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WO2012121298A1 - Corps fritté d'oxyde, son procédé de fabrication et cible l'utilisant - Google Patents

Corps fritté d'oxyde, son procédé de fabrication et cible l'utilisant Download PDF

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Publication number
WO2012121298A1
WO2012121298A1 PCT/JP2012/055855 JP2012055855W WO2012121298A1 WO 2012121298 A1 WO2012121298 A1 WO 2012121298A1 JP 2012055855 W JP2012055855 W JP 2012055855W WO 2012121298 A1 WO2012121298 A1 WO 2012121298A1
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Prior art keywords
powder
oxide powder
oxide
sintered body
zinc
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Japanese (ja)
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邦彦 中田
翔平 堀田
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • 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
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    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3237—Substoichiometric titanium oxides, e.g. Ti2O3
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    • 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
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    • 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
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • 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
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    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
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    • C04B2235/74—Physical characteristics
    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1

Definitions

  • the present invention relates to an oxide sintered body useful for forming a zinc oxide-based transparent conductive film by a sputtering method, an ion plating method, a pulse laser deposition (PLD) method, an electron beam (EB) vapor deposition method, and the like, and a method for producing the same.
  • PLD pulse laser deposition
  • EB electron beam
  • Transparent conductive films that combine electrical conductivity and light transmission have been used as electrodes in solar cells, liquid crystal display elements, and other various light receiving elements, as well as automotive windows, heat ray reflective films for buildings, and antistatic properties. It is used in a wide range of applications, such as transparent anti-fogging elements for anti-fogging in membranes and frozen showcases.
  • a transparent conductive film having a low resistance and excellent conductivity is suitable for a solar cell, a liquid crystal display element such as a liquid crystal, organic electroluminescence, and inorganic electroluminescence, a touch panel, and the like.
  • a tin oxide (SnO 2 ) -based thin film such as an antimony-doped tin oxide (ATO) film or a fluorine-doped tin oxide (FTO) film; an aluminum-doped zinc oxide (AZO) film or a gallium-doped film Zinc oxide (ZnO) -based thin films such as zinc oxide (GZO) films; and indium oxide (In 2 O 3 ) -based thin films such as tin-doped indium oxide (ITO) films are known.
  • ATO antimony-doped tin oxide
  • FTO fluorine-doped tin oxide
  • ZnO zinc oxide
  • ITO indium oxide
  • the most industrially used is an indium oxide-based transparent conductive film, and in particular, an ITO film is widely used because of its low resistance and excellent conductivity.
  • the target when an oxide film such as ITO is formed by sputtering, the target is generally an alloy target made of a metal element constituting the film (In—Sn alloy in the case of an ITO film), Alternatively, an oxide target (a sintered body or a mixture made of In—Sn—O in the case of an ITO film) formed by sintering or mixing an oxide containing a metal element constituting the film is used.
  • an alloy target when an alloy target is used, all the oxygen in the formed film is supplied from the oxygen gas in the atmosphere, so that the amount of oxygen gas in the atmosphere tends to fluctuate. As a result, it may be difficult to keep the film formation rate depending on the amount of oxygen gas in the atmosphere and the characteristics (specific resistance, transmittance) of the obtained film constant.
  • oxide targets that is, oxide sintered bodies or oxide mixtures
  • Non-Patent Document 1 reports an attempt to dope various dopants into ZnO in order to increase conductivity.
  • titanium oxide instead of tetravalent titanium oxide (TiO 2 (IV)) as a titanium source as a dopant
  • the content of titanium useful for improving chemical durability is reduced. It has been found that it can be further increased. Furthermore, it has been found that it has low resistance and excellent near-infrared transmittance which is promising for transparent conductive films such as solar cells.
  • the conductivity of a target made of normal titanium-doped zinc oxide (TZO) is inferior to that of conventionally used AZO and GZO, when a film is formed by direct current (DC) sputtering using a TZO target.
  • DC direct current
  • An object of the present invention is to provide a target capable of forming a zinc oxide-based transparent conductive film having a conductivity equivalent to that of AZO or GZO and excellent in chemical durability by a DC sputtering method and a method for producing the same Is to provide.
  • an object of the present invention is to provide an oxide sintered body useful for target production and a method for producing the same. Furthermore, the subject of this invention is providing the method of manufacturing the zinc oxide type transparent conductive film which has the same level of electroconductivity as AZO and GZO, and was excellent in chemical durability with sufficient productivity.
  • An oxide sintered body in which titanium is derived from low-valent titanium oxide represented by the formula: TiO 2 -X (X 0.1 to 1).
  • the atomic ratio [TE / (Zn + Ti + TE)] of the at least one minor additive element (TE) to the sum of the zinc, the titanium and the at least one minor additive element (TE) is 0.001.
  • the atomic ratio [Ti / (Zn + Ti + TE)] of the titanium to the sum of the zinc, the titanium, and the at least one trace additive element (TE) is greater than 0.02, and
  • a method for producing a zinc oxide-based transparent conductive film A step of putting raw material powder containing the mixed powder of (A) or (B) shown below into a graphite mold and pressure sintering at 600 ° C. to 1500 ° C.
  • the oxide sintered body and target obtained by the present invention have the same level of conductivity as AZO and GZO, and can form a zinc oxide-based transparent conductive film with high productivity.
  • a titanium-doped zinc oxide that can form a film in a stable discharge state with high productivity even in the DC sputtering method, and has both excellent conductivity and chemical durability. It is possible to stably manufacture a transparent conductive film.
  • the transparent conductive film produced in this way is extremely useful industrially because it has an advantage that indium which is a rare metal is not essential.
  • the oxide sintered body according to the present invention is substantially composed of zinc, titanium derived from a specific titanium oxide, oxygen, and a trace additive element (at least one selected from the group consisting of aluminum, gallium and indium). Become.
  • “substantially” means that 99% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, oxygen, and a trace amount of added elements.
  • preferably 99.9% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, oxygen, and a trace amount of additive elements.
  • the oxide sintered body according to the present invention has a density of 5.3 g / cm 3 or more, the conductivity of a target obtained using the oxide is preferably excellent.
  • the oxide sintered body has a density of 5.3 g / cm 3 or more, the relative density is about 95% or more.
  • the oxide sintered body of the present invention preferably has a density of 5.3 g / cm 3 to 5.6 g / cm 3 , more preferably a density of 5.5 g / cm 3 to 5.6 g / cm 3 .
  • the oxide sintered body according to the present invention usually has a specific resistance of 12 m ⁇ ⁇ cm or less.
  • the film formation rate during DC sputtering depends on the specific resistance of the oxide sintered body that is the sputtering target.
  • a sintered body such as AZO or GZO usually has a specific resistance of 12 m ⁇ ⁇ cm or less, and can increase the input power, enabling high-speed film formation and high production efficiency.
  • the specific resistance of the oxide sintered body according to the present invention is preferably as low as possible, specifically preferably 10 m ⁇ ⁇ cm or less, more preferably less than 10 m ⁇ ⁇ cm, More preferably, it is less than 8 m ⁇ ⁇ cm.
  • Titanium contained in the oxide sintered body according to the present invention is a main component of the dopant, and a trace additive element (at least one selected from the group consisting of aluminum, gallium, and indium) has an action of reducing specific resistance.
  • a trace additive element at least one selected from the group consisting of aluminum, gallium, and indium
  • Such low-valent titanium oxide is usually obtained by heating titanium dioxide (TiO 2 ) in a reducing atmosphere such as a hydrogen atmosphere using carbon or the like as a reducing agent.
  • the ratio of the low-valent titanium oxide mixture can be controlled.
  • the structure of the low valence titanium oxide can be confirmed by instrumental analysis such as an X-ray diffraction apparatus (X-Ray Diffraction, XRD), an X-ray photoelectron spectrometer (X-ray Photoelectron Spectroscopy, XPS).
  • the atomic ratio [TE / (Zn + Ti + TE)] of the trace additive element (TE) to the total of zinc, titanium and trace additive element (TE) is more than 0.001. And less than 0.005.
  • the atomic ratio [(TE) / (Zn + Ti + TE)] of the trace additive element (TE) is in the above range, the characteristics of the film formed using the oxide sintered body as a target are not impaired. The specific resistance can be further reduced.
  • the atomic ratio [TE / (Zn + Ti + TE)] of the trace additive element (TE) is 0.0015 to 0.0045, more preferably 0.002 to 0.004.
  • the atomic ratio [Ti / (Zn + Ti + TE)] of titanium to the total of zinc, titanium, and a trace additive element (TE) is greater than 0.02, and , 0.1 or less.
  • the atomic ratio [Ti / (Zn + Ti + TE)] of titanium is in the above range, the strength of the sintered body is improved and the processing of the target becomes easy. Furthermore, the chemical durability, conductivity, and transparency of the conductive film formed are further improved.
  • the atomic ratio [Ti / (Zn + Ti + TE)] of titanium is 0.03 to 0.09.
  • the oxide sintered body according to the present invention is preferably composed of a zinc oxide phase and a zinc titanate compound phase, or composed of a zinc titanate compound phase.
  • the zinc titanate compound phase is contained in the oxide sintered body as described above, the strength of the sintered body itself is increased. For example, even if the film is formed under severe conditions (high power, etc.) as a target. Less prone to cracking.
  • titanium element is dissolved in the zinc site of ZnTiO 3 , Zn 2 TiO 4 , ZnTiO 3 or Zn 2 TiO 4 , and oxygen deficiency is generated from ZnTiO 3 or Zn 2 TiO 4 ,
  • a non-stoichiometric composition having a Zn / Ti ratio slightly deviated from a ZnTiO 3 or Zn 2 TiO 4 compound may be included.
  • the zinc oxide phase includes ZnO, ZnO in which titanium, aluminum, gallium or indium is dissolved, ZnO having oxygen deficiency, ZnO having non-stoichiometric composition due to zinc deficiency, etc. It's okay.
  • the zinc oxide phase usually has a wurtzite structure.
  • the oxide sintered body according to the present invention does not substantially contain a crystal phase of titanium oxide. If the oxide sintered body contains a crystal phase of titanium oxide, the resulting film may be uneven in physical properties such as specific resistance and lack uniformity. As described above, for example, when the value of Ti / (Zn + Ti + TE) is 0.1 or less, usually, titanium oxide completely reacts with zinc oxide, and a titanium oxide crystal phase is hardly generated in the oxide sintered body. .
  • the crystal phase of titanium oxide specifically includes, in addition to Ti 2 O 3 and TiO, substances in which other elements such as Zn are dissolved in these crystals.
  • the method for producing the oxide sintered body according to the present invention is not particularly limited, and for example, the oxide sintered body according to the present invention is preferably obtained by the production method described later.
  • the first method for producing an oxide sintered body according to the present invention (hereinafter sometimes simply referred to as “the first production method of the present invention”) is the following (A) or (B) A step of forming a raw material powder containing the mixed powder, and a step of sintering the molded body obtained by the forming step at 600 ° C. to 1500 ° C.
  • the second method for producing an oxide sintered body according to the present invention is a raw material powder containing the above (A) or (B) A molded body obtained by the molding process, a sintered body obtained by sintering at 600 to 1500 ° C. in an air atmosphere or an oxidizing atmosphere, and a sintered body obtained by the sintering process, Annealing in an inert atmosphere, a vacuum, or a reducing atmosphere.
  • the above mixed powder (A) or (B) is used, preferably, (A ′) mixed powder of at least one powder selected from the group consisting of titanium oxide (III) powder, aluminum oxide powder, gallium oxide powder and indium oxide powder, and zinc oxide powder, or (B ′) titanium oxide (III) Mixed powder of at least one powder selected from the group consisting of powder and aluminum oxide powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder, Is used.
  • the zinc oxide powder a powder such as ZnO having a wurtzite structure is usually used, and further, this ZnO previously fired in a reducing atmosphere to cause oxygen deficiency may be used.
  • the zinc hydroxide powder may be amorphous or have a crystal structure.
  • the aluminum oxide powder is not particularly limited, and a normal powder such as ⁇ -alumina is used.
  • the gallium oxide powder is not particularly limited, and a normal powder such as ⁇ -gallium oxide is used.
  • the indium oxide powder is not particularly limited, and ordinary indium oxide powder or the like is used.
  • the average particle size of the compound (powder) used as the raw material powder is preferably 5 ⁇ m or less.
  • the mixing ratio of each powder in the mixed powder can be appropriately set according to the type of compound (powder) to be used. For example, what is necessary is just to set suitably so that atomic number ratio may become the range mentioned above in the oxide sintered compact finally obtained. At that time, considering that zinc has a higher vapor pressure than titanium and is likely to volatilize during sintering, it is more than the desired composition of the desired oxide sintered body (atomic ratio of Zn and Ti). It is preferable to set the mixing ratio in advance so that the amount of zinc increases.
  • the easiness of volatilization of zinc varies depending on the atmosphere during sintering.
  • the atmosphere during sintering For example, when zinc oxide powder is used, only the volatilization of zinc oxide powder itself occurs in an air atmosphere or an oxidizing atmosphere.
  • zinc oxide When sintered in a reducing atmosphere, zinc oxide is reduced and becomes metal zinc that is more easily volatilized than zinc oxide, and the amount of zinc lost increases.
  • the amount of zinc to be increased with respect to the target composition may be set in consideration of the sintering atmosphere or the like.
  • the compound (powder) used as a raw material powder may be only one kind, respectively, and may be two or more kinds.
  • the forming method in the step of forming the raw material powder included in the first manufacturing method and the second manufacturing method of the present invention is not particularly limited.
  • the raw material powder and an aqueous solvent are mixed and obtained. After the obtained slurry is sufficiently mixed by wet mixing, solid-liquid separation, drying, and granulation obtained by granulation can be mentioned.
  • the wet mixing may be performed by, for example, a wet ball mill using a hard ZrO 2 ball or a vibration mill, and the mixing time in the case of using a wet ball mill or a vibration mill is preferably about 12 hours to about 78 hours.
  • the raw material powder may be dry mixed as it is, but wet mixing is more preferable.
  • Known methods may be employed for solid-liquid separation, drying, and granulation.
  • the granulated product can be molded by putting it in a mold and pressurizing it.
  • molding the raw material powder obtained by dry-mixing and the raw material powder obtained by drying after wet-mixing it can shape
  • the pressurizing method include a method using a cold forming machine such as a cold isostatic press and a uniaxial press. Regardless of whether it is a cold isostatic press or a uniaxial press, if the pressure is too low, a stable press-molded body may not be formed. If the pressure is too high, the molded body tends to be brittle.
  • the pressure is usually 50 MPa or more and 200 MPa or less, preferably 100 MPa or more and 200 MPa or less, and in the case of a uniaxial press, it is usually 10 MPa or more and 50 MPa or less, preferably 20 MPa or more and 50 MPa or less.
  • a hot press or the like When forming by hot pressing using a hot press or the like, it is disadvantageous in terms of manufacturing cost and it may be difficult to obtain a large sintered body.
  • the shape and dimensions of the molded body are not particularly limited, and examples thereof include a cylinder and a rectangular parallelepiped.
  • a binder for example, polyvinyl alcohol, vinyl acetate, ethyl cellulose and the like can be used.
  • sintering of the molded body obtained by the molding step is performed in an inert atmosphere (for example, nitrogen, argon, helium, neon, etc.), vacuum, reducing atmosphere (for example, carbon dioxide, hydrogen, ammonia, etc.), an air atmosphere, and an oxidizing atmosphere (an atmosphere having an oxygen concentration higher than the air) are performed at 600 ° C. to 1500 ° C.
  • an oxidizing atmosphere an atmosphere having a higher oxygen concentration than the air
  • annealing is further performed in an inert atmosphere, a vacuum, or a reducing atmosphere. This annealing treatment is performed in order to cause oxygen deficiency in the oxide sintered body and lower the specific resistance. Even when sintering is performed in an inert atmosphere, a vacuum, or a reducing atmosphere, if it is desired to further reduce the specific resistance, annealing may be performed after the sintering.
  • the sintering temperature is less than 600 ° C., the sintering does not proceed sufficiently, so that the target density is lowered. On the other hand, if it exceeds 1500 ° C., zinc oxide itself is decomposed and disappears.
  • the sintering is more preferably performed at 1000 ° C. to 1300 ° C.
  • the rate of temperature increase is from 5 ° C./min to 10 ° C./min up to 600 ° C., and from 1 ° C./min to over 1500 ° C. up to 1500 ° C. It is preferable to set it to 4 ° C./min in order to make the sintered density uniform.
  • the sintering time (that is, the holding time at the sintering temperature) is preferably 3 hours to 15 hours. If the sintering time is less than 3 hours, the sintered density tends to be insufficient, and the strength of the resulting oxide sintered body tends to decrease. On the other hand, if it exceeds 15 hours, the crystal grains of the sintered body As the growth becomes remarkable, there is a tendency that the pores are coarsened and consequently the maximum pore diameter is increased, and as a result, the sintered density may be lowered.
  • the sintering method in the sintering step is not particularly limited, and examples thereof include a normal pressure firing method, a microwave sintering method, and a millimeter wave sintering method.
  • a third method for producing an oxide sintered body according to the present invention involves placing the raw material powder in a graphite mold and vacuuming.
  • a step of pressure sintering at 600 ° C. to 1500 ° C. in an inside or inert atmosphere.
  • the pressure sintering method include a hot press method, a hot isostatic pressing (HIP) method, and a discharge plasma sintering method.
  • the atmosphere during pressure sintering is a vacuum (for example, 2 Pa or less) or an inert atmosphere (for example, nitrogen, argon, helium, neon, etc.), preferably a vacuum.
  • the pressure applied to the raw material powder during pressure sintering is preferably 20 MPa to 150 MPa, more preferably 30 MPa to 100 MPa.
  • the sintering temperature during the pressure sintering is preferably 1000 ° C. to 1600 ° C., more preferably 1100 ° C. to 1400 ° C.
  • the pressure sintering time may be appropriately adjusted depending on the sintering temperature, the amount of raw material powder, etc., and is usually 30 minutes to 4 hours, more preferably 1 hour to 2 hours.
  • the oxide sintered body obtained by the third production method of the present invention may be annealed in an inert atmosphere, a vacuum, or a reducing atmosphere in order to further reduce the specific resistance.
  • a normal pressure is introduced while introducing a non-oxidizing gas such as nitrogen, argon, helium, carbon dioxide or hydrogen.
  • a method of heating under vacuum preferably 2 Pa or less. From the viewpoint of production cost, a method of carrying out at normal pressure while introducing a non-oxidizing gas is advantageous.
  • the annealing temperature is preferably 1000 ° C. to 1400 ° C., more preferably 1100 ° C. to 1300 ° C.
  • the annealing time is preferably 7 hours to 15 hours, more preferably 8 hours to 12 hours.
  • oxygen deficiency due to the annealing treatment may be insufficient.
  • the annealing temperature exceeds 1400 ° C., zinc tends to be volatilized, and the composition of the obtained oxide sintered body There is a possibility that (the atomic ratio of Zn and Ti) is different from the desired ratio.
  • the zinc oxide sintered body obtained by the first, second or third production method of the present invention usually has a density of 5.3 g / cm 3 or more and a specific resistance of 12 m ⁇ ⁇ cm or less. .
  • the target according to the present invention is a target used in various film forming methods, and in particular, is a target used for film forming by a sputtering method (preferably, a DC sputtering method excellent in mass productivity).
  • the target of the present invention is obtained by processing the above-described oxide sintered body of the present invention into a predetermined shape and a predetermined dimension.
  • the method for obtaining the target by processing the oxide sintered body according to the present invention is not particularly limited, and a known method may be adopted as appropriate.
  • the target of the present invention can be obtained by subjecting the oxide sintered body to surface grinding or the like, and then cutting the oxide sintered body into a predetermined size and attaching it to a support base. If necessary, a plurality of oxide sintered bodies may be arranged in a divided shape to form a large area target (composite target).
  • the target according to the present invention can be used preferably as a sputtering target, more preferably as a target for DC sputtering.
  • the method for producing a transparent conductive film using the target according to the present invention is not particularly limited, and a known method may be adopted as appropriate.
  • a transparent conductive film can be produced using the target according to the present invention by sputtering, ion plating, pulse laser deposition (PLD), or electron beam (EB) vapor deposition.
  • the method for forming the zinc oxide-based transparent conductive film according to the present invention is preferably a sputtering method, and more preferably a DC sputtering method.
  • the transparent conductive film formed using the oxide sintered body according to the present invention or the target according to the present invention has excellent conductivity and chemical durability (heat resistance, moisture resistance, chemical resistance (alkali resistance, acid resistance)). Etc.).
  • Such transparent conductive films include, for example, transparent electrodes such as liquid crystal displays, plasma displays, inorganic EL (electroluminescence) displays, organic EL displays, and electronic papers; window electrodes of photoelectric conversion elements of solar cells; transparent touch panels, etc. It is suitably used for applications such as an electrode of an input device; an electromagnetic shielding film of an electromagnetic shield.
  • the transparent conductive film formed using the oxide sintered body of the present invention or the target of the present invention can be used as a transparent radio wave absorber, an ultraviolet absorber, or a transparent semiconductor device with other metal films or metal oxide films. It can also be used in combination.
  • the specific resistance of the sintered body and the transparent conductive film was determined by the following method.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 5 mm.
  • the molded body was sintered at 1200 ° C. for 4 hours in an argon atmosphere at normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (1).
  • EDX-700L energy dispersive X-ray fluorescence apparatus
  • a transparent substrate (7 mm-thick alkali-free glass: Eagle XG manufactured by Corning
  • a target obtained in a sputtering apparatus (“E-200” manufactured by Canon Anelva Engineering Co., Ltd.) and Ar gas (P
  • a transparent conductive film was formed.
  • the film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of a small amount of aluminum.
  • Example 2 An oxide sintered body (2) in the same manner as in Example 1 except that gallium oxide powder (Ga 2 O 3 : manufactured by Sumitomo Chemical Co., Ltd., purity 99.99%) was used instead of aluminum oxide powder. )
  • gallium oxide powder Ga 2 O 3 : manufactured by Sumitomo Chemical Co., Ltd., purity 99.99%) was used instead of aluminum oxide powder.
  • the density of the oxide sintered body (2) was 5.41 g / cm 3 and the specific resistance was 6 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (2) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was low resistance. Therefore, there was no influence by the addition of a small amount of gallium on the transparent conductive film.
  • the density of the oxide sintered body (3) was 5.41 g / cm 3 and the specific resistance was 9 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (3) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of a small amount of indium.
  • blended so that it might become (Al + Ga) / (Zn + Ti + Al + Ga) 0.004).
  • the density of the oxide sintered body (4) was 5.41 g / cm 3 and the specific resistance was 4 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (4) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of trace amounts of aluminum and gallium.
  • the density of the oxide sintered body (5) was 5.49 g / cm 3 and the specific resistance was 10 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (5) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 1.3 ⁇ 10 ⁇ 3 ⁇ ⁇ cm and low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of a small amount of aluminum.
  • Example 6 An oxide sintered body (6) was obtained in the same manner as in Example 5 except that gallium oxide powder (Ga 2 O 3 : manufactured by Sumitomo Chemical Co., Ltd., purity 99.99%) was used instead of aluminum oxide powder. )
  • gallium oxide powder Ga 2 O 3 : manufactured by Sumitomo Chemical Co., Ltd., purity 99.99%) was used instead of aluminum oxide powder.
  • the density of the oxide sintered body (6) was 5.49 g / cm 3 , and the specific resistance was 10 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (6) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 1.5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm and low resistance. Therefore, there was no influence by the addition of a small amount of gallium on the transparent conductive film.
  • blended so that it might become (Al + Ga) / (Zn + Ti + Al + Ga) 0.004).
  • the density of the oxide sintered body (7) was 5.49 g / cm 3 , and the specific resistance was 10 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (7) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 1.3 ⁇ 10 ⁇ 3 ⁇ ⁇ cm and low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of trace amounts of aluminum and gallium.
  • the obtained mixture was put into a mold and molded by a uniaxial press at a molding pressure of 500 kg / cm 2 to obtain a disk-shaped molded body having a diameter of 100 mm and a thickness of 5 mm.
  • This molded body was sintered at 1400 ° C. for 4 hours in an atmospheric atmosphere of normal pressure (1.01325 ⁇ 10 2 kPa) to obtain an oxide sintered body (8).
  • the density of the oxide sintered body (8) was 5.52 g / cm 3 , and the specific resistance was 8 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (8) was used, and a transparent conductive film having a film thickness of 500 nm was formed on the substrate by DC sputtering as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was a low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of a small amount of indium.
  • the density of the oxide sintered body (9) was 5.52 g / cm 3 , and the specific resistance was 8 m ⁇ ⁇ cm.
  • Example 2 a target was prepared in the same manner as in Example 1 except that the oxide sintered body (9) was used, and a transparent conductive film having a thickness of 500 nm was formed on the substrate by DC sputtering in the same manner as in Example 1. A film was formed. The film formation rate was extremely high, and the specific resistance of the obtained transparent conductive film was 4.1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, which was a low resistance. Therefore, there was no influence on the transparent conductive film due to the addition of trace amounts of indium and aluminum.
  • titanium oxide (IV) powder TiO 2 ; manufactured by Wako Pure Chemical Industries, Ltd., purity 99.99%) is used in an atomic ratio without using aluminum oxide powder.
  • the density of the oxide sintered body (C1) was 5.38 g / cm 3 and the specific resistance was 6.2 K ⁇ ⁇ cm.
  • Example 1 a target was produced in the same manner as in Example 1, and an attempt was made to form a transparent conductive film by DC sputtering in the same manner as in Example 1.
  • This target can be formed by an RF sputtering method that can form a film even with an insulator target, but cannot be formed by DC sputtering suitable for industrial production.
  • the density of the oxide sintered body (C2) was 5.30 g / cm 3 , the specific resistance was more than the measurement limit (overload), and was extremely high resistance.
  • Example 2 a target was produced in the same manner as in Example 1, and an attempt was made to form a transparent conductive film by the DC sputtering method in the same manner as in Example 1.
  • This target can be formed by an RF sputtering method that can form a film even with an insulator target, but cannot be formed by DC sputtering suitable for industrial production.
  • the density of the oxide sintered body (C3) was 5.49 g / cm 3 , the specific resistance was more than the measurement limit (overload), and the resistance was extremely high.
  • Example 3 a target was produced in the same manner as in Example 1, and an attempt was made to form a transparent conductive film by the DC sputtering method in the same manner as in Example 1.
  • This target can be formed by an RF sputtering method that can form a film even with an insulator target, but cannot be formed by DC sputtering suitable for industrial production.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
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Abstract

L'invention concerne : une cible ; un procédé de fabrication de la cible ; un corps fritté d'oxyde qui est utile pour fabriquer la cible ; et un procédé de fabrication du corps fritté d'oxyde ; la cible rendant possible, même si une pulvérisation cathodique à courant continu (CC) est utilisée, de former à une productivité élevée un film électroconducteur transparent à base d'oxyde de zinc, ayant un niveau similaire d'électroconductivité à AZO ou GZO et une durabilité chimique exceptionnelle. Ce corps fritté d'oxyde comprend de façon substantielle du zinc, du titane, de l'oxygène et au moins un élément supplémentaire sous forme de traces (TE) choisi dans le groupe consistant en aluminium, gallium et indium, le titane étant issu d'oxyde de titane à faible valence représenté par la formule TiO2-X (X = 0,1 à 1).
PCT/JP2012/055855 2011-03-07 2012-03-07 Corps fritté d'oxyde, son procédé de fabrication et cible l'utilisant Ceased WO2012121298A1 (fr)

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US10316404B2 (en) 2014-12-26 2019-06-11 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing sputtering target
CN114436640A (zh) * 2020-11-06 2022-05-06 湖南七点钟文化科技有限公司 一种氧化锌铝合金靶材的制备方法

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CN104871257B (zh) * 2012-12-17 2017-03-01 住友化学株式会社 氧化锌系透明导电膜

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CN114436640A (zh) * 2020-11-06 2022-05-06 湖南七点钟文化科技有限公司 一种氧化锌铝合金靶材的制备方法

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