WO2010128572A1 - ジルコニア膜の成膜方法 - Google Patents
ジルコニア膜の成膜方法 Download PDFInfo
- Publication number
- WO2010128572A1 WO2010128572A1 PCT/JP2010/000325 JP2010000325W WO2010128572A1 WO 2010128572 A1 WO2010128572 A1 WO 2010128572A1 JP 2010000325 W JP2010000325 W JP 2010000325W WO 2010128572 A1 WO2010128572 A1 WO 2010128572A1
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- Prior art keywords
- aerosol
- zirconia
- fine particles
- film
- container
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 440
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000000443 aerosol Substances 0.000 claims abstract description 306
- 239000010419 fine particle Substances 0.000 claims abstract description 173
- 239000002245 particle Substances 0.000 claims abstract description 132
- 239000000758 substrate Substances 0.000 claims abstract description 116
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 10
- 238000007872 degassing Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 217
- 230000015572 biosynthetic process Effects 0.000 abstract description 63
- 239000010409 thin film Substances 0.000 abstract description 61
- 230000008021 deposition Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 description 146
- 239000007789 gas Substances 0.000 description 120
- 239000012159 carrier gas Substances 0.000 description 43
- 230000032258 transport Effects 0.000 description 36
- 230000007246 mechanism Effects 0.000 description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- 238000003475 lamination Methods 0.000 description 31
- 238000010438 heat treatment Methods 0.000 description 26
- 238000000151 deposition Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 239000011521 glass Substances 0.000 description 22
- 239000002390 adhesive tape Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000012387 aerosolization Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
Definitions
- the present invention relates to a method for forming a zirconia film by an aerosolized gas deposition method.
- a zirconia (zirconium oxide) film has characteristics such as high heat resistance and corrosion resistance, low heat and electrical conductivity, and is used as a heat-resistant protective film, a corrosion-resistant protective film, an optical thin film, and the like.
- the zirconia film is conventionally formed by a sol-gel method, a thermal CVD (Chemical Vapor Deposition) method, a sputtering method, a thermal spraying method, etc., but each has drawbacks in terms of film formation speed, film formation conditions, film quality, etc. There is room for improvement in the film formation method.
- raw material fine particles contained in an aerosol container are wound up with gas to be aerosolized and transported by a gas flow due to a pressure difference between the aerosol container and the film forming chamber.
- This is a film forming method in which a material is collided and deposited.
- the kinetic energy of the raw material fine particles accelerated at high speed is locally converted into thermal energy, thereby forming a film. Since the heating of the substrate is local, the substrate is hardly affected by heat (room temperature film formation), and the film forming speed is higher than other film forming methods. A film having high adhesion can be formed.
- Patent Document 1 As an aerosol gas deposition method using zirconia fine particles as a raw material, for example, methods described in Patent Document 1 and Patent Document 2 are known.
- Patent Document 1 discloses a “low temperature molding method of a brittle material fine particle film forming body” in which a thin film made of the brittle material is formed by using an aerosol type gas deposition method using brittle material fine particles containing zirconia fine particles as a raw material. ing. According to this method, by using fine particles having a non-spherical irregular shape as an aerosol raw material, an impact force is concentrated on the sharp corners of the fine particles, thereby obtaining a film-formed body having a dense and strong bonding force. Is possible.
- Patent Document 2 discloses “a ceramic firing tool material for electronic parts” in which a zirconia-based surface layer is formed by an aerosol deposition method. According to this method, an intermediate layer having a linear thermal expansion coefficient that is an intermediate value between the base material and zirconia is provided on the base material, and peeling of the zirconia-based surface layer can be prevented.
- JP 2003-73855 A (paragraph [0010], FIG. 1) JP 2008-137860 A (paragraph [0021])
- the film forming method described in Patent Document 2 refers to the case where a film is formed using zirconia powder (average particle size 0.45 ⁇ m) as an aerosol raw material.
- the zirconia film is formed on the intermediate layer formed on the base material for preventing peeling, and when the zirconia film is directly formed on the base material, cracking or peeling is caused. It is supposed to occur.
- a method for directly forming a zirconia thin film having excellent film quality on a substrate by an aerosolized gas deposition method has not been known.
- the inventors of the present invention focused on the properties (average particle size, particle size distribution, etc.) of particles of zirconia fine particles that are aerosol raw materials, and the average particles described in Patent Document 1 and Patent Document 2 described above.
- a zirconia thin film having good film quality could not be obtained even by using zirconia fine particles having a diameter.
- an object of the present invention is to provide a film forming method of a zirconia film capable of obtaining a good film quality by an aerosolized gas deposition method.
- a method for forming a zirconia film according to one embodiment of the present invention has an average particle diameter of 0.7 ⁇ m to 11 ⁇ m and a specific surface area of 1 m 2 / g to 7 m 2 / g.
- Including containing certain zirconia fine particles in a sealed container The aerosol of the zirconia fine particles is generated by introducing a gas into the sealed container. The aerosol is transported to a film forming chamber maintained at a lower pressure than the sealed container via a transport pipe connected to the sealed container. The zirconia fine particles are deposited on a substrate housed in the film forming chamber.
- a method for forming a zirconia film according to an embodiment of the present invention is a method for sealing zirconia fine particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 7 m 2 / g or less. Containment.
- the aerosol of the zirconia fine particles is generated by introducing a gas into the sealed container.
- the aerosol is transported to a film forming chamber maintained at a lower pressure than the sealed container via a transport pipe connected to the sealed container.
- the zirconia fine particles are deposited on a substrate housed in the film forming chamber.
- zirconia particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 7 m 2 / g or less As an aerosol raw material, good film quality (high density, high adhesion, etc.) It is possible to form a zirconia film having: on a substrate.
- the raw material fine particles used as the aerosol raw material for the aerosolized gas deposition method generally have a particle size of about 0.1 ⁇ m to 1 ⁇ m. This is because many materials are satisfactorily formed with such a particle size, or raw material fine particles having such a particle size are easily aerosolized.
- the present inventors have found that a zirconia film having a good film quality is formed by zirconia fine particles having a particle diameter larger than a particle diameter that is usually used.
- the “average particle diameter” in the present specification means a value (D 50 ) in which the integrated percentage of the particle size distribution measured by the laser diffraction particle size distribution measuring method is 50%.
- the average particle size was measured using a laser diffraction particle size distribution analyzer “SALD2000” manufactured by Shimadzu Corporation.
- SALD2000 laser diffraction particle size distribution analyzer manufactured by Shimadzu Corporation.
- the “specific surface area” is a value measured by a gas adsorption method, and here, a value measured by “Flow Sorb II 2300” manufactured by Shimadzu Corporation was used.
- the zirconia fine particles include stabilized (partially stabilized) zirconia fine particles containing a rare earth oxide such as yttria and high-purity zirconia fine particles. Stabilization and partially stabilized zirconia are often determined by the amount of oxide added. In this kind of stabilized zirconia film, the oxide is solid-dissolved in the zirconia crystal, so that the crystal structure is stabilized or quasi-stabilized, thereby suppressing the breakdown due to the temperature rise and fall. Therefore, a zirconia film formed with stabilized (partially stabilized) zirconia fine particles is excellent in heat resistance and thus has a wide range of industrial applications. On the other hand, a zirconia film formed with high-purity zirconia fine particles has an advantage that the characteristics derived from zirconia can be directly reflected in the film characteristics.
- the zirconia fine particles When forming a zirconia film using stabilized (partially stabilized) zirconia fine particles, the zirconia fine particles have an average particle diameter of 1 ⁇ m to 5 ⁇ m and a specific surface area of 1 m 2 / g to 4 m 2 / g. Preferably there is.
- the average particle diameter of the zirconia fine particles is less than 1 ⁇ m, or when the specific surface area exceeds 4 m 2 / g, it is difficult to form a dense film, and a green compact with a low density tends to be obtained.
- the zirconia fine particles have an average particle size of 1.9 ⁇ m to 4.6 ⁇ m.
- the yttria content in the zirconia fine particles is not particularly limited, and can be, for example, 8% by weight to 14% by weight (or 4.5% by mole to 8% by mole). According to the method for forming a zirconia film, excellent film formability can be obtained by using zirconia fine particles containing yttria in the above range. In addition to the yttria, the zirconia fine particles may further contain other oxides.
- zirconia fine particles are classified into zirconia fine particles produced by a dry method and zirconia fine particles produced by a wet method. Since zirconia fine particles have slightly different fine particle characteristics depending on the production method, a zirconia film having desired film characteristics can be stably formed by selecting the average particle diameter and specific surface area according to the production method. it can.
- zirconia fine particles produced by a dry method zirconia fine particles having an average fine particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 6.5 m 2 / g or less are used. Is preferred.
- the average particle diameter of the zirconia fine particles is less than 0.7 ⁇ m, it is difficult to form a dense film, and it tends to be a green compact (powder compact) having a low density.
- the average particle diameter is larger than 11 ⁇ m, the adhesion is weak and film peeling occurs or a green compact is formed, which is not preferable.
- the zirconia fine particles have an average particle size of 0.7 ⁇ m or more and 10.2 ⁇ m or less.
- the dry method is one of methods (breakdown method) in which solids or liquids are physically made into fine particles, and for example, a production method using electromelting can be adopted.
- a large lump is first produced by melting the raw material. Thereafter, the lump is pulverized and classified to produce fine particles having a predetermined particle size.
- the dry method it is possible to stably obtain zirconia fine particles having an average particle diameter of 1 ⁇ m or less as compared with the wet method.
- zirconia fine particles when using zirconia fine particles produced by a wet method, zirconia fine particles having an average fine particle diameter of 2 ⁇ m or more and 4 ⁇ m or less and a specific surface area of 4 m 2 / g or more and 7 m 2 / g or less are suitable.
- the average particle diameter of the zirconia fine particles is less than 2 ⁇ m, it is difficult to form a dense film, and it tends to be a green compact (powder compact) having a low density.
- the average particle diameter is larger than 4 ⁇ m, the adhesion is weak and film peeling occurs or a green compact is formed, which is not preferable.
- the zirconia fine particles have an average particle size of 2.2 ⁇ m or more and 3.5 ⁇ m or less.
- the wet method refers to a method of building up fine particles from atoms and molecules such as a chemical vapor deposition method or a liquid phase synthesis method.
- the wet method is easy to obtain high-purity zirconia fine particles as compared with the dry method.
- the average particle size of zirconia fine particles obtained by a wet method is typically the average particle size of secondary particles in which primary particles are aggregated.
- the film formation method of the zirconia film may further include a step of degassing the zirconia fine particles before the step of storing the zirconia fine particles in the sealed container.
- the step of generating the aerosol is performed by blowing up the zirconia fine particles in the container by ejecting the gas from a gas jetting body covered with the zirconia fine particles installed in the sealed container. May be mixed.
- the zirconia fine particles according to the embodiment of the present invention have a relatively large particle diameter, but can be well aerosolized by ejecting gas from the zirconia fine particles.
- FIG. 1 is a diagram showing a schematic configuration of an aerosolized gas deposition apparatus 1 (hereinafter, AGD apparatus 1) according to an embodiment of the present invention.
- the AGD apparatus 1 includes an aerosol container 2, a film forming chamber 3, an exhaust system 4, a gas supply system 5, and a transport pipe 6.
- the aerosol-generating container 2 and the film forming chamber 3 form independent chambers and are connected by a transfer pipe 6.
- the exhaust system 4 is connected to the aerosol container 2 and the film forming chamber 3.
- the gas supply system 5 is connected to the aerosol container 2.
- the aerosol raw material P is accommodated in the aerosol container 2.
- a substrate S is accommodated in the film forming chamber 3.
- the aerosolization container (sealed container) 2 accommodates the aerosol raw material P and generates aerosol therein.
- the aerosol-generating container 2 has a sealable structure and has a lid (not shown) for taking in and out the aerosol raw material P.
- the aerosolization container 2 is connected to an exhaust system 4 and a gas supply system 5.
- the aerosol-generating container 2 is provided with a vibration mechanism that vibrates the aerosol-generating container 2 in order to stir the aerosol raw material P, or a heating means that heats the aerosol raw material P in order to deaerate (remove moisture and the like). Also good.
- the film forming chamber 3 accommodates the substrate S.
- the film forming chamber 3 is configured to be able to maintain the internal atmospheric pressure.
- the film forming chamber 3 is connected to the exhaust system 4.
- the film forming chamber 3 is provided with a stage 7 for holding the substrate S and a stage driving mechanism 8 for moving the stage 7.
- the stage 7 may have a heating means for heating the substrate S in order to degas the substrate S before film formation.
- the film forming chamber 3 may be provided with a vacuum gauge that indicates the internal pressure.
- the exhaust system 4 evacuates the aerosol container 2 and the film formation chamber 3.
- the exhaust system 4 includes a vacuum pipe 9, a first valve 10, a second valve 11, and a vacuum pump 12.
- a vacuum pipe 9 connected to the vacuum pump 12 is branched and connected to the aerosol container 2 and the film forming chamber 3.
- the first valve 10 is disposed on the vacuum pipe 9 between the branch point of the vacuum pipe 9 and the aerosol container 2 and is configured to be able to block the vacuum exhaust of the aerosol container 2.
- the second valve 11 is disposed on the vacuum pipe 9 between the branch point of the vacuum pipe 9 and the film forming chamber 3, and is configured to be able to block the vacuum exhaust of the film forming chamber 3.
- the configuration of the vacuum pump 12 is not particularly limited, and may be composed of a plurality of pump units.
- the vacuum pump 12 can be, for example, a mechanical booster pump and a rotary pump connected in series.
- the gas supply system 5 regulates the pressure of the aerosol container 2 and supplies a carrier gas for forming the aerosol to the aerosol container 2.
- the carrier gas is, for example, N 2 , Ar, He or the like.
- the gas supply system 5 includes a gas pipe 13, a gas source 14, a third valve 15, a gas flow meter 16, and a gas ejection body 17.
- the gas source 14 and the gas ejection body 17 are connected by a gas pipe 13, and a third valve 15 and a gas flow meter 16 are disposed on the gas pipe 13.
- the gas source 14 is a gas cylinder, for example, and supplies a carrier gas.
- the gas ejection body 17 is arranged in the aerosol container 2 and uniformly ejects the carrier gas supplied from the gas pipe 13.
- the gas ejection body 17 can be, for example, a hollow body provided with a large number of gas ejection holes, and is disposed at a position covered with the aerosol material P to effectively wind up the aerosol material P to be aerosolized. Is possible.
- the gas flow meter 16 indicates the flow rate of the carrier gas flowing through the gas pipe 13.
- the third valve 15 is configured to be able to adjust or block the flow rate of the carrier gas flowing through the gas pipe 13.
- the transport pipe 6 transports the aerosol formed in the aerosol container 2 into the film forming chamber 3.
- One end of the transport pipe 6 is connected to the aerosol container 2 and a nozzle 18 is provided at the other end.
- the nozzle 18 has a small-diameter round hole or slit-shaped opening, and the aerosol ejection speed is defined by the opening diameter of the nozzle 18 as will be described later.
- the nozzle 18 is provided at a position facing the substrate S, and is connected to a nozzle movable mechanism that defines the position and angle of the nozzle 18 in order to define the ejection distance or the ejection angle of the aerosol with respect to the substrate S. May be.
- the base material S is made of a material such as glass, metal or ceramics. As described above, since the AGD method is a room temperature film formation and a physical film formation method that does not obtain a chemical process, a wide range of materials can be selected as a base material. Further, the substrate S is not limited to a planar one, and may be a three-dimensional one.
- the AGD apparatus 1 is configured as described above.
- the configuration of the AGD apparatus 1 is not limited to the above.
- the aerosol is formed by adjusting the pressure of the aerosol-generating container 2 and winding up the aerosol raw material P by the carrier gas supplied by the gas supply system 5.
- the pressure in the aerosol container 2 can be controlled independently of the aerosol formation state (formation amount, mainly the particle diameter to be rolled up, etc.). It is possible to adjust.
- the aerosol raw material P is aerosolized in the aerosol container 2 and formed on the substrate S.
- zirconia fine particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 7 m 2 / g or less are used.
- the zirconia fine particles include stabilized (including partial stabilization) zirconia fine particles and high-purity zirconia fine particles.
- the high-purity zirconia fine particles include zirconia fine particles produced by a dry method and zirconia fine particles produced by a wet method. Depending on the type of these zirconia fine particles, suitable ranges of the average particle diameter and specific surface area of the fine particles may be defined as follows.
- the stabilized zirconia fine particles are fine particles of zirconia (stabilized zirconia, partially stabilized zirconia) containing at least yttria (Y 2 O 3 ).
- the average particle diameter is 1 ⁇ m or more and 5 ⁇ m or less
- the specific surface area is 1 m 2 / g or more and 4 m 2 / g or less.
- zirconia fine particles having an average particle diameter of 1 ⁇ m or more and 5 ⁇ m or less as an aerosol raw material, it is possible to form a zirconia thin film having good characteristics (denseness, adhesion to the substrate S, etc.).
- the average particle diameter of the zirconia fine particles is less than 1 ⁇ m, or when the specific surface area exceeds 4 m 2 / g, it is difficult to form a dense deposited film, and it tends to be a green compact having a low density.
- the average particle diameter is larger than 5 ⁇ m, the adhesion may be weak and film peeling may occur, or a green compact (powder compact) may be formed.
- the specific surface area is 1 m 2 / g or more and 4 m when the particle size distribution is non-uniform and a large amount of particles having a small particle size and particles having a large particle size are contained. It deviates from the range of 2 / g or less.
- the aerosol raw material used in the AGD method generally has a particle size of about 0.1 ⁇ m to 1 ⁇ m, whereas the aerosol raw material P according to the present embodiment has a larger particle size.
- the content of yttria in the zirconia fine particles is not particularly limited, and may be, for example, 8% by weight to 14% by weight (4.5% by mole to 8% by mole). According to the method for forming a zirconia film, excellent film formability can be obtained by using zirconia fine particles containing yttria in the above range.
- Examples of yttria-containing zirconia fine particles having an average particle diameter of 1 ⁇ m or more and 5 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 4 m 2 / g or less include, for example, stabilized zirconia fine particles “manufactured by Daiichi Rare Element Chemical Industries, Ltd.” KYZ-8 ”(product name) (average particle size 1.9 ⁇ m, specific surface area 3.1 m 2 / g) can be used.
- zirconia fine particles having a particle diameter in the above range may be prepared by crushing and classifying zirconia fine particles having a relatively large particle diameter.
- the method for producing the zirconia fine particles is not particularly limited, and for example, a known method such as a wet method or a dry method can be employed.
- High purity zirconia fine particles (dry type)
- high purity zirconia fine particles having a ZrO 2 + HfO 2 purity of 99.50% or more are used.
- the average particle diameter is 0.7 ⁇ m or more and 11 ⁇ m or less
- the specific surface area is 1 m 2 / g or more and 6.5 m 2 / g or less.
- zirconia fine particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less as an aerosol raw material, it is possible to form a zirconia thin film having good characteristics (denseness, adhesion to the substrate S, etc.).
- the average particle diameter of the zirconia fine particles is less than 0.7 ⁇ m, it is difficult to form a dense film, and there is a tendency to become a green compact (powder compact) having a low density.
- the average particle diameter is larger than 11 ⁇ m, the adhesion may be weak and film peeling may occur or a green compact may be formed.
- the specific surface area is 1 m 2 / g when the particle size distribution is non-uniform and a large amount of particles having a small particle size and particles having a large particle size are contained. It deviates from the range of 6.5 m 2 / g or less.
- the aerosol raw material used in the AGD method generally has a particle size of about 0.1 ⁇ m to 1 ⁇ m, whereas the aerosol raw material P according to the present embodiment has a larger particle size.
- zirconia fine particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 6.5 m 2 / g or less include BR- 3QZ (product name) (average particle diameter of 2.9 ⁇ m, specific surface area of 2.7 m 2 / g) can be used.
- High purity zirconia fine particles As the high purity zirconia fine particles produced by a wet method, for example, high purity zirconia fine particles having a ZrO 2 + HfO 2 purity of 99.50% or more are used.
- this kind of zirconia fine particles is used as the aerosol raw material P, the average particle diameter is 2 ⁇ m or more and 4 ⁇ m or less, and the specific surface area is 4 m 2 / g or more and 7 m 2 / g or less.
- zirconia fine particles having an average particle diameter of 2 ⁇ m or more and 4 ⁇ m or less as an aerosol raw material, it is possible to form a zirconia thin film having good characteristics (denseness, adhesion to the substrate S, etc.).
- the average particle size of the zirconia fine particles is less than 2 ⁇ m, it is difficult to form a film, and when the average particle size is larger than 4 ⁇ m, the adhesion is weak and peeling occurs, or a green compact (powder compact) is formed. May be formed.
- the specific surface area is 4 m 2 / g or more and 7 m when the particle size distribution is non-uniform and a large amount of particles having a small particle size and particles having a large particle size are contained. It deviates from the range of 2 / g or less.
- the aerosol raw material used in the AGD method generally has a particle size of about 0.1 ⁇ m to 1 ⁇ m, whereas the aerosol raw material P according to the present embodiment has a larger particle size.
- zirconia fine particles having an average particle diameter of 2 ⁇ m or more and 4 ⁇ m or less and a specific surface area of 4 m 2 / g or more and 7 m 2 / g or less include, for example, SPZ zirconium oxide (product name, manufactured by Daiichi Rare Element Chemical Industries, Ltd.). ) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 2.5 to 4 ⁇ m, specific surface area 4 to 7 m 2 / g) can be used.
- SPZ zirconium oxide product name, manufactured by Daiichi Rare Element Chemical Industries, Ltd.
- FIG. 2 is a diagram schematically illustrating an aspect of forming a zirconia thin film by the AGD method according to the present embodiment.
- a predetermined amount of aerosol raw material P is accommodated in the aerosol-generating container 2.
- the aerosol raw material P may be heated in advance and deaerated.
- the aerosol-generating container 2 may be heated.
- the aerosol-generating container 2 and the film forming chamber 3 are evacuated by the exhaust system 4.
- the first valve 10 and the second valve 11 are opened, and the aerosol-generating container 2 and the film forming chamber 3 are evacuated until the pressure is sufficiently lowered.
- the first valve 10 is closed.
- the film formation chamber 3 is evacuated during film formation.
- a carrier gas is introduced into the aerosol container 2 by the gas supply system 5.
- the third valve 15 is opened, and the carrier gas is ejected from the gas ejection body 17 into the aerosol container 2.
- the carrier gas introduced into the aerosol container 2 raises the pressure in the aerosol container 2.
- the carrier gas flows toward the transfer pipe 6 communicating with the film forming chamber 3.
- the aerosol raw material P is wound up by the carrier gas ejected from the gas ejection body 17, floats in the aerosol container, and the aerosol raw material P is dispersed in the carrier gas (see FIG. 2). A) is formed.
- the generated aerosol flows into the transfer pipe 6 due to a pressure difference between the aerosol container 2 and the film forming chamber 3 and is ejected from the nozzle 18.
- the aerosol raw material P according to the present embodiment that is, the zirconia fine particles are larger than the normally used aerosol raw material, and are difficult to roll up.
- the aerosol raw material P by ejecting the carrier gas from the gas ejection body 17 arranged in the aerosol raw material P, the aerosol raw material P can be effectively wound up and dispersed.
- the aerosol (indicated by A ′ in FIG. 2) ejected from the nozzle 18 is ejected with a flow rate defined by the pressure difference between the aerosol-generating container 2 and the film forming chamber and the opening diameter of the nozzle 18.
- the aerosol reaches the surface of the substrate S or an already formed film, and the aerosol raw material P contained in the aerosol, that is, zirconia fine particles collides with the surface of the substrate S or the already formed film.
- the kinetic energy of the aerosol raw material P is locally converted into thermal energy, and the particles are melted or combined entirely or partially to form a film. From this, the particle diameter of the aerosol raw material P has a great influence on the magnitude of kinetic energy or the degree of melting of the fine particles. That is, the quality of the formed film depends on the particle diameter of the zirconia fine particles.
- a zirconia thin film (indicated by F in FIG. 2) is formed in a predetermined range on the substrate S.
- the stage 7 By moving the stage 7 by the stage drive mechanism 8, the relative position of the substrate S with respect to the nozzle 18 changes.
- a thin film By moving the stage 7 in one direction parallel to the film formation surface of the substrate S, a thin film can be formed in a linear shape having the same width as the opening diameter of the nozzle 18.
- a thin film is formed in a predetermined region by moving the stage 7 two-dimensionally.
- the angle of the nozzle 18 with respect to the film formation surface of the substrate S may be a right angle or an oblique angle.
- the zirconia thin film is formed as described above.
- the zirconia fine particles having an average particle diameter of 0.7 ⁇ m or more and 11 ⁇ m or more and a specific surface area of 1 m 2 / g or more and 7 m 2 / g or less are used as the aerosol raw material P. It is possible to form a zirconia thin film having high adhesion to S.
- Example 1 A plurality of stabilized zirconia fine particles having different average particle diameters and specific surface areas were prepared, zirconia films were formed by a gas deposition method using these fine particles as an aerosol raw material, and the film quality was evaluated.
- the results of the following Examples (1-1) to (1-4) and Comparative Examples (1-1) to (1-5) are shown in FIG.
- Example 1-1 As an aerosol raw material P, Stabilized zirconia fine particles (product name “KYZ-8”) (Y 2 O 3 content 13.8% by weight, average particle diameter 1.9 ⁇ m (D 50 ), 80 g of a specific surface area of 3.1 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 34 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 100 times, that is, the number of laminations was 200 times (pass).
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 16 ⁇ m (0.08 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 1-2 As an aerosol raw material P, partially stabilized zirconia fine particles (product name “UZY-8H # 4000”) manufactured by Daiichi Rare Element Chemical Co., Ltd. (Y 2 O 3 content 8.03 wt%, average particle diameter 4.6 ⁇ m) 100 g of (D 50 ) and a specific surface area of 1.7 m 2 / g) were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 14 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 38 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 to form a film on the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 2 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 100 times, that is, the number of laminations was 200 times (pass).
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 21 ⁇ m (0.11 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 1-3 As an aerosol raw material P, partially stabilized zirconia fine particles (product name “UZY-8H # 4000”) manufactured by Daiichi Rare Element Chemical Co., Ltd. (Y 2 O 3 content 8.03 wt%, average particle diameter 4.6 ⁇ m) 100 g of (D 50 ) and a specific surface area of 1.7 m 2 / g) were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 34 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 1-4 As aerosol raw material P, partially stabilized zirconia fine particles (product name “KYZ-4.5”) (Y 2 O 3 content: 8.01% by weight, average particle size: 2.0 ⁇ m, manufactured by Daiichi Rare Element Chemical Co., Ltd. 80 g of (D 50 ) and a specific surface area of 3.7 m 2 / g) were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 34 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 16 ⁇ m (0.32 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 1 As an aerosol raw material P, Stabilized zirconia fine particles (product name “HSY-8”) (Y 2 O 3 content 13.6% by weight, average particle size 3.6 ⁇ m (D 50 ), 40 g of a specific surface area of 12.0 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 36 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Example 1-2 Stabilized zirconia fine particles (product name “HSY-8”) (Y 2 O 3 content 13.7 wt%, average particle size 56.9 ⁇ m (D 50 ), 80 g of a specific surface area of 4.3 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the aerosol raw material P was accommodated in the aerosol container 2 and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. No degassing treatment was performed in the atmosphere.
- the aerosol-ized container 2 was maintained at 150 degreeC using the mantle heater during film-forming.
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 10 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 32 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm by the stage driving mechanism 8 at a speed of 1 mm / s, and the driving direction of the stage 7 was reversed and reciprocated.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the formed zirconia thin film had low adhesion to the substrate S, and peeling from the substrate was confirmed by a peeling test using an adhesive tape.
- Example 1-3 As an aerosol raw material P, stabilized zirconia fine particles (product name “KYZ-8-15”) manufactured by Daiichi Rare Element Chemical Industries, Ltd. (Y 2 O 3 content 14.2 wt%, average particle diameter 13.7 ⁇ m) 80 g of D 50 ) and specific surface area 0.4 m 2 / g) were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 6 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 26 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass). According to observation during the deposition, the deposited film had a weak adhesion, and the deposition and delamination were repeated partially with the lamination.
- HSY-8 Stabilized Zirconia Fine Particles (Product Name “HSY-8”) (Y 2 O 3 content 13.7 wt%, average particle size 0.5 ⁇ m (D 50 ), 60 g of a specific surface area of 7.2 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 36 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Example 1-5 As an aerosol raw material P, partially stabilized zirconia fine particles (product name “KYZ-4.5”) manufactured by Daiichi Rare Element Chemical Co., Ltd. (Y 2 O 3 content 7.98 wt%, average particle diameter 1.8 ⁇ m) 80 g of (D 50 ) and specific surface area of 5.4 m 2 / g) were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 34 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- the average particle size is 1 ⁇ m or more and 5 ⁇ m or less, particularly 1.9 ⁇ m or more and 4.6 ⁇ m or less. It is dense by depositing zirconia fine particles satisfying a specific surface area of 1 m 2 / g or more and 4 m 2 / g or less as an aerosol raw material by an aerosolized gas deposition method, and has good adhesion to a substrate. Zirconia thin films (stabilized zirconia thin films or partially stabilized zirconia thin films) were formed. On the other hand, when zirconia fine particles deviating from this condition were formed as an aerosol raw material, a good zirconia thin film was not formed.
- Example 2 A plurality of high-purity zirconia fine particles produced by a dry method having different average particle diameters and specific surface areas were prepared. Using these as aerosol raw materials, a zirconia film was formed by a gas deposition method, and the film quality was evaluated. The results of the following Examples (2-1) to (2-6) and Comparative Examples (2-1) to (2-2) are shown in FIG.
- Example 2-1 80 g of high-purity zirconia fine particles (product name “BR-3QZ) (average particle size 2.9 ⁇ m (D 50 ), specific surface area 2.7 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. as the aerosol raw material P
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 14 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 38 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 2-2 As an aerosol raw material P, high-purity zirconia fine particles (product name “BR-QZ”) (average particle diameter 7.4 ⁇ m (D 50 ), specific surface area 1.6 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. 80 g was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 10 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 32 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 14 ⁇ m (0.28 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 2-3 As an aerosol raw material P, high purity zirconia fine particles (product name “BR-12QZ”) (average particle size 10.2 ⁇ m (D 50 ), specific surface area 1.5 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. 80 g was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 8 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 28 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 30 ⁇ m (0.6 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 2-4 As an aerosol raw material P, high purity zirconia fine particles (product name “BR-12QZ”) (average particle size 10.2 ⁇ m (D 50 ), specific surface area 1.5 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. 80 g was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol container 2 at a flow rate of 4 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 22 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 7 ⁇ m (0.14 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 2-5 As an aerosol raw material P, high purity zirconia fine particles (product name “TMZ-T”) (average particle size 0.73 ⁇ m (D 50 ), specific surface area 6.1 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. 80 g was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 16 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 42 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 28 ⁇ m (0.56 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 2-6 As an aerosol raw material P, high purity zirconia fine particles (product name “TMZ”) (average particle size 1.12 ⁇ m (D 50 ), specific surface area 4.7 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. are used for 80 g. It was.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 36 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 6 ⁇ m (0.12 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- TMZ-T2 high purity zirconia fine particles (product name “TMZ-T2”) (average particle size 0.5 ⁇ m (D 50 ), specific surface area 8 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. are used for 80 g. It was.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced into the aerosol-generating container 2 from the gas supply system 5 at a flow rate of 16 L / min.
- the differential pressure between the aerosol container 2 and the film forming chamber 3 was 42 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Comparative Example 2-2 As an aerosol raw material P, 80 g of high-purity zirconia fine particles (product name “BR-90G”) (average particle diameter 20 ⁇ m (D 50 ), specific surface area 1 m 2 / g) manufactured by Daiichi Rare Element Chemical Co., Ltd. were used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the aerosol raw material P was accommodated in the aerosol container 2 and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. No degassing treatment was performed in the atmosphere.
- the aerosol-ized container 2 was maintained at 150 degreeC using the mantle heater during film-forming.
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 36 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (alumina) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was reversed and reciprocated.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the formed zirconia thin film had low adhesion to the substrate S, and peeling from the substrate was confirmed by a peeling test using an adhesive tape.
- the average particle size is 0.7 ⁇ m or more and 11 ⁇ m or less, particularly 0.73 ⁇ m or more and 10.
- Zirconia fine particles satisfying the condition of 2 ⁇ m or less and a specific surface area of 1 m 2 / g or more and 6.5 m 2 / g or less are formed as an aerosol raw material by an aerosolized gas deposition method. A high-purity zirconia thin film having good adhesion was formed. On the other hand, when zirconia fine particles deviating from this condition were formed as an aerosol raw material, a good zirconia thin film was not formed.
- Example 3 A plurality of high-purity zirconia fine particles produced by a wet method having different average particle diameters and specific surface areas were prepared, and zirconia films were formed by a gas deposition method using these fine particles as an aerosol raw material, and the film quality was evaluated.
- the results of the following Examples (3-1) to (3-7) and Comparative Examples (3-1) to (3-4) are shown in FIG.
- Example 3-1 As the aerosol raw material P, high purity zirconia fine particles (product name “SPZ”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 2.7 ⁇ m, specific surface area 6.5 m, manufactured by Daiichi Rare Element Chemical Co., Ltd. 2 / g) was used in an amount of 50 g.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 5 L / min.
- the pressure in the aerosol container 2 was about 47 kPa
- the pressure in the film formation chamber 3 was 240 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 47 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 15 times, that is, the number of laminations was 30 times (pass).
- the film formation took 8 minutes.
- a translucent white zirconia thin film having a width of 5 mm, a length of 15 mm, and a film thickness of 24 ⁇ m (0.8 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-2 As the aerosol raw material P, high purity zirconia fine particles (product name “SPZ”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 2.7 ⁇ m, specific surface area 6.5 m, manufactured by Daiichi Rare Element Chemical Co., Ltd. 2 / g) was used in an amount of 50 g.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 3 L / min.
- the pressure in the aerosol container 2 was about 30 kPa
- the pressure in the film formation chamber 3 was 170 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 30 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 5 times, that is, the number of laminations was 10 times (pass).
- the film formation took 3 minutes.
- a translucent white zirconia thin film having a width of 5 mm, a length of 15 mm, and a film thickness of 6 ⁇ m (0.6 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-3 As an aerosol raw material P, high purity zirconia fine particles (product name “SPZ”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 3.5 ⁇ m, specific surface area 4.5 m, manufactured by Daiichi Elemental Chemical Co., Ltd. 2 / g) was used in an amount of 70 g. 6 and 7 show a transmission electron microscope (TEM) image of the zirconia fine particles. 6 is a TEM image of 40,000 times, and FIG. 7 is a 200,000 times TEM image. From the low-magnification TEM image shown in FIG.
- SPZ high purity zirconia fine particles
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 8 L / min.
- the pressure in the aerosol container 2 was about 30 kPa
- the pressure in the film formation chamber 3 was 400 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 30 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 75 times, that is, the number of laminations was 150 times (pass).
- the film formation took 38 minutes.
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 20 ⁇ m (0.13 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-4 As an aerosol raw material P, high purity zirconia fine particles (product name “SPZ”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 3.5 ⁇ m, specific surface area 4.5 m, manufactured by Daiichi Elemental Chemical Co., Ltd. 2 / g) was used in an amount of 70 g.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 7 L / min.
- the pressure in the aerosol container 2 was about 28 kPa
- the pressure in the film formation chamber 3 was 360 Pa
- the differential pressure between the aerosol container 2 and the film formation chamber 3 was 28 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes.
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 5 ⁇ m (0.1 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-5 As an aerosol raw material P, high purity zirconia fine particles (product name “SPZ”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 3.5 ⁇ m, specific surface area 4.5 m, manufactured by Daiichi Elemental Chemical Co., Ltd. 2 / g) was used in an amount of 50 g.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 8 L / min.
- the pressure in the aerosol container 2 was about 30 kPa
- the pressure in the film formation chamber 3 was 400 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 30 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (Ni-based alloy) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 60 times, that is, the number of laminations was 120 times (pass).
- the film formation took 30 minutes.
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 20 ⁇ m (0.17 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-6 As an aerosol raw material P, zirconium oxide fine particles (product name “EP-5”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 2.2 ⁇ m, specific surface area 5. 80 g of 1 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 8 L / min.
- the pressure in the aerosol container 2 was about 27 kPa
- the pressure in the film formation chamber 3 was 360 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 27 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes.
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 2 ⁇ m (0.04 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3--7 As an aerosol raw material P, zirconium oxide fine particles (product name “EP-5”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle size 2.2 ⁇ m, specific surface area 5. 80 g of 1 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray and deaerated by heating in the atmosphere at 500 ° C. for 1 hour. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the pressure in the aerosol container 2 was about 34 kPa
- the pressure in the film formation chamber 3 was 470 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 34 kPa.
- the aerosol raw material P in the aerosol container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18, and was formed on the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes.
- a translucent white zirconia thin film having a width of 30 mm, a length of 15 mm, and a film thickness of 4 ⁇ m (0.08 ⁇ m / pass) was formed.
- the thin film was dense and had good adhesion to the substrate S (not peeled off even by a peel test using an adhesive tape).
- Example 3-1 As an aerosol raw material P, Zirconium oxide (product name “UEP”) (ZrO 2 + HfO 2 purity 99.80% or more, average particle size 0.47 ⁇ m, specific surface area 21.6 m 2 / made by Daiichi Elemental Chemical Co., Ltd. 80 g of g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray, heated to 500 ° C. in the atmosphere, maintained for 1 hour, and deaerated. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 5 L / min.
- the pressure in the aerosol container 2 was about 47 kPa
- the pressure in the film formation chamber 3 was 240 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 47 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm by the stage driving mechanism 8 at a speed of 1 mm / s, and the driving direction of the stage 7 was reversed and reciprocated.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes.
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Example 3-2 zirconium oxide (product name “UEP”) (ZrO 2 + HfO 2 purity 99.80% or more, average particle size 0.58 ⁇ m, specific surface area 82.7 m 2 / made by Daiichi Rare Element Chemical Co., Ltd. 50 g of g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the aerosol raw material P was accommodated in the aerosol container 2 and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. No degassing treatment was performed in the atmosphere.
- the aerosol-ized container 2 was maintained at 150 degreeC using the mantle heater during film-forming.
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 5 L / min.
- the pressure in the aerosol container 2 was about 47 kPa
- the pressure in the film formation chamber 3 was 240 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 47 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm by the stage driving mechanism 8 at a speed of 1 mm / s, and the driving direction of the stage 7 was reversed and reciprocated.
- the number of reciprocations was 10 times, that is, the number of laminations was 20 times (pass).
- the film formation took 5 minutes.
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Example 3-3 As an aerosol raw material P, Zirconium oxide (product name “EP”) manufactured by Daiichi Rare Element Chemical Co., Ltd. (ZrO 2 + HfO 2 purity 99.50% or more, average particle diameter 2.1 ⁇ m, specific surface area 25 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray, heated to 500 ° C. in the atmosphere, maintained for 2 hours, and deaerated. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 7 L / min.
- the pressure in the aerosol container 2 was about 59 kPa
- the pressure in the film formation chamber 3 was 290 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 59 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm by the stage driving mechanism 8 at a speed of 1 mm / s, and the driving direction of the stage 7 was reversed and reciprocated.
- the number of reciprocations was 5 times, that is, the number of laminations was 10 times (pass).
- the film formation took 3 minutes.
- a green compact of zirconia fine particles was formed on the substrate. The green compact was porous enough to be wiped off.
- Example 3-4 As an aerosol raw material P, zirconium oxide (product name “WG-8S”) manufactured by Daiichi Rare Element Chemical Industries, Ltd. (ZrO 2 + HfO 2 purity 99.90% or more, average particle diameter 6 ⁇ m, specific surface area 12 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 5 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray, heated to 500 ° C. in the atmosphere, maintained for 1 hour, and deaerated. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 5 L / min.
- the pressure in the aerosol container 2 was about 47 kPa
- the pressure in the film formation chamber 3 was 240 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 47 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes. According to observation during the deposition, the deposited film had a weak adhesion, and the deposition and delamination were repeated partially with the lamination.
- Example 3-5 zirconium oxide fine particles (product name “EP-7”) (ZrO 2 + HfO 2 purity 99.50% or more, average particle diameter 2.1 ⁇ m, specific surface area 7. 80 g of 1 m 2 / g) was used.
- the nozzle 18 was a slit-shaped nozzle having a slit length of 30 mm and a slit width of 0.3 mm.
- the above-mentioned aerosol raw material P was put in an alumina tray, heated to 500 ° C. in the atmosphere, maintained for 1 hour, and deaerated. After that, it was housed in the aerosol container 2, and the aerosol container 2 and the film forming chamber 3 were evacuated to 10 Pa or less by the exhaust system 4. In addition, in order to accelerate
- the evacuation of the aerosol-generating container 2 was stopped, and N 2 gas (carrier gas) was introduced from the gas supply system 5 into the aerosol-generating container 2 at a flow rate of 12 L / min.
- the pressure in the aerosol container 2 was about 35 kPa
- the pressure in the film formation chamber 3 was 490 Pa
- the pressure difference between the aerosol container 2 and the film formation chamber 3 was 35 kPa.
- the aerosol raw material P in the aerosol-generating container 2 was aerosolized, passed through the transport pipe 6 and ejected from the nozzle 18 and sprayed onto the substrate (slide glass) S.
- the stage 7 on which the substrate S was placed was driven 15 mm at a speed of 1 mm / s by the stage driving mechanism 8 and the driving direction of the stage 7 was repeatedly reversed to reciprocate.
- the number of reciprocations was 25, that is, the number of laminations was 50 times (pass).
- the film formation took 13 minutes.
- the deposited film thus formed had weak adhesion, and film peeling occurred, so that a dense film could not be formed.
- the average particle size is 2 ⁇ m or more and 4 ⁇ m or less, particularly 2.2 ⁇ m or more and 3.5 ⁇ m or less. It is dense by depositing zirconia fine particles satisfying a specific surface area of 4 m 2 / g or more and 7 m 2 / g or less as an aerosol raw material by an aerosolized gas deposition method, and has good adhesion to a substrate. A thin zirconia thin film was formed. On the other hand, when a zirconia fine particle deviating from this condition was formed as an aerosol raw material, a zirconia thin film was not formed.
- the present invention is not limited to the above-described embodiment, and can be modified within the scope not departing from the gist of the present invention.
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Abstract
Description
上記ジルコニア微粒子のエアロゾルは、上記密閉容器にガスを導入することによって生成される。
上記エアロゾルは、上記密閉容器に接続された搬送管を介して、上記密閉容器よりも低圧に維持された成膜室に搬送される。
上記ジルコニア微粒子は、上記成膜室に収容された基材上に堆積される。
上記ジルコニア微粒子のエアロゾルは、上記密閉容器にガスを導入することによって生成される。
上記エアロゾルは、上記密閉容器に接続された搬送管を介して、上記密閉容器よりも低圧に維持された成膜室に搬送される。
上記ジルコニア微粒子は、上記成膜室に収容された基材上に堆積される。
図1は、本発明の一実施形態に係るエアロゾル化ガスデポジション装置1(以下、AGD装置1)の概略構成を示す図である。
安定化ジルコニア微粒子とは、少なくともイットリア(Y2O3)を含有するジルコニア(安定化ジルコニア、部分安定化ジルコニア)の微粒子である。この種のジルコニア微粒子をエアロゾル原料Pとして用いる場合の平均粒子径は1μm以上5μm以下であり、比表面積は1m2/g以上4m2/g以下である。平均粒子径が1μm以上5μm以下のジルコニア微粒子をエアロゾル原料とすることによって良好な特性(緻密性、基材Sへの密着性等)を有するジルコニア薄膜を形成することが可能である。ジルコニア微粒子の平均粒子径が1μm未満の場合、あるいは比表面積が4m2/gを超える場合には、緻密に堆積成膜することが困難であり、密度の低い圧粉体となる傾向にある。平均粒子径が5μmより大きい場合は、密着力が弱く膜剥離が生じたり、圧粉体(粉末の圧縮体)が形成されたりする場合がある。
乾式法で製造された高純度ジルコニア微粒子としては、例えばZrO2+HfO2純度が99.50%以上の高純度ジルコニア微粒子が用いられる。この種のジルコニア微粒子をエアロゾル原料Pとして用いる場合の平均粒子径は0.7μm以上11μm以下であり、比表面積は1m2/g以上6.5m2/g以下である。平均粒子径が0.7μm以上11μm以下のジルコニア微粒子をエアロゾル原料とすることによって良好な特性(緻密性、基材Sへの密着性等)を有するジルコニア薄膜を形成することが可能である。ジルコニア微粒子の平均粒子径が0.7μm未満の場合には緻密な膜を成膜することが困難であり、密度の低い圧粉体(粉末の圧縮体)となる傾向がある。平均粒子径が11μmより大きい場合は、密着力が弱く膜剥離が生じたり、圧粉体が形成されたりする場合がある。
湿式法で製造された高純度ジルコニア微粒子としては、例えばZrO2+HfO2純度が99.50%以上の高純度ジルコニア微粒子が用いられる。この種のジルコニア微粒子をエアロゾル原料Pとして用いる場合の平均粒子径は2μm以上4μm以下であり、比表面積は4m2/g以上7m2/g以下である。平均粒子径が2μm以上4μm以下のジルコニア微粒子をエアロゾル原料とすることによって良好な特性(緻密性、基材Sへの密着性等)を有するジルコニア薄膜を形成することが可能である。ジルコニア微粒子の平均粒子径が2μm未満の場合は成膜することが困難であり、平均粒子径が4μmより大きい場合は、密着力が弱く剥離が生じたり、圧粉体(粉末の圧縮体)が形成されたりする場合がある。
真空ポンプ12が運転されている状態で、第1バルブ10及び第2バルブ11を開放し、エアロゾル化容器2及び成膜チャンバ3を十分に圧力が低下するまで真空排気する。エアロゾル化容器2が十分に減圧されたら、第1バルブ10を閉止する。なお、成膜チャンバ3は、成膜中は真空排気されている。
平均粒子径及び比表面積が異なる複数の安定化ジルコニア微粒子を用意し、これらをエアロゾル原料に用いてガスデポジション法によりジルコニア膜を成膜し、その膜質を評価した。以下の実施例(1-1)~(1-4)及び比較例(1-1)~(1-5)の結果を図3に示す。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、安定化ジルコニア微粒子(製品名「KYZ-8」)(Y2O3含有量13.8重量%、平均粒子径1.9μm(D50)、比表面積3.1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、部分安定化ジルコニア微粒子(製品名「UZY-8H#4000」)(Y2O3含有量8.03重量%、平均粒子径4.6μm(D50)、比表面積1.7m2/g)を100g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、部分安定化ジルコニア微粒子(製品名「UZY-8H#4000」)(Y2O3含有量8.03重量%、平均粒子径4.6μm(D50)、比表面積1.7m2/g)を100g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、部分安定化ジルコニア微粒子(製品名「KYZ-4.5」)(Y2O3含有量8.01重量%、平均粒子径2.0μm(D50)、比表面積3.7m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、安定化ジルコニア微粒子(製品名「HSY-8」)(Y2O3含有量13.6重量%、平均粒子径3.6μm(D50)、比表面積12.0m2/g)を40g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、安定化ジルコニア微粒子(製品名「HSY-8」)(Y2O3含有量13.7重量%、平均粒子径56.9μm(D50)、比表面積4.3m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
形成されたジルコニア薄膜は、基材Sとの密着性が低く、粘着テープによる剥離試験で基材からの剥離が確認された。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、安定化ジルコニア微粒子(製品名「KYZ-8-15」)(Y2O3含有量14.2重量%、平均粒子径13.7μm(D50)、比表面積0.4m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、安定化ジルコニア微粒子(製品名「HSY-8」)(Y2O3含有量13.7重量%、平均粒子径0.5μm(D50)、比表面積7.2m2/g)を60g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、部分安定化ジルコニア微粒子(製品名「KYZ-4.5」)(Y2O3含有量7.98重量%、平均粒子径1.8μm(D50)、比表面積5.4m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
平均粒子径及び比表面積が異なる、乾式法で製造された複数の高純度ジルコニア微粒子を用意し、これらをエアロゾル原料に用いてガスデポジション法によりジルコニア膜を成膜し、その膜質を評価した。以下の実施例(2-1)~(2-6)及び比較例(2-1)~(2-2)の結果を図4に示す。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「BR-3QZ)(平均粒子径2.9μm(D50)、比表面積2.7m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「BR-QZ」)(平均粒子径7.4μm(D50)、比表面積1.6m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「BR-12QZ」)(平均粒子径10.2μm(D50)、比表面積1.5m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「BR-12QZ」)(平均粒子径10.2μm(D50)、比表面積1.5m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「TMZ-T」)(平均粒子径0.73μm(D50)、比表面積6.1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「TMZ」)(平均粒子径1.12μm(D50)、比表面積4.7m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「TMZ-T2」)(平均粒子径0.5μm(D50)、比表面積8m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「BR-90G」)(平均粒子径20μm(D50)、比表面積1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
平均粒子径及び比表面積が異なる、湿式法で製造された複数の高純度ジルコニア微粒子を用意し、これらをエアロゾル原料に用いてガスデポジション法によりジルコニア膜を成膜し、その膜質を評価した。以下の実施例(3-1)~(3-7)及び比較例(3-1)~(3-4)の結果を図5に示す。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「SPZ」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.7μm、比表面積6.5m2/g)を50g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「SPZ」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.7μm、比表面積6.5m2/g)を50g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「SPZ」)(ZrO2+HfO2純度99.50%以上、平均粒子径3.5μm、比表面積4.5m2/g)を70g用いた。図6及び図7に、当該ジルコニア微粒子の透過型電子顕微鏡(TEM:transmission electron microscope)像を示す。図6は4万倍、図7は20万倍のTEM像である。図6に示す低倍率のTEM像から、当該ジルコニア微粒子は、小径の一次粒子が凝集、合体し、粒子径が数μmの二次粒子が形成されていることが解る。また、単独で存在する一次粒子はみられない。図7に示す高倍率のTEM像から、粒子径0.1~0.2μm程度の一次粒子が凝集、合体している様子が解る。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「SPZ」)(ZrO2+HfO2純度99.50%以上、平均粒子径3.5μm、比表面積4.5m2/g)を70g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、高純度ジルコニア微粒子(製品名「SPZ」)(ZrO2+HfO2純度99.50%以上、平均粒子径3.5μm、比表面積4.5m2/g)を50g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム微粒子(製品名「EP-5」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.2μm、比表面積5.1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム微粒子(製品名「EP-5」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.2μm、比表面積5.1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム(製品名「UEP」)(ZrO2+HfO2純度99.80%以上、平均粒子径0.47μm、比表面積21.6m2/g)を80g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
基材上には、ジルコニア微粒子の圧粉体が形成された。当該圧粉体は拭取れる程度のポーラスなものであった。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム(製品名「UEP」)(ZrO2+HfO2純度99.80%以上、平均粒子径0.58μm、比表面積82.7m2/g)を50g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
基材上には、ジルコニア微粒子の圧粉体が形成された。当該圧粉体は拭取れる程度のポーラスなものであった。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム(製品名「EP」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.1μm、比表面積25m2/g)を50g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
基材上には、ジルコニア微粒子の圧粉体が形成された。当該圧粉体は拭取れる程度のポーラスなものであった。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム(製品名「WG-8S」)(ZrO2+HfO2純度99.90%以上、平均粒子径6μm、比表面積12m2/g)を50g用いた。ノズル18は、スリット長5mm、スリット幅0.3mmのスリット状ノズルとした。
エアロゾル原料Pとして、第一稀元素化学工業株式会社製、酸化ジルコニウム微粒子(製品名「EP-7」)(ZrO2+HfO2純度99.50%以上、平均粒子径2.1μm、比表面積7.1m2/g)を80g用いた。ノズル18は、スリット長30mm、スリット幅0.3mmのスリット状ノズルとした。
1 エアロゾル化ガスデポジション装置
2 エアロゾル化容器
3 成膜チャンバ
4 排気系
5 ガス供給系
6 搬送管
7 ステージ
8 ステージ駆動機構
9 真空配管
10 第1バルブ
11 第2バルブ
12 真空ポンプ
13 ガス配管
14 ガス源
15 第3バルブ
16 ガス流量計
17 ガス噴出体
18 ノズル
Claims (10)
- 平均粒子径が0.7μm以上11μm以下であり、かつ比表面積が1m2/g以上7m2/g以下であるジルコニア微粒子を密閉容器に収容し、
前記密閉容器にガスを導入することによって、前記ジルコニア微粒子のエアロゾルを生成させ、
前記密閉容器に接続された搬送管を介して、前記密閉容器よりも低圧に維持された成膜室に前記エアロゾルを搬送し、
前記成膜室に収容された基材上に前記ジルコニア微粒子を堆積させる
ジルコニア膜の成膜方法。 - 請求項1に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子は、1μm以上5μm以下の平均粒子径と、1m2/g以上4m2/g以下の比表面積とを有する、イットリアを含むジルコニア微粒子である
ジルコニア膜の成膜方法。 - 請求項2に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子の平均粒子径は、1.9μm以上4.6μm以下である
ジルコニア膜の成膜方法。 - 請求項3に記載のジルコニア膜の成膜方法であって、
前記イットリアは、前記ジルコニア微粒子中に8重量%以上14重量%以下含まれる
ジルコニア膜の成膜方法。 - 請求項1に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子は、0.7μm以上11μm以下の平均粒子径と、1m2/g以上6.5m2/g以下の比表面積とを有する、乾式法で作製されたジルコニア微粒子である
ジルコニア膜の成膜方法。 - 請求項5に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子の平均粒子径は、0.7μm以上10.2μm以下である
ジルコニア膜の成膜方法。 - 請求項1に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子は、2μm以上4μm以下の平均粒子径と、4m2/g以上7m2/g以下の比表面積とを有する、湿式法で作製されたジルコニア微粒子である
ジルコニア膜の成膜方法。 - 請求項7に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子の平均粒子径は、2.2μm以上3.5μm以下である
ジルコニア膜の成膜方法。 - 請求項1に記載のジルコニア膜の成膜方法であって、
前記ジルコニア微粒子を前記密閉容器に収容する工程の前に、前記ジルコニア微粒子を脱気する工程をさらに具備する
ジルコニア膜の成膜方法。 - 請求項1に記載のジルコニア膜の成膜方法であって、
前記エアロゾルを生成する工程は、前記密閉容器内に設置された、前記ジルコニア微粒子で被覆されているガス噴出体から前記ガスを噴出させることで、前記ジルコニア微粒子を前記容器内で巻き上げ、前記ガス中に混合させる
ジルコニア膜の成膜方法。
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US13/057,514 US8137743B2 (en) | 2009-05-08 | 2010-01-21 | Method for forming zirconia film |
EP10772099.7A EP2428592B1 (en) | 2009-05-08 | 2010-01-21 | Method for forming zirconia film |
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JP2016222931A (ja) * | 2010-11-19 | 2016-12-28 | 日立化成株式会社 | ノンアスベスト摩擦材組成物、これを用いた摩擦材及び摩擦部材 |
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US9034199B2 (en) | 2012-02-21 | 2015-05-19 | Applied Materials, Inc. | Ceramic article with reduced surface defect density and process for producing a ceramic article |
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US9090046B2 (en) | 2012-04-16 | 2015-07-28 | Applied Materials, Inc. | Ceramic coated article and process for applying ceramic coating |
US9604249B2 (en) | 2012-07-26 | 2017-03-28 | Applied Materials, Inc. | Innovative top-coat approach for advanced device on-wafer particle performance |
US9343289B2 (en) | 2012-07-27 | 2016-05-17 | Applied Materials, Inc. | Chemistry compatible coating material for advanced device on-wafer particle performance |
US9708713B2 (en) * | 2013-05-24 | 2017-07-18 | Applied Materials, Inc. | Aerosol deposition coating for semiconductor chamber components |
US9865434B2 (en) | 2013-06-05 | 2018-01-09 | Applied Materials, Inc. | Rare-earth oxide based erosion resistant coatings for semiconductor application |
US9850568B2 (en) | 2013-06-20 | 2017-12-26 | Applied Materials, Inc. | Plasma erosion resistant rare-earth oxide based thin film coatings |
CN104345608B (zh) * | 2014-11-07 | 2018-09-11 | 珠海展望打印耗材有限公司 | 出粉刀涂粉工装及涂粉方法 |
JP2019520200A (ja) | 2016-06-01 | 2019-07-18 | アリゾナ ボード オブ リージェンツ オン ビハーフ オブ アリゾナ ステート ユニバーシティ | 微粒子コーティングの堆積スプレーのためのシステム及び方法 |
DE102018009153B4 (de) * | 2017-11-22 | 2021-07-08 | Mitsubishi Heavy Industries, Ltd. | Beschichtungsverfahren |
US11047035B2 (en) | 2018-02-23 | 2021-06-29 | Applied Materials, Inc. | Protective yttria coating for semiconductor equipment parts |
DE102018003289A1 (de) | 2018-04-21 | 2019-10-24 | Jörg Exner | Verfahren zur Einstellung der Kristallitgröße bei pulverförmigen Beschichtungsmaterialien für die aerosolbasierte Kaltabscheidung (Aerosol-Depositions-Methode, ADM) |
KR102445422B1 (ko) | 2022-01-24 | 2022-09-22 | 한국농어촌공사 | 마그네틱 터빈 및 부이를 활용한 파력발전형 다목적 부유식 방파제 |
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US20110305828A1 (en) | 2011-12-15 |
CN102428212A (zh) | 2012-04-25 |
KR20110028378A (ko) | 2011-03-17 |
KR101257177B1 (ko) | 2013-04-22 |
CN102428212B (zh) | 2014-04-02 |
EP2428592A1 (en) | 2012-03-14 |
EP2428592B1 (en) | 2019-12-11 |
EP2428592A4 (en) | 2015-12-16 |
US8137743B2 (en) | 2012-03-20 |
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