Yttrium quality protective film, component and method for manufacturing the same

Abstract

A yttrium quality protective film having a fracture toughness value of 0.60 MPam 1 / 2 Hereinafter, the thickness is 10.0 μm or less, the porosity is preferably 0.50% or less by volume, the crystallite size is preferably 6.0 nm to 40.0 nm, the average linear expansion coefficient at 50 to 500°C is preferably 7.0 ppm / K to 10.0 ppm / K, and the number of hydrogen atoms is preferably 5.0 x 10 21 cm 3 Hereinafter, the compressive stress is preferably 100 to 1700 MPa, and the heat resistance temperature is preferably 500°C or higher.

Description

Technical Field

[0001] This invention relates to yttrium protective films, components, and methods for manufacturing the same. Background Technology

[0002] In the manufacture of semiconductor devices, for example, the surface of a semiconductor substrate (silicon wafer) is micro-processed by dry etching using plasma with halogen-based gases in a chamber, or the chamber is cleaned by oxygen plasma after the semiconductor substrate has been removed, following dry etching.

[0003] At this point, components exposed to plasma within the chamber corrode, and the corroded parts detach from the corroded components in particle form. These detached particles (microparticles) may adhere to the semiconductor substrate, becoming foreign matter that can cause circuit defects.

[0004] Therefore, it has long been known that protective films containing yttrium oxide or yttrium fluoride (yttrium protective films) are used as protective films for components exposed to plasma.

[0005] Patent document 1 discloses a thermally sprayed coating containing yttrium oxide or yttrium fluoride formed by thermal spraying.

[0006] Existing technical documents

[0007] Patent documents

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

[0009] The inventors discovered through research that previous yttrium protective films sometimes lacked sufficient thermal cycling resistance and plasma resistance (resistance to plasma corrosion).

[0010] The present invention was made in view of the above circumstances, and its purpose is to provide a yttrium protective film with excellent thermal cycling resistance and plasma resistance.

[0011] After in-depth research, the inventors discovered that the above-mentioned objectives could be achieved by adopting the following configuration, thus completing the present invention.

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

[19] .

[0013] [1] A yttrium protective film with a fracture toughness value of 0.60 MPa. m 1 / 2 Above, the thickness is less than 10.0μm.

[0014] [2] According to the yttrium protective film described in [1] above, the porosity is less than 0.50 by volume.

[0015] [3] The yttrium protective film according to [1] or [2] above, wherein the crystallite size is 6.0 nm to 40.0 nm.

[0016] [4] The yttrium protective film according to any one of [1] to [3] above, wherein the average linear expansion coefficient at 50 to 500°C is 7.0 ppm / K to 10.0 ppm / K.

[0017] [5] The yttrium protective film according to any one of [1] to [4] above, wherein the number of hydrogen atoms is 5.0 × 10⁻⁶. 21 pcs / cm 3 the following.

[0018] [6] The yttrium protective film according to any one of [1] to [5] above, wherein the compressive stress is 100 to 1700 MPa.

[0019] [7] The yttrium protective film according to any one of [1] to [6] above, wherein the heat resistance temperature is 500°C or higher.

[0020] [8] The yttrium protective film according to any one of [1] to [7] above contains Y2O3.

[0021] [9] According to the yttrium protective film described in [8] above, the orientation degree of the (222) plane of the Y2O3 is 50.0% or more.

[0022]

[10] The yttrium protective film according to any one of [1] to [7] above, wherein the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is 60% or more.

[0023]

[11] A component comprising a substrate and any one of the above [1] to

[10] yttrium protective film in sequence.

[0024]

[12] The component according to

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

[0025]

[13] The component according to

[12] above, wherein the ceramic is at least one selected from glass, quartz and cordierite.

[0026]

[14] The component according to any one of

[11] to

[13] above, wherein one or more base layers are provided between the substrate and the yttrium protective film.

[0027]

[15] According to the component described in

[14] above, the substrate layer contains at least one compound selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, Gd2O3, Ta2O3, Nb2O5, HfO2, CeO2, WO3, TiO2, AlON, SiON, AlN and SiN.

[0028]

[16] The component according to any one of

[11] to

[15] above is used inside a plasma processing apparatus.

[0029]

[17] A method for manufacturing a component is a method for manufacturing the component described in any one of

[11] to

[16] above, wherein, in a vacuum, ions of at least one element selected from oxygen, argon, neon, krypton and xenon are irradiated from an ion gun onto the substrate, while an evaporation source is evaporated to form the yttrium protective film, and Y2O3 or Y2O3 and YF3 are used as the evaporation source.

[0030]

[18] In the manufacturing method of the component described in

[17] above, the temperature of the substrate is 200°C or higher during the formation of the yttrium protective film.

[0031]

[19] In the manufacturing method of the component according to

[17] or

[18] above, one or more base layers are formed on the surface of the substrate before the yttrium protective film is formed.

[0032] According to the present invention, a yttrium protective film with excellent thermal cycling resistance and plasma resistance can be provided. Attached Figure Description

[0033] Figure 1 This is a schematic diagram illustrating an example of a component.

[0034] Figure 2 This is a schematic diagram showing a cut in half of the annular substrate.

[0035] Figure 3 This is a schematic diagram showing a portion of the cross-section of another annular substrate.

[0036] Figure 4 This is a schematic diagram showing a portion of the cross-section of another annular substrate.

[0037] Figure 5 This is a schematic diagram showing an apparatus used to manufacture a yttrium protective film. Detailed Implementation

[0038] The terms used in this invention have the following meanings.

[0039] The range of values ​​represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0040] [Yttrium protective film]

[0041] The yttrium protective film of this embodiment has a fracture toughness value of 0.60 MPa. m 1 / 2 The thickness is 10.0 μm or less. Therefore, the yttrium protective film of this embodiment exhibits excellent plasma resistance and thermal cycling resistance.

[0042] <Fracture toughness value>

[0043] The fracture toughness of the yttrium protective film is 0.60 MPa. m 1 / 2 above.

[0044] Due to the superior thermal cycling resistance of yttrium protective films, the preferred fracture toughness value of yttrium protective films is 0.65 MPa. m 1 / 2 The above, more preferably 0.70 MPa m 1 / 2 The above is further preferably 0.75 MPa. m 1 / 2 The above is particularly preferred, with 0.80 MPa. m 1 / 2 The optimal value is 0.85 MPa. m 1 / 2 above.

[0045] There is no specific upper limit; for example, the fracture toughness value of the yttrium protective film is 1.20 MPa. m 1 / 2 The following can be 1.10 MPa m 1 / 2 The following can be 1.00 MPa m 1 / 2 the following.

[0046] The fracture toughness value of the yttrium protective film can be, for example, 0.60–1.20 MPa. m 1 / 2 It can be 0.65~1.10MPa m 1 / 2 It can be 0.70~1.00MPa m 1 / 2 It can be 0.75~1.00MPa m 1 / 2 It can be 0.80~1.00MPa m1 / 2 It can also be 0.85~1.00MPa. m 1 / 2 .

[0047] In this invention, a nanoindenter is used to determine the fracture toughness value (KC) of the yttrium protective film according to the indenter indentation method (IF method) specified in JIS R 1607.

[0048] First, under condition 1, the indenter is pressed into the yttrium protective film, and the Young's modulus and Vickers hardness are determined (ISO 14577 method). Next, under condition 2, the indenter is pressed into another part of the same yttrium protective film, and the fracture toughness value is determined using the data obtained therefrom, along with the previously determined Young's modulus and hardness (IF method).

[0049] The coefficient for the IF method formula is 0.0319.

[0050] Condition 1

[0051] Nanoindentation device: iMicro (manufactured by KLA Corporation)

[0052] Actuator: inForce1000

[0053] Indenter head: Berkovich indenter head

[0054] Measurement mode: Continuous stiffness measurement method (CSM / CSR)

[0055] Maximum load: 1000mN

[0056] Strain rate: 0.2s -1

[0057] Maximum load holding time: 10 seconds

[0058] Poisson's ratio of the sample: 0.25

[0059] Number of measurement points: 12 points each

[0060] Condition 2

[0061] Nanoindentation device: iMicro (manufactured by KLA Corporation)

[0062] Actuator: inForce1000

[0063] Compressor head: Cube Corner Compressor Head

[0064] Measurement mode: Continuous stiffness measurement method (CSM / CSR)

[0065] Maximum indentation depth: 1200nm

[0066] Strain rate: 0.2s -1

[0067] Maximum load holding time: 10 seconds

[0068] <thickness>

[0069] The thickness of the yttrium protective film is less than 10.0 μm.

[0070] Because yttrium protective films exhibit superior plasma resistance and thermal cycling tolerance, the thickness of the yttrium protective film is preferably 8.0 μm or less, more preferably 6.0 μm or less, even more preferably 4.0 μm or less, even more preferably 2.0 μm or less, particularly preferably 0.9 μm or less, and most preferably 0.6 μm or less. The thickness of the aforementioned yttrium protective film can also be 0.5 μm or less.

[0071] There is no specific lower limit. The thickness of the yttrium protective film can be, for example, 0.05 μm or more, 0.1 μm or more, or 0.3 μm or more.

[0072] The thickness of the yttrium protective film can be, for example, 0.05–10.0 μm, 0.1–8.0 μm, 0.3–6.0 μm, 0.3–4.0 μm, 0.3–2.0 μm, 0.3–0.9 μm, or 0.3–0.6 μm.

[0073] The thickness of the yttrium protective film was determined as follows.

[0074] The cross-section of the yttrium protective film was observed using a scanning electron microscope (SEM). The thickness of the yttrium protective film was measured at any 5 points, and the average value of the 5 measurements was taken as the thickness of the yttrium protective film (unit: μm).

[0075] Porosity

[0076] Due to the excellent plasma resistance of yttrium protective films, the porosity of yttrium protective films is preferably less than 0.50% by volume, more preferably less than 0.30% by volume, even more preferably less than 0.20% by volume, and particularly preferably less than 0.10% by volume.

[0077] To achieve a porosity within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0078] The porosity of the yttrium protective film was determined using the following method.

[0079] First, using a focused ion beam (FIB), a portion of the yttrium protective film and the substrate (described later) were beveled 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 was observed at 20,000x magnification using a field emission scanning electron microscope (FE-SEM), and its cross-sectional image was captured.

[0080] Cross-sectional images were taken at multiple locations. Specifically, for example, when the yttrium protective film is circular, images were taken at five points: one at the center of the yttrium protective film surface and four points at a distance of 10 mm from the outer perimeter. The size of the cross-sectional image was 6 μm × 5 μm. When the thickness of the yttrium protective film was greater than 5 μm, cross-sectional images were taken at multiple locations to allow for comprehensive observation of the cross-section of the yttrium protective film along its thickness.

[0081] Next, the obtained cross-sectional images were analyzed using image analysis software (ImageJ, manufactured by the National Institute of Health) to determine the area of ​​the pores in the cross-sectional images. The ratio of the area of ​​the pores to the area of ​​the entire cross-section of the yttrium protective film was calculated and taken as the porosity of the yttrium protective film (unit: volume %). It should be noted that for micropores (pores with a diameter of less than 20 nm) that cannot be detected by the image analysis software, their area is considered to be 0.

[0082] <composition>

[0083] The yttrium protective film may contain either yttrium oxide or yttrium oxyfluoride, or both yttrium oxide and yttrium oxyfluoride.

[0084] Yttrium oxide

[0085] First, let's explain the situation where the yttrium protective film contains yttrium oxide (Y2O3).

[0086] In this case, the Y2O3 content of the yttrium protective film is preferably 95% by mass or more, more preferably 98% by mass or more, and can be 100% by mass.

[0087] The Y2O3 content of the yttrium protective film manufactured using the manufacturing method described later, which uses only Y2O3 as the evaporation source, should meet the above-mentioned range.

[0088] (Orientation degree)

[0089] When increasing the area of ​​the yttrium protective film, from the viewpoint of suppressing the generation of cracks (including wrinkles) in the yttrium protective film, the orientation degree (hereinafter also referred to as "orientation degree") of the (222) plane of Y2O3 in the yttrium protective film is preferably higher.

[0090] Therefore, the orientation degree of the yttrium protective film is, for example, 50.0% or more, preferably 65.0% or more, more preferably 80.0% or more, even more preferably 85.0% or more, even more preferably 90.0% or more, particularly preferably 93.0% or more, even more preferably 95.0% or more, very preferably 98.0% or more, and most preferably 99.0% or more.

[0091] To achieve the orientation within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0092] Orientation degree is the proportion (in %) of the peak intensity of the (222) plane when the total peak intensity of all Y2O3 planes in the XRD pattern of the yttrium protective film is set to 100.

[0093] The XRD pattern of the yttrium protective film (and the substrate layer described later) was obtained by XRD measurement in micro-area 2D (two-dimensional) mode using an X-ray diffraction apparatus (D8 DISCOVERPlus, manufactured by Bruker) under the following conditions.

[0094] X-ray source: CuKα rays (output: 45kV, current: 120mA)

[0095] Scan range: 2θ = 10°~80°

[0096] Step time: 0.2s / step

[0097] Scanning speed: 10° / min

[0098] Step width: 0.02°

[0099] Detector: EIGER multi-mode detector (2D mode)

[0100] Incident-side optical system: multi-layered mirror + 1.0mmφ microslit + 1.0mmφ collimator

[0101] Light-receiving side optical system: OPEN

[0102] Yttrium oxyfluoride

[0103] Next, the situation where the yttrium protective film contains yttrium fluoride will be explained.

[0104] Examples of chemical formulas for yttrium oxyfluoride include YOF and Y5O4F7. YOF is an orthorhombic crystal with low hardness, while Y5O4F7 has a rhombohedral crystal structure and high hardness.

[0105] In this embodiment, the yttrium protective film preferably has a high proportion of Y5O4F7 with a rhombohedral crystal structure. That is, the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is preferably above a certain value. As a result, the yttrium protective film has high hardness, and the Vickers hardness shows a value above a certain value.

[0106] (Peak intensity ratio)

[0107] The peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern of the yttrium protective film (hereinafter also referred to as "Y5O4F7 peak intensity ratio" or simply "peak intensity ratio") is preferably 60% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.

[0108] To ensure that the peak intensity ratio of Y5O4F7 is within the above range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0109] The Y5O4F7 peak intensity ratio is the ratio (in %) of the main peak intensity of Y5O4F7 in the X-ray diffraction (XRD) pattern of the yttrium protective film when the sum of the main peak intensities of the crystalline phases shown below is set to 100.

[0110] For the main peaks of each crystalline phase, Y5O4F7 appears around 2θ=28.1°, Y2O3 appears around 2θ=29.2°, and YOF appears around 2θ=29.2°.

[0111] At the main peak position of Y5O4F7, the peaks of Y6O5F8 crystallization and Y7O6F9 crystallization overlap. Furthermore, the main peak of YF3 also overlaps with the main peak position of Y5O4F7.

[0112] All peaks located at the main peak position of Y5O4F7 are treated as peaks of Y5O4F7.

[0113] When YF3 crystals are present, the peak intensity near 2θ=24.5°, which is the second main peak of YF3 crystals, is multiplied by 1.3 to convert it into the equivalent main peak intensity, and this is taken as the main peak intensity of YF3. At the same time, the intensity of the second main peak of YF3 crystals (converted to 1.3 times the intensity of the main peak of Y5O4F7) is subtracted from the intensity of the peak of Y5O4F7 (the peak located at the position of the main peak of Y5O4F7). Assuming that the intensity (relative intensity) of the second main peak of YF3 crystals is "2.0" and the peak intensity (relative intensity) at the position of the main peak of Y5O4F7 is "6.0", the intensity of the second main peak of YF3 crystals is converted to "2.6" (=2.0×1.3). Therefore, the peak intensity at the position of the main peak of Y5O4F7 minus the converted intensity of the second main peak of YF3 crystals is "3.4" (=6.0-2.6).

[0114] The XRD pattern of the yttrium protective film was obtained by XRD measurement in micro-area 2D (two-dimensional) mode using an X-ray diffraction apparatus (D8 DISCOVER Plus, manufactured by Bruker) under the conditions described above.

[0115] (Content of each element)

[0116] When the yttrium protective film contains yttrium fluoride, it contains yttrium (Y), oxygen (O) and fluorine (F).

[0117] The Y content of the yttrium protective film is preferably 20 atomic% or more, more preferably 25 atomic% or more, further preferably 27.5 atomic% or more, particularly preferably 30 atomic% or more, and most preferably 31 atomic% or more.

[0118] On the other hand, the Y content of the yttrium protective film is preferably 40 atomic% or less, more preferably 35 atomic% or less, even more preferably 33 atomic% or less, and particularly preferably 32 atomic% or less.

[0119] The Y content of the yttrium protective film is preferably 20-40 atomic%, more preferably 25-35 atomic%, further preferably 27.5-33 atomic%, particularly preferably 30-32 atomic%, and most preferably 31-32 atomic.

[0120] The yttrium protective film preferably has an O content of 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.

[0121] On the other hand, the O 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, even more preferably 28 atomic% or less, particularly preferably 27 atomic% or less, and most preferably 26 atomic% or less.

[0122] The O content of the yttrium protective film is preferably 20-35 atoms, more preferably 21-30 atoms, even more preferably 22-29 atoms, even more preferably 23-28 atoms, particularly preferably 24-27 atoms, and most preferably 24-26 atoms.

[0123] The yttrium protective film preferably has an F content of 35 atomic% or more, more preferably 40 atomic% or more, further preferably 41 atomic% or more, particularly preferably 42 atomic% or more, and most preferably 43 atomic% or more.

[0124] On the other hand, the F content of the yttrium protective film is preferably 60 atomic% or less, more preferably 55 atomic% or less, even more preferably 50 atomic% or less, even more preferably 48 atomic% or less, particularly preferably 45 atomic% or less, and most preferably 44.5 atomic% or less.

[0125] The F content of the yttrium protective film is preferably 35-60 atoms, more preferably 40-55 atoms, even more preferably 41-50 atoms, even more preferably 42-48 atoms, particularly preferably 43-45 atoms, and most preferably 43-44.5 atoms.

[0126] In order to make the content of each element within the above range, manufacturing conditions such as the amount of evaporation source may be appropriately adjusted in the manufacturing method described later.

[0127] The content of each element in the yttrium protective film (unit: atomic %) was determined using an energy-dispersive X-ray analyzer (EX-250SE, manufactured by Horiba Corporation).

[0128] <Crystal Size>

[0129] As mentioned above, particles (microparticles) detached from components exposed to plasma may adhere to the semiconductor substrate, becoming foreign matter that causes circuit defects.

[0130] At this point, the smaller the particle size, the better it can suppress the generation of defects.

[0131] Therefore, the crystallite size of the yttrium protective film is preferably 40.0 nm or less, more preferably 30.0 nm or less, even more preferably 20.0 nm or less, particularly preferably 15.0 nm or less, and most preferably 10.0 nm or less.

[0132] On the other hand, the larger the crystallite size of the yttrium protective film, the smaller and more stable the change in crystallite size during heating, and the better the thermal cycling resistance.

[0133] Therefore, the crystallite size of the yttrium protective film is preferably 6.0 nm or more, more preferably 7.0 nm or more, even more preferably 7.5 nm or more, and particularly preferably 8.0 nm or more.

[0134] The crystallite size of the yttrium protective film is preferably 6.0–40.0 nm, more preferably 7.0–30.0 nm, even more preferably 7.5–20.0 nm, particularly preferably 7.5–15.0 nm, and most preferably 8.0–10.0 nm.

[0135] To achieve the crystallite size within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0136] The crystallite size of the yttrium protective film was determined using the Scherrer formula based on the XRD pattern data obtained from XRD measurements of the mirror-polished yttrium protective film.

[0137] <Inflation coefficient>

[0138] Because yttrium protective films have superior thermal cycling resistance, the average linear expansion coefficient (also referred to as "expansion coefficient") of yttrium protective films at 50–500°C is preferably 7.0 ppm / K or higher, more preferably 7.5 ppm / K or higher, and even more preferably 8.0 ppm / K or higher.

[0139] For the same reason, the coefficient of thermal expansion of the yttrium protective film is preferably 10.0 ppm / K or less, more preferably 9.5 ppm / K or less, and even more preferably 9.0 ppm / K or less.

[0140] The coefficient of thermal expansion of the yttrium protective film is preferably 7.0 to 10.0 ppm / K, more preferably 7.5 to 9.5 ppm / K, and even more preferably 8.0 to 9.0 ppm / K.

[0141] The coefficient of thermal expansion of the yttrium protective film was determined using a thermal dilatometer.

[0142] <Number of hydrogen atoms>

[0143] The yttrium protective film preferably contains fewer hydrogen atoms. As a result, the yttrium protective film has excellent plasma resistance.

[0144] The reasoning is speculated as follows: If there is a high hydrogen content in the yttrium protective film, the hydrogen readily reacts with fluorine contained in the plasma (or the gas used to generate the plasma), resulting in easy damage to the yttrium protective film. On the other hand, if there is a low hydrogen content in the yttrium protective film, the reaction with fluorine is relatively reduced, and damage to the yttrium protective film is suppressed.

[0145] Specifically, the preferred number of hydrogen atoms in the yttrium protective film is 5.0 × 10⁻⁶. 21 pcs / cm 3 The following is more preferably 4.5×10 21 pcs / cm 3 The following is a further preferred value: 3.5 × 10⁻⁶21 pcs / cm 3 The following is a further preferred value: 3.0 × 10 21 pcs / cm 3 The following is particularly preferred: 2.5 × 10⁻⁶ 21 pcs / cm 3 The following is particularly preferred: 2.3 × 10⁻⁶ 21 pcs / cm 3 The preferred value is 2.0 × 10⁻⁶. 21 pcs / cm 3 The optimal value is 1.9 × 10⁻⁶. 21 pcs / cm 3 the following.

[0146] It should be noted that the hydrogen in the yttrium protective film is likely influenced by the moisture content in the substrate, as described later. In particular, when the substrate is ceramic, the number of hydrogen atoms in the resulting yttrium protective film can be reduced by heating the substrate before forming the film (preheating).

[0147] On the other hand, the number of hydrogen atoms in the yttrium protective film is preferably 0.1 × 10⁻⁶. 21 pcs / cm 3 The above, more preferably 0.5×10 21 pcs / cm 3 above.

[0148] The preferred number of hydrogen atoms in the yttrium protective film is 0.1 × 10⁻⁶. 21 pcs / cm 3 ~5.0×10 21 pcs / cm 3 More preferably 0.5×10 21 pcs / cm 3 ~4.5×10 21 pcs / cm 3 A further preferred value is 0.5 × 10⁻⁶. 21 pcs / cm 3 ~3.5×10 21 pcs / cm 3 A further preferred value is 0.5 × 10⁻⁶. 21 pcs / cm 3 ~3.0×10 21 pcs / cm 3 The preferred value is 0.5×10. 21 pcs / cm 3 ~2.5×10 21 pcs / cm 3 The preferred value is 0.5×10. 21 pcs / cm 3 ~2.3×10 21 pcs / cm 3The most preferred value is 0.5 × 10⁻⁶. 21 pcs / cm 3 ~2.0×10 21 pcs / cm 3 The optimal value is 0.5 × 10⁻⁶. 21 pcs / cm 3 ~1.9×10 21 pcs / cm 3 .

[0149] The number of hydrogen atoms in the yttrium protective film was determined using a secondary ion mass spectrometry (IMS-6f, Ametek) instrument, with the primary ion species being Cs. + The results were obtained under the conditions of a single accelerating voltage of 15.0 kV, a detection area of ​​φ8 μm, and a measurement depth of 500 nm.

[0150] <Compressive Stress>

[0151] The stress (internal stress, residual stress) of the yttrium protective film is preferably compressive stress rather than tensile stress.

[0152] The compressive stress of the yttrium protective film is preferably 100 MPa or more, more preferably 300 MPa or more, further preferably 500 MPa or more, particularly preferably 700 MPa or more, and most preferably 1200 MPa or more.

[0153] On the other hand, the compressive stress of the yttrium protective film is preferably 1700 MPa or less, more preferably 1600 MPa or less, even more preferably 1500 MPa or less, and particularly preferably 1400 MPa or less.

[0154] The compressive stress of the yttrium protective film is preferably 100-1700 MPa, more preferably 300-1600 MPa, even more preferably 500-1500 MPa, particularly preferably 700-1400 MPa, and most preferably 1200-1400 MPa.

[0155] The compressive stress of the yttrium protective film is obtained as follows.

[0156] 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 241SD2-13, manufactured by Tokyo Seimitsu Co., Ltd.). The compressive stress (film stress σ) of the yttrium protective film is calculated according to the Stoney formula (the following formula).

[0157]

[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 yttrium protective film, and c: radius of curvature.

[0159] <Heat resistance temperature>

[0160] The heat resistance temperature of the yttrium protective film is preferably above 300°C, more preferably above 350°C, even more preferably above 450°C, even more preferably above 500°C, particularly preferably above 550°C, very preferably above 650°C, and most preferably above 750°C.

[0161] In order to achieve the heat resistance temperature within the above range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0162] The heat resistance temperature of the yttrium protective film is determined by performing the following test (heat resistance test).

[0163] First, using an atmospheric sintering furnace, samples of components with a yttrium protective film were heated at a rate of 300°C / hr and then heated at an arbitrary temperature T for 1 hour. Afterward, the samples were cooled at 50°C / hr and removed. Subsequently, an optical microscope was used to confirm whether cracks had formed in the yttrium protective film.

[0164] Such heat resistance tests were conducted at temperatures ranging from 100°C to 800°C (in 50°C increments), and the highest temperature T at which no cracks were produced was taken as the heat resistance temperature of the yttrium protective film.

[0165] [part]

[0166] Next, the components of this embodiment will be described.

[0167] First, based on Figure 1 The components of this embodiment will be described in general terms.

[0168] Figure 1 This is a schematic diagram illustrating an example of component 6.

[0169] Component 6 has at least a substrate 5 and a yttrium protective film 4 in sequence.

[0170] In this embodiment, the yttrium protective film described in this embodiment is used as yttrium protective film 4.

[0171] like Figure 1 As shown, a base layer (base layer 1, base layer 2 and base layer 3) may be disposed between the substrate 5 and the yttrium protective film 4.

[0172] However, the basal layer is not limited to 3 layers.

[0173] Hereinafter, the components included in the components of this embodiment will be described in detail.

[0174] <Substrate>

[0175] The substrate has at least one surface for forming a yttrium protective film (or base layer). Hereinafter, this surface will sometimes be conveniently referred to as the "film-forming surface".

[0176] Material

[0177] The material of the base material is selected appropriately based on the intended use of the component.

[0178] The substrate is composed of at least one selected from carbon (C), ceramics and metals.

[0179] The ceramic is, for example, selected from at least one of glass (soda-lime glass, etc.), quartz, alumina (Al2O3), aluminum nitride (AlN), cordierite, yttrium oxide, silicon carbide (SiC), Si-containing silicon carbide, silicon nitride (SiN), silane, and aluminum oxynitride (AlON).

[0180] Si-containing silicon carbide is obtained by heating and melting elemental Si and then infiltrating it into silicon carbide (SiC).

[0181] As a ceramic material, yttrium protective film has superior thermal cycling resistance, and is preferably selected from at least one of glass, quartz and cordierite, more preferably quartz.

[0182] The metal is, for example, at least one selected from aluminum (Al) and alloys containing aluminum (Al).

[0183] "shape"

[0184] The shape of the substrate is not particularly limited; for example, it can be flat, ring-shaped, dome-shaped, concave, or convex, and the appropriate shape can be selected according to the purpose of the component.

[0185] Surface roughness of the film-forming surface

[0186] The smaller the surface roughness of the substrate's film-forming surface, the easier it is to increase the orientation degree of the yttrium protective film formed on the film-forming surface.

[0187] Therefore, the surface roughness of the film-forming surface of the substrate, measured by arithmetic mean roughness Ra, is preferably less than 1.00 μm, more preferably less than 0.60 μm, even more preferably less than 0.40 μm, particularly preferably less than 0.20 μm, and most preferably less than 0.08 μm.

[0188] On the other hand, there is no particular lower limit. The surface roughness of the substrate film-forming surface, measured by arithmetic mean roughness Ra, is, for example, 0.00005 μm or more, 0.001 μm or more, or 0.01 μm or more.

[0189] The surface roughness of the substrate film-forming surface, measured by the arithmetic mean roughness Ra, can be, for example, greater than or equal to 0.00005 μm and less than 1.00 μm, or 0.001 μm to 0.60 μm, or 0.01 μm to 0.40 μm, or 0.01 μm to 0.20 μm, or 0.01 μm to 0.08 μm.

[0190] The surface roughness (arithmetic mean roughness Ra) of the film-forming surface is determined according to JIS B 0601:2001.

[0191] Maximum length of the film-forming surface

[0192] The maximum length of the film-forming surface of the substrate is preferably 30 mm or more, more preferably 70 mm or more, further preferably 100 mm or more, particularly preferably 150 mm or more, and most preferably 300 mm or more.

[0193] It should be noted that "maximum length" refers to the maximum length of the film-forming surface. Specifically, for example, it is the diameter when the film-forming surface is circular in a plan view, the outer diameter when it is annular in a plan view, and the maximum diagonal length when it is quadrilateral in a plan view.

[0194] 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, further preferably 700 mm or less, and most preferably 500 mm or less.

[0195] The maximum length of the film-forming surface is, for example, 30-2000 mm, preferably 70-1500 mm, more preferably 100-1000 mm, even more preferably 150-700 mm, and most preferably 300-500 mm.

[0196] Figure 2 This is a schematic diagram showing that half of the annular substrate 5 has been cut off.

[0197] for Figure 2 The substrate 5 shown, for example, has a maximum length of 100 mm when the outer diameter D1 is 100 mm, the inner diameter D2 is 90 mm, and the thickness t is 5 mm.

[0198] Substrate 5 has a film-forming surface 7, but as Figure 2 As shown, 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 can be formed.

[0199] The area of ​​the second film-forming surface 7b is, for example, less than 60% of the total area of ​​the film-forming surface 7.

[0200] Figure 3This is a schematic diagram showing a portion of the cross-section of another annular substrate 5.

[0201] like Figure 3 As shown, the substrate 5 may have multiple second film-forming surfaces 7b.

[0202] Figure 4 This is a schematic diagram showing a portion of the cross-section of another annular substrate 5.

[0203] The angle between the first film-forming surface 7a and the second film-forming surface 7b is, for example, 20° to 150°. Figure 4 In the substrate 5 shown, the angle between the first film-forming surface 7a and the second film-forming surface 7b connected to the first film-forming surface 7a is approximately 30°.

[0204] <Basal layer>

[0205] As described above, a base layer can be disposed between the substrate and the yttrium protective film.

[0206] By configuring one or more base layers between the substrate and the yttrium protective film, the tensile stress of the yttrium protective film can be mitigated and compressive stress generated, or the adhesion of the yttrium protective film to the substrate can be improved.

[0207] Number of Layers

[0208] The number of base layers is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and particularly preferably 2 or less.

[0209] "composition"

[0210] The base layer contains, for example, at least one compound (oxide, oxynitride, nitride) selected from Al2O3 (including "β-Al2O3", hereinafter the same), SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, Gd2O3, Ta2O3, Nb2O5, HfO2, CeO2, WO3, TiO2, AlON, SiON, AlN, and SiN.

[0211] The base layer compound can be at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, Gd2O3, Ta2O3, Nb2O5, HfO2, CeO2, WO3, and TiO2.

[0212] The oxide used as the base layer is preferably at least one selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, B2O3 and ZrO2, more preferably at least one selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO and B2O3, and even more preferably at least one selected from Al2O3, SiO2 and Y2O3.

[0213] When the substrate 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 even more preferably 70 / 30 to 40 / 60.

[0214] The compound of the base layer may be at least one oxynitride selected from AlON and SiON, or at least one nitride selected from AlN and SiN.

[0215] Because yttrium protective films have superior thermal cycling resistance, the compound used as the base layer is preferably at least one nitride selected from AlN and SiN.

[0216] When two or more base layers are disposed between the substrate and the yttrium protective film, the compounds (oxides, oxynitrides, nitrides) between adjacent base layers are preferably different from each other.

[0217] Examples of cases where the compounds in adjacent base layers are different include base layer 1 having "SiO2", base layer 2 having "Al2O3+SiO2", and base layer 3 having "Al2O3".

[0218] The content of each compound in the basal layer (in mol%) was determined using an energy-dispersive X-ray analyzer (EX-250SE, manufactured by Horiba Corporation).

[0219] For example, when the molar ratio of Y, Al and Si (Y / Al / Si) is 25 / 25 / 50, and no other elements are detected besides Y, Al, Si and O, the content of Y2O3 is considered to be 25 mol%, the content of Al2O3 is considered to be 25 mol%, and the content of SiO2 is considered to be 50 mol%.

[0220] The State of the Layer

[0221] The substrate layer is preferably an amorphous layer.

[0222] However, the base layer, which is an amorphous layer, can contain crystals.

[0223] "thickness"

[0224] The thickness of each substrate layer 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 0.3 μm or more, and particularly preferably 0.4 μm or more.

[0225] On the other hand, the thickness of each substrate layer is preferably 2.0 μm or less, more preferably 1.8 μm or less, even more preferably 1.6 μm or less, and particularly preferably 1.4 μm or less.

[0226] The thickness of each substrate layer is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.8 μm, even more preferably 0.2 to 1.6 μm, even more preferably 0.3 to 1.4 μm, and particularly preferably 0.4 to 1.4 μm.

[0227] The thickness of the substrate layer was measured in the same way as the thickness of the yttrium protective film.

[0228] <Use of the component>

[0229] The components of this embodiment are used, for example, as top plates or other components inside a plasma processing apparatus.

[0230] Examples of plasma processing devices include plasma etching devices, plasma CVD devices, plasma ALD devices, and plasma modification devices, which are used, for example, in the manufacture of semiconductor devices.

[0231] However, the uses of the components are not limited to these.

[0232] [Manufacturing method of yttrium protective film and components]

[0233] Next, the method for manufacturing the yttrium protective film of this embodiment will be described.

[0234] The following description also serves as an explanation of the manufacturing method of the components in this embodiment.

[0235] In this embodiment, ion-assisted vapor deposition (IAD) is used.

[0236] In general, in a vacuum, ions are irradiated onto the substrate while the evaporation source (Y2O3, YF3, etc.) evaporates, thereby forming a yttrium protective film.

[0237] A very dense yttrium protective film can be formed using the IAD method. That is, the resulting yttrium protective film has low porosity.

[0238] In contrast, yttrium protective films obtained by methods such as thermal spraying, aerosol deposition (AD), and ion plating (IP) tend to have more residual pores.

[0239] <Device Structure>

[0240] Figure 5 This is a schematic diagram showing an apparatus used to manufacture a yttrium protective film.

[0241] Figure 5 The device shown has a chamber 11. A vacuum can be created by venting the interior of the chamber 11 by driving a vacuum pump (not shown).

[0242] Inside chamber 11 are arranged crucibles 12 and 13, and ion gun 14, with a holder 17 positioned above these components.

[0243] The retainer 17 is integrated with the support shaft 16 and rotates as the support shaft 16 rotates. A heater 15 is arranged around the retainer 17.

[0244] The substrate 5 is held in the holder 17 with its film-forming surface facing down. The substrate 5 held in the holder 17 rotates as the holder 17 rotates while being heated by the heater 15.

[0245] In addition, crystal film thickness monitors 18 and 19 are installed in chamber 11.

[0246] <Formation of Yttrium Protective Film (Part 1)>

[0247] For Figure 5 In the apparatus shown, a yttrium protective film containing yttrium oxide (Y₂O₃) is formed on substrate 5. Figure 5 The following explanation will be provided for cases not shown in the diagram.

[0248] First, fill one or both of crucibles 12 and 13 with the evaporation source Y2O3.

[0249] After holding the substrate 5 in the holder 17, the interior of the chamber 11 is vented to create a vacuum.

[0250] Next, the heater 15 is driven while the retainer 17 is rotated. Thus, the substrate 5 is heated and rotated simultaneously.

[0251] Ion-assisted evaporation is performed in this state to form a film on substrate 5.

[0252] That is, while irradiating ions (ion beam) from ion gun 14, the evaporation source Y2O3 filled in one or both of crucibles 12 and 13 is evaporated.

[0253] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0254] In this way, the evaporation source of the evaporation adheres to the film-forming surface of the substrate 5 (or, if there is a base layer, the surface), forming a yttrium protective film containing yttrium oxide (Y2O3).

[0255] The ions irradiated by the ion gun 14 are preferably ions selected from at least one element selected from oxygen, argon, neon, krypton and xenon.

[0256] The ions used for irradiation by the ion gun 14 are preferably ions selected from at least two elements chosen from oxygen, argon, neon, krypton and xenon, and are even more preferably ions that use both oxygen and argon.

[0257] Intracavitary pressure

[0258] Film formation is carried out in a vacuum; specifically, the pressure inside chamber 11 is preferably 6 × 10⁻⁶. -2 Pa or less, more preferably 5×10 Pa -2 Pa or less, more preferably 3×10 Pa -2 Below Pa.

[0259] On the other hand, the pressure inside chamber 11 is preferably higher than 1×10 -6 Pa, preferably 1×10 -5 Pa or higher, more preferably 1×10 Pa -4 Pa or above.

[0260] The internal pressure of chamber 11 is preferably higher than 1×10 -6 Pa and is 6 × 10 -2 Pa or less, more preferably 1×10 Pa -5 Pa ~ 5 × 10 -2 Pa, more preferably 1×10 -4 Pa~3×10 -2 Pa.

[0261] Temperature of the substrate

[0262] Because it is easy to form a yttrium protective film with excellent resistance to plasma and thermal cycling, the temperature of the substrate 5 heated by the heater 15 during film formation is preferably 200°C or higher, more preferably 250°C or higher, even more preferably 300°C or higher, particularly preferably 350°C or higher, and most preferably 400°C or higher.

[0263] On the other hand, the temperature is preferably below 700°C, more preferably below 650°C, and even more preferably below 600°C.

[0264] The above-mentioned temperature is preferably 200-700℃, more preferably 250-650℃, further preferably 300-600℃, particularly preferably 350-600℃, and most preferably 400-600℃.

[0265] Film Formation Speed

[0266] The rate at which the evaporation source in crucibles 12 and 13 evaporates and forms a film (film formation rate) is monitored in advance using crystal film thickness monitors 18 and 19, respectively.

[0267] The film formation rate is adjusted by controlling the conditions of the electron beam irradiating the evaporation source and the conditions of the ion beam of the ion gun 14 (current value, current density, etc.).

[0268] During the formation of the yttrium protective film, the film formation rate (unit: nm / min) of each evaporation source is adjusted to the required value.

[0269] The film formation rate of the evaporation source Y2O3 is preferably 1.00 nm / min or higher, more preferably 1.50 nm / min or higher, and even more preferably 2.00 nm / min or higher.

[0270] The film formation rate of the evaporation source Y2O3 is preferably 20.00 nm / min or less, more preferably 15.00 nm / min or less, even more preferably 10.00 nm / min or less, even more preferably 5.00 nm / min or less, and particularly preferably 3.50 nm / min or less.

[0271] The film-forming rate of the evaporation source Y2O3 is preferably 1.00-20.00 nm / min, more preferably 1.50-15.00 nm / min, even more preferably 2.00-10.00 nm / min, even more preferably 2.00-5.00 nm / min, and particularly preferably 2.00-3.50 nm / min.

[0272] Ionizing Irradiation Conditions

[0273] Because it is easy to form a yttrium protective film with excellent thermal cycling resistance, the distance between the ion gun 14 and the substrate 5 is preferably 700 mm or more, more preferably 750 mm or more, even more preferably 800 mm or more, and particularly preferably 850 mm or more.

[0274] For the same reason, the distance between the ion gun 14 and the substrate 5 is preferably 1050 mm or less, and more preferably 1000 mm or less.

[0275] The distance between the ion gun 14 and the substrate 5 is preferably 700-1050 mm, more preferably 750-1000 mm, further preferably 800-1000 mm, and particularly preferably 850-1000 mm.

[0276] The current value of the ion beam is preferably 1000mA or more, and more preferably 1500mA or more.

[0277] On the other hand, the current value of the ion beam is preferably 3000mA or less, and more preferably 2500mA or less.

[0278] The preferred current value of the ion beam is 1000-3000 mA, more preferably 1500-2500 mA.

[0279] The preferred current density of the ion beam is 40 μA / cm. 2 The above is preferred, and more preferably is 65 μA / cm. 2 The above is further preferred to be 75 μA / cm. 2 The above is particularly preferred, with 77 μA / cm. 2 above.

[0280] On the other hand, the preferred current density of the ion beam is 140 μA / cm. 2 Below, 120 μA / cm is more preferred. 2 Hereinafter, 100 μA / cm is further preferred. 2 the following.

[0281] The preferred current density of the ion beam is 40–140 μA / cm. 2 More preferably 65–120 μA / cm 2 More preferably 75–100 μA / cm 2 Especially preferred is 77–100 μA / cm 2 .

[0282] "Ar / O Ratio"

[0283] As described above, argon ions and oxygen ions are preferably used simultaneously as the ions irradiated from the ion gun 14.

[0284] At this point, 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 more, even more preferably greater than 4 / 50, and particularly preferably 5 / 50 or more.

[0285] 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.

[0286] The Ar / O ratio is preferably greater than 2 / 50 and less than 25 / 50, more preferably 4 / 50 to 20 / 50, even more preferably greater than 4 / 50 and less than 15 / 50, and particularly preferably 5 / 50 to 12 / 50.

[0287] The Ar / O ratio is the amount of argon (Ar) ions (unit: W / m³) irradiated from the ion gun 14 onto the substrate 5. 2 The amount of oxygen (O) ions (unit: W / m³) irradiated from ion gun 14 onto substrate 5. 2 The ratio of ).

[0288] Here, "W / m" 2 "Ion flux" is a unit representing the kinetic energy (ion flux) that passes through a unit area per unit time.

[0289] <Formation of Yttrium Protective Film (Part 2)>

[0290] Next, it will be explained that a yttrium protective film containing yttrium fluoride is formed on substrate 5. Figure 5 (The situation is not illustrated in the figure).

[0291] First, an evaporation source Y2O3 is filled in one crucible 12, and an evaporation source YF3 is filled in another crucible 13.

[0292] After holding the substrate 5 in the holder 17, the interior of the chamber 11 is vented to create a vacuum.

[0293] Next, the heater 15 is driven while the retainer 17 is rotated. Thus, the substrate 5 is heated and rotated simultaneously.

[0294] Ion-assisted evaporation is performed in this state to form a film on substrate 5.

[0295] That is, while ionizing (ion beam) from ion gun 14, the evaporation source Y2O3 of crucible 12 and the evaporation source YF3 of crucible 13 are evaporated in parallel.

[0296] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0297] In this way, the evaporation source of the evaporation adheres to the film-forming surface of the substrate 5 (or, if there is a base layer, the surface itself), forming a yttrium protective film containing yttrium fluoride.

[0298] The ions irradiated by the ion gun 14 are the same as those used to form a yttrium protective film containing yttrium oxide (Y2O3).

[0299] Film Formation Speed

[0300] The film-forming rate ratio (Y2O3 / YF3) of the evaporation source Y2O3 (unit: nm / min) to the film-forming rate of the evaporation source YF3 (unit: nm / min) is preferably 1 / 9.5 or more, more preferably 1 / 8.0 or more, even more preferably 1 / 6.0 or more, even more preferably 1 / 4.5 or more, particularly preferably 1 / 2.0 or more, and most preferably 1 / 1.9 or more.

[0301] On the other hand, the film-forming rate ratio (Y2O3 / YF3) is preferably 1 / 1.0 or less, more preferably 1 / 1.1 or less, even more preferably 1 / 1.2 or less, even more preferably 1 / 1.3 or less, particularly preferably 1 / 1.4 or less, very preferably 1 / 1.5 or less, and most preferably 1 / 1.6 or less.

[0302] The film-forming rate ratio (Y2O3 / YF3) is preferably 1 / 9.5 to 1 / 1.0, more preferably 1 / 8.0 to 1 / 1.1, even more preferably 1 / 6.0 to 1 / 1.2, even more preferably 1 / 4.5 to 1 / 1.3, particularly preferably 1 / 2.0 to 1 / 1.4, very preferably 1 / 1.9 to 1 / 1.5, and most preferably 1 / 1.9 to 1 / 1.6.

[0303] The combined film-forming rate of the evaporation source Y2O3 and the film-forming rate of the evaporation source YF3 is preferably 5.00 nm / min or higher, more preferably 8.00 nm / min or higher, and even more preferably 10.00 nm / min or higher.

[0304] On the other hand, the total speed is preferably 50.00 nm / min or less, more preferably 35.00 nm / min or less, and even more preferably 20.00 nm / min or less.

[0305] The total velocity is preferably 5.00 to 50.00 nm / min, more preferably 8.00 to 35.00 nm / min, and even more preferably 10.00 to 20.00 nm / min.

[0306] The chamber pressure, substrate temperature, ion irradiation conditions, and Ar / O ratio for forming a yttrium protective film containing yttrium fluoride oxide are the same as those for forming a yttrium protective film containing yttrium oxide (Y2O3).

[0307] <Formation of the basal layer>

[0308] Before forming the yttrium protective film, one or more base layers (e.g., base layer 1, base layer 2 and base layer 3) can be formed on the film-forming surface of the substrate 5.

[0309] The substrate layer, like the yttrium protective film, is formed by ion-assisted evaporation.

[0310] For example, when forming a substrate layer composed of SiO2, SiO2 is filled in one or both of crucibles 12 and 13 as an evaporation source, and while ions (ion beam) are irradiated from ion gun 14, the evaporation source evaporates and adheres to the film-forming surface of substrate 5.

[0311] Furthermore, for example, when forming a substrate layer containing Y2O3 and SiO2, Y2O3 is filled in crucible 12 as an evaporation source and SiO2 is filled in crucible 13 as an evaporation source. While irradiating ions (ion beam) from ion gun 14, the evaporation source evaporates and adheres to the film-forming surface of substrate 5.

[0312] The conditions for forming the base layer are the same as those for forming the yttrium protective film.

[0313] In addition, the substrate sometimes contains water of crystallization.

[0314] If the water originating from the substrate's water of crystallization is included in the formed yttrium protective film, the number of hydrogen atoms in the yttrium protective film is likely to increase.

[0315] Therefore, it is preferable to form a base layer on the film-forming surface of the substrate before the evaporation source Y2O3 is attached to the film-forming surface of the substrate (i.e., to form a yttrium protective film).

[0316] Therefore, since at least the film-forming surface of the substrate is covered, the water of crystallization of the substrate is not easily contained in the formed yttrium protective film, resulting in a reduction in the number of hydrogen atoms in the yttrium protective film, which is therefore preferred.

[0317] <Preheating of substrate>

[0318] Since the crystal water of the substrate is not easily contained in the yttrium protective film, it is preferable to heat the substrate at a high temperature (preheating) before forming the yttrium protective film.

[0319] 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.

[0320] On the other hand, the preheating temperature is, for example, below 800°C, preferably below 750°C, and more preferably below 700°C.

[0321] The preheating temperature is preferably 300–800°C, more preferably 400–750°C, even more preferably 450–700°C, and particularly preferably 500–700°C.

[0322] 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.

[0323] 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.

[0324] The preheating time is preferably 60 to 1200 minutes, more preferably 120 to 1000 minutes, even more preferably 240 to 800 minutes, and particularly preferably 480 to 600 minutes.

[0325] The preheated atmosphere is, for example, an atmospheric atmosphere.

[0326] Example

[0327] The present invention will now be specifically described by way of examples. However, the present invention is not limited to the examples described below.

[0328] Hereinafter, Examples 3 to 8 are examples, and Examples 1 to 2 and Examples 9 to 11 are comparative examples.

[0329] 〈Example 1~Example 11〉

[0330] Use based on Figure 5 The apparatus described herein manufactures components with a yttrium protective film under the conditions shown in Table 1 below.

[0331] As a substrate, a circular substrate (thickness: 10 mm) with a film-forming surface having a diameter (maximum length) as shown in Table 1 below is used.

[0332] With the substrate held in the holder within the cavity, preheating is performed under atmospheric conditions at the preheating temperatures shown in Table 1 below. The preheating time is 600 minutes.

[0333] Next, under the manufacturing conditions shown in Table 1 below, the IAD method is used to sequentially form the base layer and the yttrium protective film containing yttrium oxide shown in Table 1 below on the film-forming surface of the substrate.

[0334] If no basal layer has formed, it will be recorded as "-" in the corresponding column of Table 1 below.

[0335] As for the manufacturing conditions not described in Table 1 below, the current value of the ion beam is 2000mA.

[0336] During the formation of the yttrium protective film, argon (Ar) ions and oxygen (O) ions are irradiated from the ion gun onto the substrate, with an Ar / O ratio of 6 / 50.

[0337] During the formation of the basal layer, oxygen (O) ions are irradiated only from the ion gun.

[0338] The composition of the basal layer is described in Table 1 below.

[0339] Regarding the base layer, for example, "30Y2O3+70SiO2" means that the content of Y2O3 is 30mol% and the content of SiO2 is 70mol%.

[0340] Furthermore, for the basal layer and yttrium protective film, the items listed in Table 1 below were determined using the methods described above. The results are shown in Table 1 below. Items not measured are marked as "-" in the corresponding column of Table 1 below.

[0341] <Etching amount>

[0342] Ion etching was performed on the yttrium protective films of each example to evaluate their plasma resistance.

[0343] Specifically, firstly, a 10mm × 5mm section of the yttrium protective film is mirror-finished, and then a portion of the mirror-finished section (referred to as the "test section") is covered with Capton tape for masking.

[0344] Next, a CCP-type plasma etching apparatus was used to discharge in the gas under a pressure of 10 Pa and an RF power of 600 W, thereby generating plasma. The test surface was then exposed to the generated plasma to carry out the test (exposure test).

[0345] More specifically, a discharge (plasma generation) is performed using CF4 gas (flow rate: 100 sccm) and O2 gas (flow rate: 100 sccm), generating CF4 ions in the plasma.

[0346] The 15-minute discharge (plasma generation) was repeated 10 times, for a total of 150 minutes of exposure testing. In this way, the unshielded parts of the test surface were etched.

[0347] The etching amount was then determined by measuring the step difference between the shaded and unshaded portions of the test surface using a stylus-type surface shape measuring machine (ULVAC, Dektak 150). The results are shown in Table 1 below.

[0348] The smaller the etching amount (unit: nm), the better the plasma resistance.

[0349] Thermal cycling test

[0350] Using an electric furnace (SS-2030PKP, manufactured by Tokyo Motoyama Shokai Co., Ltd.), the components for each example were heated at a rate of 4°C / min and heated at an arbitrary temperature T1 for 3 hours, then cooled at a rate of 4°C / min. This was considered one cycle, and the process was repeated 10 times.

[0351] Such thermal cycling tests were performed at the temperature T1 shown in Table 1 below.

[0352] Subsequently, an optical microscope was used to confirm whether cracks had formed in the yttrium protective film. No cracks were recorded as "A", and cracks were recorded as "B", as shown in Table 1 below.

[0353] When no cracks are generated at temperature T1, it is evaluated as having superior thermal cycling resistance.

[0354]

[0355] <Summary of Evaluation Results>

[0356] As shown in Table 1 above, the yttrium protective films of Examples 3 to 8 exhibit good plasma resistance and thermal cycling resistance. In contrast, the yttrium protective films of Examples 1 to 2 and Examples 9 to 11 show insufficient thermal cycling resistance.

[0357] Although the invention has been described in detail with reference to specific methods, 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.

[0358] It should be noted that this application is based on Japanese patent application (Japanese Patent Application No. 2024-024616) filed on February 21, 2024, the contents of which are incorporated herein by reference.

[0359] Symbol Explanation

[0360] 1, 2, 3: Basal layer

[0361] 4: Yttrium protective film

[0362] 5: Substrate

[0363] 6: Components

[0364] 7: Film-forming surface

[0365] 7a: First film-forming surface

[0366] 7b: Second film-forming surface

[0367] 11: Chamber

[0368] 12, 13: Crucible

[0369] 14: Ion gun

[0370] 15: Heater

[0371] 16: Support shaft

[0372] 17: Retainer

[0373] 18, 19: Crystal-type film thickness monitor

Claims

1. A yttrium protective film with a fracture toughness value of 0.60 MPa. m 1 / 2 above, The thickness is less than 10.0 μm.

2. The yttrium protective film according to claim 1 has a porosity of less than 0.50% by volume.

3. The yttrium protective film according to claim 1 has a crystallite size of 6.0 nm to 40.0 nm.

4. The yttrium protective film according to claim 1 has an average linear expansion coefficient of 7.0 ppm / K to 10.0 ppm / K at 50 to 500°C.

5. The yttrium protective film according to claim 1, wherein the number of hydrogen atoms is 5.0 × 10⁻⁶. 21 pcs / cm 3 the following.

6. The yttrium protective film according to claim 1 has a compressive stress of 100-1700 MPa.

7. The yttrium protective film according to claim 1 has a heat resistance temperature of 500°C or higher.

8. The yttrium protective film according to claim 1, comprising Y2O3.

9. The yttrium protective film according to claim 8, wherein, The orientation degree of the (222) plane of the Y2O3 is above 50.0%.

10. The yttrium protective film according to claim 1, wherein, The peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is above 60%.

11. A component comprising a substrate and a yttrium protective film according to any one of claims 1 to 10.

12. The component according to claim 11, wherein, The substrate is composed of at least one selected from carbon, ceramics and metals.

13. The component according to claim 12, wherein, The ceramic is at least one selected from glass, quartz, and cordierite.

14. The component according to claim 11, wherein, There is one or more base layers between the substrate and the yttrium protective film.

15. The component according to claim 14, wherein, The substrate layer contains at least one compound selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, Gd2O3, Ta2O3, Nb2O5, HfO2, CeO2, WO3, TiO2, AlON, SiON, AlN, and SiN.

16. The component according to claim 11, used inside a plasma processing apparatus.

17. A method for manufacturing a component, which is the method for manufacturing the component according to claim 11. In a vacuum, while irradiating the substrate with ions selected from at least one element chosen from oxygen, argon, neon, krypton, and xenon from an ion gun, the evaporation source is evaporated to form the yttrium protective film. Furthermore, Y2O3, or a combination of Y2O3 and YF3, is used as the evaporation source.

18. The method for manufacturing the component according to claim 17, wherein, During the formation of the yttrium protective film, the temperature of the substrate is above 200°C.

19. The method for manufacturing the component according to claim 17, wherein, Before forming the yttrium protective film, one or more base layers are formed on the surface of the substrate.

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