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WO2024171917A1 - Corrosion-resistant member - Google Patents

Corrosion-resistant member Download PDF

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Publication number
WO2024171917A1
WO2024171917A1 PCT/JP2024/004043 JP2024004043W WO2024171917A1 WO 2024171917 A1 WO2024171917 A1 WO 2024171917A1 JP 2024004043 W JP2024004043 W JP 2024004043W WO 2024171917 A1 WO2024171917 A1 WO 2024171917A1
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WIPO (PCT)
Prior art keywords
corrosion
layer
resistant coating
magnesium fluoride
resistant
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Ceased
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PCT/JP2024/004043
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French (fr)
Japanese (ja)
Inventor
加奈子 古樫
修一郎 足立
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Resonac Corp
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Resonac Corp
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Priority to JP2025501091A priority Critical patent/JPWO2024171917A1/ja
Publication of WO2024171917A1 publication Critical patent/WO2024171917A1/en
Anticipated expiration legal-status Critical
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
    • H01L21/2015—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate the substrate being of crystalline semiconductor material, e.g. lattice adaptation, heteroepitaxy

Definitions

  • the present invention relates to corrosion-resistant components.
  • Patent Document 1 discloses a corrosion-resistant member in which a corrosion-resistant coating made of a magnesium fluoride film is formed on the surface of a metal substrate
  • Patent Document 2 discloses a corrosion-resistant aluminum alloy material in which the surface of a substrate made of an aluminum alloy containing magnesium is coated with a corrosion-resistant coating made of a fluoride passivation film containing magnesium fluoride.
  • An object of the present invention is to provide a corrosion-resistant member having a corrosion-resistant coating that is not easily peeled off from a substrate even when subjected to thermal history.
  • a corrosion-resistant coating comprising a metal substrate and a corrosion-resistant coating containing magnesium fluoride formed on a surface of the substrate, the corrosion-resistant coating has a laminated portion in which a first layer and a second layer are laminated on the substrate in this order; the first layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of 100 nm or more and less than 1000 nm, The second layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of less than 100 nm.
  • the corrosion-resistant coating of the corrosion-resistant member of the present invention is unlikely to peel off from the base material even when subjected to thermal history.
  • FIG. 1 is a schematic cross-sectional view illustrating a configuration of a corrosion-resistant member according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view illustrating details of a first layer and a second layer of the corrosion-resistant coating of the corrosion-resistant member of FIG. 1 .
  • the corrosion-resistant member comprises a metal substrate 10 and a corrosion-resistant coating 20 that is formed on the surface of the substrate 10 and contains magnesium fluoride.
  • Figures 1 and 2 are schematic diagrams of a cross section of the corrosion-resistant member that appears when the corrosion-resistant member is cut along a plane perpendicular to the surface of the corrosion-resistant coating 20.
  • This corrosion-resistant coating 20 has a laminated portion in which a first layer 21 and a second layer 22 are laminated on a substrate 10 in the order listed.
  • the first layer 21 is a layer having magnesium fluoride crystal grains with an average crystal grain size of 100 nm or more and less than 1000 nm.
  • the second layer 22 is a layer having magnesium fluoride crystal grains with an average crystal grain size of less than 100 nm.
  • the corrosion-resistant member according to this embodiment has the corrosion-resistant coating 20 containing magnesium fluoride, and therefore has excellent corrosion resistance even in highly corrosive gases and plasmas such as chlorine gas (Cl 2 ) and fluorine gas (F 2 ).
  • the corrosion-resistant member according to this embodiment has the corrosion-resistant coating 20 containing magnesium fluoride, and therefore the corrosion-resistant coating 20 is unlikely to peel off from the substrate 10 even when subjected to a thermal history.
  • the reasons for the above effects are explained in detail below.
  • the corrosion-resistant coating 20 have the first layer 21 and the second layer 22, it is possible to achieve both corrosion resistance against highly corrosive gases and the property that the corrosion-resistant coating 20 is less likely to peel off from the substrate 10 and is less likely to crack even when subjected to thermal history.
  • the adhesion of the corrosion-resistant coating 20 to the substrate 10 even when subjected to thermal history, the generation of particles resulting from peeling of the corrosion-resistant coating 20 is suppressed.
  • the corrosion-resistant member according to this embodiment is suitable as a member that requires corrosion resistance and heat resistance, for example, as a component of semiconductor manufacturing equipment (particularly, a film-forming device using a chemical vapor deposition method). As a specific example, it is suitable as a susceptor or shower head of a film-forming device that forms a thin film on a wafer while plasma is generated. If the corrosion-resistant member according to this embodiment is used as a component of semiconductor manufacturing equipment, particle generation is suppressed, and semiconductors can be manufactured with a high yield.
  • the corrosion-resistant member according to this embodiment will be described in further detail below.
  • the metal constituting the base material 10 is not particularly limited, and may be a simple metal (containing unavoidable impurities) or an alloy, such as aluminum or an aluminum alloy.
  • the corrosion-resistant coating 20 of the corrosion-resistant member according to this embodiment contains magnesium fluoride. That is, the corrosion-resistant coating 20 may be formed of magnesium fluoride, or may be formed of magnesium fluoride and another material.
  • the type of magnesium fluoride is not particularly limited, and examples thereof include magnesium fluoride (MgF 2 ) and magnesium oxyfluoride.
  • the type of magnesium fluoride can be evaluated by energy dispersive X-ray analysis (EDS), X-ray diffraction (XRD), or the like.
  • the corrosion-resistant coating 20 provided on the corrosion-resistant member according to this embodiment has a laminated portion in which a first layer 21 and a second layer 22 are laminated on a substrate 10 in the order described above.
  • a structure may be used in which a layered first layer 21 is laminated on a substrate 10, and a layered second layer 22 is further laminated on the first layer 21.
  • the laminated portion in which the first layer 21 and the second layer 22 are laminated may form the entire corrosion-resistant coating 20 (see Figures 1 and 2), or may form only a part of the corrosion-resistant coating 20 (not shown).
  • the laminated portion in which the first layer 21 and the second layer 22 are laminated may cover the entire surface of the substrate 10 (see Figures 1 and 2), or may cover only a part of the surface of the substrate 10 (not shown).
  • the method for measuring the thickness of the corrosion-resistant coating 20, the method for measuring the average crystal grain size of the magnesium fluoride crystal grains contained in the corrosion-resistant coating 20, and the method for distinguishing the first layer 21 and the second layer 22 are not particularly limited, but all of them can be performed by performing electron microscope observation using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), a scanning electron microscope (SEM), or the like to obtain an electron microscope image.
  • the magnification of the electron microscope observation is not particularly limited, but can be, for example, 30,000 times or more and 50,000 times or less.
  • the object to be observed is not particularly limited as long as it is the inside of the corrosion-resistant coating 20, but examples of the object include a cross section that appears when the corrosion-resistant coating 20 is cut.
  • the type of cross section is also not particularly limited, but examples of the object include a cross section of a corrosion-resistant member that appears when the corrosion-resistant member is cut in a plane perpendicular to the surface of the corrosion-resistant coating 20.
  • the cross section that appears when the corrosion-resistant coating 20 is cut in a plane parallel to the surface of the corrosion-resistant coating 20 may be used.
  • the corrosion-resistant member is cut to expose the cross section, and a transmission electron microscope image of the cross section is obtained using a transmission electron microscope.
  • the thickness of the corrosion-resistant coating 20 can be obtained by measuring the length of the portion of the transmission electron microscope image that corresponds to magnesium fluoride.
  • One type of cross section is, for example, the cross section of the corrosion-resistant member that appears when the corrosion-resistant member is cut on a plane perpendicular to the surface of the corrosion-resistant coating 20.
  • the thickness of the corrosion-resistant coating 20 is not particularly limited, but is preferably 0.1 ⁇ m to 20 ⁇ m, more preferably 0.15 ⁇ m to 10 ⁇ m, and even more preferably 0.2 ⁇ m to 1 ⁇ m. If the thickness of the corrosion-resistant coating 20 is 0.1 ⁇ m or more, the corrosion resistance of the corrosion-resistant coating 20 can be sufficiently ensured. Furthermore, if the thickness of the corrosion-resistant coating 20 is 20 ⁇ m or less, the corrosion-resistant coating 20 is less likely to crack even when subjected to a thermal history.
  • the corrosion-resistant member is cut to expose the cross section, and a transmission electron microscope image of the cross section is obtained using a transmission electron microscope.
  • the boundaries of the crystal grains are confirmed in the transmission electron microscope image, and the average crystal grain size of the magnesium fluoride crystal grains can be calculated from the average value of the circle equivalent diameters of the crystal grains.
  • the presence of the first layer 21 and the second layer 22 in the corrosion-resistant coating 20 can be confirmed by calculating the average crystal grain size of any region from the crystal grain size measured by the above method.
  • the average crystal grain size of the magnesium fluoride crystal grains in the first layer 21 must be 100 nm or more and 1000 nm or less, preferably 110 nm or more and 600 nm or less, and more preferably 120 nm or more and 300 nm or less. If the average crystal grain size is within the above range, the adhesion between the substrate 10 and the corrosion-resistant coating 20 will be higher.
  • the average crystal grain size of the magnesium fluoride crystal grains in the second layer 22 must be less than 100 nm, preferably 1 nm to 80 nm, and more preferably 10 nm to 50 nm. If the average crystal grain size is within the above range, the mechanical strength is high and the corrosion-resistant coating 20 is less likely to crack.
  • the ratio of the thickness of the second layer 22 to the thickness of the corrosion-resistant coating 20 is preferably 5% or more and 95% or less, more preferably 7% or more and 90% or less, and even more preferably 10% or more and 80% or less. With this configuration, the corrosion resistance of the corrosion-resistant coating 20 can be sufficiently ensured, and the adhesion between the substrate 10 and the corrosion-resistant coating 20 is further improved.
  • the thicknesses of the first layer 21 and the second layer 22 can be determined as follows: That is, as shown in Fig. 2, an interface between the first layer 21 and the second layer 22 is set based on the average crystal grain size of the crystal grains, and the average value of the distance from the substrate 10 to the interface (the length in the direction perpendicular to the surface of the corrosion-resistant coating 20) is defined as the thickness of the first layer 21, and the average value of the distance from the interface to the surface of the corrosion-resistant coating 20 (the length in the direction perpendicular to the surface of the corrosion-resistant coating 20) is defined as the thickness of the second layer 22.
  • the crystallinity of the magnesium fluoride in the first layer 21 and the second layer 22 is not particularly limited. That is, the crystal grains in the first layer 21 and the second layer 22 may contain a plurality of crystallites or an amorphous phase.
  • the method for manufacturing the corrosion-resistant member according to this embodiment is not particularly limited, but one example includes a method in which a magnesium fluoride layer is formed on the surface of a substrate by a method such as vapor deposition, followed by heat treatment, and then a further magnesium fluoride layer is laminated on top of the heat-treated magnesium fluoride layer by a method such as vapor deposition.
  • the magnesium fluoride layer before heat treatment contains crystalline magnesium fluoride, but when heat treatment is performed in an atmosphere such as a fluorine gas atmosphere, sintering (grain growth) of the magnesium fluoride particles occurs, and the crystal grain size of the magnesium fluoride crystal grains in the magnesium fluoride layer increases. Therefore, by forming a magnesium fluoride layer on the surface of the substrate and then performing heat treatment, a crystalline layer equivalent to the first layer is formed. Then, by forming a magnesium fluoride layer on the layer equivalent to the first layer, a crystalline layer equivalent to the second layer is formed, and a laminated portion in which the first layer and second layer are laminated is formed.
  • the magnesium fluoride layer can be formed by a method such as vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, or the like.
  • the holding temperature during the heat treatment is preferably 200° C. or higher and 500° C. or lower, more preferably 300° C. or higher and 475° C. or lower, and further preferably 350° C. or higher and 450° C. or lower. If the holding temperature during the heat treatment is 200° C. or higher, the crystal grain size of magnesium fluoride crystal grains in the magnesium fluoride layer tends to grow and become large. If the holding temperature during the heat treatment is 500° C. or lower, cracks are unlikely to occur in the magnesium fluoride layer.
  • the holding time during the heat treatment is preferably 1 hour or more and 250 hours or less, more preferably 3 hours or more and 150 hours or less, and even more preferably 5 hours or more and 100 hours or less. If the holding time during the heat treatment is 1 hour or more, the crystal grain size of the magnesium fluoride crystal grains in the magnesium fluoride layer tends to grow and become large. If the holding time during the heat treatment is 250 hours or less, productivity tends to be good.
  • Example 1 The substrate was first pretreated, and then a magnesium fluoride layer was formed on the surface of the substrate by vacuum deposition. The magnesium fluoride layer was then heat-treated to form a first layer. A magnesium fluoride layer equivalent to the second layer was then newly formed on the first layer by vacuum deposition, forming a corrosion-resistant coating that was a laminate of the first layer and the second layer, thereby obtaining a corrosion-resistant member.
  • the metal constituting the substrate is an aluminum alloy A5052 containing 2.55 mass % of magnesium, and the substrate is in the form of a plate having a length of 50 mm, a width of 30 mm, and a thickness of 3 mm.
  • the substrate was pretreated as follows: First, 70 g of S-clean AL-13 (manufactured by Sasaki Chemical Co., Ltd.) was dissolved in 1 L of water and the temperature was adjusted to 50° C. to prepare a degreasing solution, and the substrate was degreased by immersing it in the degreasing solution for 10 minutes and then washed with pure water.
  • the conditions of vacuum deposition when forming the magnesium fluoride layer as the first layer on the surface of the substrate are as follows. First, the pretreated substrate was placed in a vacuum chamber, and then the vacuum chamber was evacuated until the degree of vacuum reached 2 ⁇ 10 ⁇ 4 Pa. The pretreated substrate was then heated to 400° C. A magnesium fluoride sintered material was used as the deposition material, and the sintered material was irradiated with an electron beam, and a shutter was opened to form a magnesium fluoride layer with a thickness of 210 nm on the substrate held at 400° C. The input power of the electron beam at this time was about 40 mA at an acceleration voltage of 5 kV, and the degree of vacuum during deposition was 5 ⁇ 10 ⁇ 4 Pa.
  • the heat treatment conditions were as follows: The substrate on which the magnesium fluoride layer was formed was heated to 450°C in a mixed gas atmosphere of 20% by volume of fluorine gas and 80% by volume of nitrogen gas, and heat treated for 50 hours. This heat treatment caused the magnesium fluoride crystal grains in the magnesium fluoride layer to grow and become larger, forming the first layer.
  • the conditions of vacuum deposition when forming the magnesium fluoride layer, which is the second layer, on the first layer are as follows. First, the substrate on which the first layer has been formed was placed in a vacuum chamber, and then the vacuum chamber was evacuated until the degree of vacuum reached 2 ⁇ 10 ⁇ 4 Pa. Then, the substrate on which the first layer has been formed was heated to 400° C. A magnesium fluoride sintered body material was used as the deposition material, and the sintered body material was irradiated with an electron beam, and the shutter was opened to form a magnesium fluoride layer with a thickness of 90 nm on the first layer of the substrate. The input power of the electron beam at this time was about 40 mA at an acceleration voltage of 5 kV, and the degree of vacuum during deposition was 5 ⁇ 10 ⁇ 4 Pa.
  • the corrosion-resistant member of Example 1 thus obtained was cut to expose a cross section of the corrosion-resistant coating.
  • This cross section was the cross section of the corrosion-resistant coating that appears when the corrosion-resistant member is cut in a plane perpendicular to the surface of the corrosion-resistant coating.
  • the cross section was then processed using a precision ion polishing system Model 691 manufactured by Gatan.
  • the processed cross section was observed using a TITAN G2 60-300 transmission electron microscope manufactured by FEI, and a transmission electron microscope image was obtained.
  • the thickness of the corrosion-resistant coating was determined from the obtained transmission electron microscope image.
  • the thickness of the corrosion-resistant coating was determined for five fields of view in the transmission electron microscope image, and the average value of the five fields of view was taken as the thickness of the corrosion-resistant coating of the corrosion-resistant member of Example 1.
  • the conditions for electron microscope observation were an acceleration voltage of 300 kV and a magnification of 30,000 times.
  • a transmission electron microscope image of the cross section of the corrosion-resistant component was obtained in the same manner as above, except that the magnification of the electron microscope observation was 100,000 times, and the average crystal grain size of the magnesium fluoride crystal grains in the corrosion-resistant coating was calculated. That is, in the transmission electron microscope image, the boundaries (grain boundaries) of all crystal grains in the corrosion-resistant coating were confirmed, and the average crystal grain size was calculated from the average value of the circle equivalent diameters of the crystal grains. The interface between the first layer and the second layer was then determined.
  • the thickness of the corrosion-resistant coating of the corrosion-resistant member of Example 1 was 0.32 ⁇ m.
  • the average crystal grain size of the magnesium fluoride crystal grains in the first layer was 208 nm, and the average crystal grain size of the magnesium fluoride crystal grains in the second layer was 32 nm.
  • the ratio of the thickness of the second layer to the thickness of the corrosion-resistant coating was 31%.
  • Example 1 a heating test was conducted on the obtained corrosion-resistant member of Example 1 to evaluate the state of peeling of the corrosion-resistant coating.
  • the heating test conditions were as follows: one cycle was to hold the material at 300°C in a nitrogen gas atmosphere for 300 minutes, and then naturally cool it to room temperature; this cycle was repeated 10 times in succession.
  • a corrosion test was conducted on the obtained corrosion-resistant member of Example 1 to evaluate the state of peeling of the corrosion-resistant coating.
  • the corrosion test was conducted by carrying out heat treatment in an atmosphere of a mixed gas of fluorine gas and an inert gas.
  • the corrosion test conditions were a fluorine gas concentration in the mixed gas of 1 volume %, a heat treatment temperature of 300°C, and a heat treatment time of 300 minutes. Note that for the corrosion test, a sample of the corrosion-resistant member different from the sample used in the heating test was prepared in the same manner and used.
  • Example 2 A corrosion-resistant member was produced in the same manner as in Example 1, except that the magnesium fluoride layer formed on the substrate had a thickness of 90 nm, and the magnesium fluoride layer formed on the first layer had a thickness of 210 nm. The obtained corrosion-resistant member of Example 2 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A corrosion-resistant member was produced in the same manner as in Example 1, except that the magnesium fluoride layer formed on the substrate had a thickness of 270 nm, and the magnesium fluoride layer formed on the first layer had a thickness of 30 nm. The obtained corrosion-resistant member of Example 3 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 1 A corrosion-resistant member was manufactured in the same manner as in Example 1, except that the thickness of the magnesium fluoride layer formed on the substrate was 300 nm, no heat treatment was performed, and no additional magnesium fluoride layer was formed on the magnesium fluoride layer formed on the substrate.
  • the obtained corrosion-resistant member of Comparative Example 1 did not undergo heat treatment or second vacuum deposition, so the corrosion-resistant coating did not have a first layer and consisted only of a second layer.
  • the obtained corrosion-resistant member of Comparative Example 1 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 2 A corrosion-resistant member was manufactured in the same manner as in Example 1, except that the thickness of the magnesium fluoride layer formed on the substrate was 300 nm, and no additional magnesium fluoride layer was formed on the magnesium fluoride layer formed on the substrate.
  • the corrosion-resistant member of Comparative Example 2 obtained did not undergo a second vacuum deposition, and therefore the corrosion-resistant coating did not have a second layer, and consisted of only the first layer.
  • the corrosion-resistant member of Comparative Example 2 obtained was then evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the corrosion-resistant members of Examples 1 to 3 hardly experienced peeling of the corrosion-resistant coating from the substrate even when subjected to the thermal history of the heating test. Also, the corrosion-resistant members of Examples 1 to 3 hardly experienced peeling of the corrosion-resistant coating from the substrate even when subjected to corrosion in the corrosion test.
  • the corrosion-resistant coating of the corrosion-resistant member of Comparative Example 1 which does not have a first layer, peeled off during a heating test in which the temperature was repeatedly increased and decreased. It is believed that the corrosion-resistant coating of Comparative Example 1, which is made up only of the second layer with a small average crystal grain size, has low adhesion to the substrate. Furthermore, the corrosion-resistant member of Comparative Example 2, which does not have a second layer, peeled off during the corrosion test. It is believed that the first layer, which has a large average crystal grain size, is prone to cracking due to internal stress caused by corrosion, and corrosion progresses easily.
  • Substrate 20 Corrosion-resistant coating 21: First layer 22: Second layer

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Abstract

Provided is a corrosion-resistant member in which a corrosion-resistant coating film is unlikely to be detached from a base material even when being subjected to a thermal history. The corrosion-resistant member is provided with a metallic base material (10), and a corrosion-resistant coating film (20) that is formed on the surface of the base material (10) and that contains magnesium fluoride. The corrosion-resistant coating film (20) has a lamination part in which a first layer (21) and a second layer (22) are laminated on the base material (10) in the stated order. The first layer (21) is a layer having crystalline particles of magnesium fluoride having an average crystalline particle diameter of not less than 100 nm but less than 1000 nm. The second layer (22) is a layer having crystalline particles of magnesium fluoride having an average crystalline particle diameter of less than 100 nm.

Description

耐食性部材Corrosion-resistant materials

　本発明は耐食性部材に関する。 The present invention relates to corrosion-resistant components.

　半導体製造プロセスにおいては、塩素ガス、フッ素ガス等の腐食性の強いガスが使用される場合があるため、半導体製造装置を構成する部材には耐食性が要求される。半導体製造装置を構成する部材の例としては、チャンバー、配管、ガス貯蔵装置、バルブ、サセプター、シャワーヘッド等が挙げられる。
　特許文献１には、金属からなる基材の表面にマグネシウムフッ化物膜からなる耐食性被膜を形成してなる耐食性部材が開示されている。また、特許文献２には、マグネシウムを含有するアルミニウム合金からなる基材の表面が、フッ化マグネシウムを含むフッ化不働態膜からなる耐食性被膜で被覆された耐食性アルミニウム合金材が開示されている。 In semiconductor manufacturing processes, highly corrosive gases such as chlorine gas and fluorine gas may be used, and therefore corrosion resistance is required for components constituting semiconductor manufacturing equipment. Examples of components constituting semiconductor manufacturing equipment include chambers, piping, gas storage devices, valves, susceptors, shower heads, etc.
Patent Document 1 discloses a corrosion-resistant member in which a corrosion-resistant coating made of a magnesium fluoride film is formed on the surface of a metal substrate, while Patent Document 2 discloses a corrosion-resistant aluminum alloy material in which the surface of a substrate made of an aluminum alloy containing magnesium is coated with a corrosion-resistant coating made of a fluoride passivation film containing magnesium fluoride.

日本国特許公開公報　２０００年第１６９９５３号Japan Patent Publication No. 2000-169953 日本国特許公開公報　平成４年第６６６５７号Japanese Patent Publication No. 66657, 1992

　しかしながら、特許文献１、２に開示の部材は、熱履歴によって耐食性被膜が基材から剥離しやすいという問題点を有していた。
　本発明は、熱履歴を受けても耐食性被膜が基材から剥離しにくい耐食性部材を提供することを課題とする。 However, the members disclosed in Patent Documents 1 and 2 have a problem in that the corrosion-resistant coating is easily peeled off from the substrate due to thermal history.
An object of the present invention is to provide a corrosion-resistant member having a corrosion-resistant coating that is not easily peeled off from a substrate even when subjected to thermal history.

　前記課題を解決するため、本発明の一態様は以下の［１］～［４］の通りである。
［１］　金属製の基材と、前記基材の表面に形成され且つマグネシウムフッ化物を含有する耐食性被膜と、を備え、
　前記耐食性被膜は、前記基材上に第一の層と第二の層とがこの記載順で積層された積層部を有し、
　前記第一の層は、平均結晶粒径が１００ｎｍ以上１０００ｎｍ未満である前記マグネシウムフッ化物の結晶粒を有する層であり、
　前記第二の層は、平均結晶粒径が１００ｎｍ未満である前記マグネシウムフッ化物の結晶粒を有する層である耐食性部材。 In order to solve the above problems, one aspect of the present invention is as follows [1] to [4].
[1] A corrosion-resistant coating comprising a metal substrate and a corrosion-resistant coating containing magnesium fluoride formed on a surface of the substrate,
the corrosion-resistant coating has a laminated portion in which a first layer and a second layer are laminated on the substrate in this order;
the first layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of 100 nm or more and less than 1000 nm,
The second layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of less than 100 nm.

［２］　前記マグネシウムフッ化物がフッ化マグネシウムを含有する［１］に記載の耐食性部材。
［３］　前記耐食性被膜の厚さが０．１μｍ以上２０μｍ以下である［１］又は［２］に記載の耐食性部材。
［４］　前記耐食性被膜の厚さにおける前記第二の層の厚さの割合が５％以上９５％以下である［１］～［３］のいずれか一項に記載の耐食性部材。 [2] The corrosion-resistant member according to [1], wherein the magnesium fluoride contains magnesium fluoride.
[3] The corrosion-resistant member according to [1] or [2], wherein the thickness of the corrosion-resistant coating is 0.1 μm or more and 20 μm or less.
[4] The corrosion-resistant member according to any one of [1] to [3], wherein a ratio of a thickness of the second layer to a thickness of the corrosion-resistant coating is 5% or more and 95% or less.

　本発明に係る耐食性部材は、熱履歴を受けても耐食性被膜が基材から剥離しにくい。 The corrosion-resistant coating of the corrosion-resistant member of the present invention is unlikely to peel off from the base material even when subjected to thermal history.

本発明の一実施形態に係る耐食性部材の構成を説明する模式的断面図である。1 is a schematic cross-sectional view illustrating a configuration of a corrosion-resistant member according to an embodiment of the present invention. 図１の耐食性部材の耐食性被膜が有する第一の層と第二の層の詳細を説明する模式的断面図である。FIG. 2 is a schematic cross-sectional view illustrating details of a first layer and a second layer of the corrosion-resistant coating of the corrosion-resistant member of FIG. 1 .

　本発明の一実施形態について以下に説明する。なお、本実施形態は本発明の一例を示したものであって、本発明は本実施形態に限定されるものではない。また、本実施形態には種々の変更又は改良を加えることが可能であり、その様な変更又は改良を加えた形態も本発明に含まれ得る。 One embodiment of the present invention will be described below. Note that this embodiment is merely an example of the present invention, and the present invention is not limited to this embodiment. In addition, various modifications and improvements can be made to this embodiment, and forms incorporating such modifications or improvements can also be included in the present invention.

　本実施形態に係る耐食性部材は、図１、２に示すように、金属製の基材１０と、基材１０の表面に形成され且つマグネシウムフッ化物を含有する耐食性被膜２０と、を備える。なお、図１、２は、耐食性被膜２０の表面に直交する平面で耐食性部材を切断した場合に現れる耐食性部材の断面の模式図である。 As shown in Figures 1 and 2, the corrosion-resistant member according to this embodiment comprises a metal substrate 10 and a corrosion-resistant coating 20 that is formed on the surface of the substrate 10 and contains magnesium fluoride. Note that Figures 1 and 2 are schematic diagrams of a cross section of the corrosion-resistant member that appears when the corrosion-resistant member is cut along a plane perpendicular to the surface of the corrosion-resistant coating 20.

　この耐食性被膜２０は、基材１０上に第一の層２１と第二の層２２とがこの記載順で積層された積層部を有する。そして、第一の層２１は、平均結晶粒径が１００ｎｍ以上１０００ｎｍ未満であるマグネシウムフッ化物の結晶粒を有する層である。また、第二の層２２は、平均結晶粒径が１００ｎｍ未満であるマグネシウムフッ化物の結晶粒を有する層である。 This corrosion-resistant coating 20 has a laminated portion in which a first layer 21 and a second layer 22 are laminated on a substrate 10 in the order listed. The first layer 21 is a layer having magnesium fluoride crystal grains with an average crystal grain size of 100 nm or more and less than 1000 nm. The second layer 22 is a layer having magnesium fluoride crystal grains with an average crystal grain size of less than 100 nm.

　本実施形態に係る耐食性部材は、マグネシウムフッ化物を含有する耐食性被膜２０を備えているため、塩素ガス（Ｃｌ2）、フッ素ガス（Ｆ2）等の腐食性の強いガスやプラズマの中でも優れた耐食性を有する。また、本実施形態に係る耐食性部材は、マグネシウムフッ化物を含有する耐食性被膜２０を備えているため、熱履歴を受けても耐食性被膜２０が基材１０から剥離しにくい。 The corrosion-resistant member according to this embodiment has the corrosion-resistant coating 20 containing magnesium fluoride, and therefore has excellent corrosion resistance even in highly corrosive gases and plasmas such as chlorine gas (Cl 2 ) and fluorine gas (F 2 ). In addition, the corrosion-resistant member according to this embodiment has the corrosion-resistant coating 20 containing magnesium fluoride, and therefore the corrosion-resistant coating 20 is unlikely to peel off from the substrate 10 even when subjected to a thermal history.

　上記効果が奏される理由を、以下に詳細に説明する。耐食性被膜２０のうちマグネシウムフッ化物の結晶粒の平均結晶粒径が比較的大きい第一の層２１は、基材１０に対する耐食性被膜２０の密着性の向上に寄与する。また、マグネシウムフッ化物の結晶粒の平均結晶粒径が比較的小さい第二の層２２は、腐食性の強いガスに対する耐食性被膜２０の耐食性の向上に寄与する。 The reasons for the above effects are explained in detail below. The first layer 21 of the corrosion-resistant coating 20, in which the average crystal grain size of the magnesium fluoride crystal grains is relatively large, contributes to improving the adhesion of the corrosion-resistant coating 20 to the substrate 10. The second layer 22, in which the average crystal grain size of the magnesium fluoride crystal grains is relatively small, contributes to improving the corrosion resistance of the corrosion-resistant coating 20 against highly corrosive gases.

　すなわち、耐食性被膜２０が第一の層２１と第二の層２２を有することによって、腐食性の強いガスに対する耐食性と、熱履歴を受けても耐食性被膜２０が基材１０から剥離しにくく且つ割れが生じにくくなる特性とが両立される。特に、熱履歴を受けても耐食性被膜２０の基材１０に対する密着性が確保されることで、耐食性被膜２０の剥離に由来するパーティクルの発生が抑制される。 In other words, by having the corrosion-resistant coating 20 have the first layer 21 and the second layer 22, it is possible to achieve both corrosion resistance against highly corrosive gases and the property that the corrosion-resistant coating 20 is less likely to peel off from the substrate 10 and is less likely to crack even when subjected to thermal history. In particular, by ensuring the adhesion of the corrosion-resistant coating 20 to the substrate 10 even when subjected to thermal history, the generation of particles resulting from peeling of the corrosion-resistant coating 20 is suppressed.

　このような本実施形態に係る耐食性部材は、耐食性及び耐熱性が必要とされる部材として好適であり、例えば、半導体製造装置（特に、化学蒸着法を用いた成膜装置）を構成する部材として好適である。具体例を挙げると、プラズマを発生させた状態でウェハ上に薄膜を形成する成膜装置のサセプターやシャワーヘッドとして好適である。半導体製造装置を構成する部材として本実施形態に係る耐食性部材を用いれば、パーティクルの発生が抑制されるので、高い歩留まりで半導体を製造することができる。 The corrosion-resistant member according to this embodiment is suitable as a member that requires corrosion resistance and heat resistance, for example, as a component of semiconductor manufacturing equipment (particularly, a film-forming device using a chemical vapor deposition method). As a specific example, it is suitable as a susceptor or shower head of a film-forming device that forms a thin film on a wafer while plasma is generated. If the corrosion-resistant member according to this embodiment is used as a component of semiconductor manufacturing equipment, particle generation is suppressed, and semiconductors can be manufactured with a high yield.

　以下に、本実施形態に係る耐食性部材について、さらに詳細に説明する。
〔基材〕
　基材１０を構成する金属は、特に限定されるものではなく、単体の金属（不可避的不純物は含有する）であってもよいし、合金であってもよい。例えば、アルミニウム又はアルミニウム合金であってもよい。 The corrosion-resistant member according to this embodiment will be described in further detail below.
[Substrate]
The metal constituting the base material 10 is not particularly limited, and may be a simple metal (containing unavoidable impurities) or an alloy, such as aluminum or an aluminum alloy.

〔耐食性被膜〕
　本実施形態に係る耐食性部材が備える耐食性被膜２０は、マグネシウムフッ化物を含有する。すなわち、耐食性被膜２０は、マグネシウムフッ化物で形成されていてもよいし、マグネシウムフッ化物と他の材料とで形成されていてもよい。マグネシウムフッ化物の種類は特に限定されるものではないが、例えば、フッ化マグネシウム（ＭｇＦ2）、酸フッ化マグネシウムが挙げられる。マグネシウムフッ化物の種類は、エネルギー分散型Ｘ線分析（ＥＤＳ）、Ｘ線回折法（ＸＲＤ）等で評価することができる。 [Corrosion-resistant coating]
The corrosion-resistant coating 20 of the corrosion-resistant member according to this embodiment contains magnesium fluoride. That is, the corrosion-resistant coating 20 may be formed of magnesium fluoride, or may be formed of magnesium fluoride and another material. The type of magnesium fluoride is not particularly limited, and examples thereof include magnesium fluoride (MgF 2 ) and magnesium oxyfluoride. The type of magnesium fluoride can be evaluated by energy dispersive X-ray analysis (EDS), X-ray diffraction (XRD), or the like.

　本実施形態に係る耐食性部材が備える耐食性被膜２０は、基材１０上に第一の層２１と第二の層２２とがこの記載順で積層された積層部を有している。例えば、図１、２に示すように、基材１０上に層状の第一の層２１が積層され、その第一の層２１の上に層状の第二の層２２がさらに積層された構造であってもよい。 The corrosion-resistant coating 20 provided on the corrosion-resistant member according to this embodiment has a laminated portion in which a first layer 21 and a second layer 22 are laminated on a substrate 10 in the order described above. For example, as shown in Figures 1 and 2, a structure may be used in which a layered first layer 21 is laminated on a substrate 10, and a layered second layer 22 is further laminated on the first layer 21.

　第一の層２１と第二の層２２とが積層された積層部が、耐食性被膜２０の全体をなしていてもよいし（図１、２を参照）、耐食性被膜２０の一部分をなしていてもよい（図示せず）。すなわち、第一の層２１と第二の層２２とが積層された積層部が、基材１０の表面の全面を覆っていてもよいし（図１、２を参照）、基材１０の表面の一部分を覆っていてもよい（図示せず）。 The laminated portion in which the first layer 21 and the second layer 22 are laminated may form the entire corrosion-resistant coating 20 (see Figures 1 and 2), or may form only a part of the corrosion-resistant coating 20 (not shown). In other words, the laminated portion in which the first layer 21 and the second layer 22 are laminated may cover the entire surface of the substrate 10 (see Figures 1 and 2), or may cover only a part of the surface of the substrate 10 (not shown).

　次に、本実施形態に係る耐食性部材において、耐食性被膜２０の厚さを測定する方法、耐食性被膜２０が含有するマグネシウムフッ化物の結晶粒の平均結晶粒径を測定する方法、及び、第一の層２１と第二の層２２を識別する方法について、図１及び図２を参照しながら以下に詳細に説明する。 Next, a method for measuring the thickness of the corrosion-resistant coating 20, a method for measuring the average crystal grain size of the magnesium fluoride crystal grains contained in the corrosion-resistant coating 20, and a method for distinguishing the first layer 21 and the second layer 22 in the corrosion-resistant member according to this embodiment will be described in detail below with reference to Figures 1 and 2.

　耐食性被膜２０の厚さを測定する方法、耐食性被膜２０が含有するマグネシウムフッ化物の結晶粒の平均結晶粒径を測定する方法、及び、第一の層２１と第二の層２２を識別する方法は、特に限定されるものではないが、いずれも透過型電子顕微鏡（ＴＥＭ）、走査型透過電子顕微鏡（ＳＴＥＭ）、走査型電子顕微鏡（ＳＥＭ）等を用いて電子顕微鏡観察を行い、電子顕微鏡像を得ることによって行うことができる。電子顕微鏡観察の倍率は特に限定されるものではないが、例えば３００００倍以上５００００倍以下とすることができる。 The method for measuring the thickness of the corrosion-resistant coating 20, the method for measuring the average crystal grain size of the magnesium fluoride crystal grains contained in the corrosion-resistant coating 20, and the method for distinguishing the first layer 21 and the second layer 22 are not particularly limited, but all of them can be performed by performing electron microscope observation using a transmission electron microscope (TEM), a scanning transmission electron microscope (STEM), a scanning electron microscope (SEM), or the like to obtain an electron microscope image. The magnification of the electron microscope observation is not particularly limited, but can be, for example, 30,000 times or more and 50,000 times or less.

　観察する対象は、耐食性被膜２０の内部であれば特に限定されるものではないが、例えば、耐食性被膜２０を切断した場合に現れる断面が挙げられる。断面の種類についても特に限定されるものではないが、例えば、耐食性被膜２０の表面に直交する平面で耐食性部材を切断した場合に現れる耐食性部材の断面が挙げられる。あるいは、耐食性被膜２０の表面に平行な平面で耐食性被膜２０を切断した場合に現れる断面でもよい。 The object to be observed is not particularly limited as long as it is the inside of the corrosion-resistant coating 20, but examples of the object include a cross section that appears when the corrosion-resistant coating 20 is cut. The type of cross section is also not particularly limited, but examples of the object include a cross section of a corrosion-resistant member that appears when the corrosion-resistant member is cut in a plane perpendicular to the surface of the corrosion-resistant coating 20. Alternatively, the cross section that appears when the corrosion-resistant coating 20 is cut in a plane parallel to the surface of the corrosion-resistant coating 20 may be used.

　耐食性被膜２０の厚さの測定方法の一例を挙げる。耐食性部材を切断して断面を露出させ、透過型電子顕微鏡を用いてその断面の透過型電子顕微鏡像を得て、透過型電子顕微鏡像においてマグネシウムフッ化物に該当する箇所を測長することによって、耐食性被膜２０の厚さを求めることができる。断面の種類としては、例えば、耐食性被膜２０の表面に直交する平面で耐食性部材を切断した場合に現れる耐食性部材の断面が挙げられる。 An example of a method for measuring the thickness of the corrosion-resistant coating 20 is given below. The corrosion-resistant member is cut to expose the cross section, and a transmission electron microscope image of the cross section is obtained using a transmission electron microscope. The thickness of the corrosion-resistant coating 20 can be obtained by measuring the length of the portion of the transmission electron microscope image that corresponds to magnesium fluoride. One type of cross section is, for example, the cross section of the corrosion-resistant member that appears when the corrosion-resistant member is cut on a plane perpendicular to the surface of the corrosion-resistant coating 20.

　耐食性被膜２０の厚さは特に限定されるものではないが、０．１μｍ以上２０μｍ以下であることが好ましく、０．１５μｍ以上１０μｍ以下であることがより好ましく、０．２μｍ以上１μｍ以下であることがさらに好ましい。耐食性被膜２０の厚さが０．１μｍ以上であれば、耐食性被膜２０の耐食性を十分に確保することができる。また、耐食性被膜２０の厚さが２０μｍ以下であれば、熱履歴を受けても耐食性被膜２０に割れが生じにくい。 The thickness of the corrosion-resistant coating 20 is not particularly limited, but is preferably 0.1 μm to 20 μm, more preferably 0.15 μm to 10 μm, and even more preferably 0.2 μm to 1 μm. If the thickness of the corrosion-resistant coating 20 is 0.1 μm or more, the corrosion resistance of the corrosion-resistant coating 20 can be sufficiently ensured. Furthermore, if the thickness of the corrosion-resistant coating 20 is 20 μm or less, the corrosion-resistant coating 20 is less likely to crack even when subjected to a thermal history.

　耐食性被膜２０が含有するマグネシウムフッ化物の結晶粒の平均結晶粒径を測定する方法の一例を挙げる。耐食性部材を切断して断面を露出させ、透過型電子顕微鏡を用いてその断面の透過型電子顕微鏡像を得て、その透過型電子顕微鏡像において結晶粒の境界を確認し、結晶粒の円相当直径の平均値から、マグネシウムフッ化物の結晶粒の平均結晶粒径を算出することができる。耐食性被膜２０に第一の層２１及び第二の層２２が存在することは、上記の方法で測定した結晶粒径から任意の領域の平均結晶粒径を算出することによって確認することができる。 Here is an example of a method for measuring the average crystal grain size of magnesium fluoride crystal grains contained in the corrosion-resistant coating 20. The corrosion-resistant member is cut to expose the cross section, and a transmission electron microscope image of the cross section is obtained using a transmission electron microscope. The boundaries of the crystal grains are confirmed in the transmission electron microscope image, and the average crystal grain size of the magnesium fluoride crystal grains can be calculated from the average value of the circle equivalent diameters of the crystal grains. The presence of the first layer 21 and the second layer 22 in the corrosion-resistant coating 20 can be confirmed by calculating the average crystal grain size of any region from the crystal grain size measured by the above method.

　第一の層２１におけるマグネシウムフッ化物の結晶粒の平均結晶粒径は、１００ｎｍ以上１０００ｎｍ以下である必要があり、１１０ｎｍ以上６００ｎｍ以下であることが好ましく、１２０ｎｍ以上３００ｎｍ以下であることがより好ましい。平均結晶粒径が上記範囲内であれば、基材１０と耐食性被膜２０との密着性がより高くなる。 The average crystal grain size of the magnesium fluoride crystal grains in the first layer 21 must be 100 nm or more and 1000 nm or less, preferably 110 nm or more and 600 nm or less, and more preferably 120 nm or more and 300 nm or less. If the average crystal grain size is within the above range, the adhesion between the substrate 10 and the corrosion-resistant coating 20 will be higher.

　第二の層２２におけるマグネシウムフッ化物の結晶粒の平均結晶粒径は、１００ｎｍ未満である必要があり、１ｎｍ以上８０ｎｍ以下であることが好ましく、１０ｎｍ以上５０ｎｍ以下であることがより好ましい。平均結晶粒径が上記範囲内であれば、機械的強度が高く耐食性被膜２０に割れが生じにくい。 The average crystal grain size of the magnesium fluoride crystal grains in the second layer 22 must be less than 100 nm, preferably 1 nm to 80 nm, and more preferably 10 nm to 50 nm. If the average crystal grain size is within the above range, the mechanical strength is high and the corrosion-resistant coating 20 is less likely to crack.

　耐食性被膜２０の厚さにおける第二の層２２の厚さの割合は、５％以上９５％以下であることが好ましく、７％以上９０％以下であることがより好ましく、１０％以上８０％以下であることがさらに好ましい。このような構成であれば、耐食性被膜２０の耐食性を十分に確保することができるとともに、基材１０と耐食性被膜２０との密着性がより高くなる。 The ratio of the thickness of the second layer 22 to the thickness of the corrosion-resistant coating 20 is preferably 5% or more and 95% or less, more preferably 7% or more and 90% or less, and even more preferably 10% or more and 80% or less. With this configuration, the corrosion resistance of the corrosion-resistant coating 20 can be sufficiently ensured, and the adhesion between the substrate 10 and the corrosion-resistant coating 20 is further improved.

　第一の層２１及び第二の層２２のそれぞれの厚さは、以下のようにして求めることができる。すなわち、図２に示すように、結晶粒の平均結晶粒径に基づいて第一の層２１と第二の層２２の界面を設定し、基材１０から該界面までの距離（耐食性被膜２０の表面に直交する方向の長さ）の平均値を第一の層２１の厚さとし、該界面から耐食性被膜２０の表面までの距離（耐食性被膜２０の表面に直交する方向の長さ）の平均値を第二の層２２の厚さとすることができる。
　なお、第一の層２１及び第二の層２２におけるマグネシウムフッ化物の結晶性は、特に制限されない。すなわち、第一の層２１及び第二の層２２の結晶粒の中には、複数の結晶子が含まれてもよく、アモルファス相が含まれていてもよい。 The thicknesses of the first layer 21 and the second layer 22 can be determined as follows: That is, as shown in Fig. 2, an interface between the first layer 21 and the second layer 22 is set based on the average crystal grain size of the crystal grains, and the average value of the distance from the substrate 10 to the interface (the length in the direction perpendicular to the surface of the corrosion-resistant coating 20) is defined as the thickness of the first layer 21, and the average value of the distance from the interface to the surface of the corrosion-resistant coating 20 (the length in the direction perpendicular to the surface of the corrosion-resistant coating 20) is defined as the thickness of the second layer 22.
The crystallinity of the magnesium fluoride in the first layer 21 and the second layer 22 is not particularly limited. That is, the crystal grains in the first layer 21 and the second layer 22 may contain a plurality of crystallites or an amorphous phase.

〔耐食性部材の製造方法〕
　本実施形態に係る耐食性部材を製造する方法は特に限定されるものではないが、一例を挙げると、基材の表面上に蒸着等の方法によってフッ化マグネシウム層を形成した後に熱処理し、その熱処理したフッ化マグネシウム層の上にさらに蒸着等の方法によってフッ化マグネシウム層を積層して形成する方法が挙げられる。 [Method for manufacturing corrosion-resistant member]
The method for manufacturing the corrosion-resistant member according to this embodiment is not particularly limited, but one example includes a method in which a magnesium fluoride layer is formed on the surface of a substrate by a method such as vapor deposition, followed by heat treatment, and then a further magnesium fluoride layer is laminated on top of the heat-treated magnesium fluoride layer by a method such as vapor deposition.

　熱処理前のフッ化マグネシウム層は、結晶質のフッ化マグネシウムを含有しているが、フッ素ガス雰囲気等の雰囲気中で熱処理を施すと、フッ化マグネシウム粒子の焼結（粒成長）が生じ、フッ化マグネシウム層中のフッ化マグネシウムの結晶粒の結晶粒径が大きくなる。よって、基材の表面上にフッ化マグネシウム層を形成した後に熱処理することによって、第一の層に相当する結晶質の層が形成される。そして、第一の層に相当する層の上にフッ化マグネシウム層を形成することによって、第二の層に相当する結晶質の層が形成され、第一の層と第二の層が積層した積層部が形成される。 The magnesium fluoride layer before heat treatment contains crystalline magnesium fluoride, but when heat treatment is performed in an atmosphere such as a fluorine gas atmosphere, sintering (grain growth) of the magnesium fluoride particles occurs, and the crystal grain size of the magnesium fluoride crystal grains in the magnesium fluoride layer increases. Therefore, by forming a magnesium fluoride layer on the surface of the substrate and then performing heat treatment, a crystalline layer equivalent to the first layer is formed. Then, by forming a magnesium fluoride layer on the layer equivalent to the first layer, a crystalline layer equivalent to the second layer is formed, and a laminated portion in which the first layer and second layer are laminated is formed.

　フッ化マグネシウム層は、例えば、真空蒸着、物理蒸着（ＰＶＤ）、化学蒸着（ＣＶＤ）、スパッタリング等の方法によって形成することができる。
　熱処理時の保持温度は、好ましくは２００℃以上５００℃以下であって、より好ましくは３００℃以上４７５℃以下であって、さらに好ましくは３５０℃以上４５０℃以下である。熱処理時の保持温度が２００℃以上であれば、フッ化マグネシウム層のフッ化マグネシウムの結晶粒の結晶粒径が成長して大きくなりやすい。熱処理時の保持温度が５００℃以下であれば、フッ化マグネシウム層にクラックが発生しにくい。 The magnesium fluoride layer can be formed by a method such as vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), sputtering, or the like.
The holding temperature during the heat treatment is preferably 200° C. or higher and 500° C. or lower, more preferably 300° C. or higher and 475° C. or lower, and further preferably 350° C. or higher and 450° C. or lower. If the holding temperature during the heat treatment is 200° C. or higher, the crystal grain size of magnesium fluoride crystal grains in the magnesium fluoride layer tends to grow and become large. If the holding temperature during the heat treatment is 500° C. or lower, cracks are unlikely to occur in the magnesium fluoride layer.

　熱処理時の保持時間は、好ましくは１時間以上２５０時間以下であって、より好ましくは３時間以上１５０時間以下であって、さらに好ましくは５時間以上１００時間以下である。熱処理時の保持時間が１時間以上であれば、フッ化マグネシウム層のフッ化マグネシウムの結晶粒の結晶粒径が成長して大きくなりやすい。熱処理時の保持時間が２５０時間以下であれば、生産性が良好となりやすい。 The holding time during the heat treatment is preferably 1 hour or more and 250 hours or less, more preferably 3 hours or more and 150 hours or less, and even more preferably 5 hours or more and 100 hours or less. If the holding time during the heat treatment is 1 hour or more, the crystal grain size of the magnesium fluoride crystal grains in the magnesium fluoride layer tends to grow and become large. If the holding time during the heat treatment is 250 hours or less, productivity tends to be good.

　以下に実施例及び比較例を示して、本発明をより具体的に説明する。
〔実施例１〕
　基材に対してまず前処理を行い、その後に真空蒸着を行って基材の表面上にフッ化マグネシウム層を形成した。その後に熱処理を行うことにより、フッ化マグネシウム層を第一の層とした。さらに、第一の層の上に、第二の層に相当するフッ化マグネシウム層を真空蒸着によって新たに形成することにより、第一の層と第二の層が積層した積層部である耐食性被膜を形成して、耐食性部材を得た。 The present invention will be described more specifically below with reference to examples and comparative examples.
Example 1
The substrate was first pretreated, and then a magnesium fluoride layer was formed on the surface of the substrate by vacuum deposition. The magnesium fluoride layer was then heat-treated to form a first layer. A magnesium fluoride layer equivalent to the second layer was then newly formed on the first layer by vacuum deposition, forming a corrosion-resistant coating that was a laminate of the first layer and the second layer, thereby obtaining a corrosion-resistant member.

　基材を構成する金属は、マグネシウムを２．５５質量％含有するアルミニウム合金Ａ５０５２である。また、基材は、縦５０ｍｍ、横３０ｍｍ、厚さ３ｍｍの板状である。
　基材に対する前処理は、次のように行った。まず、エスクリーンＡＬ－１３（佐々木化学薬品株式会社製）７０ｇを水１Ｌに溶かし温度を５０℃としたものを脱脂液とし、この脱脂液中に基材を１０分間浸漬させて脱脂を行い、純水にて洗浄した。 The metal constituting the substrate is an aluminum alloy A5052 containing 2.55 mass % of magnesium, and the substrate is in the form of a plate having a length of 50 mm, a width of 30 mm, and a thickness of 3 mm.
The substrate was pretreated as follows: First, 70 g of S-clean AL-13 (manufactured by Sasaki Chemical Co., Ltd.) was dissolved in 1 L of water and the temperature was adjusted to 50° C. to prepare a degreasing solution, and the substrate was degreased by immersing it in the degreasing solution for 10 minutes and then washed with pure water.

　次に、エスクリーンＡＬ－５０００（佐々木化学薬品株式会社製）５００ｇを７０℃に加熱したものをエッチング液とし、このエッチング液中に、上記脱脂した基材を１分間浸漬させてエッチングを行い、純水にて洗浄した。
　その後、硝酸を含有するスマットクリーン（ライキ株式会社製）２００ｇを水４００ｇに溶かし温度を２５℃としたものをスマット除去液とし、このスマット除去液中に、上記エッチングした基材を３０秒間浸漬させてスマット除去を行い、純水にて洗浄した。そして、上記スマット除去した基材を真空乾燥させて、前処理を完了した。 Next, 500 g of S-clean AL-5000 (manufactured by Sasaki Chemical Co., Ltd.) heated to 70° C. was used as an etching solution, and the degreased substrate was immersed in this etching solution for 1 minute to perform etching, and then washed with pure water.
Thereafter, 200 g of Smut Clean (manufactured by Raiki Co., Ltd.) containing nitric acid was dissolved in 400 g of water and the temperature was adjusted to 25° C. to prepare a smut removal solution, and the etched substrate was immersed in the smut removal solution for 30 seconds to remove smut, and then washed with pure water. The substrate from which the smut was removed was then vacuum dried to complete the pretreatment.

　第一の層となるフッ化マグネシウム層を基材の表面上に形成する際の真空蒸着の条件は、次のとおりである。まず、前処理を施した基材を真空チャンバー内に設置した後に、真空度が２×１０-4Ｐａとなるまで真空チャンバー内を排気した。その後、前処理を施した基材を４００℃に加熱した。蒸着材料としてフッ化マグネシウム焼結体材料を用い、この焼結体材料に電子ビームを照射し、シャッターを開け、４００℃に保持した基材上に厚さ２１０ｎｍのフッ化マグネシウム層を形成した。このときの電子ビームの投入電力は、５ｋＶの加速電圧で４０ｍＡ程度であり、蒸着時の真空度は５×１０-4Ｐａとした。 The conditions of vacuum deposition when forming the magnesium fluoride layer as the first layer on the surface of the substrate are as follows. First, the pretreated substrate was placed in a vacuum chamber, and then the vacuum chamber was evacuated until the degree of vacuum reached 2×10 −4 Pa. The pretreated substrate was then heated to 400° C. A magnesium fluoride sintered material was used as the deposition material, and the sintered material was irradiated with an electron beam, and a shutter was opened to form a magnesium fluoride layer with a thickness of 210 nm on the substrate held at 400° C. The input power of the electron beam at this time was about 40 mA at an acceleration voltage of 5 kV, and the degree of vacuum during deposition was 5×10 −4 Pa.

　熱処理の条件は、次のとおりである。フッ化マグネシウム層を形成した基材を、２０体積％のフッ素ガスと８０体積％の窒素ガスの混合ガス雰囲気中で４５０℃に加熱し、５０時間熱処理を施した。この熱処理により、フッ化マグネシウム層中のフッ化マグネシウムの結晶粒が成長して大きくなり、第一の層が形成された。 The heat treatment conditions were as follows: The substrate on which the magnesium fluoride layer was formed was heated to 450°C in a mixed gas atmosphere of 20% by volume of fluorine gas and 80% by volume of nitrogen gas, and heat treated for 50 hours. This heat treatment caused the magnesium fluoride crystal grains in the magnesium fluoride layer to grow and become larger, forming the first layer.

　第二の層であるフッ化マグネシウム層を第一の層の上に形成する際の真空蒸着の条件は、次のとおりである。まず、第一の層を形成した基材を真空チャンバー内に設置した後に、真空度が２×１０-4Ｐａとなるまで真空チャンバー内を排気した。その後、第一の層を形成した基材を４００℃に加熱した。蒸着材料としてフッ化マグネシウム焼結体材料を用い、この焼結体材料に電子ビームを照射し、シャッターを開け、基材の第一の層の上に厚さ９０ｎｍのフッ化マグネシウム層を形成した。このときの電子ビームの投入電力は、５ｋＶの加速電圧で４０ｍＡ程度であり、蒸着時の真空度は５×１０-4Ｐａとした。 The conditions of vacuum deposition when forming the magnesium fluoride layer, which is the second layer, on the first layer are as follows. First, the substrate on which the first layer has been formed was placed in a vacuum chamber, and then the vacuum chamber was evacuated until the degree of vacuum reached 2×10 −4 Pa. Then, the substrate on which the first layer has been formed was heated to 400° C. A magnesium fluoride sintered body material was used as the deposition material, and the sintered body material was irradiated with an electron beam, and the shutter was opened to form a magnesium fluoride layer with a thickness of 90 nm on the first layer of the substrate. The input power of the electron beam at this time was about 40 mA at an acceleration voltage of 5 kV, and the degree of vacuum during deposition was 5×10 −4 Pa.

　こうして得られた実施例１の耐食性部材を切断して、耐食性被膜の断面を露出させた。この断面は、耐食性被膜の表面に直交する平面で耐食性部材を切断した場合に現れる耐食性被膜の断面とした。そして、Ｇａｔａｎ社製の精密イオンポリッシングシステムＭｏｄｅｌ６９１を用いて、上記断面を加工した。 The corrosion-resistant member of Example 1 thus obtained was cut to expose a cross section of the corrosion-resistant coating. This cross section was the cross section of the corrosion-resistant coating that appears when the corrosion-resistant member is cut in a plane perpendicular to the surface of the corrosion-resistant coating. The cross section was then processed using a precision ion polishing system Model 691 manufactured by Gatan.

　上記加工した断面を、ＦＥＩ社製の透過型電子顕微鏡ＴＩＴＡＮ　Ｇ２　６０－３００を用いて観察し、透過型電子顕微鏡像を得て、得られた透過型電子顕微鏡像から耐食性被膜の膜厚を求めた。透過型電子顕微鏡像の中の５つの視野について耐食性被膜の膜厚を求め、５つの視野の平均値を実施例１の耐食性部材の耐食性被膜の膜厚とした。電子顕微鏡観察の条件は、加速電圧３００ｋＶ、倍率３００００倍である。 The processed cross section was observed using a TITAN G2 60-300 transmission electron microscope manufactured by FEI, and a transmission electron microscope image was obtained. The thickness of the corrosion-resistant coating was determined from the obtained transmission electron microscope image. The thickness of the corrosion-resistant coating was determined for five fields of view in the transmission electron microscope image, and the average value of the five fields of view was taken as the thickness of the corrosion-resistant coating of the corrosion-resistant member of Example 1. The conditions for electron microscope observation were an acceleration voltage of 300 kV and a magnification of 30,000 times.

　また、電子顕微鏡観察の倍率が１０万倍であること以外は上記と同様にして耐食性部材の断面の透過型電子顕微鏡像を得て、耐食性被膜中のフッ化マグネシウムの結晶粒の平均結晶粒径の算出を行った。すなわち、透過型電子顕微鏡像において、耐食性被膜中のすべての結晶粒の境界（粒界）を確認し、結晶粒の円相当直径の平均値から平均結晶粒径を算出した。その後、第一の層と第二の層の界面を決定した。 Furthermore, a transmission electron microscope image of the cross section of the corrosion-resistant component was obtained in the same manner as above, except that the magnification of the electron microscope observation was 100,000 times, and the average crystal grain size of the magnesium fluoride crystal grains in the corrosion-resistant coating was calculated. That is, in the transmission electron microscope image, the boundaries (grain boundaries) of all crystal grains in the corrosion-resistant coating were confirmed, and the average crystal grain size was calculated from the average value of the circle equivalent diameters of the crystal grains. The interface between the first layer and the second layer was then determined.

　このように上記加工した断面を分析した結果、実施例１の耐食性部材の耐食性被膜の膜厚は０．３２μｍであった。また、第一の層中のフッ化マグネシウムの結晶粒の平均結晶粒径は２０８ｎｍであり、第二の層中のフッ化マグネシウムの結晶粒の平均結晶粒径は３２ｎｍであった。さらに、耐食性被膜の厚さにおける第二の層の厚さの割合は、３１％であった。 As a result of analyzing the cross section thus machined, the thickness of the corrosion-resistant coating of the corrosion-resistant member of Example 1 was 0.32 μm. The average crystal grain size of the magnesium fluoride crystal grains in the first layer was 208 nm, and the average crystal grain size of the magnesium fluoride crystal grains in the second layer was 32 nm. Furthermore, the ratio of the thickness of the second layer to the thickness of the corrosion-resistant coating was 31%.

　次に、得られた実施例１の耐食性部材に対して加熱試験を行い、耐食性被膜の剥離の状態を評価した。加熱試験の条件は、窒素ガス雰囲気中で３００℃で３００ｍｉｎ保持した後に室温まで自然冷却するという工程を１サイクルとして、これを１０サイクル連続して行うというものである。 Next, a heating test was conducted on the obtained corrosion-resistant member of Example 1 to evaluate the state of peeling of the corrosion-resistant coating. The heating test conditions were as follows: one cycle was to hold the material at 300°C in a nitrogen gas atmosphere for 300 minutes, and then naturally cool it to room temperature; this cycle was repeated 10 times in succession.

　加熱試験が終了したら、耐食性部材の表面を走査型電子顕微鏡で観察し、耐食性被膜の剥離の程度を評価した。結果を表１に示す。表１においては、耐食性被膜のうち剥離した部分の面積が耐食性被膜の面積の１％未満であった場合は「ＳＡ」、１％以上５％未満であった場合は「Ａ」、５％以上３０％未満であった場合は「Ｂ」、３０％以上であった場合は「Ｃ」で示してある。なお、表１中の「－」は、当該層が形成されていないことを示す。 Once the heating test was completed, the surface of the corrosion-resistant component was observed with a scanning electron microscope to evaluate the degree of peeling of the corrosion-resistant coating. The results are shown in Table 1. In Table 1, if the area of the peeled portion of the corrosion-resistant coating was less than 1% of the area of the corrosion-resistant coating, it is indicated as "SA", if it was 1% or more but less than 5%, it is indicated as "A", if it was 5% or more but less than 30%, it is indicated as "B", and if it was 30% or more, it is indicated as "C". In Table 1, "-" indicates that the layer in question was not formed.

　また、得られた実施例１の耐食性部材に対して腐食試験を行い、耐食性被膜の剥離の状態を評価した。腐食試験は、フッ素ガスと不活性ガスの混合ガス雰囲気下で熱処理を行うというものである。腐食試験の条件は、混合ガス中のフッ素ガスの濃度が１体積％、熱処理温度が３００℃、熱処理時間が３００ｍｉｎである。なお、腐食試験には、加熱試験に使用した耐食性部材のサンプルとは別のサンプルを同様に作製して使用した。 Furthermore, a corrosion test was conducted on the obtained corrosion-resistant member of Example 1 to evaluate the state of peeling of the corrosion-resistant coating. The corrosion test was conducted by carrying out heat treatment in an atmosphere of a mixed gas of fluorine gas and an inert gas. The corrosion test conditions were a fluorine gas concentration in the mixed gas of 1 volume %, a heat treatment temperature of 300°C, and a heat treatment time of 300 minutes. Note that for the corrosion test, a sample of the corrosion-resistant member different from the sample used in the heating test was prepared in the same manner and used.

　腐食試験が終了したら、耐食性部材の表面を走査型電子顕微鏡で観察し、耐食性被膜の剥離の程度を評価した。結果を表１に示す。表１においては、耐食性被膜のうち剥離した部分の面積が耐食性被膜の面積の１％未満であった場合は「ＳＡ」、１％以上１０％未満であった場合は「Ａ」、１０％以上５０％未満であった場合は「Ｂ」、５０％以上であった場合は「Ｃ」で示してある。 Once the corrosion test was completed, the surface of the corrosion-resistant component was observed with a scanning electron microscope to evaluate the degree of peeling of the corrosion-resistant coating. The results are shown in Table 1. In Table 1, if the area of the peeled portion of the corrosion-resistant coating was less than 1% of the area of the corrosion-resistant coating, it is indicated as "SA", if it was 1% or more but less than 10%, it is indicated as "A", if it was 10% or more but less than 50%, it is indicated as "B", and if it was 50% or more, it is indicated as "C".

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

〔実施例２〕
　基材上に形成するフッ化マグネシウム層の厚さを９０ｎｍ、第一の層の上に形成するフッ化マグネシウム層の厚さを２１０ｎｍとする点を除いては、実施例１と同様にして耐食性部材を製造した。そして、得られた実施例２の耐食性部材に対して、実施例１と同様の評価を行った。結果を表１に示す。 Example 2
A corrosion-resistant member was produced in the same manner as in Example 1, except that the magnesium fluoride layer formed on the substrate had a thickness of 90 nm, and the magnesium fluoride layer formed on the first layer had a thickness of 210 nm. The obtained corrosion-resistant member of Example 2 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.

〔実施例３〕
　基材上に形成するフッ化マグネシウム層の厚さを２７０ｎｍ、第一の層の上に形成するフッ化マグネシウム層の厚さを３０ｎｍとする点を除いては、実施例１と同様にして耐食性部材を製造した。そして、得られた実施例３の耐食性部材に対して、実施例１と同様の評価を行った。結果を表１に示す。 Example 3
A corrosion-resistant member was produced in the same manner as in Example 1, except that the magnesium fluoride layer formed on the substrate had a thickness of 270 nm, and the magnesium fluoride layer formed on the first layer had a thickness of 30 nm. The obtained corrosion-resistant member of Example 3 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.

〔比較例１〕
　基材上に形成するフッ化マグネシウム層の厚さを３００ｎｍとする点と、熱処理を行わない点と、基材上に形成したフッ化マグネシウム層の上にさらなるフッ化マグネシウム層を形成しない点とを除いては、実施例１と同様にして耐食性部材を製造した。得られた比較例１の耐食性部材は、熱処理及び２回目の真空蒸着を行わなかったため、耐食性被膜が第一の層を有しておらず、第二の層のみからなる。そして、得られた比較例１の耐食性部材に対して、実施例１と同様の評価を行った。結果を表１に示す。 Comparative Example 1
A corrosion-resistant member was manufactured in the same manner as in Example 1, except that the thickness of the magnesium fluoride layer formed on the substrate was 300 nm, no heat treatment was performed, and no additional magnesium fluoride layer was formed on the magnesium fluoride layer formed on the substrate. The obtained corrosion-resistant member of Comparative Example 1 did not undergo heat treatment or second vacuum deposition, so the corrosion-resistant coating did not have a first layer and consisted only of a second layer. The obtained corrosion-resistant member of Comparative Example 1 was then evaluated in the same manner as in Example 1. The results are shown in Table 1.

〔比較例２〕
　基材上に形成するフッ化マグネシウム層の厚さを３００ｎｍとする点と、基材上に形成したフッ化マグネシウム層の上にさらなるフッ化マグネシウム層を形成しない点とを除いては、実施例１と同様にして耐食性部材を製造した。得られた比較例２の耐食性部材は、２回目の真空蒸着を行わなかったため、耐食性被膜が第二の層を有しておらず、第一の層のみからなる。そして、得られた比較例２の耐食性部材に対して、実施例１と同様の評価を行った。結果を表１に示す。 Comparative Example 2
A corrosion-resistant member was manufactured in the same manner as in Example 1, except that the thickness of the magnesium fluoride layer formed on the substrate was 300 nm, and no additional magnesium fluoride layer was formed on the magnesium fluoride layer formed on the substrate. The corrosion-resistant member of Comparative Example 2 obtained did not undergo a second vacuum deposition, and therefore the corrosion-resistant coating did not have a second layer, and consisted of only the first layer. The corrosion-resistant member of Comparative Example 2 obtained was then evaluated in the same manner as in Example 1. The results are shown in Table 1.

　表１に示す結果から分かるように、実施例１～３の耐食性部材は、加熱試験による熱履歴を受けても、基材からの耐食性被膜の剥離がほとんど生じなかった。また、実施例１～３の耐食性部材は、腐食試験による腐食を受けても、基材からの耐食性被膜の剥離がほとんど生じなかった。 As can be seen from the results shown in Table 1, the corrosion-resistant members of Examples 1 to 3 hardly experienced peeling of the corrosion-resistant coating from the substrate even when subjected to the thermal history of the heating test. Also, the corrosion-resistant members of Examples 1 to 3 hardly experienced peeling of the corrosion-resistant coating from the substrate even when subjected to corrosion in the corrosion test.

　これに対して、耐食性被膜が第一の層を有していない比較例１の耐食性部材は、昇温と降温を繰り返す加熱試験によって耐食性被膜の剥離が生じた。平均結晶粒径が小さい第二の層のみからなる比較例１の耐食性被膜は、基材との密着性が低いと考えられる。また、耐食性被膜が第二の層を有していない比較例２の耐食性部材は、腐食試験によって耐食性被膜の剥離が生じた。平均結晶粒径が大きい第一の層は、腐食による内部応力によって割れが発生し、腐食が進行しやすいと考えられる。 In contrast, the corrosion-resistant coating of the corrosion-resistant member of Comparative Example 1, which does not have a first layer, peeled off during a heating test in which the temperature was repeatedly increased and decreased. It is believed that the corrosion-resistant coating of Comparative Example 1, which is made up only of the second layer with a small average crystal grain size, has low adhesion to the substrate. Furthermore, the corrosion-resistant member of Comparative Example 2, which does not have a second layer, peeled off during the corrosion test. It is believed that the first layer, which has a large average crystal grain size, is prone to cracking due to internal stress caused by corrosion, and corrosion progresses easily.

　　　１０・・・基材
　　　２０・・・耐食性被膜
　　　２１・・・第一の層
　　　２２・・・第二の層 10: Substrate 20: Corrosion-resistant coating 21: First layer 22: Second layer

Claims (4)

　金属製の基材と、前記基材の表面に形成され且つマグネシウムフッ化物を含有する耐食性被膜と、を備え、
　前記耐食性被膜は、前記基材上に第一の層と第二の層とがこの記載順で積層された積層部を有し、
　前記第一の層は、平均結晶粒径が１００ｎｍ以上１０００ｎｍ未満である前記マグネシウムフッ化物の結晶粒を有する層であり、
　前記第二の層は、平均結晶粒径が１００ｎｍ未満である前記マグネシウムフッ化物の結晶粒を有する層である耐食性部材。 A corrosion-resistant coating including a metal substrate and a magnesium fluoride-containing corrosion-resistant coating formed on a surface of the substrate,
the corrosion-resistant coating has a laminated portion in which a first layer and a second layer are laminated on the substrate in this order;
the first layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of 100 nm or more and less than 1000 nm,
The second layer is a layer having crystal grains of the magnesium fluoride having an average crystal grain size of less than 100 nm. 　前記マグネシウムフッ化物がフッ化マグネシウムを含有する請求項１に記載の耐食性部材。 The corrosion-resistant member according to claim 1, wherein the magnesium fluoride contains magnesium fluoride. 　前記耐食性被膜の厚さが０．１μｍ以上２０μｍ以下である請求項１又は請求項２に記載の耐食性部材。 The corrosion-resistant member according to claim 1 or 2, wherein the thickness of the corrosion-resistant coating is 0.1 μm or more and 20 μm or less. 　前記耐食性被膜の厚さにおける前記第二の層の厚さの割合が５％以上９５％以下である請求項１又は請求項２に記載の耐食性部材。 The corrosion-resistant member according to claim 1 or 2, wherein the ratio of the thickness of the second layer to the thickness of the corrosion-resistant coating is 5% or more and 95% or less.
PCT/JP2024/004043 2023-02-13 2024-02-07 Corrosion-resistant member Ceased WO2024171917A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06128721A (en) * 1992-10-19 1994-05-10 Mitsubishi Electric Corp Method for forming sensitive thin film for nitrogen oxide gas sensor
JP2004004443A (en) * 2001-09-20 2004-01-08 Shin Meiwa Ind Co Ltd Optical system
WO2021182107A1 (en) * 2020-03-11 2021-09-16 昭和電工株式会社 Corrosion-resistant member

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06128721A (en) * 1992-10-19 1994-05-10 Mitsubishi Electric Corp Method for forming sensitive thin film for nitrogen oxide gas sensor
JP2004004443A (en) * 2001-09-20 2004-01-08 Shin Meiwa Ind Co Ltd Optical system
WO2021182107A1 (en) * 2020-03-11 2021-09-16 昭和電工株式会社 Corrosion-resistant member

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