view showing a part of the cross-section of another annular substrate 5.

[0183] As Figure 3 shown, the substrate 5 can have a plurality of second film-forming surfaces 7b.

[0184] Figure 4 It is a schematic view showing a part of the cross-section of yet another annular substrate 5.

[0185] The angle formed by the first film-forming surface 7a and the second film-forming surface 7b is preferably 20° to 120°. In the Figure 4 substrate 5 shown, the angle formed by the first film-forming surface 7a and the second film-forming surface 7b connected to the first film-forming surface 7a is about 30°.

[0186] 〈Stress Relief Layer〉

[0187] As described above, one or more stress relaxation layers are disposed between the substrate and the yttrium-based protective film (this protective film). Thus, the heat resistance of this protective film is excellent. It is presumed that this is because the stress (tensile stress) of this protective film is relaxed by the stress relaxation layer.

[0188] 《Number of Layers》

[0189] The upper limit of the number of stress relaxation layers is not particularly limited, preferably 5 layers or less, more preferably 4 layers or less, further preferably 3 layers or less, particularly preferably 2 layers or less, and most preferably 1 layer.

[0190] 《Composition》

[0191] The stress relaxation layer preferably contains at least one oxide selected from the group (for convenience, referred to as "Group G") consisting of Al2O3 (including "β - Al2O3", the same applies hereinafter), SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

[0192] The stress relaxation layer preferably contains at least two oxides selected from Group G.

[0193] Group G preferably consists of Al2O3, SiO2, Y2O3, MgO, CaO, SrO, B2O3, and ZrO2, more preferably consists of Al2O3, SiO2, Y2O3, MgO, CaO, SrO, and B2O3, and further preferably consists of Al2O3, SiO2, and Y2O3.

[0194] When the stress relaxation layer contains only one oxide (for example, Al2O3), the content of this oxide (for example, Al2O3) in the stress relaxation layer is preferably 100 mol%.

[0195] For example, when the material of the substrate is aluminum nitride (AlN), the stress relaxation layer in contact with this substrate preferably contains only one oxide (such as Al2O3, MgO, or ZrO2, etc.).

[0196] The content of Al2O3 in the stress relaxation layer is preferably 0 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, still further preferably 15 mol% or more, particularly preferably 20 mol% or more, extremely preferably 25 mol% or more, and most preferably 30 mol% or more.

[0197] On the other hand, the content of Al2O3 in the stress relaxation layer is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 45 mol% or less, particularly preferably 40 mol% or less, and most preferably 35 mol% or less.

[0198] The content of SiO2 in the stress relaxation layer is preferably 0 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 45 mol% or more, and most preferably 50 mol% or more.

[0199] On the other hand, the content of SiO2 in the stress relaxation layer is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, even more preferably 75 mol% or less, particularly preferably 70 mol% or less, extremely preferably 65 mol% or less, very preferably 60 mol% or less, and most preferably 55 mol% or less.

[0200] The content of Y2O3 in the stress relaxation layer is preferably 0 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, even more preferably 13 mol% or more, particularly preferably 16 mol% or more, and most preferably 19 mol% or more.

[0201] On the other hand, the content of Y2O3 in the stress relaxation layer is preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% or less, and most preferably 20 mol% or less.

[0202] When the stress relaxation layer contains Al2O3, SiO2, and Y2O3, the content of oxides other than Al2O3, SiO2, and Y2O3 (for example, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3) in the stress relaxation layer is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, particularly preferably 1 mol% or less, and most preferably 0 mol% or less.

[0203] When the stress relaxation layer contains SiO2 and Y2O3, the molar ratio of SiO2 to Y2O3 (SiO2 / Y2O3) is preferably 90 / 10 to 20 / 80, more preferably 80 / 20 to 30 / 70, and still more preferably 70 / 30 to 40 / 60.

[0204] At this time, the content of oxides other than SiO2 and Y2O3 (for example, Al2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3) is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 1 mol% or less, and particularly preferably 0 mol%.

[0205] The content (unit: mol%) of each oxide in the stress relaxation layer is measured using an energy dispersive X-ray analyzer (EX-250SE, manufactured by Horiba, Ltd.).

[0206] For example, when the molar ratio of Y to Al to Si (Y / Al / Si) is 25 / 25 / 50 and no elements other than Y, Al, Si, and O are detected, the content of Y2O3 is 25 mol%, the content of Al2O3 is 25 mol%, and the content of SiO2 is 50 mol%.

[0207] The same applies to the base layer described below.

[0208] 《State of the layer》

[0209] The stress relaxation layer is preferably an amorphous layer.

[0210] However, the stress relaxation layer as an amorphous layer may also contain crystals.

[0211] 《Thermal stability temperature》

[0212] The thermal stability temperature of the stress relaxation layer is preferably 300 °C or higher, more preferably 350 °C or higher, still more preferably 400 °C or higher, and particularly preferably 450 °C or higher.

[0213] The thermal stability temperature of the stress relaxation layer is determined by conducting the following test.

[0214] First, prepare a sample having a stress relaxation layer (without a yttrium-based protective film) on quartz. Next, heat the prepared sample in an air calcination furnace at a heating rate of 300 °C / hr, heat it at an arbitrary temperature T2 for 1 hour, and take out the sample by cooling at 50 °C / hr. Then, perform XRD measurement of the sample to confirm whether crystals are formed.

[0215] Perform such a test at a temperature T2 of 100 °C to 500 °C (every 50 °C), and take the maximum temperature T2 at which no crystals are formed as the thermal stability temperature of the stress relaxation layer.

[0216] 《Thickness》

[0217] The thickness of the stress relaxation layer is preferably 0.05 μm or more, more preferably 0.5 μm or more, further preferably 0.8 μm or more, still further preferably 1.1 μm or more, particularly preferably 1.4 μm or more, very preferably 1.7 μm or more, and most preferably 2.0 μm or more, respectively.

[0218] On the other hand, the thickness of the stress relaxation layer is preferably 9.0 μm or less, more preferably 5.0 μm or less, further preferably 7.0 μm or less, and particularly preferably 3.0 μm or less, respectively.

[0219] The thickness of the stress relaxation layer is measured in the same manner as the thickness of the yttrium-based protective film.

[0220] 〈Base layer〉

[0221] As described above, one or more base layers may be disposed between the substrate and the stress relaxation layer.

[0222] By forming the base layer, the tensile stress of the yttrium-based protective film is relaxed and compressive stress is generated, and the adhesion of the yttrium-based protective film to the substrate is increased.

[0223] It should be noted that in the plurality of layers constituting the stress relaxation layer, one or more layers on the substrate side may be regarded as the base layer.

[0224] That is, the base layer may be a layer different from the stress relaxation layer or may be at least a part of the stress relaxation layer.

[0225] 《Number of layers》

[0226] The upper limit of the number of layers of the base layer is not particularly limited, and is preferably 5 layers or less, more preferably 4 layers or less, further preferably 3 layers or less, particularly preferably 2 layers or less, and most preferably 1 layer.

[0227] 《State of the layer》

[0228] The base layer is preferably an amorphous layer or a microcrystalline layer (an amorphous layer containing crystals).

[0229] 《Composition》

[0230] When the base layer is at least one layer of the stress relaxation layer, as the composition of the base layer, the composition described as the composition of the stress relaxation layer can be preferably selected.

[0231] On the other hand, when the base layer is a layer different from the stress relaxation layer, the base layer preferably contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

[0232] The base layer more preferably contains SiO2, or contains at least two oxides selected from Al2O3, SiO2, and Y2O3.

[0233] When two or more base layers are disposed between the base material and the yttrium-based protective film, the oxides of the base layers are preferably different from each other between adjacent base layers.

[0234] In the case where the oxides are different from each other between adjacent base layers, specifically, for example, the case where the oxide of base layer 1 is "SiO2", the oxide of base layer 2 is "Al2O3 + SiO2", and the oxide of base layer 3 is "Al2O3" can be cited.

[0235] 《Thickness》

[0236] The thickness of each base layer is preferably 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.2 μm or more, still further preferably 0.5 μm or more, particularly preferably 0.8 μm or more, and most preferably 1.1 μm or more.

[0237] On the other hand, the thickness of each base layer is preferably 15.0 μm or less, more preferably 10.0 μm or less, further preferably 7.0 μm or less, particularly preferably 5.0 μm or less, and most preferably 3.0 μm or less.

[0238] The thickness of the base layer is measured in the same manner as the thickness of the yttrium-based protective film.

[0239] 〈Use of the component〉

[0240] This component is used, for example, as a top plate or the like inside a semiconductor device manufacturing apparatus (such as a plasma etching apparatus, a plasma CVD apparatus).

[0241] However, the use of this component is not limited thereto.

[0242] [Manufacturing method of the component]

[0243] Next, a method for manufacturing the component of the present embodiment (hereinafter, also referred to as "this manufacturing method" for convenience) will be described.

[0244] This manufacturing method is a so-called ion-assisted evaporation deposition (IAD) method.

[0245] Briefly, while irradiating ions in a vacuum, an evaporation source (Y2O3, YF3, etc.) is evaporated and attached to a base material, thereby forming a yttrium-based protective film.

[0246] According to this manufacturing method, a yttrium-based protective film can be formed very densely. That is, the obtained yttrium-based protective film has a small porosity. In addition, the crystallite size is also small.

[0247] Furthermore, since the tensile stress of the yttrium protective film is relaxed by forming the stress relaxation layer, cracks are less likely to occur even when heated at high temperatures, and the film has excellent heat resistance.

[0248] In addition, the surface roughness (arithmetic mean roughness Ra) of the film-forming surface of the substrate is preferably within the above range. This makes the formed yttrium protective film denser and harder and less likely to crack.

[0249] In addition, in the thermal spraying method, the aerosol deposition (AD) method, the ion plating (IP) method, etc., many pores tend to remain in the yttrium protective film obtained.

[0250] <Device Configuration>

[0251] based on Figure 5 This production method will be described in more detail.

[0252] Figure 5 This is a schematic diagram showing an apparatus used for producing the yttrium protective film.

[0253] Figure 5 The device shown has a chamber 11. The interior of the chamber 11 can be evacuated by driving a vacuum pump (not shown) to achieve a vacuum.

[0254] Crucibles 12 and 13 and an ion gun 14 are arranged inside the chamber 11 , and a support plate 17 is arranged above them.

[0255] The support plate 17 is integrated with the support shaft 16, and rotates with the rotation of the support shaft 16. The heater 15 is arranged around the support plate 17.

[0256] The substrate 5 is held on the pallet 17 in a state where the film-forming surface thereof faces downward. The substrate 5 held on the pallet 17 is rotated as the pallet 17 rotates while being heated by the heater 15 .

[0257] Furthermore, quartz crystal film thickness monitors 18 and 19 are installed in the chamber 11 .

[0258] 〈Formation of yttrium protective film (Part 1)〉

[0259] Figure 5 In the apparatus shown in FIG. 1 , a yttrium protective film (in Figure 5 The situation (not shown in the figure) is explained below.

[0260] First, one or both of the crucibles 12 and 13 are filled with the evaporation source Y 2 O 3 .

[0261] After the substrate 5 is held on the support plate 17 , the interior of the chamber 11 is evacuated to a vacuum.

[0262] Next, while driving the heater 15, the pallet 17 is rotated. Thereby, the substrate 5 is rotated while being heated.

[0263] In this state, ion-assisted evaporation is performed to form a film on the substrate 5.

[0264] That is, while irradiating ions (ion beam) from the ion gun 14, the evaporation source Y2O3 filled in one or both of the crucibles 12 and 13 is evaporated.

[0265] The ions irradiated by the ion gun 14 are preferably ions of at least one element selected from oxygen, argon, neon, krypton, and xenon.

[0266] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0267] Thereby, the evaporated evaporation source adheres to the substrate 5 (film-forming surface), and a yttrium-based protective film containing yttrium oxide (Y2O3) is formed.

[0268] 《Chamber pressure》

[0269] The film formation is carried out in a vacuum. Specifically, the pressure inside the chamber 11 is preferably 6×10 －2 Pa or less, more preferably 5×10 －2 Pa or less, and further preferably 3×10 －2 Pa or less.

[0270] On the other hand, the pressure inside the chamber 11 is preferably greater than 1×10 －6 Pa, preferably 1×10 －5 Pa or more, and more preferably 1×10 －4 Pa or more.

[0271] 《Substrate temperature》

[0272] During film formation, for the reason that the heat resistance of the formed yttrium-based protective film is more excellent, the temperature of the substrate 5 heated by the heater 15 is preferably 200 °C or more, more preferably 270 °C or more, further preferably 320 °C or more, particularly preferably 370 °C or more, and most preferably 400 °C or more.

[0273] On the other hand, this temperature is preferably 600 °C or less, preferably 500 °C or less, and more preferably 450 °C or less.

[0274] 《Film formation rate》

[0275] The evaporation rate (film formation rate) of the evaporation sources in the crucibles 12 and 13 for forming a film is monitored in advance using the quartz crystal film thickness monitors 18 and 19, respectively.

[0276] The film formation rate is adjusted by controlling the conditions of the electron beam irradiated to the evaporation source and the conditions of the ion beam of the ion gun 14 (current value, current density, etc.).

[0277] During the film formation of the yttrium-based protective film, the film formation rate (unit: nm / min) of each evaporation source is adjusted to a desired value.

[0278] The film formation rate of the evaporation source Y2O3 is preferably 1 nm / min or more, more preferably 1.5 nm / min or more, and further preferably 2 nm / min or more.

[0279] The film formation rate of the evaporation source Y2O3 is preferably 20 nm / min or less, more preferably 15 nm / min or less, further preferably 10 nm / min or less, still more preferably 5 nm / min or less, particularly preferably 3.5 nm / min or less, and most preferably 2.1 nm / min or less.

[0280] 《Ion Irradiation Conditions》

[0281] The distance between the ion gun 14 and the substrate 5 is preferably 700 mm or more, more preferably 900 mm or more. On the other hand, this distance is preferably 1500 mm or less, more preferably 1300 mm or less.

[0282] The current value of the ion beam is preferably 1000 mA or more, more preferably 1500 mA or more. On the other hand, the ion beam current value is preferably 3000 mA or less, more preferably 2500 mA or less.

[0283] For the reason that the obtained yttrium-based protective film becomes harder, the ion beam current density is preferably 40 μA / cm 2 or more, more preferably 65 μA / cm 2 or more, further preferably 75 μA / cm 2 or more, particularly preferably 77 μA / cm 2 or more.

[0284] On the other hand, the ion beam current density is preferably 140 μA / cm 2 or less, more preferably 120 μA / cm 2 or less, further preferably 100 μA / cm 2 or less.

[0285] 〈Formation of Yttrium-Based Protective Film (Part 2)〉

[0286] Next, the case of forming a yttrium-based protective film containing yttrium oxyfluoride on the substrate 5 (not shown in Figure 5 ) will be described.

[0287] First, fill one of the crucibles 12 with the evaporation source Y2O3, and fill the other crucible 13 with the evaporation source YF3.

[0288] After the substrate 5 is held on the pallet 17, evacuate the inside of the chamber 11 to reach a vacuum.

[0289] Next, while driving the heater 15, rotate the pallet 17. Thereby, the substrate 5 is heated and rotated.

[0290] In this state, ion-assisted evaporation is performed to form a film on the substrate 5.

[0291] That is, while irradiating ions (ion beam) from the ion gun 14, the evaporation sources Y2O3 in the crucible 12 and the evaporation source YF3 in the crucible 13 are evaporated simultaneously.

[0292] The ions irradiated by the ion gun 14 are preferably ions of at least one element selected from oxygen, argon, neon, krypton, and xenon.

[0293] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0294] Thereby, the evaporated evaporation source adheres to the substrate 5 (more specifically, the surface of the stress relaxation layer described later), and a yttrium-based protective film containing yttrium oxyfluoride is formed.

[0295] "Film Formation Rate"

[0296] The film formation rate ratio (Y2O3 / YF3) of the film formation rate (unit: nm / min) of the evaporation source Y2O3 to the film formation rate (unit: nm / min) of the evaporation source YF3 is preferably 1 / 9.5 or more, more preferably 1 / 8.0 or more, further preferably 1 / 6.0 or more, and particularly preferably 1 / 4.5 or more.

[0297] On the other hand, this film formation rate ratio (Y2O3 / YF3) is preferably 1 / 1.1 or less, more preferably 1 / 1.3 or less, further preferably 1 / 1.8 or less, and particularly preferably 1 / 2.5 or less.

[0298] The total rate of the film formation rate of the evaporation source Y2O3 and the film formation rate of the evaporation source YF3 is preferably 5 nm / min or more, more preferably 8 nm / min or more, and further preferably 10 nm / min or more. On the other hand, this total rate is preferably 50 nm / min or less, more preferably 35 nm / min or less, and further preferably 20 nm / min or less.

[0299] "Chamber Pressure, Substrate Temperature, and Ion Irradiation Conditions"

[0300] The chamber pressure, the temperature of the substrate, and the conditions for ion irradiation when forming the yttrium-based protective film containing yttrium oxyfluoride are based on the case of forming the yttrium-based protective film containing yttrium oxide (Y2O3).

[0301] <Formation of stress relaxation layer>

[0302] Preferably, the above stress relaxation layers (for example, stress relaxation layer 8 and stress relaxation layer 9) are formed on the film-forming surface of the substrate 5 before forming the yttrium-based protective film.

[0303] The stress relaxation layer is formed by ion-assisted evaporation in the same manner as the yttrium-based protective film.

[0304] For example, in the case of forming a stress relaxation layer containing Y2O3 and SiO2, Y2O3 as an evaporation source is filled in the crucible 12, SiO2 as an evaporation source is filled in the crucible 13, and while irradiating ions (ion beam) from the ion gun 14, the evaporation source is evaporated and attached to the film-forming surface of the substrate 5.

[0305] In the case of forming a stress relaxation layer containing three or more oxides, another crucible and a quartz crystal film thickness monitor (both not shown) are further provided in the chamber 11 to form the stress relaxation layer.

[0306] For example, in the case of forming a stress relaxation layer containing Y2O3, SiO2, and Al2O3, Y2O3 as an evaporation source is filled in the crucible 12, SiO2 as an evaporation source is filled in the crucible 13, and Al2O3 as an evaporation source is filled in another crucible (not shown), and while irradiating ions (ion beam) from the ion gun 14, the evaporation source is evaporated and attached to the film-forming surface of the substrate 5.

[0307] The conditions for forming the stress relaxation layer are based on the conditions for forming the yttrium-based protective film.

[0308] <Formation of base layer>

[0309] Preferably, the above base layers (for example, base layer 1, base layer 2, and base layer 3) are formed on the film-forming surface of the substrate 5 before forming the yttrium-based protective film.

[0310] The base layer is formed by ion-assisted evaporation in the same manner as the yttrium-based protective film.

[0311] For example, in the case of forming a base layer composed of Al2O3, Al2O3 as an evaporation source is filled in one or both of the crucibles 12 and 13, and while irradiating ions (ion beam) from the ion gun 14, the evaporation source is evaporated and attached to the film-forming surface of the substrate 5.

[0312] The conditions for forming the base layer are based on the conditions for forming the yttrium-based protective film.

[0313] However, the base material sometimes contains water of crystallization.

[0314] For example, when a base material made of alumina (Al2O3) is heated from room temperature, the generation of water of crystallization caused by a hydrate of a low-temperature stable phase of alumina (e.g., boehmite γ-alumina) is observed around 520°C.

[0315] When moisture caused by the water of crystallization of the base material is included in the formed yttrium-based protective film, the number of hydrogen atoms in the yttrium-based protective film tends to increase.

[0316] Therefore, before attaching the evaporation source Y2O3 to the film-forming surface of the base material (i.e., forming a yttrium-based protective film), a stress relaxation layer (or a stress relaxation layer and a base layer) is formed on the film-forming surface of the base material.

[0317] Thereby, at least the film-forming surface of the base material is covered, so that the water of crystallization of the base material is not easily included in the formed yttrium-based protective film, and further the number of hydrogen atoms in the yttrium-based protective film is reduced, which is thus preferred.

[0318] 〈Preheating of the base material〉

[0319] For the reason that the water of crystallization of the base material is not easily included in the yttrium-based protective film, it is preferred to heat the base material at a high temperature (preheat) before forming the yttrium-based protective film.

[0320] The preheating temperature is preferably 300°C or higher, more preferably 400°C or higher, further preferably 450°C or higher, and particularly preferably 500°C or higher.

[0321] On the other hand, the preheating temperature is preferably 800°C or lower, more preferably 750°C or lower, and further preferably 700°C or lower.

[0322] The preheating time is preferably 60 minutes or longer, more preferably 120 minutes or longer, further preferably 240 minutes or longer, and particularly preferably 480 minutes or longer.

[0323] On the other hand, the preheating time is preferably 1200 minutes or shorter, more preferably 1000 minutes or shorter, further preferably 800 minutes or shorter, and particularly preferably 600 minutes or shorter.

[0324] The preheating environment is, for example, an atmospheric environment.

[0325] Examples

[0326] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the examples described below.

[0327] Hereinafter, Examples 1 to 49, Examples 53 to 58, and Examples 61 to 82 are examples, and Examples 50 to 52 and Examples 59 to 60 are comparative examples.

[0328] <Example 1>

[0329] Using the device based on Figure 5 as described, components with a yttrium-based protective film were manufactured according to the conditions shown in Tables 1 to 8 below.

[0330] As the substrate, a circular substrate (thickness: 10 mm) made of quartz and having a film-forming surface with a diameter (maximum length) of the values shown in Tables 1 to 8 below was used.

[0331] The substrate was preheated in an atmospheric environment while being held on a pallet in a chamber. The preheating temperature was 550 °C and the preheating time was 600 minutes.

[0332] Next, according to the manufacturing conditions shown in Tables 1 to 8 below, a base layer, a stress relaxation layer, and a yttrium-based protective film shown in Tables 1 to 8 below were sequentially formed on the film-forming surface of the substrate.

[0333] As manufacturing conditions not described in Tables 1 to 8 below, oxygen (O) ions were irradiated by an ion gun, the distance between the ion gun and the substrate was 1100 mm, and the current value of the ion beam was 2000 mA.

[0334] <Examples 2 to 82>

[0335] In Examples 2 to 82, one or more conditions were changed compared to Example 1. Other than that, the base layer, the stress relaxation layer, and the yttrium-based protective film were sequentially formed in the same manner as in Example 1.

[0336] In the case where the base layer and / or the stress relaxation layer was not formed, "-" was recorded in the corresponding columns of Tables 1 to 8 below.

[0337] In short, as follows. The points of change compared to Example 1 are mainly outlined.

[0338] In Examples 2 to 4, the temperature of the substrate during the formation of the yttrium-based protective film was changed.

[0339] In Example 5, the material of the substrate was changed to alumina (Al2O3).

[0340] In Example 6, the base layer was not formed.

[0341] In Examples 7 to 9, the thickness of the yttrium-based protective film was changed.

[0342] In Examples 10 to 16, the composition of the stress relaxation layer was changed.

[0343] In Examples 17 to 20, the number of base layers was changed.

[0344] In Examples 21 to 27, the composition and / or the number of layers of the stress relaxation layer were changed.

[0345] In Examples 28 to 31, the thickness of the stress relaxation layer was changed.

[0346] In Examples 32 to 38, the Ra of the film-forming surface was mainly changed.

[0347] In Example 39, the material of the substrate was changed to glass (soda-lime glass of a commercially available product).

[0348] In Example 40, the material of the substrate was changed to aluminum (Al).

[0349] In Example 41, an anodic oxidation treatment was performed on one surface side of a substrate made of single-crystal aluminum, and then a polishing treatment was performed, whereby a base layer made of Al2O3 was formed. This base layer is described as "anodic oxidation" in Tables 1 to 8 below.

[0350] In Example 42, the material of the substrate was changed to aluminum nitride (AlN).

[0351] In Example 43, the material of the substrate was changed to cordierite.

[0352] In Examples 44 to 45, the area of the film-forming surface was changed (increased area).

[0353] In Examples 46 to 48, Y2O3 and YF3 were used as evaporation sources to form a yttrium-based protective film containing yttrium oxyfluoride.

[0354] In Example 49, as described later, after forming the yttrium-based protective film, heating was performed to precipitate crystals.

[0355] In Examples 50 to 52, the stress relaxation layer was not formed.

[0356] In Examples 53 to 54, the composition of the stress relaxation layer was changed.

[0357] In Example 55, the thickness of the yttrium-based protective film was increased.

[0358] In Example 56, the Ra of the film-forming surface was increased.

[0359] In Example 57, the crystal grain size of the yttrium-based protective film was decreased.

[0360] In Example 58, the temperature of the substrate during the formation of the yttrium-based protective film was changed.

[0361] In Examples 59 to 60, the IAD method was not used, and the yttrium-based protective film was formed using the IP method and the CVD method, respectively.

[0362] In Examples 61 to 82, the material of the substrate was changed to aluminum nitride (AlN).

[0363] 〈Composition〉

[0364] For the base layer, stress relaxation layer, and yttrium-based protective film of each example, the compositions are listed in Tables 1 to 8 below.

[0365] Regarding the base layer and the stress relaxation layer, for example, "30Y2O3 + 70SiO2" means that the content of Y2O3 is 30 mol% and the content of SiO2 is 70 mol%.

[0366] When forming a yttrium-based protective film containing yttrium oxyfluoride, in Tables 1 to 8 below, the composition obtained from the content of each element (Y, O, F, etc.) is listed as its composition.

[0367] 〈State of stress relaxation layer〉

[0368] Perform XRD measurement on the obtained component.

[0369] When no peaks are generated except for the components of the yttrium-based protective film (yttrium oxide or yttrium oxyfluoride), it is determined that the stress relaxation layer is an amorphous layer and is recorded as "amorphous" in Table 3 below. On the other hand, when peaks are generated, it is determined that the stress relaxation layer contains crystals and is recorded as "crystal".

[0370] In Example 49, after forming the yttrium-based protective film, it was heated at 450 °C for 30 minutes, and crystals (Y2Si7O7 crystals) were partially precipitated. The content of the crystals was not clear. The peak intensity of the Y2Si7O7 crystals generated in the stress relaxation layer with almost the same thickness was 2.85% relative to the peak intensity of the yttrium-based protective film (Y2O3) with a thickness of 1 μm. Therefore, it is considered that the amount of crystals generated is scarce.

[0371] 〈Physical properties〉

[0372] For the base layer of each example, the thickness is obtained based on the above method.

[0373] For the stress relaxation layer of each example, the thickness and thermal stability temperature are obtained based on the above method.

[0374] For the yttrium-based protective film of each example, the number of hydrogen atoms, Vickers hardness, porosity, crystallite size, orientation degree (or peak intensity ratio), thickness, and compressive stress are obtained based on the above method.

[0375] The results are all shown in Tables 1 to 8 below. It should be noted that for the compressive stress, the value is recorded as a negative number.

[0376] 〈Etching amount〉

[0377] Perform ion etching on the yttrium-based protective film of each example and evaluate the plasma resistance.

[0378] Specifically, first, a 10 mm × 5 mm surface of the yttrium-based protective film is mirror-finished, and a part of the surface after mirror finishing (referred to as the "test surface") is covered with Kapton tape.

[0379] Next, using a CCP type plasma etching device, under the conditions of a pressure of 10 Pa and an RF power of 600 W, a plasma is generated by discharging in a gas, and a test of exposing the test surface to the generated plasma (exposure test) is carried out.

[0380] More specifically, using CF4 gas (flow rate: 100 sccm) and O2 gas (flow rate: 100 sccm), a discharge (generation of plasma) is carried out to generate ions of CF4 in the plasma.

[0381] The discharge (generation of plasma) for 15 minutes is repeated 5 times, and an exposure test for a total of 150 minutes is carried out. Thereby, the unmasked part of the test surface is etched.

[0382] Then, using a probe type surface shape measuring instrument (manufactured by ULVAC, Dectak150), the height difference generated between the masked part and the unmasked part of the test surface is measured, and the etching amount is obtained. The results are shown in Tables 1 to 8 below.

[0383] The smaller the etching amount (unit: nm), the more excellent the plasma resistance can be evaluated.

[0384] Specifically, if the etching amount is 200 nm or less, the plasma resistance can be evaluated as excellent.

[0385] 〈Heat resistance temperature〉

[0386] For the components of each example, the above-mentioned heat resistance test is carried out, and the maximum temperature T1 at which no crack occurs in the yttrium-based protective film is obtained as the heat resistance temperature (unit: °C). The results are shown in Tables 1 to 8 below.

[0387] If the heat resistance temperature is 300 °C or higher, the heat resistance can be evaluated as excellent.

[0388] 〈Thermal cycle test〉

[0389] For the components of some examples, a test of repeating the heat resistance test 3 times at the obtained heat resistance temperature (thermal cycle test) is carried out. Then, visually check the end part (including the part of the end face) and the part other than the end part of the yttrium-based protective film to confirm the presence or absence of cracks.

[0390] In Tables 1 to 8 below, the case without cracks is recorded as "○", the case where there is a crack less than 10 mm at the end and no crack in the part other than the end is recorded as "△", and the case where there is a crack of 10 mm or more at the end and / or there is a crack in the part other than the end is recorded as "×".

[0391] From the viewpoint of more excellent heat resistance, "○" or "△" is preferred, and "○" is more preferred.

[0392] [Table 1]

[0393]

[0394] [Table 2]

[0395]

[0396] [Table 3]

[0397]

[0398] [Table 4]

[0399]

[0400] [Table 5]

[0401]

[0402] [Table 6]

[0403]

[0404] [Table 7]

[0405]

[0406] [Table 8]

[0407]

[0408] 〈Summary of evaluation results〉

[0409] As shown in Tables 1 to 8 above, it can be seen that Examples 1 to 49, Examples 53 to 58, and Examples 61 to 82 have excellent heat resistance and plasma resistance.

[0410] In contrast, at least any one of the heat resistance and plasma resistance of Examples 50 to 52 without a stress relaxation layer and Examples 59 to 60 with a Vickers hardness of the yttrium-based protective film less than 800 HV is insufficient.

[0411] The present invention has been described in detail with reference to specific embodiments, but those skilled in the art can of course make various changes and modifications without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application No. 2022-181022 filed on November 11, 2022 and Japanese Patent Application No. 2023-053613 filed on March 29, 2023, the contents of which are incorporated herein by reference.

[0412] Symbol Explanation

[0413] 1, 2, 3: Base layer

[0414] 4: Yttrium-based protective film

[0415] 5: Substrate

[0416] 6: Component

[0417] 7: Film-forming surface

[0418] 7a: First film-forming surface

[0419] 7b: Second film-forming surface

[0420] 8, 9: Stress relaxation layer

[0421] 11: Chamber

[0422] 12, 13: Crucible

[0423] 14: Ion gun

[0424] 15: Heater

[0425] 16: Support shaft

[0426] 17: Pallet

[0427] 18, 19: Quartz crystal film thickness monitor

Claims

1. A component having, in sequence, a base material, one or more stress relief layers, and a yttrium-based protective film, wherein the Vickers hardness of the yttrium-based protective film is 800 HV or more.

2. The component according to claim 1, wherein, The heat-resistant temperature of the yttrium-based protective film is 300 °C or higher.

3. The component according to claim 1, wherein, The thickness of the stress relaxation layer is 0.05 to 9.0 μm.

4. The component according to claim 1, wherein, The surface roughness of the film-forming surface of the substrate is 0.001 μm or more and less than 4.5 μm in terms of arithmetic mean roughness Ra.

5. The component according to claim 1, wherein, The stress relaxation layer 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.

6. The component according to claim 5, wherein, The stress relaxation layer contains at least two oxides selected from the group.

7. The component according to claim 5, wherein, The stress relaxation layer contains at least one selected from Al2O3, SiO2, and Y2O3. The content of Al2O3 is 0 to 70 mol%. The content of SiO2 is 0 to 90 mol%. The content of Y2O3 is 0 to 60 mol%. The content of the oxides other than Al2O3, SiO2, and Y2O3 is 20 mol% or less.

8. The component according to claim 5, wherein, The stress relaxation layer contains SiO2 and Y2O3. The molar ratio of SiO2 to Y2O3, SiO2 / Y2O3, is 90 / 10 to 20 / 80. The content of the oxides other than SiO2 and Y2O3 is 10 mol% or less.

9. The component according to claim 5, wherein, The stress relaxation layer contains Al2O3, and the content of Al2O3 is 10 to 70 mol%.

10. The component according to claim 1, wherein, There is one or more base layers between the substrate and the stress relaxation layer. The base layer contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

11. The component according to claim 10, wherein, There are two or more of the base layers. The oxides are different from each other between the adjacent base layers.

12. The component according to claim 10, wherein, The base layer contains SiO2, or contains at least two oxides selected from Al2O3, SiO2, and Y2O3.

13. The component according to claim 1, wherein, The porosity of the yttrium-based protective film is less than 2.0% by volume.

14. The component according to claim 1, wherein, The thickness of the yttrium-based protective film is 0.3 μm to 15 μm.

15. The component according to claim 1, wherein, The crystallite size of the yttrium-based protective film is 6 nm to 40 nm.

16. The component according to claim 1, wherein, The yttrium-based protective film contains yttrium oxide.

17. The component according to claim 16, wherein, The orientation degree of the (222) crystal plane of Y2O3 in the yttrium-based protective film is 50% or more.

18. The component according to claim 1, wherein, The peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern of the yttrium-based protective film is 60% or more.

19. The component according to claim 1, wherein, The substrate is composed of at least one selected from carbon, ceramics, and metals.

20. The component according to claim 19, wherein, The ceramics are alumina or quartz.

21. The component according to claim 1, wherein, The maximum length of the film-forming surface of the substrate is 30 mm or more. The substrate has a first film-forming surface with a specified maximum length and a second film-forming surface different from the first film-forming surface as the film-forming surface. The angle formed by the first film-forming surface and the second film-forming surface is 20° to 120°. The ratio of the area of the second film-forming surface to the total area of the film-forming surface is 60% or less.

22. The component according to claim 1, which is used inside a plasma etching apparatus or a plasma CVD apparatus.

23. A method for manufacturing a component, which is a method for manufacturing the component according to any one of claims 1 to 22, The yttrium-based protective film is formed by irradiating ions of at least one element selected from oxygen, argon, neon, krypton, and xenon while evaporating an evaporation source in a vacuum and attaching the evaporated material to the surface of the stress relaxation layer. Y2O3, or Y2O3 and YF3 are used as the evaporation source.

24. The method for manufacturing a component according to claim 23, wherein, In the formation of the yttrium-based protective film, the temperature of the substrate is 320 °C or higher.

25. The method for manufacturing a component according to claim 23, wherein, Before forming the yttrium-based protective film, one or more of the stress relaxation layers are formed on the surface of the substrate.

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