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WO2012014688A1 - Matériau fritté pour une cible de pulvérisation cathodique à base de zno-mgo - Google Patents

Matériau fritté pour une cible de pulvérisation cathodique à base de zno-mgo Download PDF

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Publication number
WO2012014688A1
WO2012014688A1 PCT/JP2011/066039 JP2011066039W WO2012014688A1 WO 2012014688 A1 WO2012014688 A1 WO 2012014688A1 JP 2011066039 W JP2011066039 W JP 2011066039W WO 2012014688 A1 WO2012014688 A1 WO 2012014688A1
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Prior art keywords
mgo
zno
sputtering target
sintered body
phase
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Japanese (ja)
Inventor
英生 高見
坂本　勝
浩由 山本
友哉 田村
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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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
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/62615—High energy or reactive ball milling
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron

Definitions

  • the present invention relates to a sintered body for a ZnO—MgO sputtering target used for forming a window layer material of a Cu—In—Ga—Se (hereinafter referred to as CIGS) solar cell.
  • CIGS Cu—In—Ga—Se
  • Patent Document 1 discloses a method of forming a thin film to be a window layer by sputtering a sputtering target such as ZnO or (Zn, Mg) O by a magnetron sputtering method.
  • a sputtering target such as ZnO or (Zn, Mg) O
  • a magnetron sputtering method a method of forming a thin film to be a window layer by sputtering a sputtering target such as ZnO or (Zn, Mg) O by a magnetron sputtering method.
  • characteristics such as the structure and density of the sputtering target that affect the sputtering characteristics are not clarified at all.
  • Patent Document 2 discloses that a semiconductor film made of an n-type semiconductor such as ZnO or ZnMgO is used as an n-type window layer of a solar cell. However, the method for producing this ZnO film or ZnMgO film has not been clarified at all.
  • Patent Document 3 discloses that a layer made of an oxide containing Mg and O is formed by sputtering as a window layer of a solar cell. Further, it is described that the composition of the layer can be easily controlled by changing the composition of the sputtering target. However, it is described that the oxide layer is formed using a ZnO target, an MgO target, or a Ga 2 O 3 target, and is not formed using a ZnO—MgO-based alloy target. In addition, the organization is not described at all.
  • Patent Document 4 discloses that in an oxide sintered body target containing zinc oxide as a main component and further containing magnesium, the magnesium content is 0.02 to 0.30 in terms of the Mg / (Zn + Mg) atomic ratio. Describes that a zinc oxide-based transparent conductive film having high chemical resistance to acids and alkalis and having low resistance is obtained.
  • this oxide sintered body preferably has as little composite oxide MgGa 2 O 4 phase and composite oxide MgAl 2 O 4 phase as possible, and does not contain any of them, and only the zinc oxide phase is observed.
  • arcing cannot be sufficiently suppressed in practice.
  • Patent Document 5 discloses an additive element having at least one element type other than zinc (Zn) and oxygen (O) as an element type in a sputtering target for forming a zinc oxide thin film containing zinc oxide as a main component.
  • a sputtering target for forming a zinc oxide thin film wherein the additive element is a compound that does not contain oxygen in the target.
  • the presence of an additive element not containing oxygen in the target is likely to cause arcing.
  • An object of the present invention is to provide a ZnO—MgO-based sputtering target that generates less nodules and particles during sputtering.
  • the present inventors have conducted intensive research.
  • the MgO phase (MgO-rich solid solution phase) is adjusted by adjusting the sintering temperature during pulverization and sintering during raw material powder production. It has been found that a sintered body for a ZnO—MgO-based sputtering target with a fine crystal grain size can be produced, and that when such a target is used, there are few nodules and particles generated during sputtering. It came to complete.
  • the present invention A sintered body for a ZnO-MgO-based sputtering target containing ZnO and MgO, containing 3 to 50 mol% of Mg in terms of MgO, and a maximum crystal grain size of MgO phase (including MgO-rich solid solution phase) of 10 ⁇ m
  • a sintered body for a ZnO-MgO-based sputtering target characterized by having a uniformly dispersed structure, 2.
  • I1 / I2 is 0.02 or less.
  • the ZnO—MgO-based sputtering target according to the present invention has an excellent effect that a film having excellent in-plane uniformity of the film composition can be produced with little generation of nodules and particles even when sputtered for a long time.
  • the Mg content in the sintered body for ZnO—MgO based sputtering target of the present invention is 3 to 50 mol% in terms of MgO. This is because if the content of Mg is less than 3 mol% or exceeds 50 mol% in terms of MgO, a function sufficient as a window layer material of a solar cell cannot be exhibited.
  • the maximum crystal grain size of the MgO phase is 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the maximum crystal grain size is too large, large irregularities are likely to be generated on the surface, and particle generation is likely to increase due to abnormal discharge starting from the surface.
  • the crystal grain size was determined by polishing the surface of a sample collected from an arbitrary part of the sintered body and then analyzing the surface of an electron probe microanalyzer (hereinafter referred to as EPMA) by using an MgO phase (MgO rich). The size of the solid solution phase was measured.
  • EPMA electron probe microanalyzer
  • MgO rich MgO rich
  • the sintered body is processed into, for example, a diameter of 6 inches and a thickness of 6 mm, and indium or the like is pasted on the backing plate as a brazing material, and this is actually sputtered. Can be examined.
  • One of the important points of the sintered body for a ZnO—MgO-based sputtering target of the present invention is to have a structure in which the MgO phase (including the MgO-rich solid solution phase) is uniformly dispersed. This is because it is not preferable that the MgO phase (including the MgO-rich solid solution phase) is locally aggregated because it causes problems such as abnormal discharge and film composition shift.
  • One of the important points of the sintered body for a ZnO—MgO-based sputtering target of the present invention is that the maximum intensity of the X-ray diffraction peak corresponding to the MgO phase (200) is I1, and the X corresponding to the ZnO phase (101).
  • I1 / I2 is 0.02 or less.
  • the intensity of the X-ray diffraction peak was measured by X-ray diffraction (hereinafter referred to as XRD) on the surface of a sample collected from an arbitrary part of the sintered body.
  • XRD X-ray diffraction
  • An intensity ratio I1 / I2 exceeding 0.02 is not preferable because it causes problems such as nodules, abnormal discharge, and film composition deviation during long-time sputtering.
  • the relative density of the sintered body is 95% or more.
  • the relative density is a ratio of values obtained by dividing the actual absolute density of the sintered compact target measured by the Archimedes method by the theoretical density of the target having the composition.
  • a low target relative density means that there are many internal vacancies in the target, so splashing and abnormal discharge starting from the vacancy area occurs when the internal vacancies are exposed during sputtering. It becomes easy to do. For this reason, the number of particles generated on the film increases, and the surface unevenness progresses at an early stage, so that abnormal discharge or the like starting from surface protrusions (nodules) easily occurs. This contributes to a decrease in conversion efficiency of the CIGS solar cell.
  • Example 1 A ZnO powder having a purity of 4 N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3 N and an average particle diameter of 1 ⁇ m was prepared, and the ZnO powder was mixed by 97 mol% and the MgO powder was prepared by 3 mol%. Both powders were mixed with a wet ball mill and uniformly dispersed, and then calcined without calcination, and the powder was finely pulverized with a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • This slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere.
  • the sintering temperature was 1200 ° C.
  • the sintering holding time was 5 hours.
  • Sintering is desirably performed at 1200 ° C to 1500 ° C. This is because the density is difficult to increase outside this temperature range. In particular, when the sintering temperature is low, the MgO phase tends to exist in an aggregated state.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 5 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.01, and a relative density of 99.5%.
  • This sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm to obtain a sputtering target, and RF sputtering was performed.
  • the sputtering power was 500 W
  • the atmosphere gas was argon
  • the gas flow rate was 50 sccm
  • the sputtering pressure was 0.5 Pa.
  • the number of protrusions (nodules) generated on the target surface was counted and found to be 1.2 / cm 2 .
  • Table 1 shows the target characteristics and the results of sputtering evaluation.
  • Example 2 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared.
  • the ZnO powder was prepared at 80 mol% and the MgO powder was prepared at 20 mol%. Both powders were mixed by a wet ball mill and dispersed uniformly, and then calcined at 1100 ° C. The calcination is desirably performed at 1000 ° C. to 1300 ° C. This is because if the temperature is too low, there is almost no effect of calcination, while if the temperature is too high, pulverization becomes difficult.
  • the calcined powder was pulverized by a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • the slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1250 ° C. and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 2 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.02, and a relative density of 97.5%.
  • FIG. 1 shows an SEM image
  • FIG. 2 shows an EPMA image. In both images, it can be seen that the granular portion is the MgO phase (including the MgO-rich solid solution phase), the maximum crystal grain size is 10 ⁇ m or less, and is uniformly dispersed in the target plane.
  • the sintered body was processed to form a sputtering target, RF sputtering was performed, and the number of protrusions (nodules) generated on the target surface was counted to be 1.7 pieces / cm 2 . Very few and good results.
  • Example 3 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared.
  • the ZnO powder was prepared at 80 mol% and the MgO powder was prepared at 20 mol%. Both powders were mixed by a wet ball mill and dispersed uniformly, and then calcined at 1100 ° C. The calcined powder was pulverized by a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • the slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1350 ° C. and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of less than 0.5 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of less than 0.005, and a relative density of 98.2%.
  • Example 2 Under the same conditions as in Example 1, by processing the sintered body, and a sputtering target, performs RF sputtering, was counted the number of projections generated on the target surface (nodules), and 0.5 pieces / cm 2 Very few and good results.
  • Example 4 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared. The ZnO powder was prepared at 65 mol% and the MgO powder was prepared at 35 mol%. Both powders were mixed by a wet ball mill and dispersed uniformly, and then calcined at 1100 ° C. The calcined powder was pulverized by a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • the slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1350 ° C. and the sintering holding time was 5 hours.
  • the maximum crystal grain size was less than 0.5 ⁇ m
  • the X-ray diffraction intensity peak intensity ratio I1 / I2 was less than 0.005
  • the relative density was 96.8%.
  • Example 2 Under the same conditions as in Example 1, by processing the sintered body, and a sputtering target, performs RF sputtering, was counted the number of projections generated on the target surface (nodules), and 0.8 pieces / cm 2 Very few and good results.
  • Example 5 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared.
  • the ZnO powder was prepared at 50 mol% and the MgO powder was prepared at 50 mol%. Both powders were mixed with a wet ball mill and uniformly dispersed, and then calcined, and the powder was finely pulverized with a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • the slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1500 ° C., and the sintering holding time was 5 hours.
  • the maximum grain size of the obtained ZnO—MgO sintered body was 10 ⁇ m, the X-ray diffraction intensity peak intensity ratio I1 / I2 was 0.05, and the relative density was 95%.
  • the sintered body was processed to form a sputtering target, RF sputtering was performed, and the number of protrusions (nodules) generated on the target surface was counted to be 4.8 pieces / cm 2 . There were few good results.
  • a ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared.
  • the ZnO powder was prepared at 80 mol% and the MgO powder was prepared at 20 mol%. Both powders were mixed by a dry method and uniformly dispersed, and then calcined, and the powder was finely pulverized for about 20 hours or more by a dry method to produce a powder of 1 ⁇ m or less.
  • This powder was filled in a 200 ⁇ mold having a predetermined shape, cold-molded, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1200 ° C., and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 15 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.08, and a relative density of 95.5%.
  • the sintered body was processed to form a sputtering target, RF sputtering was performed, and the number of protrusions (nodules) generated on the target surface was counted to be 6.3 / cm 2 . Increased.
  • Example 2 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 2 ⁇ m was prepared.
  • the ZnO powder was prepared at 80 mol% and the MgO powder was prepared at 20 mol%. Both powders were mixed by a dry method and uniformly dispersed, and then calcined, and the powder was finely pulverized for about 20 hours or more by a dry method to produce a powder of 1 ⁇ m or less.
  • This powder was filled in a 200 ⁇ mold having a predetermined shape, cold-molded, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1150 ° C. and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 20 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.1, and a relative density of 94%.
  • the sintered body was processed into a sputtering target, RF sputtering was performed, and the number of protrusions (nodules) generated on the target surface was counted to be 11.3 pieces / cm 2 . Increased.
  • This slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1000 ° C., and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 10 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.06, and a relative density of 94.5%.
  • FIG. 3 shows an SEM image
  • FIG. 4 shows an EPMA image.
  • the granular portion is the MgO phase (including the MgO-rich solid solution phase), and there are some whose maximum crystal grain size exceeds 10 ⁇ m, and it can be seen that they are partially aggregated in the target plane.
  • the sintered body was processed to form a sputtering target, RF sputtering was performed, and the number of protrusions (nodules) generated on the target surface was counted to be 6.4 / cm 2 . Increased.
  • Example 4 A ZnO powder having a purity of 4N and an average particle diameter of 1 ⁇ m was prepared, and an MgO powder having a purity of 3N and an average particle diameter of 1 ⁇ m was prepared.
  • the ZnO powder was prepared at 65 mol% and the MgO powder was prepared at 35 mol%. Both powders were mixed with a wet ball mill and uniformly dispersed, and then calcined without calcination, and the powder was finely pulverized with a wet ball mill for about 20 hours or more to prepare a slurry having a particle size of 1 ⁇ m or less.
  • This slurry was granulated and dried with a spray dryer, filled in a 200 ⁇ mold having a predetermined shape, cold-formed, and sintered at atmospheric pressure in the atmosphere. At this time, the sintering temperature was 1100 ° C. and the sintering holding time was 5 hours.
  • the obtained ZnO—MgO sintered body had a maximum crystal grain size of 10 ⁇ m, an X-ray diffraction intensity peak intensity ratio I1 / I2 of 0.05, and a relative density of 93%.
  • Example 2 Under the same conditions as in Example 1, by processing the sintered body, and a sputtering target, performs RF sputtering, was counted the number of projections generated on the target surface (nodules), and 15.3 pieces / cm 2 Increased.
  • the maximum crystal grain size of the MgO phase is 10 ⁇ m or less.
  • this is used to form a film by one-time sputtering, there is almost no abnormal discharge even when sputtered for a long time, and an excellent effect that a film having excellent in-plane uniformity of the film composition can be obtained. It is what you have.
  • it is useful as a light absorption layer material for thin film solar cells and as a window layer material for CIGS quaternary solar cells.

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Abstract

L'invention concerne un matériau fritté pour une cible de pulvérisation cathodique à base de ZnO-MgO qui comprend du ZnO et du MgO et qui est caractérisé en ce que Mg est contenu dans une quantité de 3-50 % en moles en termes de MgO, une phase de MgO (contenant une phase de solution solide riche en MgO) a le diamètre de particule cristalline le plus large de 10 µm ou moins, et le matériau fritté a une structure dispersée de façon homogène. L'objectif de la présente invention est de fournir un matériau fritté pour une cible de pulvérisation cathodique à base de ZnO-MgO qui subit rarement la formation de nodules ou de particules, même lorsque la pulvérisation cathodique est mise en œuvre pendant une longue période de temps, et qui permet la production d'un film dont la composition a une excellente uniformité dans le plan.
PCT/JP2011/066039 2010-07-30 2011-07-14 Matériau fritté pour une cible de pulvérisation cathodique à base de zno-mgo Ceased WO2012014688A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
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JP2014114207A (ja) * 2012-11-19 2014-06-26 Tosoh Corp 酸化物焼結体、それを用いたスパッタリングターゲット及び酸化物膜
JP2016190757A (ja) * 2015-03-31 2016-11-10 Ｊｘ金属株式会社 ＺｎＯ−ＭｇＯ系スパッタリングターゲット用焼結体及びその製造方法
JP2017151408A (ja) * 2016-02-22 2017-08-31 株式会社タムロン 赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置
WO2020067235A1 (fr) 2018-09-26 2020-04-02 出光興産株式会社 Corps multicouche d'oxyde et son procédé de fabrication
WO2020090867A1 (fr) 2018-10-31 2020-05-07 出光興産株式会社 Corps fritté

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000169956A (ja) * 1998-12-03 2000-06-20 Japan Energy Corp スパッタリング用ＭｇＯターゲット及びその製造方法
WO2000040769A1 (fr) * 1998-12-28 2000-07-13 Japan Energy Corporation Cible de pulverisation cathodique
JP2004259549A (ja) * 2003-02-25 2004-09-16 Rohm Co Ltd 透明電極膜
WO2007141994A1 (fr) * 2006-06-08 2007-12-13 Sumitomo Metal Mining Co., Ltd. Sinter d'oxyde, cible, film conducteur transparent obtenu à partir de celle-ci et base conductrice transparente

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5369444B2 (ja) * 2008-02-06 2013-12-18 住友金属鉱山株式会社 Ｇｚｏ焼結体の製造方法
CN102046835B (zh) * 2008-06-03 2013-01-02 Jx日矿日石金属株式会社 溅射靶及非晶光学薄膜
CN102066025A (zh) * 2008-08-28 2011-05-18 Jx日矿日石金属株式会社 包含贵金属粉末和氧化物粉末的混合粉末的制造方法及包含贵金属粉末和氧化物粉末的混合粉末

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000169956A (ja) * 1998-12-03 2000-06-20 Japan Energy Corp スパッタリング用ＭｇＯターゲット及びその製造方法
WO2000040769A1 (fr) * 1998-12-28 2000-07-13 Japan Energy Corporation Cible de pulverisation cathodique
JP2004259549A (ja) * 2003-02-25 2004-09-16 Rohm Co Ltd 透明電極膜
WO2007141994A1 (fr) * 2006-06-08 2007-12-13 Sumitomo Metal Mining Co., Ltd. Sinter d'oxyde, cible, film conducteur transparent obtenu à partir de celle-ci et base conductrice transparente

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAGAKU DAI JITEN 3, REDUCED-SIZE EDITION 23RD PRINT, 10 November 1979 (1979-11-10), pages 890, 940 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014114207A (ja) * 2012-11-19 2014-06-26 Tosoh Corp 酸化物焼結体、それを用いたスパッタリングターゲット及び酸化物膜
JP2016190757A (ja) * 2015-03-31 2016-11-10 Ｊｘ金属株式会社 ＺｎＯ−ＭｇＯ系スパッタリングターゲット用焼結体及びその製造方法
JP2017151408A (ja) * 2016-02-22 2017-08-31 株式会社タムロン 赤外線透過膜、光学膜、反射防止膜、光学部品、光学系及び撮像装置
WO2020067235A1 (fr) 2018-09-26 2020-04-02 出光興産株式会社 Corps multicouche d'oxyde et son procédé de fabrication
WO2020090867A1 (fr) 2018-10-31 2020-05-07 出光興産株式会社 Corps fritté
CN112912355A (zh) * 2018-10-31 2021-06-04 出光兴产株式会社 烧结体
KR20210080391A (ko) 2018-10-31 2021-06-30 이데미쓰 고산 가부시키가이샤 소결체
US11434172B2 (en) 2018-10-31 2022-09-06 Idemitsu Kosan Co., Ltd. Sintered body

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