EP0902101A1 - Matériau métallique ou couche mince ayant une surface fluorée et procédé de fluoration - Google Patents

Matériau métallique ou couche mince ayant une surface fluorée et procédé de fluoration Download PDF

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EP0902101A1
EP0902101A1 EP98117280A EP98117280A EP0902101A1 EP 0902101 A1 EP0902101 A1 EP 0902101A1 EP 98117280 A EP98117280 A EP 98117280A EP 98117280 A EP98117280 A EP 98117280A EP 0902101 A1 EP0902101 A1 EP 0902101A1
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metal
film
gas
fluorinated
layer
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EP0902101B1 (fr
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Kunio Kashiwada
Takanori Kodama
Hiroyasu Kawasaki Works Showa Denko K.K. Taguchi
Satoshi Kawasaki Works Showa Denko K.K. Hirano
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Resonac Holdings Corp
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Showa Denko KK
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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied

Definitions

  • the present invention relates to metallic material or film having a fluorinated surface layer, and a fluorination method of the metallic material or film. More particularly, the present invention provides fluorinated metal, on the top surface of which a thick fluoride layer greately enhances the corrosion resistance.
  • the metal may be in any form capable of forming the fluoride layer thereon.
  • the metal may be monolithic material or film formed on the substrate.
  • the metallic material or film be used in a production apparatus of semiconductor devices and the like, so as to realize extremely advantageous corrosion performance against halogen-based corrosive gases, such as chlorine-, fluorine- or bromine-based gases.
  • halogen-based corrosive gases such as chlorine-, fluorine- or bromine-based gases.
  • halogen-based, reactive and strongly corrosive special gases such as hydrogen chloride (HCl), boron trichloride (BCl 3 ), fluorine (F 2 ), nitrogen trifluoride (NF 3 ), chlorine trifluroride (ClF 3 ) and hydrogen bromide (HBr) are used.
  • gases are easily hydrolyzed by the presence of water in the environment, thus generating hydrochloric acid, hydrofluoric acid, hydrobromic acid and the like.
  • the constructional metallic material or film of a valve, coupling, pipings, reaction chamber and the like for treating these gases is easily corroded and problems incurr.
  • these corrosive gases are converted to plasma or are thermally decomposed. They are decomposed to active atom species and are used for etching the oxide film or metallic film and are used for dry-cleaning the reaction chamber as well.
  • the amount of such gases used has abruptly increased. The highest quality of cleanliness and corrosion performance is required for the plant materials, such as the surface of a reaction chamber.
  • fluorine gas is mixed with inert gas (krypton, neon, argon) and is oscillated in the field of an excimer laser, extremely strict corrosion performance is required for the material surface of a plant against the fluorine radicals.
  • inert gas krypton, neon, argon
  • Electrolytically polished stainless steel SUS 316L can allegedly solve the above described problems and is usually used. Such stainless steel is subjected to baking at 250°C prior to use. However, the corrosion resistance of stainless steel does not satisfactorily meet the requirements. Various nickel-based alloys have, therefore, been employed with halogen gas such as gaseous hydrechloric-acid at high temperature.
  • Hastelloy-C Ni-Cr-Mo-W alloy
  • Hastelloy-C exhibits extremely improved corrosion resistance against the oxidizing acid and also exhibits improved corrosion resistance against even the reducing acid, such as hydrochloric acid, when used at room temperature.
  • Hastelloy-C exhibits remarkable resistance against pitting corrosion and crevice corrosion.
  • the corrosion resistance of Hastelloy-C is poor against the fluorine gases and the fluorine radicals mentioned above, Hastelloy-C is not usable.
  • Japanese Unexamined Patent Publication (kokai) No. 2-263972 is related to the invention entitled "Metallic Materials with Fluorinated Passivation Film Formed Thereon and Apparatus with the Use of Such Metallic Materials".
  • the publication discloses the metallic material or film, on which the passivation film is formed, and an apparatus, in which the metallic material and coating are used.
  • a passivation film is formed by means of fluorine gas on the metal which is at least one selected from nickel, nickel alloy, aluminum, aluminum alloy, copper, copper alloy and chromium, among the metals.
  • the corrosion resistance disclosed is of improved quality.
  • the film formed is of from 1000 to 3000 angstrom thick and hence ultra thin.
  • the surface state of aluminum, stainless steel, copper and nickel plates to be fluorinated in this publication is a polished surface.
  • Japanese Unexamined Patent Publication (kokai) No. 2-175855 is related metallic material or film, on which the fluorinated passivation film is formed, as well as an apparatus, in which the metallic material and film are used.
  • the publication discloses a process for forming on the surface of stainless steel a mixed fluoride layer of iron fluoride and chromium fluoride.
  • a fluorinated passivation film in the order of sub-micron thickness as well as the material with such film are disclosed. Improved corrosion resistance is disclosed. Thickness of the film formed is 4000 angstrom and is ultra thin.
  • the polished SUS316L sheet is subjected to the fluorination.
  • the fluorinated passivation films formed in the above publications are of approximately 4000 angstroms or less in thickness, they are easily removed by flaws, friction and the like. It is, therefore, difficult to say that the films are appropriate as the material of production apparatuses of semiconductor devices from the viewpoints of durability and longevity.
  • the present invention aims to solve the problems involved in the prior art described above.
  • the conventional passivation techniques are characterized in that the material surface is cleaned by polishing and the like and is then fluorinated to passivate it. It was discovered that, when the surface is oxidized to passivate it and is then fluorinated, surprisingly, not only the passivated and oxidized surface exhibits no hindrance to the fluorination, but also a rather thick fluorinated layer can be formed.
  • a fluorinated metal having 1 ⁇ m or more thick fluorinated layer formed by forcibly oxidizing a surface of said metal and thereafter fluorinating the forcibly oxidized surface.
  • the present invention is, therefore, characterized in that the surface of the metallic material or film is forcibly oxidized and, thereafter, the fluorinated layer having 1 ⁇ m or more of film thickness is formed on said surface.
  • the fluorination process according to the present invention is, therefore, characterized in that the metallic material or film is forcibly oxidized by oxidizing material, and, thereafter the oxidized film is brought into contact with the fluorination gas.
  • the metal which is fluorinated in the present invention, may be any one which is reactive with fluorine and forms a stable fluoride.
  • nickel, copper, silver and aluminum are preferable metal, since their corrosion resistance is greatly enhanced by fluorination.
  • Iron is excluded in the present invention, because the iron fluoride formed is decomposed and dissociated due to the moisture in air. Corrosion is, therefore, promoted in an environment containing moisture (exposure to air). There is, thus, a danger of incurring a practical problem.
  • the metal may be an alloy containing nickel and the like.
  • the metallic film to be fluorinated according to the present invention can be the film of electrolytic plating, electroless plating, physical vapor deposition (PVD) and the like of nickel, silver or aluminum, or an alloy containing at least one of them.
  • PVD physical vapor deposition
  • Ni plating Ni-Cu plating, Ni-W plating and the like are mentioned.
  • electroless plating Ni-P plating, Ni-B plating, Ni-P-W plating, Ni-P-B plating and the like are mentioned.
  • PVD the sputtering of Ni or its alloy is mentioned.
  • the substrate for forming a film are various metallic materials, such as stainless steel, aluminum-alloy, steels and the like, sintered metal, ceramics, engineering plastics. These materials are subjected to known surface preparation such as degreasing, pickling, polishing, and shot-blasting, prior to formation of the metallic film.
  • the metallic (alloy) material and the metallic (alloy) film is abbreviated as "metal".
  • the metallic surface is first forcibly oxidized and subsequently the metallic oxide film is brought into reaction with fluorine.
  • the thickness of the oxide film is from a few tens to a few hundreds angstroms at the highest.
  • the metals, on which strong oxide can be formed in the case of natural oxidation are limited to the specified metals, such aluminum.
  • natural oxidation is defined in GLOSSARY OF TECHNICAL TERMS IN JAPANESE INDUSTRIAL STANDARDS, Fourth Edition (page 729) to mean the oxidizing reaction which occurs in air without artificial acceleration.
  • the natural oxidation film is well known in aluminum materials (c.f., Fundamentals and Industrial Techniques of Aluminum Materials (in Japanese) publlished on May 1, 1985, page 186).
  • the forced oxidizing method is used in the present invention as described in detail hereinafter.
  • the fluorination is carried out after the forced oxidation, the substitution reaction of oxygen and fluorine takes place to form the fluorinated layer.
  • the thickness of the fluorinated layer increases, therefore, in proportion to the thickness of the forced oxidizing layer and amounts to a few tens of ⁇ m.
  • the forced oxidizing layer becomes extremely thick, its adhesion to the substrate is lowered. Thickness of the layer seems to be limited to 10 ⁇ m.
  • the thickness of fluoride formed on the metallic surface can be made thicker than that obtained by the so-called passivation.
  • Aluminum alloys, copper, nickel or its alloy have affinity to oxygen, and, hence, a natural oxide film is readily formed on the surface in the atmosphere. This natural oxide film has an extremely dense structure and is chemically stable as well.
  • Oxygen diffusion into the metal interior is, therefore, impeded at normal temperature, due to the presence of the oxide film.
  • the natural oxide film retains ultra thin thickness amounting to only a few tens to hundreds angstroms. It is, therefore, necessary to thicken the oxide film by means of the so-called forced oxidation.
  • a workpiece having a natural-oxide film is not directly fluorinated but is forcibly oxidized and then fluorinated.
  • the thickness of the forcibly oxidized layer is greater than that of the natural oxide film and is preferably approximately 1000 angstroms or more.
  • the wear resistance, corrosion resistance and durability of the so-formed fluoride layer are improved to such a level that it is satisfactorily usable in a practicable way.
  • the fluoride layer is, broadly speaking, a layer which contains fluorine and preferably consists essentially of fluoride.
  • the fluorination herein has a substantial meaning. That is, it is not necessary for 100% of the metallic to be replaced with fluoride.
  • the oxygen is preferably replaced with fluorine to a level lower than the detection level of oxygen.
  • the metal need not be necessarily uniformly fluorinated. Rarther, the fluorinated layer may be of non-uniform thickness, and the fluoride region and fluorine diffusion region may be mixed.
  • the fluorinated layer consists of the first layer essentially consisting of metallic fluoride and a second layer, underlying the first layer, and into which fluorine has been diffused.
  • gas-phase oxidation is a means to enable the forced oxidation.
  • oxygen or its gas mixture with neutral or inert gas is preferable.
  • nitrous oxide, nitrogen peroxide, ozone, or their mixture with neutral or inert gas are also preferable. In such cases, the gases are brought into contact with the metal at high temperature.
  • Liquid-phase oxidation can be mentioned as another means for the forced oxidation. This can be carried out by means of immersion into a solution, such as nitric acid and hydrogen-peroxide water.
  • the metallic material may be anodically oxidized using an electrolyte, such as alkali, to form an oxide film on the surface thereof.
  • an electrolyte such as alkali
  • oxygen formed on the anode is a means for the forced oxidation.
  • aluminnum alloys It is broadly known in the case of aluminnum alloys that an oxide film amounting to a few microns to a few tens of microns can be formed on the surface of aluminum alloys by the so-called alumite treatment (anodic oxidation treatment). It has been put into practical application, and, therefore can be employed.
  • the gases capable of use for the fluorination are 100% gases such fluorine, chlorine trifluoride and nitrogen trifluoride, their diluted gases by inert gases such as nitrogen, helium, argon and the like, or plasma gases of fluorine or the like.
  • the fluorination is a production method of a fluorine diffusion layer and a film of fluoride by means of bringing the gases into reaction with the oxidized film formed on the top surface-layer of the metal.
  • the metal as described above is loaded in a normal-pressure gas-phase flowing-type reaction furnace. While the oxidizing gas is flowing, the reaction furnace is heated to a predetermined temperature and is held for a predetermined time. The furnace is then filled with fluorination gas at a predetermined temperature. The reaction is carried out for a predetermined time to fluorinate the surface.
  • the metal prior to loading the metal into a reaction furnace, the metal is degreased or demoisturized as usual, and the forced oxidation is subsequently formed. The purity of the subsequently formed, forcibly oxidized layer is therefore enhanced and defects are not formed in the layer. Since a thin natural oxide film of a few tens of angstroms, remaining on the metallic surface is forcibly oxidized together with the bulk, the thin natural oxide film need not be removed prior to the forced oxidation.
  • the temperature of a reaction furnace for forcibly oxidizing nickel and copper is usually from 200°C to 600°C, in particular, preferably from 300°C to 500°C.
  • Reaction time is usually from 1 hour to 48 hours, in particular, preferably from 3 to 24 hours.
  • Aluminum is preferably anodically oxidized.
  • the fluorination temperature is usually from 100°C to 700°C, in particular, preferably from 150°C to 500°C under the normal pressure.
  • the reaction time is usually from 1 to 48 hours, particularly preferably from 3 hour to 24 hours.
  • the oxygen of the forcibly oxidized layer is not satisfactorily replaced with fluorine, and, furthermore, diffusion of fluorine from the top surface is not satisfactory.
  • the upper limits of temperature and time are exceeded, the reaction of fluorine is so abrupt that cracks generate in the film formed.
  • the plating was carried out by using commercially available lustrous nickel plating reagents of the so-called Watt bath, mainly composed of NiSO 4 (nickel sulfate), NiCl 2 (nickel chloride), H 3 BO 3 (boric acid), and brightener.
  • Stainless steel (SUS 316L) was preliminarily subjected to surface preparation by pickling. Film was then formed by conducting a current for a predetermined time at 1A/dm 2 of current density.
  • the acidic chemical nickel plating which is referred to as the so-called chemical plating, has been put into practice.
  • the reagents which are based on reduction with hypophosphorous acid are commercially available.
  • the reagents used in the present production example were a commercially available reagent of chemical nickel plating, with the use of dimethylamine borane as the reducing agent, and a commercially available reagent of the chemical nickel plating, in which importance is attached to the corrosion resistance, that is, the nickel-phosphorus plating (Ni-P alloy plating).
  • These reagents consist of 25 g/L of NiSO 4 (nickel sulfate) as the main component, 20g/L of NaHPO 2 (sodium hypophosphite) as the reducing agent, a complexing agent, stabilizing agent and brightener.
  • NiSO 4 nickel sulfate
  • NaHPO 2 sodium hypophosphite
  • the stainless steel sheets were preliminarily subjected to surface preparation, then immersed in a plating liquor solution, which has been elevated to a temperature of 90°C, so as to cause a reaction for a predetermined time and hence to form a film.
  • the reagent used was commercially available alkaline chemical plating, in which importance is attached to the wear resistance and the post-heat treatment corrosion resistance, and which is carried out in a nickel-phosphorous-tungsten (Ni-P-W) bath.
  • This reagent consists of 15g/L of NiSO 4 (nickel sulfate) and Na 2 WO 3 (sodium tungstate), i.e., the metallic component, 20g/L of NaHPO 2 (sodium hypophosphite) as the reducing agent, complexing agent, a stabilizing agent, and brightener.
  • the stainless steel sheets were preliminarily subjected to a predetermined surface conditioning, as in the above-described examples, and then immersed in a plating liquor tank, which has been elevated to a temperature of 85°C, so as to cause a reaction for a predetermined time and hence to form a film.
  • A5083 was taken as an example of the so-called aluminum alloy, and its surface was mirror-polished. A5083 was then exposed for 30 days in air, so as to thoroughly form a natural oxide film on the surface. Thus, specimens were provided.
  • C1100P copper material was taken as an example of a Cu-alloy, and its surface was mirror-polished. C1100P was then exposed for 30 days in air so as to form thoroughly a natural oxide film on the surface. Thus, specimens were provided.
  • Specimens which were prepared by the procedure described in Production Example 1, were loaded in the interior of a normal-pressure, gas-phase flowing-type reaction furnace.
  • the specimens were pretreated by baking for 1 hour at 200°C under reduced pressure to expel the adsorbed moisture and the like.
  • the temperature was then elevated to 500°C while introducing the oxygen gas (99.999%).
  • the temperature was then held at that temperature for 12 hours so as to forcibly oxidize the metallic surface.
  • the temperature was lowered while replacing the oxygen gas with nitrogen gas.
  • 20% F 2 gas diluted with nitrogen
  • the surface fluorination was carried out by holding for 24 hours. After a predetermined time, the fluorine gas was replaced with nitrogen gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • Specimens which were prepared by the procedure described in Production Example 1, were loaded in the interior of a normal-pressure, gas-phase flowing-type reaction furnace.
  • the specimens were pretreated by baking for 1 hour at 200°C under reduced pressure.
  • the temperature was then elevated to 500°C while introducing the oxygen gas (99.999%).
  • the temperature was then held at that temperature for 12 hours so as to forcibly oxidize the metallic surface.
  • the gas-replacement with nitrogen was carried out.
  • the 20% F 2 gas diluted with nitrogen
  • the surface fluorination was carried out by maintainig the conditions for 12 hours.
  • the fluorine gas was replaced with nitrogen gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • Specimens which were prepared by the procedure described in Production Example 2, were loaded in the interior of a normal-pressure, gas-phase flowing-type reaction furnace.
  • the specimens were pretreated by baking for 1 hour at 200°C under reduced pressure.
  • the temperature was then elevated to 500°C while introducing the oxygen gas (99.999%).
  • the temperature was then maintained at 500°C for 12 hours so as to forcibly oxidize the metallic surface.
  • the gas-replacement with nitrogen was carried out, while lowering the temperature.
  • the 20% F 2 gas diluted with nitrogen
  • the surface fluorination was carried out by holding the conditions for 12 hours. After a predetermined time, the fluorine gas was replaced with nitrogen gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • Specimens which were prepared by the procedure described in Production Example 2, were loaded in the interior of a normal-pressure, gas-phase flowing-type reaction furnace.
  • the specimens were pretreated by baking for 1 hour at 200°C under reduced pressure.
  • the temperature was then elevated to 500°C while introducing the oxygen gas (99.999%).
  • the temperature was then held at 500°C for 12 hours so as to forcibly oxidize the metallic surface.
  • the gas-replacement with nitrogen was carried out.
  • the 20% F 2 gas diluted with nitrogen
  • the surface fluorination was carried out by holding for 12 hours.
  • the fluorine gas was replaced with nitrogen gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • the specimens were pretreated by baking for 1 hour at 200°C under reduced pressure.
  • the temperature was then elevated to 500°C while introducing the oxygen gas (99.999%).
  • the temperature was then held at that temperature for 12 hours so as to forcedly oxidize the metallic surface.
  • the gas replacement with nitrogen gas was carried out.
  • the 20% F 2 gas (diluted with nitrogen) was introduced for replacement of nitrogen.
  • the surface fluorination was carried out by holding the same temperature for 12 hours. After a predetermined time, the fluorine gas was replaced with the nitrogen gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • the specimen prepared by the procedure of Production Example 2 was immersed for 10 minutes in a 5% nitric-acid aqueous solution, the temperature of which had been elevated to 50°C. The specimen was further thoroughly washed with pure water and then left as it was, in the pure water for 8 hours to oxidize the surface. This specimen was loaded in a normal-pressure gas-phase flowing-type reaction furnace. The nitrogen gas was introduced into the furnace to replace the oxygen gas. After the replacement, the baking pretreatment was carried out at 200°C for 1 hour under reduced pressure. Immediately after baking, the temperature was lowered.
  • the specimen which was prepared by the procedure of Production Example 3, was loaded into a normal-pressure gasphase flowing-type reaction-furnace. Baking pretreatment was carried out at 200°C for 1 hour. Temperature was then elevated. When the furnace temperature reached 400°C, 20% F 2 gas (diluted with nitrogen) was introduced, followed by maintaining that state for 6 hours, hence carring out the fluorination of the metallic material. This is broadly known as the passiavation method of nickel materials. After that, nitrogen gas was introduced to replace the fluorine gas. After keeping the temperature at this level for 1 hour, the temperature was lowered.
  • Film thickness of the fluorinated layer was deemed as the thickness where the fluorine atoms could be detected by the above-mentioned argon sputtering.
  • a similar measurement was preliminarily carried out with regard to the oxygen-detection thickness of SiO 2 thin film, the thickness of which was already known.
  • the sputter rate measured was 115 angstroms per minute (hereinafter referred to as "SiO 2 correction"). As a result, it turned out that the thickness of the fluorinated layer amounted to 1.2 ⁇ m or more.
  • diffraction peaks of Ni or Ni 3 P appear very slightly, and the predominant peaks and most of the other peaks are NiF 2 . These peaks are detected at high intensity.
  • the measurement by a thin-film method was carried out at an incident angle ( ⁇ ) 1° of X-ray. Theoretically, the analyzed thickness corresponds to 2.1 ⁇ m from the surface. The fluoride film is, therefore, in the order of ⁇ m thickness on the surface of the electroless nickel plating.
  • Fig. 8 is shown the analysis results of the specimen according to Example 3 by AES (Auger Electron Spectroscopy).
  • the element composition on the top surface layer is shown in Table 1.
  • the atomic proportion of Ni and F is approximately 1 : 2. It could be confirmed from this result with the above-described results of X-ray diffraction, that the nickel fluoride (NiF 2 ) was formed on the top surface layer.
  • Fig. 9 are shown the AES analytical results of specimens of Example 4.
  • the element composition on the top surface is shown in Table 2.
  • the atomic proportion of Ni and F is approximately 1 : 2. It could be confirmed from this result together with the above-described results of X-ray diffraction, that nickel fluoride (NiF 2 ) was formed on the top surface layer.
  • Fig. 10 are shown the AES analytical results of specimens of Comparative Example 1.
  • the element composition on the top surface is shown in Table 3.
  • the atomic proportion of Ni and F is approximately 1 : 2.
  • the detection intensity of fluorine decreased after a few minutes from the beginning of sputtering, and the fluorine was not detected at approximately 20 minutes.
  • Corrosion-resistance test of various materials was carried out. The results are shown in Table 4.
  • the evaluation of the corrosion resistance test was expressed by the weight loss of the various materials which were immersed in the 35% hydrochloric-acid aqueous solution at room temperature (25°C) for 24 hours.
  • the surface-treated specimens formed in Production Examples 2 and 3 as the comparative materials and the specimens of Examples 3, 4, 5 and 6 were used. The weight loss was measured upon withdrawal after 24 hours. As a result of comparison, it turned out that weight loss of Example 5 was the smallest.
  • the corrosion-resistance test of the specimens of Example 3 was carried out. The results are shown in Fig. 11 (Table 5).
  • a solution or reagents such as 20% nitric acid, 50% hydrofluoric acid, 20% sulfuric acid, 20% phosphoric acid, 28% ammonia water, 28% caustic soda, 50% formic acid, 20% acetic acid, oxalic acid, organic solvent (acetone), ethanol, EDTA, tetramine and hydrochloric acid hydroxylamine were prepared.
  • Various materials were immersed in the solutions or reagents at room temperature (30°C) for 24 hours. The evaluation of corrosion resistance was expressed by the weight loss during the immersion.
  • Example 3 In every testing liquid, the specimens of Example 3 exhibited improved corrosion resistance from the viewpoint of weight loss and observation of appearance as compared with the electroless nickel plated and un-fluorinated specimens according to Example 3.
  • Example 3 01 Nitric acid (20%) 1795 646 02 Hydrofluoric acid (50%) 22.5 1.1 03 Sulfuric acid (20%) 133 106 04 Phosphoric acid (20%) 66.2 4.6 05 Ammonia water (28%) 222 32.8 06 Caustic soda (1N) 4.0 2.4 07 Formic acid (50%) 43.1 1.5 08 Acetic acid (20%) 104 1.2 09 Oxalic acid 2.4 0.6 10 Acetone 0.0 0.0 11 Ethanol 0.0 0.9 12 EDTA 18.9 7.3 13 Tetramine 0.0 1.8 14 Hydrochloric acid hydroxylamine 770 22.2
  • Example 4 The wear-resistance test was carried out under a constant load. As a result of the test, the sliding friction performance and film durability in terms of the sliding time until the film breaks only one time in Production Example 2, while it is 30 times in Example 3 and 208 times in Example 4. Particularly, since in Example 4, in which the fluoride film which is thick in the order of ⁇ m exhibited wear-resistance and durability better than those of the electroless nickel-plating, it was clarified that the durability of Example 4 is of a level satisfactory for practical use.
  • Example 3 were forcibly oxidized by the oxygen gas. At this stage, the specimens were withdrawn from the reaction furnace. It is clear that the oxidation film of such specimens amounts to approximately 0.6 ⁇ m contrary to Example 9, since the oxide film is removed by the argon-ion sputtering of approximately 55 minutes.
  • the thick fluorinated layer attained by the present invention has improved resistance against acid and alkali, and is therefore extremely useful for the plant members of the semiconductor-related machinery and devices among others.
  • the metallic material or film, on which the surfacial fluorinated layer is formed, is, therefore, extremely useful for the production apparatuses of semiconductor devices, and plant members of vacuum-related machineries and devices.

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  • Engineering & Computer Science (AREA)
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EP98117280A 1997-09-12 1998-09-11 Matériau métallique ou couche mince ayant une surface fluorée et procédé de fluoration Expired - Lifetime EP0902101B1 (fr)

Applications Claiming Priority (3)

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JP24823197 1997-09-12
JP248231/97 1997-09-12
JP09248231A JP3094000B2 (ja) 1997-09-12 1997-09-12 フッ化表面層を有する金属材料もしくは金属皮膜ならびにフッ化方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003036216A1 (fr) * 2001-10-25 2003-05-01 Showa Denko K.K. Echangeur thermique, procede de fluoration dudit echangeur thermique ou de ses elements constitutifs, et procede de fabrication associe
WO2003002454A3 (fr) * 2001-06-29 2003-05-30 Showa Denko Kk Fluor gazeux de grande purete, production et utilisation de ce dernier, et procede d'analyse d'impuretes a l'etat de traces dans du fluor gazeux de grande purete
EP2211061A1 (fr) * 2007-10-24 2010-07-28 IHI Corporation Procédé de renforcement de la résistance à l'abrasion et structure coulissante

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP4829485B2 (ja) * 2003-06-10 2011-12-07 有限会社真空実験室 真空部品用材料、真空部品、真空装置、真空部品用材料の製造方法、真空部品の処理方法及び真空装置の処理方法
KR100499793B1 (ko) * 2004-09-16 2005-07-07 주식회사 부광 무전해 도금처리 방법
JP4584754B2 (ja) * 2005-04-06 2010-11-24 株式会社日立産機システム ナノプリント金型、その製造方法及びこの金型を用いたナノプリント装置並びにナノプリント方法
JP5000236B2 (ja) * 2006-08-30 2012-08-15 昭和電工株式会社 最表面層がフッ化ニッケル膜である金属材料およびその製造方法
JP5317321B2 (ja) * 2008-02-21 2013-10-16 岩谷産業株式会社 金属材料及びこれを用いた保存容器、ガス配管、装置、並びに、その製造方法、ＣｌＦ３の保存方法
SG155111A1 (en) 2008-02-26 2009-09-30 Kobe Steel Ltd Surface treatment material for semiconductor manufacturing system and method for producing same
JP2010077529A (ja) * 2008-08-26 2010-04-08 Showa Denko Kk 摺動部品およびその製造方法
EP4006201A4 (fr) 2019-07-31 2023-11-29 Resonac Corporation Stratifié et procédé de production associé
CN110508299B (zh) * 2019-09-03 2022-04-19 北京邮电大学 一种迅速升温制备二维局域氧化的过渡族金属氟化物催化剂方法
CN113874550B (zh) 2019-09-13 2024-01-30 株式会社力森诺科 层叠体及其制造方法
SG11202113223VA (en) 2019-10-10 2021-12-30 Showa Denko Kk Laminate and method for producing same
KR102448366B1 (ko) 2020-12-21 2022-09-29 에스케이스페셜티 주식회사 내스크래치성이 향상된 고순도 불화수소의 저장 용기용 금속재료 및 이의 제조 방법
KR102489717B1 (ko) 2020-12-21 2023-01-19 에스케이스페셜티 주식회사 저 내부식성 금속 기재를 이용한 고순도 불화수소를 저장하기 위한 용기 및 이의 제조방법
KR20220089724A (ko) 2020-12-21 2022-06-29 에스케이스페셜티 주식회사 고순도 불화수소를 저장하기 위한 용기 및 이의 제조방법
KR102535282B1 (ko) * 2021-07-05 2023-05-26 연성열 휴대용 안경닦이
WO2024127901A1 (fr) * 2022-12-15 2024-06-20 セントラル硝子株式会社 Récipient rempli de gaz liquéfié et procédé de production de récipient rempli de gaz liquéfié

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111762A (en) * 1975-01-31 1978-09-05 Martin Marietta Corporation Optically black coating and process for forming it
EP0352061A2 (fr) * 1988-07-20 1990-01-24 Hashimoto Chemical Industries Co., Ltd. Matériau métallique avec film passivé par fluoration et appareil constitué par ce matériau
EP0460700A1 (fr) * 1990-06-07 1991-12-11 Applied Materials, Inc. Revêtement protecteur résistant à la corrosion sur un substrat ou une surface d'aluminium et procédé de formation
JPH04202755A (ja) * 1990-11-30 1992-07-23 Daido Sanso Kk 鋼材の酸化方法
JPH0673596A (ja) * 1992-08-26 1994-03-15 Kobe Steel Ltd 高耐食性ＭｇまたはＭｇ合金材
EP0702098A1 (fr) * 1994-08-15 1996-03-20 Applied Materials, Inc. Article d'aluminium résistant à la corrosion pour appareil de traitement de semi-conducteurs

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2954716B2 (ja) * 1990-03-08 1999-09-27 三菱アルミニウム株式会社 フッ化不働態膜を形成した工業材料およびその製造方法
US5192610A (en) * 1990-06-07 1993-03-09 Applied Materials, Inc. Corrosion-resistant protective coating on aluminum substrate and method of forming same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4111762A (en) * 1975-01-31 1978-09-05 Martin Marietta Corporation Optically black coating and process for forming it
EP0352061A2 (fr) * 1988-07-20 1990-01-24 Hashimoto Chemical Industries Co., Ltd. Matériau métallique avec film passivé par fluoration et appareil constitué par ce matériau
EP0460700A1 (fr) * 1990-06-07 1991-12-11 Applied Materials, Inc. Revêtement protecteur résistant à la corrosion sur un substrat ou une surface d'aluminium et procédé de formation
EP0460701A1 (fr) * 1990-06-07 1991-12-11 Applied Materials, Inc. Procédé de formation d'un revêtement protecteur résistant à la corrosion sur un substrat d'aluminium
JPH04202755A (ja) * 1990-11-30 1992-07-23 Daido Sanso Kk 鋼材の酸化方法
JPH0673596A (ja) * 1992-08-26 1994-03-15 Kobe Steel Ltd 高耐食性ＭｇまたはＭｇ合金材
EP0702098A1 (fr) * 1994-08-15 1996-03-20 Applied Materials, Inc. Article d'aluminium résistant à la corrosion pour appareil de traitement de semi-conducteurs

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 016, no. 544 (C - 1004) 13 November 1992 (1992-11-13) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 328 (C - 1215) 22 June 1994 (1994-06-22) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003002454A3 (fr) * 2001-06-29 2003-05-30 Showa Denko Kk Fluor gazeux de grande purete, production et utilisation de ce dernier, et procede d'analyse d'impuretes a l'etat de traces dans du fluor gazeux de grande purete
US6955801B2 (en) 2001-06-29 2005-10-18 Showa Denka K.K. High-purity fluorine gas, production and use thereof, and method for analyzing trace impurities in high-purity fluorine gas
WO2003036216A1 (fr) * 2001-10-25 2003-05-01 Showa Denko K.K. Echangeur thermique, procede de fluoration dudit echangeur thermique ou de ses elements constitutifs, et procede de fabrication associe
EP2211061A1 (fr) * 2007-10-24 2010-07-28 IHI Corporation Procédé de renforcement de la résistance à l'abrasion et structure coulissante
CN101835991A (zh) * 2007-10-24 2010-09-15 株式会社Ihi 耐磨损增强方法以及滑动构造体
EP2211061A4 (fr) * 2007-10-24 2012-05-30 Ihi Corp Procédé de renforcement de la résistance à l'abrasion et structure coulissante

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DE69811446T2 (de) 2003-10-23
JPH1192912A (ja) 1999-04-06
EP0902101B1 (fr) 2003-02-19
DE69811446D1 (de) 2003-03-27
KR100308688B1 (ko) 2001-11-30
TW402646B (en) 2000-08-21
JP3094000B2 (ja) 2000-10-03
DE69811446T4 (de) 2004-07-08
KR19990029675A (ko) 1999-04-26

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