WO2020044796A1 - Cible de pulvérisation et procédé de production de cible de pulvérisation - Google Patents

Cible de pulvérisation et procédé de production de cible de pulvérisation Download PDF

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WO2020044796A1
WO2020044796A1 PCT/JP2019/026945 JP2019026945W WO2020044796A1 WO 2020044796 A1 WO2020044796 A1 WO 2020044796A1 JP 2019026945 W JP2019026945 W JP 2019026945W WO 2020044796 A1 WO2020044796 A1 WO 2020044796A1
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powder
oxide
phase
sputtering target
metal
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PCT/JP2019/026945
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English (en)
Japanese (ja)
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啓太 梅本
齋藤　淳
孝典 白井
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三菱マテリアル株式会社
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Priority to CN201980054614.9A priority Critical patent/CN112585296A/zh
Priority to KR1020217005739A priority patent/KR20210049815A/ko
Publication of WO2020044796A1 publication Critical patent/WO2020044796A1/fr

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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
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    • 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
    • C04B35/45—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 copper oxide or solid solutions thereof with other oxides
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • 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
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • 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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/407—Copper
    • 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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron

Definitions

  • the present invention relates to a sputtering target used for forming an oxide film, and a method for manufacturing the sputtering target.
  • a sputtering target used for forming an oxide film
  • a method for manufacturing the sputtering target Priority is claimed on Japanese Patent Application No. 2018-159246, filed on August 28, 2018, the content of which is incorporated herein by reference.
  • sensing electrodes are formed for touch position detection.
  • This sensing electrode is usually formed by patterning, and an X electrode extending in the X direction and a Y electrode extending in the Y direction orthogonal to the X direction are formed on one surface of the transparent substrate. And these are arranged in a grid.
  • the pattern of the electrode is visually recognized from the outside because the metal film has a metallic luster. For this reason, it is conceivable that the visibility of the electrode is reduced by forming a low-reflectance film having a low visible light reflectance on the metal thin film.
  • a color filter for color display is employed.
  • a black member called a black matrix is formed for the purpose of improving contrast and color purity and improving visibility.
  • the above-described low-reflectance film can also be used as this black matrix (hereinafter, referred to as “BM”).
  • a back electrode of the solar cell when sunlight is incident through a glass substrate or the like, a back electrode of the solar cell is formed on the opposite side.
  • a metal film such as molybdenum (Mo) or silver (Ag) is used.
  • Mo molybdenum
  • Ag silver
  • Patent Literatures 1 and 2 propose an oxide film suitable as the above-described low reflectance film and a sputtering target used for forming the oxide film.
  • a metal element one or two of Mo and In and one or two of Cu and Fe are used as main components, and these metal elements are used. Is partially or entirely made of an oxide.
  • the sputtering target described in Patent Document 2 contains Fe and Mo as metal elements, and some or all of these metal elements exist in the form of oxides, and the oxide phase contains Fe-Mo. It is supposed that the compound contains an -O-based compound.
  • the sputtering target for forming the above oxide film when the density ratio is low, vacancies are formed inside, and abnormal discharge is likely to occur during sputtering film formation.
  • the sputtering target for forming the above oxide film when the sintering temperature is set high to improve the density ratio, the oxide powder is reduced and the composition of the sputtering target after sintering is reduced. There was a risk of instability.
  • the pressure load is increased in order to increase the density ratio of the sputtering target, there is a problem that the sputtering target made of an oxide is cracked and the production yield is reduced.
  • it is difficult to sufficiently improve the density ratio because the melting point of the oxide powder is high and the sinterability is insufficient. Was.
  • the present invention has been made in view of the above-described circumstances, and provides a sputtering target having a sufficiently high density ratio and capable of stably forming an oxide film by sputtering, and a method for manufacturing the sputtering target.
  • the purpose is to do.
  • a sputtering target of the present invention contains Cu and In as metal components, has a composite structure of a metal phase and an oxide phase, and has an area ratio of the oxide phase of 5% or more. It is characterized by being within a range of 96% or less and a density ratio of 90% or more.
  • the sputtering target having this configuration Cu and In are contained as metal components, and the composite target has a composite structure of a metal phase and an oxide phase. Therefore, an oxide film containing Cu and In as metal components is formed by sputtering. It becomes possible to film. Further, since the density ratio is set to 90% or more, it is possible to suppress occurrence of abnormal discharge caused by holes. Further, according to the sputtering target having this configuration, the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is in the range of 5% or more and 96% or less. Are secured, the discharge state is stabilized on the entire target sputtering surface, and occurrence of abnormal discharge can be suppressed.
  • the content of Cu in the metal component is in the range of 10 at% to 90 at%.
  • an oxide film having a composition in which the content of Cu in the metal component is in the range of 10 atomic% to 90 atomic% can be formed, the visible light reflectance is low, and the low reflectance is low.
  • An oxide film that can be used as a film can be reliably formed.
  • the sputtering target of the present invention may have a structure in which the metal phase is dispersed in a matrix composed of the oxide phase, and the average particle diameter of the metal phase is 56 ⁇ m or less.
  • the metal phase since the average particle size of the metal phase dispersed in the matrix composed of the oxide phase is limited to 56 ⁇ m or less, the metal phase is not locally aggregated, and the discharge state is generated on the entire target sputtering surface. And the occurrence of abnormal discharge can be further suppressed.
  • the sputtering target of the present invention may have a structure in which the oxide phase is dispersed in a matrix composed of the metal phase, and the average crystal particle diameter of the metal phase is 100 ⁇ m or less.
  • the structure is such that the oxide phase is dispersed in the matrix composed of the metal phase, and the average crystal grain size of the metal phase, which is the matrix, is limited to 100 ⁇ m or less. Generation can be suppressed, and manufacturing yield can be improved.
  • the sputtering proceeds, no large irregularities are formed on the target sputtering surface, the occurrence of abnormal discharge can be suppressed, and the sputtering film can be stably formed.
  • the method for manufacturing a sputtering target according to the present invention is a method for manufacturing a sputtering target for manufacturing the above-described sputtering target, comprising: a metal powder comprising one or both of a Cu powder and a Cu—In alloy powder; An oxide powder composed of one or both of 2 O 3 powders, and a ratio D M / D O of the median diameter D M of the metal powder to the median diameter D O of the oxide powder is 0.1.
  • a metal powder composed of one or both of a Cu powder and a Cu—In alloy powder, and an oxide composed of one or both of a CuO powder and an In 2 O 3 powder
  • a ratio of the median diameter D M of the metal powder to the median diameter D O of the oxide powder D M / D O is in the range of 0.5 to 200. Since sintering is used, voids are eliminated by sintering, filling voids between oxide powders while deforming a ductile metal phase, thereby reliably improving the density ratio. Can be.
  • the sintering step is performed in which the sintering raw material powder is pressed and heated to a temperature of less than 1000 ° C. to obtain a sintered body. Is relatively low, and reduction of oxide powder can be suppressed.
  • the oxide powder preferably has a median diameter D O of 5 ⁇ m or less.
  • the median diameter D O of the oxide powder is relatively fine, that is, 5 ⁇ m or less, the contact area between the oxide powders increases, the sinterability can be improved, and the density ratio can be improved. It is possible to further improve.
  • a sputtering target having a sufficiently high density ratio and capable of stably forming an oxide film by sputtering, and a method for manufacturing the sputtering target.
  • FIG. 3 is an explanatory view showing a structure in which a metal phase is dispersed in a matrix composed of an oxide phase in the sputtering target according to one embodiment of the present invention.
  • FIG. 3 is an explanatory view showing a structure in which an oxide phase is dispersed in a parent phase composed of a metal phase in the sputtering target according to one embodiment of the present invention. It is a flow figure showing the manufacturing method of the sputtering target concerning one embodiment of the present invention.
  • the sputtering target according to the present embodiment contains Cu and In as metal components and has a composite structure of a metal phase and an oxide phase.
  • the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is in the range of 5% to 96%, and the density ratio is 90% or more.
  • it is preferable that the content of Cu in the metal component is in the range of 10 at% to 90 at%.
  • the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is in the range of 5% or more and 96% or less.
  • the ratio is high, the structure is such that the metal phase is dispersed in the matrix composed of the oxide phase.
  • the ratio of the metal phase is high, the structure is such that the oxide phase is dispersed in the matrix composed of the metal phase.
  • FIG. 1 is an example of a structure in which the metal phase is dispersed in a matrix composed of an oxide phase, and is a structure in which a metal phase 12 is dispersed in a matrix composed of an oxide phase 11.
  • the average particle size of the dispersed metal phase 12 (that is, the size of the dispersed metal phase 12 itself) is preferably 56 ⁇ m or less.
  • FIG. 2 is an actual example of a structure in which an oxide phase is dispersed in a matrix composed of a metal phase, and is a structure in which an oxide phase 11 is dispersed in a matrix composed of a metal phase 12.
  • the average crystal grain size in the metal phase 12, which is the parent phase be 100 ⁇ m or less.
  • the area ratio of the oxide phase, the density ratio, the content of Cu in the metal component, the average particle size of the dispersed metal phase, the average crystal particle of the metal phase as the parent phase The reason for defining the diameter as described above will be described.
  • the sputtering target according to the present embodiment has a composite structure of a metal phase and an oxide phase, and the density ratio is improved by the metal phase.
  • the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is less than 5%, an oxide phase having a higher electric resistance than the metal phase is present in isolation. An abnormal discharge may occur during sputtering due to the oxide phase.
  • the area ratio of the oxide phase exceeds 96% of the area of the cut and polished surface of the sputtering target, the metal phase is insufficient, and the density ratio may not be sufficiently improved. From the above, in the present embodiment, the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is set in the range of 5% or more and 96% or less.
  • the lower limit of the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is preferably 15% or more, and 30% or less. It is more preferable to make the above.
  • the upper limit of the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is preferably set to 90% or less, more preferably 85% or less.
  • the density ratio of the sputtering target When the density ratio of the sputtering target is low, there are many holes inside, and abnormal discharge may easily occur during sputtering film formation. In particular, in a sputtering target composed of an oxide phase, the density ratio tends to be low due to insufficient sinterability of the oxide, and abnormal discharge is likely to occur. Therefore, in the sputtering target according to the present embodiment, the density ratio is set to 90% or more.
  • the density ratio is preferably at least 92%, more preferably at least 94%.
  • the density ratio refers to an area ratio of a portion other than a hole in a value obtained by calculating an area ratio between a hole and another portion on a cut and polished surface of a sputtering target.
  • An oxide film formed using the sputtering target of this embodiment has a composition equivalent to that of the above-described sputtering target.
  • the sputtering target according to the present embodiment when the content of Cu in the metal component is in the range of 10 atomic% to 90 atomic%, the average reflectance in visible light (wavelength 400 to 800 nm) is reduced.
  • an oxide film having a sufficiently low reflectance can be formed.
  • the lower limit of the Cu content in the metal component of the sputtering target is preferably set to 20 atom% or more, and 30 atom% or more. More preferably, Further, the upper limit of the content of Cu in the metal component is preferably set to 80 atomic% or less, more preferably 70 atomic% or less.
  • a sputtering target having a structure in which a metal phase is dispersed in a matrix composed of an oxide phase by reducing the average particle size of the dispersed metal phase, a locally low electric resistance portion may be present on the target sputtering surface. Instead, the discharge state is stabilized on the entire target sputtering surface, and it is possible to suppress the occurrence of abnormal discharge during sputtering film formation. Therefore, when the sputtering target of the present embodiment has a structure in which the metal phase is dispersed in the matrix composed of the oxide phase, it is preferable to limit the average particle diameter of the dispersed metal phase to 56 ⁇ m or less.
  • the average particle size of the metal phase dispersed in the matrix composed of the oxide phase is preferably 45 ⁇ m or less, and more preferably 35 ⁇ m or less.
  • the average crystal particle diameter of the metal phase that is the parent phase is limited to 100 ⁇ m or less. Is preferred.
  • the average crystal particle diameter of the metal phase as the parent phase is preferably 75 ⁇ m or less, more preferably 50 ⁇ m or less.
  • a metal powder composed of one or both of Cu powder and In—Cu alloy powder, and an oxide powder composed of one or both of CuO powder and In 2 O 3 powder are prepared.
  • the Cu powder preferably has a purity of 99.99 mass% or more.
  • the In—Cu alloy powder it is preferable to use one having a Cu content in the range of 5 mass% to 50 mass% and the balance being In and unavoidable impurities.
  • the CuO powder preferably has a purity of 99 mass% or more.
  • the In 2 O 3 powder preferably has a purity of 99 mass% or more.
  • the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder is in the range of 0.5 to 200. Adjust to be inside.
  • the median diameter D O of the oxide powder is preferably 5 ⁇ m or less.
  • D50 (median diameter) is a particle diameter at which the cumulative frequency becomes 50% in the particle diameter distribution measurement.
  • median diameter D O of the oxide powder the median diameter D In2 O3 median diameter D CuO and In 2 O 3 powder CuO powder oxide It is calculated as follows from the mass ratio W CuO of the CuO powder in the material powder and the mass ratio W In2O3 of the In 2 O 3 powder in the oxide powder.
  • D O (D CuO ⁇ W CuO + D In2O3 ⁇ W In2O3 )
  • the above-mentioned metal powder and oxide powder are mixed at a predetermined ratio to obtain a sintering raw material powder.
  • a mixing device such as a ball mill.
  • (Sintering step S02) the above-mentioned sintering raw material powder is sintered by heating while applying pressure to obtain a sintered body.
  • a hot press is used.
  • the voids between the oxide powders are filled while the ductile metal phase is deformed, so that pores are eliminated from the sintered body, and the density ratio of the sputtering target is improved. Will be.
  • the sintering temperature in the sintering step S02 is lower than 1000 ° C., the holding time at the sintering temperature is within a range of 0.5 to 10 hours, and the pressure is 5 MPa to 50 MPa.
  • the obtained sintered body is machined so as to have a predetermined size.
  • the sputtering target according to the present embodiment is manufactured.
  • a sintered body is manufactured by pressing and heating a sintering raw material powder obtained by mixing a metal powder and an oxide powder.
  • the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder is less than 0.5, the voids between the oxide powders are filled with fine metal powder.
  • the voids between the oxide powders cannot be filled while the ductile metal phase is deformed, and the voids cannot be efficiently eliminated, There is a possibility that the density ratio cannot be improved.
  • the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder is set in the range of 0.5 to 200. .
  • the upper limit of the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder is preferably 150 or less, more preferably 100 or less.
  • the median diameter D O of oxide powder is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the sintering temperature is less than 1000 ° C. Thereby, in the sintering step S02, reduction of the oxide powder can be suppressed, and a sputtering target having a predetermined composition and structure can be manufactured.
  • the upper limit of the sintering temperature is preferably lower than 980 ° C, more preferably lower than 950 ° C.
  • the lower limit of the sintering temperature is preferably 800 ° C. or higher, more preferably 850 ° C. or higher.
  • the holding time at the sintering temperature By setting the holding time at the sintering temperature in the range of 0.5 hours or more and 10 hours or less, sintering can be reliably advanced.
  • the lower limit of the holding time at the sintering temperature is preferably at least 1 hour, more preferably at least 2 hours.
  • the upper limit of the holding time at the sintering temperature is preferably 8 hours or less, and more preferably 6 hours or less.
  • the density ratio can be sufficiently improved.
  • the lower limit of the pressure is preferably 10 MPa or more, and more preferably 15 MPa or more.
  • the upper limit of the pressurizing pressure is preferably at most 48 MPa, more preferably at most 45 MPa.
  • the density ratio is set to 90% or more, it is possible to suppress occurrence of abnormal discharge due to holes. Further, since the area ratio of the oxide phase in the area of the cut and polished surface of the sputtering target is in the range of 5% or more and 96% or less, the areas of the metal phase and the oxide phase are secured, respectively. The discharge state is stabilized on the entire sputtering surface, and occurrence of abnormal discharge can be suppressed.
  • the present embodiment when the content of Cu in the metal component is in the range of 10 atomic% to 90 atomic%, an oxide film having the above composition can be formed, The reflectance of visible light is low, and an oxide film suitable for a low reflectance film can be reliably formed.
  • the structure is such that a metal phase is dispersed in a matrix composed of an oxide phase, and when the average particle size of the metal phase is 56 ⁇ m or less, the metal phase is locally formed. It is not agglomerated, the discharge state is stable on the entire target sputter surface, and the occurrence of abnormal discharge during sputter film formation can be suppressed, and the sputter film can be stably formed.
  • the sputtering target of the present embodiment when the oxide phase is dispersed in a parent phase composed of a metal phase, and the average crystal grain size of the parent metal phase is 100 ⁇ m or less, the sputtering The generation of large irregularities in the parent phase of the metal phase when the gas progresses can be suppressed, and the occurrence of abnormal discharge can be suppressed. In addition, workability is improved, generation of cracks when processing a sintered body to produce a sputtering target can be suppressed, and production yield can be improved.
  • a metal powder composed of one or both of Cu powder and Cu—In alloy powder, and a metal powder composed of one or both of CuO powder and In 2 O 3 powder are used.
  • the ductile metal phase deforms and fills the voids between the oxide powders during sintering, eliminating pores during sintering and ensuring a density ratio. Can be improved.
  • the sintering raw material powder is heated to a temperature of less than 1000 ° C. while being pressed, so that the sintering temperature can be relatively low, and reduction of the oxide powder can be suppressed. Can be. Further, since the above-mentioned sintering raw material powder is used, even if the sintering temperature is lower than 1000 ° C., the density ratio can be sufficiently improved.
  • the median diameter D O of the oxide powder when the median diameter D O of the oxide powder is set to 5 ⁇ m or less, the contact area between the oxide powders increases, the sinterability can be improved, and the density ratio can be further improved. It is possible to do.
  • a metal powder (Cu has a purity of 99.99% by mass or more) and an oxide powder (all have a purity of 99% by mass or more) shown in Table 1 are prepared, and a total of 2 kg is weighed so as to have a compounding amount shown in Table 1, respectively. And 6 kg of the zirconia balls were charged into a ball mill container and mixed using a ball mill to obtain a sintering raw material powder. The median diameter D M of the metal powder and the median diameter D O of the oxide powder were calculated using the equations described in the section of the embodiment.
  • the obtained sintering raw material powder is filled in a carbon mold for hot pressing, the sintering temperature is 950 ° C., the holding time at the sintering temperature is 3 hours, and the pressing pressure is 35 MPa.
  • the obtained sintered body was machined to a size of 152.4 mm in diameter and 6 mm in thickness. This was soldered to a backing plate using an In solder material.
  • the average crystal grain size, the state of occurrence of cracks during processing, the number of abnormal discharges during sputtering film formation, and the reflectance of the formed oxide film were evaluated as follows.
  • a sample having a size of 10 mm ⁇ 10 mm ⁇ 5 mmt was collected from the obtained sintered body, the cut surface was polished, and a composition image and an element mapping image of Cu, In, and O were obtained using an electron probe microanalyzer (EPMA).
  • EPMA electron probe microanalyzer
  • the metal phase and the oxide phase are distinguished from each other, and the image analysis software WinRoof (manufactured by Mitani Corporation) converts the captured image into monochrome, and binarizes the image with a threshold setting in which hue, lightness, and saturation are adjusted.
  • the area ratio of the oxide phase to the entire image was calculated.
  • a silver film with a thickness of 200 nm was formed over a glass substrate, and an oxide film was formed with a thickness of 50 nm over the silver film using the above-described sputtering target.
  • the reflectance of the stacked film of the silver film and the oxide film formed on the glass substrate as described above was measured. Using a spectrophotometer (U4100 manufactured by Hitachi, Ltd.), measurement was performed at a wavelength of 400 to 800 nm from the side of the formed film. The average value of the measured reflectance was defined as “average reflectance of the oxide film”.
  • Comparative Example 1 In Comparative Example 1 in which the metal powder was not used and the area ratio of the oxide phase was 100%, the density ratio was as low as 81.2% and the number of abnormal discharges was as large as 125 times. In addition, cracks were observed during processing. It is presumed that the sinterability was insufficient and that many pores existed inside. In Comparative Example 2 in which the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder was 0.3, the density ratio was as low as 87.4%, and the number of abnormal discharges Increased to 64 times. It is presumed that at the time of sintering, the voids between the oxide powders could not be filled while the ductile metal phase deformed, and the voids could not be efficiently eliminated.
  • Comparative Example 3 in which the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder was 217, the density ratio was as low as 83.6%, and the number of abnormal discharges was 74. More times. It is presumed that the number of oxide powders in contact with the metal powder during sintering was small, and the voids between the oxide powders could not be sufficiently filled with the metal phase. In Comparative Example 4 in which the area ratio of the oxide phase was 4.0%, the number of abnormal discharges increased to 43. It is presumed that an oxide phase having a higher electric resistance than the metal phase was present in isolation, and abnormal discharge occurred due to the oxide phase.
  • the ratio D M / D O between the median diameter D M of the metal powder and the median diameter D O of the oxide powder is in the range of 0.5 to 200, and the density ratio is 90% or more
  • the area ratio of the phase was in the range of 5% or more and 96% or less
  • the number of abnormal discharges was as small as 15 times or less, and no crack was observed during processing.
  • the average particle diameter of the matrix metal was relatively large at 111 ⁇ m, and although cracks were observed after processing, no effect on abnormal discharge was observed.
  • the average reflectance of the formed oxide film was 21% or less, and an oxide film usable as a low reflectance film could be formed.
  • Example 8 of the present invention Comparing Inventive Example 3 with Inventive Example 7, it was confirmed that the occurrence of abnormal discharge could be further suppressed by setting the average particle diameter of the metal phase to 56 ⁇ m or less when the parent phase was an oxide phase.
  • the number of abnormal discharges was slightly increased because the density ratio was lower than that of the other examples of the present invention.
  • a sputtering target having a sufficiently high density ratio and capable of stably forming an oxide film by sputtering, and a method for manufacturing the sputtering target.

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Abstract

La présente invention concerne une cible de pulvérisation qui contient du Cu et et de l'In en tant que composants métalliques, et est composée d'une structure composite qui comprend une phase métallique (12) et une phase oxyde (11), la phase oxyde (11) ayant un pourcentage de surface dans une plage de 5 à 96 % et ayant un rapport de densité d'au moins 90 %. Le procédé de production de cible de pulvérisation selon la présente invention comprend : une étape de formation de poudre de matière première de frittage (S01) pour obtenir une poudre de matière première de frittage qui comprend une poudre métallique comprenant de la poudre de Cu et/ou de la poudre d'alliage In-Cu et une poudre d'oxyde comprenant de la poudre de CuO et/ou de la poudre d'In2O3, le rapport DM/DO d'un diamètre médian DM de la poudre métallique sur un diamètre médian DO de la poudre d'oxyde se situant dans une plage de 0,5 à 200 ; et une étape de frittage (S02) pour obtenir un corps fritté par application d'une pression sur la poudre de matière première de frittage et chauffage de ladite poudre de matière première jusqu'à une température inférieure à 1000° C.
PCT/JP2019/026945 2018-08-28 2019-07-08 Cible de pulvérisation et procédé de production de cible de pulvérisation WO2020044796A1 (fr)

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JP2014237889A (ja) * 2013-05-07 2014-12-18 三菱マテリアル株式会社 薄膜形成用スパッタリングターゲット及びその製造方法
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