WO2016017605A1 - Sintered oxide - Google Patents
Sintered oxide Download PDFInfo
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- WO2016017605A1 WO2016017605A1 PCT/JP2015/071304 JP2015071304W WO2016017605A1 WO 2016017605 A1 WO2016017605 A1 WO 2016017605A1 JP 2015071304 W JP2015071304 W JP 2015071304W WO 2016017605 A1 WO2016017605 A1 WO 2016017605A1
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- sintered body
- oxide sintered
- oxide
- powder
- density
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
Definitions
- the present invention relates to an oxide sintered body.
- An oxide semiconductor film formed from an oxide sintered body containing In, Ga, and Zn has an advantage of higher carrier mobility than an amorphous silicon film.
- this oxide semiconductor film is generally formed by a sputtering method using a sputtering target including an oxide sintered body containing In, Ga, and Zn.
- the Vickers hardness is 724
- the relative density is 96%
- the bulk resistance value is 9.5 ⁇ 10 ⁇ 4 ⁇ ⁇
- Oxide sintered body that is cm an oxide sintered body that has a Vickers hardness of 534, a relative density of 96%, and a bulk resistance value of 1.4 ⁇ 10 ⁇ 3 ⁇ ⁇ cm
- a Vickers hardness Is an oxide sintered body having a relative density of 97% and a bulk resistance value of 4.2 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
- Patent Document 2 discloses an InGaZnO 4 single-phase oxide sintered body having a bending strength of 117 MPa and a relative density of 95.9%, a bending strength of 151 MPa, and a relative density of 96. 8% oxide sintered body and the InGaZnO 4 single phase is bending strength is 157MPa, relative density oxide sintered body and the InGaZnO 4 single phase is 96.1%, flexural strength 206MPa InGaZnO 4 single-phase oxide sintered body having a relative density of 97.2% is described.
- An object of the present invention is to provide an oxide sintered body having a high mechanical strength, a high relative density, a low bulk resistance value, and a uniform composition.
- the present invention provides the following inventions.
- the oxide sintered body of the present invention has a high mechanical strength, a high relative density, a small bulk resistance value, and a uniform composition.
- the oxide sintered body of the present invention contains indium (In), gallium (Ga), and zinc (Zn), further contains oxygen (O) as a constituent element, and preferably 99% or more of the atoms are indium. It consists of gallium, zinc, and oxygen and can be expressed by the following formula.
- These two compositions are preferable in terms of characteristics.
- the oxide sintered body of the present invention preferably contains substantially no impurity metal element (M) such as Sn, Zr, Ti, Mo, Si, Cr, W, Ge, V, Mn, etc.
- the content [M / (In + Ga + Zn + M): weight ratio] of (M) is usually less than 10 ppm.
- the content of the impurity metal element (M) in the oxide sintered body can be measured by a high frequency inductively coupled plasma (ICP) analyzer.
- ICP inductively coupled plasma
- L * in the L * a * b * color system of the oxide sintered body of the present invention is usually 35 or less, preferably 34.5 or less, more preferably 34 or less, and still more preferably 33. .5 or less.
- the a * in the L * a * b * color system of the oxide sintered body of the present invention is usually ⁇ 0.6 or less, preferably ⁇ 1.0 or less.
- L * and a * in the L * a * b * color system of the oxide sintered body of the present invention are the surface roughness (Ra) of the surface of the oxide sintered body with abrasive paper by a wet polishing machine. After performing wet polishing until the thickness becomes 0.5 ⁇ m or less, the chromaticity a *, chromaticity b *, and lightness L * of the polished surface are measured with a spectrocolorimeter, and the results are evaluated in the CIE 1976 space. This can be calculated.
- L *, a * and b * in the L * a * b * color system It is preferable to use a known sample as a standard sample and measure its L *, a * and b * to confirm whether or not it matches the known value.
- the Vickers hardness of the oxide sintered body of the present invention is usually 400 or more, preferably 405 or more, more preferably 450 or more, and further preferably 470 or more. Since the oxide sintered body of the present invention has a high Vickers hardness, it is particularly suitable as a target in the DC sputtering method, and even when the generation of particles is small and the sputtering power is high, the target is not cracked and is formed. The speed can be increased and the oxide semiconductor film can be manufactured with good production efficiency.
- the bending strength of the oxide sintered body of the present invention is usually 90 MPa or more, preferably 95 MPa or more, more preferably 130 MPa or more, and further preferably 150 MPa or more. Since the oxide sintered body of the present invention has a high bending strength, it is particularly suitable as a target in the DC sputtering method, and even when the generation of particles is small and the sputtering power is high, the target is not cracked and is formed. The film speed can be increased, and the oxide semiconductor film can be manufactured with good production efficiency.
- the relative density of the oxide sintered body of the present invention usually exceeds 97%, preferably 99% or more, more preferably 99.5% or more, and further preferably 99.7% or more.
- the “relative density” in the present specification is the ratio of the density of the oxide sintered body actually obtained to the theoretical density of the oxide sintered body, and is obtained from the following formula.
- Relative density (%) 100 ⁇ [(density of oxide sintered body) / (theoretical density of oxide sintered body)]
- the density of the oxide sintered body can be measured by a length measurement method.
- the theoretical density of an oxide sintered body is, in principle, a value obtained by multiplying the single element density of each metal oxide that is the raw material of the oxide sintered body by the mixing weight ratio of each metal oxide powder and taking the sum of these.
- the oxide sintered body is made of indium oxide, gallium oxide and zinc oxide, it can be obtained from the following formula.
- Theoretical density of sintered oxide (Indium oxide simple substance density x mixing weight ratio) + (Gallium oxide simple substance density x mixing weight ratio) + (Zinc oxide simple substance density x mixing weight ratio)
- the proportion of metal atoms in the mixed powder does not match the proportion of metal atoms in the single-phase crystal described in the JCPDS card, but the deviation is within 5%, the single atom described in the JCPDS card
- the theoretical density of the phase crystal can be the theoretical density in the above formula.
- the bulk resistance value of the oxide sintered body of the present invention is usually less than 1.0 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, preferably 9 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and more preferably 8.5 ⁇ . 10 ⁇ 4 ⁇ ⁇ cm or less. Since the oxide sintered body of the present invention is also excellent in conductivity, it is particularly suitable as a target in the DC sputtering method, and from the oxide sintered body of the present invention, there is no abnormal discharge, stably and at high speed. A uniform semiconductor film can be formed efficiently.
- the bulk resistance value can usually be measured with a resistivity meter.
- the single phase ratio of the oxide sintered body of the present invention is usually 97.5% or more, preferably 99% or more, more preferably 99.5% or more, and further preferably 99.7% or more. It is.
- the single phase ratio means a content ratio of InGaZnO 4 or In 2 Ga 2 ZnO 7 which is a homologous crystal structure contained in the oxide sintered body.
- the single phase ratio can be calculated by X-ray diffraction measurement of the oxide sintered body. Specifically, the oxide sintered body is measured by X-ray diffraction, and the obtained X-ray diffraction pattern is an X-ray diffraction pattern of InGaZnO 4 or In 2 Ga 2 ZnO 7 having a homologous crystal structure (for example, JCPDS (Joint It is confirmed whether or not the homologous phase crystal structure X-ray diffraction pattern obtained from the Committee of Powder Diffraction Standards card).
- the single-phase ratio is 100 %.
- the peak that is not assigned is identified, and the crystal structure of the homologous phase in the oxide sintered body And the sum of the proportions of the other crystal structures are taken as 100%, and the proportion of the homologous crystal structure is derived by Rietveld analysis.
- the crystal grain size of the oxide sintered body of the present invention is usually 9 ⁇ m or less, preferably 8 ⁇ m or less, more preferably 4.5 ⁇ m or less, still more preferably less than 4.0 ⁇ m, and further preferably It is 3.5 ⁇ m or less, more preferably 2 ⁇ m or less.
- the crystal grain size of the oxide sintered body is measured as follows. SEM-EBSD measurement was performed on the oxide sintered body, and the area (cross-sectional area) of each individual particle was measured by image analysis of the obtained Image Quality Map. The diameter of the circle was calculated assuming that the cross section of the grain was the closest circle.
- the calculated diameter was multiplied by the occupation ratio of the grains with respect to the entire area, and the diameter per occupied area of the grains was calculated. For all the grains, the diameter per occupied area was calculated, and the total of the calculated diameters per occupied area was defined as the area average diameter, that is, the crystal grain size.
- One form of the manufacturing method of the oxide sintered compact of this invention includes the following process (A) and process (B).
- the average particle diameter of the indium oxide powder in the mixed powder obtained in the step (A) is less than 0.6 ⁇ m.
- the average particle diameter of the powder is a 50% cumulative volume fraction particle diameter in a particle size distribution measured by a laser diffraction / scattering method.
- step (B) the filling rate of the mixed powder obtained in step (A) into the capsule container is 50% or more, preferably 55% or more, and more preferably 60% or more.
- the filling rate is calculated by the following equation.
- Filling rate (%) (tap density of mixed powder / theoretical density of oxide sintered body) ⁇ 100
- step (A) after calcining at least one powder selected from the group consisting of indium oxide powder, gallium oxide powder and zinc oxide powder, these powders are mixed to obtain a mixed powder, or indium oxide powder And gallium oxide powder and zinc oxide powder are mixed, and the obtained mixed powder is calcined to obtain a mixed powder.
- the filling rate of the mixed powder is easily set to 50% or more. can do.
- the step (A) when calcining at least one powder selected from the group consisting of indium oxide powder, gallium oxide powder and zinc oxide powder and then mixing these powders to obtain a mixed powder, preferably indium oxide
- a mixed powder preferably indium oxide
- the powder, gallium oxide powder and zinc oxide powder is calcined separately, and the calcined powders are mixed to obtain a mixed powder. Since the tap density of indium oxide powder is not easily increased by calcining, the mixed powder is composed of calcined indium oxide powder, calcined gallium oxide powder and calcined zinc oxide powder, or is not calcined. It is preferably made of indium oxide powder, calcined gallium oxide powder and calcined zinc oxide powder.
- the molar ratio (In: Ga: Zn) of indium oxide powder: gallium oxide powder: zinc oxide powder is 2: 2:
- the mixing ratio is 1, it is preferable to prepare a mixed powder made of calcined indium oxide powder, calcined gallium oxide powder and calcined zinc oxide powder.
- the shrinkage rate of the capsule container in the capsule hot isostatic pressing process (capsule HIP process) can be made 50% or less.
- the mixed powder can be pressure-sintered without destroying, and volatilization of zinc derived from the zinc oxide powder and indium derived from the indium oxide powder during the production of the sintered body can be suppressed.
- the shrinkage rate of the capsule container is represented by the following formula.
- Shrinkage rate of capsule container (%) [1 ⁇ (inner volume of capsule container after capsule HIP treatment / inner volume of capsule container before capsule HIP process)] ⁇ 100
- the purity of indium oxide (In 2 O 3 ) powder, gallium oxide (Ga 2 O 3 ) powder and zinc oxide (ZnO) powder is 4N or more Is preferred.
- the tap density is based on JIS K5101. After a powder of a certain volume is filled with a natural drop, an impact due to a certain vibration (tapping) is further applied to the container, and the volume change of the powder disappears. It means the mass of powder per unit volume. The mass of powder per unit volume when the powder is filled into a container with a certain volume by natural dropping and the inner volume is taken as the volume is called bulk density. Generally, the tap density is the bulk density. 1.1 to 1.3 times as large as
- the indium oxide powder a commercially available indium oxide powder is usually used.
- the tap density of commercially available indium oxide powder is usually 1.95 g / cm 3 or less, although it varies depending on the average particle size and particle size distribution.
- the simple substance density (upper limit of tap density) of indium oxide is 7.18 g / cm 3 .
- a calcining apparatus such as a vertical electric furnace, a tubular furnace, a muffle furnace, a tube furnace, a hearth raising / lowering electric furnace, a box type electric furnace or the like is usually used.
- the calcination temperature is usually 1200 to 1600 ° C., preferably 1400 to 1600 ° C.
- the calcination time is usually 8 hours or more and 24 hours or less, preferably 10 hours or more and 15 hours or less.
- the tap density of the indium oxide powder after calcination is preferably 2.70 g / cm 3 or more, more preferably 3.0 g / cm 3 or more.
- the calcination may be performed in an atmospheric atmosphere, an oxidizing atmosphere such as an oxidizing atmosphere having a higher oxygen concentration than the air, an inert gas atmosphere such as nitrogen, argon, helium, vacuum, carbon dioxide, hydrogen, You may perform in non-oxidizing atmospheres, such as reducing gas atmospheres, such as carbon monoxide, hydrogen sulfide, and sulfur dioxide. It is preferable to calcine in an oxidizing atmosphere.
- the calcined indium oxide powder may be crushed by a known means such as a George crusher, a roll crusher, a stamp mill, a hammer mill, or a mortar.
- gallium oxide powder a commercially available gallium oxide powder is usually used.
- the tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.45 g / cm 3 or less.
- the single-piece density (upper limit of tap density) of gallium oxide is 5.88 g / cm 3 .
- the average particle diameter of the gallium oxide powder is usually 0.2 ⁇ m or more and 5 ⁇ m or less, preferably 0.2 ⁇ m or more and 2 ⁇ m or less.
- the calcination of the gallium oxide powder is usually performed in the same manner as the calcination of the indium oxide powder.
- the tap density of the calcined gallium oxide powder is preferably 4.0 g / cm 3 or more. It is preferable to perform calcination in an oxidizing atmosphere.
- the tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.12 g / cm 3 or less.
- the single-piece density (upper limit of tap density) of zinc oxide is 5.6 g / cm 3 .
- the average particle diameter of the zinc oxide powder is usually 0.6 ⁇ m or more and 5 ⁇ m or less, preferably 1 ⁇ m or more and 5 ⁇ m or less.
- the calcination of the zinc oxide powder is usually performed in the same manner as the calcination of the indium oxide powder.
- the tap density of the calcined zinc oxide powder is preferably 4.1 g / cm 3 or more. It is preferable to perform calcination in an oxidizing atmosphere.
- the tap density of the mixed powder is preferably 3.25 g / cm 3 or more, and the capsule container can be filled with a large amount of the mixed powder, and the capsule container after the capsule HIP treatment contracts symmetrically and becomes easy to process. Therefore, it is more preferably 3.8 to 6.4 g / cm 3 .
- the tap density of the mixed powder is preferably 3.18 g / cm 3 or more, more preferably 3.8 to 6.3 g / cm 3 .
- each powder is not limited as long as the powder can be uniformly mixed, and may be dry-mixed by a super mixer, intensive mixer, Henschel mixer, automatic mortar, etc., ball mill, vibration mill, planetary ball mill, etc. May be wet mixed. If uniform mixing is insufficient, each component segregates in the manufactured target, and the resistance distribution of the target becomes non-uniform. That is, the high resistance region and the low resistance region exist depending on the target site, which causes abnormal discharge such as arcing due to charging in the high resistance region during sputtering film formation.
- the calcined mixed powder is usually also calcined as described above. It is carried out in the same way as firing.
- the calcining temperature is 1200 to 1650 ° C., preferably 1400 to 1600 ° C. in an oxidizing atmosphere.
- the tap density of the mixed powder after calcination is preferably 3.18 g / cm 3 or more, more preferably 3.8 to 6.3 g / cm 3 .
- step (B) the capsule powder is filled with the above-described mixed powder, and then the capsule HIP treatment is performed to obtain the oxide sintered body of the present invention.
- the mixed powder is enclosed in a vacuum-sealed capsule container. Since the mixed powder is filled in the enclosed space and the capsule HIP process is performed, volatilization of zinc and indium is suppressed unlike pressure sintering such as hot pressing, and as a result, the obtained oxide sintered body and The composition does not easily deviate from the raw material mixed powder, and an oxide sintered body having a high relative density and a high single-phase ratio can be obtained.
- the material of the capsule container usually includes iron, stainless steel, titanium, aluminum, stainless steel, tantalum, niobium, copper and nickel, and can be appropriately selected depending on the processing temperature of the capsule HIP process.
- a capsule container made of copper, nickel or aluminum is usually used.
- the processing temperature is in the range of 1000 ° C. to 1350 ° C., it is made of iron, titanium or stainless steel.
- Capsule containers are usually used. In the region where the processing temperature is higher than 1350 ° C., capsule containers made of tantalum or niobium are usually used.
- capsule containers made of aluminum, iron or stainless steel are preferable in terms of cost.
- the shape and dimensions of the capsule container are not limited as long as it is isotropically pressurized during the capsule HIP process. Specifically, a cylindrical container and a rectangular parallelepiped container are mentioned.
- the wall thickness of the capsule container is preferably 1.5 mm to 4 mm. Within this range, the capsule container can be easily softened and deformed, and can shrink following the oxide sintered body as the sintering reaction proceeds.
- the pressure in the capsule container is usually decreased to 1.33 ⁇ 10 ⁇ 2 Pa or less while heating the capsule container to 100 ° C. or more and 600 ° C. or less.
- the pressure in the capsule container becomes 1.33 ⁇ 10 ⁇ 2 Pa or less, the capsule container is sealed and the capsule HIP process is performed.
- Capsule HIP treatment is performed by placing a sealed capsule container filled with mixed powder in a HIP apparatus, applying pressure to the capsule container itself using a gas under high temperature and high pressure as a pressure medium, and mixing the capsule container The powder is pressure sintered.
- the pressure medium an inert gas such as nitrogen or argon is preferable.
- the pressure applied to the capsule container is preferably 50 MPa or more.
- the treatment time is preferably 1 hour or longer.
- the treatment temperature is usually 1000 to 1400 ° C., preferably 1100 ° C. to 1300 ° C. It is preferable that the sintering temperature is 1000 ° C. to 1400 ° C. and the pressure is 50 MPa or more and the treatment is performed for 1 hour or more.
- Another form of the method for producing an oxide sintered body of the present invention includes the following step (a), step (b) and step (c).
- the average particle diameter of the indium oxide powder in the mixed powder obtained in the step (a) is less than 0.6 ⁇ m.
- the average particle diameter of the powder is a 50% cumulative volume fraction particle diameter in a particle size distribution measured by a laser diffraction / scattering method.
- the purity of indium oxide (In 2 O 3 ) powder, gallium oxide (Ga 2 O 3 ) powder and zinc oxide (ZnO) powder is 4N or more Is preferred.
- the tap density is based on JIS K5101. After filling a container of a certain volume with powder by natural dropping, the container is further subjected to an impact by a certain vibration (tapping), and the volume change of the powder is eliminated. It means the mass of powder per unit volume. The mass of powder per unit volume when the powder is filled into a container with a certain volume by natural dropping and the inner volume is taken as the volume is called bulk density. Generally, the tap density is the bulk density. 1.1 to 1.3 times as large as
- the indium oxide powder a commercially available indium oxide powder is usually used.
- the tap density of commercially available indium oxide powder is usually 1.95 g / cm 3 or less, although it varies depending on the average particle size and particle size distribution.
- the simple substance density (upper limit of tap density) of indium oxide is 7.18 g / cm 3 .
- gallium oxide powder a commercially available gallium oxide powder is usually used.
- the tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.45 g / cm 3 or less.
- the single-piece density (upper limit of tap density) of gallium oxide is 5.88 g / cm 3 .
- the average particle diameter of the gallium oxide powder is usually 0.2 ⁇ m or more and 5 ⁇ m or less, preferably 0.2 ⁇ m or more and 2 ⁇ m or less.
- the tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.12 g / cm 3 or less.
- the single-piece density (upper limit of tap density) of zinc oxide is 5.6 g / cm 3 .
- the average particle diameter of the zinc oxide powder is usually 0.6 ⁇ m or more and 5 ⁇ m or less, preferably 1 ⁇ m or more and 5 ⁇ m or less.
- each powder is not limited as long as the powder can be uniformly mixed, and may be dry-mixed by a super mixer, intensive mixer, Henschel mixer, automatic mortar, etc., ball mill, vibration mill, planetary ball mill, etc. May be wet mixed. If uniform mixing is insufficient, each component segregates in the manufactured target, and the resistance distribution of the target becomes non-uniform. That is, the high resistance region and the low resistance region exist depending on the target site, which causes abnormal discharge such as arcing due to charging in the high resistance region during sputtering film formation.
- step (b) when the mixed powder obtained in step (a) is molded to obtain a molded body, it is preferable to perform pressure molding to obtain the molded body.
- An example of a method for pressure-molding the mixed powder is a cold isostatic pressing method.
- the pressure during pressure molding is usually 50 to 300 MPa, preferably 100 to 300 MPa.
- a uniaxial press for example, a cold isostatic press (CIP), or the like can be used.
- CIP cold isostatic press
- a uniaxial press and a cold isostatic press (CIP) may be used in combination.
- the pressing pressure when forming the mixed powder is preferably at least 30 MPa and less than 100 MPa, more preferably 40 MPa or more. If it is less than 30 MPa, there is a possibility that a stable press-molded body cannot be produced. If it is 100 MPa or more, the molded product may be brittle and easily cracked.
- pressure molding is preferably performed at a pressing pressure of 40 to 90 MPa, more preferably 50 to 80 MPa.
- the pressing pressure is preferably at least 50 MPa and less than 400 MPa, more preferably 100 MPa or more. If it is less than 50 MPa, there is a possibility that a stable press-molded product cannot be produced. If it is 400 MPa or more, the apparatus becomes too large, which is uneconomical and the molded product may be fragile.
- the holding time is 1 to 30 minutes. If the holding time is less than 1 minute, the density may not increase, and if it exceeds 60 minutes, it may take too much time and be uneconomical.
- an organic binder may be blended into the mixed powder and molded.
- an organic binder is preferably blended.
- the addition amount of the organic binder is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the mixed powder.
- the raw material powder and the organic binder are mixed to form a mixed powder, and pressure molded to form a pressure molded body. And before performing a capsule HIP process to this press-molded body, an organic binder is usually removed.
- Organic binders include butyral resin, polyvinyl alcohol, acrylic resin, poly ⁇ -methylstyrene, ethyl cellulose, polymethyl lactate, (poly) vinyl butyral, (poly) vinyl acetate, (poly) vinyl alcohol, polyethylene, polystyrene, polybutadiene, (Poly) vinyl pyrrolidone, polyamide, polyethylene oxide, polypropylene oxide, polyacrylamide, polymethacrylate and various acrylic polymers and their copolymers and terpolymers, resins such as methylcellulose, ethylcellulose, hydroxyethylcellulose, nitrocellulose and their derivatives Etc.
- butyral resin polyvinyl alcohol, acrylic resin, poly ⁇ -methylstyrene, ethyl cellulose, polymethyl lactate, (poly) vinyl butyral, (poly) vinyl acetate, (poly) vinyl alcohol, polyethylene, polystyrene, polybutadiene, (Poly) vinyl
- the method of blending the organic binder includes a method of mixing the raw material powder, the organic binder, and a solvent and drying the resulting slurry.
- the obtained molded body may be processed by cutting, grinding or the like according to the shape and size of the capsule container used in the step (c).
- the mixed powder obtained in the step (a) is granulated to obtain a granulated powder
- the mixed powder, a solvent and an organic binder are mixed, and the resulting slurry is granulated
- the granulation method include rolling granulation, fluidized bed (spouted bed) granulation, stirring and mixing granulation, compression granulation, extrusion granulation, pulverization granulation, melt granulation, spray granulation, and the like.
- the granulator include a bread granulator, a trough granulator, a compression granulator, and a spray dryer.
- the granulation format either dry or wet can be selected, but wet granulation using the adhesive force of water or a binder (binder) is preferable. Among these, a spray dryer is preferable.
- the solvent used in preparing the slurry water, an alcohol solvent and a ketone solvent are preferable in terms of uniformity of the particle size distribution of the mixed powder and easy evaporation of the solvent.
- the alcohol solvent include methanol, ethanol, and isopropyl alcohol
- examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone.
- Halogenated hydrocarbon solvents such as methyl chloride, chloroform, 1,2 dichloroethane and trichloroethylene, ester solvents such as methyl acetate, ethyl acetate, propylene carbonate and propyl acetate, nitrogen-containing solvents such as propiontolyl and N-methylpyrrolidone, dimethyl sulfoxide Sulfur-containing solvents such as tetrahydrofuran, dioxane, propylene oxide, ether solvents such as 2-ethoxyethyl acetate, and hydrocarbon solvents such as benzene and styrene can also be used.
- the amount of the solvent used is usually 60 to 200 parts by mass with respect to 100 parts by mass of the mixed powder.
- the wet mixing may be performed by, for example, a wet ball mill using a hard ZrO 2 ball or a vibration mill, and the mixing time when using the wet ball mill or the vibration mill is preferably about 12 to 78 hours.
- the slurry is supplied to a normal spray dryer, sprayed and dried to obtain a granulated powder.
- the inlet temperature is usually set to 180 to 250 ° C.
- the outlet temperature is usually set to 90 to 130 ° C.
- the density of the molded body or the tap density of the granulated powder is preferably 3.25 g / cm 3 or more, and the capsule container can be filled with many molded bodies or granulated powder, and the capsule container after the capsule HIP treatment Is more preferably 3.8 to 6.4 g / cm 3 , since it shrinks symmetrically to facilitate processing.
- the density of the molded body or the tap density of the granulated powder is preferably 3.18 g / cm 3 or more, more preferably 3.8 to 6.3 g / cm 3 .
- step (c) the filling rate of the molded product or granulated powder obtained in step (b) into the capsule container is 50% or more, preferably 55% or more, and preferably 60% or more. Is more preferable.
- the filling rate is calculated by the following equation.
- Filling rate (%) (packing density of molded body or tap density of granulated powder / theoretical density of oxide sintered body) ⁇ 100
- the filling density of the molded body is calculated by the following formula.
- Filling density weight of molded body / inner volume of capsule container
- the shrinkage rate of the capsule container in the capsule hot isostatic pressing process (capsule HIP process) can be set to 50% or less. Therefore, the molded body or granulated powder can be pressure-sintered without destroying the capsule container, and the volatilization of zinc derived from zinc oxide powder or indium derived from indium oxide powder during the production of the sintered body can be suppressed.
- the shrinkage rate of the capsule container is represented by the following formula.
- Shrinkage rate of capsule container (%) [1 ⁇ (inner volume of capsule container after capsule HIP treatment / inner volume of capsule container before capsule HIP process)] ⁇ 100
- step (c) the capsule body is filled with the above-mentioned molded body or granulated powder, and then capsule HIP treatment is performed to obtain the oxide sintered body of the present invention.
- the molded body or the granulated powder is enclosed in a vacuum sealed capsule container. Since the molded body or granulated powder is filled in the enclosed space and capsule HIP treatment is performed, volatilization of zinc and indium is suppressed unlike pressure sintering such as hot pressing, and the resulting oxide
- the composition does not easily shift between the sintered body and the molded body or granulated powder as the raw material, and an oxide sintered body having a high relative density and a high single-phase ratio can be obtained.
- the material of the capsule container usually includes iron, stainless steel, titanium, aluminum, tantalum, niobium, copper and nickel, and can be appropriately selected depending on the processing temperature of the capsule HIP processing.
- a capsule container made of copper, nickel or aluminum is usually used.
- a capsule container made of iron or stainless steel Is usually used.
- capsule containers made of tantalum or niobium are usually used.
- capsule containers made of aluminum, iron or stainless steel are preferable in terms of cost.
- the shape and dimensions of the capsule container are not limited as long as it is isotropically pressurized during the capsule HIP process. Specifically, a cylindrical container and a rectangular parallelepiped container are mentioned.
- the wall thickness of the capsule container is preferably 1.5 mm to 4 mm. Within this range, the capsule container can be easily softened and deformed, and can shrink following the oxide sintered body as the sintering reaction proceeds.
- the capsule container is usually heated to remove the binder contained in the molded body, the solvent contained in the granulated powder, and the organic binder. Thereafter, the capsule container is sealed and a capsule HIP process is performed. Further, the pressure in the capsule container may be decreased to 1.33 ⁇ 10 ⁇ 2 Pa or less while heating the capsule container filled with the molded body or the granulated powder to 100 ° C. or more and 600 ° C. or less. . Thereby, the solvent and organic binder which are contained in the binder and granulated powder which are contained in a molded object are removed. When the pressure in the capsule container becomes 1.33 ⁇ 10 ⁇ 2 Pa or less, the capsule container is sealed and the capsule HIP process is performed.
- Capsule HIP treatment is performed by placing a sealed capsule container filled with a molded body or granulated powder in a HIP apparatus, applying pressure to the capsule container itself using a gas under high temperature and high pressure as a pressure medium, The mixed powder in the container is subjected to pressure sintering.
- the pressure medium an inert gas such as nitrogen or argon is preferable.
- the pressure applied to the capsule container is preferably 50 MPa or more.
- the treatment time is preferably 1 hour or longer.
- the treatment temperature is usually 1000 to 1400 ° C., preferably 1100 ° C. to 1300 ° C. It is preferable that the sintering temperature is 1000 ° C. to 1400 ° C. and the pressure is 50 MPa or more and the treatment is performed for 1 hour or more.
- a sputtering target can be manufactured by processing the oxide sintered body of the present invention into a predetermined shape and a predetermined dimension.
- a sputtering target having an outer diameter of 152 mm ⁇ 5 mm can be produced by cylindrical grinding of the outer periphery and surface grinding of the surface side.
- the surface roughness (Ra) of the sputtering target is preferably 5 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
- the sputtering target is further used in a form in which an indium alloy or the like is bonded as a bonding metal to a backing plate or backing tube made of copper, titanium, or the like.
- the method of manufacturing the sputtering target by processing the oxide sintered body of the present invention is not limited, and a known method is employed.
- the sputtering target is used for film formation by sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) evaporation. Since the target of the present invention has a high relative density and a high single-phase ratio, abnormal discharge during film formation hardly occurs and film formation can be performed stably. Note that a solid material used in the film formation may be referred to as a “tablet”, but in the present specification, these are referred to as a “sputtering target”. In addition, since the sputtering target of the present invention has a high relative density and a high single-phase ratio, the frequency of nodules and the frequency of abnormal discharge can be reduced as the sputtering time elapses. Production efficiency is also improved, and the resulting film properties are excellent. With the oxide sintered body or sputtering target of the present invention, a transparent semiconductor film having good characteristics as a channel layer of a thin film transistor exhibiting stable semiconductor characteristics can be formed.
- the film thickness of the transparent semiconductor film is usually 0.5 to 500 nm, preferably 1 to 150 nm, more preferably 3 to 80 nm, from the viewpoint of a semiconductor having high mobility and low S value.
- the thickness is preferably 10 to 60 nm. If it is 0.5 nm or more, it is possible to form an industrially uniform film. On the other hand, if it is 500 nm or less, the film formation time will not be too long. When the thickness is in the range of 3 to 80 nm, TFT characteristics such as mobility and on / off ratio are particularly good.
- the sputtering method examples include a DC sputtering method, an AC sputtering method, an RF magnetron sputtering method, an electron beam evaporation method, and an ion plating method, and a DC sputtering method is preferable.
- the pressure in the chamber during sputtering is usually 0.1 to 2.0 MPa, preferably 0.3 to 0.8 MPa.
- input power per unit area of the target surface during sputtering is usually 0.5 ⁇ 6.0W / cm 2, preferably 1.0 ⁇ 5.0W / cm 2.
- Examples of the carrier gas at the time of sputtering include oxygen, helium, argon, xenon, and krypton, and a mixed gas of argon and oxygen is preferable.
- the ratio of argon: oxygen (Ar: O 2 ) in the mixed gas of argon and oxygen is usually 100: 0 to 80:20, preferably 99.5: 0.5 to 80:20, more preferably Is 99.5: 0.5 to 90:10.
- Examples of the substrate include glass and resin (PET, PES, etc.).
- the film formation temperature during sputtering (the temperature of the substrate on which the thin film is formed) is usually 25 ° C. to 450 ° C., preferably 30 ° C. to 250 ° C., more preferably 35 ° C. to 150 ° C.
- the Vickers hardness of the oxide sintered body was measured by a micro hardness meter (HMV) manufactured by Shimadzu Corporation.
- Example 1 Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 ⁇ m) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle diameter: 1.5 ⁇ m), zinc oxide powder (manufactured by Hakusuitec Co., Ltd., tap density: 1.02 g / cm 3 , average particle diameter: 1.5 ⁇ m), indium element and gallium element Weighing was performed so that the atomic ratio with zinc element (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 60 minutes to obtain a mixed powder.
- Indium oxide powder manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 ⁇ m
- gallium oxide powder manufactured by Yamanaka Futec Co., Ltd., tap density: 1.
- the obtained mixed powder was put into an electric furnace (manufactured by Kitahama Corporation), heated in the atmosphere at a heating rate of 10 ° C./min from room temperature to 1400 ° C., and calcined at 1400 ° C. for 12 hours Went.
- the obtained powder was lightly pulverized in a mortar to obtain a mixed powder after calcining.
- the mixed powder after calcining was filled into a stainless steel (SUS304) capsule container (outer diameter 83 mm, inner diameter 80 mm, height 78 mm inside the container) while applying vibration until the volume of the mixed powder disappeared.
- the tap density of the mixed powder is 4.32 g / cm 3, since the theoretical density of 6.379g / cm 3, the filling ratio was 67.7%.
- the single crystal theoretical density (6.379 g / cm 3 ) was employed.
- the exhaust pipe was welded to the upper lid of the capsule container filled with the mixed powder, and then the upper lid and the capsule container were welded.
- a He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container.
- the amount of leakage at this time was 1 ⁇ 10 ⁇ 6 Torr ⁇ L / sec or less.
- the exhaust pipe was closed and the capsule container was sealed.
- the sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing.
- the treatment temperature was 1200 ° C.
- the treatment pressure was 118 MPa
- the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
- the capsule container was removed to obtain a cylindrical oxide sintered body.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 8.31 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the density of the sintered body was measured by a length measurement method, and the theoretical density of InGaZnO 4 (JCPDS card number: 381104) described in the JCPDS card was adopted as the theoretical density of the sintered body.
- the obtained oxide sintered body had an average crystal grain size of 6.8 ⁇ m, a Vickers hardness of 411.0, and a bending strength of 100 MPa.
- L * of the obtained oxide sintered body was 28.77, a * was ⁇ 0.69, b * was ⁇ 4.07, and ⁇ L was 68.51.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.31 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 2 In Example 1, using gallium oxide powder having an average particle diameter of 0.6 ⁇ m, and carrying out the same procedure as in Example 1 except that the filling rate of the mixed powder after calcining into the capsule container was set to 66.5%. An oxide sintered body was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 8.21 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 8.9 ⁇ m, the Vickers hardness was 410.1, and the bending strength was 99 MPa.
- L * of the obtained oxide sintered body was 32.49, a * was ⁇ 2.27, b * was ⁇ 3.47, and ⁇ L was 64.79.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.21 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 3 The same procedure as in Example 1 was performed except that gallium oxide powder having an average particle diameter of 0.3 ⁇ m was used in Example 1, and the filling rate of the mixed powder after calcining into the capsule container was set to 65.7%. An oxide sintered body was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 8.11 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.3 ⁇ m, the Vickers hardness was 422.3, and the bending strength was 105 MPa.
- L * of the obtained oxide sintered body was 31.42, a * was -2.14, b * was -3.23, and ⁇ L was 65.84.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.11 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 4 In Example 1, the mixture is weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element is 2: 2: 1, and the mixed powder after calcination is filled into the capsule container
- the oxide sintered body was obtained in the same manner as in Example 1 except that the rate was 63.3%.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 5.65 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.0 ⁇ m, the Vickers hardness was 408.3, and the bending strength was 98 MPa.
- L * of the obtained oxide sintered body was 29.78, a * was ⁇ 1.22, b * was ⁇ 3.88, and ⁇ L was 67.50.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP high frequency inductively coupled plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 5.65 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 5 gallium oxide powder having an average particle size of 0.6 ⁇ m was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element and zinc element was 2: 2: 1. And it implemented like Example 1 except the filling rate to the capsule container of the mixed powder after calcination having been 62.8%, and obtained oxide sinter.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 5.53 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.2 ⁇ m, the Vickers hardness was 408.5, and the bending strength was 98 MPa.
- L * of the obtained oxide sintered body was 33.21, a * was -2.38, b * was -3.33, and ⁇ L was 64.07.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP high frequency inductively coupled plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, (2217) a single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 5.53 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 6 gallium oxide powder having an average particle size of 0.3 ⁇ m was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1. And it implemented like Example 1 except having made the filling rate to the capsule container of the mixed powder after calcination 61.5%, and obtained oxide sinter.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 5.43 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.1 ⁇ m, the Vickers hardness was 411.3, and the bending strength was 100 MPa.
- L * of the obtained oxide sintered body was 32.32, a * was ⁇ 2.30, b * was ⁇ 3.16, and ⁇ L was 64.90.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP high frequency inductively coupled plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 5.43 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 7 Indium oxide powder (made by rare metal), tap density: 1.62 g / cm 3 , average particle diameter: 0.56 ⁇ m) and gallium oxide powder (made by rare metal, Inc., tap density 1.50 g) / Cm 3 , average particle size: 1.0 ⁇ m), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: 1.5 ⁇ m), indium element and gallium element And zinc element were weighed so that the atomic ratio (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 60 minutes to obtain a mixed powder.
- the obtained mixed powder was put into an electric furnace (manufactured by Kitahama Corporation), heated in the atmosphere at a heating rate of 10 ° C./min from room temperature to 1400 ° C., and calcined at 1400 ° C. for 12 hours Went.
- the obtained powder was lightly pulverized in a mortar to obtain a mixed powder after calcining.
- the mixed powder after calcining was filled into a stainless steel (SUS304) capsule container (outer diameter 83 mm, inner diameter 80 mm, height 78 mm inside the container) while applying vibration until the volume of the mixed powder disappeared.
- the tap density of the mixed powder is 4.10 g / cm 3, since the theoretical density of 6.379g / cm 3, the filling ratio was 64.3%.
- the single crystal theoretical density (6.379 g / cm 3 ) was employed.
- the exhaust pipe was welded to the upper lid of the capsule container filled with the mixed powder, and then the upper lid and the capsule container were welded.
- a He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container.
- the amount of leakage at this time was 1 ⁇ 10 ⁇ 6 Torr ⁇ L / sec or less.
- the exhaust pipe was closed and the capsule container was sealed.
- the sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing.
- the treatment temperature was 1220 ° C.
- the treatment pressure was 118 MPa
- the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
- the capsule container was removed to obtain a cylindrical oxide sintered body.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 8.40 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the density of the sintered body was measured by a length measurement method, and the theoretical density of InGaZnO 4 (JCPDS card number: 381104) described in the JCPDS card was adopted as the theoretical density of the sintered body.
- the obtained oxide sintered body had an average crystal grain size of 2.1 ⁇ m, a Vickers hardness of 521.4, and a bending strength of 152 MPa.
- L * of the obtained oxide sintered body was 32.02, a * was -0.72, b * was -1.15, and ⁇ L was 65.14.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (resistivity) of 8.40 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
- Example 1 gallium oxide powder having an average particle diameter of 3 ⁇ m was used, calcining was not performed, and the filling rate of the mixed powder (tap density: 2.21 g / cm 3 ) into the capsule container was set to 34.8%. Except for this, the same procedure as in Example 1 was performed, but the capsule burst and an oxide sintered body was not obtained.
- Example 2 In Example 1, an indium oxide powder having an average particle size of 1 ⁇ m was used, and the same procedure as in Example 1 was performed except that the filling rate of the mixed powder after calcining into the capsule container was 57.4%. A sintered product was obtained.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 6.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 6.9 ⁇ m, the Vickers hardness was 398.6, and the bending strength was 98 MPa.
- L * of the obtained oxide sintered body was 35.89, a * was ⁇ 0.21, b * was ⁇ 4.99, and ⁇ L was 61.48.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 90.2%, and a bulk resistance value (specific resistance) of 6.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. For this reason, the uniformity of the composition of the sputtered film was reduced although it was high density.
- Comparative Example 3 In Comparative Example 2, the mixture was weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1, and the mixed powder after calcination was filled into the capsule container An oxide sintered body was obtained in the same manner as in Comparative Example 2 except that the rate was changed to 54.2%.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 4.50 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.0 ⁇ m, the Vickers hardness was 396.4, and the bending strength was 97 MPa.
- L * of the obtained oxide sintered body was 36.45, a * was ⁇ 0.34, b * was ⁇ 4.87, and ⁇ L was 60.90.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 84.5%, and a bulk resistance value (specific resistance) of 4.5 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. For this reason, the uniformity of the composition of the sputtered film was reduced although it was high density.
- Comparative Example 4 In Comparative Example 2, the same procedure as in Comparative Example 2 was performed except that gallium oxide powder having an average particle diameter of 0.6 ⁇ m was used and the filling rate of the mixed powder after calcining into the capsule container was 63.1%. An oxide sintered body was obtained.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 6.30 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 7.2 ⁇ m, the Vickers hardness was 392.4, and the bending strength was 93 MPa.
- L * of the obtained oxide sintered body was 36.56, a * was ⁇ 0.34, b * was ⁇ 5.12, and ⁇ L was 60.80.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 90.4%, and a bulk resistance value (specific resistance) of 6.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. For this reason, the uniformity of the composition of the sputtered film was reduced although it was high density.
- Comparative Example 5 gallium oxide powder having an average particle diameter of 0.6 ⁇ m was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1. And it implemented similarly to the comparative example 2 except the filling rate to the capsule container of the mixed powder after calcination having been 59.9%, and obtained oxide sinter.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 4.30 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 7.4 ⁇ m, a Vickers hardness of 390.2, and a bending strength of 92 MPa.
- L * of the obtained oxide sintered body was 37.5, a * was ⁇ 0.56, b * was ⁇ 4.74, and ⁇ L was 59.90.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 83.8%, and a bulk resistance value (specific resistance) of 4.3 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Therefore, although the density was high, the uniformity of the composition of the sputtered film was reduced.
- Example 8 Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 ⁇ m) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle size: about 1.5 ⁇ m), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: about 1.5 ⁇ m), indium element and gallium Weighing was performed so that the atomic ratio of the element and zinc element (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 1 hour to obtain a mixed powder.
- the obtained mixed powder was subjected to pressure molding at a pressure of 300 MPa by a cold isostatic pressing method, and the obtained molded product was cut to obtain a cylindrical molded body having a diameter of 115 mm and a height of 40 mm.
- the density of the cylindrical molded body was 3.52 g / cm 3 .
- the density of the molded body was calculated by measuring the diameter and height of the molded body, calculating the volume, and dividing the separately measured weight of the molded body by the calculated volume.
- the cylindrical molded body was transferred to a capsule container (outer diameter 121 mm, inner diameter 115 mm, inner height 40 mm) made of stainless steel (SUS304) so that the molded body did not collapse and filled into the capsule container.
- the filling density of the mixed powder was 3.52 g / cm 3
- the theoretical density of the sintered body was 6.379 g / cm 3 , so that the filling rate of the mixed powder was 55.2%.
- the single crystal theoretical density (6.379 g / cm 3 ) was employed.
- the exhaust pipe was welded to the upper lid of the capsule container filled with the cylindrical molded body, and then the upper lid and the capsule container were welded. A He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container. The amount of leakage at this time was 1 ⁇ 10 ⁇ 6 Torr ⁇ L / sec or less. After removing the gas in the capsule container from the exhaust pipe at 550 ° C. for 7 hours, the exhaust pipe was closed and the capsule container was sealed. The sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing.
- a HIP processing apparatus manufactured by Kobe Steel, Ltd.
- the treatment temperature was 1200 ° C.
- the treatment pressure was 118 MPa
- the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
- the capsule container was removed to obtain a cylindrical oxide sintered body.
- the obtained cylindrical oxide sintered body had a diameter of 94.3 mm and a height of 32.8 mm.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the density of the sintered body was measured by a length measurement method, and the theoretical density of InGaZnO 4 (JCPDS card number: 381104) described in the JCPDS card was adopted as the theoretical density of the sintered body.
- the average grain size of the obtained oxide sintered body was 0.77 ⁇ m, the Vickers hardness was 648.1, and the bending strength was 210 MPa.
- L * of the obtained oxide sintered body was 22.08, a * was ⁇ 1.03, b * was ⁇ 2.48, and ⁇ L was 75.1.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 9 In Example 8, a gallium oxide powder having an average particle size of 3 ⁇ m was used, and the filling rate of the cylindrical molded body into the capsule container was changed to 57.4%. A ligature was obtained.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 9.80 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 4.2 ⁇ m, Vickers hardness of 473.1, and flexural strength of 133 MPa.
- L * of the obtained oxide sintered body was 33.67, a * was ⁇ 1.94, b * was ⁇ 3.53, and ⁇ L was 63.6.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 9.8 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 10 In Example 8, the same procedure as in Example 8 was performed except that gallium oxide powder having an average particle size of 0.3 ⁇ m was used and the filling rate of the cylindrical molded body into the capsule container was 54.4%. A sintered product was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 7.54 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 0.92 ⁇ m, Vickers hardness of 652.3, and bending strength of 212 MPa.
- L * of the obtained oxide sintered body was 21.98, a * was ⁇ 0.99, b * was ⁇ 2.39, and ⁇ L was 75.2.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 7.54 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value that allows DC sputtering sufficiently, a small crystal grain size, a fine structure, and a high Vickers hardness.
- the generation can also be suppressed (the occurrence of abnormal discharge is suppressed), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even when the sputtering power is increased, and the production efficiency is good.
- Example 11 In Example 8, a gallium oxide powder having an average particle diameter of 1 ⁇ m was used, and the filling rate of the cylindrical molded body into the capsule container was changed to 55.1%. A ligature was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 9.20 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 3.5 ⁇ m, Vickers hardness of 538.5, and flexural strength of 162 MPa.
- L * of the obtained oxide sintered body was 27.46, a * was ⁇ 1.45, b * was ⁇ 3.03, and ⁇ L was 69.8.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (resistivity) of 9.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 12 Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 ⁇ m) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle size: about 1.5 ⁇ m), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: about 1.5 ⁇ m), indium element and gallium Weighing was performed so that the atomic ratio of element to zinc element (In: Ga: Zn) was 1: 1: 1, and the weighed powders were mixed to obtain a mixed powder.
- Indium oxide powder manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 ⁇ m
- gallium oxide powder manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3
- the obtained mixed powder, polypropylene carbonate (molecular weight: 200,000), 2 mm ⁇ zirconia balls, ethanol and acetone were mixed to prepare a slurry, and the slurry was wet-mixed by a wet ball mill mixing method.
- 2 mass parts of polypropylene carbonate was used with respect to 98 mass parts of mixed powder.
- the slurry After removing the zirconia balls from the slurry, the slurry is sprayed with an explosion-proof spray dryer (DL410 manufactured by Yamato Scientific Co., Ltd.) equipped with a two-fluid nozzle type (orifice diameter 0.7 mm) atomizer and dried at normal pressure. And granulated to obtain a granulated powder having a particle size of 95 ⁇ m and a tap density of 3.43 g / cm 3 .
- the temperature of the hot air supplied to the spray dryer was 250 ° C., and the temperature at the outlet of the dryer was 93 ° C.
- the particle size of the granulated powder was measured as follows.
- the collected powder and hexametaphosphoric acid (dispersing agent) are put into water, irradiated with ultrasonic waves for 3 minutes, and then a laser diffraction / scattering particle size distribution analyzer (Beckman Coulter, Inc.)
- the particle size distribution was measured by LS-230, manufactured, and the particle size of the granulated powder was defined as a particle size with an integrated volume fraction of 50%.
- the tap density of the granulated powder was calculated based on JIS K5101 by filling the granulated powder into a graduated cylinder of a predetermined size while applying vibration until the volume of the granulated powder disappeared.
- the capsule container filled with the granulated powder was kept at 400 ° C. for 5 hours in an air atmosphere to remove the polypropylene carbonate.
- the tap density of the powder after removing the polypropylene carbonate was 3.31 g / cm 3 , and the filling rate was 51.9%.
- the exhaust pipe was welded to the upper lid of the capsule container, and then the upper lid and the capsule container were welded.
- a He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container.
- the amount of leakage at this time was 1 ⁇ 10 ⁇ 9 Pa ⁇ m 3 / sec or less.
- the exhaust pipe was closed and the capsule container was sealed.
- the sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing.
- the treatment temperature was 1200 ° C.
- the treatment pressure was 118 MPa
- the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
- the capsule container was removed to obtain a cylindrical oxide sintered body.
- the obtained cylindrical oxide sintered body had a diameter of 64.1 mm and a height of 62.4 mm.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the density of the sintered body was measured by a length measurement method, and the theoretical density of InGaZnO 4 (JCPDS card number: 381104) described in the JCPDS card was adopted as the theoretical density of the sintered body.
- the average grain size of the obtained oxide sintered body was 0.77 ⁇ m, the Vickers hardness was 648.1, and the bending strength was 210 MPa.
- L * of the obtained oxide sintered body was 22.08, a * was ⁇ 1.03, b * was ⁇ 2.48, and ⁇ L was 75.1.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 13 In Example 12, the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was weighed to be 2: 2: 1, and the filling rate of the granulated powder into the capsule container was 56.
- the oxide sintered body was obtained in the same manner as in Example 12 except that the content was 2%.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 5.43 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 0.93 ⁇ m, the Vickers hardness was 610.3, and the bending strength was 195 MPa.
- L * of the obtained oxide sintered body was 19.62, a * was ⁇ 0.46, b * was ⁇ 0.346, and ⁇ L was 77.52.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP high frequency inductively coupled plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 5.43 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 14 In Example 8, a zinc oxide powder having an average particle diameter of 60 nm was used, and the same procedure as in Example 8 was performed except that the filling rate of the mixed powder after calcining into the capsule container was 54.6%. A sintered product was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 0.72 ⁇ m, Vickers hardness of 674.1, and flexural strength of 225 MPa.
- L * of the obtained oxide sintered body was 21,82, a * was ⁇ 1.01, b * was ⁇ 2.43, and ⁇ L was 75.4.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 15 Indium oxide powder (made by rare metal), tap density: 1.62 g / cm 3 , average particle diameter: 0.56 ⁇ m) and gallium oxide powder (made by rare metal, Inc., tap density 1.50 g) / Cm 3 , average particle size: 1.0 ⁇ m), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: 1.5 ⁇ m), indium element and gallium element And zinc element were weighed so that the atomic ratio (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 1 hour to obtain a mixed powder.
- the obtained mixed powder was subjected to pressure molding at a pressure of 300 MPa by a cold isostatic pressing method, and the obtained molded product was cut to obtain a cylindrical molded body having a diameter of 115 mm and a height of 40 mm.
- the density of the cylindrical molded body was 3.66 g / cm 3 .
- the density of the molded body was calculated by measuring the diameter and height of the molded body, calculating the volume, and dividing the separately measured weight of the molded body by the calculated volume.
- the cylindrical molded body was transferred to a capsule container (outer diameter 121 mm, inner diameter 115 mm, inner height 40 mm) made of stainless steel (SUS304) so that the molded body did not collapse and filled into the capsule container.
- the filling density of the mixed powder was 3.66 g / cm 3
- the theoretical density of the sintered body was 6.379 g / cm 3 , so that the filling rate of the mixed powder was 57.3%.
- the single crystal theoretical density (6.379 g / cm 3 ) was employed.
- the exhaust pipe was welded to the upper lid of the capsule container filled with the cylindrical molded body, and then the upper lid and the capsule container were welded. A He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container. The amount of leakage at this time was 1 ⁇ 10 ⁇ 6 Torr ⁇ L / sec or less. After removing the gas in the capsule container from the exhaust pipe at 550 ° C. for 7 hours, the exhaust pipe was closed and the capsule container was sealed. The sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing.
- a HIP processing apparatus manufactured by Kobe Steel, Ltd.
- the treatment temperature was 1220 ° C.
- the treatment pressure was 118 MPa
- the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
- the capsule container was removed to obtain a cylindrical oxide sintered body.
- the obtained cylindrical oxide sintered body had a diameter of 94.3 mm and a height of 32.8 mm.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 8.30 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the density of the sintered body was measured by a length measurement method, and the theoretical density of InGaZnO 4 (JCPDS card number: 381104) described in the JCPDS card was adopted as the theoretical density of the sintered body.
- the average grain size of the obtained oxide sintered body was 1.20 ⁇ m, the Vickers hardness was 595.0, and the bending strength was 188 MPa.
- L * of the obtained oxide sintered body was 34.2, a * was ⁇ 1.55, b * was ⁇ 2.93, and ⁇ L was 63.0.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (specific resistance) of 8.18 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. It has a high density, no defects as a sputtering target, a low resistance value sufficient for DC sputtering, a small crystal grain size, a fine structure, and a high Vickers hardness, resulting in less generation of particles. Production can be suppressed (suppressing the occurrence of abnormal discharge), and since the mechanical strength is high, the film formation rate can be increased without cracking the target even if the sputtering power is increased, and the production efficiency is good. .
- Example 8 was carried out in the same manner as in Example 8 except that indium oxide powder having an average particle size of 4.0 ⁇ m (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used. .6 mm, height 32.9 mm).
- the density of the cylindrical molded body was 3.55 g / cm 3 .
- the capsule container was filled with a cylindrical molded body, and the calculated filling density was 3.55 g / cm 3 . Therefore, the filling rate of the cylindrical molded body into the capsule container was 55.7%.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 1.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 7.9 ⁇ m, a Vickers hardness of 421.3, and a bending strength of 107 MPa.
- L * of the obtained oxide sintered body was 35.32, a * was ⁇ 2.08, b * was ⁇ 0.367, and ⁇ L was 59.5.
- the surface of the obtained oxide sintered body was ground, the outer periphery was ground, and the surface was further polished to prepare a sintered body having a diameter of 50.8 mm and a thickness of 3 mm.
- ICP High Frequency Inductively Coupled Plasma
- the atomic ratio of In, Ga and Zn In: Ga: Zn
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 70%, and a bulk resistance value (specific resistance) of 1.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Although the density was high, the uniformity of the composition of the sputtered film was reduced.
- Comparative Example 7 In Comparative Example 6, the atomic ratio of indium element, gallium element, and zinc element (In: Ga: Zn) was weighed to be 2: 2: 1, and the filling rate of the cylindrical molded body into the capsule container was determined. An oxide sintered body was obtained in the same manner as in Comparative Example 6 except that the content was 55.9%.
- the relative density of the obtained oxide sintered body was 100%, and the bulk resistance value (specific resistance) was 1.7 ⁇ 10 ⁇ 2 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 8.3 ⁇ m, the Vickers hardness was 398.5, and the bending strength was 96 MPa.
- L * of the obtained oxide sintered body was 45.8, a * was ⁇ 2.83, b * was ⁇ 3.97, and ⁇ L was 51.6.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 4%, and a bulk resistance value (specific resistance) of 1.7 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Although the density was high, the uniformity of the composition of the sputtered film was reduced.
- Comparative Example 8 In Comparative Example 6, the same procedure as in Comparative Example 6 was performed except that indium oxide powder having an average particle size of 1.0 ⁇ m was used and the filling rate of the cylindrical molded body into the capsule container was set to 56.6%. A sintered product was obtained.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the obtained oxide sintered body had an average crystal grain size of 4.8 ⁇ m, a Vickers hardness of 421.3, and a bending strength of 107 MPa.
- L * of the obtained oxide sintered body was 38.3, a * was ⁇ 1.88, b * was ⁇ 2.54, and ⁇ L was 58.9.
- This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 88.60%, and a bulk resistance value (specific resistance) of 6.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. For this reason, the uniformity of the composition of the sputtered film was reduced although it was high density.
- Comparative Example 9 In Comparative Example 8, the atomic ratio of indium element, gallium element and zinc element (In: Ga: Zn) was weighed to be 2: 2: 1, and the filling rate of the cylindrical molded body into the capsule container was determined. An oxide sintered body was obtained in the same manner as in Comparative Example 8 except that the content was 54.8%.
- the obtained oxide sintered body had a relative density of 100% and a bulk resistance value (specific resistance) of 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm.
- the average grain size of the obtained oxide sintered body was 4.7 ⁇ m, the Vickers hardness was 436.2, and the bending strength was 114 MPa.
- L * of the obtained oxide sintered body was 39.4, a * was -1.93, b * was -3.21, and ⁇ L was 57.9.
- This oxide sintered body was bonded using indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate.
- This oxide sintered body has a relative density of 100%, a (2217) single-phase ratio of 85.6%, and a bulk resistance value (specific resistance) of 4.2 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. For this reason, the uniformity of the composition of the sputtered film was reduced although it was high density.
- the oxide sintered body of the present invention is useful as a sputtering target because of its high mechanical strength, high relative density, low bulk resistance, and uniform composition.
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Abstract
Description
本発明の酸化物焼結体の製造方法の1つの形態は、下記工程(A)および工程(B)を含む。 [Production Method of Oxide Sintered Body (1)]
One form of the manufacturing method of the oxide sintered compact of this invention includes the following process (A) and process (B).
酸化ガリウム粉末の平均粒子径は、通常0.2μm以上5μm以下、好ましくは0.2μm以上2μm以下である。 As the gallium oxide powder, a commercially available gallium oxide powder is usually used. The tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.45 g / cm 3 or less. The single-piece density (upper limit of tap density) of gallium oxide is 5.88 g / cm 3 .
The average particle diameter of the gallium oxide powder is usually 0.2 μm or more and 5 μm or less, preferably 0.2 μm or more and 2 μm or less.
均一な混合が不十分であると、製造したターゲット中に各成分が偏析して、ターゲットの抵抗分布が不均一になる。すなわち、ターゲットの部位により、高抵抗領域と低抵抗領域が存在することになるため、スパッタ成膜時に高抵抗領域での帯電等によるアーキングなどの異常放電の原因となる。 The mixing method of each powder is not limited as long as the powder can be uniformly mixed, and may be dry-mixed by a super mixer, intensive mixer, Henschel mixer, automatic mortar, etc., ball mill, vibration mill, planetary ball mill, etc. May be wet mixed.
If uniform mixing is insufficient, each component segregates in the manufactured target, and the resistance distribution of the target becomes non-uniform. That is, the high resistance region and the low resistance region exist depending on the target site, which causes abnormal discharge such as arcing due to charging in the high resistance region during sputtering film formation.
カプセル容器の壁厚は、1.5mm~4mmが好ましい。この範囲内であれば、カプセル容器が容易に軟化し、変形することができ、焼結反応が進むに従い、酸化物焼結体に追随して収縮することができる。 The shape and dimensions of the capsule container are not limited as long as it is isotropically pressurized during the capsule HIP process. Specifically, a cylindrical container and a rectangular parallelepiped container are mentioned.
The wall thickness of the capsule container is preferably 1.5 mm to 4 mm. Within this range, the capsule container can be easily softened and deformed, and can shrink following the oxide sintered body as the sintering reaction proceeds.
処理温度は、通常1000~1400℃であり、好ましくは1100℃~1300℃である。焼結温度が1000℃~1400℃で、圧力50MPa以上で、1時間以上処理することが好ましい。 As the pressure medium, an inert gas such as nitrogen or argon is preferable. The pressure applied to the capsule container is preferably 50 MPa or more. The treatment time is preferably 1 hour or longer.
The treatment temperature is usually 1000 to 1400 ° C., preferably 1100 ° C. to 1300 ° C. It is preferable that the sintering temperature is 1000 ° C. to 1400 ° C. and the pressure is 50 MPa or more and the treatment is performed for 1 hour or more.
本発明の酸化物焼結体の製造方法のもう1つの形態は、下記工程(a)、工程(b)および工程(c)を含む。 [Production Method of Oxide Sintered Body (2)]
Another form of the method for producing an oxide sintered body of the present invention includes the following step (a), step (b) and step (c).
酸化ガリウム粉末の平均粒子径は、通常0.2μm以上5μm以下、好ましくは0.2μm以上2μm以下である。 As the gallium oxide powder, a commercially available gallium oxide powder is usually used. The tap density of commercially available gallium oxide powder varies depending on the average particle size and particle size distribution, but is usually 1.45 g / cm 3 or less. The single-piece density (upper limit of tap density) of gallium oxide is 5.88 g / cm 3 .
The average particle diameter of the gallium oxide powder is usually 0.2 μm or more and 5 μm or less, preferably 0.2 μm or more and 2 μm or less.
均一な混合が不十分であると、製造したターゲット中に各成分が偏析して、ターゲットの抵抗分布が不均一になる。すなわち、ターゲットの部位により、高抵抗領域と低抵抗領域が存在することになるため、スパッタ成膜時に高抵抗領域での帯電等によるアーキングなどの異常放電の原因となる。 The mixing method of each powder is not limited as long as the powder can be uniformly mixed, and may be dry-mixed by a super mixer, intensive mixer, Henschel mixer, automatic mortar, etc., ball mill, vibration mill, planetary ball mill, etc. May be wet mixed.
If uniform mixing is insufficient, each component segregates in the manufactured target, and the resistance distribution of the target becomes non-uniform. That is, the high resistance region and the low resistance region exist depending on the target site, which causes abnormal discharge such as arcing due to charging in the high resistance region during sputtering film formation.
カプセル容器の壁厚は、1.5mm~4mmが好ましい。この範囲内であれば、カプセル容器が容易に軟化し、変形することができ、焼結反応が進むに従い、酸化物焼結体に追随して収縮することができる。 The shape and dimensions of the capsule container are not limited as long as it is isotropically pressurized during the capsule HIP process. Specifically, a cylindrical container and a rectangular parallelepiped container are mentioned.
The wall thickness of the capsule container is preferably 1.5 mm to 4 mm. Within this range, the capsule container can be easily softened and deformed, and can shrink following the oxide sintered body as the sintering reaction proceeds.
本発明の酸化物焼結体を、所定の形状および所定の寸法に加工することにより、スパッタリングターゲットを製造することができる。本発明の酸化物焼結体について、外周の円筒研削、面側の平面研削をすることにより、例えば外径152mm×5mmのスパッタリングターゲットを製造することができる。スパッタリングターゲットの表面粗さ(Ra)は、5μm以下が好ましく、0.5μm以下がより好ましい。通常、スパッタリングターゲットは、さらに、銅やチタン等からなるバッキングプレートやバッキングチューブに、インジウム系合金などをボンディングメタルとして、貼り合わせた形態で用いられる。 [Sputtering target]
A sputtering target can be manufactured by processing the oxide sintered body of the present invention into a predetermined shape and a predetermined dimension. For the oxide sintered body of the present invention, for example, a sputtering target having an outer diameter of 152 mm × 5 mm can be produced by cylindrical grinding of the outer periphery and surface grinding of the surface side. The surface roughness (Ra) of the sputtering target is preferably 5 μm or less, and more preferably 0.5 μm or less. Usually, the sputtering target is further used in a form in which an indium alloy or the like is bonded as a bonding metal to a backing plate or backing tube made of copper, titanium, or the like.
また、本発明のスパッタリングターゲットは、高い相対密度を有し、単相割合も高いため、スパッタ時間の経過に伴って、ノジュールの発生の頻度や異常放電の発生頻度も減らすことができ、スパッタの生産効率も向上し、得られる膜特性にも優れる。本発明の酸化物焼結体またはスパッタリングターゲットにより、安定した半導体特性を示す薄膜トランジスタのチャネル層として良好な特性を備える透明半導体膜を形成することができる。 The sputtering target is used for film formation by sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) evaporation. Since the target of the present invention has a high relative density and a high single-phase ratio, abnormal discharge during film formation hardly occurs and film formation can be performed stably. Note that a solid material used in the film formation may be referred to as a “tablet”, but in the present specification, these are referred to as a “sputtering target”.
In addition, since the sputtering target of the present invention has a high relative density and a high single-phase ratio, the frequency of nodules and the frequency of abnormal discharge can be reduced as the sputtering time elapses. Production efficiency is also improved, and the resulting film properties are excellent. With the oxide sintered body or sputtering target of the present invention, a transparent semiconductor film having good characteristics as a channel layer of a thin film transistor exhibiting stable semiconductor characteristics can be formed.
DCスパッタ法の場合、スパッタリング時のチャンバー内の圧力は、通常0.1~2.0MPaであり、好ましくは0.3~0.8MPaである。DCスパッタ法の場合、スパッタ時におけるターゲット面の単位面積当たりの投入電力は、通常0.5~6.0W/cm2であり、好ましくは1.0~5.0W/cm2である。スパッタ時のキャリアーガスとしては、酸素、ヘリウム、アルゴン、キセノンおよびクリプトンが挙げられ、好ましくはアルゴンと酸素の混合ガスである。アルゴンと酸素の混合ガス中のアルゴン:酸素の比(Ar:O2)は、通常100:0~80:20であり、好ましくは99.5:0.5~80:20であり、より好ましくは99.5:0.5~90:10である。基板としては、ガラス、樹脂(PET、PES等)などが挙げられる。スパッタ時の成膜温度(薄膜を形成する基板の温度)は、通常25℃~450℃、好ましくは30℃~250℃、より好ましくは35℃~150℃である。 Examples of the sputtering method include a DC sputtering method, an AC sputtering method, an RF magnetron sputtering method, an electron beam evaporation method, and an ion plating method, and a DC sputtering method is preferable.
In the case of DC sputtering, the pressure in the chamber during sputtering is usually 0.1 to 2.0 MPa, preferably 0.3 to 0.8 MPa. For DC sputtering input power per unit area of the target surface during sputtering is usually 0.5 ~ 6.0W / cm 2, preferably 1.0 ~ 5.0W / cm 2. Examples of the carrier gas at the time of sputtering include oxygen, helium, argon, xenon, and krypton, and a mixed gas of argon and oxygen is preferable. The ratio of argon: oxygen (Ar: O 2 ) in the mixed gas of argon and oxygen is usually 100: 0 to 80:20, preferably 99.5: 0.5 to 80:20, more preferably Is 99.5: 0.5 to 90:10. Examples of the substrate include glass and resin (PET, PES, etc.). The film formation temperature during sputtering (the temperature of the substrate on which the thin film is formed) is usually 25 ° C. to 450 ° C., preferably 30 ° C. to 250 ° C., more preferably 35 ° C. to 150 ° C.
レーザー回折式粒度分布測定装置(島津製作所製SALD-2200)により、各粉末の粒度分布を測定し、体積累積基準D50を平均粒子径とした。さらに、FE-SEMにより粉末の形状およびサイズを測定した。 <Measurement of particle size distribution of powder>
The particle size distribution of each powder was measured with a laser diffraction particle size distribution analyzer (SALD-2200, manufactured by Shimadzu Corporation), and the volume cumulative standard D50 was defined as the average particle size. Further, the shape and size of the powder were measured by FE-SEM.
加速電圧15kV、ワーキングディスタンス15mm、倍率1500倍の条件で、酸化物焼結体のSEM-EBSD測定を実施し、得られたImage Qulity Mapの像解析により個別の粒の面積(断面積)を測定した。該粒の断面を最も大きさの近い円形と仮定して、当該円形の径を算出した。算出した径に、その粒が全体の面積に対する占有割合を乗じ、その粒の占有面積あたりの径を算出した。すべての粒について、占有面積あたりの径を算出し、算出したすべての占有面積あたりの径の合計を面積平均径、すなわち、結晶粒径とした。 <Measurement of crystal grain size of oxide sintered body>
SEM-EBSD measurement of the oxide sintered body was performed under the conditions of an acceleration voltage of 15 kV, a working distance of 15 mm, and a magnification of 1500 times, and the area (cross-sectional area) of each individual particle was measured by image analysis of the obtained Image Quality Map. did. The diameter of the circle was calculated assuming that the cross section of the grain was the closest circle. The calculated diameter was multiplied by the occupation ratio of the grains with respect to the entire area, and the diameter per occupied area of the grains was calculated. For all the grains, the diameter per occupied area was calculated, and the total of the calculated diameters per occupied area was defined as the area average diameter, that is, the crystal grain size.
酸化物焼結体のビッカース硬度を、島津製作所製微小硬度計(HMV)により測定した。 <Measurement of Vickers hardness of sintered oxide>
The Vickers hardness of the oxide sintered body was measured by a micro hardness meter (HMV) manufactured by Shimadzu Corporation.
酸化物焼結体の抗折強度を、万能材料試験機(Instron 5584(ロードセル 5kN))により、JIS R1601に準拠して測定した。
試験方法:3点曲げ試験
支点間距離:30mm
支持アンビル:R=2mm
加圧アンビル:R=3mm
試料サイズ:3×4×40mm
ヘッド速度:0.5mm/min
試験温度:22℃ <Measurement of bending strength of sintered oxide>
The bending strength of the oxide sintered body was measured in accordance with JIS R1601 using a universal material testing machine (Instron 5584 (load cell 5 kN)).
Test method: 3-point bending test fulcrum distance: 30 mm
Supporting anvil: R = 2mm
Pressurized anvil: R = 3mm
Sample size: 3x4x40mm
Head speed: 0.5 mm / min
Test temperature: 22 ° C
湿式研磨機(株式会社マルトー製マルトーラップ)により、研磨紙(#60)、次いで研磨紙(#180)を用いて、酸化物焼結体の表面を、表面粗さ(Ra)が0.5μm以下となるまで湿式研磨を行った。研磨した面の色度a*、色度b*、明度L*を、分光測色計(日本電色工業株式会社製Z-300A)により測定し、その結果をCIE1976空間で評価した。 <Measurement of color difference of sintered oxide>
Using a wet polishing machine (Malto Wrap Co., Ltd. manufactured by Maruto Co., Ltd.), the surface of the oxide sintered body is polished to a surface roughness (Ra) of 0.5 μm using polishing paper (# 60) and then polishing paper (# 180). Wet polishing was performed until the following. The polished surface was measured for chromaticity a *, chromaticity b *, and lightness L * with a spectrocolorimeter (Z-300A manufactured by Nippon Denshoku Industries Co., Ltd.), and the results were evaluated in the CIE 1976 space.
酸化インジウム粉末(稀産金属(株)製、タップ密度:1.62g/cm3、平均粒子径:0.56μm)と、酸化ガリウム粉末(ヤマナカヒューテック(株)製、タップ密度が1.39g/cm3、平均粒子径:1.5μm)と、酸化亜鉛粉末(ハクスイテック(株)製、タップ密度:1.02g/cm3、平均粒子径:1.5μm)とを、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が1:1:1となるように秤量し、スーパーミキサーにて、3000rpmで60分、乾式混合を行い、混合粉末を得た。 [Example 1]
Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 μm) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle diameter: 1.5 μm), zinc oxide powder (manufactured by Hakusuitec Co., Ltd., tap density: 1.02 g / cm 3 , average particle diameter: 1.5 μm), indium element and gallium element Weighing was performed so that the atomic ratio with zinc element (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 60 minutes to obtain a mixed powder.
カプセルHIP処理後、カプセル容器を取り外し、円柱型の酸化物焼結体を得た。 The exhaust pipe was welded to the upper lid of the capsule container filled with the mixed powder, and then the upper lid and the capsule container were welded. A He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container. The amount of leakage at this time was 1 × 10 −6 Torr · L / sec or less. After removing the gas in the capsule container from the exhaust pipe at 550 ° C. for 7 hours, the exhaust pipe was closed and the capsule container was sealed. The sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing. The treatment temperature was 1200 ° C., the treatment pressure was 118 MPa, and the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
After the capsule HIP treatment, the capsule container was removed to obtain a cylindrical oxide sintered body.
実施例1において、平均粒径が0.6μmの酸化ガリウム粉末を用い、仮焼後の混合粉末のカプセル容器への充填率を66.5%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Example 2]
In Example 1, using gallium oxide powder having an average particle diameter of 0.6 μm, and carrying out the same procedure as in Example 1 except that the filling rate of the mixed powder after calcining into the capsule container was set to 66.5%. An oxide sintered body was obtained.
実施例1において、平均粒径が0.3μmの酸化ガリウム粉末を用い、仮焼後の混合粉末のカプセル容器への充填率を65.7%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Example 3]
The same procedure as in Example 1 was performed except that gallium oxide powder having an average particle diameter of 0.3 μm was used in Example 1, and the filling rate of the mixed powder after calcining into the capsule container was set to 65.7%. An oxide sintered body was obtained.
実施例1において、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、仮焼後の混合粉末のカプセル容器への充填率を63.3%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Example 4]
In Example 1, the mixture is weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element is 2: 2: 1, and the mixed powder after calcination is filled into the capsule container The oxide sintered body was obtained in the same manner as in Example 1 except that the rate was 63.3%.
実施例1において、平均粒径が0.6μmの酸化ガリウム粉末を用い、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、仮焼後の混合粉末のカプセル容器への充填率を62.8%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Example 5]
In Example 1, gallium oxide powder having an average particle size of 0.6 μm was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element and zinc element was 2: 2: 1. And it implemented like Example 1 except the filling rate to the capsule container of the mixed powder after calcination having been 62.8%, and obtained oxide sinter.
実施例1において、平均粒径が0.3μmの酸化ガリウム粉末を用い、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、仮焼後の混合粉末のカプセル容器への充填率を61.5%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Example 6]
In Example 1, gallium oxide powder having an average particle size of 0.3 μm was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1. And it implemented like Example 1 except having made the filling rate to the capsule container of the mixed powder after calcination 61.5%, and obtained oxide sinter.
酸化インジウム粉末(稀産金属(株)製、タップ密度:1.62g/cm3、平均粒子径:0.56μm)と、酸化ガリウム粉末(稀産金属(株)製、タップ密度が1.50g/cm3、平均粒子径:1.0μm)と、酸化亜鉛粉末(ハクスイテック(株)製、タップ密度:1.02g/cm3、平均粒子径:1.5μm)とを、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が1:1:1となるように秤量し、スーパーミキサーにて、3000rpmで60分、乾式混合を行い、混合粉末を得た。 [Example 7]
Indium oxide powder (made by rare metal), tap density: 1.62 g / cm 3 , average particle diameter: 0.56 μm) and gallium oxide powder (made by rare metal, Inc., tap density 1.50 g) / Cm 3 , average particle size: 1.0 μm), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: 1.5 μm), indium element and gallium element And zinc element were weighed so that the atomic ratio (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 60 minutes to obtain a mixed powder.
カプセルHIP処理後、カプセル容器を取り外し、円柱型の酸化物焼結体を得た。 The exhaust pipe was welded to the upper lid of the capsule container filled with the mixed powder, and then the upper lid and the capsule container were welded. A He leak test was performed to confirm whether there was any gas leak from the welded portion of the capsule container. The amount of leakage at this time was 1 × 10 −6 Torr · L / sec or less. After removing the gas in the capsule container from the exhaust pipe at 550 ° C. for 7 hours, the exhaust pipe was closed and the capsule container was sealed. The sealed capsule container was placed in a HIP processing apparatus (manufactured by Kobe Steel, Ltd.) and subjected to capsule HIP processing. The treatment temperature was 1220 ° C., the treatment pressure was 118 MPa, and the treatment was performed for 4 hours using argon gas (purity 99.9%) as a pressure medium.
After the capsule HIP treatment, the capsule container was removed to obtain a cylindrical oxide sintered body.
[比較例1]
実施例1において、平均粒径が3μmの酸化ガリウム粉末を用い、仮焼を行わず、混合粉末(タップ密度:2.21g/cm3)のカプセル容器への充填率を34.8%とした以外は、実施例1と同様に実施したが、カプセルが破裂し、酸化物焼結体が得られなかった。 This oxide sintered body was bonded with indium solder using a copper plate as a backing plate to obtain a sputtering target. Using this, an oxide semiconductor film was formed on a transparent substrate (non-alkali glass substrate) by a DC sputtering method to obtain a transparent semiconductor substrate. This oxide sintered body has a relative density of 100%, a (1114) single-phase ratio of 100%, and a bulk resistance value (resistivity) of 8.40 × 10 −4 Ω · cm. Because of its low density, high density, no defects as a sputtering target, and sufficient DC sputtering, it is possible to suppress the occurrence of abnormal discharge and to efficiently form a uniform oxide semiconductor film. It was.
[Comparative Example 1]
In Example 1, gallium oxide powder having an average particle diameter of 3 μm was used, calcining was not performed, and the filling rate of the mixed powder (tap density: 2.21 g / cm 3 ) into the capsule container was set to 34.8%. Except for this, the same procedure as in Example 1 was performed, but the capsule burst and an oxide sintered body was not obtained.
実施例1において、平均粒径が1μmの酸化インジウム粉末を用い、仮焼後の混合粉末のカプセル容器への充填率を57.4%とした以外は、実施例1と同様に実施し、酸化物焼結体を得た。 [Comparative Example 2]
In Example 1, an indium oxide powder having an average particle size of 1 μm was used, and the same procedure as in Example 1 was performed except that the filling rate of the mixed powder after calcining into the capsule container was 57.4%. A sintered product was obtained.
比較例2において、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、仮焼後の混合粉末のカプセル容器への充填率を54.2%とした以外は、比較例2と同様に実施し、酸化物焼結体を得た。 [Comparative Example 3]
In Comparative Example 2, the mixture was weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1, and the mixed powder after calcination was filled into the capsule container An oxide sintered body was obtained in the same manner as in Comparative Example 2 except that the rate was changed to 54.2%.
比較例2において、平均粒径が0.6μmの酸化ガリウム粉末を用い、仮焼後の混合粉末のカプセル容器への充填率を63.1%とした以外は、比較例2と同様に実施し、酸化物焼結体を得た。 [Comparative Example 4]
In Comparative Example 2, the same procedure as in Comparative Example 2 was performed except that gallium oxide powder having an average particle diameter of 0.6 μm was used and the filling rate of the mixed powder after calcining into the capsule container was 63.1%. An oxide sintered body was obtained.
比較例2において、平均粒径が0.6μmの酸化ガリウム粉末を用い、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、仮焼後の混合粉末のカプセル容器への充填率を59.9%とした以外は、比較例2と同様に実施し、酸化物焼結体を得た。 [Comparative Example 5]
In Comparative Example 2, gallium oxide powder having an average particle diameter of 0.6 μm was used and weighed so that the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was 2: 2: 1. And it implemented similarly to the comparative example 2 except the filling rate to the capsule container of the mixed powder after calcination having been 59.9%, and obtained oxide sinter.
酸化インジウム粉末(稀産金属(株)製、タップ密度:1.62g/cm3、平均粒子径:0.56μm)と、酸化ガリウム粉末(ヤマナカヒューテック(株)製、タップ密度が1.39g/cm3、平均粒子径:約1.5μm)と、酸化亜鉛粉末(ハクスイテック(株)製、タップ密度:1.02g/cm3、平均粒子径:約1.5μm)とを、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が1:1:1となるように秤量し、スーパーミキサーにて、3000rpmで1時間、乾式混合を行い、混合粉末を得た。 [Example 8]
Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 μm) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle size: about 1.5 μm), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: about 1.5 μm), indium element and gallium Weighing was performed so that the atomic ratio of the element and zinc element (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 1 hour to obtain a mixed powder.
実施例8において、平均粒径が3μmの酸化ガリウム粉末を用い、円柱状成型体のカプセル容器への充填率を57.4%とした以外は、実施例8と同様に実施し、酸化物焼結体を得た。 [Example 9]
In Example 8, a gallium oxide powder having an average particle size of 3 μm was used, and the filling rate of the cylindrical molded body into the capsule container was changed to 57.4%. A ligature was obtained.
実施例8において、平均粒径が0.3μmの酸化ガリウム粉末を用い、円柱状成型体のカプセル容器への充填率を54.4%とした以外は、実施例8と同様に実施し、酸化物焼結体を得た。 [Example 10]
In Example 8, the same procedure as in Example 8 was performed except that gallium oxide powder having an average particle size of 0.3 μm was used and the filling rate of the cylindrical molded body into the capsule container was 54.4%. A sintered product was obtained.
実施例8において、平均粒径が1μmの酸化ガリウム粉末を用い、円柱状成型体のカプセル容器への充填率を55.1%とした以外は、実施例8と同様に実施し、酸化物焼結体を得た。 [Example 11]
In Example 8, a gallium oxide powder having an average particle diameter of 1 μm was used, and the filling rate of the cylindrical molded body into the capsule container was changed to 55.1%. A ligature was obtained.
酸化インジウム粉末(稀産金属(株)製、タップ密度:1.62g/cm3、平均粒子径:0.56μm)と、酸化ガリウム粉末(ヤマナカヒューテック(株)製、タップ密度が1.39g/cm3、平均粒子径:約1.5μm)と、酸化亜鉛粉末(ハクスイテック(株)製、タップ密度:1.02g/cm3、平均粒子径:約1.5μm)とを、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が1:1:1となるように秤量し、秤量した各粉末を混合し、混合粉末を得た。 [Example 12]
Indium oxide powder (manufactured by Rare Metal Co., Ltd., tap density: 1.62 g / cm 3 , average particle size: 0.56 μm) and gallium oxide powder (manufactured by Yamanaka Futec Co., Ltd., tap density: 1.39 g / cm 3 , average particle size: about 1.5 μm), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: about 1.5 μm), indium element and gallium Weighing was performed so that the atomic ratio of element to zinc element (In: Ga: Zn) was 1: 1: 1, and the weighed powders were mixed to obtain a mixed powder.
実施例12において、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、造粒粉末のカプセル容器への充填率を56.2%とした以外は、実施例12と同様に実施し、酸化物焼結体を得た。 [Example 13]
In Example 12, the atomic ratio (In: Ga: Zn) of indium element, gallium element, and zinc element was weighed to be 2: 2: 1, and the filling rate of the granulated powder into the capsule container was 56. The oxide sintered body was obtained in the same manner as in Example 12 except that the content was 2%.
実施例8において、平均粒径が60nmの酸化亜鉛粉末を用い、仮焼後の混合粉末のカプセル容器への充填率を54.6%とした以外は、実施例8と同様に実施し、酸化物焼結体を得た。 [Example 14]
In Example 8, a zinc oxide powder having an average particle diameter of 60 nm was used, and the same procedure as in Example 8 was performed except that the filling rate of the mixed powder after calcining into the capsule container was 54.6%. A sintered product was obtained.
酸化インジウム粉末(稀産金属(株)製、タップ密度:1.62g/cm3、平均粒子径:0.56μm)と、酸化ガリウム粉末(稀産金属(株)製、タップ密度が1.50g/cm3、平均粒子径:1.0μm)と、酸化亜鉛粉末(ハクスイテック(株)製、タップ密度:1.02g/cm3、平均粒子径:1.5μm)とを、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が1:1:1となるように秤量し、スーパーミキサーにて、3000rpmで1時間、乾式混合を行い、混合粉末を得た。 [Example 15]
Indium oxide powder (made by rare metal), tap density: 1.62 g / cm 3 , average particle diameter: 0.56 μm) and gallium oxide powder (made by rare metal, Inc., tap density 1.50 g) / Cm 3 , average particle size: 1.0 μm), zinc oxide powder (manufactured by Hakusui Tech Co., Ltd., tap density: 1.02 g / cm 3 , average particle size: 1.5 μm), indium element and gallium element And zinc element were weighed so that the atomic ratio (In: Ga: Zn) was 1: 1: 1, and dry mixing was performed with a super mixer at 3000 rpm for 1 hour to obtain a mixed powder.
実施例8において、平均粒径が4.0μmの酸化インジウム粉末(高純度化学研究所(株)製)を用いた以外は、実施例8と同様に実施し、酸化物焼結体(直径94.6mm、高さ32.9mm)を得た。円柱状成型体の密度は3.55g/cm3であった。また、カプセル容器に円柱状成型体を充填し、算出した充填密度は3.55g/cm3であった。したがって、円柱状成型体のカプセル容器への充填率は55.7%であった。 [Comparative Example 6]
Example 8 was carried out in the same manner as in Example 8 except that indium oxide powder having an average particle size of 4.0 μm (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was used. .6 mm, height 32.9 mm). The density of the cylindrical molded body was 3.55 g / cm 3 . The capsule container was filled with a cylindrical molded body, and the calculated filling density was 3.55 g / cm 3 . Therefore, the filling rate of the cylindrical molded body into the capsule container was 55.7%.
比較例6において、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、円柱状成型体のカプセル容器への充填率を55.9%とした以外は、比較例6と同様に実施し、酸化物焼結体を得た。 [Comparative Example 7]
In Comparative Example 6, the atomic ratio of indium element, gallium element, and zinc element (In: Ga: Zn) was weighed to be 2: 2: 1, and the filling rate of the cylindrical molded body into the capsule container was determined. An oxide sintered body was obtained in the same manner as in Comparative Example 6 except that the content was 55.9%.
比較例6において、平均粒径が1.0μmの酸化インジウム粉末を用い、円柱状成型体のカプセル容器への充填率を56.6%とした以外は、比較例6と同様に実施し、酸化物焼結体を得た。 [Comparative Example 8]
In Comparative Example 6, the same procedure as in Comparative Example 6 was performed except that indium oxide powder having an average particle size of 1.0 μm was used and the filling rate of the cylindrical molded body into the capsule container was set to 56.6%. A sintered product was obtained.
比較例8において、インジウム元素とガリウム元素と亜鉛元素との原子数比(In:Ga:Zn)が2:2:1となるように秤量し、円柱状成型体のカプセル容器への充填率を54.8%とした以外は、比較例8と同様に実施し、酸化物焼結体を得た。 [Comparative Example 9]
In Comparative Example 8, the atomic ratio of indium element, gallium element and zinc element (In: Ga: Zn) was weighed to be 2: 2: 1, and the filling rate of the cylindrical molded body into the capsule container was determined. An oxide sintered body was obtained in the same manner as in Comparative Example 8 except that the content was 54.8%.
Claims (17)
- In、GaおよびZnを含む酸化物焼結体であって、L*a*b*表色系におけるL*が35以下である酸化物焼結体。 An oxide sintered body containing In, Ga, and Zn, wherein L * in the L * a * b * color system is 35 or less.
- L*a*b*表色系におけるa*が-0.6以下である請求項1に記載の酸化物焼結体。 The oxide sintered body according to claim 1, wherein a * in the L * a * b * color system is -0.6 or less.
- ビッカース硬度が400以上である請求項1または2に記載の酸化物焼結体。 The oxide sintered body according to claim 1 or 2, wherein the Vickers hardness is 400 or more.
- 抗折強度が90MPa以上である請求項1~3のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 3, wherein the bending strength is 90 MPa or more.
- 相対密度が99.5%以上である請求項1~4のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 4, wherein the relative density is 99.5% or more.
- バルク抵抗値が1.0×10-3Ω・cm未満である請求項1~5のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 5, wherein a bulk resistance value is less than 1.0 × 10 -3 Ω · cm.
- 単相割合が97.5%以上である請求項1~6のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 6, wherein a single phase ratio is 97.5% or more.
- 結晶粒径が9μm以下である請求項1~7のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 1 to 7, wherein the crystal grain size is 9 µm or less.
- In、GaおよびZnを含む酸化物焼結体であって、ビッカース硬度が450以上であり、相対密度が97%を超え、バルク抵抗値が1.0×10-3Ω・cm未満である酸化物焼結体。 An oxide sintered body containing In, Ga and Zn, having a Vickers hardness of 450 or more, a relative density of more than 97%, and a bulk resistance value of less than 1.0 × 10 −3 Ω · cm Sintered product.
- In、GaおよびZnを含む酸化物焼結体であって、抗折強度が130MPa以上であり、相対密度が97%を超え、バルク抵抗値が1.0×10-3Ω・cm未満である酸化物焼結体。 An oxide sintered body containing In, Ga, and Zn, having a bending strength of 130 MPa or more, a relative density of over 97%, and a bulk resistance value of less than 1.0 × 10 −3 Ω · cm. Oxide sintered body.
- ビッカース硬度が450以上である請求項10に記載の酸化物焼結体。 The oxide sintered body according to claim 10, having a Vickers hardness of 450 or more.
- L*a*b*表色系におけるL*が35以下である請求項9~11のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 9 to 11, wherein L * in the L * a * b * color system is 35 or less.
- L*a*b*表色系におけるa*が-0.6以下である請求項9~12のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 9 to 12, wherein a * in the L * a * b * color system is -0.6 or less.
- 相対密度が99.5%以上である請求項9~13のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 9 to 13, having a relative density of 99.5% or more.
- 単相割合が97.5%以上である請求項9~14のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 9 to 14, wherein a single phase ratio is 97.5% or more.
- 結晶粒径が4.5μm以下である請求項9~15のいずれかに記載の酸化物焼結体。 The oxide sintered body according to any one of claims 9 to 15, wherein the crystal grain size is 4.5 µm or less.
- 請求項1~16のいずれかに記載の酸化物焼結体を含むスパッタリングターゲット。 A sputtering target comprising the oxide sintered body according to any one of claims 1 to 16.
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JP2007223849A (en) * | 2006-02-24 | 2007-09-06 | Sumitomo Metal Mining Co Ltd | Gallium oxide-based sintered compact and method of manufacturing the same |
WO2009157535A1 (en) * | 2008-06-27 | 2009-12-30 | 出光興産株式会社 | Sputtering target for oxide semiconductor, comprising ingao3(zno) crystal phase and process for producing the sputtering target |
WO2010070832A1 (en) * | 2008-12-15 | 2010-06-24 | 出光興産株式会社 | Sintered complex oxide and sputtering target comprising same |
WO2012017659A1 (en) * | 2010-08-05 | 2012-02-09 | 三菱マテリアル株式会社 | Method for producing sputtering target, and sputtering target |
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KR101267164B1 (en) * | 2009-06-05 | 2013-05-24 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Oxide sintered body, method for producing same, and starting material powder for producing oxide sintered body |
US20120184066A1 (en) * | 2009-09-30 | 2012-07-19 | Idemitsu Kosan Co., Ltd. | SINTERED In-Ga-Zn-O-TYPE OXIDE |
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JP2007223849A (en) * | 2006-02-24 | 2007-09-06 | Sumitomo Metal Mining Co Ltd | Gallium oxide-based sintered compact and method of manufacturing the same |
WO2009157535A1 (en) * | 2008-06-27 | 2009-12-30 | 出光興産株式会社 | Sputtering target for oxide semiconductor, comprising ingao3(zno) crystal phase and process for producing the sputtering target |
WO2010070832A1 (en) * | 2008-12-15 | 2010-06-24 | 出光興産株式会社 | Sintered complex oxide and sputtering target comprising same |
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JPWO2018179556A1 (en) * | 2017-03-31 | 2019-04-04 | Jx金属株式会社 | Sputtering target and manufacturing method thereof |
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