+

WO2014112369A1 - Cible de pulvérisation, couche mince d'oxydes semi-conducteurs et procédé de fabrication de celles-ci - Google Patents

Cible de pulvérisation, couche mince d'oxydes semi-conducteurs et procédé de fabrication de celles-ci Download PDF

Info

Publication number
WO2014112369A1
WO2014112369A1 PCT/JP2014/000149 JP2014000149W WO2014112369A1 WO 2014112369 A1 WO2014112369 A1 WO 2014112369A1 JP 2014000149 W JP2014000149 W JP 2014000149W WO 2014112369 A1 WO2014112369 A1 WO 2014112369A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
compound represented
sputtering
sputtering target
structural compound
Prior art date
Application number
PCT/JP2014/000149
Other languages
English (en)
Japanese (ja)
Inventor
一晃 江端
望 但馬
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to JP2014557405A priority Critical patent/JPWO2014112369A1/ja
Publication of WO2014112369A1 publication Critical patent/WO2014112369A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
    • H10D30/6756—Amorphous oxide semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D99/00—Subject matter not provided for in other groups of this subclass
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
    • 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
    • C04B2235/02—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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • 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
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • 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
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/762—Cubic symmetry, e.g. beta-SiC
    • C04B2235/763—Spinel structure AB2O4
    • 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
    • C04B2235/77—Density
    • 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
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation

Definitions

  • the present invention relates to a sputtering target, an oxide semiconductor thin film, and a manufacturing method thereof. More specifically, the present invention relates to a sputtering target containing indium element (In), tin element (Sn), zinc element (Zn), and aluminum element (Al), a thin film manufactured using the target, and a thin film transistor including the thin film.
  • a sputtering target containing indium element (In), tin element (Sn), zinc element (Zn), and aluminum element (Al)
  • Al aluminum element
  • TFTs thin film transistors
  • LCD liquid crystal display devices
  • EL electroluminescence display devices
  • FED field emission displays
  • a silicon semiconductor compound As a material for a semiconductor layer (channel layer) which is a main member of a field effect transistor, a silicon semiconductor compound is most widely used.
  • a silicon single crystal is used for a high-frequency amplifying element or an integrated circuit element that requires high-speed operation.
  • an amorphous silicon semiconductor (amorphous silicon) is used for a liquid crystal driving element or the like because of a demand for a large area.
  • an amorphous silicon thin film can be formed at a relatively low temperature, its switching speed is slower than that of a crystalline thin film, so when used as a switching element for driving a display device, it may not be able to follow the display of high-speed movies. is there.
  • amorphous silicon having a mobility of 0.5 to 1 cm 2 / Vs could be used, but when the resolution is SXGA, UXGA, QXGA or higher, 2 cm 2 / Mobility greater than Vs is required.
  • the driving frequency is increased in order to improve the image quality, higher mobility is required.
  • the crystalline silicon-based thin film has a high mobility, there are problems such as requiring a large amount of energy and the number of processes for manufacturing, and a problem that it is difficult to increase the area. For example, when annealing a silicon-based thin film, laser annealing using a high temperature of 800 ° C. or higher and expensive equipment is necessary. In addition, since the crystalline silicon-based thin film is normally limited to the top gate configuration of the TFT, the cost reduction such as reduction of the number of masks is difficult.
  • a thin film transistor using an oxide semiconductor film made of indium oxide, zinc oxide, and gallium oxide has been studied.
  • such an oxide semiconductor thin film is produced by sputtering using a target (sputtering target) made of an oxide sintered body.
  • a target made of the above oxide sintered body for example, a target made of a homologous crystal structure compound represented by In 2 Ga 2 ZnO 7 and / or InGaZnO 4 is known (Patent Documents 1, 2, and 3).
  • Patent Documents 1, 2, and 3 a target made of a homologous crystal structure compound represented by In 2 Ga 2 ZnO 7 and / or InGaZnO 4
  • Patent Documents 1, 2, and 3 in order to increase the sintering density (relative density) of the target, it is necessary to sinter in an oxidizing atmosphere.
  • Patent Document 4 a thin film transistor using an amorphous oxide semiconductor film made of indium oxide and zinc oxide without containing gallium has also been proposed (Patent Document 4).
  • Patent Document 4 a sputtering target for a protective layer of an optical information recording medium in which an additive element such as Ta, Y and Si is added to an In 2 O 3 —SnO 2 —ZnO-based oxide mainly composed of tin oxide has been studied ( Patent Documents 5 and 6).
  • these targets are not for oxide semiconductors, and there are problems that aggregates of insulating materials are easily formed, resistance values are increased, and abnormal discharge is likely to occur.
  • JP-A-8-245220 JP 2007-73312 A International Publication No. 2009/084537 Pamphlet International Publication No. 2005/088726 Pamphlet International Publication No. 2005/0778152 Pamphlet International Publication No. 2005/078153 Pamphlet
  • a sputtering target containing a homologous structural compound represented by (ZnO) m (m is 0.1 to 10), a bixbite structural compound represented by In 2 O 3 and a spinel structural compound represented by Zn 2 SnO 4 It was found that a TFT having a high relative density and a low resistance and using a thin film manufactured using the target for the channel layer showed high reliability, and the present invention was completed.
  • the following sputtering target and the like are provided.
  • It consists of an oxide containing indium element (In), tin element (Sn), zinc element (Zn) and aluminum element (Al),
  • a sputtering target comprising a homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10), a bixbite structural compound represented by In 2 O 3 , and a spinel structural compound represented by Zn 2 SnO 4 .
  • the homologous structural compound represented by InAlO 3 (ZnO) m is a homologous structural compound represented by InAlZn 4 O 7 , a homologous structural compound represented by InAlZn 3 O 6 , or InAlZn 2 O 5.
  • the homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) is one or more selected from a homologous structural compound represented by InAlZn 2 O 5 and a homologous structural compound represented by InAlZnO 4 2.
  • the sputtering target according to any one of 1 to 4 comprising a homologous structural compound represented by Zn 2 In 2 O 5 or a spinel structural compound represented by ZnAl 2 O 4 . 6).
  • 11. 11 The method for producing an oxide semiconductor thin film according to 10, wherein the mixed gas is a mixed gas containing at least water vapor and a rare gas.
  • the substrate is sequentially transferred to a position facing three or more targets arranged in parallel in the vacuum chamber at a predetermined interval, and a negative potential and a positive potential are alternately applied to each target from an AC power source. In this case, plasma is generated on the target while switching the target to which a potential is applied between two or more targets that are branched and connected to at least one of the outputs from the AC power source.
  • a display device comprising the thin film transistor according to 16 or 17.
  • the sputtering target for oxide semiconductors of a high density and a low resistance can be provided.
  • a highly reliable thin film transistor can be provided.
  • FIG. 3 is an X-ray diffraction chart of the sintered body obtained in Example 1.
  • FIG. 3 is an X-ray diffraction chart of a sintered body obtained in Example 2.
  • FIG. 4 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 3.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 4.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 5.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 6.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 7.
  • FIG. 6 is a diagram showing an X-ray diffraction chart of a sintered body obtained in Example 8.
  • FIG. 6 is a view showing an X-ray diffraction chart of a sintered body obtained in Example 25.
  • FIG. 6 is a view showing an X-ray diffraction chart of a sintered body obtained in Example 26.
  • FIG. It is a figure which shows the sputtering device used for one Embodiment of this invention.
  • the sputtering target of the present invention is made of an oxide containing indium element (In), tin element (Sn), zinc element (Zn), and aluminum element (Al).
  • InAlO 3 (ZnO) m (m is 0.1 To 10), a bixbite structure compound represented by In 2 O 3 , and a spinel structure compound represented by Zn 2 SnO 4 .
  • the sputtering target of the present invention includes a homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10), a bixbite structural compound represented by In 2 O 3 , and a spinel represented by Zn 2 SnO 4. By including the structural compound at the same time, it becomes a high-density and low-resistance target.
  • the sputtering target of the present invention having high density and low resistance can suppress the occurrence of abnormal discharge during sputtering, and can form a high-quality oxide semiconductor thin film efficiently, inexpensively and with energy saving. .
  • the homologous structure compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) included in the target of the present invention is different from the homologous crystal structure in that it has a long period in which several crystal layers of different substances are stacked. It is a crystal structure consisting of a “natural superlattice” structure.
  • the homologous crystal structure compound is a single crystal or a mixed crystal in which each layer is uniformly mixed depending on the combination of the chemical composition and thickness of each layer. Inherent properties that are different from the properties of
  • RAO 3 (MO) m As an oxide crystal having a homologous crystal structure, an oxide crystal represented by RAO 3 (MO) m can be given.
  • R is a positive trivalent metal element, and examples thereof include In, Ga, Al, Fe, and B.
  • A is a positive trivalent metal element different from R, and examples thereof include Ga, Al, and Fe.
  • M is a positive divalent metal element, and examples thereof include Zn and Mg.
  • In the homologous structure compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) R is In, A is Al, and M is Zn.
  • m is preferably 0.1 to 10, more preferably 0.5 to 8, and further preferably 1 ⁇ 7.
  • M is preferably an integer.
  • the homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) is preferably a homologous structural compound represented by InAlZn 4 O 7 , a homologous structural compound represented by InAlZn 3 O 6 , or InAlZn 2
  • the homologous crystal structure compound represented by InAlO 3 (ZnO) m contained in the target may be a single type or a mixture of two or more types.
  • the homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) is preferably one or more selected from a homologous structural compound represented by InAlZn 2 O 5 and a homologous structural compound represented by InAlZnO 4 It is.
  • the homologous structural compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10) is preferably a homologous structural compound represented by InAlZn 2 O 5 and a homologous structural compound represented by InAlZnO 4 .
  • the target of the present invention preferably contains a homologous structural compound represented by Zn 2 In 2 O 5 or a spinel structural compound represented by ZnAl 2 O 4 .
  • the homologous structure compound in the target can be confirmed by X-ray diffraction.
  • the X-ray diffraction pattern in the powder obtained by pulverizing the target matches the crystal structure X-ray diffraction pattern of the homologous phase assumed from the composition ratio. It can be confirmed from.
  • the crystal structure X-ray diffraction pattern of the homologous phase obtained from JCPDS (Joint Committee of Powder Diffraction Standards) card or ICSD (The Inorganic Crystal Structure Database) can be confirmed.
  • the JCPDS database peak pattern in X-ray diffraction is, for example, as follows: Homologous structure represented by InAlZnO 4 : No. in JCPDS database A homologous structure represented by a peak pattern of 40-0258 or a similar (shifted) pattern InAlZn 2 O 5 : No. JCPDS database 40-0259 peak pattern or similar (shifted) pattern Homologous structure represented by InAlZn 3 O 6 : No. of JCPDS database A homologous structure represented by a peak pattern of 40-0260 or a similar (shifted) pattern InAlZn 4 O 7 : No. JCPDS database 40-0261 peak pattern or similar (shifted) pattern
  • bixbite is also referred to as a rare earth oxide C-type or Mn 2 O 3 (I) -type oxide.
  • the stoichiometric ratio is M 2 X 3 (M is a cation, X is an anion, usually an oxygen ion), and one unit cell is composed of 16 molecules of M 2 X 3 and a total of 80 atoms (M is 32, X is 48) Yes.
  • Bixbite structure compounds include substituted solid solutions in which atoms and ions in the crystal structure are partially substituted with other atoms, and interstitial solid solutions in which other atoms are added to interstitial positions.
  • the bixbite structure compound represented by In 2 O 3 in the target can be confirmed by X-ray diffraction.
  • the bixbite structure compound represented by In 2 O 3 is X-ray diffraction and has a No. of JCPDS database. A peak pattern of 06-0416 or a similar (shifted) pattern is shown.
  • the spinel structure compound represented by Zn 2 SnO 4 contained in the target of the present invention is usually AB 2 X 4 as disclosed in “Crystal Chemistry” (Kodansha, Mitsuko Nakahira, 1973) and the like.
  • Type or A 2 BX 4 type structure and a compound having such a crystal structure is called a spinel structure compound.
  • anions usually oxygen
  • cations are present in a part of the tetrahedral gap and octahedral gap.
  • a substituted solid solution in which atoms or ions in the crystal structure are partially substituted with other atoms, and an interstitial solid solution in which other atoms are added to interstitial positions are also included in the spinel structure compound.
  • the spinel structure compound represented by Zn 2 SnO 4 in the target can be confirmed by observing the peak of the spinel structure compound by X-ray diffraction measurement.
  • the spinel structure compound represented by Zn 2 SnO 4 is X-ray diffraction and has a No. of JCPDS database. A peak pattern of 24-1470 or a similar (shifted) pattern is shown.
  • the atomic ratio of each element preferably satisfies the following formulas (1) to (4).
  • the target described later Relative density of 98% or more and bulk resistance of 10 m ⁇ cm or less.
  • the target resistance can be prevented from increasing, so that abnormal discharge is unlikely to occur during sputtering film formation, and film formation is easy to stabilize.
  • the atomic ratio of the Sn element is 0.40 or less, it is possible to prevent the solubility of the obtained thin film in the wet etchant from being lowered, and wet etching can be performed without any problem.
  • the sputtering target of the present invention may contain other metal elements other than the above-described In, Sn, Zn and Al within a range not impairing the effects of the present invention, and substantially includes In, Sn, Zn and It may consist of only Al or only In, Sn, Zn and Al.
  • “substantially” means that 95 wt% or more and 100 wt% or less (preferably 98 wt% or more and 100 wt% or less) of the metal element of the sputtering target is In, Sn, Zn, and Al.
  • the sputtering target of the present invention may contain inevitable impurities in addition to In, Sn, Zn and Al as long as the effects of the present invention are not impaired.
  • the atomic ratio of each element contained in the target can be obtained by quantitative analysis of the contained elements using an inductively coupled plasma emission spectrometer (ICP-AES). Specifically, when a solution sample is atomized with a nebulizer and introduced into an argon plasma (about 6000 to 8000 ° C.), the elements in the sample are excited by absorbing thermal energy, and orbital electrons are excited from the ground state. Move to the orbit. These orbital electrons move to a lower energy level orbit in about 10 ⁇ 7 to 10 ⁇ 8 seconds. At this time, the energy difference is emitted as light to emit light.
  • ICP-AES inductively coupled plasma emission spectrometer
  • this light shows a wavelength (spectral line) unique to the element
  • the presence of the element can be confirmed by the presence or absence of the spectral line (qualitative analysis).
  • the magnitude (luminescence intensity) of each spectral line is proportional to the number of elements in the sample
  • the sample concentration can be obtained by comparing with a standard solution having a known concentration (quantitative analysis). After identifying the elements contained in the qualitative analysis, the content is obtained by quantitative analysis, and the atomic ratio of each element is obtained from the result.
  • the sputtering target of the present invention preferably has a relative density of 98% or more.
  • the relative density is preferably 98% or more.
  • the relative density is a density calculated relative to the theoretical density calculated from the weighted average.
  • the density calculated from the weighted average of the density of each raw material is the theoretical density, which is defined as 100%. If the relative density is 98% or more, a stable sputtering state is maintained. In the case of forming a film by increasing the sputtering output on a large substrate, if the relative density is 98% or more, the target surface is hardly blackened and abnormal discharge is not easily generated.
  • the relative density is preferably 98.5% or more, more preferably 99% or more.
  • the relative density of the target can be calculated from the measured density and the theoretical density measured by the Archimedes method.
  • the relative density is preferably 100% or less.
  • the metal particles are hardly generated in the sintered body and the generation of lower oxides is suppressed, so that it is not necessary to strictly adjust the oxygen supply amount during film formation.
  • the density can be adjusted by performing a post-treatment step such as a heat treatment operation in a reducing atmosphere.
  • a reducing atmosphere an atmosphere of argon, nitrogen, hydrogen, or a mixed gas atmosphere thereof is used.
  • the sputtering target of the present invention is preferably 10 m ⁇ cm or less, more preferably a bulk specific resistance is 8 m ⁇ cm or less, and further preferably 5 m ⁇ cm or less.
  • a bulk specific resistance is 8 m ⁇ cm or less, and further preferably 5 m ⁇ cm or less.
  • the bulk resistivity can be measured based on the four-probe method using a resistivity meter, for example.
  • the maximum crystal grain size in the oxide constituting the sputtering target is preferably 8 ⁇ m or less.
  • production of a nodule can be suppressed as the maximum particle diameter of a crystal
  • the cutting speed varies depending on the direction of the crystal plane, and irregularities are generated on the target surface.
  • the size of the unevenness depends on the crystal grain size present in the sintered body. In a target made of a sintered body having a large crystal grain size, the unevenness is increased, and it is considered that nodules are generated from the convex portion.
  • the maximum grain size of the sputtering target crystal is the midpoint between the center point (one place) of the circle and the center point on the two center lines orthogonal to the center point and the peripheral part.
  • the center point (1 location) and the midpoint (4 locations) between the center point and the corner on the diagonal of the rectangle The maximum diameter of the particles having the maximum diameter observed in a 100 ⁇ m square frame at the five locations is measured, and the average particle size of the maximum particles present in each of the five frame locations is expressed.
  • the particle size is measured for the major axis of the crystal grains.
  • the crystal grains can be observed with a scanning electron microscope (SEM).
  • the manufacturing method of the sputtering target of the present invention includes the following two steps. (1) Process of mixing raw material compounds and molding to form a molded body (2) Process of sintering the molded body Hereinafter, these processes will be described.
  • the raw material compound is not particularly limited, and a compound containing one or more elements selected from In, Sn, Zn and Al can be used, preferably It adjusts so that the mixture of the raw material compound to be used may satisfy the following atomic ratio.
  • Examples of the compound containing one or more elements selected from In, Sn, Zn, and Al include, for example, a combination of indium oxide, tin oxide, zinc oxide, and aluminum metal, and a combination of indium oxide, tin oxide, zinc oxide, and aluminum oxide. It is preferable that it is a mixed powder of indium oxide, tin oxide, zinc oxide and aluminum oxide.
  • a single metal for example, a combination of indium oxide, tin oxide, zinc oxide and aluminum metal Is used as a raw material powder, there are metal particles of aluminum in the obtained sintered body, metal particles on the surface of the target may melt and not be released from the target during film formation, and the composition of the film obtained The composition of the sintered body may vary greatly.
  • the raw material compound is preferably a powder, and when the raw material compound is a powder, the average particle size of the raw material powder is preferably 0.1 ⁇ m to 1.2 ⁇ m, more preferably 0.1 ⁇ m to 1.0 ⁇ m. is there.
  • the average particle diameter of the raw material powder can be measured with a laser diffraction type particle size distribution apparatus or the like.
  • an oxide containing Al 2 O 3 powder having an average particle size of 0.1 ⁇ m to 1.2 ⁇ m is used as a raw material powder, and these may be prepared at a ratio satisfying the above formulas (1) to (4).
  • the method of mixing and molding the raw material compounds is not particularly limited, and can be performed using a known method.
  • an aqueous solvent is blended with a raw material powder containing a mixed powder of oxides containing indium oxide powder, tin oxide powder, zinc oxide and aluminum oxide powder, and the resulting slurry is mixed for 12 hours or more, and then solid-liquid Separation, drying, and granulation are performed, and then this granulated product is put in a mold and molded to obtain a molded body.
  • a wet or dry ball mill, vibration mill, bead mill, or the like can be used.
  • a bead mill mixing method is most preferable because the crushing efficiency of the agglomerates is high in a short time and the additive is well dispersed.
  • the mixing time is preferably 15 hours or longer, more preferably 19 hours or longer. If the mixing time by the ball mill is 15 hours or more, a high resistance compound such as Al 2 O 3 is hardly generated in the finally obtained sintered body.
  • the mixing time varies depending on the size of the apparatus and the amount of slurry to be processed, but may be appropriately adjusted so that the particle size distribution in the slurry is all uniform at 1 ⁇ m or less. In any mixing means, it is preferable to add an arbitrary amount of a binder when mixing, and to perform mixing at the same time.
  • the binder polyvinyl alcohol, vinyl acetate, or the like can be used.
  • the granulation of the raw material powder slurry obtained by mixing is preferably made into granulated powder by rapid drying granulation.
  • a spray dryer is widely used as an apparatus for rapid drying granulation.
  • the specific drying conditions are determined by various conditions such as the slurry concentration of the slurry to be dried, the temperature of hot air used for drying, the air volume, etc., and therefore, it is necessary to obtain optimum conditions in advance. If it is quick-drying granulation, uniform granulated powder is obtained. That is, separation of In 2 O 3 powder, SnO 2 powder, ZnO powder and Al 2 O 3 powder can be prevented by the difference in sedimentation speed due to the difference in specific gravity of the raw material powder.
  • target prepared from a uniform granulated powder it is possible to prevent abnormal discharge during sputtering due to the presence such as Al 2 O 3.
  • a pressure of, for example, 1.2 ton / cm 2 or more to the obtained granulated powder by a die press or a cold isostatic press (CIP)
  • CIP cold isostatic press
  • a sintered body can be obtained by sintering the obtained molded object.
  • the sintering preferably includes a temperature raising step and a holding step.
  • the temperature is raised from 700 to 1400 ° C. at an average temperature raising rate of 0.1 to 0.9 ° C./min. Holding at a sintering temperature of 1200 to 1650 ° C. for 5 to 50 hours.
  • the average heating rate in the temperature range of 700 to 1400 ° C. is more preferably 0.2 to 0.5 ° C./min.
  • the average rate of temperature rise in the temperature range of 700 to 1400 ° C. is a value obtained by dividing the temperature difference from 700 ° C. to the temperature reached temperature rise by the time required for temperature rise.
  • the average temperature rising rate (first average temperature rising rate) at 400 ° C. or more and less than 700 ° C. is preferably 0.2 to 2.0 ° C./min, and the average at 700 ° C. or more and less than 1100 ° C.
  • the heating rate (second average heating rate) is 0.05 to 1.2 ° C./min
  • the average heating rate (third average heating rate) at 1100 ° C. to 1400 ° C. is 0.03 to Set to 1.0 ° C./min.
  • the second average heating rate is more preferably 0.3 to 0.5 ° C./min.
  • the third average temperature rising rate is more preferably 0.15 to 0.4 ° C./min.
  • the first average temperature increase rate is 0.2 ° C./min or more
  • the required time does not increase excessively, and the production efficiency can be improved.
  • the first average heating rate is 2.0 ° C./min or less
  • the binder does not remain even if the molded body contains a binder, and the occurrence of cracks in the target is suppressed. Can do.
  • the second average temperature increase rate is 0.05 ° C./min or more
  • the required time does not increase excessively, and the crystal does not grow abnormally, and voids are generated inside the obtained sintered body. Can be suppressed.
  • the second average temperature rising rate is 1.2 ° C./min or less, no distribution occurs at the start of sintering, and the occurrence of warpage can be suppressed.
  • the third average temperature increase rate is 0.03 ° C./min or more, the required time does not increase excessively, and it is possible to suppress the occurrence of composition deviation due to evaporation of Zn.
  • the third average temperature rising rate is 1.0 ° C./min or less, tensile stress due to the distribution of shrinkage does not occur, and the sintered density can be easily increased.
  • the relationship between the first to third average temperature rising rates preferably satisfies the second average temperature rising rate> the third average speed, and the first average temperature rising rate> second average temperature rising rate> first More preferably, the average heating rate of 3 is satisfied.
  • the second average temperature rising rate> the third average temperature rising rate it can be expected that the generation of nodules is more effectively suppressed even if the sputtering is performed for a long time.
  • the heating rate at 400 ° C. or higher and lower than 700 ° C. is preferably in the range of 0.2 to 2.0 ° C./min.
  • the heating rate at 700 ° C. or higher and lower than 1100 ° C. is preferably in the range of 0.05 to 1.2 ° C./min.
  • the heating rate at 1100 ° C. or higher and 1400 ° C. or lower is preferably in the range of 0.03 to 1.0 ° C./min.
  • the rate of temperature increase when the temperature of the molded body is raised to a temperature higher than 1400 ° C. and not higher than 1650 ° C. is not particularly limited, but is usually about 0.15 to 0.4 ° C./min.
  • sintering is performed by holding at a sintering temperature of 1200 to 1650 ° C. for 5 to 50 hours (holding step).
  • the sintering temperature is preferably 1300 to 1600 ° C.
  • the sintering time is preferably 10 to 25 hours.
  • the sintering temperature is 1200 ° C. or higher or the sintering time is 5 hours or longer, Al 2 O 3 or the like is not formed inside the sintered body, and abnormal discharge is unlikely to occur.
  • the firing temperature is 1650 ° C. or less or the firing time is 50 hours or less, there is no increase in the average crystal grain size due to significant crystal grain growth, and no generation of coarse pores, resulting in a decrease in sintered body strength or abnormal discharge. Can be suppressed.
  • a pressure sintering method such as hot press, oxygen pressurization, hot isostatic pressurization and the like can be employed in addition to the normal pressure sintering method.
  • a normal pressure sintering method it is preferable to employ a normal pressure sintering method from the viewpoints of reducing manufacturing costs, possibility of mass production, and easy production of large sintered bodies.
  • the compact is sintered in an air atmosphere or an oxidizing gas atmosphere, preferably an oxidizing gas atmosphere.
  • the oxidizing gas atmosphere is preferably an oxygen gas atmosphere.
  • the oxygen gas atmosphere is preferably an atmosphere having an oxygen concentration of, for example, 10 to 100% by volume.
  • the density of the sintered body can be further increased by introducing an oxygen gas atmosphere in the temperature raising process.
  • a reduction step may be provided as necessary.
  • the reduction method include a method using a reducing gas, vacuum firing, or reduction using an inert gas.
  • a reducing gas hydrogen, methane, carbon monoxide, a mixed gas of these gases and oxygen, or the like can be used.
  • reduction treatment by firing in an inert gas nitrogen, argon, a mixed gas of these gases and oxygen, or the like can be used.
  • the temperature during the reduction treatment is usually 100 to 800 ° C, preferably 200 to 800 ° C.
  • the reduction treatment time is usually 0.01 to 10 hours, preferably 0.05 to 5 hours.
  • the temperature lowering rate (cooling rate) during firing is usually 10 ° C./min or less, preferably 9 ° C./min or less, more preferably 8 ° C./min or less, further preferably 7 ° C./min or less, particularly preferably 5 ° C./min. Is less than a minute.
  • rate of temperature decrease is 10 ° C./min or less, the crystal form of the present invention is easily obtained, and cracks are unlikely to occur during temperature decrease.
  • the method for producing a sintered body used in the present invention is, for example, a slurry obtained by blending an aqueous solvent into a raw material powder containing a mixed powder of indium oxide powder, zinc oxide powder and aluminum oxide powder. After mixing for 12 hours or more, solid-liquid separation, drying and granulation were carried out, and then this granulated product was put into a mold and molded, and then the obtained molded product was 700-1400 ° C. in an oxygen-containing atmosphere. Temperature raising step at an average temperature rising rate of 0.1 to 0.9 ° C./min and a holding step of holding at 1200 to 1650 ° C. for 5 to 50 hours, followed by a temperature lowering rate (cooling rate) of 10 ° C./min
  • a sintered body can be obtained by a sintering process having a temperature lowering process described below.
  • the sputtering target of the present invention can be obtained by processing the sintered body obtained above.
  • a sputtering target material can be obtained by cutting the sintered body into a shape suitable for mounting on a sputtering apparatus, and a sputtering target can be obtained by bonding the target material to a backing plate.
  • the sintered body is ground with, for example, a surface grinder to obtain a material having a surface roughness Ra of 0.5 ⁇ m or less.
  • the sputter surface of the target material may be further mirror-finished so that the average surface roughness Ra may be 1000 angstroms or less.
  • known polishing techniques such as mechanical polishing, chemical polishing, and mechanochemical polishing (a combination of mechanical polishing and chemical polishing) can be used.
  • polishing to # 2000 or more with a fixed abrasive polisher polishing liquid: water
  • lapping with loose abrasive lapping abrasive: SiC paste, etc.
  • lapping by changing the abrasive to diamond paste can be obtained by:
  • Such a polishing method is not particularly limited.
  • the surface of the target material is preferably finished with a 200 to 10,000 diamond grindstone, particularly preferably with a 400 to 5,000 diamond grindstone.
  • a diamond grindstone of No. 200 or more or 10,000 or less, it is possible to prevent the target material from cracking.
  • the target material has a surface roughness Ra of 0.5 ⁇ m or less and has a non-directional ground surface. If Ra is 0.5 ⁇ m or less and a non-directional polished surface is provided, abnormal discharge and generation of particles can be prevented.
  • the obtained target material is cleaned.
  • Air blow or running water washing can be used for the cleaning treatment.
  • When removing foreign matter by air blow it is possible to remove the foreign matter more effectively by suctioning with a dust collector from the opposite side of the nozzle.
  • ultrasonic cleaning etc. can also be performed. This ultrasonic cleaning is effective by performing multiple oscillations at a frequency of 25 to 300 kHz. For example, it is preferable to perform ultrasonic cleaning by multiplying twelve frequencies in 25 kHz increments between frequencies of 25 to 300 kHz.
  • the thickness of the target material is usually 2 to 20 mm, preferably 3 to 12 mm, particularly preferably 4 to 6 mm.
  • a sputtering target can be obtained by bonding the target material obtained as described above to a backing plate. Further, a plurality of target materials may be attached to one backing plate to substantially serve as one target.
  • the sputtering target of the present invention has high density and low resistance, and can efficiently form an oxide semiconductor thin film with low cost and energy saving.
  • the oxide semiconductor thin film of the present invention can be obtained by depositing the sputtering target of the present invention by a sputtering method.
  • the carrier concentration of the oxide semiconductor thin film of the present invention is usually 10 19 / cm 3 or less, preferably 10 13 to 10 18 / cm 3 , more preferably 10 14 to 10 18 / cm 3 , particularly Preferably, it is 10 15 to 10 18 / cm 3 .
  • the carrier concentration of the oxide layer is 10 19 cm ⁇ 3 or less, it is possible to prevent leakage current, normally-on and a decrease in on-off ratio when a device such as a thin film transistor is configured, and to have good transistor performance Can be demonstrated.
  • the carrier concentration is 10 13 cm ⁇ 3 or more, the TFT can be driven without any problem.
  • the carrier concentration of the oxide semiconductor thin film can be measured by a Hall effect measurement method. Specifically, it can be measured by the method described in the examples.
  • the sputtering target of the present invention has high conductivity, a DC sputtering method having a high deposition rate can be applied as the sputtering method.
  • the present invention can be applied to an RF sputtering method, an AC sputtering method, and a pulsed DC sputtering method, and sputtering without abnormal discharge is possible.
  • the oxide semiconductor thin film of the present invention can be produced by using the sintered body by a vapor deposition method, an ion plating method, a pulse laser vapor deposition method, or the like, in addition to the sputtering method.
  • a mixed gas of a rare gas such as argon and an oxidizing gas can be used.
  • the oxidizing gas include O 2 , CO 2 , O 3 , H 2 O, and N 2 O.
  • the sputtering gas is preferably a mixed gas containing a rare gas and one or more gases selected from water vapor, oxygen gas and nitrous oxide gas, and more preferably a mixed gas containing a rare gas and at least water vapor.
  • the oxygen partial pressure ratio during sputtering film formation is preferably 0% or more and less than 40%.
  • the oxygen partial pressure ratio is less than 40%, the carrier concentration of the manufactured thin film is not significantly reduced, and the carrier concentration can be prevented from becoming less than 10 13 cm ⁇ 3, for example.
  • the oxygen partial pressure ratio is more preferably 0% to 30%, and particularly preferably 0% to 20%.
  • the partial pressure ratio of water vapor contained in the sputtering gas (atmosphere) when depositing the oxide thin film is 0.1. It is preferably ⁇ 25%.
  • the partial pressure ratio of water in the atmosphere during sputtering is more preferably 0.7 to 13%, particularly preferably 1 to 6%.
  • the substrate temperature when forming a film by sputtering is preferably 25 to 120 ° C., more preferably 25 to 100 ° C., and particularly preferably 25 to 90 ° C.
  • the substrate temperature at the time of film formation is 120 ° C. or lower, oxygen or the like introduced at the time of film formation can be sufficiently taken in, and an excessive increase in the carrier concentration of the thin film after heating can be prevented.
  • the substrate temperature at the time of film formation is 25 ° C. or higher, the film density of the thin film does not decrease and the mobility of the TFT can be prevented from decreasing.
  • the oxide thin film obtained by sputtering is further annealed by holding at 150 to 500 ° C. for 15 minutes to 5 hours.
  • the annealing temperature after film formation is more preferably 200 ° C. or higher and 450 ° C. or lower, and further preferably 250 ° C. or higher and 350 ° C. or lower. By performing the annealing, semiconductor characteristics can be obtained.
  • the atmosphere during heating is not particularly limited, but from the viewpoint of carrier controllability, an air atmosphere or an oxygen circulation atmosphere is preferable.
  • a lamp annealing device In the post-treatment annealing step of the oxide thin film, a lamp annealing device, a laser annealing device, a thermal plasma device, a hot air heating device, a contact heating device, or the like can be used in the presence or absence of oxygen.
  • the distance between the target and the substrate during sputtering is preferably 1 to 15 cm, more preferably 2 to 8 cm in the direction perpendicular to the film formation surface of the substrate.
  • this distance is 1 cm or more, the kinetic energy of the target constituent element particles reaching the substrate does not become too large, and good film characteristics can be obtained. In addition, in-plane distribution of film thickness and electrical characteristics can be prevented.
  • the distance between the target and the substrate is 15 cm or less, the kinetic energy of the particles of the target constituent element that reaches the substrate does not become too small, and a dense film can be obtained. In addition, good semiconductor characteristics can be obtained.
  • the oxide thin film is preferably formed by sputtering in an atmosphere having a magnetic field strength of 300 to 1500 gauss.
  • the magnetic field strength is 300 gauss or more, a decrease in plasma density can be prevented, and sputtering can be performed without any problem even in the case of a high-resistance sputtering target.
  • it is 1500 gauss or less, deterioration of controllability of the film thickness and electrical characteristics in the film can be suppressed.
  • the pressure in the gas atmosphere is not particularly limited as long as the plasma can be stably discharged, but is preferably 0.1 to 3.0 Pa, more preferably 0.1 to 1.5 Pa. Particularly preferred is 0.1 to 1.0 Pa.
  • the sputtering pressure is 3.0 Pa or less, the mean free process of sputtered particles does not become too short, and a decrease in thin film density can be prevented. Further, when the sputtering pressure is 0.1 Pa or more, it is possible to prevent the formation of microcrystals in the film during film formation.
  • the sputtering pressure refers to the total pressure in the system at the start of sputtering after introducing a rare gas such as argon, water vapor, oxygen gas or the like.
  • the oxide semiconductor thin film may be formed by AC sputtering as described below.
  • the substrate is sequentially transported to a position facing three or more targets arranged in parallel at a predetermined interval in the vacuum chamber, and negative and positive potentials are alternately applied to each target from an AC power source. Then, plasma is generated on the target to form a film on the substrate surface.
  • at least one of the outputs from the AC power supply is performed while switching a target to which a potential is applied between two or more targets that are branched and connected. That is, at least one of the outputs from the AC power supply is branched and connected to two or more targets, and film formation is performed while applying different potentials to adjacent targets.
  • an oxide semiconductor thin film is formed by AC sputtering
  • sputtering is performed in an atmosphere of a mixed gas containing a rare gas and one or more gases selected from water vapor, oxygen gas, and nitrous oxide gas. It is preferable to perform, and it is particularly preferable to perform sputtering in an atmosphere of a mixed gas containing water vapor.
  • the film is formed by AC sputtering, an oxide layer having industrially excellent large area uniformity can be obtained, and improvement in the utilization efficiency of the target can be expected.
  • the AC sputtering apparatus described in Japanese Patent Laid-Open No. 2005-290550 includes a vacuum chamber, a substrate holder disposed inside the vacuum chamber, and a sputtering source disposed at a position facing the substrate holder. .
  • FIG. 11 shows a main part of the sputtering source of the AC sputtering apparatus.
  • the sputter source has a plurality of sputter units, each of which has plate-like targets 31a to 31f, and the surfaces to be sputtered of the targets 31a to 31f are sputter surfaces. It arrange
  • Each target 31a to 31f is formed in an elongated shape having a longitudinal direction, each target has the same shape, and edge portions (side surfaces) in the longitudinal direction of the sputtering surface are arranged in parallel with a predetermined interval therebetween. Therefore, the side surfaces of the adjacent targets 31a to 31f are parallel.
  • AC power supplies 17a to 17c are arranged outside the vacuum chamber, and one of the two terminals of each AC power supply 17a to 17c is connected to one of the two adjacent electrodes, The other terminal is connected to the other electrode.
  • Two terminals of each of the AC power supplies 17a to 17c output voltages of positive and negative different polarities, and the targets 31a to 31f are attached in close contact with the electrodes, so that the two adjacent targets 31a to 31f are adjacent to each other.
  • AC voltages having different polarities are applied from the AC power sources 17a to 17c. Therefore, when one of the targets 31a to 31f adjacent to each other is placed at a positive potential, the other is placed at a negative potential.
  • Magnetic field forming means 40a to 40f are arranged on the surface of the electrode opposite to the targets 31a to 31f.
  • Each of the magnetic field forming means 40a to 40f has an elongated ring-shaped magnet whose outer periphery is substantially equal to the outer periphery of the targets 31a to 31f, and a bar-shaped magnet shorter than the length of the ring-shaped magnet.
  • Each ring-shaped magnet is disposed in parallel with the longitudinal direction of the targets 31a to 31f at a position directly behind the corresponding one of the targets 31a to 31f. As described above, since the targets 31a to 31f are arranged in parallel at a predetermined interval, the ring magnets are also arranged at the same interval as the targets 31a to 31f.
  • the AC power density when using an oxide target in AC sputtering is preferably 3 W / cm 2 or more and 20 W / cm 2 or less.
  • the power density is 3 W / cm 2 or more, the film formation rate does not become too slow, and production economy can be ensured. If it is 20 W / cm 2 or less, damage to the target can be suppressed.
  • a more preferable power density is 3 W / cm 2 to 15 W / cm 2 .
  • the frequency of AC sputtering is preferably in the range of 10 kHz to 1 MHz. When the frequency is 10 kHz or more, the problem of noise hardly occurs.
  • the frequency is 1 MHz or less, it is possible to prevent the plasma from spreading too much and performing sputtering at a position other than the desired target position, so that uniformity can be maintained.
  • a more preferable frequency of AC sputtering is 20 kHz to 500 kHz. What is necessary is just to select suitably the conditions at the time of sputtering other than the above from what was mentioned above.
  • the oxide semiconductor thin film can be used for a thin film transistor (TFT), and can be particularly preferably used as a channel layer.
  • TFT thin film transistor
  • its element structure is not particularly limited, and various known element structures can be adopted.
  • the TFT of the present invention preferably has a field effect mobility of 10 cm 2 / Vs or more, more preferably 13 cm 2 / Vs or more. The field effect mobility can be measured by the method described in the examples.
  • the thickness of the channel layer in the thin film transistor of the present invention is usually 10 to 300 nm, preferably 20 to 250 nm, more preferably 30 to 200 nm, still more preferably 35 to 120 nm, and particularly preferably 40 to 80 nm.
  • the thickness of the channel layer is 10 nm or more, even when the channel layer is formed in a large area, the film thickness is unlikely to be uniform, and the characteristics of the manufactured TFT can be made uniform in the plane.
  • the film thickness is 300 nm or less, the film formation time does not become too long.
  • the channel layer in the thin film transistor of the present invention is usually used in an N-type region, but a PN junction transistor or the like in combination with various P-type semiconductors such as a P-type Si-based semiconductor, a P-type oxide semiconductor, and a P-type organic semiconductor. It can be used for various semiconductor devices.
  • the channel layer of the thin film transistor of the present invention may be partially crystallized at least in a region overlapping with the gate electrode after annealing.
  • crystallization means that crystal nuclei are generated from an amorphous state or crystal grains are grown from a state where crystal nuclei are generated.
  • CVD process chemical vapor deposition process
  • the crystallized region can be confirmed from, for example, an electron beam diffraction image of a transmission electron microscope (TEM).
  • the oxide semiconductor thin film of the channel layer can be wet-etched with an organic acid-based etchant (eg, oxalic acid etchant), and an inorganic acid-based wet etchant (eg, phosphoric acid / nitric acid / acetic acid mixed acid wet etchant: PAN) It is difficult to melt, and the selectivity of wet etching with Mo (molybdenum) or Al (aluminum) used for the electrode is large. Therefore, a channel-etched thin film transistor can be manufactured by using the above oxide thin film for a channel layer.
  • an organic acid-based etchant eg, oxalic acid etchant
  • an inorganic acid-based wet etchant eg, phosphoric acid / nitric acid / acetic acid mixed acid wet etchant: PAN
  • an insulating film having a thickness of about several nm may be formed on the surface of the oxide semiconductor thin film before applying the resist. Through this step, it is possible to avoid direct contact between the oxide semiconductor film and the resist, and impurities contained in the resist can be prevented from entering the oxide semiconductor film.
  • the thin film transistor of the present invention preferably includes a protective film on the channel layer.
  • the protective film in the thin film transistor of the present invention preferably contains at least SiN x . Since SiN x can form a dense film as compared with SiO 2 , it has an advantage of a high TFT deterioration suppressing effect.
  • the protective film may be, for example, SiO 2 , Al 2 O 3 , Ta 2 O 5 , TiO 2 , MgO, ZrO 2 , CeO 2 , K 2 O, Li 2 O, Na 2 O, Rb 2 O, Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2 O 6 , Sm 2 O 3 , SrTiO 3, or an oxide such as AlN can be included.
  • the oxide thin film containing indium element (In), tin element (Sn), zinc element (Zn), and aluminum element (Al) according to the present invention contains Al, so that the reduction resistance by the CVD process is improved.
  • the back channel side is not easily reduced by the process of forming the protective film, and SiN x can be used as the protective film.
  • the channel layer is preferably subjected to ozone treatment, oxygen plasma treatment, nitrogen dioxide plasma treatment, or nitrous oxide plasma treatment.
  • ozone treatment oxygen plasma treatment, nitrogen dioxide plasma treatment, or nitrous oxide plasma treatment.
  • Such treatment may be performed at any timing after the channel layer is formed and before the protective film is formed, but is preferably performed immediately before the protective film is formed.
  • ozone treatment oxygen plasma treatment, nitrogen dioxide plasma treatment, or nitrous oxide plasma treatment.
  • the surface of the semiconductor substrate or the gate insulating film is cleaned in order to remove metal contamination due to Cu or the like of the semiconductor substrate and to reduce the surface level caused by dangling bonds on the surface of the gate insulating film. It is preferable to carry out.
  • a cyan-containing solution having a cyan (CN) content of 100 ppm or less, preferably 10 ppm to 1 ppm as an upper limit and a hydrogen ion concentration index (pH) of 9 to 14 can be used.
  • the cyan-containing solution is heated to a temperature in the range of 50 ° C. or lower (preferably 30 ° C. to 40 ° C.), and the semiconductor substrate or the gate insulating film surface is preferably cleaned.
  • cyanide ions (CN ⁇ ) react with copper on the substrate surface to form [Cu (CN) 2 ] ⁇ and remove contaminated copper.
  • Cyanide (CN) -containing solution used for washing is hydrogen cyanide (HCN) purified water or ultrapure water, alcohol solvents and ketone solvents, nitrile solvents, aromatic hydrocarbon solvents, carbon tetrachloride, ether solvents, It is dissolved in at least one solvent selected from an aliphatic alkane solvent or a mixed solvent thereof, and further diluted to a predetermined concentration, and a hydrogen ion concentration index in the solution, that is, a so-called pH value is preferably 9 with an aqueous ammonia solution or the like. It is preferable to adjust and use in the range of ⁇ 14.
  • a thin film transistor usually includes a substrate, a gate electrode, a gate insulating layer, an organic semiconductor layer (channel layer), a source electrode, and a drain electrode.
  • the channel layer is as described above, and a known material can be used for the substrate.
  • the material for forming the gate insulating film in the thin film transistor of the present invention is not particularly limited, and a commonly used material can be arbitrarily selected. Specifically, for example, SiO 2, SiN x, Al 2 O 3, Ta 2 O 5, TiO 2, MgO, ZrO 2, CeO 2, K 2 O, Li 2 O, Na 2 O, Rb 2 O, A compound such as Sc 2 O 3 , Y 2 O 3 , HfO 2 , CaHfO 3 , PbTiO 3 , BaTa 2 O 6 , SrTiO 3 , Sm 2 O 3 , or AlN can be used. Among them, preferred are SiO 2, SiN x, Al 2 O 3, Y 2 O 3, HfO 2, CaHfO 3, more preferably SiO 2, SiN x, HfO 2 , Al 2 O 3.
  • the gate insulating film can be formed by, for example, a plasma CVD (Chemical Vapor Deposition) method.
  • a gate insulating film is formed by plasma CVD and a channel layer is formed on the gate insulating film, hydrogen in the gate insulating film may diffuse into the channel layer, leading to deterioration in channel layer quality and TFT reliability. is there.
  • the gate insulating film may be subjected to ozone treatment, oxygen plasma treatment, nitrogen dioxide plasma treatment or nitrous oxide plasma treatment before forming the channel layer. preferable. By performing such pretreatment, it is possible to prevent deterioration of the channel layer film quality and TFT reliability.
  • the number of oxygen in the oxide does not necessarily match the stoichiometric ratio, and may be, for example, SiO 2 or SiO x .
  • the gate insulating film may have a structure in which two or more insulating films made of different materials are stacked.
  • the gate insulating film may be crystalline, polycrystalline, or amorphous, but is preferably polycrystalline or amorphous that can be easily manufactured industrially.
  • each of the drain electrode, the source electrode, and the gate electrode in the thin film transistor of the present invention there are no particular limitations on the material for forming each of the drain electrode, the source electrode, and the gate electrode in the thin film transistor of the present invention, and a commonly used material can be arbitrarily selected.
  • a transparent electrode such as ITO, indium zinc oxide, ZnO, SnO 2 , a metal electrode such as Al, Ag, Cu, Cr, Ni, Mo, Au, Ti, Ta, or a metal electrode of an alloy including these electrodes.
  • a metal electrode such as Al, Ag, Cu, Cr, Ni, Mo, Au, Ti, Ta, or a metal electrode of an alloy including these electrodes.
  • Each of the drain electrode, the source electrode, and the gate electrode can have a multilayer structure in which two or more different conductive layers are stacked.
  • a good conductor such as Al or Cu may be sandwiched with a metal having excellent adhesion such as Ti or Mo.
  • the thin film transistor of the present invention can be applied to various integrated circuits such as a field effect transistor, a logic circuit, a memory circuit, and a differential amplifier circuit. Further, in addition to the field effect transistor, it can be applied to an electrostatic induction transistor, a Schottky barrier transistor, a Schottky diode, and a resistance element.
  • the structure of the thin film transistor of the present invention known structures such as a bottom gate, a bottom contact, and a top contact can be adopted without limitation.
  • the bottom gate structure is advantageous because high performance can be obtained as compared with thin film transistors of amorphous silicon or ZnO.
  • the bottom gate configuration is preferable because it is easy to reduce the number of masks at the time of manufacturing, and it is easy to reduce the manufacturing cost for uses such as a large display.
  • the thin film transistor of the present invention can be suitably used for a display device.
  • a channel etch type bottom gate thin film transistor is particularly preferable.
  • a channel-etched bottom gate thin film transistor has a small number of photomasks at the time of a photolithography process, and can produce a display panel at a low cost.
  • a channel-etched bottom gate structure and a top contact structure thin film transistor are particularly preferable because they have good characteristics such as mobility and are easily industrialized.
  • the S value of the thin film transistor can be derived from the reciprocal of this slope by creating a graph of Log (Id) -Vg from the result of the transfer characteristics.
  • the unit of the S value is V / decade and is preferably a small value.
  • the S value (Swing Factor) is a value indicating the steepness of the drain current that rises sharply from the off state to the on state when the gate voltage is increased from the off state.
  • an increment of the gate voltage when the drain current increases by one digit (10 times) is defined as an S value.
  • S value dVg / dlog (Ids) The smaller the S value, the sharper the rise ("All about Thin Film Transistor Technology", Ikuhiro Ukai, 2007, Industrial Research Committee).
  • the S value is large, it is necessary to apply a high gate voltage when switching from on to off, and power consumption may increase.
  • S value is preferably 0.8 V / dec or less, more preferably 0.5 V / dec or less, further preferably 0.3 V / dec or less, and particularly preferably 0.2 V / dec or less. If it is 0.8 V / dec or less, the driving voltage becomes small and the power consumption may be reduced. In particular, when used in an organic EL display, it is preferable to set the S value to 0.3 V / dec or less because of direct current drive because power consumption can be greatly reduced.
  • Example 1-8 [Production of sintered oxide] The following oxide powder was used as a raw material powder.
  • the median diameter D50 was employed as the average particle diameter of the following oxide powder, and the average particle diameter was measured with a laser diffraction particle size distribution analyzer SALD-300V (manufactured by Shimadzu Corporation).
  • Indium oxide powder Average particle size 0.98 ⁇ m
  • Tin oxide powder Average particle size 0.98 ⁇ m
  • Zinc oxide powder Average particle size 0.96 ⁇ m
  • Aluminum oxide powder Average particle size 0.98 ⁇ m
  • the above powder was weighed so as to have the atomic ratio shown in Table 1, and was uniformly pulverized and mixed, and then granulated by adding a molding binder.
  • this raw material mixed powder was uniformly filled into a mold, and pressure-molded with a cold press machine at a press pressure of 140 MPa.
  • the molded body thus obtained was sintered in a sintering furnace at a heating rate, a sintering temperature, a sintering time, and a cooling rate shown in Table 1 to produce a sintered body. During the temperature increase, an oxygen atmosphere was used, and the other was in the air (atmosphere).
  • the crystal structure of the obtained sintered body was examined using an X-ray diffraction measurement apparatus (XRD).
  • X-ray diffraction charts of the sintered bodies obtained in Example 1-8 are shown in FIGS. 1-8, respectively.
  • the measurement conditions of X-ray diffraction measurement (XRD) are as follows. ⁇ Equipment: Ultimate-III manufactured by Rigaku Corporation -X-ray: Cu-K ⁇ ray (wavelength 1.5406mm, monochromatized with graphite monochromator) ⁇ 2 ⁇ - ⁇ reflection method, continuous scan (1.0 ° / min) ⁇ Sampling interval: 0.02 ° ⁇ Slit DS, SS: 2/3 °, RS: 0.6 mm
  • the sintered body of Example 1 has a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 , and Zn 2 In 2 O 5.
  • the homologous structure of was observed. These crystal structures were confirmed with a JCPDS card.
  • the homologous structure of InAlZn 2 O 5 is the same as that of JCPDS database No. It is a peak pattern of 40-0259.
  • the spinel structure of Zn 2 SnO 4 is No. 1 in the JCPDS database. It is a peak pattern of 24-1470.
  • In 2 O 3 has a big byte structure of No. of JCPDS database. This is a peak pattern of 06-0416.
  • the homologous structure of Zn 2 In 2 O 5 is No. 1 in the JCPDS database. 20-1442 peak pattern.
  • Example 2 In the sintered body of Example 2, a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 and a homologous structure of Zn 2 In 2 O 5 were observed.
  • Example 3 In the sintered body of Example 3, a homologous structure of InAlZn 2 O 5, a homologous structure of InAlZnO 4 , a spinel structure of Zn 2 SnO 4 and a bixbite structure of In 2 O 3 were observed.
  • Example 4 In the sintered body of Example 4, a homologous structure of InAlZnO 4 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 and a spinel structure of ZnAl 2 O 4 were observed.
  • Example 5 In the sintered body of Example 5, a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 and a homologous structure of Zn 2 In 2 O 5 were observed.
  • Example 6 In the sintered body of Example 6, a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 and a homologous structure of Zn 2 In 2 O 5 were observed.
  • the sintered body of Example 7 includes InAlZn 2 O 5 homologous structure, InAlZnO 4 homologous structure, Zn 2 SnO 4 spinel structure, In 2 O 3 bixbite structure, and Zn 2 In 2 O 5 homologous structure. Was observed.
  • Example 8 In the sintered body of Example 8, a homologous structure of InAlZnO 4 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 and a spinel structure of ZnAl 2 O 4 were observed.
  • the homologous structure of InAlZnO 4 is the same as that of JCPDS database No. It is a peak pattern of 40-0258, and the spinel structure of ZnAl 2 O 4 is No. of JCPDS database. It is a peak pattern of 05-0669.
  • the sintered bodies of Example 1-8 are a homologous structure compound represented by InAlO 3 (ZnO) m (m is 0.1 to 10), a bixbite structure compound of In 2 O 3 , and Zn 2 SnO 4. It was confirmed that the sintered body contained the spinel structure compound.
  • Example 1-8 For the sintered body of Example 1-8, the dispersion of Al and Sn was examined by electron microanalyzer (EPMA) measurement. As a result, no aggregates of Al and Sn having a major axis of 8 ⁇ m or more were observed. The aggregate is a portion where other elements are not detected in EPMA observation. For example, in the case of an aggregate of Al, only Al is observed except for oxygen and impurities that can be detected in the background in EPMA observation. From this result, it can be seen that the sputtering target of Example 1-8 is extremely excellent in dispersibility and uniformity.
  • EPMA electron microanalyzer
  • the measurement conditions for EPMA are as follows. Device name: JEOL Ltd. JXA-8200 Acceleration voltage: 15 kV Irradiation current: 50 nA Irradiation time (per point): 50mS
  • Example 1-8 The surface of the sintered body obtained in Example 1-8 was ground with a surface grinder, the sides were cut with a diamond cutter, and bonded to a backing plate to prepare sputtering targets each having a diameter of 4 inches. In addition, six targets each having a width of 200 mm, a length of 1700 mm, and a thickness of 10 mm were prepared for AC sputtering film formation.
  • the obtained sputtering target having a diameter of 4 inches was mounted on a DC sputtering apparatus, and a mixed gas in which 2% of H 2 O gas was added to argon gas at a partial pressure ratio was used as the atmosphere, the sputtering pressure was 0.4 Pa, and the substrate temperature was room temperature. Then, 10 kWh continuous sputtering was performed at a DC output of 400 W. Voltage fluctuations during sputtering were accumulated in a data logger, and the presence or absence of abnormal discharge was confirmed. The results are shown in Table 1. In addition, the presence or absence of abnormal discharge was performed by monitoring voltage fluctuation and detecting abnormal discharge.
  • the abnormal discharge was determined when the voltage fluctuation generated during the measurement time of 5 minutes was 10% or more of the steady voltage during the sputtering operation.
  • the steady-state voltage during sputtering operation varies by ⁇ 10% in 0.1 second, a micro arc, which is an abnormal discharge of the sputter discharge, has occurred, and the device yield may decrease, making it unsuitable for mass production. is there.
  • Nodules are measured after sputtering at a total of five points: the center point (one place) of the circular sputtering target and the center point (four places) between the center point and the peripheral part on two center lines orthogonal to the center point.
  • a method of measuring the number average of nodules having a major axis of 20 ⁇ m or more generated in a visual field of 3 mm 2 was observed by observing the change of the target surface 50 times with a stereomicroscope. Table 1 shows the number of nodules generated.
  • Comparative Example 1-2 The raw material powder was mixed at the atomic ratio shown in Table 1 and sintered at the heating rate, sintering temperature, sintering time, and cooling rate shown in Table 1, and the sintered body and Each sputtering target was manufactured and evaluated. The results are shown in Table 1. In addition, about the sintered compact of the comparative example 1, 6 targets of width 200mm, length 1700mm, and thickness 10mm were produced for AC sputtering film-forming.
  • Examples 9-16 Manufacture and evaluation of oxide semiconductor thin films
  • a 4-inch target having the composition shown in Tables 2 and 3 prepared in Example 1-8 was mounted on a magnetron sputtering apparatus, and a slide glass (# 1737 manufactured by Corning) was mounted as a substrate.
  • a DC magnetron sputtering method an amorphous film having a thickness of 50 nm was formed on a slide glass under the following conditions to produce a thin film evaluation element.
  • Ar gas, O 2 gas, and H 2 O gas were introduced at a partial pressure ratio (%) shown in Tables 2 and 3.
  • the substrate on which the amorphous film was formed was heated in the atmosphere at 300 ° C. for 60 minutes to form an oxide semiconductor film.
  • the sputtering conditions are as follows. Substrate temperature: 25 ° C Ultimate pressure: 8.5 ⁇ 10 ⁇ 5 Pa Atmospheric gas: Ar gas, O 2 gas, H 2 O gas (see Tables 2 and 3 for partial pressure) Sputtering pressure (total pressure): 0.4 Pa Input power: DC100W S (substrate)-T (target) distance: 70mm
  • the thin film evaluation element which is a laminate of the obtained glass substrate and oxide semiconductor film, was confirmed by ICP-AES analysis that the atomic ratio of each element contained in the oxide thin film was the same as that of the sputtering target. Moreover, the element for thin film evaluation was set to ResiTest8300 type (made by Toyo Technica Co., Ltd.), and the Hall effect (Hole mobility and carrier concentration) was evaluated at room temperature. The results are shown in Tables 2 and 3.
  • the crystal structure of the oxide semiconductor thin film on the glass substrate was examined by an X-ray diffractometer (Ultima-III manufactured by Rigaku). As a result, it was confirmed that the oxide semiconductor thin film of Example 9-16 was amorphous with no diffraction peak observed immediately after deposition of the thin film. Further, it was confirmed that the oxide semiconductor thin film of Example 9-16 was amorphous with no diffraction peak observed even after heat treatment (annealing) at 300 ° C. for 60 minutes in the air.
  • the measurement conditions for the XRD are as follows. Equipment: Ultimate-III manufactured by Rigaku Corporation X-ray: Cu-K ⁇ ray (wavelength 1.5406mm, monochromatized with graphite monochromator) 2 ⁇ - ⁇ reflection method, continuous scan (1.0 ° / min) Sampling interval: 0.02 ° Slit DS, SS: 2/3 °, RS: 0.6 mm
  • a conductive silicon substrate with a thermal oxide film having a thickness of 100 nm was used as a conductive silicon substrate with a thermal oxide film having a thickness of 100 nm.
  • the thermal oxide film functions as a gate insulating film, and the conductive silicon portion functions as a gate electrode.
  • a sputter film was formed on the gate insulating film under the conditions shown in Tables 2 and 3 to produce an amorphous thin film having a thickness of 50 nm.
  • OFPR # 800 manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • pre-baking 80 ° C., 5 minutes
  • the oxide semiconductor film was subjected to nitrous oxide plasma treatment as a pre-stage treatment for forming the protective film.
  • the SiO x was 100nm deposited by plasma CVD (PECVD), further SiN x was 150nm deposited by plasma CVD (PECVD) on the SiO x, protecting laminate of SiO x and SiN x A membrane was obtained. A contact hole was opened using dry etching to produce a thin film transistor.
  • PECVD plasma CVD
  • the thin film transistor was evaluated for field effect mobility ( ⁇ ), threshold voltage (Vth), and S value.
  • ⁇ field effect mobility
  • Vth threshold voltage
  • S value S value.
  • Tables 2 and 3 These characteristic values were measured using a semiconductor parameter analyzer (4200SCS manufactured by Keithley Instruments Co., Ltd.) at room temperature in a light-shielding environment (in a shield box).
  • the transfer characteristics of the mounted transistors were evaluated with a drain voltage (Vd) of 1 V and a gate voltage (Vg) of ⁇ 15 to 20 V.
  • Vd drain voltage
  • Vg gate voltage
  • the field effect mobility ( ⁇ ) was calculated from the linear mobility and defined as the maximum value of Vg ⁇ .
  • Comparative Examples 3 and 4 Using the 4-inch target produced in Comparative Examples 1 and 2, according to the sputtering conditions, heating (annealing) treatment conditions, and protective film formation pretreatment shown in Table 3, the oxide semiconductor thin film and Thin film transistors were fabricated and evaluated. The results are shown in Table 3. As shown in Table 3, in the thin film transistors of Comparative Examples 3 and 4, the field effect mobility was less than 10 cm 2 / Vs, and the field effect mobility was significantly reduced as compared with the elements of Examples 9-16. I understand. In addition, as a result of the stress test, it was found that the threshold voltage fluctuated by 1 V or more and the characteristics of the thin film transistors of Comparative Examples 3 and 4 were significantly deteriorated.
  • Examples 17-24 According to the film formation conditions and annealing conditions shown in Tables 4 and 5, an oxide semiconductor thin film and a thin film transistor were manufactured and evaluated using the targets of Example 1-8 in the same manner as in Example 9-16. The results are shown in Tables 4 and 5.
  • film formation by AC sputtering was performed instead of DC sputtering, and source / drain patterning was performed by dry etching.
  • ICP-AES analysis of the obtained oxide semiconductor thin film it was confirmed that the atomic ratio of each element contained in the oxide thin film of Examples 17-24 was the same atomic ratio as the sputtering target used.
  • Example 17 For the AC sputtering, a film forming apparatus shown in FIG. 11 disclosed in Japanese Patent Application Laid-Open No. 2005-290550 was used.
  • Example 17 six targets 31a to 31f having a width of 200 mm, a length of 1700 mm, and a thickness of 10 mm manufactured in Example 1 are used, and the targets 31a to 31f are parallel to the width direction of the substrate and the distance is 2 mm. Arranged to be.
  • the width of the magnetic field forming means 40a to 40f was 200 mm, which is the same as that of the targets 31a to 31f.
  • Ar, H 2 O and O 2 as sputtering gases were introduced into the system from the gas supply system.
  • a film was formed for 10 seconds under the conditions, and the thickness of the obtained thin film was measured to be 12 nm.
  • the film formation rate is as high as 72 nm / min and is suitable for mass production.
  • the obtained glass substrate with a thin film was put into an electric furnace, heat-treated in air at 300 ° C. for 60 minutes (under atmospheric atmosphere), cut into a size of 1 cm 2 , and hole measurement was performed by a 4-probe method.
  • the carrier concentration was 9.03 ⁇ 10 16 cm ⁇ 3 , and it was confirmed that the semiconductor was sufficiently semiconductorized. Further, from XRD measurement, it was confirmed that the film was amorphous immediately after deposition of the thin film and was amorphous after heat treatment in air at 300 ° C. for 60 minutes.
  • Comparative Example 5 In place of the target prepared in Example 1-8, six targets 31a to 31f having a width of 200 mm, a length of 1700 mm, and a thickness of 10 mm manufactured in Comparative Example 1 were used, and the film formation conditions and annealing conditions shown in Table 5 were used. Thus, an oxide semiconductor thin film and a thin film transistor were prepared and evaluated in the same manner as in Examples 17-24. The results are shown in Table 5. As shown in Table 5, it can be seen that the device of Comparative Example 5 has significantly lower field effect mobility and higher threshold voltage and S value than the devices of Examples 17-24.
  • Example 25 [Production of sintered oxide] Example 1 except that raw material powders were mixed at the atomic ratios shown in Table 6 and sintered at the heating rate, sintering temperature, heating rate, maximum temperature, maximum temperature holding time and cooling rate shown in Table 6. A sintered body was produced in the same manner as in Example 8.
  • X-ray diffraction measurement apparatus 9 and 10 show X-ray diffraction charts of the sintered bodies obtained in Examples 25 and 26, respectively.
  • the measurement conditions of X-ray diffraction measurement are as follows. ⁇ Equipment: Ultimate-III manufactured by Rigaku Corporation -X-ray: Cu-K ⁇ ray (wavelength 1.5406mm, monochromatized with graphite monochromator) ⁇ 2 ⁇ - ⁇ reflection method, continuous scan (1.0 ° / min) ⁇ Sampling interval: 0.02 ° ⁇ Slit DS, SS: 2/3 °, RS: 0.6 mm
  • the sintered body of Example 25 has a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 , and Zn 2 In 2 O 5. The homologous structure of was observed. These crystal structures were confirmed with a JCPDS card.
  • the sintered body of Example 26 includes a homologous structure of InAlZn 2 O 5 , a spinel structure of Zn 2 SnO 4 , a bixbite structure of In 2 O 3 , and Zn 2 In as in the sintered body of Example 25. A homologous structure of 2 O 5 was observed.
  • the homologous structure of InAlZn 2 O 5 is the same as that of JCPDS database No. It is a peak pattern of 40-0259.
  • the spinel structure of Zn 2 SnO 4 is No. 1 in the JCPDS database. It is a peak pattern of 24-1470.
  • In 2 O 3 has a big byte structure of No. of JCPDS database. This is a peak pattern of 06-0416.
  • the homologous structure of Zn 2 In 2 O 5 is No. 1 in the JCPDS database. 20-1442 peak pattern.
  • the sintered bodies of Examples 25 to 26 are homologous structure compounds represented by InAlO 3 (ZnO) m (m is 0.1 to 10), bixbite structure compounds of In 2 O 3 and Zn 2 SnO 4, respectively. It was confirmed that the sintered body contained the spinel structure compound.
  • each aggregate of Al and Sn having a major axis of 8 ⁇ m or more was not observed.
  • the aggregate is a portion where other elements are not detected in EPMA observation.
  • an aggregate of Al only Al is observed except for oxygen and impurities that can be detected in the background in EPMA observation. From this result, it was found that the sputtering targets of Examples 25 and 26 were extremely excellent in dispersibility and uniformity.
  • the measurement conditions for EPMA are as follows. Device name: JEOL Ltd. JXA-8200 Acceleration voltage: 15 kV Irradiation current: 50 nA Irradiation time (per point): 50mS
  • the obtained sputtering target having a diameter of 4 inches was mounted on a DC sputtering apparatus, and a mixed gas in which 2% of H 2 O gas was added to argon gas at a partial pressure ratio was used as the atmosphere, the sputtering pressure was 0.4 Pa, and the substrate temperature was room temperature. Then, 10 kWh continuous sputtering was performed at a DC output of 400 W. Voltage fluctuations during sputtering were accumulated in a data logger, and the presence or absence of abnormal discharge was confirmed. The results are shown in Table 6. In addition, the presence or absence of abnormal discharge was performed by monitoring voltage fluctuation and detecting abnormal discharge.
  • the abnormal discharge was determined when the voltage fluctuation generated during the measurement time of 5 minutes was 10% or more of the steady voltage during the sputtering operation.
  • the steady-state voltage during sputtering operation varies by ⁇ 10% in 0.1 second, a micro arc, which is an abnormal discharge of the sputter discharge, has occurred, and the device yield may decrease, making it unsuitable for mass production. is there.
  • Nodules are measured after sputtering at a total of five points: the center point (one place) of the circular sputtering target and the center point (four places) between the center point and the peripheral part on two center lines orthogonal to the center point.
  • a method of measuring the number average of nodules having a major axis of 20 ⁇ m or more generated in a visual field of 3 mm 2 was observed by observing the change of the target surface 50 times with a stereomicroscope. Table 6 shows the number of nodules generated.
  • Examples 27-30 [Manufacture of thin film transistors]
  • a conductive silicon substrate with a thermal oxide film having a thickness of 100 nm was used as the substrate.
  • the thermal oxide film functions as a gate insulating film, and the conductive silicon portion functions as a gate electrode.
  • the conductive silicon substrate with the thermal oxide film was cleaned with an extremely low concentration HCN aqueous solution (cleaning solution) of 1 ppm and pH 10. Washing was performed with the temperature set at 30 ° C.
  • HCN aqueous solution cleaning solution
  • OFPR # 800 manufactured by Tokyo Ohka Kogyo Co., Ltd. was used as a resist, and coating, pre-baking (80 ° C., 5 minutes), and exposure were performed. After development, it was post-baked (120 ° C., 5 minutes), etched with oxalic acid, and patterned into a desired shape. Thereafter, the elements of Examples 27 and 28 were subjected to heat treatment (annealing) at 450 ° C. for 60 minutes in a hot air heating furnace, and the elements of Examples 29 and 30 were subjected to heat treatment (annealing) at 300 ° C. for 60 minutes. Treatment). Thereafter, Mo (200 nm) was formed by sputtering film formation.
  • the source / drain electrodes were patterned into a desired shape by channel etching.
  • nitrous oxide plasma treatment was performed on the oxide semiconductor film as a pre-treatment for forming a protective film as shown in Table 7.
  • a SiOx film having a thickness of 100 nm was formed by a plasma CVD method (PECVD), and a SiNx film having a thickness of 150 nm was formed on the SiOx by a plasma CVD method (PECVD), and a laminate of SiOx and SiNx was used as a protective film.
  • a contact hole was opened using dry etching to manufacture a back channel etch type thin film transistor.
  • the crystallinity of the channel layer of the thin film transistor with a protective film was evaluated by an electron beam diffraction pattern using a cross-sectional TEM (Transmission Electron Microscope).
  • a cross-sectional TEM Transmission Electron Microscope
  • Hitachi field emission type transmission electron microscope HF-2100 was used.
  • the diffraction pattern was not observed on the front channel side and was amorphous, but the diffraction pattern was partially observed on the back channel side. It was found to have a crystallized region.
  • no diffraction pattern was observed on the front channel side and the back channel side, and it was confirmed to be amorphous.
  • the transfer characteristics were evaluated with a drain voltage (Vd) of 1 V and a gate voltage (Vg) of ⁇ 15 to 20 V. These results are shown in Table 7.
  • the field effect mobility ( ⁇ ) was calculated from the linear mobility and defined as the maximum value of Vg ⁇ .
  • Comparative Examples 6 and 7 Same as Example 27-30, except that the target prepared in Comparative Examples 1 and 2 was used and cleaning with HCN aqueous solution (cleaning liquid) and nitrous oxide plasma treatment were not performed on the channel according to the sputtering conditions and annealing conditions shown in Table 8 A back channel etch type thin film transistor was fabricated and evaluated. The results are shown in Table 8. As shown in Table 8, the back channel etch thin film transistors of Comparative Examples 6 and 7 have a field effect mobility of less than 10 cm 2 / Vs, which is significantly lower than the back channel etch thin film transistors of Examples 27-30. I understand.
  • the threshold voltage was significantly shifted in the positive direction as compared with the TFTs of Examples 27-30, and it was found that the TFTs of the comparative examples had low reliability.
  • no diffraction pattern was observed on the front channel side and the back channel side, and it was confirmed that the channel layer was amorphous.
  • a thin film transistor including an oxide semiconductor thin film obtained using the sputtering target of the present invention can be used for a display device, particularly for a large-area display.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Physical Vapour Deposition (AREA)
  • Thin Film Transistor (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)

Abstract

L'invention concerne une cible de pulvérisation, qui est constituée d'oxydes contenant de l'indium (In), de l'étain (Sn), du zinc (Zn) et de l'aluminium (Al), et comprend un composé a structure homologue représenté par la formule InAlO3(ZnO)m (m étant compris entre 0,1 et 10), un composé à structure de bixbyite représenté par la formule In2O3 et un composé à structure de spinelle, représenté par la formule Zn2SnO4.
PCT/JP2014/000149 2013-01-16 2014-01-15 Cible de pulvérisation, couche mince d'oxydes semi-conducteurs et procédé de fabrication de celles-ci WO2014112369A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014557405A JPWO2014112369A1 (ja) 2013-01-16 2014-01-15 スパッタリングターゲット、酸化物半導体薄膜及びこれらの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013005666 2013-01-16
JP2013-005666 2013-01-16
JP2013-042289 2013-03-04
JP2013042289 2013-03-04

Publications (1)

Publication Number Publication Date
WO2014112369A1 true WO2014112369A1 (fr) 2014-07-24

Family

ID=51209465

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/000149 WO2014112369A1 (fr) 2013-01-16 2014-01-15 Cible de pulvérisation, couche mince d'oxydes semi-conducteurs et procédé de fabrication de celles-ci

Country Status (3)

Country Link
JP (1) JPWO2014112369A1 (fr)
TW (1) TW201435120A (fr)
WO (1) WO2014112369A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019026954A1 (fr) * 2017-08-01 2019-02-07 出光興産株式会社 Cible de pulvérisation, couche mince semi-conductrice à oxyde, transistor à couches minces et dispositif électronique
JPWO2019131876A1 (ja) * 2017-12-28 2020-12-10 三井金属鉱業株式会社 酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜
WO2021112006A1 (fr) * 2019-12-02 2021-06-10 三菱マテリアル株式会社 Cible de pulvérisation d'oxyde, et procédé de production de cible de pulvérisation d'oxyde
WO2021111970A1 (fr) * 2019-12-02 2021-06-10 三菱マテリアル株式会社 Cible de pulvérisation d'oxyde et procédé de production de cible de pulvérisation d'oxyde

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142289A1 (fr) * 2008-05-22 2009-11-26 出光興産株式会社 Cible de pulvérisation, procédé de formation d’un film mince d’oxyde amorphe l’utilisant et procédé de fabrication d’un transistor à couche mince
WO2010058533A1 (fr) * 2008-11-20 2010-05-27 出光興産株式会社 OXYDE FRITTÉ À BASE DE ZnO-SnO2-In2O3 ET FILM CONDUCTEUR TRANSPARENT AMORPHE
WO2012127883A1 (fr) * 2011-03-24 2012-09-27 出光興産株式会社 Matériau fritté et son procédé de fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009142289A1 (fr) * 2008-05-22 2009-11-26 出光興産株式会社 Cible de pulvérisation, procédé de formation d’un film mince d’oxyde amorphe l’utilisant et procédé de fabrication d’un transistor à couche mince
WO2010058533A1 (fr) * 2008-11-20 2010-05-27 出光興産株式会社 OXYDE FRITTÉ À BASE DE ZnO-SnO2-In2O3 ET FILM CONDUCTEUR TRANSPARENT AMORPHE
WO2012127883A1 (fr) * 2011-03-24 2012-09-27 出光興産株式会社 Matériau fritté et son procédé de fabrication

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019026954A1 (fr) * 2017-08-01 2019-02-07 出光興産株式会社 Cible de pulvérisation, couche mince semi-conductrice à oxyde, transistor à couches minces et dispositif électronique
JPWO2019026954A1 (ja) * 2017-08-01 2020-09-10 出光興産株式会社 スパッタリングターゲット、酸化物半導体薄膜、薄膜トランジスタおよび電子機器
JP7075934B2 (ja) 2017-08-01 2022-05-26 出光興産株式会社 スパッタリングターゲット、酸化物半導体薄膜、薄膜トランジスタおよび電子機器
JPWO2019131876A1 (ja) * 2017-12-28 2020-12-10 三井金属鉱業株式会社 酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜
JP7269886B2 (ja) 2017-12-28 2023-05-09 三井金属鉱業株式会社 酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜
WO2021112006A1 (fr) * 2019-12-02 2021-06-10 三菱マテリアル株式会社 Cible de pulvérisation d'oxyde, et procédé de production de cible de pulvérisation d'oxyde
WO2021111970A1 (fr) * 2019-12-02 2021-06-10 三菱マテリアル株式会社 Cible de pulvérisation d'oxyde et procédé de production de cible de pulvérisation d'oxyde
CN114616218A (zh) * 2019-12-02 2022-06-10 三菱综合材料株式会社 氧化物溅射靶及氧化物溅射靶的制造方法

Also Published As

Publication number Publication date
JPWO2014112369A1 (ja) 2017-01-19
TW201435120A (zh) 2014-09-16

Similar Documents

Publication Publication Date Title
JP5965338B2 (ja) スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
JP6284710B2 (ja) スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
JP6622855B2 (ja) スパッタリングターゲット、酸化物半導体薄膜及び当該酸化物半導体薄膜を備える薄膜トランジスタ
WO2014073210A1 (fr) Cible de pulvérisation, film mince semi-conducteur à oxyde et procédés permettant de fabriquer ces produits
JP2014218706A (ja) スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
JP2014214359A (ja) スパッタリングターゲット、酸化物半導体薄膜及び当該酸化物半導体薄膜を備える薄膜トランジスタ
CN104704138B (zh) 溅射靶、氧化物半导体薄膜及它们的制造方法
JP6353369B2 (ja) スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
WO2014112369A1 (fr) Cible de pulvérisation, couche mince d'oxydes semi-conducteurs et procédé de fabrication de celles-ci
JP6141332B2 (ja) スパッタリングターゲット、酸化物半導体薄膜及びそれらの製造方法
JP6470352B2 (ja) 酸化物半導体薄膜
JP6188712B2 (ja) スパッタリングターゲット
JP6006055B2 (ja) スパッタリングターゲット
WO2014034122A1 (fr) Cible de pulvérisation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14740688

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014557405

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14740688

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载