WO2024101367A1 - イットリウム質保護膜およびその製造方法ならびに部材 - Google Patents

イットリウム質保護膜およびその製造方法ならびに部材 Download PDF

Info

Publication number
WO2024101367A1
WO2024101367A1 PCT/JP2023/040118 JP2023040118W WO2024101367A1 WO 2024101367 A1 WO2024101367 A1 WO 2024101367A1 JP 2023040118 W JP2023040118 W JP 2023040118W WO 2024101367 A1 WO2024101367 A1 WO 2024101367A1
Authority
WO
WIPO (PCT)
Prior art keywords
protective film
yttrium
substrate
less
based protective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/040118
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
修平 小川
朝敬 小川
道夫 石川
径夫 谷村
岡田　英一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsubasa Science Corp
AGC Inc
Original Assignee
Tsubasa Science Corp
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsubasa Science Corp, Asahi Glass Co Ltd filed Critical Tsubasa Science Corp
Priority to KR1020257014200A priority Critical patent/KR20250108597A/ko
Priority to JP2024557429A priority patent/JPWO2024101367A1/ja
Priority to CN202380078199.7A priority patent/CN120187888A/zh
Publication of WO2024101367A1 publication Critical patent/WO2024101367A1/ja
Priority to US19/201,450 priority patent/US20250270685A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5055—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0026—Activation or excitation of reactive gases outside the coating chamber
    • C23C14/0031—Bombardment of substrates by reactive ion beams
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/221—Ion beam deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/243—Crucibles for source material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/46—Sputtering by ion beam produced by an external ion source
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
    • C23C14/546—Controlling the film thickness or evaporation rate using measurement on deposited material using crystal oscillators
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32458—Vessel
    • H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
    • H01J37/32495—Means for protecting the vessel against plasma

Definitions

  • the present invention relates to an yttrium-based protective film, its manufacturing method, and components.
  • the surface of a semiconductor substrate is microfabricated by dry etching using halogen-based gas plasma in a chamber, and the chamber from which the semiconductor substrate is removed after dry etching is cleaned using oxygen gas plasma.
  • the components exposed to the plasma gas in the chamber corrode, and the corroded parts may fall off in the form of particles.
  • the fallen particles can adhere to the semiconductor substrate and become foreign matter that causes defects in the circuit.
  • Patent Document 1 discloses a thermal spray coating containing yttrium oxyfluoride (yttrium oxyfluoride) formed by thermal spraying.
  • the present invention was made in consideration of the above points, and aims to provide an yttrium-based protective film with excellent plasma resistance.
  • the present invention provides the following [1] to [18].
  • the peak intensity ratio of Y 5 O 4 F 7 in the X-ray diffraction pattern is 60% or more;
  • [6] The yttrium-based protective film according to any one of [1] to [5] above, having a thickness of 0.3 ⁇ m or more.
  • [7] The yttrium-based protective film according to any one of the above [1] to [6], wherein the half-width of the rocking curve of the (151) plane of Y 5 O 4 F 7 is 40° or less.
  • [8] A member having a substrate and the yttrium-based protective film according to any one of [1] to [7] above, in this order.
  • [9] The member according to [8] above, wherein the surface roughness of the film-forming surface of the substrate is 0.01 to 1.2 ⁇ m in arithmetic mean roughness Ra.
  • the porosity of the substrate is 2.0 volume % or less.
  • the substrate is composed of at least one material selected from the group consisting of carbon, ceramics, and metals.
  • the ceramic is at least one selected from the group consisting of glass, quartz, aluminum oxide, aluminum nitride, Si-impregnated silicon carbide, and aluminum oxynitride
  • the metal is at least one selected from the group consisting of aluminum and alloys containing aluminum.
  • the substrate has, as a deposition surface, a first deposition surface that defines a maximum length and a second deposition surface different from the first deposition surface, the angle between the first deposition surface and the second deposition surface is 20° to 120°, and the ratio of the area of the second deposition surface to the total area of the deposition surfaces is 60% or less.
  • the present invention provides an yttrium-based protective film with excellent plasma resistance.
  • FIG. 1 is a schematic diagram showing an example of a member.
  • FIG. 2 is a schematic diagram showing a ring-shaped substrate with half cut away.
  • FIG. 3 is a schematic diagram showing a part of a cross section of another ring-shaped substrate.
  • FIG. 4 is a schematic diagram showing a part of a cross section of still another ring-shaped substrate.
  • FIG. 5 is a schematic diagram showing an apparatus used for producing the yttrium-based protective film.
  • the yttrium-based protective film of this embodiment has a Y 5 O 4 F 7 peak intensity ratio of 60% or more in an X-ray diffraction pattern, a porosity of less than 1.5 volume %, and a Vickers hardness of 800 HV or more.
  • the yttrium-based protective film will be referred to simply as the "protective film,” and the yttrium-based protective film (protective film) of this embodiment will be referred to as the "present protective film.”
  • the yttrium-based protective film contains yttrium oxyfluoride.
  • Chemical formulas representing yttrium oxyfluoride include YOF and Y 5 O 4 F 7.
  • YOF is an orthorhombic crystal with low hardness
  • Y 5 O 4 F 7 has a special crystal structure called a rhombohedron and has high hardness.
  • This protective film has a high proportion of Y5O4F7 having a rhombohedral crystal structure. That is, the peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern is a certain value or more.
  • the protective film is formed by the method (the present manufacturing method) described below, it is dense and has a small porosity. Such a protective film has excellent plasma resistance.
  • the protective film will be described in more detail below.
  • Y5O4F7 peak intensity ratio The peak intensity ratio of Y5O4F7 in the X-ray diffraction pattern of this protective film ( hereinafter also referred to as " Y5O4F7 peak intensity ratio") is 60% or more, preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, even more preferably 98% or more, particularly preferably 99% or more, and most preferably 100%.
  • the protective film In order to set the Y 5 O 4 F 7 peak intensity ratio in the above range, it is preferable to produce the protective film by the method (the present production method) described below.
  • the Y 5 O 4 F 7 peak intensity ratio is the ratio (unit: %) of the main peak intensity of Y 5 O 4 F 7 in the X-ray diffraction (XRD) pattern of the protective film, relative to the total main peak intensities of the following crystal phases being 100:
  • the peak of the Y 6 O 5 F 8 crystal and the peak of the Y 7 O 6 F 9 crystal appear overlapping at the main peak position of Y 5 O 4 F 7.
  • the main peak of YF 3 also appears overlapping at the main peak position of Y 5 O 4 F 7 . All peaks at the main peak position of Y 5 O 4 F 7 are treated as Y 5 O 4 F 7 peaks.
  • the intensity of the second main peak of the YF3 crystals, converted by 1.3 is also subtracted from the intensity of the Y5O4F7 peak (peak at the position of the main peak of Y5O4F7 ).
  • the intensity (relative intensity) of the second main peak of the YF3 crystal is " 2.0 " and the intensity (relative intensity) of the peak at the position of the main peak of Y5O4F7 is "6.0"
  • the XRD pattern of the protective film is obtained by XRD measurement in a micro 2D (two-dimensional) mode using an X-ray diffraction device (D8 DISCOVER Plus, manufactured by Bruker Corporation) under the following conditions.
  • Detector Multi-mode detector EIGER (2D mode)
  • ⁇ Input optical system Multilayer mirror + 1.0 mm ⁇ microslit + 1.0 mm ⁇ collimator
  • ⁇ Receiver optical system OPEN
  • the Vickers hardness of the protective film is 800 HV or more, preferably 900 HV or more, more preferably 950 HV or more, even more preferably 1000 HV or more, and particularly preferably 1050 HV or more.
  • the Vickers hardness of the present protective film is preferably 1800 HV or less, more preferably 1600 HV or less, and even more preferably 1400 HV or less.
  • the Vickers hardness of the protective film is determined in accordance with JIS Z 2244 (2009). More specifically, it is the Vickers hardness (HV0.005) determined when a test force of 4.9 mN (0.049 N) is applied using a diamond indenter with a facing angle of 136° using a micro Vickers hardness tester (HM-220, manufactured by Mitutoyo Corporation).
  • the porosity of the protective film is less than 1.5 vol.%, preferably 1.0 vol.% or less, more preferably 0.5 vol.% or less, even more preferably 0.2 vol.% or less, particularly preferably 0.10 vol.% or less, and most preferably 0.05 vol.% or less.
  • the porosity of the protective film is determined as follows. First, a focused ion beam (FIB) is used to perform a slope process in the thickness direction from the surface of the protective film toward the substrate at an angle of 52° on the protective film and a portion of the substrate described below, thereby exposing a cross section. The exposed cross section is observed at a magnification of 20,000 times using a field emission scanning electron microscope (FE-SEM), and an image of the cross section is taken. The cross-sectional image is taken at a plurality of locations.
  • FIB focused ion beam
  • the images are taken at a total of five locations, including one point at the center of the surface of the protective film (or the surface of the substrate) and four points 10 mm away from the outer periphery, and the size of the cross-sectional image is 6 ⁇ m ⁇ 5 ⁇ m.
  • the thickness of the protective film is 5 ⁇ m or more
  • cross-sectional images are taken at a plurality of locations so that the cross-section of the protective film can be observed in the thickness direction.
  • the cross-sectional image obtained is then analyzed using image analysis software (ImageJ, National Institute of Health) to identify the area of the pores in the cross-sectional image.
  • the ratio of the area of the pores to the area of the entire cross section of the protective film is calculated, and this is regarded as the porosity (unit: volume %) of the protective film. Note that the area of pores that are too fine to be detected by the image analysis software (pores with a pore diameter of 20 nm or less) is regarded as 0.
  • This protective film contains yttrium oxyfluoride (Y 5 O 4 F 7 ), and therefore contains yttrium (Y), oxygen (O) and fluorine (F).
  • the Y content of the 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.
  • the Y content of the protective film is preferably 35 atomic % or less, more preferably 30 atomic % or less, further preferably 29 atomic % or less, and particularly preferably 28 atomic % or less.
  • the O content of the protective film is preferably 20 atomic % or more, more preferably 21 atomic % or more, further preferably 22 atomic % or more, particularly preferably 23 atomic % or more, and most preferably 24 atomic % or more.
  • the O content of the protective film is preferably 35 atomic % or less, more preferably 30 atomic % or less, further preferably 28 atomic % or less, particularly preferably 26 atomic % or less, and most preferably 25 atomic % or less.
  • the F content of the protective film is preferably 35 atomic % or more, more preferably 40 atomic % or more, further preferably 44 atomic % or more, particularly preferably 47 atomic % or more, and most preferably 48 atomic % or more.
  • the F content of the protective film is preferably 55 atomic % or less, more preferably 50 atomic % or less, further preferably 49.5 atomic % or less, particularly preferably 49 atomic % or less, and most preferably 48.5 atomic % or less.
  • the manufacturing conditions such as the amount of evaporation source are appropriately adjusted.
  • the Y, O and F contents (unit: atomic %) in the protective film are measured using an energy dispersive X-ray analyzer (EX-250SE, manufactured by Horiba, Ltd.).
  • the F/O ratio which is the ratio of the F content (unit: atomic %) to the O content (unit: atomic %) in the protective film, is preferably less than 2.80, more preferably less than 2.50, and even more preferably less than 2.15.
  • the F/O ratio is preferably greater than 1.50, more preferably greater than 1.70, and even more preferably greater than 1.90.
  • the degree of orientation of the (151) plane of Y 5 O 4 F 7 in the protective film (hereinafter simply referred to as "degree of orientation") is high in order to prevent cracks from occurring in the protective film.
  • degree of orientation the degree of orientation of the (151) plane of Y 5 O 4 F 7 in the protective film
  • the half-width of the rocking curve of the ( 151 ) plane of Y5O4F7 is used as an index of the degree of orientation.
  • the rocking curve of the peak of the (151) plane of Y5O4F7 obtained using a two-dimensional mode detector is integrated in the 2 ⁇ direction, and the half-width is used to evaluate the orientation. The smaller this half-width (unit: °), the higher the degree of orientation.
  • the half width of the rocking curve of the (151) plane of Y 5 O 4 F 7 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.
  • the crystallite size of the present protective film is preferably 30 nm or less, more preferably 20 nm or less, even more preferably 17 nm or less, even more preferably 15 nm or less, and particularly preferably 13 nm or less.
  • the crystallite size of the present protective film is preferably 2 nm or more, more preferably 5 nm or more, even more preferably 6 nm or more, particularly preferably 8 nm or more, and most preferably 10 nm or more.
  • the crystallite size in the protective film is determined using the Scherrer equation based on the XRD pattern data obtained by XRD measurement of the mirror-polished protective film.
  • the thickness of the protective film is preferably 0.3 ⁇ m or more, more preferably 1 ⁇ m or more, even more preferably 5 ⁇ m or more, even more preferably 10 ⁇ m or more, particularly preferably 15 ⁇ m or more, and most preferably 20 ⁇ m or more.
  • the upper limit of the thickness of the protective film is not particularly limited, and is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 100 ⁇ m or less, particularly preferably 50 ⁇ m or less, and most preferably 30 ⁇ m or less.
  • the thickness of the protective film is measured as follows. A cross section of the protective film is observed using a scanning electron microscope (SEM), the thickness of the protective film is measured at any five points, and the average value of the five measured points is regarded as the thickness (unit: ⁇ m) of the protective film.
  • SEM scanning electron microscope
  • the stress (internal stress, residual stress) of the protective film is preferably compressive stress rather than tensile stress.
  • the compressive stress of the present protective film is preferably 1000 MPa or more, more preferably 1100 MPa or more, even more preferably 1200 MPa or more, even more preferably 1250 MPa or more, particularly preferably 1300 MPa or more, and most preferably 1350 MPa or more.
  • the compressive stress of the present 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.
  • the compressive stress of the protective film is determined as follows. A protective film is formed on a quartz glass substrate, and the surface shape of the formed protective film is measured using a surface shape measuring device (Surfcom NEX 241 SD2-13, manufactured by Tokyo Seimitsu Co., Ltd.), and the compressive stress (film stress ⁇ ) of the protective film is calculated using Stoney's formula (the following formula).
  • ⁇ is the film stress
  • Y is the Young's modulus of the substrate
  • d is the thickness of the substrate
  • ⁇ is the Poisson's ratio of the substrate
  • t is the thickness of the protective film
  • c is the radius of curvature.
  • FIG. 1 is a schematic diagram showing an example of the member 6 .
  • the member 6 has a substrate 5 and an yttrium-based protective film 4 .
  • 1, underlayers (underlayer 1, underlayer 2, and underlayer 3) may be disposed between the substrate 5 and the yttrium-based protective film 4.
  • the number of underlayers is not limited to three.
  • the member of this embodiment (hereinafter also referred to as the "present member") has the above-mentioned present protective film as the yttrium-based protective film. Since the surface of the present member is covered with the present protective film, the present member has excellent plasma resistance, similar to the present protective film.
  • the substrate has at least a surface on which the yttrium-based protective film (or the undercoat layer described below) is formed.
  • this surface may be referred to as the "film formation surface" for convenience.
  • the material of the substrate is appropriately selected depending on the application of the member.
  • the substrate is made of, for example, at least one material selected from the group consisting of carbon (C), ceramics, and metals.
  • the ceramic is, for example, at least one selected from the group consisting of glass (soda-lime glass, etc.), quartz, aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), cordierite, yttrium oxide, silicon carbide (SiC), Si-impregnated silicon carbide, silicon nitride (SiN), sialon, and aluminum oxynitride (AlON).
  • the ceramic is preferably at least one selected from the group consisting of glass, quartz, aluminum oxide, aluminum nitride, Si-impregnated silicon carbide, and aluminum oxynitride.
  • the Si-impregnated silicon carbide can be obtained by heating and melting elemental Si and impregnating it into silicon carbide (SiC).
  • the metal is, for example, at least one selected from the group consisting of aluminum (Al) and an alloy containing aluminum (Al).
  • the porosity of the substrate is preferably 2.0 vol. % or less, more preferably 1.2 vol. % or less, even more preferably 0.7 vol. % or less, even more preferably 0.5 vol. % or less, particularly preferably 0.3 vol. % or less, and most preferably 0.1 vol. % or less.
  • the porosity of the substrate is determined by Archimedes' method.
  • shape The shape of the substrate is not particularly limited and may be, for example, a flat plate, a ring, a dome, a concave or a convex shape, and may be appropriately selected depending on the application of the member.
  • the surface roughness of the film-forming surface of the substrate is preferably 1.2 ⁇ m or less, more preferably 1.0 ⁇ m or less, even more preferably 0.8 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less, in terms of arithmetic mean roughness Ra.
  • the surface roughness of the substrate on which the film is to be formed is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, even more preferably 0.05 ⁇ m or more, and particularly preferably 0.10 ⁇ m or more, in terms of arithmetic mean roughness Ra.
  • the surface roughness (arithmetic mean roughness Ra) of the coating surface is measured in accordance with JIS B 0601:2001.
  • the maximum length of the film-forming surface of the substrate is preferably 30 mm or more, more preferably 100 mm or more, even more preferably 200 mm or more, even more preferably 300 mm or more, particularly preferably 500 mm or more, very preferably 800 mm or more, and most preferably 1000 mm or more.
  • maximum length means the maximum length of the deposition surface. Specifically, for example, if the deposition surface is a circle in plan view, it is the diameter of the circle, if the deposition surface is a ring in plan view, it is the outer diameter of the circle, and if the deposition surface is a rectangle in plan view, it is the length of the maximum diagonal line.
  • the upper limit of the maximum length of the film-forming surface is not particularly limited, but is preferably 2000 mm or less, and more preferably 1500 mm or less.
  • FIG. 2 is a schematic diagram showing a ring-shaped substrate 5 with one half cut away.
  • the substrate 5 shown in FIG. 2 for example, when the outer diameter D1 is 100 mm, the inner diameter D2 is 90 mm, and the thickness t is 5 mm, the maximum length is 100 mm.
  • the substrate 5 has a film formation surface 7, which may have a first film formation surface 7a that defines the maximum length (outer diameter D 1 ) and a second film formation surface 7b that is different from the first film formation surface 7a, as shown in FIG. 2 .
  • the ratio of the area of the second film-forming surface 7b to the total area of the film-forming surface 7 is preferably 60% or less.
  • FIG. 3 is a schematic diagram showing a part of a cross section of another ring-shaped substrate 5. As shown in FIG. As shown in FIG. 3, the substrate 5 may have a plurality of second film formation surfaces 7b.
  • FIG. 4 is a schematic diagram showing a part of a cross section of still another ring-shaped substrate 5.
  • the angle between the first film forming surface 7a and the second film forming surface 7b is, for example, 20° to 120°.
  • 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 about 30°.
  • one or more underlayers may be disposed between the substrate and the yttrium-based protective coating.
  • the stress of the yttrium-based protective film is alleviated and the adhesion of the yttrium-based protective film to the substrate is increased.
  • the number of undercoat layers is not particularly limited, but 5 layers or less is preferable, 4 layers or less is more preferable, 3 layers or less is even more preferable, 2 layers or less is particularly preferable, and 1 layer is most preferable.
  • the underlayer is preferably an amorphous film or a microcrystalline film.
  • the underlayer preferably contains at least one oxide selected from the group consisting of Al2O3 , SiO2 , Y2O3 , MgO , CaO , SrO, BaO, B2O3 , SnO2 , P2O5 , Li2O , Na2O , K2O , ZrO2 , La2O3 , Nd2O3 , Yb2O3 , Eu2O3 and Gd2O3 .
  • the oxides of the underlayers are preferably different from each other between adjacent underlayers.
  • a specific example of a case in which the oxides of adjacent underlayers are different from each other is a case in which the oxide of underlayer 1 is "SiO 2 ", the oxide of underlayer 2 is "Al 2 O 3 +SiO 2 ", and the oxide of underlayer 3 is "Al 2 O 3 ".
  • the thickness of the underlayer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 1.0 ⁇ m or more, even more preferably 1.5 ⁇ m or more, particularly preferably 2.0 ⁇ m or more, very preferably 2.5 ⁇ m or more, and most preferably 3.0 ⁇ m or more.
  • the thickness of the underlayer is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 7 ⁇ m or less, and particularly preferably 4 ⁇ m or less.
  • the thickness of the undercoat layer is measured in the same manner as the thickness of the yttrium-based protective film.
  • This member is used, for example, as a member such as a top plate inside semiconductor device manufacturing equipment (plasma etching equipment, plasma CVD equipment, etc.). However, the use of this member is not limited to this.
  • This manufacturing method is a so-called ion-assisted deposition (IAD) method.
  • IAD ion-assisted deposition
  • an yttrium -based protective film having a high ratio of Y5O4F7 is formed by evaporating evaporation sources ( Y2O3 and YF3 ) and depositing them on a substrate while irradiating the substrate with ions in a vacuum.
  • This manufacturing method allows the formation of a very dense yttrium-based protective film.
  • the resulting yttrium-based protective film has a low porosity and a small crystallite size.
  • the thicker the yttrium protective film the more likely it is to crack. Furthermore, as the area of the deposition surface increases, the area of the yttrium-based protective film formed on the deposition surface also increases, and in this case too, the yttrium-based protective film is prone to cracking.
  • the present manufacturing method makes it possible to obtain a dense and hard yttrium-based protective film. Furthermore, when an underlayer is formed, the stress of the yttrium protective film is relieved. Therefore, the yttrium-based protective film obtained by this manufacturing method is less susceptible to cracking even when its thickness or area is increased.
  • the surface roughness (arithmetic mean roughness Ra) of the substrate's coating surface is preferably in the range described above. This makes the yttrium protective film that is formed denser and harder, and less prone to cracking.
  • the resulting yttrium-based protective film is likely to have many residual pores. Furthermore, with these methods, it is difficult to control the fluorine content in the resulting yttrium-based protective film, and it may be difficult to stably obtain a desired composition.
  • Another method different from the IAD method is the sputtering method, in which, for example, a sputtering target of YO x F y is bombarded with plasma of argon and oxygen in a vacuum to form a film on a substrate.
  • a sputtering target of YO x F y is bombarded with plasma of argon and oxygen in a vacuum to form a film on a substrate.
  • the fluorine content is prone to change, and it is still difficult to stably form an yttrium-based protective film that has a high proportion of Y 5 O 4 F 7 having a rhombohedral crystal structure.
  • FIG. 5 is a schematic diagram showing an apparatus used for producing the yttrium-based protective film.
  • 5 includes a chamber 11.
  • the inside of the chamber 11 can be evacuated to a vacuum by driving a vacuum pump (not shown).
  • crucibles 12 and 13 and an ion gun 14 are arranged, and above these, a holder 17 is arranged.
  • the holder 17 is integrated with the support shaft 16 and rotates with the rotation of the support shaft 16.
  • a heater 15 is disposed.
  • the substrate 5 described above is held in a state where its film forming surface faces downward on the holder 17.
  • the substrate 5 held by the holder 17 rotates in accordance with the rotation of the holder 17 while being heated by the heater 15.
  • the chamber 11 is equipped with quartz crystal film thickness monitors 18 and 19 .
  • ⁇ Formation of yttrium-based protective film> The case of forming an yttrium-based protective film (not shown in FIG. 5) on the substrate 5 in the apparatus shown in FIG. 5 will be described.
  • one crucible 12 is filled with the evaporation source Y 2 O 3
  • the other crucible 13 is filled with the evaporation source YF 3 .
  • the inside of the chamber 11 is evacuated to a vacuum.
  • the pressure inside the chamber 11 is preferably 5 ⁇ 10 ⁇ 4 Pa or less.
  • the holder 17 is rotated. This causes the substrate 5 to rotate while being heated.
  • ion-assisted deposition is carried out to form a film on the substrate 5 . That is, while ions (ion beam) are irradiated from the ion gun 14, the evaporation source Y 2 O 3 in the crucible 12 and the evaporation source YF 3 in the crucible 13 are evaporated in parallel. The evaporation source is melted and evaporated by irradiating it with an electron beam (not shown). In this manner, the evaporated evaporation source adheres to the substrate 5 (the film formation surface) and a protective yttrium film is formed.
  • the ions irradiated by the ion gun 14 are preferably ions of at least one element selected from the group consisting of oxygen, argon, neon, krypton, and xenon. It is more preferable to use ions of at least two elements selected from the group consisting of oxygen, argon, neon, krypton and xenon as the ions irradiated by the ion gun 14, and it is even more preferable to use oxygen and argon ions in combination. This improves the Vickers hardness of the yttrium-based protective film that is formed.
  • the film formation is carried out in a vacuum, and specifically, the pressure inside the chamber 11 is preferably 8 ⁇ 10 ⁇ 2 Pa or less, more preferably 6 ⁇ 10 ⁇ 2 Pa or less, further preferably 5 ⁇ 10 ⁇ 2 Pa or less, and particularly preferably 3 ⁇ 10 ⁇ 2 Pa or less.
  • the pressure inside the chamber 11 is preferably 0.5 ⁇ 10 ⁇ 2 Pa or more, and more preferably 0.5 ⁇ 10 ⁇ 2 Pa or more.
  • the temperature of the substrate 5 heated by the heater 15 is preferably 200° C. or higher, and more preferably 250° C. or higher. On the other hand, this temperature is preferably 400° C. or lower, and more preferably 350° C. or lower.
  • the film formation rate is adjusted by controlling the conditions of the electron beam irradiated onto the evaporation source and the conditions of the ion beam of the ion gun 14 (current value, current density, etc.). During the formation of the yttrium protective film, the film formation rate (unit: nm/min) of each evaporation source is adjusted to a desired value.
  • the film formation rate ratio (Y 2 O 3 / YF 3 ) of the film formation rate (unit: nm/min) of the evaporation source Y 2 O 3 to the film formation rate (unit: nm/min) of the evaporation source YF 3 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.
  • the film formation rate ratio (Y 2 O 3 /YF 3 ) is preferably 1/1.1 or less, more preferably 1/1.3 or less, further preferably 1/1.8 or less, and particularly preferably 1/2.5 or less.
  • the total rate of the deposition rate of the evaporation source Y2O3 and the deposition 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 total rate is preferably 50 nm/min or less, more preferably 35 nm/min or less, and even more preferably 20 nm/min or less.
  • the distance between the ion gun 14 and the substrate 5 is preferably 700 mm or more, and more preferably 900 mm or more, while the distance is preferably 1500 mm or less, and more preferably 1300 mm or less.
  • the current value of the ion beam is preferably 1000 mA or more, and more preferably 1500 mA or more.
  • the ion beam current value is preferably 3000 mA or less, and more preferably 2500 mA or less.
  • the ion beam current density is preferably 40 ⁇ A/cm 2 or more, more preferably 65 ⁇ A/cm 2 or more, further preferably 75 ⁇ A/cm 2 or more, and particularly preferably 85 ⁇ A/cm 2 or more.
  • the ion beam current density is preferably 140 ⁇ A/cm 2 or less, and more preferably 120 ⁇ A/cm 2 or less.
  • Ar/O ratio As described above, it is preferable to use a combination of argon ions and oxygen ions as the ions irradiated from the ion gun 14 .
  • the Ar/O ratio which is the ratio of argon (Ar) ions to oxygen (O) ions, is preferably 1/50 or more, more preferably 1.5/50 or more, and even more preferably 2/50 or more, while the Ar/O ratio is preferably 4/50 or less, more preferably 3.5/50 or less, and even more preferably 3/50 or less.
  • the Ar/O ratio is the ratio between the amount of argon (Ar) ions per unit time (unit: W/ m2 ) irradiated from the ion gun 14 toward the substrate 5 and the amount of oxygen (O) ions per unit time (unit: W/ m2 ) irradiated from the ion gun 14 toward the substrate 5.
  • W/ m2 is a unit indicating the kinetic energy (ion energy flux) crossing a unit area in a unit time.
  • the underlayer is formed by ion-assisted deposition in the same manner as the yttrium-based protective film.
  • the crucible 12 and/or the crucible 13 is filled with Al 2 O 3 as an evaporation source, and the evaporation source is evaporated while ions (ion beam) are irradiated from the ion gun 14, and adhered to the film formation surface of the substrate 5.
  • the conditions for forming the underlayer are similar to those for forming the yttrium-based protective film.
  • Example 1 Using the apparatus described with reference to FIG. 5, an yttrium-based protective film (protective film) was produced. More specifically, underlayers and protective films shown in Tables 1 to 3 were formed on the deposition surface of the substrate under the manufacturing conditions shown in Tables 1 to 3. A circular substrate (thickness: 10 mm) having a deposition surface with a diameter (maximum length) of 200 mm was used as the substrate. The composition of the protective film was determined from the content of each element (Y, O, F, etc.). When forming the protective film, argon (Ar) ions and oxygen (O) ions were irradiated from an ion gun toward the substrate at the Ar/O ratios shown in Tables 1 to 3 below. As manufacturing conditions not shown in Tables 1 to 3 below, the distance between the ion gun and the substrate was 1100 mm, and the current value of the ion beam was 2000 mA.
  • Ar argon
  • O oxygen
  • Example 2 to Example 26 In Examples 2 to 26, one or more conditions were changed from those in Examples 1 to Table 3. Otherwise, the underlayer and the yttrium-based protective film were formed in this order in the same manner as in Example 1. When no undercoat layer was formed, "-" is entered in the corresponding column in Tables 1 to 3 below.
  • Example 2 the deposition rate was changed. In Example 3, no undercoat layer was formed. In Example 4, the deposition rate was changed. In Example 5, the deposition rate was changed, and no underlayer was formed. In Examples 6 to 8, the Ra of the film-forming surface of the substrate was changed. In Examples 9 to 14, the material of the substrate was changed. In Example 10, one side of the substrate made of aluminum (Al) was anodized to form a base layer made of Al 2 O 3. This base layer is described as "anodized” in the following Tables 1 to 3. In Example 13, commercially available soda lime glass was used as the substrate (glass). In Example 15, the area of the film formation surface was changed (increased).
  • Example 16 and 17 the thickness of the protective film formed was changed by adjusting the film formation time (not shown in Tables 1 to 3 below).
  • Example 18 a highly porous substrate was used.
  • Example 19 the ion beam current density was changed.
  • Example 20 the ion beam current density was changed and the Ar/O ratio was changed (only oxygen ions were irradiated).
  • Example 21 the Ar/O ratio was changed (only oxygen ions were irradiated).
  • Example 22 the deposition rate was changed.
  • Examples 23 to 25 the Ar/O ratio was changed (only oxygen ions were irradiated).
  • Example 26 the deposition rate was changed.
  • Etching Amount The etching amount of the protective film of each example was determined, and the plasma resistance was evaluated. Specifically, a 10 mm x 5 mm surface of the protective film was mirror-finished. A part of the mirror-finished surface was masked with Kapton tape and etched with plasma gas. Then, a stylus-type surface profiler (Dectak150, manufactured by ULVAC, Inc.) was used to measure the step between the etched and non-etched parts to determine the amount of etching. EXAM (manufactured by Shinko Seiki Co., Ltd., model: POEM type) was used as the plasma etching device.
  • EXAM manufactured by Shinko Seiki Co., Ltd., model: POEM type
  • etching In RIE mode (reactive ion etching mode), first, under a pressure of 10 Pa and an output of 350 W, etching was performed for 180 minutes using a gas obtained by mixing CF 4 gas (flow rate: 100 sccm) with O 2 gas (flow rate: 10 sccm). Next, etching was performed for 180 minutes using CF 4 gas (flow rate: 100 sccm). After that, etching was performed for 180 minutes using a gas obtained by mixing CF 4 gas (flow rate: 100 sccm) with O 2 gas (flow rate: 10 sccm), and finally, etching was performed for 180 minutes using CF 4 gas (flow rate: 100 sccm). The smaller the etching amount (unit: nm), the better the plasma resistance can be evaluated. Specifically, if the etching amount was 150 nm or less, the plasma resistance was evaluated as excellent.
  • F content change amount ⁇ (F content before etching) ⁇ (F content after etching) ⁇ /(F content before etching)
  • the change in F content is preferably 10 atomic % or less, more preferably 5 atomic % or less, and even more preferably 3 atomic % or less.
  • Examples 1 to 18 were excellent in plasma resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2023/040118 2022-11-11 2023-11-07 イットリウム質保護膜およびその製造方法ならびに部材 Ceased WO2024101367A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020257014200A KR20250108597A (ko) 2022-11-11 2023-11-07 이트륨질 보호막 및 그 제조 방법 그리고 부재
JP2024557429A JPWO2024101367A1 (https=) 2022-11-11 2023-11-07
CN202380078199.7A CN120187888A (zh) 2022-11-11 2023-11-07 钇质保护膜和其制造方法以及构件
US19/201,450 US20250270685A1 (en) 2022-11-11 2025-05-07 Yttrium-based protective film, method for producing same, and member

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022181113 2022-11-11
JP2022-181113 2022-11-11

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US19/201,450 Continuation US20250270685A1 (en) 2022-11-11 2025-05-07 Yttrium-based protective film, method for producing same, and member

Publications (1)

Publication Number Publication Date
WO2024101367A1 true WO2024101367A1 (ja) 2024-05-16

Family

ID=91032544

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/040118 Ceased WO2024101367A1 (ja) 2022-11-11 2023-11-07 イットリウム質保護膜およびその製造方法ならびに部材

Country Status (6)

Country Link
US (1) US20250270685A1 (https=)
JP (1) JPWO2024101367A1 (https=)
KR (1) KR20250108597A (https=)
CN (1) CN120187888A (https=)
TW (1) TW202435309A (https=)
WO (1) WO2024101367A1 (https=)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010121203A (ja) * 2008-07-14 2010-06-03 Toto Ltd 複合構造物及びその作製方法
JP2016211072A (ja) * 2015-05-08 2016-12-15 東京エレクトロン株式会社 溶射用材料、溶射皮膜および溶射皮膜付部材
JP2020525640A (ja) * 2017-05-26 2020-08-27 イオンズ カンパニー リミテッド フッ化イットリウムオキシドコーティング膜の形成方法およびこれによるフッ化イットリウムオキシドコーティング膜
JP2021185267A (ja) * 2013-07-20 2021-12-09 アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated 蓋及びノズル上の希土類酸化物系コーティング用イオンアシスト蒸着
JP7154517B1 (ja) * 2022-02-18 2022-10-18 Ａｇｃ株式会社 イットリウム質保護膜およびその製造方法ならびに部材
JP2023084911A (ja) * 2021-12-08 2023-06-20 三星電子株式会社 焼結体、焼結体の製造方法、プラズマ装置用部材、半導体製造装置用部材の製造方法、半導体製造装置、及び半導体製造装置の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6650385B2 (ja) 2016-11-07 2020-02-19 東京エレクトロン株式会社 溶射用材料、溶射皮膜および溶射皮膜付部材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010121203A (ja) * 2008-07-14 2010-06-03 Toto Ltd 複合構造物及びその作製方法
JP2021185267A (ja) * 2013-07-20 2021-12-09 アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated 蓋及びノズル上の希土類酸化物系コーティング用イオンアシスト蒸着
JP2016211072A (ja) * 2015-05-08 2016-12-15 東京エレクトロン株式会社 溶射用材料、溶射皮膜および溶射皮膜付部材
JP2020525640A (ja) * 2017-05-26 2020-08-27 イオンズ カンパニー リミテッド フッ化イットリウムオキシドコーティング膜の形成方法およびこれによるフッ化イットリウムオキシドコーティング膜
JP2023084911A (ja) * 2021-12-08 2023-06-20 三星電子株式会社 焼結体、焼結体の製造方法、プラズマ装置用部材、半導体製造装置用部材の製造方法、半導体製造装置、及び半導体製造装置の製造方法
JP7154517B1 (ja) * 2022-02-18 2022-10-18 Ａｇｃ株式会社 イットリウム質保護膜およびその製造方法ならびに部材

Also Published As

Publication number Publication date
JPWO2024101367A1 (https=) 2024-05-16
US20250270685A1 (en) 2025-08-28
TW202435309A (zh) 2024-09-01
CN120187888A (zh) 2025-06-20
KR20250108597A (ko) 2025-07-15

Similar Documents

Publication Publication Date Title
JP7154517B1 (ja) イットリウム質保護膜およびその製造方法ならびに部材
JP7833151B2 (ja) イットリウム質保護膜およびその製造方法ならびに部材
US11312637B1 (en) Yittrium granular powder for thermal spray and thermal spray coating produced using the same
TW201126600A (en) Methods of coating substrate with plasma resistant coatings and related coated substrates
JPH04305037A (ja) 炭素被膜付撥水ガラス
JP5324029B2 (ja) 半導体加工装置用セラミック被覆部材
JP7290716B2 (ja) プラズマ処理装置用部材およびプラズマ処理装置
WO2024101367A1 (ja) イットリウム質保護膜およびその製造方法ならびに部材
KR102582528B1 (ko) 복합 구조물 및 복합 구조물을 구비한 반도체 제조 장치
JP5031259B2 (ja) 耐食性部材とその製造方法およびこれを用いた半導体・液晶製造装置
WO2024101102A1 (ja) 部材およびその製造方法
WO2025089225A1 (ja) イットリウム質保護膜およびその製造方法ならびに部材
WO2025177799A1 (ja) イットリウム質保護膜、部材およびその製造方法
WO2025089226A1 (ja) イットリウム質保護膜およびその製造方法ならびに部材
JP2026069667A (ja) イットリウム質保護膜およびその製造方法ならびに部材
JP7752558B2 (ja) プラズマ処理装置用部材
JP2003115478A (ja) プラズマ処理装置用窓部材
US20250270099A1 (en) Composite structure and semiconductor manufacturing apparatus including composite structure
JP5849083B2 (ja) 多孔質構造体の製造方法及び多孔質自立膜
TW202238998A (zh) 複合結構物及具備複合結構物之半導體製造裝置
JP2025124277A (ja) 耐プラズマ性部材
TW202346240A (zh) 複合結構物及具備複合結構物之半導體製造裝置
TW202237397A (zh) 複合結構物及具備複合結構物之半導體製造裝置
JP2000169953A (ja) 耐食性部材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23888714

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2024557429

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202380078199.7

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 202380078199.7

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020257014200

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 23888714

Country of ref document: EP

Kind code of ref document: A1