WO2022149557A1 - Oxide sputtering target and method for producing oxide sputtering target - Google Patents
Oxide sputtering target and method for producing oxide sputtering target Download PDFInfo
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- WO2022149557A1 WO2022149557A1 PCT/JP2021/048909 JP2021048909W WO2022149557A1 WO 2022149557 A1 WO2022149557 A1 WO 2022149557A1 JP 2021048909 W JP2021048909 W JP 2021048909W WO 2022149557 A1 WO2022149557 A1 WO 2022149557A1
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- oxide
- sputtering target
- oxide sputtering
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010304 firing Methods 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 abstract description 23
- 238000001354 calcination Methods 0.000 abstract description 8
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 description 19
- 239000010936 titanium Substances 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
Definitions
- the present invention relates to an oxide sputtering target made of an oxide sintered body containing Zn as a main component as a metal component, and a method for manufacturing the oxide sputtering target.
- the present application claims priority based on Japanese Patent Application No. 2021-000440 filed in Japan on January 5, 2021, and the contents thereof are incorporated herein by reference.
- a protective film is formed in order to protect the recording layer and the light reflecting film.
- patterned wiring films and electrodes are widely used in electronic devices such as touch panels, solar cells, and organic EL displays, and these wiring films and electrodes have a structure in which a protective film is laminated on a metal film. It is said that.
- Patent Documents 1 and 2 oxide films such as ITO film and ZnO film having excellent visible light transmittance are used.
- the above-mentioned oxide film is formed by a sputtering method using an oxide sputtering target.
- Patent Documents 3 and 4 propose adding various elements to an oxide sputtering target in order to improve the characteristics of a ZnO film formed by a sputtering method.
- Patent Document 3 describes an oxide sputtering target in which Ti and one or more selected from Ga or Al are added to ZnO.
- the content of Ga or Al is 0.03 or less as the atomic number ratio of (Ga + Al) / (Zn + Ti + Ga + Al), and the content of Ti is 0.05 to 0 as the atomic number ratio of Ti / (Zn + Ti + Ga + Al). It is said to be .25.
- Patent Document 4 describes an oxide sputtering target in which Ti and Ga are added to ZnO.
- the Ti and Ga contents are in the range of Ti 1.1 at% or more or Ga 4.5 at% or more
- the Ga content y (at%) is the Ti content x (at%). It is in the range of the value represented by (-2.5x + 9.8) or less and the range of the value represented by the titanium content x (at%) (-0.5x + 1.1) or more.
- Japanese Patent Application Laid-Open No. 07-114841 A) Japanese Patent Application Laid-Open No. 2009-252576 (A) Japanese Patent Application Laid-Open No. 2009-298649 (A) Japanese Patent No. 4295811 (B)
- the characteristics of the formed oxide film vary depending on the initial / middle / final stage of the sputter film formation. In some cases, it was not possible to form an oxide film in a stable manner.
- the present invention has been made in view of the above-mentioned circumstances, and is an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputtering deposition.
- An object of the present invention is to provide a method for producing the oxide sputtering target.
- the oxide sputtering target of the present invention was made based on the above findings, and is composed of an oxide sintered body containing Zn as a main component as a metal component, and has a coefficient of variation of specific resistance value in the thickness direction. It is characterized by being 0.20 or less.
- the oxide sputtering target having the above configuration is composed of an oxide sintered body containing Zn as a main component as a metal component, and the fluctuation coefficient of the specific resistance value in the thickness direction is suppressed to 0.20 or less.
- the reduction state does not differ significantly between the surface layer, which is the sputtered surface of the target, and the inside, and even when sputtering progresses, it is possible to suppress variations in the film resistance of the deposited oxide film. , It becomes possible to stably form a uniform oxide film.
- Ga is 10.0 atomic% or more and 20.0 atomic% or less
- Ti is 0.5 atomic% or more and 5. It is preferably composed of an oxide containing 0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
- an oxide film can be stably formed by a normal sputtering method such as a DC (direct current) sputtering method. Further, when a laminated film with a metal is produced, a laminated film having excellent environmental resistance can be obtained.
- the oxide sputtering target of the present invention further, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, A total of at least one or two or more additive elements selected from the element group consisting of elements of the Pb, Sb, Bi and lanthanoid series, 0.01 atomic% or more and 10.0 with the total metal component as 100 atomic%. It is preferably contained in the range of atomic% or less. In this case, it is possible to form an oxide film having further improved environmental resistance and a lower resistance value.
- the oxide has a composite oxide and the abundance ratio of the composite oxide is 15% or more.
- the oxide sintered body becomes dense, and cracks and cracks during sputtering can be more reliably suppressed.
- the method for producing an oxide sputtering target of the present invention is a method for producing an oxide sputtering target for producing the above-mentioned oxide sputtering target, which is a temporary firing step of tentatively firing a sintered raw material powder and a calcined raw material. It includes a crushing step of crushing the powder and a sintering step of sintering the crushed sintered raw material powder to obtain a sintered body, and the degree of vacuum in the preliminary firing step is within the range of 15 Pa or less. It is characterized in that the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less.
- a calcination step of calcination raw material powder is provided, and the calcination conditions of the calcination step are defined as described above.
- the raw material powder can be reduced to a certain extent, and the local reduction reaction in the subsequent sintering step can be suppressed. As a result, the difference in the degree of reduction in the thickness direction becomes small, and the variation in the specific resistance value in the thickness direction can be suppressed.
- the degree of vacuum in the sintering step is within the range of 15 Pa or less
- the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower
- the sintering temperature is high. It is preferable that the holding time is within the range of 2 hours or more and 6 hours or less.
- the sintering conditions in the sintering step are defined as described above, the composite oxide can be sufficiently produced and a dense oxide sintered body can be obtained.
- an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputter film formation, and a method for manufacturing the oxide sputtering target are provided. Can be provided.
- oxide sputtering target which is an embodiment of the present invention, and a method for manufacturing the oxide sputtering target will be described.
- the oxide sputtering target of the present embodiment is, for example, a protective film of an optical recording medium, a water vapor barrier film in various devices such as a liquid crystal display element, an organic EL element, and a solar cell, a touch panel, a solar cell, an organic EL display, and the like. It is used when forming an oxide film that serves as a wiring film and a protective film for electrodes in an electronic device.
- This oxide film is required to have excellent visible light transmittance, and in the present embodiment, it is an oxide film containing Zn as a main component as a metal component.
- the oxide sputtering target of the present embodiment is made of an oxide sintered body containing Zn as a main component as a metal component.
- the range of the Zn content ratio is preferably 60 atomic% or more and 90 atomic% or less.
- the coefficient of variation of the specific resistance value in the thickness direction is 0.20 or less, and the variation of the specific resistance value is suppressed to be small at least in the thickness direction of the sputtered surface.
- the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less, and the coefficient of variation of the specific resistance value in the thickness direction is more preferably 0.10 or less.
- the lower limit of the coefficient of variation is not particularly limited, but may be 0.001.
- the thickness direction of the oxide sputtering target in the present embodiment means a direction substantially perpendicular to the main surface to be a sputtering surface, that is, a depth direction from the sputtering surface.
- the sputtered surface means a surface on which the sputtering particles are discharged when the sputtering process is performed.
- the oxide sputtering target has a flat plate shape, and the specific resistance value is set at a plurality of points in the thickness direction in one or more, preferably three or more regions in the main surface.
- the coefficient of variation is calculated by the following formula from the average value and standard deviation.
- Ga is 10.0 atomic% or more and 20.0 atomic% or less
- Ti is 0.5 atomic% or more and Ti is 0.5 atomic% or more, assuming that the total of the metal components is 100 atomic%. It may be composed of an oxide containing 5.0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
- additive elements selected from the element group consisting of elements of the lanthanoid series, 0.01 atomic% or more and 10.0 atoms with the total metal component as 100 atomic%. It may be contained in the range of% or less.
- the oxide sputtering target of the present embodiment may have either a single-phase oxide which is an oxide containing a single metal element or a composite oxide which is an oxide containing a plurality of metal elements.
- the abundance ratio of the composite oxide is preferably 15% or more. Further, the abundance ratio of the composite oxide is preferably 50% or less.
- the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less.
- the composite oxide for example, when Ga and Ti are contained in addition to Zn, ZnGa 2 O 4 , ZnTIO 3 , Zn 2 TIO 4 , and the like can be mentioned.
- the abundance ratio of the composite oxide can be calculated from the intensity of the main peak of each phase (single phase oxide, composite oxide) by X-ray diffraction measurement (XRD).
- raw material powder such as zinc oxide powder is prepared.
- gallium oxide powder and titanium oxide powder are prepared in addition to zinc oxide powder, weighed so as to have a predetermined ratio, and mixed with a ball mill or the like. By mixing using an apparatus, a sintered raw material powder is obtained.
- Temporal firing step S02 Next, the sintered raw material powder is tentatively fired.
- the sintered raw material powder is inserted into the carbon crucible and temporarily fired in a vacuum atmosphere.
- the entire sintered raw material powder is slightly reduced.
- the sintered raw material powder may be temporarily fired in a reducing atmosphere such as CO gas or H2 gas.
- the degree of vacuum in the temporary firing step S02 is within the range of 15 Pa or less
- the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower
- the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less. It is said that.
- the crushed sintered raw material powder is filled in a molding die, pressed and heated to be sintered, and a sintered body is obtained.
- sintering is performed by a hot press device.
- the sintering temperature at this time is in the range of 900 ° C. or higher and 1100 ° C. or lower
- the holding time at the sintering temperature is in the range of 2 hours or more and 6 hours or less
- the pressurizing pressure is in the range of 10 MPa or higher and 35 MPa or lower. It is preferably inside.
- the atmosphere is preferably a vacuum atmosphere (15 Pa or less).
- a sufficient density can be obtained by setting the sintering temperature to 900 ° C. or higher.
- by setting the sintering temperature to 1100 ° C. or lower sublimation of zinc oxide can be suppressed, and composition deviation and occurrence of cracking of the sintered body can be suppressed.
- the oxide sputtering target of the present embodiment having the above configuration is composed of an oxide sintered body containing Zn as a main component as a metal component, and the coefficient of variation of the specific resistance value in the thickness direction is 0. Since it is suppressed to 20 or less, it is possible to suppress variations in the film resistivity of the oxide film formed even when sputtering progresses, and to stably form a uniform oxide film. Is possible.
- Ga is 10.0 atomic% or more and 20.0 atomic% or less
- Ti is 0.5 atomic% or more and 5.0, assuming that the total of the metal components is 100 atomic%.
- a stable oxide film is formed by a normal sputtering method such as a DC (DC) sputtering method. be able to. Further, in this case, an oxide film having excellent environmental resistance and alkali resistance can be formed.
- DC DC
- the environmental resistance of the oxide sputtering target is further improved, and an oxide film having a lower resistance value can be formed in the state after sputtering.
- the oxide sintered body becomes dense and cracks and cracks are more surely generated during sputtering. Can be suppressed.
- the method for producing an oxide sputtering target according to the present embodiment includes a tentative firing step S02 for tentatively firing the sintered raw material powder, in which the degree of vacuum in the tentative firing step S02 is within the range of 15 Pa or less and the firing temperature is 600. Since the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less within the range of ° C. or higher and 1000 ° C. or lower, the sintering raw material powder can be slightly reduced in advance, and the subsequent sintering can be performed. The local reduction reaction in the process can be suppressed. As a result, at least the difference in the degree of reduction in the thickness direction substantially perpendicular to the sputtered surface of the sintered body becomes small, and the variation in the specific resistance value in the thickness direction can be suppressed.
- the degree of vacuum in the sintering step S04 is within the range of 15 Pa or less
- the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower
- the holding time at the sintering temperature is 2 hours or more and 6 hours.
- the present invention is not limited to this, and can be appropriately changed without departing from the technical idea of the invention.
- the present invention is not limited to this, and a cylindrical-shaped sputtering target may be used, or a sputtering target having another shape may be used. May be good.
- the thickness direction is the radial direction of the cylinder.
- a protective film for an optical recording medium a steam barrier film for various devices such as a liquid crystal display element, an organic EL element, and a solar cell, and a wiring film for an electronic device such as a touch panel, a solar cell, and an organic EL display.
- a steam barrier film for various devices such as a liquid crystal display element, an organic EL element, and a solar cell
- a wiring film for an electronic device such as a touch panel, a solar cell, and an organic EL display.
- raw material powder zinc oxide (ZnO) powder with an average particle size of 1 ⁇ m and a purity of 99.50 mass% or more, gallium oxide (Ga 2 O 3 ) powder with an average particle size of 2 ⁇ m and a purity of 99.99 mass% or more, and an average particle size of 15 ⁇ m. Titanium oxide (TiO 2 ) powder having a purity of 99.00 mass% or more was prepared. These raw material powders were weighed so as to have the composition shown in Table 1 and mixed uniformly with a ball mill device to obtain sintered raw material powders.
- the obtained sintered raw material powder was filled in a carbon crucible, and temporary firing (vacuum firing) was carried out under the conditions shown in Table 1. Then, the calcined raw material powder that had been calcined was crushed by a ball mill device. The sintered raw material powder after crushing was charged into a hot press device in a state of being filled in a carbon mold, and hot pressed under the conditions of atmosphere: vacuum, pressure 25 MPa, sintering temperature and holding time shown in Table 1. By grinding the obtained sintered body, Examples 1 to 14 and Comparative Examples 1 to 5 of the present invention having the same composition as the compounding composition of Table 1 having a diameter of 178 ⁇ 126 ⁇ 6 mm. Oxide sputtering target was prepared.
- ZnO (101) ICDD 01-080-0074 TiO 2 : (110) ICDD 01-076-1939 Ga 2 O 3 : (111) ICDD 01-087-1901 ZnGa 2 O 4 : (311) ICDD 01-086-0410 ZnTIO 3 : (104) ICDD 00-026-1500 Zn 2 TiO 4 : (311) ICDD 00-025-1164
- the specific resistance values were measured on the sputtered surface of the oxide sputtering targets of Examples 1 to 14 of the present invention and the surface ground by 1 mm from the sputtered surface, the surface grinded by 2 mm, and the surface grinded by 3 mm, respectively.
- the specific resistance value was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation. The temperature at the time of measurement was 23 ⁇ 5 ° C., and the humidity was 50 ⁇ 20%.
- the mean value and standard deviation were obtained from the measurement results of four points, and the coefficient of variation of the specific resistance value in the thickness direction was calculated by acid.
- the film resistance of the oxide film formed at the initial stage of spatter film formation and the oxide film formed 2 hours after the start of spatter film formation was measured as follows.
- the film resistance was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation.
- the firing temperature in the temporary firing step was 400 ° C., and the coefficient of variation of the specific resistance value of the oxide sputtering target was as large as 0.210.
- the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
- the holding time at the firing temperature in the temporary firing step was set to 1 hour, and the coefficient of variation of the specific resistance value of the oxide sputtering target was as large as 0.220.
- the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
- Comparative Examples 4 and 5 the temporary firing step was not carried out, and the coefficient of variation of the specific resistance value of the oxide sputtering target became as large as 0.240 and 0.310, respectively. As a result, the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation. Further, in Comparative Examples 4 and 5, the contents of Ga and Ti were smaller than those in Comparative Example 3, and the composite oxide was not sufficiently produced. Therefore, cracks having a length of 2 mm or more were confirmed after the sputtering film formation.
- the firing temperature in the temporary firing step is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less.
- the coefficient of variation of the specific resistance value of the oxide sputtering target was 0.20 or less. As a result, the amount of change in film resistance was suppressed between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
- Example 11 of the present invention set at ° C. and Example 13 of the present invention in which the holding time at the firing temperature was 2 hours in the calcination step the composite oxide was not sufficiently formed and the length was 2 mm or more after the sputter film formation. Crack was confirmed.
- an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputtering deposition, and an oxide thereof. It was confirmed that it is possible to provide a method for manufacturing a sputtering target.
Abstract
This oxide sputtering target is characterized by: being composed of an oxide sintered body including, as a main component, a metal component of zinc; and having a coefficient of variation of the specific resistance value in the direction of thickness of not more than 0.20. This method for producing an oxide sputtering target is characterized by comprising: a temporary calcination step for temporarily calcinating a sintering material powder; a disaggregation step for disaggregating the calcinated sintering material powder; and a sintering step for sintering the disaggregated sintering material powder to obtain a sintered body. The method is also and is characterized in that: the degree of vacuum in the temporary calcination step is in a range of no more than 15 Pa; the sintering temperature is in a range of 600-1,000°C; and the retention time at the sintering temperature is in a range of 2-6 hours.
Description
本発明は、金属成分としてＺｎを主成分とする酸化物焼結体からなる酸化物スパッタリングターゲット、および、この酸化物スパッタリングターゲットの製造方法に関する。
本願は、２０２１年１月５日に、日本に出願された特願２０２１－０００４４０号に基づき優先権を主張し、それらの内容をここに援用する。 The present invention relates to an oxide sputtering target made of an oxide sintered body containing Zn as a main component as a metal component, and a method for manufacturing the oxide sputtering target.
The present application claims priority based on Japanese Patent Application No. 2021-000440 filed in Japan on January 5, 2021, and the contents thereof are incorporated herein by reference.
本願は、２０２１年１月５日に、日本に出願された特願２０２１－０００４４０号に基づき優先権を主張し、それらの内容をここに援用する。 The present invention relates to an oxide sputtering target made of an oxide sintered body containing Zn as a main component as a metal component, and a method for manufacturing the oxide sputtering target.
The present application claims priority based on Japanese Patent Application No. 2021-000440 filed in Japan on January 5, 2021, and the contents thereof are incorporated herein by reference.
従来、光ディスク等の光記録媒体においては、記録層や光反射膜を保護するために、保護膜が形成されている。
また、タッチパネルや太陽電池、有機ＥＬディスプレイなどの電子デバイスにはパターニングされた配線膜や電極が広く使用されており、これら配線膜や電極においては、金属膜の上に保護膜が積層された構造とされている。 Conventionally, in an optical recording medium such as an optical disc, a protective film is formed in order to protect the recording layer and the light reflecting film.
In addition, patterned wiring films and electrodes are widely used in electronic devices such as touch panels, solar cells, and organic EL displays, and these wiring films and electrodes have a structure in which a protective film is laminated on a metal film. It is said that.
また、タッチパネルや太陽電池、有機ＥＬディスプレイなどの電子デバイスにはパターニングされた配線膜や電極が広く使用されており、これら配線膜や電極においては、金属膜の上に保護膜が積層された構造とされている。 Conventionally, in an optical recording medium such as an optical disc, a protective film is formed in order to protect the recording layer and the light reflecting film.
In addition, patterned wiring films and electrodes are widely used in electronic devices such as touch panels, solar cells, and organic EL displays, and these wiring films and electrodes have a structure in which a protective film is laminated on a metal film. It is said that.
上述の保護膜として、例えば特許文献１，２に示すように、可視光の透過率に優れたＩＴＯ膜やＺｎＯ膜などの酸化物膜が利用されている。
ここで、上述の酸化物膜は、酸化物スパッタリングターゲットを用いたスパッタ法によって成膜される。例えば、特許文献３，４には、スパッタ法により成膜されるＺｎＯ膜の特性を向上させるために、酸化物スパッタリングターゲットに各種元素を添加することが提案されている。 As the above-mentioned protective film, for example, as shown in Patent Documents 1 and 2, oxide films such as ITO film and ZnO film having excellent visible light transmittance are used.
Here, the above-mentioned oxide film is formed by a sputtering method using an oxide sputtering target. For example, Patent Documents 3 and 4 propose adding various elements to an oxide sputtering target in order to improve the characteristics of a ZnO film formed by a sputtering method.
ここで、上述の酸化物膜は、酸化物スパッタリングターゲットを用いたスパッタ法によって成膜される。例えば、特許文献３，４には、スパッタ法により成膜されるＺｎＯ膜の特性を向上させるために、酸化物スパッタリングターゲットに各種元素を添加することが提案されている。 As the above-mentioned protective film, for example, as shown in Patent Documents 1 and 2, oxide films such as ITO film and ZnO film having excellent visible light transmittance are used.
Here, the above-mentioned oxide film is formed by a sputtering method using an oxide sputtering target. For example, Patent Documents 3 and 4 propose adding various elements to an oxide sputtering target in order to improve the characteristics of a ZnO film formed by a sputtering method.
特許文献３には、ＺｎＯに、Ｔｉと、Ｇａ又はＡｌから選ばれる１種以上を添加した酸化物スパッタリングターゲットが記載されている。この特許文献３では、Ｇａ又はＡｌの含有量は、（Ｇａ＋Ａｌ）／（Ｚｎ＋Ｔｉ＋Ｇａ＋Ａｌ）原子数比として０．０３以下、Ｔｉの含有量は、Ｔｉ／（Ｚｎ＋Ｔｉ＋Ｇａ＋Ａｌ）原子数比として０．０５～０．２５とされている。
Patent Document 3 describes an oxide sputtering target in which Ti and one or more selected from Ga or Al are added to ZnO. In this Patent Document 3, the content of Ga or Al is 0.03 or less as the atomic number ratio of (Ga + Al) / (Zn + Ti + Ga + Al), and the content of Ti is 0.05 to 0 as the atomic number ratio of Ti / (Zn + Ti + Ga + Al). It is said to be .25.
特許文献４には、ＺｎＯに、ＴｉとＧａを添加した酸化物スパッタリングターゲットが記載されている。この特許文献４では、ＴｉとＧａの含有量は、Ｔｉ１．１ａｔ％以上又はＧａ４．５ａｔ％以上の範囲で、且つＧａの含有量ｙ（ａｔ％）が、Ｔｉの含有量ｘ（ａｔ％）で表される値（－２．５ｘ＋９．８）以下の範囲で且つチタンの含有量ｘ（ａｔ％）で表される値（－０．５ｘ＋１．１）以上の範囲とされている。
Patent Document 4 describes an oxide sputtering target in which Ti and Ga are added to ZnO. In Patent Document 4, the Ti and Ga contents are in the range of Ti 1.1 at% or more or Ga 4.5 at% or more, and the Ga content y (at%) is the Ti content x (at%). It is in the range of the value represented by (-2.5x + 9.8) or less and the range of the value represented by the titanium content x (at%) (-0.5x + 1.1) or more.
ところで、金属成分としてＺｎを主成分とする酸化物焼結体からなる酸化物スパッタリングターゲットにおいては、スパッタ成膜の初期／中期／終期で、成膜された酸化物膜の特性にばらつきが生じ、安定して酸化物膜を成膜できないことがあった。
By the way, in an oxide sputtering target made of an oxide sintered body containing Zn as a main component as a metal component, the characteristics of the formed oxide film vary depending on the initial / middle / final stage of the sputter film formation. In some cases, it was not possible to form an oxide film in a stable manner.
この発明は、前述した事情に鑑みてなされたものであって、スパッタ成膜の初期／中期／終期で特性のばらつきが少なく均一な酸化物膜を安定して成膜可能な酸化物スパッタリングターゲット、および、この酸化物スパッタリングターゲットの製造方法を提供することを目的とする。
The present invention has been made in view of the above-mentioned circumstances, and is an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputtering deposition. An object of the present invention is to provide a method for producing the oxide sputtering target.
上記課題を解決するために、本発明者らが鋭意検討した結果、以下のような知見を得た。金属成分としてＺｎを主成分とする酸化物焼結体からなる酸化物スパッタリングターゲットにおいては、焼結時に表層部分が局所的に還元されてしまい、表層と内部とで還元状態が異なることがわかった。そして、この還元状態の違いによって、該ターゲットにおける比抵抗値が変動することがわかった。
As a result of diligent studies by the present inventors in order to solve the above problems, the following findings were obtained. It was found that in an oxide sputtering target composed of an oxide sintered body containing Zn as a main component as a metal component, the surface layer portion is locally reduced during sintering, and the reduced state differs between the surface layer and the inside. .. Then, it was found that the specific resistance value in the target fluctuates depending on the difference in the reduction state.
本発明の酸化物スパッタリングターゲットは、上述の知見に基づいてなされたものであって、金属成分としてＺｎを主成分とする酸化物焼結体からなり、厚さ方向における比抵抗値の変動係数が０．２０以下であることを特徴としている。
The oxide sputtering target of the present invention was made based on the above findings, and is composed of an oxide sintered body containing Zn as a main component as a metal component, and has a coefficient of variation of specific resistance value in the thickness direction. It is characterized by being 0.20 or less.
上述の構成の酸化物スパッタリングターゲットによれば、金属成分としてＺｎを主成分とする酸化物焼結体からなり、厚さ方向における比抵抗値の変動係数が０．２０以下に抑えられているので、該ターゲットのスパッタ面となる表層と内部とで還元状態がそれぞれ大きく異なっておらず、スパッタが進行した場合であっても、成膜した酸化物膜の膜抵抗にばらつきが生じることが抑えられ、均一な酸化物膜を安定して成膜することが可能となる。
According to the oxide sputtering target having the above configuration, it is composed of an oxide sintered body containing Zn as a main component as a metal component, and the fluctuation coefficient of the specific resistance value in the thickness direction is suppressed to 0.20 or less. The reduction state does not differ significantly between the surface layer, which is the sputtered surface of the target, and the inside, and even when sputtering progresses, it is possible to suppress variations in the film resistance of the deposited oxide film. , It becomes possible to stably form a uniform oxide film.
ここで、本発明の酸化物スパッタリングターゲットにおいては、金属成分の合計を１００原子％として、Ｇａが１０．０原子％以上かつ２０．０原子％以下、Ｔｉが０．５原子％以上かつ５．０原子％以下、残部がＺｎおよび不可避不純物金属元素とされた割合で含有する酸化物からなることが好ましい。
この場合、上述の組成の酸化物で構成されているので、ＤＣ（直流）スパッタ法などの通常のスパッタ法により安定して酸化物膜を成膜することができる。また、金属との積層膜を作成した際に、耐環境性に優れた積層膜を得ることができる。 Here, in the oxide sputtering target of the present invention, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and 5. It is preferably composed of an oxide containing 0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
In this case, since it is composed of an oxide having the above-mentioned composition, an oxide film can be stably formed by a normal sputtering method such as a DC (direct current) sputtering method. Further, when a laminated film with a metal is produced, a laminated film having excellent environmental resistance can be obtained.
この場合、上述の組成の酸化物で構成されているので、ＤＣ（直流）スパッタ法などの通常のスパッタ法により安定して酸化物膜を成膜することができる。また、金属との積層膜を作成した際に、耐環境性に優れた積層膜を得ることができる。 Here, in the oxide sputtering target of the present invention, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and 5. It is preferably composed of an oxide containing 0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
In this case, since it is composed of an oxide having the above-mentioned composition, an oxide film can be stably formed by a normal sputtering method such as a DC (direct current) sputtering method. Further, when a laminated film with a metal is produced, a laminated film having excellent environmental resistance can be obtained.
また、本発明の酸化物スパッタリングターゲットにおいては、さらに、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｂ、Ａｌ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ及びランタノイド系列の元素からなる元素群より選ばれる少なくとも１種または２種以上の添加元素を合計で、金属成分の合計を１００原子％として０．０１原子％以上かつ１０．０原子％以下の範囲内で含有することが好ましい。
この場合、耐環境性がより向上し、抵抗値がより低減した酸化物膜を成膜することができる。 Further, in the oxide sputtering target of the present invention, further, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, A total of at least one or two or more additive elements selected from the element group consisting of elements of the Pb, Sb, Bi and lanthanoid series, 0.01 atomic% or more and 10.0 with the total metal component as 100 atomic%. It is preferably contained in the range of atomic% or less.
In this case, it is possible to form an oxide film having further improved environmental resistance and a lower resistance value.
この場合、耐環境性がより向上し、抵抗値がより低減した酸化物膜を成膜することができる。 Further, in the oxide sputtering target of the present invention, further, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, A total of at least one or two or more additive elements selected from the element group consisting of elements of the Pb, Sb, Bi and lanthanoid series, 0.01 atomic% or more and 10.0 with the total metal component as 100 atomic%. It is preferably contained in the range of atomic% or less.
In this case, it is possible to form an oxide film having further improved environmental resistance and a lower resistance value.
さらに、本発明の酸化物スパッタリングターゲットにおいては、複合酸化物を有し、複合酸化物の存在比率が１５％以上であることが好ましい。
この場合、複合酸化物の存在比率が１５％以上とされているので、酸化物焼結体が緻密となり、スパッタリング時の割れや亀裂の発生をより確実に抑制できる。 Further, in the oxide sputtering target of the present invention, it is preferable that the oxide has a composite oxide and the abundance ratio of the composite oxide is 15% or more.
In this case, since the abundance ratio of the composite oxide is 15% or more, the oxide sintered body becomes dense, and cracks and cracks during sputtering can be more reliably suppressed.
この場合、複合酸化物の存在比率が１５％以上とされているので、酸化物焼結体が緻密となり、スパッタリング時の割れや亀裂の発生をより確実に抑制できる。 Further, in the oxide sputtering target of the present invention, it is preferable that the oxide has a composite oxide and the abundance ratio of the composite oxide is 15% or more.
In this case, since the abundance ratio of the composite oxide is 15% or more, the oxide sintered body becomes dense, and cracks and cracks during sputtering can be more reliably suppressed.
本発明の酸化物スパッタリングターゲットの製造方法は、上述の酸化物スパッタリングターゲットを製造する酸化物スパッタリングターゲットの製造方法であって、焼結原料粉を仮焼成する仮焼成工程と、焼成した焼結原料粉を解砕する解砕工程と、解砕した焼結原料粉を焼結して焼結体を得る焼結工程と、を備えており、前記仮焼成工程における真空度が１５Ｐａ以下の範囲内、焼成温度が６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされていることを特徴としている。
The method for producing an oxide sputtering target of the present invention is a method for producing an oxide sputtering target for producing the above-mentioned oxide sputtering target, which is a temporary firing step of tentatively firing a sintered raw material powder and a calcined raw material. It includes a crushing step of crushing the powder and a sintering step of sintering the crushed sintered raw material powder to obtain a sintered body, and the degree of vacuum in the preliminary firing step is within the range of 15 Pa or less. It is characterized in that the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less.
上述の構成の酸化物スパッタリングターゲットの製造方法によれば、焼結原料粉を仮焼成する仮焼成工程を備えており、仮焼成工程の焼成条件が上述のように規定されているので、焼結原料粉を一定程度還元処理することができ、その後の焼結工程における局所的な還元反応を抑制することができる。これにより、厚さ方向における還元度の差が小さくなり、厚さ方向における比抵抗値のばらつきを抑えることができる。
According to the method for manufacturing an oxide sputtering target having the above configuration, a calcination step of calcination raw material powder is provided, and the calcination conditions of the calcination step are defined as described above. The raw material powder can be reduced to a certain extent, and the local reduction reaction in the subsequent sintering step can be suppressed. As a result, the difference in the degree of reduction in the thickness direction becomes small, and the variation in the specific resistance value in the thickness direction can be suppressed.
ここで、本発明の酸化物スパッタリングターゲットの製造方法においては、前記焼結工程における真空度が１５Ｐａ以下の範囲内、焼結温度が９００℃以上かつ１１００℃以下の範囲内、焼結温度での保持時間が２時間以上かつ６時間以下の範囲内とされていることが好ましい。
この場合、焼結工程における焼結条件が上述のように規定されているので、複合酸化物を十分に生成することができ、緻密な酸化物焼結体を得ることができる。 Here, in the method for manufacturing an oxide sputtering target of the present invention, the degree of vacuum in the sintering step is within the range of 15 Pa or less, the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower, and the sintering temperature is high. It is preferable that the holding time is within the range of 2 hours or more and 6 hours or less.
In this case, since the sintering conditions in the sintering step are defined as described above, the composite oxide can be sufficiently produced and a dense oxide sintered body can be obtained.
この場合、焼結工程における焼結条件が上述のように規定されているので、複合酸化物を十分に生成することができ、緻密な酸化物焼結体を得ることができる。 Here, in the method for manufacturing an oxide sputtering target of the present invention, the degree of vacuum in the sintering step is within the range of 15 Pa or less, the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower, and the sintering temperature is high. It is preferable that the holding time is within the range of 2 hours or more and 6 hours or less.
In this case, since the sintering conditions in the sintering step are defined as described above, the composite oxide can be sufficiently produced and a dense oxide sintered body can be obtained.
本発明によれば、スパッタ成膜の初期／中期／終期で特性のばらつきが少なく均一な酸化物膜を安定して成膜可能な酸化物スパッタリングターゲット、および、この酸化物スパッタリングターゲットの製造方法を提供することができる。
According to the present invention, an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputter film formation, and a method for manufacturing the oxide sputtering target are provided. Can be provided.
以下に、本発明の一実施形態である酸化物スパッタリングターゲット、および、酸化物スパッタリングターゲットの製造方法について説明する。
Hereinafter, an oxide sputtering target, which is an embodiment of the present invention, and a method for manufacturing the oxide sputtering target will be described.
本実施形態である酸化物スパッタリングターゲットは、例えば、光記録媒体の保護膜、あるいは、液晶表示素子、有機ＥＬ素子、太陽電池等の各種デバイスにおける水蒸気バリア膜、タッチパネルや太陽電池、有機ＥＬディスプレイなどの電子デバイスにおける配線膜および電極の保護膜となる酸化物膜を成膜する際に用いられるものである。
この酸化物膜は、可視光の透過率に優れていることが求められており、本実施形態では、金属成分としてＺｎを主成分とする酸化物膜とされている。 The oxide sputtering target of the present embodiment is, for example, a protective film of an optical recording medium, a water vapor barrier film in various devices such as a liquid crystal display element, an organic EL element, and a solar cell, a touch panel, a solar cell, an organic EL display, and the like. It is used when forming an oxide film that serves as a wiring film and a protective film for electrodes in an electronic device.
This oxide film is required to have excellent visible light transmittance, and in the present embodiment, it is an oxide film containing Zn as a main component as a metal component.
この酸化物膜は、可視光の透過率に優れていることが求められており、本実施形態では、金属成分としてＺｎを主成分とする酸化物膜とされている。 The oxide sputtering target of the present embodiment is, for example, a protective film of an optical recording medium, a water vapor barrier film in various devices such as a liquid crystal display element, an organic EL element, and a solar cell, a touch panel, a solar cell, an organic EL display, and the like. It is used when forming an oxide film that serves as a wiring film and a protective film for electrodes in an electronic device.
This oxide film is required to have excellent visible light transmittance, and in the present embodiment, it is an oxide film containing Zn as a main component as a metal component.
本実施形態である酸化物スパッタリングターゲットは、金属成分としてＺｎを主成分とする酸化物焼結体からなる。金属成分の合計を１００原子％とした場合のＺｎの含有比率の範囲は、６０原子％以上かつ９０原子％以下であることが好ましい。
そして、本実施形態である酸化物スパッタリングターゲットにおいては、厚さ方向における比抵抗値の変動係数が０．２０以下とされており、少なくともスパッタ面の厚さ方向において比抵抗値のばらつきが小さく抑えられている。また、厚さ方向における比抵抗値の変動係数は０．１２以下が好ましく、更には厚さ方向における比抵抗値の変動係数は０．１０以下がより好ましい。変動係数の下限値については、特に限定されないが、０．００１としてもよい。
本実施形態における酸化物スパッタリングターゲットの厚さ方向は、スパッタ面となる主面に略垂直な方向、すなわち、スパッタ面からの深さ方向を意味している。スパッタ面は、スパッタリング処理を行う際に、スパッタリング粒子が放出される面を意味している。
なお、本実施形態では、酸化物スパッタリングターゲットは、平板形状をなしており、主面内の一つ以上、好ましくは三つ以上の領域において、その厚さ方向の複数の点で比抵抗値を測定し、その平均値と標準偏差とから、下記の式によって変動係数が算出される。比抵抗値を複数領域で測定する場合、測定した全領域で算出される変動係数の平均を、酸化物スパッタリングターゲットの変動係数とする。
（変動係数）＝（標準偏差）／（平均値） The oxide sputtering target of the present embodiment is made of an oxide sintered body containing Zn as a main component as a metal component. When the total of the metal components is 100 atomic%, the range of the Zn content ratio is preferably 60 atomic% or more and 90 atomic% or less.
In the oxide sputtering target of the present embodiment, the coefficient of variation of the specific resistance value in the thickness direction is 0.20 or less, and the variation of the specific resistance value is suppressed to be small at least in the thickness direction of the sputtered surface. Has been done. Further, the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less, and the coefficient of variation of the specific resistance value in the thickness direction is more preferably 0.10 or less. The lower limit of the coefficient of variation is not particularly limited, but may be 0.001.
The thickness direction of the oxide sputtering target in the present embodiment means a direction substantially perpendicular to the main surface to be a sputtering surface, that is, a depth direction from the sputtering surface. The sputtered surface means a surface on which the sputtering particles are discharged when the sputtering process is performed.
In the present embodiment, the oxide sputtering target has a flat plate shape, and the specific resistance value is set at a plurality of points in the thickness direction in one or more, preferably three or more regions in the main surface. The coefficient of variation is calculated by the following formula from the average value and standard deviation. When the specific resistance value is measured in a plurality of regions, the average of the coefficients of variation calculated in all the measured regions is taken as the coefficient of variation of the oxide sputtering target.
(Coefficient of variation) = (standard deviation) / (mean value)
そして、本実施形態である酸化物スパッタリングターゲットにおいては、厚さ方向における比抵抗値の変動係数が０．２０以下とされており、少なくともスパッタ面の厚さ方向において比抵抗値のばらつきが小さく抑えられている。また、厚さ方向における比抵抗値の変動係数は０．１２以下が好ましく、更には厚さ方向における比抵抗値の変動係数は０．１０以下がより好ましい。変動係数の下限値については、特に限定されないが、０．００１としてもよい。
本実施形態における酸化物スパッタリングターゲットの厚さ方向は、スパッタ面となる主面に略垂直な方向、すなわち、スパッタ面からの深さ方向を意味している。スパッタ面は、スパッタリング処理を行う際に、スパッタリング粒子が放出される面を意味している。
なお、本実施形態では、酸化物スパッタリングターゲットは、平板形状をなしており、主面内の一つ以上、好ましくは三つ以上の領域において、その厚さ方向の複数の点で比抵抗値を測定し、その平均値と標準偏差とから、下記の式によって変動係数が算出される。比抵抗値を複数領域で測定する場合、測定した全領域で算出される変動係数の平均を、酸化物スパッタリングターゲットの変動係数とする。
（変動係数）＝（標準偏差）／（平均値） The oxide sputtering target of the present embodiment is made of an oxide sintered body containing Zn as a main component as a metal component. When the total of the metal components is 100 atomic%, the range of the Zn content ratio is preferably 60 atomic% or more and 90 atomic% or less.
In the oxide sputtering target of the present embodiment, the coefficient of variation of the specific resistance value in the thickness direction is 0.20 or less, and the variation of the specific resistance value is suppressed to be small at least in the thickness direction of the sputtered surface. Has been done. Further, the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less, and the coefficient of variation of the specific resistance value in the thickness direction is more preferably 0.10 or less. The lower limit of the coefficient of variation is not particularly limited, but may be 0.001.
The thickness direction of the oxide sputtering target in the present embodiment means a direction substantially perpendicular to the main surface to be a sputtering surface, that is, a depth direction from the sputtering surface. The sputtered surface means a surface on which the sputtering particles are discharged when the sputtering process is performed.
In the present embodiment, the oxide sputtering target has a flat plate shape, and the specific resistance value is set at a plurality of points in the thickness direction in one or more, preferably three or more regions in the main surface. The coefficient of variation is calculated by the following formula from the average value and standard deviation. When the specific resistance value is measured in a plurality of regions, the average of the coefficients of variation calculated in all the measured regions is taken as the coefficient of variation of the oxide sputtering target.
(Coefficient of variation) = (standard deviation) / (mean value)
ここで、本実施形態である酸化物スパッタリングターゲットにおいては、金属成分の合計を１００原子％として、Ｇａが１０．０原子％以上かつ２０．０原子％以下、Ｔｉが０．５原子％以上かつ５．０原子％以下、残部がＺｎおよび不可避不純物金属元素とされた割合で含有する酸化物で構成されていてもよい。
また、Ｇａ，Ｔｉ，Ｚｎに加えて、さらに、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｂ、Ａｌ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ及びランタノイド系列の元素からなる元素群より選ばれる少なくとも１種または２種以上の添加元素を合計で、金属成分の合計を１００原子％として０．０１原子％以上かつ１０．０原子％以下の範囲内で含有していてもよい。 Here, in the oxide sputtering target of the present embodiment, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and Ti is 0.5 atomic% or more, assuming that the total of the metal components is 100 atomic%. It may be composed of an oxide containing 5.0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
In addition to Ga, Ti, and Zn, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, and Pb. , Sb, Bi and at least one or more additive elements selected from the element group consisting of elements of the lanthanoid series, 0.01 atomic% or more and 10.0 atoms with the total metal component as 100 atomic%. It may be contained in the range of% or less.
また、Ｇａ，Ｔｉ，Ｚｎに加えて、さらに、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｂ、Ａｌ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ及びランタノイド系列の元素からなる元素群より選ばれる少なくとも１種または２種以上の添加元素を合計で、金属成分の合計を１００原子％として０．０１原子％以上かつ１０．０原子％以下の範囲内で含有していてもよい。 Here, in the oxide sputtering target of the present embodiment, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and Ti is 0.5 atomic% or more, assuming that the total of the metal components is 100 atomic%. It may be composed of an oxide containing 5.0 atomic% or less and the balance being Zn and an unavoidable impurity metal element.
In addition to Ga, Ti, and Zn, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, and Pb. , Sb, Bi and at least one or more additive elements selected from the element group consisting of elements of the lanthanoid series, 0.01 atomic% or more and 10.0 atoms with the total metal component as 100 atomic%. It may be contained in the range of% or less.
また、本実施形態である酸化物スパッタリングターゲットは、単数の金属元素を含む酸化物である単相酸化物、複数の金属元素を含む酸化物である複合酸化物のいずれを有してもよい。酸化物スパッタリングターゲットを構成する酸化物のうち、複合酸化物の存在比率が１５％以上であることが好ましい。また、複合酸化物の存在比率は５０％以下であることが好ましい。なお、酸化物スパッタリングターゲットにおける複合酸化物の存在比率が１５％以上である場合、厚さ方向における比抵抗値の変動係数は０．１２以下が好ましい。
ここで、複合酸化物としては、例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、ＺｎＧａ２Ｏ４，ＺｎＴｉＯ３，Ｚｎ２ＴｉＯ４等が挙げられる。
なお、複合酸化物の存在比率は、Ｘ線回折測定（ＸＲＤ）による各相（単相酸化物、複合酸化物）のメインピークの強度から算出することができる。例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、ＺｎＯ相，Ｇａ２Ｏ３相，ＴｉＯ２相のピーク強度の合計Ａと、上述の複合酸化物（ＺｎＧａ２Ｏ４，ＺｎＴｉＯ３，Ｚｎ２ＴｉＯ４等）のピーク強度の合計Ｂとから、複合酸化物の存在比率は、以下の式で算出される。
複合酸化物の存在比率（％）＝Ｂ／（Ａ＋Ｂ）×１００ Further, the oxide sputtering target of the present embodiment may have either a single-phase oxide which is an oxide containing a single metal element or a composite oxide which is an oxide containing a plurality of metal elements. Of the oxides constituting the oxide sputtering target, the abundance ratio of the composite oxide is preferably 15% or more. Further, the abundance ratio of the composite oxide is preferably 50% or less. When the abundance ratio of the composite oxide in the oxide sputtering target is 15% or more, the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less.
Here, as the composite oxide, for example, when Ga and Ti are contained in addition to Zn, ZnGa 2 O 4 , ZnTIO 3 , Zn 2 TIO 4 , and the like can be mentioned.
The abundance ratio of the composite oxide can be calculated from the intensity of the main peak of each phase (single phase oxide, composite oxide) by X-ray diffraction measurement (XRD). For example, when Ga and Ti are contained in addition to Zn, the sum A of the peak intensities of the ZnO phase, Ga 2O 3 phase, and TIO 2 phase and the above-mentioned composite oxide (ZnGa 2 O 4 , ZnTIO 3 and so on) From the total peak intensity B of Zn 2 TiO 4 etc.), the abundance ratio of the composite oxide is calculated by the following formula.
Absence ratio of composite oxide (%) = B / (A + B) × 100
ここで、複合酸化物としては、例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、ＺｎＧａ２Ｏ４，ＺｎＴｉＯ３，Ｚｎ２ＴｉＯ４等が挙げられる。
なお、複合酸化物の存在比率は、Ｘ線回折測定（ＸＲＤ）による各相（単相酸化物、複合酸化物）のメインピークの強度から算出することができる。例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、ＺｎＯ相，Ｇａ２Ｏ３相，ＴｉＯ２相のピーク強度の合計Ａと、上述の複合酸化物（ＺｎＧａ２Ｏ４，ＺｎＴｉＯ３，Ｚｎ２ＴｉＯ４等）のピーク強度の合計Ｂとから、複合酸化物の存在比率は、以下の式で算出される。
複合酸化物の存在比率（％）＝Ｂ／（Ａ＋Ｂ）×１００ Further, the oxide sputtering target of the present embodiment may have either a single-phase oxide which is an oxide containing a single metal element or a composite oxide which is an oxide containing a plurality of metal elements. Of the oxides constituting the oxide sputtering target, the abundance ratio of the composite oxide is preferably 15% or more. Further, the abundance ratio of the composite oxide is preferably 50% or less. When the abundance ratio of the composite oxide in the oxide sputtering target is 15% or more, the coefficient of variation of the specific resistance value in the thickness direction is preferably 0.12 or less.
Here, as the composite oxide, for example, when Ga and Ti are contained in addition to Zn, ZnGa 2 O 4 , ZnTIO 3 , Zn 2 TIO 4 , and the like can be mentioned.
The abundance ratio of the composite oxide can be calculated from the intensity of the main peak of each phase (single phase oxide, composite oxide) by X-ray diffraction measurement (XRD). For example, when Ga and Ti are contained in addition to Zn, the sum A of the peak intensities of the ZnO phase, Ga 2O 3 phase, and TIO 2 phase and the above-mentioned composite oxide (ZnGa 2 O 4 , ZnTIO 3 and so on) From the total peak intensity B of Zn 2 TiO 4 etc.), the abundance ratio of the composite oxide is calculated by the following formula.
Absence ratio of composite oxide (%) = B / (A + B) × 100
次に、本実施形態である酸化物スパッタリングターゲットの製造方法について、図１のフロー図を参照して説明する。
Next, the method for manufacturing the oxide sputtering target according to the present embodiment will be described with reference to the flow chart of FIG.
（焼結原料粉形成工程Ｓ０１）
まず、酸化亜鉛粉等の原料粉を準備する。例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、酸化亜鉛粉の他に酸化ガリウム粉と酸化チタン粉を準備し、これらを所定の割合となるように秤量して、ボールミル等の混合装置を用いて混合することにより、焼結原料粉を得る。 (Sintered raw material powder forming step S01)
First, raw material powder such as zinc oxide powder is prepared. For example, when Ga and Ti are contained in addition to Zn, gallium oxide powder and titanium oxide powder are prepared in addition to zinc oxide powder, weighed so as to have a predetermined ratio, and mixed with a ball mill or the like. By mixing using an apparatus, a sintered raw material powder is obtained.
まず、酸化亜鉛粉等の原料粉を準備する。例えば、Ｚｎの他にＧａ、Ｔｉを含有する場合には、酸化亜鉛粉の他に酸化ガリウム粉と酸化チタン粉を準備し、これらを所定の割合となるように秤量して、ボールミル等の混合装置を用いて混合することにより、焼結原料粉を得る。 (Sintered raw material powder forming step S01)
First, raw material powder such as zinc oxide powder is prepared. For example, when Ga and Ti are contained in addition to Zn, gallium oxide powder and titanium oxide powder are prepared in addition to zinc oxide powder, weighed so as to have a predetermined ratio, and mixed with a ball mill or the like. By mixing using an apparatus, a sintered raw material powder is obtained.
（仮焼成工程Ｓ０２）
次に、焼結原料粉を仮焼成する。本実施形態では、カーボン坩堝内に焼結原料粉を挿入し、真空雰囲気で仮焼成する。この仮焼成工程Ｓ０２により、焼結原料粉の全体を微還元処理しておく。なお、仮焼成工程Ｓ０２においては、ＣＯガス、Ｈ２ガス等の還元雰囲気下で焼結原料粉を仮焼成してもよい。
ここで、仮焼成工程Ｓ０２における真空度は１５Ｐａ以下の範囲内とされ、焼成温度は６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされている。 (Temporary firing step S02)
Next, the sintered raw material powder is tentatively fired. In the present embodiment, the sintered raw material powder is inserted into the carbon crucible and temporarily fired in a vacuum atmosphere. In this temporary firing step S02, the entire sintered raw material powder is slightly reduced. In the temporary firing step S02, the sintered raw material powder may be temporarily fired in a reducing atmosphere such as CO gas or H2 gas.
Here, the degree of vacuum in the temporary firing step S02 is within the range of 15 Pa or less, the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less. It is said that.
次に、焼結原料粉を仮焼成する。本実施形態では、カーボン坩堝内に焼結原料粉を挿入し、真空雰囲気で仮焼成する。この仮焼成工程Ｓ０２により、焼結原料粉の全体を微還元処理しておく。なお、仮焼成工程Ｓ０２においては、ＣＯガス、Ｈ２ガス等の還元雰囲気下で焼結原料粉を仮焼成してもよい。
ここで、仮焼成工程Ｓ０２における真空度は１５Ｐａ以下の範囲内とされ、焼成温度は６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされている。 (Temporary firing step S02)
Next, the sintered raw material powder is tentatively fired. In the present embodiment, the sintered raw material powder is inserted into the carbon crucible and temporarily fired in a vacuum atmosphere. In this temporary firing step S02, the entire sintered raw material powder is slightly reduced. In the temporary firing step S02, the sintered raw material powder may be temporarily fired in a reducing atmosphere such as CO gas or H2 gas.
Here, the degree of vacuum in the temporary firing step S02 is within the range of 15 Pa or less, the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less. It is said that.
（解砕工程Ｓ０３）
次に、仮焼成工程Ｓ０２によって仮焼成した焼結原料粉を、ボールミル装置等を用いて解砕する。 (Crushing step S03)
Next, the sintered raw material powder temporarily fired in the temporary firing step S02 is crushed using a ball mill device or the like.
次に、仮焼成工程Ｓ０２によって仮焼成した焼結原料粉を、ボールミル装置等を用いて解砕する。 (Crushing step S03)
Next, the sintered raw material powder temporarily fired in the temporary firing step S02 is crushed using a ball mill device or the like.
（焼結工程Ｓ０４）
解砕した焼結原料粉を成形型に充填し、加圧および加熱して焼結し、焼結体を得る。本実施形態では、ホットプレス装置によって焼結を行う。
なお、このときの焼結温度は９００℃以上かつ１１００℃以下の範囲内、焼結温度での保持時間は２時間以上かつ６時間以下の範囲内、加圧圧力は１０ＭＰａ以上かつ３５ＭＰａ以下の範囲内とすることが好ましい。また、雰囲気は真空雰囲気（１５Ｐａ以下）とすることが好ましい。
焼結温度を９００℃以上とすることで十分な密度が得ることができる。一方、焼結温度を１１００℃以下とすることで、酸化亜鉛の昇華を抑え、組成ずれや焼結体割れの発生を抑制することができる。 (Sintering step S04)
The crushed sintered raw material powder is filled in a molding die, pressed and heated to be sintered, and a sintered body is obtained. In this embodiment, sintering is performed by a hot press device.
The sintering temperature at this time is in the range of 900 ° C. or higher and 1100 ° C. or lower, the holding time at the sintering temperature is in the range of 2 hours or more and 6 hours or less, and the pressurizing pressure is in the range of 10 MPa or higher and 35 MPa or lower. It is preferably inside. The atmosphere is preferably a vacuum atmosphere (15 Pa or less).
A sufficient density can be obtained by setting the sintering temperature to 900 ° C. or higher. On the other hand, by setting the sintering temperature to 1100 ° C. or lower, sublimation of zinc oxide can be suppressed, and composition deviation and occurrence of cracking of the sintered body can be suppressed.
解砕した焼結原料粉を成形型に充填し、加圧および加熱して焼結し、焼結体を得る。本実施形態では、ホットプレス装置によって焼結を行う。
なお、このときの焼結温度は９００℃以上かつ１１００℃以下の範囲内、焼結温度での保持時間は２時間以上かつ６時間以下の範囲内、加圧圧力は１０ＭＰａ以上かつ３５ＭＰａ以下の範囲内とすることが好ましい。また、雰囲気は真空雰囲気（１５Ｐａ以下）とすることが好ましい。
焼結温度を９００℃以上とすることで十分な密度が得ることができる。一方、焼結温度を１１００℃以下とすることで、酸化亜鉛の昇華を抑え、組成ずれや焼結体割れの発生を抑制することができる。 (Sintering step S04)
The crushed sintered raw material powder is filled in a molding die, pressed and heated to be sintered, and a sintered body is obtained. In this embodiment, sintering is performed by a hot press device.
The sintering temperature at this time is in the range of 900 ° C. or higher and 1100 ° C. or lower, the holding time at the sintering temperature is in the range of 2 hours or more and 6 hours or less, and the pressurizing pressure is in the range of 10 MPa or higher and 35 MPa or lower. It is preferably inside. The atmosphere is preferably a vacuum atmosphere (15 Pa or less).
A sufficient density can be obtained by setting the sintering temperature to 900 ° C. or higher. On the other hand, by setting the sintering temperature to 1100 ° C. or lower, sublimation of zinc oxide can be suppressed, and composition deviation and occurrence of cracking of the sintered body can be suppressed.
（機械加工工程Ｓ０５）
次に、得られた焼結体を機械加工する。これにより、本実施形態である酸化物スパッタリングターゲットが製造される。 (Machining process S05)
Next, the obtained sintered body is machined. As a result, the oxide sputtering target according to the present embodiment is manufactured.
次に、得られた焼結体を機械加工する。これにより、本実施形態である酸化物スパッタリングターゲットが製造される。 (Machining process S05)
Next, the obtained sintered body is machined. As a result, the oxide sputtering target according to the present embodiment is manufactured.
以上のような構成とされた本実施形態である酸化物スパッタリングターゲットにおいては、金属成分としてＺｎを主成分とする酸化物焼結体からなり、厚さ方向における比抵抗値の変動係数が０．２０以下に抑えられているので、スパッタが進行した場合であっても、成膜した酸化物膜の膜抵抗にばらつきが生じることが抑えられ、均一な酸化物膜を安定して成膜することが可能となる。
The oxide sputtering target of the present embodiment having the above configuration is composed of an oxide sintered body containing Zn as a main component as a metal component, and the coefficient of variation of the specific resistance value in the thickness direction is 0. Since it is suppressed to 20 or less, it is possible to suppress variations in the film resistivity of the oxide film formed even when sputtering progresses, and to stably form a uniform oxide film. Is possible.
また、本実施形態の酸化物スパッタリングターゲットが、金属成分の合計を１００原子％として、Ｇａが１０．０原子％以上かつ２０．０原子％以下、Ｔｉが０．５原子％以上かつ５．０原子％以下、残部がＺｎおよび不可避不純物金属元素とされた割合で含有する酸化物からなる場合には、ＤＣ（直流）スパッタ法などの通常のスパッタ法により安定して酸化物膜を成膜することができる。また、この場合には、耐環境性と耐アルカリ性に優れた酸化物膜を成膜することができる。
Further, in the oxide sputtering target of the present embodiment, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and 5.0, assuming that the total of the metal components is 100 atomic%. When it is composed of an oxide containing atomic% or less and the balance being Zn and an unavoidable impurity metal element, a stable oxide film is formed by a normal sputtering method such as a DC (DC) sputtering method. be able to. Further, in this case, an oxide film having excellent environmental resistance and alkali resistance can be formed.
Ｚｎ，Ｇａ，Ｔｉに加えて、さらにＺｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｂ、Ａｌ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ及びランタノイド系列の元素からなる元素群より選ばれる少なくとも１種または２種以上の添加元素を合計で、金属成分の合計を１００原子％として０．０１原子％以上かつ１０．０原子％以下の範囲内で含有する場合には、酸化物スパッタリングターゲットの耐環境性がより向上し、スパッタリング後の状態で抵抗値がより低減した酸化物膜を成膜することができる。
In addition to Zn, Ga, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, Pb, Sb, A total of at least one or two or more additive elements selected from the element group consisting of Bi and lanthanoid series elements, with the total metal component being 100 atomic%, 0.01 atomic% or more and 10.0 atomic% or less. When it is contained within the range, the environmental resistance of the oxide sputtering target is further improved, and an oxide film having a lower resistance value can be formed in the state after sputtering.
さらに、本実施形態において、複合酸化物を有し、複合酸化物の存在比率が１５％以上である場合には、酸化物焼結体が緻密となり、スパッタリング時の割れや亀裂の発生をより確実に抑制できる。
Further, in the present embodiment, when the composite oxide is contained and the abundance ratio of the composite oxide is 15% or more, the oxide sintered body becomes dense and cracks and cracks are more surely generated during sputtering. Can be suppressed.
本実施形態である酸化物スパッタリングターゲットの製造方法においては、焼結原料粉を仮焼成する仮焼成工程Ｓ０２を備えており、仮焼成工程Ｓ０２における真空度が１５Ｐａ以下の範囲内、焼成温度が６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされているので、予め焼結原料粉を微還元することができ、その後の焼結工程における局所的な還元反応を抑制することができる。これにより、少なくとも焼結体のスパッタ面と略垂直な厚さ方向における還元度の差が小さくなり、該厚さ方向における比抵抗値のばらつきを抑えることができる。
The method for producing an oxide sputtering target according to the present embodiment includes a tentative firing step S02 for tentatively firing the sintered raw material powder, in which the degree of vacuum in the tentative firing step S02 is within the range of 15 Pa or less and the firing temperature is 600. Since the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less within the range of ° C. or higher and 1000 ° C. or lower, the sintering raw material powder can be slightly reduced in advance, and the subsequent sintering can be performed. The local reduction reaction in the process can be suppressed. As a result, at least the difference in the degree of reduction in the thickness direction substantially perpendicular to the sputtered surface of the sintered body becomes small, and the variation in the specific resistance value in the thickness direction can be suppressed.
また、本実施形態において、焼結工程Ｓ０４における真空度が１５Ｐａ以下の範囲内、焼結温度が９００℃以上かつ１１００℃以下の範囲内、焼結温度での保持時間が２時間以上かつ６時間以下の範囲内とされている場合には、複合酸化物を十分に生成することができ、緻密な酸化物焼結体をえることができる。
Further, in the present embodiment, the degree of vacuum in the sintering step S04 is within the range of 15 Pa or less, the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower, and the holding time at the sintering temperature is 2 hours or more and 6 hours. When the temperature is within the following range, the composite oxide can be sufficiently produced and a dense oxide sintered body can be obtained.
以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。
例えば、本実施形態では、平板形状のスパッタリングターゲットを用いる場合について説明したが、これに限定されることはなく、円筒形状のスパッタリングターゲットを用いてもよいし、他の形状のスパッタリングターゲットを用いてもよい。円筒形状のスパッタリングターゲットを用いる場合の厚さ方向は、円筒の径方向となる。 Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the technical idea of the invention.
For example, in the present embodiment, the case where a flat plate-shaped sputtering target is used has been described, but the present invention is not limited to this, and a cylindrical-shaped sputtering target may be used, or a sputtering target having another shape may be used. May be good. When a cylindrical sputtering target is used, the thickness direction is the radial direction of the cylinder.
例えば、本実施形態では、平板形状のスパッタリングターゲットを用いる場合について説明したが、これに限定されることはなく、円筒形状のスパッタリングターゲットを用いてもよいし、他の形状のスパッタリングターゲットを用いてもよい。円筒形状のスパッタリングターゲットを用いる場合の厚さ方向は、円筒の径方向となる。 Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the technical idea of the invention.
For example, in the present embodiment, the case where a flat plate-shaped sputtering target is used has been described, but the present invention is not limited to this, and a cylindrical-shaped sputtering target may be used, or a sputtering target having another shape may be used. May be good. When a cylindrical sputtering target is used, the thickness direction is the radial direction of the cylinder.
また、本実施形態では、光記録媒体の保護膜、あるいは、液晶表示素子、有機ＥＬ素子、太陽電池等の各種デバイスにおける水蒸気バリア膜、タッチパネルや太陽電池、有機ＥＬディスプレイなどの電子デバイスにおける配線膜および電極の保護膜となる酸化物膜を成膜する際に用いられるものとして説明したが、これに限定されることはなく、その他の用途で用いられる膜を成膜するものとしてもよい。
Further, in the present embodiment, a protective film for an optical recording medium, a steam barrier film for various devices such as a liquid crystal display element, an organic EL element, and a solar cell, and a wiring film for an electronic device such as a touch panel, a solar cell, and an organic EL display. Although it has been described as being used when forming an oxide film as a protective film for an electrode, the present invention is not limited to this, and a film used for other purposes may be formed.
以下に、本発明の作用効果について評価した評価試験の結果を説明する。
The results of the evaluation test for evaluating the action and effect of the present invention will be described below.
原料粉末として、平均粒径１μｍで純度９９．５０ｍａｓｓ％以上の酸化亜鉛（ＺｎＯ）粉末、平均粒径２μｍで純度９９．９９ｍａｓｓ％以上の酸化ガリウム（Ｇａ２Ｏ３）粉末、平均粒径１５μｍで純度９９．００ｍａｓｓ％以上の酸化チタン（ＴｉＯ２）粉末、を用意した。
これら原料粉末を表１に示される配合組成となるように秤量し、ボールミル装置で均一に混合し、焼結原料粉を得た。 As raw material powder, zinc oxide (ZnO) powder with an average particle size of 1 μm and a purity of 99.50 mass% or more, gallium oxide (Ga 2 O 3 ) powder with an average particle size of 2 μm and a purity of 99.99 mass% or more, and an average particle size of 15 μm. Titanium oxide (TiO 2 ) powder having a purity of 99.00 mass% or more was prepared.
These raw material powders were weighed so as to have the composition shown in Table 1 and mixed uniformly with a ball mill device to obtain sintered raw material powders.
これら原料粉末を表１に示される配合組成となるように秤量し、ボールミル装置で均一に混合し、焼結原料粉を得た。 As raw material powder, zinc oxide (ZnO) powder with an average particle size of 1 μm and a purity of 99.50 mass% or more, gallium oxide (Ga 2 O 3 ) powder with an average particle size of 2 μm and a purity of 99.99 mass% or more, and an average particle size of 15 μm. Titanium oxide (TiO 2 ) powder having a purity of 99.00 mass% or more was prepared.
These raw material powders were weighed so as to have the composition shown in Table 1 and mixed uniformly with a ball mill device to obtain sintered raw material powders.
得られた焼結原料粉をカーボン坩堝に充填し、表１に示す条件で仮焼成（真空焼成）を実施した。その後、仮焼成した焼結原料粉をボールミル装置で解砕した。
解砕後の焼結原料粉を、カーボン型に充填した状態で、ホットプレス装置に装入し、雰囲気：真空、圧力２５ＭＰａ、表１に示す焼結温度および保持時間の条件でホットプレスした。
得られた焼結体を研削加工することにより、いずれも直径：１７８×１２６×６ｍｍの寸法をもった表１の配合組成と同じ成分組成を有する本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットを作製した。 The obtained sintered raw material powder was filled in a carbon crucible, and temporary firing (vacuum firing) was carried out under the conditions shown in Table 1. Then, the calcined raw material powder that had been calcined was crushed by a ball mill device.
The sintered raw material powder after crushing was charged into a hot press device in a state of being filled in a carbon mold, and hot pressed under the conditions of atmosphere: vacuum, pressure 25 MPa, sintering temperature and holding time shown in Table 1.
By grinding the obtained sintered body, Examples 1 to 14 and Comparative Examples 1 to 5 of the present invention having the same composition as the compounding composition of Table 1 having a diameter of 178 × 126 × 6 mm. Oxide sputtering target was prepared.
解砕後の焼結原料粉を、カーボン型に充填した状態で、ホットプレス装置に装入し、雰囲気：真空、圧力２５ＭＰａ、表１に示す焼結温度および保持時間の条件でホットプレスした。
得られた焼結体を研削加工することにより、いずれも直径：１７８×１２６×６ｍｍの寸法をもった表１の配合組成と同じ成分組成を有する本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットを作製した。 The obtained sintered raw material powder was filled in a carbon crucible, and temporary firing (vacuum firing) was carried out under the conditions shown in Table 1. Then, the calcined raw material powder that had been calcined was crushed by a ball mill device.
The sintered raw material powder after crushing was charged into a hot press device in a state of being filled in a carbon mold, and hot pressed under the conditions of atmosphere: vacuum, pressure 25 MPa, sintering temperature and holding time shown in Table 1.
By grinding the obtained sintered body, Examples 1 to 14 and Comparative Examples 1 to 5 of the present invention having the same composition as the compounding composition of Table 1 having a diameter of 178 × 126 × 6 mm. Oxide sputtering target was prepared.
得られた本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットについて、以下の項目について評価した。評価結果を表２に示す。
The following items were evaluated for the obtained oxide sputtering targets of Examples 1 to 14 of the present invention and Comparative Examples 1 to 5. The evaluation results are shown in Table 2.
（複合酸化物の存在比率）
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットから観察試料を採取し、Ｘ線回折測定（ＸＲＤ）を実施し、実施形態に記載した手順により、各相のメインピークの強度から複合酸化物の存在比率を算出した。なお、Ｘ線回折測定（ＸＲＤ）条件を以下に示す。
装置：理学電気社製（ＲＩＮＴ－Ｕｌｔｉｍａ／ＰＣ）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査範囲（２θ）：１０度～９０度
スリット：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、
受光（ＲＳ）０．８ｍｍ
測定ステップ幅：２θで０．０４度
スキャンスピード：毎分２度
試料台回転スピード：３０ｒｐｍ (Abundance ratio of composite oxide)
Observation samples were taken from the oxide sputtering targets of Examples 1 to 14 of the present invention and Comparative Examples 1 to 5, X-ray diffraction measurement (XRD) was performed, and the intensity of the main peak of each phase was according to the procedure described in the embodiment. The abundance ratio of the composite oxide was calculated from. The X-ray diffraction measurement (XRD) conditions are shown below.
Equipment: Made by Rigaku Denki Co., Ltd. (RINT-Ultima / PC)
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA
Scanning range (2θ): 10 degrees to 90 degrees Slit: Divergence (DS) 2/3 degrees, Scattering (SS) 2/3 degrees,
Light receiving (RS) 0.8 mm
Measurement step width: 0.04 degrees at 2θ Scan speed: 2 degrees per minute Sample table rotation speed: 30 rpm
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットから観察試料を採取し、Ｘ線回折測定（ＸＲＤ）を実施し、実施形態に記載した手順により、各相のメインピークの強度から複合酸化物の存在比率を算出した。なお、Ｘ線回折測定（ＸＲＤ）条件を以下に示す。
装置：理学電気社製（ＲＩＮＴ－Ｕｌｔｉｍａ／ＰＣ）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査範囲（２θ）：１０度～９０度
スリット：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、
受光（ＲＳ）０．８ｍｍ
測定ステップ幅：２θで０．０４度
スキャンスピード：毎分２度
試料台回転スピード：３０ｒｐｍ (Abundance ratio of composite oxide)
Observation samples were taken from the oxide sputtering targets of Examples 1 to 14 of the present invention and Comparative Examples 1 to 5, X-ray diffraction measurement (XRD) was performed, and the intensity of the main peak of each phase was according to the procedure described in the embodiment. The abundance ratio of the composite oxide was calculated from. The X-ray diffraction measurement (XRD) conditions are shown below.
Equipment: Made by Rigaku Denki Co., Ltd. (RINT-Ultima / PC)
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA
Scanning range (2θ): 10 degrees to 90 degrees Slit: Divergence (DS) 2/3 degrees, Scattering (SS) 2/3 degrees,
Light receiving (RS) 0.8 mm
Measurement step width: 0.04 degrees at 2θ Scan speed: 2 degrees per minute Sample table rotation speed: 30 rpm
また、測定した各相のメインピークを以下に示す。
ＺｎＯ：（１０１） ＩＣＤＤ ０１－０８０－００７４
ＴｉＯ２：（１１０） ＩＣＤＤ ０１－０７６－１９３９
Ｇａ２Ｏ３：（１１１） ＩＣＤＤ ０１－０８７－１９０１
ＺｎＧａ２Ｏ４：（３１１） ＩＣＤＤ ０１－０８６－０４１０
ＺｎＴｉＯ３：（１０４） ＩＣＤＤ ００－０２６－１５００
Ｚｎ２ＴｉＯ４：（３１１） ＩＣＤＤ ００－０２５－１１６４ The main peaks of each measured phase are shown below.
ZnO: (101) ICDD 01-080-0074
TiO 2 : (110) ICDD 01-076-1939
Ga 2 O 3 : (111) ICDD 01-087-1901
ZnGa 2 O 4 : (311) ICDD 01-086-0410
ZnTIO 3 : (104) ICDD 00-026-1500
Zn 2 TiO 4 : (311) ICDD 00-025-1164
ＺｎＯ：（１０１） ＩＣＤＤ ０１－０８０－００７４
ＴｉＯ２：（１１０） ＩＣＤＤ ０１－０７６－１９３９
Ｇａ２Ｏ３：（１１１） ＩＣＤＤ ０１－０８７－１９０１
ＺｎＧａ２Ｏ４：（３１１） ＩＣＤＤ ０１－０８６－０４１０
ＺｎＴｉＯ３：（１０４） ＩＣＤＤ ００－０２６－１５００
Ｚｎ２ＴｉＯ４：（３１１） ＩＣＤＤ ００－０２５－１１６４ The main peaks of each measured phase are shown below.
ZnO: (101) ICDD 01-080-0074
TiO 2 : (110) ICDD 01-076-1939
Ga 2 O 3 : (111) ICDD 01-087-1901
ZnGa 2 O 4 : (311) ICDD 01-086-0410
ZnTIO 3 : (104) ICDD 00-026-1500
Zn 2 TiO 4 : (311) ICDD 00-025-1164
（比抵抗）
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットのスパッタ面、スパッタ面から１ｍｍ研削した面、２ｍｍ研削した面、３ｍｍ研削した面で、それぞれ比抵抗値を測定した。比抵抗値は、三菱化学株式会社製の低抵抗率計（Ｌｏｒｅｓｔａ－ＧＰ）を用い、四探針法で測定した。測定時の温度は２３±５℃、湿度は５０±２０％にて測定した。
４点の測定結果から平均値および標準偏差を求め、比抵抗値の厚さ方向の変動係数を酸算出した。 (Specific resistivity)
The specific resistance values were measured on the sputtered surface of the oxide sputtering targets of Examples 1 to 14 of the present invention and the surface ground by 1 mm from the sputtered surface, the surface grinded by 2 mm, and the surface grinded by 3 mm, respectively. The specific resistance value was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation. The temperature at the time of measurement was 23 ± 5 ° C., and the humidity was 50 ± 20%.
The mean value and standard deviation were obtained from the measurement results of four points, and the coefficient of variation of the specific resistance value in the thickness direction was calculated by acid.
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットのスパッタ面、スパッタ面から１ｍｍ研削した面、２ｍｍ研削した面、３ｍｍ研削した面で、それぞれ比抵抗値を測定した。比抵抗値は、三菱化学株式会社製の低抵抗率計（Ｌｏｒｅｓｔａ－ＧＰ）を用い、四探針法で測定した。測定時の温度は２３±５℃、湿度は５０±２０％にて測定した。
４点の測定結果から平均値および標準偏差を求め、比抵抗値の厚さ方向の変動係数を酸算出した。 (Specific resistivity)
The specific resistance values were measured on the sputtered surface of the oxide sputtering targets of Examples 1 to 14 of the present invention and the surface ground by 1 mm from the sputtered surface, the surface grinded by 2 mm, and the surface grinded by 3 mm, respectively. The specific resistance value was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation. The temperature at the time of measurement was 23 ± 5 ° C., and the humidity was 50 ± 20%.
The mean value and standard deviation were obtained from the measurement results of four points, and the coefficient of variation of the specific resistance value in the thickness direction was calculated by acid.
（酸化物膜の膜抵抗）
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットを用いて、下記の条件にて、膜厚４０ｎｍの酸化物膜をガラス基板上にスパッタ成膜した。
電源：ＤＣ
電力：３００Ｗ
全圧：０．６７Ｐａ
ガス：Ａｒ：５０．０ｓｃｃｍ (Membrane resistance of oxide film)
Using the oxide sputtering targets of Examples 1 to 14 of the present invention and Comparative Examples 1 to 5, an oxide film having a film thickness of 40 nm was sputtered onto a glass substrate under the following conditions.
Power supply: DC
Power: 300W
Total pressure: 0.67Pa
Gas: Ar: 50.0sccm
本発明例１～１４および比較例１～５の酸化物スパッタリングターゲットを用いて、下記の条件にて、膜厚４０ｎｍの酸化物膜をガラス基板上にスパッタ成膜した。
電源：ＤＣ
電力：３００Ｗ
全圧：０．６７Ｐａ
ガス：Ａｒ：５０．０ｓｃｃｍ (Membrane resistance of oxide film)
Using the oxide sputtering targets of Examples 1 to 14 of the present invention and Comparative Examples 1 to 5, an oxide film having a film thickness of 40 nm was sputtered onto a glass substrate under the following conditions.
Power supply: DC
Power: 300W
Total pressure: 0.67Pa
Gas: Ar: 50.0sccm
スパッタ成膜初期に成膜された酸化物膜と、スパッタ成膜開始から２時間経過時に成膜された酸化物膜について、以下のように膜抵抗を測定した。
膜抵抗は、三菱化学株式会社製の低抵抗率計（Ｌｏｒｅｓｔａ－ＧＰ）を用い、四探針法で測定した。 The film resistance of the oxide film formed at the initial stage of spatter film formation and the oxide film formed 2 hours after the start of spatter film formation was measured as follows.
The film resistance was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation.
膜抵抗は、三菱化学株式会社製の低抵抗率計（Ｌｏｒｅｓｔａ－ＧＰ）を用い、四探針法で測定した。 The film resistance of the oxide film formed at the initial stage of spatter film formation and the oxide film formed 2 hours after the start of spatter film formation was measured as follows.
The film resistance was measured by a four-probe method using a low resistivity meter (Loresta-GP) manufactured by Mitsubishi Chemical Corporation.
（スパッタ後の割れ・亀裂の有無）
上述の条件でスパッタ成膜を２時間実施した後の酸化物スパッタリングターゲットの割れおよび亀裂の有無を評価した。
スパッタリングターゲット表面において、長さ２ｍｍ以上の割れおよび亀裂が一つ以上存在するものを、割れ・亀裂「有り」と評価し、長さ２ｍｍ以上の割れおよび亀裂が存在しないものを、割れ・亀裂「なし」と評価した。 (Presence / absence of cracks / cracks after spattering)
The presence or absence of cracks and cracks in the oxide sputtering target after the sputtering deposition was carried out for 2 hours under the above conditions was evaluated.
On the surface of the sputtering target, those having one or more cracks and cracks having a length of 2 mm or more are evaluated as having cracks / cracks, and those having no cracks / cracks having a length of 2 mm or more are evaluated as having cracks / cracks. None ".
上述の条件でスパッタ成膜を２時間実施した後の酸化物スパッタリングターゲットの割れおよび亀裂の有無を評価した。
スパッタリングターゲット表面において、長さ２ｍｍ以上の割れおよび亀裂が一つ以上存在するものを、割れ・亀裂「有り」と評価し、長さ２ｍｍ以上の割れおよび亀裂が存在しないものを、割れ・亀裂「なし」と評価した。 (Presence / absence of cracks / cracks after spattering)
The presence or absence of cracks and cracks in the oxide sputtering target after the sputtering deposition was carried out for 2 hours under the above conditions was evaluated.
On the surface of the sputtering target, those having one or more cracks and cracks having a length of 2 mm or more are evaluated as having cracks / cracks, and those having no cracks / cracks having a length of 2 mm or more are evaluated as having cracks / cracks. None ".
比較例１においては、仮焼成工程における焼成温度が４００℃とされており、酸化物スパッタリングターゲットの比抵抗値の変動係数が０．２１０と大きくなった。これにより、スパッタ成膜初期に成膜された酸化物膜とスパッタ成膜開始から２時間経過時に成膜された酸化物膜とで、膜抵抗が大きく変化した。
In Comparative Example 1, the firing temperature in the temporary firing step was 400 ° C., and the coefficient of variation of the specific resistance value of the oxide sputtering target was as large as 0.210. As a result, the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
比較例２においては、仮焼成工程における焼成温度での保持時間が１時間とされており、酸化物スパッタリングターゲットの比抵抗値の変動係数が０．２２０と大きくなった。これにより、スパッタ成膜初期に成膜された酸化物膜とスパッタ成膜開始から２時間経過時に成膜された酸化物膜とで、膜抵抗が大きく変化した。
In Comparative Example 2, the holding time at the firing temperature in the temporary firing step was set to 1 hour, and the coefficient of variation of the specific resistance value of the oxide sputtering target was as large as 0.220. As a result, the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
比較例３においては、仮焼成工程を実施しておらず、酸化物スパッタリングターゲットの比抵抗値の変動係数が０．２７０と大きくなった。これにより、スパッタ成膜初期に成膜された酸化物膜とスパッタ成膜開始から２時間経過時に成膜された酸化物膜とで、膜抵抗が大きく変化した。
In Comparative Example 3, the temporary firing step was not carried out, and the coefficient of variation of the specific resistance value of the oxide sputtering target became as large as 0.270. As a result, the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
比較例４，５においては、仮焼成工程を実施しておらず、酸化物スパッタリングターゲットの比抵抗値の変動係数がそれぞれ０．２４０，０．３１０と大きくなった。これにより、スパッタ成膜初期に成膜された酸化物膜とスパッタ成膜開始から２時間経過時に成膜された酸化物膜とで、膜抵抗が大きく変化した。また、比較例４，５においては、比較例３に比べてＧａおよびＴｉの含有量が少なく、複合酸化物が十分に生成しなかった。このため、スパッタ成膜後に長さ２ｍｍ以上の割れが確認された。
In Comparative Examples 4 and 5, the temporary firing step was not carried out, and the coefficient of variation of the specific resistance value of the oxide sputtering target became as large as 0.240 and 0.310, respectively. As a result, the film resistance changed significantly between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation. Further, in Comparative Examples 4 and 5, the contents of Ga and Ti were smaller than those in Comparative Example 3, and the composite oxide was not sufficiently produced. Therefore, cracks having a length of 2 mm or more were confirmed after the sputtering film formation.
これに対して、本発明例１～１４においては、仮焼成工程における焼成温度が６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされており、酸化物スパッタリングターゲットの比抵抗値の変動係数が０．２０以下となった。これにより、スパッタ成膜初期に成膜された酸化物膜とスパッタ成膜開始から２時間経過時に成膜された酸化物膜とで膜抵抗の変化量が抑えられていた。
On the other hand, in Examples 1 to 14 of the present invention, the firing temperature in the temporary firing step is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less. The coefficient of variation of the specific resistance value of the oxide sputtering target was 0.20 or less. As a result, the amount of change in film resistance was suppressed between the oxide film formed at the initial stage of sputter film formation and the oxide film formed 2 hours after the start of sputter film formation.
なお、焼結工程において焼結温度での保持時間が１時間とされた本発明例７、焼結工程において焼結温度が７５０℃とされた本発明例８、仮焼成工程において焼成温度が６００℃とされた本発明例１１、仮焼成工程において焼成温度での保持時間が２時間とされた本発明例１３においては、複合酸化物が十分に生成せず、スパッタ成膜後に長さ２ｍｍ以上の割れが確認された。
In addition, Example 7 of the present invention in which the holding time at the sintering step was 1 hour in the sintering step, Example 8 of the present invention in which the sintering temperature was 750 ° C. in the sintering step, and the firing temperature of 600 in the temporary firing step. In Example 11 of the present invention set at ° C. and Example 13 of the present invention in which the holding time at the firing temperature was 2 hours in the calcination step, the composite oxide was not sufficiently formed and the length was 2 mm or more after the sputter film formation. Crack was confirmed.
以上の結果から、本発明例によれば、スパッタ成膜の初期／中期／終期で特性のばらつきが少なく均一な酸化物膜を安定して成膜可能な酸化物スパッタリングターゲット、および、この酸化物スパッタリングターゲットの製造方法を提供可能であることが確認された。
From the above results, according to the example of the present invention, an oxide sputtering target capable of stably forming a uniform oxide film with little variation in characteristics at the initial / middle / final stage of sputtering deposition, and an oxide thereof. It was confirmed that it is possible to provide a method for manufacturing a sputtering target.
Claims (6)
- 金属成分としてＺｎを主成分とする酸化物焼結体からなり、
厚さ方向における比抵抗値の変動係数が０．２０以下であることを特徴とする酸化物スパッタリングターゲット。 It consists of an oxide sintered body whose main component is Zn as a metal component.
An oxide sputtering target characterized in that the coefficient of variation of the specific resistance value in the thickness direction is 0.20 or less. - 金属成分の合計を１００原子％として、Ｇａが１０．０原子％以上かつ２０．０原子％以下、Ｔｉが０．５原子％以上かつ５．０原子％以下、残部がＺｎおよび不可避不純物金属元素とされた割合で含有する酸化物からなることを特徴とする請求項１に記載の酸化物スパッタリングターゲット。 Assuming that the total of the metal components is 100 atomic%, Ga is 10.0 atomic% or more and 20.0 atomic% or less, Ti is 0.5 atomic% or more and 5.0 atomic% or less, and the balance is Zn and unavoidable impurity metal elements. The oxide sputtering target according to claim 1, wherein the oxide sputtering target is composed of an oxide contained in the above-mentioned ratio.
- さらに、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｂ、Ａｌ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ及びランタノイド系列の元素からなる元素群より選ばれる少なくとも１種または２種以上の添加元素を合計で、金属成分の合計を１００原子％として０．０１原子％以上かつ１０．０原子％以下の範囲内で含有することを特徴とする請求項２に記載の酸化物スパッタリングターゲット。 Further, it is composed of elements of the Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, B, Al, In, Si, Ge, Sn, Pb, Sb, Bi and lanthanoid series. It is characterized by containing at least one or two or more additive elements selected from the element group in the range of 0.01 atomic% or more and 10.0 atomic% or less with the total metal component as 100 atomic%. The oxide sputtering target according to claim 2.
- 複合酸化物を有し、複合酸化物の存在比率が１５％以上であることを特徴とする請求項２又は請求項３のいずれか一項に記載の酸化物スパッタリングターゲット。 The oxide sputtering target according to any one of claims 2 or 3, wherein the oxide sputtering target has a composite oxide and the abundance ratio of the composite oxide is 15% or more.
- 請求項１から請求項４のいずれか一項に記載の酸化物スパッタリングターゲットを製造する酸化物スパッタリングターゲットの製造方法であって、
焼結原料粉を仮焼成する仮焼成工程と、焼成した焼結原料粉を解砕する解砕工程と、解砕した焼結原料粉を焼結して焼結体を得る焼結工程と、を備えており、
前記仮焼成工程における真空度が１５Ｐａ以下の範囲内、焼成温度が６００℃以上かつ１０００℃以下の範囲内、焼成温度での保持時間が２時間以上かつ６時間以下の範囲内とされていることを特徴とする酸化物スパッタリングターゲットの製造方法。 The method for manufacturing an oxide sputtering target for manufacturing the oxide sputtering target according to any one of claims 1 to 4.
A temporary firing step of temporarily firing the sintered raw material powder, a crushing step of crushing the fired sintered raw material powder, and a sintering step of sintering the crushed sintered raw material powder to obtain a sintered body. Equipped with
The degree of vacuum in the temporary firing step is within the range of 15 Pa or less, the firing temperature is within the range of 600 ° C. or higher and 1000 ° C. or lower, and the holding time at the firing temperature is within the range of 2 hours or more and 6 hours or less. A method for manufacturing an oxide sputtering target. - 前記焼結工程における真空度が１５Ｐａ以下の範囲内、焼結温度が９００℃以上かつ１１００℃以下の範囲内、焼結温度での保持時間が２時間以上かつ６時間以下の範囲内とされていることを特徴とする請求項５に記載の酸化物スパッタリングターゲットの製造方法。 The degree of vacuum in the sintering step is within the range of 15 Pa or less, the sintering temperature is within the range of 900 ° C. or higher and 1100 ° C. or lower, and the holding time at the sintering temperature is within the range of 2 hours or more and 6 hours or less. The method for producing an oxide sputtering target according to claim 5, wherein the oxide sputtering target is produced.
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| JP2004244723A (en) * | 2003-01-22 | 2004-09-02 | Canon Inc | Sintered compact, and film deposition method using the same |
| JP2015052165A (en) * | 2013-08-06 | 2015-03-19 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of the same |
| JP2016098396A (en) * | 2014-11-20 | 2016-05-30 | Tdk株式会社 | Sputtering target, transparent conductive oxide thin film, and conductive film |
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| JP2015052165A (en) * | 2013-08-06 | 2015-03-19 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of the same |
| JP2016098396A (en) * | 2014-11-20 | 2016-05-30 | Tdk株式会社 | Sputtering target, transparent conductive oxide thin film, and conductive film |
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