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WO2007013640A1 - Film y2o3 et processus de formation de celui-ci - Google Patents

Film y2o3 et processus de formation de celui-ci Download PDF

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Publication number
WO2007013640A1
WO2007013640A1 PCT/JP2006/315082 JP2006315082W WO2007013640A1 WO 2007013640 A1 WO2007013640 A1 WO 2007013640A1 JP 2006315082 W JP2006315082 W JP 2006315082W WO 2007013640 A1 WO2007013640 A1 WO 2007013640A1
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WIPO (PCT)
Prior art keywords
film
slurry
producing
average particle
particle diameter
Prior art date
Application number
PCT/JP2006/315082
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English (en)
Inventor
Takashi Ueda
Masakazu Kobayashi
Akira Kojima
Makoto Saito
Original Assignee
Showa Denko K.K.
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Filing date
Publication date
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Publication of WO2007013640A1 publication Critical patent/WO2007013640A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/228—Other specific oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying

Definitions

  • the present invention relates to a member having excellent resistance to plasma corrosion and a process for producing the member.
  • the present invention includes an Y2O3 film which is formed on a substrate using an Y 2 Q3 nanoparticle slurry as a raw material in order to enhance resistance to plasma corrosion, a member and a process for forming the film.
  • the plasma corrosion-resistant member of the invention is applicable to a plasma etching chamber of a semiconductor manufacturing apparatus or a plasma treatment apparatus for a liquid crystal device or the like.
  • Examples of substrates generally used for members of a plasma etching apparatus that is an apparatus for manufacturing semiconductors and liquid crystal devices include a metal material, such as Al or Al alloy, an anodized film of Al formed on a surface of the metal material, and a film of a sintered product, such as Al 2 O 3 or Si 3 N4. It is known that these materials suffer chemical damages when they are brought into contact with highly corrosive halogen ions or suffer corrosion damages due to fine parties, such as SiO 2 or Si 3 N 4 , and due to ions excited by plasma.
  • the CVD method is limited in applications, that is, this method cannot be used when the decomposition temperature of the CVD material is higher than the heat-resistant temperature of the substrate, and in case of, for example, aluminum used for an etching chamber, the upper limit of the heat-resistant temperature is in the range of 300 0 C to 400 0 C, so that application of the CVD method to aluminum is difficult.
  • the thermal spraying method and the sol- gel method there are many defects in the resulting films, and in order to completely coat a substrate with Y 2 O3, a large film thickness of about 300 nm is necessary. Unless such a large film thickness of about 300 nm is given, a continuous defect reaching the substrate takes place, and sufficient plasma corrosion resistance cannot be obtained.
  • Patent document 1 Japanese Patent Laid-Open Publication No. 4083/1998
  • Patent document 2 Japanese Patent No. 3510993
  • Patent document 3 Japanese Patent Laid-Open Publication No. 335589/2003
  • the present inventors have earnestly studied in view of the prior art as mentioned above, and as a result, they have made the present invention of the following constitution.
  • a process for producing an Y 2 O3 film comprising drying an Y 2 O3 slurry having a volume-average particle, diameter, in a dispersed state, of 10 nm to 300 nm and heat-treating the dried product.
  • a dense and strong film of Y 2 O 3 can be readily formed on a surface of a plasma treatment container or a surface of a member in the plasma treatment container at a low temperature without selecting a material of a substrate, as described above.
  • the film is excellent in that a metal that becomes a contamination source when it is used for a semiconductor manufacturing apparatus is not contained.
  • the member provided with the film by the invention is markedly superior to thermal spraying films in the plasma erosion resistance in an atmosphere containing a halogen compound, in spite of a small film thickness. Therefore, the cost for film formation can be greatly decreased, and besides, it becomes possible to efficiently manufacture high-quality products because contamination of the chamber interior with particles is low even if plasma treatment is continued over a long period of time.
  • a dispersant and a binder may be added to the Y2O 3 slurry.
  • a dispersant and a binder each of which does not contain a metal that becomes a contamination source when the slurry is used for a semiconductor manufacturing apparatus, a film causing no contamination of the chamber interior can be formed.
  • the film formed by the invention is excellent in various properties generally required for films, such as film hardness, bonding to a substrate and heat cycle resistance.
  • Fig. 1 is a schematic view of an apparatus for preparing Y2O3 nanoparticles .
  • Fig. 2 is a schematic view of spray equipment for applying an Y 2 O 3 slurry.
  • Fig. 3 is an electron microscope photograph of an Y 2 O3 film (glass substrate) of Example 3.
  • the Y 2 O 3 film and the process for producing the film according to the invention are described in detail hereinafter.
  • Y 2 O 3 film The Y 2 O 3 film of the invention comprises an aggregate of Y 2 O 3 particles having a volume-average particle diameter of 10 nm to 300 nm.
  • the term "aggregate” referred to herein means a state where the Y 2 O 3 nanoparticles physically adhere to one another very firmly by van der Waals force or the like or they are chemically bonded (sintered) to one another.
  • This film is extremely dense and has no continuous defect reaching a substrate, so that the film exhibits sufficient plasma corrosion resistance even in a film thickness of 200 nm
  • a dispersant, a binder and the like may be contained, when needed.
  • the film comprises an aggregate of Y 2 O 3 nanoparticles having a volume-average particle diameter of 10 nm to 300 nm, by measuring diameters of the particles (not less than 100 particles) from a photograph taken by an electron microscope, determining a particle size distribution and calculating a volume-average particle diameter. Also in case of a distribution having two peaks, the same calculation as above is carried out.
  • Y 2 O 3 slurry
  • the Y 2 O 3 film of the invention is formed by the use of an Y 2 O 3 slurry having a particle diameter, in a dispersed state, of 10 nm to 300 nm (volume-average particle diameter) .
  • the particle diameter in a dispersed state means a volume average value measured when the particles are in a state of a slurry in which they are dispersed (or in a state of a slurry diluted with a dispersion medium) , and it can be measured by a laser Doppler method.
  • the particle diameter of the Y 2 O 3 particles in a dispersed state in a slurry is more preferably 10 nm to 200 nm, most preferably 10 nm to 100 nm.
  • Such Y 2 O 3 particles having a particle diameter of nano order are referred to as "Y 2 O 3 nanoparticles" . If the particle diameter in a dispersed state exceeds 300 nm, aggregation of particles becomes insufficient in the heat treatment at a low temperature, so that the temperature for the heat treatment needs to be raised, and as a result, it becomes difficult to use a substrate having a low heat- resistant temperature (e.g., aluminum plate) . If the heat treatment temperature is lowered, aggregation of Y 2 O 3 nanoparticles does not proceed. As a result, a film defect becomes large, and in order to satisfy desired plasma corrosion resistance, a film of larger thickness is necessary.
  • a vapor phase process Japanese Patent Laid-Open Publication No. . 168641/2004
  • a co-precipitation process Japanese Patent Laid-Open Publication No. 127773/1996) or the like
  • an ultrasonic method for dispersing the nanoparticles in a dispersion medium
  • a ball mill method for dispersing the nanoparticles in a dispersion medium
  • a bead mill method or the like for dispersing the nanoparticles in a dispersion medium.
  • zirconia or the like is employable as a material of the bead, and beads having diameters of 5 ⁇ m to 1 mm are employable .
  • the dispersion medium of the Y2O3 slurry is desirably a polyhydric alcohol derivative.
  • the Y2O3 nanoparticles exhibit extremely strong mutual interactions and have properties such that they are liable to be aggregated, but by the use of the above dispersion medium, it becomes possible to disperse the Y 2 O 3 nanoparticles with almost no aggregation.
  • the dispersing quality of the dispersion medium greatly varies depending upon the type of the dispersion medium, and from the viewpoints of dipole moment, viscosity and the like, a polyhydric alcohol derivative is preferable.
  • the polyhydric alchol derivative is preferably a monoether, diether, monoeser or diester of a polyhydric alcohol.
  • the polyhydric alcohol derivatives include derivatives of dihydric alcohols, such as 1- methoxy-2-propanol, l-ethoxy-2-propanol, l-butoxy-2- propanol, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether,
  • Dispersant of slurry The Y 2 O3 slurry may contain a dispersant.
  • ⁇ -diketone which does not contain an alkali metal or the like that is avoided in the use for a semiconductor manufacturing apparatus, proved to be particularly useful as a dispersant.
  • DPM-H 2, 6, 6-tetramethylheptane-3, 5-dione
  • DMHD-H 2, 6-dimethyl-3,5-heptanedione
  • acac-H 2,4- pentanedione
  • ⁇ -ketoesters such as methyl-3-oxopentanoate, ethyl-3-oxopentanoate, r ⁇ ethyl-4-methyl-3-oxopentanoate, ethyl-4-methyl-3- oxopentanoate, methyl ⁇ 4, 4-dimethyl-3-oxopentanoate and ethyl-4 , 4-dimethyl-3-oxopentanoate .
  • ⁇ -diketone is volatile, it is vaporized in the heat treatment after coating operation and does not remain in the resulting film.
  • the ⁇ -diketone is added in an amount of 1 part by mass to 10 parts by mass, preferably 5 parts by mass to 10 parts by mass, based on 100 parts by mass of Y2O3.
  • a nonionic surfactant can be added as a dispersant.
  • the nonionic surfactants include those of ether type, such as polyoxyethylene alkyl. ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene, polyoxypropylene block copolymer and polyoxyethylene polyoxypropylene alkyl ether; those of ester ether type, such as polyoxyethylene glycerol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened castor oil and polyoxyethylene sorbitol fatty acid ester.
  • the nonionic surfactant is added in an amount of 1 part by mass to 10 parts by mass, preferably 5 parts by mass to 10 parts by mass, based on 100 parts by mass of Y2O3.
  • a ⁇ -diketone metal complex which does not contain an alkali metal or the like that is avoided in the use for a semiconductor manufacturing apparatus, may be contained as a binder.
  • yttrium is preferable.
  • ⁇ -diketone metal complex an yttrium complex of 2,2, 6, 6-tetramethylheptane ⁇ 3, 5-dione (DPM-H), 2,6- dimethyl-3, 5-heptanedione (DMHD-H), 2, 4-pentanedione (acac-H) or the like is employable, and specifically, Y (DPM) 3, Y (DMHD) 3, Y(acac)3 or the like is employable.
  • metal complexes of ⁇ - ketoesters such as metal complexes of methyl-3- oxopentanoate, ethyl-3-oxopentanoate, methyl-4-methyl-3- oxopentanoate, ethyl-4-methyl-3-oxopentanoate, methyl- 4, 4-dimethyl-3-oxopentanoate and ethyl-4, 4-dimethyl-3- oxopentanoate .
  • the ⁇ -diketone metal complex is added in an amount of 1 part by mass to 10 parts by mass, preferably 5 parts by mass to 10 parts by mass, based on 100 parts by mass of Y 2 O 3 . If the amount of the binder is too large, the binder remains as impurities in the film, and the impurities derived from the binder are scattered in the plasma treatment, or pinholes formed by scatting of the binder sometimes cause corrosion of a member. If the amount of the binder is too small, sufficient dispersion effect is not obtained.
  • Y 2 O 3 nanoparticles For producing Y2O3 nanoparticles to be dispersed in the slurry of the invention, vapor phase oxidation of a
  • ⁇ -diketone metal complex is employable.
  • This process is a process comprising mixing vapor containing a gaseous ⁇ -diketone metal complex obtained by vaporizing a solution of a ⁇ -diketone metal complex with an oxygen-containing gas or oxygen, quantitatively feeding the mixture to a heating device such as a tubular electric furnace and allowing the ⁇ -diketone metal complex to undergo thermal decomposition/oxidation reaction to obtain metal oxide fine particles.
  • a heating device such as a tubular electric furnace
  • Other processes publicly known, such as co-precipitation, are also employable.
  • the Y 2 O 3 nanoparticles obtained by the vapor phase oxidation of a ⁇ -diketone metal complex usually contain several % of a carbon residue as impurities. If the amount of the carbon residue is large, the carbon residue remains as impurities in the film, and the carbon is scattered in the plasma treatment, or pinholes formed by scattering of the carbon cause corrosion, so that such an amount is undesirable. In order to avoid such a phenomenon, it is preferable to carry out calcining treatment at 100 0 C to 1000 0 C for 1 to 12 hours in an atmosphere of air to decrease the amount of the carbon residue after the treatment to less than 0.5% by mass.
  • the Y 2 O 3 nanoparticles synthesized by the above process are present in the form of aggregates, and in order to obtain a stable slurry, it is necessary to pulverize and finely disperse the aggregates by a proper method and to stably maintain the dispersed state.
  • methods to finely disperse the aggregates various methods, such as a bead mill method, a jet mill method and a ball mill method, are known.
  • a bead mill method is preferable.
  • the material of the beads is preferably zirconium oxide having excellent abrasion resistance.
  • the filling proportion of the beads to the container is in the range of preferably 85% to 95%, and the Y2O 3 nanoparticles are used in amounts of 1% by mass to 50% by mass based on the total 100% by mass of the Y2O3 nanoparticles, the organic dispersion medium, the dispersant and the binder.
  • the stirring time is properly determined according to the desired ultimate particle diameter of dispersed particles, it is in the range of usually about 10 minutes to 12 hours.
  • the dispersed particle diameter of the Y 2 O 3 nanoparticles in the resulting slurry is in the range of preferably 10 nm to 200 nm, more preferably 10 nm to 100 nm.
  • the Y 2 O 3 slurry is desirably a mixed slurry of two or more kinds of slurries having dispersed particle diameters of different volume-average particle diameters.
  • slurries having different dispersed particle diameters are mixed, small particles enter gaps among large particles, whereby further densification of the film becomes possible.
  • a combination of a distribution peak diameter of 200 nm to 300 nm and a distribution peak diameter of 10 nm and 100 run, or a combination of a distribution peak diameter of 300 nm to 200 nm and a distribution peak diameter of 10 nm and 50 nm is applicable.
  • a difference between the distribution peak diameters is desirably in the range of 50 to 200 nm. Formation of Y 2 O 3 film
  • Preferred examples of the substrates to be coated with the Y 2 O 3 film include aluminum and aluminum alloy which are used for semiconductor manufacturing apparatuses or the like, various iron and steel materials including stainless steel, tungsten, tungsten alloy, titanium, titanium alloy, molybdenum, molybdenum alloy, oxide type ceramics such as glass, carbon, and non-oxide type ceramics.
  • these substrates Prior to the film formation, these substrates may have been subjected to blasting if necessary, or may have been provided with a film composed of a metal material having high resistance to halogen gas corrosion.
  • the slurry In the application of the slurry to the substrate, the slurry has an Y 2 O 3 concentration of 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 10% by mass. If the concentration of the slurry is too high, the film sometimes suffers cracks. If the concentration is too low, productivity is lowered.
  • the film thickness based on one film-forming operation is in the range of usually 10 ru ⁇ to 5 ⁇ m, more preferably 100 nm to 3 ⁇ m. If the film thickness based on one film-forming operation is too large, the film sometimes suffers cracks. If the film thickness based on one film-forming operation is too small, productivity is lowered.
  • the film thickness based on one film-forming operation can be controlled by slurry concentration, slurry viscosity, coating weight, etc.
  • the final thickness of the Y 2 O 3 film is in the range
  • the film of the invention exhibits sufficient plasma resistance even in a thickness
  • a method of applying the slurry can be appropriately selected from conventional methods, such as air spraying, dip coating and spin coating, according to the size, shape, etc. of the substrate to be coated.
  • Heat treatment of Y2O3 The heat treatment temperature after application of the slurry is in the range of preferably 100 to 300°C, more preferably 200 to 300 0 C. Even if the heat treatment temperature is higher than 300 0 C, aggregation of nanoparticles proceeds and no problem takes place particularly, but it is difficult to apply such a high temperature to a member of low heat resistance such as aluminum.
  • the heat treatment time is in the range of preferably 10 minutes to 5 hours, more preferably 30 minutes to 1 hour.
  • the result of heat treatment of long time and the result of heat treatment of short time are the same as the result of heat treatment of high temperature and the result of heat treatment of low temperature, respectively.
  • a rectangular or cylindrical electric calcining furnace, a microwave calcining furnace or the like is employable for the heat treatment.
  • the heat treatment effect is obtained also by irradiation with plasma.
  • application of the slurry and heat treatment may be carried out in the clean environment such as a clean room or a clean booth. Examples of formation of Y2O3 film
  • Formation of an Y 2 O 3 film by air spraying is carried out in the following manner.
  • the Y2O3 slurry is diluted to 0.1% by mass to 40% by mass with an organic dispersion medium (preferably the same dispersion medium in the Y 2 O 3 slurry) .
  • the diluted .slurry is sprayed onto a member using air spray equipment and then dried for 1 minute to 1 hour to volatilize the organic dispersion medium.
  • heat treatment is carried out at 100 0 C to 300 0 C for 10 minutes to 5 hours in an atmosphere of air to promote aggregation of the Y 2 O 3 nanoparticles and to bring about decomposition/oxidation reaction of the binder, whereby a dense and strong Y 2 O 3 film is formed on a surface of the member .
  • the film thickness based on one film-forming operation is properly determined according to the dilution concentration of the slurry and the quantity of the slurry sprayed, it is preferable to carry out the operation so that the film thickness should become 10 nm to 5 ⁇ m, preferably 100 nm to 3 ⁇ m, after drying. If the film thickness based on one film-forming operation is, too large, the film suffers cracks, and if the film thickness based on one film-forming operation is too small, productivity is lowered, so that such a thickness is undesirable.
  • the heat treatment temperature after application of the slurry is in the range of preferably 200 0 C to 300 0 C.
  • a heat treatment temperature is high, aggregation of nanoparticles proceeds but it is difficult to apply a high temperature to a member of low heat resistance such as aluminum. If the heat treatment temperature is too low, aggregation does not proceed and many defects are produced in the film, resulting in troubles such as lowering of film strength and remaining of a dispersant and a binder as impurities in the film, so that such a temperature is undesirable.
  • formation of an Y2O3 film by dip coating is carried out in the following manner.
  • the Y 2 O 3 slurry is diluted to 0.1% by mass to 40% by mass with an organic dispersion medium (preferably the same dispersion medium in the Y 2 O3 slurry) .
  • the diluted slurry is applied to a member using dip coating equipment and then dried for 1 minute to 1 hour to volatilize the organic dispersion medium. Then, heat treatment is carried out at 100 0 C to 300 0 C for 10 minutes to 5 hours in an atmosphere of air to promote aggregation of the Y2O 3 nanoparticles and to bring about decomposition/oxidation reaction of the binder, whereby a dense and strong Y 2 O 3 film is formed on a surface of the member.
  • the film thickness based on one film-forming operation is properly determined according to the dilution concentration of the slurry and the pull-up rate of the member, it is preferable to carry out the operation so that the film thickness should become 10 nm to 5 ⁇ m, preferably 100 nm to 3 ⁇ m, after drying. If the film thickness based on one film-forming operation is too large, the film sometimes suffers cracks, and if the film thickness based on one film-forming operation is too small, productivity is sometimes lowered.
  • the heat treatment temperature after application of the slurry is in the range of preferably 200 0 C to 300 0 C.
  • Y 2 O 3 film by spin coating is carried out in the following manner.
  • the Y 2 O 3 slurry is diluted to 0.1% by mass to 40% by mass with an organic dispersion medium (preferably the same dispersion medium in the Y2O3 slurry) .
  • the diluted slurry is applied to a member using spin coating equipment and then dried for 1 minute to 1 hour to volatilize the organic dispersion medium. Then, heat treatment is carried out at 100 0 C to 300 0 C for 10 minutes to 5 hours in an atmosphere of air to promote aggregation of the Y 2 O 3 nanoparticles and to bring about decomposition/oxidation reaction of the binder, whereby a dense and strong Y 2 O 3 film is formed on a surface of the member.
  • the film thickness based on one film-forming operation is properly determined according to the dilution concentration of the slurry, the quantity of the slurry dropped, and the number of revolutions and the revolution time of the member, it is preferable to carry out the operation so that the film thickness should become 10 nm to 5 ⁇ m, preferably 100 nm to 3 ⁇ m, after drying. If the film thickness based on one film-forming operation is too large, the film sometimes suffers cracks, and if the film thickness based on one film-forming operation is too small, productivity is sometimes lowered.
  • the final thickness of the Y 2 O3 film is in the range of 0.05 ⁇ m to 500 ⁇ m, preferably 0.5 ⁇ m to 50 ⁇ m.
  • the member of the invention is obtained by forming the above-described Y2O3 film on a surface of a substrate.
  • the thickness of the Y2O3 film formed is not specifically restricted, it is in the range of preferably
  • the member of the invention is particularly preferably an etching chamber member. Since the member of the invention has high resistance to plasma corrosion, the member is preferably used for, for example, a plasma etching chamber and a plasma treatment apparatus for a liquid crystal device or the like. Examples
  • Preparation Example 1 Using an apparatus having a constitution shown in Fig. 1, Y 2 O 3 nanoparticles were prepared. First, to a vaporizer (6) heated to 200 0 C, a mixed solution of 300 g of yttrium tridipivaloylmethane and 700 g of methanol was fed at a flow rate of 4 ml/min, and the solution was vaporized. To a preheater (5) , air was fed as an oxidizing substance (1) at a flow rate of 40 1/min, and the air was heated to 200 °C.
  • the gaseous yttrium tridipivaloylmethane and methanol, and the air were fed to a coaxial nozzle at an entrance of a tubular electric furnace (7) .
  • the combustion temperature in the tubular electric furnace was set at 950 0 C, and the yttrium tridipivaloylmethane and methanol were oxidized to form Y 2 O 3 .
  • a yield of the Y 2 O 3 nanoparticles collected by a collector (8) was not less than 95%.
  • the Y 2 O 3 nanoparticles contained several % of a carbon residue as impurities .
  • calcining treatment was carried out at 500 0 C for 8 hours in an atmosphere of air.
  • the amount of the carbon residue was less than 0.5% by mass.
  • the primary particle diameter of the Y 2 O 3 particles was about 20 nm.
  • the dried precipitate was placed in a porcelain crucible and calcined at 700 0 C for 3 hours in an atmosphere of air to obtain Y 2 O 3 .
  • a yield of the resulting Y2O 3 nanoparticles was not less than 99%.
  • the primary particle diameter of the Y2O3 particles was about 20 nm.
  • the slurry was treated by a bead mill (manufactured by Kotobuki Engineering & Manufacturing Co., Ltd., UAM-015) containing 400 g of zirconium oxide beads having a diameter of 50 ⁇ m for 6 hours to obtain an Y 2 O 3 slurry of 4% by mass.
  • a particle size distribution meter manufactured by Nikkiso Co., Ltd., Nanotrac UPA-EX150
  • the volume-average particle diameter was 18 nm
  • the maximum particle diameter was 102 nm.
  • Dmin the minimum particle diameter
  • Dav volume-average particle diameter
  • Dmax the maximum particle diameter
  • the Y2O3 slurries obtained in Examples 1 and 2 were each diluted with l-methoxy-2-propanol so that the Y 2 O 3 concentration should become 1% by mass.
  • the diluted slurry was sprayed onto an aluminum specimen as a substrate (size: 50 mm (width) x 50 mm (length) x 5 mm (thickness) ) by means of such air spray equipment as shown in Fig. 2 and dried for 5 minutes in an atmosphere of air to volatilize l-methoxy-2-propanol.
  • the specimen' was heat-treated at 300 0 C for 1 hour in an atmosphere of air to form an Y 2 O 3 film on the specimen surface.
  • the film thickness based on one film-forming operation was made 200 nm, and this operation was repeated 5 times to
  • the film thickness based on one film-forming operation was made 1 ⁇ m, and this operation was repeated 10 times to produce a film having a thickness of 10 ⁇ m. Furthermore, the film thickness based on film-forming operation was made 2 ⁇ m, and this operation was repeated 25 times to produce a film having a thickness of 50 ⁇ m. Also on a glass specimen, production of a film having a thickness of 1 ⁇ m was carried out. The film thickness was measured by the aforesaid field emission type scanning electron microscope. An electron microscope photograph of the film having a thickness of 1 ⁇ m produced on the glass substrate using the slurry of Example 1 is shown in Fig. 3. The film proved to be a dense film because it was formed from nanoparticles .
  • Example 4 Y 2 Oa film having a thickness of 1 ⁇ m are formed on an aluminum specimen and a glass specimen, respectively, in the same manner as Example 3 except that the Y 2 O 3 slurry obtained in Example 1 was diluted with methanol so that the Y 2 O 3 concentration should become 1% by mass.
  • Example 4
  • the Y 2 O 3 slurry obtained in Example 1 was diluted with l-methoxy-2-propanol so that the Y2O3 concentration should become 1% by mass.
  • the diluted slurry was applied onto an aluminum specimen (size: 50 mm (width) x 50 mm (length) x 5 mm (thickness) ) by the use of dip coating equipment (pull-up rate: 3 cm/min) and dried for 5 minutes in an atmosphere of air to volatilize 1-methoxy- 2-propanol .
  • the specimen was heat-treated at 300 0 C for 1 hour in an atmosphere of air to form an Y2O3 film on the specimen surface. This operation was repeated to obtain a film having a thickness of 1 ⁇ m, a film having a thickness of 10 ⁇ m and a film having a thickness of 50 ⁇ m.
  • the Y 2 O3 slurry obtained in Example 1 was diluted with l-methoxy-2-propanol so that the Y2O3 concentration should become 1% by mass.
  • the diluted slurry was applied onto an aluminum specimen (size: 50 mm (width) x 50 mm (length) x 5 mm (thickness) ) by the use of spin coating equipment (number of revolutions: 30 rpm, 30 seconds) and dried for 5 minutes in an atmosphere of air to volatilize l-methoxy-2-propanol.
  • the specimen was heat-treated at 300 0 C for 1 hour in an atmosphere of air to form an Y 2 O 3 film on the specimen surface. This operation was
  • an Y 2 O 3 thermal spraying film was formed by means of atmospheric plasma thermal spraying.
  • the plasma thermal spraying is a method wherein an Y 2 O 3 powder as a plasma thermal spraying material is heated by a plasma jet to give molten droplets and the molten droplets are sprayed onto a substrate at a high speed.
  • the specimens prepared in Examples 3 to 5 and Comparative Examples 2 to 5 were subjected to bond strength measurement and thermal shock test (test wherein operations of heating a specimen for 20 minutes in an electric furnace kept at 500 0 C and quenching it outside the furnace were taken as one cycle and this cycle is repeated ten times) .
  • the aluminum specimens were each subjected to plasma etching treatment under the following conditions, then the number of particles adhering to a surface of a silicon wafer of 8-inch diameter having been allowed to stand still in a chamber was measured, and a period of time taken until the number of particles exceeded a control limit of a general chamber interior, i.e., 30, was measured.
  • the surface inspection equipment used was equipment to . count the number of particles utilizing scattering of a laser beam, and the number of particles having a particle diameter of not less than 0.2 ⁇ m was measured.
  • the bond strength is measured in accordance with JIS-H8666 (ceramic thermal spraying film test method) .
  • Example 3 With regard to the films obtained by air spraying in Example 3, it was confirmed that irrespective of type of specimen and film thickness, the bond strength was markedly higher than that of Comparative Examples 2 to 4, similarly to the Y 2 O 3 slurries obtained in Examples 1 and 2. Further, it was also confirmed that irrespective of film thickness, the time taken until the number of particles exceeded 30 was sufficiently longer than that of the thermal spraying films of comparative Examples 3 and 4, and in spite that the film thickness was small, the plasma erosion resistance in an atmosphere containing a halogen compound was markedly higher than that of the thermal spraying films.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

L’invention concerne un élément de résistance élevé à la corrosion de plasma nécessaire à la chambre d’attaque chimique au plasma d’un appareil de fabrication de semi-conducteurs ou d’un appareil de traitement au plasma pour dispositif à cristaux liquides ou similaire. Elle concerne un film Y2O3 comprenant un agrégat de particules Y2O3 d’un diamètre de particules moyen volumique compris entre 10 nm et 300 nm. Elle concerne aussi un film Y2O3 obtenu par séchage d’un laitier de Y2O3 d’un diamètre de particules moyen volumique, à l’état dispersé, compris entre 10 nm et 300 nm et par traitement thermique du produit séché. Un milieu de dispersion du laitier de Y2O3 est un dérivé d’alcool polyhydrique. Le laitier de Y2O3 contient du b-dicétone comme dispersant. Le laitier de Y2O3 contient un complexe de métal b-dicétone comme liant. Le laitier de Y2O3 est un mélange de deux ou plus de deux types de laitiers ayant des diamètres de particules dispersées de différents diamètres de particules moyens volumiques. L’invention concerne également un processus de fabrication d‘un film de Y2O3, consistant à appliquer sur un substrat un laitier de Y2O3 d’un diamètre de particules moyen volumique, à l’état dispersé, compris entre 10 nm et 300 nm et d’une concentration en Y2O3 allant de 0,1% en masse à 40% en masse pour que l’épaisseur de film au bout d’une opération de formation de film soit comprise entre 10 nm et 5 mm et à réaliser un traitement thermique à une température de 100°C à 300°C pendant une durée de traitement thermique allant de 10 minutes à 5 heures après la formation du film.
PCT/JP2006/315082 2005-07-27 2006-07-24 Film y2o3 et processus de formation de celui-ci WO2007013640A1 (fr)

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JP2005-292221 2005-10-05

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7987613B2 (en) * 2004-10-12 2011-08-02 Great River Energy Control system for particulate material drying apparatus and process
WO2013137818A1 (fr) * 2012-03-14 2013-09-19 National University Of Singapore Procédé de préparation de films minces d'oxyde métallique
EP2799587A4 (fr) * 2011-12-28 2015-09-02 Fujimi Inc Film de revêtement en oxyde d'yttrium
WO2018035494A1 (fr) 2016-08-19 2018-02-22 GKN Aerospace Transparency Systems, Inc. Revêtements hydrophobes transparents d'oxyde mixte et procédés
CN110099880A (zh) * 2016-08-19 2019-08-06 吉凯恩航空透明系统有限公司 透明的疏水性混合氧化物涂料和方法

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US5405491A (en) * 1994-03-04 1995-04-11 Motorola Inc. Plasma etching process
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JP2000054160A (ja) * 1998-08-04 2000-02-22 Laser Atom Separation Eng Res Assoc Of Japan コーティング材料およびこれを使用するコーティング方法
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PATENT ABSTRACTS OF JAPAN vol. 2002, no. 10 10 October 2002 (2002-10-10) *
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7987613B2 (en) * 2004-10-12 2011-08-02 Great River Energy Control system for particulate material drying apparatus and process
EP2799587A4 (fr) * 2011-12-28 2015-09-02 Fujimi Inc Film de revêtement en oxyde d'yttrium
WO2013137818A1 (fr) * 2012-03-14 2013-09-19 National University Of Singapore Procédé de préparation de films minces d'oxyde métallique
WO2018035494A1 (fr) 2016-08-19 2018-02-22 GKN Aerospace Transparency Systems, Inc. Revêtements hydrophobes transparents d'oxyde mixte et procédés
CN110099880A (zh) * 2016-08-19 2019-08-06 吉凯恩航空透明系统有限公司 透明的疏水性混合氧化物涂料和方法
EP3500540A4 (fr) * 2016-08-19 2020-04-15 GKN Aerospace Transparency Systems, Inc. Revêtements hydrophobes transparents d'oxyde mixte et procédés
US11053163B2 (en) 2016-08-19 2021-07-06 GKN Aerospace Transparency Systems, Inc. Transparent hydrophobic mixed oxide coatings and methods

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