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

Abstract

An object of the present application is to provide a yttria protective film having excellent plasma resistance. The present application relates to a yttria protective film having a porosity of less than 1.5 vol%, a Young's modulus of 100.00 GPa or more, and a Vickers hardness of 8.50 GPa or more, and a member having the above yttria protective film.

Description

Technical Field

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

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

[0003] At this point, components exposed to plasma within the chamber corrode, and sometimes the corroded parts detach from the corroded components in the form of particles. These detached particles adhere to the semiconductor substrate and become foreign matter that causes circuit defects.

[0004] Therefore, in the past, protective films containing yttrium oxide or yttrium oxyfluoride (yttrium protective films) have been known as protective films for components exposed to plasma.

[0005] Patent document 1 discloses a thermally sprayed coating containing yttrium oxide or yttrium oxyfluoride 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 conducted research and found that conventional yttrium protective films have insufficient plasma resistance (resistance to plasma corrosion).

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

[0011] The inventors conducted in-depth research and found 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

[30] .

[0013] [1] A yttrium protective film with a porosity of less than 1.5% by volume, a Young's modulus of 100.00 GPa or more, and a Vickers hardness of 8.50 GPa or more.

[0014] [2] According to the yttrium protective film described in [1] above, the Young's modulus / Vickers hardness is 16.5 or less.

[0015] [3] The yttrium protective film according to [1] or [2] above contains 0.10 to 3.00 atomic percent argon.

[0016] [4] The yttrium protective film according to any one of [1] to [3] above, wherein it contains 5 atomic% or more of yttrium.

[0017] [5] The yttrium protective film according to any one of [1] to [4] above, wherein it contains 25 to 65 atomic percent fluorine.

[0018] [6] The yttrium protective film according to any one of [1] to [5] above, wherein the ratio of fluorine content to oxygen content, i.e., the F / O ratio, is less than 2.80. Wherein, the units for both fluorine content and oxygen content are atomic percent.

[0019] [7] The yttrium protective film according to any one of [1] to [6] above, wherein the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is 60% or more.

[0020] [8] The yttrium protective film according to any one of [1] to [7] above, wherein the crystallite size is 5 to 30 nm.

[0021] [9] The yttrium protective film according to any one of [1] to [8] above, wherein the thickness is 0.01 to 30.0 μm.

[0022]

[10] A component comprising a substrate and any one of the above [1] to [9] yttrium protective film.

[0023]

[11] According to the component described in

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

[0024]

[12] According to the component described in

[11] above, wherein the Vickers hardness HV2 of the second film is y of the Vickers hardness HV1 of the first film. A Within a range of ±40%. Specifically, within the range where the angle between the first film-forming surface and the second film-forming surface is set to 0° to 90°. A At x A When the angle is 0 to 60°, y is calculated according to the following formula (1). A , in x A When the angle is greater than 60° and less than 90°, y is calculated according to the following formula (2). A .

[0025] (1) y A= -0.00034751x A 2 +0.01538782x A +1.00625521

[0026] (2) y A = -0.00197743x A +0.75229358

[0027]

[13] According to the component described in

[11] or

[12] above, wherein the thickness t2 of the second film is y of the thickness t1 of the first film. B Within a range of ±40%. Specifically, within the range where the angle between the first film-forming surface and the second film-forming surface is set to 0–170°. B At x B When the angle is 0 to 90°, y is calculated according to the following formula (3). B , in x B When the angle is greater than 90° and less than 170°, y is calculated according to the following formula (4). B .

[0028] (3) y B = -0.00012389x B 2 +0.00659698x B +0.99721254

[0029] (4) y B = -0.00005913x B 2 +0.01099778x B -0.26784922

[0030]

[14] The component according to any one of

[11] to

[13] above, wherein the crystallite size S2 of the second film is y of the crystallite size S1 of the first film. C Within a range of ±40%. Specifically, within the range where the angle between the first film-forming surface and the second film-forming surface is set to 0–170°. C When, y is calculated according to the following formula (5). C .

[0031] (5) y C =0.00009729x C 2 -0.00273425x C +0.99976959

[0032]

[15] The component according to any one of

[11] to

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

[0033]

[16] The component according to any one of

[11] to

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

[0034]

[17] The component according to any one of

[11] to

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

[0035]

[18] The component according to any one of

[11] to

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

[0036]

[19] The component according to any one of

[11] to

[18] above, wherein the angle between the first film-forming surface and the second film-forming surface is 90°, and the ratio of the crystallite size S1 of the first film to the crystallite size S2 of the second film, i.e., the S1 / S2 ratio, is 0.35 to 0.90. Wherein, the unit of crystallite size is nm.

[0037]

[20] According to the component described in

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

[0038]

[21] According to the component described in

[19] or

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

[0039]

[22] The component according to any one of

[10] to

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

[0040]

[23] The component according to any one of

[10] to

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

[0041]

[24] The component according to any one of

[10] to

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

[0042]

[25] According to the component described in

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

[0043]

[26] The component according to any one of

[10] to

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

[0044]

[27] The component according to any one of

[10] to

[26] above, wherein there is one or more base layers between the substrate and the yttrium protective film, and the base layer contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3 and Gd2O3.

[0045]

[28] The component according to any one of

[10] to

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

[0046]

[29] A method for manufacturing a yttrium protective film is a method for manufacturing a yttrium protective film as described in any one of [1] to [9] above, wherein, in a vacuum, an evaporation source is evaporated and attached to a substrate while irradiating ions of at least one element selected from oxygen, argon, neon, krypton and xenon from an ion gun, and Y2O3 or Y2O3 and YF3 are used as the evaporation source.

[0047]

[30] In the method for manufacturing the yttrium protective film according to

[29] above, at least argon ions are irradiated from the ion gun toward the substrate.

[0048] According to the present invention, a yttrium protective film with excellent plasma resistance can be provided. Attached Figure Description

[0049] Figure 1 This is a schematic diagram representing an example of a component.

[0050] Figure 2 This is a schematic diagram showing that half of the annular substrate has been cut off.

[0051] Figure 3 This is a schematic diagram showing a portion of the cross-section of another annular substrate.

[0052] Figure 4 This is a schematic diagram showing a portion of the cross-section of another annular substrate.

[0053] Figure 5This is a schematic diagram showing the apparatus used in the manufacture of yttrium protective films.

[0054] Figure 6 This is a schematic diagram showing a substrate having a first film-forming surface and a second film-forming surface. Detailed Implementation

[0055] The meanings of the terms used in this invention are as follows.

[0056] The range of values ​​represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits.

[0057] [Yttrium protective film]

[0058] The yttrium protective film of this embodiment exhibits excellent plasma resistance due to its porosity of less than 1.5% by volume, Young's modulus of 100.00 GPa or higher, and Vickers hardness of 8.50 GPa or higher.

[0059] The yttrium protective film of this embodiment will be described in more detail below.

[0060] Porosity

[0061] Based on the excellent plasma resistance of yttrium protective films, the porosity of yttrium protective films is less than 1.5% by volume, preferably less than 1.0% by volume, more preferably less than 0.5% by volume, further preferably less than 0.3% by volume, particularly preferably less than 0.2% by volume, and most preferably less than 0.1% by volume.

[0062] To achieve a porosity within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0063] The porosity of the yttrium protective film is calculated as follows.

[0064] First, using a focused ion beam (FIB), a bevel process was performed on a portion of the yttrium protective film and the substrate at a 52° angle in the thickness direction, exposing the cross-section. The exposed cross-section was then observed at 20,000x magnification using a field emission scanning electron microscope (FE-SEM), and cross-sectional images were captured.

[0065] Cross-sectional images are taken at multiple locations. Specifically, for example, when the yttrium protective film is circular, images are taken at five points: one at the center of the surface and four at points 10 mm from the outer perimeter. The cross-sectional image size is 6 μm × 5 μm. When the thickness of the yttrium protective film is 5 μm or more, cross-sectional images are taken at multiple locations to allow observation of the entire cross-section of the yttrium protective film in the thickness direction.

[0066] Next, the area of ​​the pores in the obtained cross-sectional images was determined by analyzing the images using image analysis software (ImageJ, manufactured by the National Institute of Health). The ratio of the pore area to the total cross-sectional area of ​​the yttrium protective film was calculated and used as the porosity (in volume %) of the yttrium protective film. 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 was considered to be 0.

[0067] Young's Modulus

[0068] Based on the excellent plasma resistance of yttrium protective films, the Young's modulus of the yttrium protective film is 100.00 GPa or more, preferably 110.00 GPa or more, more preferably 120.00 GPa or more, and even more preferably 130.00 GPa or more.

[0069] On the other hand, the Young's modulus of the yttrium protective film is, for example, 250.00 GPa or less, preferably 200.00 GPa or less.

[0070] The Young's modulus of the yttrium protective film was determined at 20°C using the dynamic elastic modulus test method (ultrasonic pulse method) described in the Japanese Industrial Standard (JIS R1602:1995).

[0071] Vickers hardness

[0072] Based on the excellent plasma resistance of yttrium protective films, the Vickers hardness of the yttrium protective film is 8.50 GPa or higher, preferably 9.50 GPa or higher, more preferably 10.50 GPa or higher, even more preferably 11.50 GPa or higher, and particularly preferably 12.50 GPa or higher.

[0073] On the other hand, the Vickers hardness of the yttrium protective film is, for example, 20.00 GPa or less, preferably 18.00 GPa or less.

[0074] To achieve the Vickers hardness within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0075] The Vickers hardness of the yttrium protective film was measured using a nanoindenter (iMicro, KLA). More specifically, the nanoindentation hardness (unit: GPa) was measured by varying the load between 0 and 50 mN. Measurements were performed at 20 sites, and the average value was taken as the Vickers hardness.

[0076] Other experimental conditions are as follows.

[0077] As a nanoindentation testing machine, the "iMicro" manufactured by KLA Corporation is used to fix the sample (a yttrium protective film disposed on the surface of the substrate) on its sample stage.

[0078] The samples were fixed using Aremco's thermoplastic temporary adhesive "CRYSTALBOND 555" (flowing temperature: 48°C).

[0079] As an actuator, select "inForce50", which can be used in the range of loads below 50mN.

[0080] As the indenter, a Berkovich indenter with a triangular pyramidal front end (front end curvature radius: 20nm) is used.

[0081] Young's modulus / Vickers hardness

[0082] Based on the excellent plasma resistance of the yttrium protective film, in the yttrium protective film of this embodiment, the ratio of Young's modulus (unit: GPa) to Vickers hardness (unit: GPa) (Young's modulus / Vickers hardness) is preferably 16.5 or less, more preferably 15.5 or less, even more preferably 14.5 or less, and particularly preferably 13.5 or less.

[0083] On the other hand, based on the reason that the yttrium protective film will not become brittle, the ratio (Young's modulus / Vickers hardness) is preferably 8.0 or higher, and more preferably 9.0 or higher.

[0084] <Ar content>

[0085] In this embodiment, the yttrium protective film contains a certain amount of argon (Ar). As a result, the yttrium protective film has a relatively high Vickers hardness.

[0086] First, in this embodiment, the yttrium protective film is formed by ion-assisted vapor deposition (IAD). IAD is a method in which ions are irradiated in a vacuum while the evaporation source is evaporated and adhered to the substrate.

[0087] At this point, for example, when irradiated with high-energy argon (Ar) instead of just oxygen (O) ions, the bombardment intensity of the evaporated source on the substrate increases.

[0088] This results in the formation of a yttrium protective film containing Ar, and it is speculated that the Vickers hardness of the formed yttrium protective film is increased.

[0089] Specifically, based on the reason for the increased Vickers hardness of the yttrium protective film, the argon content (Ar content) in the yttrium protective film is preferably 0.10 atomic% or more, more preferably 0.15 atomic% or more, and even more preferably 0.20 atomic% or more.

[0090] However, if the Ar content of the yttrium protective film is too high, the Vickers hardness of the yttrium protective film is prone to decrease.

[0091] Therefore, the Ar content of the yttrium protective film is preferably 3.00 atomic% or less, more preferably 2.00 atomic% or less, even more preferably 1.50 atomic% or less, particularly preferably 1.00 atomic% or less, and most preferably 0.50 atomic% or less.

[0092] That is, the Ar content in the yttrium protective film is preferably 0.10 to 3.00 atomic%.

[0093] The method for determining the Ar content of the yttrium protective film will be described later.

[0094] <composition>

[0095] In this embodiment, based on the excellent plasma resistance of the yttrium protective film, the yttrium content of the yttrium protective film is preferably 5 atomic% or more, more preferably 10 atomic% or more, and even more preferably 20 atomic% or more. From the viewpoint of improving electrical insulation, the yttrium content of the yttrium protective film is preferably 70 atomic% or less, more preferably 60 atomic% or less, and even more preferably 50 atomic% or less.

[0096] In this embodiment, the yttrium protective film preferably contains, for example, yttrium oxide or yttrium oxyfluoride.

[0097] The following sections will explain the different cases where the yttrium protective film contains yttrium oxide or yttrium oxyfluoride.

[0098] Yttrium oxide

[0099] First, the case where the yttrium protective film contains yttrium oxide (Y2O3) will be explained.

[0100] In this case, the Y2O3 content of the yttrium protective film is preferably 95% by mass or more, and more preferably 98% by mass or more.

[0101] The yttrium protective film manufactured using the method described later, which uses only Y2O3 as the evaporation source, has a Y2O3 content that meets the above-mentioned range.

[0102] (Orientation degree)

[0103] In the case of making the yttrium protective film large-area, from the viewpoint of suppressing the generation of cracks (including wrinkles) in the yttrium protective film, it is preferable that the orientation degree (hereinafter also simply referred to as "orientation degree") of the (222) crystal plane of Y2O3 in the yttrium protective film is high.

[0104] Therefore, the orientation degree of the yttrium protective film is preferably 50% or more, more preferably 65% ​​or more, further preferably 80% or more, even more preferably 85% or more, particularly preferably 90% or more, even more preferably 95% or more, very preferably 98% or more, and most preferably 99% or more.

[0105] To achieve the orientation within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0106] Orientation degree is the percentage (in %) of the peak intensity of the (222) crystal plane when the sum of the peak intensities of all planes of Y2O3 is set to 100 in the XRD pattern of the yttrium protective film.

[0107] The XRD patterns of the yttrium protective film (and the substrate layer described later) were obtained by XRD determination in micro-area 2D (two-dimensional) mode using an X-ray diffraction apparatus (D8 DISCOVER Plus, manufactured by Bruker) under the conditions described below.

[0108] • X-ray source: CuKα rays (output: 45kV, current: 120mA)

[0109] • Scanning range: 2θ = 10°~80°

[0110] • Step time: 0.2s / step

[0111] • Scanning speed: 10° / min

[0112] • Step size: 0.02°

[0113] • Detector: EIGER multi-mode detector (2D mode)

[0114] • Incident-side optical system: Multilayer mirror + 1.0mmφ microslit + 1.0mmφ collimator

[0115] • Receiver-side optical system: OPEN

[0116] Yttrium oxyfluoride

[0117] Next, we will explain the case where the yttrium protective film contains yttrium oxyfluoride.

[0118] Examples of chemical formulas for yttrium oxyfluoride include YOF and Y5O4F7. YOF is an orthorhombic crystal with relatively low hardness, while Y5O4F7 has a special rhombohedral crystal structure with higher hardness.

[0119] In this embodiment, the yttrium protective film preferably contains a higher 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 is relatively hard, and its Vickers hardness is above a certain value.

[0120] (Peak intensity ratio)

[0121] 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.

[0122] To achieve the peak intensity ratio of Y5O4F7 within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0123] The Y5O4F7 peak intensity ratio is the ratio (in %) of the main peak intensity of Y5O4F7 when the sum of the main peak intensities of the crystalline phases shown below is set to 100 in the X-ray diffraction (XRD) pattern of the yttrium protective film.

[0124] 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°.

[0125] The peaks of Y6O5F8 and Y7O6F9 crystals overlap at the main peak position of Y5O4F7. Furthermore, the main peak of YF3 also overlaps at the main peak position of Y5O4F7.

[0126] All peaks located at the main peak position of Y5O4F7 are treated as peaks of Y5O4F7.

[0127] In the presence of YF3 crystal, the intensity of the second main peak of YF3 crystal, i.e., the peak near 2θ = 24.5°, is multiplied by 1.3 to convert it into the equivalent main peak intensity, which is then taken as the main peak intensity of YF3. At this point, the intensity of the second main peak of YF3 crystal (converted to the 1.3-fold equivalent) is subtracted from the intensity of the peak of Y5O4F7 (the peak located at the main peak position of Y5O4F7). Assuming the relative intensity of the second main peak of YF3 crystal is "2.0", and the relative intensity of the peak located at the main peak position of Y5O4F7 is "6.0", the intensity of the second main peak of YF3 crystal is converted to "2.6" (= 2.0 × 1.3). Therefore, the intensity of the peak located at the main peak position of Y5O4F7 minus the converted intensity of the second main peak of YF3 crystal is "3.4" (= 6.0 - 2.6).

[0128] 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.

[0129] (Content of each element)

[0130] In the case of yttrium oxyfluoride, the yttrium protective film contains yttrium (Y), oxygen (O) and fluorine (F).

[0131] The Y content of the yttrium 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.

[0132] On the other hand, the Y content of the yttrium protective film is preferably 35 atomic% or less, more preferably 30 atomic% or less, even more preferably 29 atomic% or less, and particularly preferably 28 atomic% or less.

[0133] 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.

[0134] 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 28 atomic% or less, particularly preferably 26 atomic% or less, and most preferably 25 atomic% or less.

[0135] The yttrium protective film has an F content of, for example, 25 atomic% or more, 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.

[0136] On the other hand, the F content of the yttrium protective film is, for example, 65 atomic% or less, preferably 60 atomic% or less, more preferably 55 atomic% or less, even more preferably 52 atomic% or less, even more preferably 50 atomic% or less, particularly preferably 49.5 atomic% or less, and most preferably 49 atomic% or less.

[0137] 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.

[0138] 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).

[0139] (F / O ratio)

[0140] The ratio of F content (atomic %) to O content (atomic %) in the yttrium protective film, i.e., the F / O ratio, is preferably less than 2.80, more preferably less than 2.50, and even more preferably less than 2.15.

[0141] On the other hand, the F / O ratio of the yttrium protective film is preferably greater than 1.50, more preferably greater than 1.70, and even more preferably greater than 1.90.

[0142] (Orientation: half-width at half-maximum of the oscillating curve)

[0143] From the viewpoint of suppressing crack formation in the yttrium protective film, it is preferable that the orientation degree (hereinafter also referred to as "orientation degree") of the (151) crystal plane of Y5O4F7 in the yttrium protective film is high.

[0144] The full width at half maximum (FWHM) of the rocking curve of the (151) crystal plane of Y5O4F7 is used as an indicator of orientation. 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 its FWHM is used to evaluate orientation. It can be said that the smaller the FWHM (unit: °), the higher the orientation.

[0145] The half-width at half-maximum (WHM) of the rocking curve of the (151) crystal plane of Y5O4F7 is preferably 40° or less, more preferably 30° or less, even more preferably 25° or less, even more preferably 20° or less, particularly preferably 15° or less, and most preferably 10° or less.

[0146] To achieve the orientation within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0147] <Crystal Size>

[0148] As described above, for example, particles (granules) detached from components exposed to plasma can adhere to semiconductor substrates and become foreign objects that cause circuit defects.

[0149] At this point, the smaller the particle size, the better it can suppress the generation of defects.

[0150] Therefore, the crystallite size of the yttrium protective film is preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less.

[0151] On the other hand, the larger the crystallite size of the yttrium protective film, the smaller and more stable the change in crystallite size when heated, thus improving its heat resistance.

[0152] Therefore, the crystallite size of the yttrium protective film is preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more.

[0153] Therefore, the crystallite size of the yttrium protective film is preferably 5 to 30 nm.

[0154] To achieve the crystallite size within the aforementioned range, it is preferable to manufacture the yttrium protective film using the manufacturing method described later.

[0155] The crystallite size in the yttrium protective film was determined using the Scherrer formula based on the XRD pattern data obtained from the XRD measurement of the mirror-polished yttrium protective film.

[0156] <thickness>

[0157] The thickness of the yttrium protective film is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.5 μm or more, particularly preferably 1.0 μm or more, and most preferably 2.0 μm or more.

[0158] On the other hand, the thickness of the yttrium protective film is preferably 30.0 μm or less, more preferably 25.0 μm or less, even more preferably 20.0 μm or less, particularly preferably 15.0 μm or less, and most preferably 10.0 μm or less.

[0159] Therefore, the thickness of the yttrium protective film is preferably 0.01 to 30.0 μm.

[0160] The thickness of the yttrium protective film was measured as follows.

[0161] 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).

[0162] <Compressive Stress>

[0163] The stress (internal stress, residual stress) of the yttrium protective film is not tensile stress, but preferably compressive stress.

[0164] The compressive stress of the yttrium protective film is preferably 100 MPa or more, more preferably 300 MPa or more, even more preferably 500 MPa or more, and particularly preferably 700 MPa or more.

[0165] On the other hand, the compressive stress of the yttrium protective film is preferably 1700 MPa or less, more preferably 1600 MPa or less, and even more preferably 1500 MPa or less.

[0166] The compressive stress of the yttrium protective film is calculated as follows.

[0167] A yttrium protective film is formed on a quartz glass substrate. The surface shape of the formed yttrium protective film is measured using a surface shape measuring device (Surfcom NEX 241 SD2-13, manufactured by Tokyo Seimitsu Co., Ltd.). The compressive stress (film stress σ) of the yttrium protective film is calculated according to the Stoney formula (hereinafter).

[0168] σ=Yd 2 / (6c(1-ν)t)

[0169] 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.

[0170] [part]

[0171] Next, the components will be explained.

[0172] First, based on Figure 1 A brief description of the components is provided.

[0173] Figure 1 This is a schematic diagram showing an example of component 6.

[0174] Component 6 has at least a substrate 5 and a yttrium protective film 4 in sequence.

[0175] For example, the yttrium protective film of this embodiment described above is used as yttrium protective film 4.

[0176] like Figure 1 As shown, a base layer (base layer 1, base layer 2 and base layer 3) can be disposed between the substrate 5 and the yttrium protective film 4.

[0177] However, the basal layer is not limited to three layers.

[0178] The following is a detailed description of each component.

[0179] <Substrate>

[0180] The substrate has at least one surface on which a yttrium protective film (or base layer) is formed. Hereinafter, for convenience, this surface will sometimes be referred to as the "film-forming surface".

[0181] Material

[0182] The material of the base material can be selected appropriately according to the purpose of the component.

[0183] The substrate is composed of at least one of, for example, carbon (C), ceramics and metals.

[0184] Here, ceramics are, for example, selected from at least one of glass (soda-lime glass, etc.), quartz, alumina (Al2O3), aluminum nitride (AlN), silicon carbide impregnated with Si, and aluminum oxynitride (AlON).

[0185] Silicon carbide impregnated with Si is obtained by heating and melting elemental Si and then impregnating it with silicon carbide (SiC).

[0186] The metal is, for example, at least one selected from aluminum (Al) and alloys containing aluminum (Al). Al is preferred as the metal.

[0187] "shape"

[0188] 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.

[0189] Surface roughness of the film-forming surface

[0190] The surface roughness of the film-forming surface of the substrate, measured by arithmetic mean roughness Ra, is preferably 3.00 μm or less, more preferably 2.50 μm or less, even more preferably 1.50 μm or less, even more preferably 1.00 μm or less, particularly preferably 0.60 μm or less, even more preferably 0.40 μm or less, very preferably 0.20 μm or less, and most preferably 0.08 μm or less.

[0191] On the other hand, the surface roughness of the film-forming surface of the substrate, measured by arithmetic mean roughness Ra, is preferably 0.001 μm or more, and more preferably 0.01 μm or more.

[0192] The surface roughness (arithmetic mean roughness Ra) of the film-forming surface was measured according to JIS B 0601:2001.

[0193] Maximum length of the film-forming surface

[0194] The maximum length of the film-forming surface of the substrate is preferably 30 mm or more, more preferably 70 mm or more, even more preferably 100 mm or more, and particularly preferably 150 mm or more.

[0195] It should be noted that "maximum length" refers to the maximum length of the film-forming surface. Specifically, for example, when the film-forming surface is a circle viewed from above, it is its diameter; when it is an annular shape viewed from above, it is its outer diameter; and when it is a quadrilateral viewed from above, it is the length of the longest diagonal.

[0196] On the other hand, the maximum length of the film-forming surface is, for example, 2000 mm or less, preferably 1500 mm or less, more preferably 1000 mm or less, even more preferably 700 mm or less, and most preferably 500 mm or less.

[0197] Figure 2 This is a schematic diagram showing that half of the annular substrate 5 has been cut off.

[0198] for Figure 2 The substrate 5 shown, for example, has an outer diameter D1 of 100 mm, an inner diameter D2 of 90 mm, and a thickness t of 5 mm, and its maximum length is 100 mm.

[0199] Substrate 5 has a film-forming surface 7, or it can be like... Figure 2 The diagram shows a first film-forming surface 7a and a second film-forming surface 7b that is different from the first film-forming surface 7a. The first film-forming surface 7a, for example, defines the maximum length (outer diameter D1) of the film-forming surface 7.

[0200] 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.

[0201] Figure 3 This is a schematic diagram showing a portion of the cross-section of another annular substrate 5.

[0202] like Figure 3 As shown, the substrate 5 may have multiple second film-forming surfaces 7b.

[0203] Figure 4 This is a schematic diagram showing a portion of the cross-section of another annular substrate 5.

[0204] <Basal layer>

[0205] As described above, one or more base layers can be disposed between the substrate and the yttrium protective film.

[0206] By forming a base layer, the tensile stress of the yttrium protective film is mitigated, thereby generating compressive stress and increasing the adhesion between the yttrium protective film and the substrate.

[0207] Number of Layers

[0208] There is no particular upper limit to the number of base layers, but it is preferred to have 5 or fewer layers, more preferably 4 or fewer layers, even more preferably 3 or fewer layers, particularly preferably 2 or fewer layers, and most preferably 1 layer.

[0209] The State of the Layer

[0210] The substrate layer is preferably an amorphous layer or a microcrystalline layer (an amorphous layer containing crystals).

[0211] "composition"

[0212] The substrate layer preferably contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

[0213] When two or more base layers are disposed between the substrate and the yttrium protective film, the oxides of the base layers are preferably different from each other in adjacent base layers.

[0214] In the case where adjacent substrate layers have different oxides, for example, substrate 1 has an oxide of "SiO2", substrate 2 has an oxide of "Al2O3 + SiO2" and substrate 3 has an oxide of "Al2O3".

[0215] "thickness"

[0216] The thickness of the 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 0.5 μm or more, particularly preferably 0.8 μm or more, and most preferably 1.1 μm or more.

[0217] On the other hand, the thickness of the substrate layer is, for example, 15.0 μm or less, preferably 10.0 μm or less, more preferably 7.0 μm or less, even more preferably 5.0 μm or less, and particularly preferably 3.0 μm or less.

[0218] The thickness of the substrate was measured in the same manner as the thickness of the yttrium protective film.

[0219] <Use of the component>

[0220] The components in this embodiment are used, for example, as top plates or other components inside semiconductor device manufacturing apparatus (plasma etching apparatus, plasma CVD apparatus, etc.).

[0221] However, its uses are not limited to this.

[0222] [Manufacturing method of yttrium protective film and components]

[0223] Next, the method for manufacturing the yttrium protective film of this embodiment will be described.

[0224] The following description also serves as a description of the method for manufacturing the components of this embodiment.

[0225] This embodiment uses ion-assisted vapor deposition (IAD).

[0226] In general, in a vacuum, ions are irradiated while the evaporation source (Y2O3, YF3, etc.) evaporates and adheres to the substrate, thereby forming a yttrium protective film.

[0227] By using the IAD method, a very dense yttrium protective film can be formed. That is, the resulting yttrium protective film has a low porosity.

[0228] In contrast, yttrium protective films obtained by methods such as thermal spraying, aerosol deposition (AD), and ion plating (IP) are prone to having many residual pores.

[0229] <Device Composition>

[0230] Figure 5 This is a schematic diagram showing the apparatus used in the manufacture of yttrium protective films.

[0231] Figure 5 The device shown has a chamber 11. The interior of chamber 11 can be evacuated by driving a vacuum pump (not shown) to create a vacuum.

[0232] The chamber 11 contains crucibles 12 and 13, as well as an ion gun 14, and a support 17 is positioned above them.

[0233] The bracket 17 is integrated with the support shaft 16 and rotates as the support shaft 16 rotates. A heater 15 is arranged around the bracket 17.

[0234] The substrate 5 is held on the support 17 with its film-forming surface facing downwards. The substrate 5 held on the support 17 is heated by the heater 15 and rotates as the support 17 rotates.

[0235] In addition, crystal film thickness monitors 18 and 19 are installed in chamber 11.

[0236] <Formation of Yttrium Protective Film (Part 1)>

[0237] 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.

[0238] First, fill one or both of crucibles 12 and 13 with the evaporation source Y2O3.

[0239] After holding the substrate 5 in the support 17, the interior of the chamber 11 is vented to create a vacuum.

[0240] Next, the heater 15 is driven while the support 17 is rotated. Thus, the substrate 5 is heated and rotated at the same time.

[0241] In this state, ion-assisted evaporation is performed to form a film on substrate 5.

[0242] That is, while ion gun 14 irradiates ions (ion beam), the evaporation source Y2O3 filled in one or both of crucibles 12 and 13 evaporates.

[0243] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0244] Thus, the evaporated evaporation source is attached to the film-forming surface of the substrate 5 (or, if a base layer is present, its surface) to form a yttrium protective film containing yttrium oxide (Y2O3).

[0245] 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, and more preferably argon ions.

[0246] The ions irradiated by the ion gun 14 are preferably ions selected from at least two elements chosen from oxygen, argon, neon, krypton and xenon, and even more preferably ions using both oxygen and argon.

[0247] It is speculated that the resulting yttrium protective film contains a certain amount of argon (Ar).

[0248] Intracavitary pressure

[0249] Film formation is carried out in a vacuum. Specifically, based on the premise that the porosity of the formed yttrium protective film is reduced, the internal pressure of chamber 11 is preferably 6 × 10⁻⁶. －2 Below Pa, 5×10 －2 More preferably, for Pa below 3×10 Pa, is 3×10 Pa. －2 Pa or less is preferred.

[0250] On the other hand, the pressure inside chamber 11 is preferably greater than 1×10⁻⁶. －6 Pa, preferably 1×10 －5 Pa or higher, more preferably 1×10 Pa －4 Pa or above.

[0251] Temperature of the substrate

[0252] During film formation, the temperature of the substrate 5 heated by the heater 15 is preferably 200°C or higher, more preferably 270°C or higher, even more preferably 320°C or higher, particularly preferably 370°C or higher, and most preferably 400°C or higher.

[0253] On the other hand, the temperature is preferably below 600°C, more preferably below 500°C, and even more preferably below 450°C.

[0254] Film Formation Speed

[0255] Beforehand, crystal film thickness monitors 18 and 19 were used to monitor the rate at which the film was formed by evaporation of the evaporation source in crucibles 12 and 13 (film formation rate).

[0256] 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.).

[0257] In the formation of the yttrium protective film, the film formation rate (unit: nm / min) of each evaporation source is adjusted to the desired value.

[0258] The film formation rate of the evaporation source Y2O3 is preferably 1 nm / min or higher, more preferably 1.5 nm / min or higher, and even more preferably 2 nm / min or higher.

[0259] The film formation rate of the evaporation source Y2O3 is preferably 20 nm / min or less, more preferably 15 nm / min or less, even more preferably 10 nm / min or less, even more preferably 5 nm / min or less, particularly preferably 3.5 nm / min or less, and most preferably 2.1 nm / min or less.

[0260] Conditions for Ion Irradiation

[0261] 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.

[0262] The current value of the ion beam is preferably 1000 mA or more, and more preferably 1500 mA or more. On the other hand, the current value of the ion beam is preferably 3000 mA or less, and more preferably 2500 mA or less.

[0263] The preferred ion beam current density is 40 μA / cm. 2 The above, more preferably 65 μA / cm 2 The above is further preferably 75 μA / cm. 2 The above is particularly preferred, with 77 μA / cm. 2 That's all. On the other hand, the preferred ion beam current density is 140 μA / cm². 2 Below, 120 μA / cm is more preferred. 2 Hereinafter, 100 μA / cm is further preferred. 2 the following.

[0264] "Ar / O Ratio"

[0265] As described above, the ions irradiated by the ion gun 14 are preferably argon ions and oxygen ions.

[0266] At this point, the ratio of argon (Ar) ions to oxygen (O) ions, i.e., the Ar / O ratio, is preferably greater than 2 / 50, more preferably 4 / 50 or more, even more preferably greater than 4 / 50, even more preferably 5 / 50 or more, particularly preferably 6 / 50 or more, even more preferably 7 / 50 or more, very preferably 8 / 50 or more, and most preferably 10 / 50 or more.

[0267] 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.

[0268] The Ar / O ratio is the amount of argon (Ar) ions (unit: W / m³) irradiated by ion gun 14 toward substrate 5. 2 The amount of oxygen (O) ions (unit: W / m³) irradiated by the ion gun 14 toward the substrate 5. 2 The ratio of ).

[0269] Here, "W / m" 2 "Ion energy flux" is a unit representing the kinetic energy (ion energy flux) that passes through a unit area per unit time.

[0270] <Formation of Yttrium Protective Film (Part 2)>

[0271] Next, a yttrium protective film containing yttrium oxyfluoride is formed on substrate 5. Figure 5 The following explanation will be provided for cases not shown in the diagram.

[0272] First, evaporation source Y2O3 is filled into one crucible 12, and evaporation source YF3 is filled into the other crucible 13.

[0273] After holding the substrate 5 in the support 17, the interior of the chamber 11 is vented to create a vacuum.

[0274] Next, the heater 15 is driven while the support 17 is rotated. This causes the substrate 5 to rotate while being heated.

[0275] In this state, ion-assisted evaporation is performed to form a film on substrate 5.

[0276] That is, while ions (ion beam) are irradiated by ion gun 14, the evaporation source Y2O3 of crucible 12 and the evaporation source YF3 of crucible 13 are evaporated simultaneously.

[0277] The evaporation source is melted and evaporated by irradiating an electron beam (not shown).

[0278] Thus, the evaporated evaporation source is attached to the film-forming surface of the substrate 5 (or, if a base layer is present, its surface) to form a yttrium protective film containing yttrium oxyfluoride.

[0279] The ions irradiated by the ion gun 14 form a yttrium protective film containing yttrium oxide (Y2O3).

[0280] Film Formation Speed

[0281] The ratio of the film-forming rate (Y2O3 / YF3) of the evaporation source Y2O3 to the film-forming rate (YF3 / Y2O3) of the evaporation source YF3 is preferably 1 / 9.5 or more, more preferably 1 / 8.0 or more, even more preferably 1 / 6.0 or more, and particularly preferably 1 / 4.5 or more.

[0282] On the other hand, the film-forming rate ratio (Y2O3 / YF3) is preferably 1 / 1.1 or less, more preferably 1 / 1.3 or less, even more preferably 1 / 1.8 or less, and particularly preferably 1 / 2.5 or less.

[0283] The combined film-forming rate of the evaporation source Y2O3 and the film-forming rate of the evaporation source YF3 is preferably 5 nm / min or more, more preferably 8 nm / min or more, and even more preferably 10 nm / min or more. On the other hand, this combined rate is preferably 50 nm / min or less, more preferably 35 nm / min or less, and even more preferably 20 nm / min or less.

[0284] "Intracavitary pressure, substrate temperature, ion irradiation conditions, and Ar / O ratio"

[0285] The chamber pressure, substrate temperature, ion irradiation conditions, and Ar / O ratio during the formation of a yttrium protective film containing yttrium oxyfluoride are determined according to the conditions for forming a yttrium protective film containing yttrium oxide (Y2O3).

[0286] <Formation of the basal layer>

[0287] Preferably, the aforementioned base layer (e.g., base layer 1, base layer 2, and base layer 3) is formed on the film-forming surface of the substrate 5 before the yttrium protective film is formed.

[0288] The substrate layer and the yttrium protective film are both formed by ion-assisted evaporation.

[0289] For example, when forming a substrate layer composed of Al2O3, Al2O3 is filled into one or both of crucibles 12 and 13 as an evaporation source, and while ion gun 14 irradiates ions (ion beam), the evaporation source evaporates and adheres to the film-forming surface of substrate 5.

[0290] The conditions for forming the base layer are the same as those for forming the yttrium protective film.

[0291] However, the substrate sometimes contains water of crystallization.

[0292] For example, when an alumina (Al2O3) substrate is heated from room temperature, the formation of water of crystallization caused by hydrates of a low-temperature stable phase of alumina (such as boehmite γ-alumina) is observed around 520°C.

[0293] When moisture caused by the crystal water of the substrate is present in the formed yttrium protective film, the number of hydrogen atoms in the yttrium protective film tends to increase.

[0294] Therefore, a base layer is formed 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).

[0295] As a result, at least the film-forming surface of the substrate is covered, so the water of crystallization of the substrate is less likely to exist in the formed yttrium protective film, thereby reducing the number of hydrogen atoms in the yttrium protective film, which is therefore preferred.

[0296] <Preheating of the substrate>

[0297] Based on the reason that the crystal water of the substrate is not easily present in the yttrium protective film, it is preferable to heat the substrate at a high temperature (preheating) before forming the yttrium protective film.

[0298] 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.

[0299] On the other hand, the preheating temperature is, for example, below 800°C, preferably below 750°C, and more preferably below 700°C.

[0300] 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.

[0301] 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.

[0302] The preheated atmosphere is, for example, an atmospheric atmosphere.

[0303] Angle Dependency

[0304] Figure 6 This is a schematic diagram showing a substrate 5 having a first film-forming surface 7a and a second film-forming surface 7b.

[0305] Figure 6 The substrate 5 shown is in chamber 11 ( Figure 6 (Not shown in the figure) The first film-forming surface 7a is held on the support 17 in a downward-facing position. Other configurations are based on... Figure 5The apparatus described is the same, therefore the description is omitted.

[0306] The angle θ formed by the first film-forming surface 7a and the second film-forming surface 7b is, for example, 0° or more, preferably 10° or more. On the other hand, the angle θ is, for example, 180° or less, preferably 170° or less, and more preferably 160° or less. The angle θ may also be 90°.

[0307] A yttrium protective film is formed on the film-forming surfaces (first film-forming surface and second film-forming surface) of the substrate using the manufacturing method described above.

[0308] The yttrium protective film formed on the first film-forming surface is called the "first film", and the yttrium protective film formed on the second film-forming surface is called the "second film".

[0309] The first membrane is, for example, the yttrium protective membrane described in this embodiment.

[0310] The second membrane is, for example, a yttrium protective membrane that is different from the first membrane.

[0311] It should be noted that the substrate has at least a first film-forming surface and a second film-forming surface as film-forming surfaces, and may further have other film-forming surfaces.

[0312] Vickers Hardness of Yttrium Protective Films

[0313] The Vickers hardness HV2 of the second membrane is preferably a fraction of the Vickers hardness HV1 of the first membrane. A The range is within ±40%, more preferably within ±30%, and even more preferably within ±20%.

[0314] Among them, the angle θ between the first film-forming surface and the second film-forming surface is set to 0 to 90°. A At x A When the angle is 0 to 60°, y is calculated according to the following formula (1). A , in x A When the angle is greater than 60° and less than 90°, y is calculated according to the following formula (2). A .

[0315] (1) y A = -0.00034751x A 2 +0.01538782x A +1.00625521

[0316] (2) y A = -0.00197743x A +0.75229358

[0317] When the angle θ between the first film-forming surface and the second film-forming surface is 90°, the ratio of the Vickers hardness HV1 of the first film to the Vickers hardness HV2 of the second film, i.e., the HV1 / HV2 ratio, is preferably 1.05 or more, more preferably 1.20 or more, and even more preferably 1.35 or more. On the other hand, in this case, the HV1 / HV2 ratio is preferably 2.50 or less, more preferably 2.30 or less, and even more preferably 2.10 or less.

[0318] Thickness of Yttrium Protective Film

[0319] The thickness t2 of the second membrane is preferably a fraction of the thickness t1 of the first membrane. B The range is within ±40%, more preferably within ±30%, and even more preferably within ±20%.

[0320] Among them, the angle θ between the first film-forming surface and the second film-forming surface is set to 0 to 170°. B At x B When the angle is 0 to 90°, y is calculated according to the following formula (3). B , in x B When the angle is greater than 90° and less than 170°, y is calculated according to the following formula (4). B .

[0321] (3) y B = -0.00012389x B 2 +0.00659698x B +0.99721254

[0322] (4) y B = -0.00005913x B 2 +0.01099778x B -0.26784922

[0323] The thickness t1 of the first membrane is likely to be greater than the thickness t2 of the second membrane.

[0324] Specifically, when the angle θ between the first film-forming surface and the second film-forming surface is 90°, the ratio of the thickness t1 (unit: μm) of the first film to the thickness t2 (unit: μm) of the second film, i.e., the t1 / t2 ratio, is preferably 1.5 or more, and more preferably 1.6 or more.

[0325] On the other hand, in this case, the t1 / t2 ratio is, for example, 3.5 or less, preferably 3.0 or less.

[0326] However, when the angle θ between the first film-forming surface and the second film-forming surface is 90°, the surface of the substrate opposite to the second film-forming surface ( Figure 6The surface 7c in the middle sometimes becomes the second film-forming surface, forming a second film (yttrium protective film).

[0327] In this case, the t1 / t2 ratio is larger, specifically, preferably 2.0 or more, more preferably 3.0 or more, and even more preferably 4.0 or more. On the other hand, in this case, the t1 / t2 ratio is, for example, 6.0 or less, preferably 5.5 or less.

[0328] Microcrystal Size of Yttrium Protective Films

[0329] The crystallite size S2 of the second membrane is preferably a fraction of the crystallite size S1 of the first membrane. C The range is within ±40%, more preferably within ±30%, and even more preferably within ±20%.

[0330] Among them, the angle θ between the first film-forming surface and the second film-forming surface is set to 0 to 170°. C When, y is calculated according to the following formula (5). C .

[0331] (5) y C =0.00009729x C 2 -0.00273425x C +0.99976959

[0332] The crystallite size S1 of the first membrane is easily smaller than the crystallite size S2 of the second membrane.

[0333] Specifically, when the angle θ between the first film-forming surface and the second film-forming surface is 90°, the ratio of the crystallite size S1 (unit: nm) of the first film to the crystallite size S2 (unit: nm) of the second film, i.e., the S1 / S2 ratio, is preferably 0.90 or less, more preferably 0.80 or less, and even more preferably 0.70 or less.

[0334] On the other hand, in this case, the S1 / S2 ratio is, for example, 0.35 or more, preferably 0.45 or more.

[0335] In this case, the crystallite size S1 of the first film is preferably less than 20 nm, more preferably less than 18 nm, and even more preferably less than 15 nm. The crystallite size S2 of the second film is preferably 15 nm or more, more preferably 17 nm or more, and even more preferably 18 nm or more.

[0336] Example

[0337] The present invention will now be specifically described with reference to specific embodiments. However, the present invention is not limited to the embodiments described below.

[0338] Hereinafter, Examples 1 to 21 are examples, and Examples 22 to 24 are comparative examples.

[0339] 〈Example 1~Example 24〉

[0340] Use based on Figure 5 The apparatus described herein manufactures components having a yttrium protective film under the conditions shown in Tables 1 to 3 below.

[0341] A plate-shaped substrate with film-forming surfaces (first film-forming surface and second film-forming surface) having values ​​shown in Tables 1 to 3 below is used as the substrate. More specifically, a substrate that is bent midway along its long side to form the first film-forming surface (length: 100 mm) and the second film-forming surface (length: 100 mm) is used. The angle θ (unit: °) between the first film-forming surface and the second film-forming surface is described in Tables 1 to 3 below.

[0342] The substrate was preheated in an atmospheric atmosphere while held in a support position within the cavity. The preheating temperature was 550°C, and the preheating time was 600 minutes.

[0343] Next, using the IAD method, a base layer and a yttrium protective film (first film and second film) as shown in Tables 1 to 3 are formed on the film-forming surfaces (first film-forming surface and second film-forming surface) of the substrate under the manufacturing conditions shown in Tables 1 to 3 below.

[0344] It should be noted that the second film in Example 5 refers to the side opposite to the second film-forming surface connected to the first film-forming surface (equivalent to...). Figure 6 A yttrium protective film (second film) is formed on the surface 7c of the film. Therefore, the "angle" column of the "film-forming surface" in Tables 1 to 3 below is recorded as "back side".

[0345] If no basal layer has been formed, it will be recorded as "-" in the corresponding column of Tables 1 to 3 below.

[0346] When forming a yttrium protective film, argon (Ar) ions and oxygen (O) ions are irradiated onto the substrate by an ion gun at the Ar / O ratio shown in Tables 1 to 3 below.

[0347] During the formation of the basal layer, oxygen (O) ions are irradiated only by an ion gun.

[0348] As for the manufacturing conditions not listed in Tables 1 to 3 below, the distance between the ion gun and the substrate is 1100 mm, and the current value of the ion beam is 2000 mA.

[0349] The composition of the base layer and the yttrium protective film is described in Tables 1 to 3 below.

[0350] When forming a yttrium protective film containing yttrium oxide, its composition is recorded as "Y2O3" in Tables 1 to 3 below.

[0351] When forming a yttrium protective film containing yttrium oxyfluoride, the composition is recorded in Tables 1 to 3 below as determined by the content of each element (Y, O, F, etc.).

[0352] In Example 13, an Al2O3 substrate layer was formed by anodizing one side of an aluminum (Al) substrate. This substrate layer is referred to as "anodized" in Tables 1 to 3 below.

[0353] In addition, for the base layer and yttrium protective film, the items (Ar content, etc.) listed in Tables 1 to 3 below were determined using the methods described above. The results are shown in Tables 1 to 3 below.

[0354] It should be noted that compressive stress is recorded as a negative value.

[0355] For yttrium protective films (first film and second film), the values ​​shown in Tables 1 to 3 below are for the first film unless otherwise specified.

[0356] It should be noted that the composition of the second membrane is the same as that of the first membrane.

[0357] <Etching amount>

[0358] Ion etching was performed on the yttrium protective films of each example to evaluate plasma resistance.

[0359] Specifically, firstly, a 10mm × 5mm surface of the yttrium protective film is mirror-finished, and a portion of the mirror-finished surface (referred to as the "test surface") is covered with polyimide tape for masking.

[0360] Next, plasma was generated by discharging in gas using a CCP-type plasma etching device under a pressure of 10 Pa and an RF power of 600 W, and the test surface was exposed to the generated plasma (exposure test).

[0361] More specifically, a discharge (plasma generation) is performed using CF4 gas (flow rate: 100 sccm) and O2 gas (flow rate: 100 sccm), producing CF4 ions in the plasma.

[0362] Repeat the discharge (plasma generation) for 15 minutes 10 times, for a total exposure test of 150 minutes. Then etch the unshielded part of the test surface.

[0363] Then, the height difference between the shaded and unshaded areas of the test surface was measured using a probe-type surface profilometer (ULVAC, Dectak 150), and the etching amount was determined accordingly. The results are shown in Tables 1-3 below.

[0364] The smaller the etching amount (unit: nm), the better the plasma resistance.

[0365]

[0366]

[0367]

[0368] <Summary of Evaluation Results>

[0369] As shown in Tables 1-3 above, it can be seen that compared with Examples 22-24, Examples 1-21 have a smaller etching amount of yttrium protective film (first film) and good plasma resistance.

[0370] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2023-184119, filed on October 26, 2023, the contents of which are incorporated herein by reference.

[0371] Symbol Explanation

[0372] 1, 2, 3: Basal layer

[0373] 4: Yttrium protective film

[0374] 5: Substrate

[0375] 6: Components

[0376] 7: Film-forming surface

[0377] 7a: First film-forming surface

[0378] 7b: Second film-forming surface

[0379] 7c: Noodles

[0380] 11: Chamber

[0381] 12, 13: Crucible

[0382] 14: Ion gun

[0383] 15: Heater

[0384] 16: Support shaft

[0385] 17: Bracket

[0386] 18, 19: Crystal-type film thickness monitor

Claims

1. A yttrium protective film having a porosity of less than 1.5% by volume, a Young's modulus of 100.00 GPa or more, and a Vickers hardness of 8.50 GPa or more.

2. The yttrium protective film according to claim 1, wherein, The Young's modulus / Vickers hardness is below 16.

5.

3. The yttrium protective film according to claim 1, wherein, It contains 0.10 to 3.00 atomic percent argon.

4. The yttrium protective film according to claim 1, wherein, It contains more than 5 atomic percent yttrium.

5. The yttrium protective film according to claim 1, wherein, It contains 25 to 65 atomic percent fluorine.

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

80. The units for both fluorine and oxygen content are atomic.

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

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

9. The yttrium protective film according to claim 1, wherein, The thickness ranges from 0.01 to 30.0 μm.

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

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

12. The component according to claim 11, wherein, The Vickers hardness HV2 of the second film is y times the Vickers hardness HV1 of the first film. A Within a range of ±40%, wherein the angle between the first film-forming surface and the second film-forming surface is set to 0 to 90° in x A At x A When the angle is 0 to 60°, y is calculated according to the following formula (1). A , in x A When the angle is greater than 60° and less than 90°, y is calculated according to the following formula (2). A , (1)y A =-0.00034751x A 2 +0.01538782x A +1.00625521 (2)y A =-0.00197743x A +0.75229358。 13. The component according to claim 11, wherein, The thickness t2 of the second film is y of the thickness t1 of the first film. B Within a range of ±40%, Wherein, the angle between the first film-forming surface and the second film-forming surface is set to 0–170°. B At x B When the angle is 0 to 90°, y is calculated according to the following formula (3). B , in x B When the angle is greater than 90° and less than 170°, y is calculated according to the following formula (4). B , (3)y B =-0.00012389x B 2 +0.00659698x B +0.99721254 (4)y B =-0.00005913x B 2 +0.01099778x B -0.26784922。 14. The component according to claim 11, wherein, The crystallite size S2 of the second film is y times the crystallite size S1 of the first film. C Within a range of ±40%, Wherein, the angle between the first film-forming surface and the second film-forming surface is set to x, which is between 0 and 170°. C y is calculated according to the following formula (5). C , (5)y C =0.00009729x C 2 -0.00273425x C +0.99976959。 15. The component according to claim 11, wherein, The angle between the first film-forming surface and the second film-forming surface is 10° to 160°.

16. The component according to claim 11, wherein, The angle between the first film-forming surface and the second film-forming surface is 90°. The ratio of the Vickers hardness HV1 of the first film to the Vickers hardness HV2 of the second film, i.e., the HV1 / HV2 ratio, is 1.05 to 2.

50.

17. The component according to claim 11, wherein, The angle between the first film-forming surface and the second film-forming surface is 90°. The ratio of the thickness t1 of the first membrane to the thickness t2 of the second membrane, i.e., the t1 / t2 ratio, is 1.5 to 3.

5. The unit for thickness is μm.

18. The component according to claim 11, wherein, The angle between the first film-forming surface and the second film-forming surface is 90°. The ratio of the thickness t1 of the first membrane to the thickness t2 of the second membrane, i.e., the t1 / t2 ratio, is 2.0 to 6.

0. The unit for thickness is μm.

19. The component according to claim 11, wherein, The angle between the first film-forming surface and the second film-forming surface is 90°. The ratio of the crystallite size S1 of the first film to the crystallite size S2 of the second film, i.e., the S1 / S2 ratio, is 0.35 to 0.

90. The unit for crystallite size is nm.

20. The component according to claim 19, wherein, The crystallite size S1 of the first film is less than 20 nm.

21. The component according to claim 19, wherein, The crystallite size S2 of the second film is 15 nm or more.

22. The component according to claim 10, wherein, The surface roughness of the film-forming surface of the substrate is 0.001 to 3.00 μm, calculated as an arithmetic mean roughness Ra.

23. The component according to claim 10, wherein, The porosity of the substrate is less than 2.0% by volume.

24. The component according to claim 10, wherein, The substrate is composed of at least one selected from carbon, ceramics and metals.

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

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

27. The component according to claim 10, wherein, There is one or more base layers between the substrate and the yttrium protective film. The base layer contains at least one oxide selected from Al2O3, SiO2, Y2O3, MgO, CaO, SrO, BaO, B2O3, SnO2, P2O5, Li2O, Na2O, K2O, ZrO2, La2O3, Nd2O3, Yb2O3, Eu2O3, and Gd2O3.

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

29. A method for manufacturing a yttrium protective film, comprising the method for manufacturing the yttrium protective film according to any one of claims 1 to 9. In a vacuum, ions selected from at least one element chosen from oxygen, argon, neon, krypton, and xenon are irradiated from an ion gun while the evaporation source evaporates and adheres to the substrate. Y2O3 or a combination of Y2O3 and YF3 can be used as the evaporation source.

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

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