WO2019202753A1 - 酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜の製造方法 - Google Patents

酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜の製造方法 Download PDF

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WO2019202753A1
WO2019202753A1 PCT/JP2018/032028 JP2018032028W WO2019202753A1 WO 2019202753 A1 WO2019202753 A1 WO 2019202753A1 JP 2018032028 W JP2018032028 W JP 2018032028W WO 2019202753 A1 WO2019202753 A1 WO 2019202753A1
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sintered body
oxide sintered
sputtering target
sputtering
oxide
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PCT/JP2018/032028
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English (en)
French (fr)
Japanese (ja)
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享祐 寺村
功児 深川
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三井金属鉱業株式会社
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Priority to JP2019500522A priority Critical patent/JP6511209B1/ja
Priority to CN201880041330.1A priority patent/CN110770191B/zh
Priority to KR1020197036451A priority patent/KR102380914B1/ko
Publication of WO2019202753A1 publication Critical patent/WO2019202753A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • 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
    • H01L21/203—
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the disclosed embodiment relates to a method for manufacturing an oxide sintered body, a sputtering target, and an oxide thin film.
  • a sputtering method which is a thin film forming method using a sputtering target, is extremely effective as a method for forming a thin film with a large area and high precision, and the sputtering method is widely used in display devices such as liquid crystal display devices.
  • TFT thin film transistors
  • IGZO oxides represented by In—Ga—Zn composite oxide (hereinafter also referred to as “IGZO”) instead of amorphous silicon.
  • IGZO oxides represented by In—Ga—Zn composite oxide
  • problems such as abnormal quality of the formed thin film and occurrence of cracks in the sputtering target during sputtering may occur due to occurrence of abnormal discharge.
  • One technique for avoiding these problems is to increase the density of the sputtering target.
  • abnormal discharge may occur even with high-density targets.
  • the crystal phase constituting the target is a double phase and there is a resistance difference between different crystal phases, there is a risk that abnormal discharge will occur.
  • Patent Document 2 discusses a ratio in which the ratio of each metal element is In ⁇ Ga ⁇ Zn.
  • the ratio of In, Ga, and Zn in the IGZO sputtering target can be adjusted as appropriate so that predetermined semiconductor characteristics can be obtained.
  • a target having a homologous crystal structure represented by InGaZnO 4 or In 2 Ga 2 ZnO 7 has been studied.
  • the sputtering target is preferably a single phase having a homologous crystal structure.
  • a high-density sputtering target composed of a single phase tends to have a larger crystal grain size than a sputtering target composed of multiple phases. And when crystal grain size enlarges, the mechanical strength of a sputtering target will fall and a crack may generate
  • the sputtering target has a uniform distribution of the above characteristics within the sputtering plane. If the distribution of density and the like is not uniform within the surface, abnormal discharge or cracking during sputtering may occur. In the case of an IGZO sputtering target, the nonuniformity of the characteristic distribution on the sputtering surface may appear as the color difference.
  • One aspect of the embodiment has been made in view of the above, and an object thereof is to provide a sputtering target capable of stably performing sputtering and an oxide sintered body for producing the sputtering target.
  • the oxide sintered body according to one aspect of the embodiment is an oxide sintered body containing indium, gallium, and zinc in a ratio satisfying the following formulas (1) to (3), and is a single-phase crystal phase:
  • the average particle size of the crystal phase is 15.0 ⁇ m or less. 0.01 ⁇ In / (In + Ga + Zn) ⁇ 0.20 (1) 0.10 ⁇ Ga / (In + Ga + Zn) ⁇ 0.49 (2) 0.50 ⁇ Zn / (In + Ga + Zn) ⁇ 0.89 (3)
  • sputtering can be performed stably.
  • FIG. 1 is an SEM image (50 times) of an oxide sintered body in Example 1.
  • FIG. 2 is an SEM image (500 times) of the oxide sintered body in Example 1.
  • FIG. 3 is an SEM image (500 times) of the oxide sintered body in Comparative Example 2.
  • FIG. 4 is an X-ray diffraction chart of the oxide sintered body in Example 1.
  • FIG. 5 is a diagram comparing the X-ray diffraction chart of the oxide sintered body in Example 1 and the peak positions in the X-ray diffraction charts of InGaZnO 4 , In 2 Ga 2 ZnO 7 and Ga 2 ZnO 4 .
  • the oxide sintered body of the embodiment is an oxide sintered body containing indium (In), gallium (Ga), and zinc (Zn), and can be used as a sputtering target.
  • the oxide sintered body of the embodiment is composed of a single-phase crystal phase, and the average grain size of the crystal phase is 15.0 ⁇ m or less. Thereby, the bending strength of the oxide sintered body can be increased. In addition, when grinding such an oxide sintered body, it is possible to prevent the surface from becoming rough due to peeling of the enlarged particles on the surface, and thus it is easy to obtain a smooth surface.
  • the oxide sintered body of the embodiment preferably has an average particle size of 10.0 ⁇ m or less, more preferably 8.0 ⁇ m or less, and even more preferably 6.0 ⁇ m or less. More preferably, it is 0 ⁇ m or less.
  • the lower limit of the average particle diameter is not particularly defined, but is usually 1.0 ⁇ m or more.
  • the oxide sintered body is composed of a single-phase crystal phase, the distribution of each element in the oxide sintered body can be made uniform. Therefore, according to the embodiment, the distribution of each element in the oxide semiconductor thin film formed by sputtering can be made uniform.
  • the atomic ratio of each element satisfies the following formulas (1) to (3). 0.01 ⁇ In / (In + Ga + Zn) ⁇ 0.20 (1) 0.10 ⁇ Ga / (In + Ga + Zn) ⁇ 0.49 (2) 0.50 ⁇ Zn / (In + Ga + Zn) ⁇ 0.89 (3)
  • the atomic ratio of each element preferably satisfies the following formulas (4) to (6), 0.05 ⁇ In / (In + Ga + Zn) ⁇ 0.15 (4) 0.15 ⁇ Ga / (In + Ga + Zn) ⁇ 0.45 (5) 0.50 ⁇ Zn / (In + Ga + Zn) ⁇ 0.80 (6) More preferably, the atomic ratio of each element satisfies the following formulas (7) to (9). 0.05 ⁇ In / (In + Ga + Zn) ⁇ 0.15 (7) 0.20 ⁇ Ga / (In + Ga + Zn) ⁇ 0.40 (8) 0.50 ⁇ Zn / (In + Ga + Zn) ⁇ 0.70 (9)
  • the oxide sintered body of the embodiment may contain inevitable impurities derived from raw materials and the like.
  • Inevitable impurities in the oxide sintered body of the embodiment include Fe, Cr, Ni, Si, W, Cu, Al, and the like, and their contents are each usually 100 ppm or less.
  • diffraction peaks are observed in the following regions A to P in the single-phase crystal phase constituting the oxide sintered body of the embodiment. preferable.
  • this oxide sintered body when used as a sputtering target, it is possible to suppress the occurrence of abnormal discharge. Therefore, according to the embodiment, the generation of particles due to such abnormal discharge can be suppressed, so that the production yield of TFT can be improved.
  • the oxide sintered body of the embodiment preferably has a relative density of 97.0% or more.
  • this oxide sintered compact is used as a sputtering target, the discharge state of DC sputtering can be stabilized.
  • a relative density is 98.0% or more, and it is further more preferable that a relative density is 99.0% or more.
  • the relative density is 97.0% or more
  • voids can be reduced in the sputtering target, and it is easy to prevent uptake of gas components in the atmosphere.
  • abnormal discharge starting from such voids, cracking of the sputtering target, and the like are less likely to occur.
  • the oxide sintered body of the embodiment preferably has a bending strength of 40 MPa or more. Therefore, when manufacturing a sputtering target using this oxide sintered compact, or when performing sputtering with this sputtering target, it can suppress that an oxide sintered compact is damaged.
  • the oxide sintered body of the embodiment preferably has a bending strength of 50 MPa or more, more preferably 60 MPa or more, and even more preferably 70 MPa or more.
  • the upper limit value of the bending strength is not particularly defined, but is usually 300 MPa or less.
  • the oxide sintered body used for the sputtering target of the embodiment preferably has a maximum surface roughness height Ry of 15.0 ⁇ m or less. Therefore, when sputtering using this sputtering target, it can suppress that a nodule generate
  • the maximum height Ry is 11.0 micrometers or less, and it is further more preferable that it is 10.0 micrometers or less.
  • the lower limit value of the maximum height Ry is not particularly defined, but is usually 0.1 ⁇ m or more.
  • the oxide sintered body of the embodiment preferably has a specific resistance of 40 m ⁇ ⁇ cm or less.
  • this oxide sintered compact is used as a sputtering target, sputtering using an inexpensive DC power source is possible, and the film formation rate can be improved. Thereby, generation
  • the oxide sintered body of the embodiment preferably has a specific resistance of 35 m ⁇ ⁇ cm or less, and more preferably has a specific resistance of 30 m ⁇ ⁇ cm or less.
  • the lower limit value of the specific resistance is not particularly defined, but is usually 0.1 m ⁇ ⁇ cm or more.
  • the color difference ⁇ E * on the surface of the sputtering target is preferably 10 or less.
  • ⁇ E * is preferably 10 or less in the color difference in the depth direction of the sputtering target.
  • the sputtering target of the embodiment more preferably the color difference of the entire surface and depth Delta] E * is 9 or less, and further preferably the color difference Delta] E * is 8 or less.
  • the oxide sputtering target of the embodiment can be manufactured by the following method, for example. First, the raw material powder is mixed.
  • the raw material powder is usually In 2 O 3 powder, Ga 2 O 3 powder and ZnO powder.
  • the mixing ratio of the raw material powders is appropriately determined so as to obtain a desired constituent element ratio in the oxide sintered body.
  • Each raw material powder is preferably dry-mixed in advance.
  • It can mix using various mixers, such as a container rotation type mixer and a container fixed type mixer.
  • a high-speed mixer manufactured by Earth Technica Co., Ltd., for example.
  • the raw powder is uniformly dispersed and mixed by performing dry mixing in advance as described above, it is easy to obtain a sintered body having a single-phase structure, and the color difference is preferably within the above-mentioned range.
  • Examples of a method for producing a molded body from the mixed powder thus mixed include a slip casting method and CIP (Cold Isostatic Pressing). Subsequently, two types of methods will be described as specific examples of the forming method.
  • a slurry containing a mixed powder and an organic additive is prepared using a dispersion medium, and the slurry is poured into a mold to remove the dispersion medium.
  • Organic additives that can be used here are known binders and dispersants.
  • the dispersion medium used for preparing the slurry is not particularly limited, and can be appropriately selected from water, alcohol and the like according to the purpose.
  • the ball mill mixing which puts mixed powder, an organic additive, and a dispersion medium in a pot and can be used can be used.
  • the slurry thus obtained is poured into a mold, and the dispersion medium is removed to produce a molded body.
  • the mold that can be used here include a metal mold, a gypsum mold, and a resin mold that pressurizes and removes the dispersion medium.
  • CIP method In the CIP method described here, a slurry containing a mixed powder and an organic additive is prepared using a dispersion medium, and a dry powder obtained by spray-drying the slurry is filled in a mold and subjected to pressure molding. I do.
  • Organic additives that can be used here are known binders and dispersants.
  • the dispersion medium used for preparing the slurry is not particularly limited, and can be appropriately selected from water, alcohol and the like according to the purpose. Moreover, there is no restriction
  • the slurry thus obtained is spray-dried to produce a dry powder having a water content of 1% or less, and the dry powder is filled into a mold and pressure-molded by the CIP method to produce a molded body. .
  • the obtained molded body is fired to produce a sintered body.
  • the kiln which can be used for manufacture of a ceramic sintered compact can be used.
  • the firing temperature is 1350 ° C. to 1580 ° C., preferably 1400 ° C. to 1550 ° C., more preferably 1450 ° C. to 1550 ° C. While the higher the firing temperature, the higher the density of the sintered body is obtained. On the other hand, it is preferable to control the temperature below the above temperature from the viewpoint of suppressing the enlargement of the structure of the sintered body and preventing cracking. Further, if the firing temperature is lower than 1350 ° C., it is difficult to form a single-phase crystal phase, which is not preferable.
  • the obtained sintered body is cut.
  • Such cutting is performed using a surface grinder or the like.
  • the maximum height Ry of the surface roughness after cutting can be appropriately controlled by selecting the size of the abrasive grains of the grindstone used for the cutting, but the grain size of the sintered body is enlarged. If so, the maximum height Ry is increased due to peeling of the enlarged particles.
  • a sputtering target is prepared by bonding the sintered body that has been cut to a substrate.
  • Stainless steel, copper, titanium or the like can be appropriately selected as the material of the base material.
  • a low melting point solder such as indium can be used as the bonding material.
  • Example 1 In 2 O 3 powder having an average particle diameter of 0.6 ⁇ m, Ga 2 O 3 powder having an average particle diameter of 1.5 ⁇ m, and ZnO powder having an average particle diameter of 0.8 ⁇ m manufactured by Earth Technica Co., Ltd. The dry powder was mixed using a high speed mixer to prepare a mixed powder.
  • the average particle size of the raw material powder was measured using a particle size distribution measuring apparatus HRA manufactured by Nikkiso Co., Ltd. In this measurement, water was used as the solvent, and the measurement was performed with a refractive index of 2.20. The same measurement conditions were used for the average particle diameter of the raw material powder described below.
  • the average particle size of the raw material powder is the volume cumulative particle diameter D 50 in the cumulative volume 50% by volume by laser diffraction scattering particle size distribution measuring method.
  • the prepared slurry was poured into a metal mold sandwiching a filter and drained to obtain a molded body.
  • this molded body was fired to produce a sintered body. The firing was performed at a firing temperature of 1500 ° C., a firing time of 10 hours, a heating rate of 100 ° C./h, and a cooling rate of 100 ° C./h.
  • the obtained sintered body was cut to obtain a sputtering target having a width of 210 mm, a length of 710 mm, and a thickness of 6 mm.
  • a # 170 grindstone was used for the cutting process.
  • Example 2 to 3 A sputtering target was obtained using the same method as in Example 1. In Examples 2 to 3, when preparing the mixed powder, each raw material powder was blended so that the atomic ratio of the metal elements contained in all the raw material powders was the atomic ratio shown in Table 1.
  • the atomic ratio of each metal element measured when preparing each raw material powder is equal to the atomic ratio of each metal element in the obtained oxide sintered body. It was confirmed.
  • the atomic ratio of each metal element in the oxide sintered body can be measured by, for example, ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy).
  • the air mass of the sputtering target is divided by the volume (the mass of the sintered body in water / the specific gravity of water at the measurement temperature), and the percentage value relative to the theoretical density ⁇ (g / cm 3 ) is expressed as a relative density (unit:%). ).
  • C 1 to C 3 and ⁇ 1 to ⁇ 3 in the above formulas represent the following values, respectively.
  • C 1 mass% of In 2 O 3 powder used for the production of the oxide sintered body ⁇ ⁇ 1 : Density of In 2 O 3 (7.18 g / cm 3 )
  • C 2 mass% of Ga 2 O 3 powder used for production of oxide sintered body ⁇ ⁇ 2 : density of Ga 2 O 3 (5.95 g / cm 3 )
  • C 3 mass% of ZnO powder used for the production of oxide sintered body ⁇ ⁇ 3 : ZnO density (5.60 g / cm 3 )
  • the probe is applied to the surface of the oxide sintered body after processing, and AUTO RANGE Measured in mode.
  • the measurement locations were a total of five locations near the center and four corners of the oxide sintered body, and the average value of each measurement value was taken as the bulk resistance value of the sintered body.
  • the bending strength of each of the sputtering targets of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above was measured.
  • Such bending strength is obtained by using JIS-R-1601 (bending strength of fine ceramics) using a sample piece (overall length 36 mm, width 4.0 mm, thickness 3.0 mm) cut from an oxide sintered body by wire electric discharge machining. It was measured according to the three-point bending strength measuring method in (Testing method).
  • the atomic ratio of each element contained in the mixed powder the presence or absence of dry mixing during the production of the oxide sintered body, the firing temperature, the oxide Table 1 shows the relative density, specific resistance (bulk resistance), and bending strength measurement results of the sintered body.
  • the oxide sintered bodies of Examples 1 to 3 all have a relative density of 97.0% or more. Therefore, according to the embodiment, when such an oxide sintered body is used as a sputtering target, the discharge state of DC sputtering can be stabilized.
  • the oxide sintered bodies of Examples 1 to 3 all have a specific resistance of 40 m ⁇ cm or less. Therefore, according to the embodiment, when an oxide sintered body is used as a sputtering target, sputtering using an inexpensive DC power source is possible, and the film formation rate can be improved.
  • the oxide sintered bodies of Examples 1 to 3 all have a bending strength of 40 MPa or more. Therefore, according to the embodiment, the oxide sintered body can be prevented from being damaged when the sputtering target is manufactured using the oxide sintered body or when sputtering is performed using the sputtering target. .
  • the cut surface obtained by cutting the oxide sintered body is polished step by step using emery paper # 180, # 400, # 800, # 1000, # 2000, and finally buffed. And finished to a mirror surface.
  • etching solution nitric acid (60 to 61% aqueous solution, manufactured by Kanto Chemical Co., Ltd.), hydrochloric acid (35.0 to 37.0% aqueous solution, manufactured by Kanto Chemical Co., Ltd.) and pure water at a volume ratio of 40 ° C.
  • ImageJ 1.51k http://imageJ.nih.gov/ij/) provided by the National Institutes of Health (NIH) was used.
  • FIGS. 1 and 2 are SEM images of the oxide sintered body in Example 1.
  • FIG. 1 and 2 black portions are chipped portions due to surface polishing.
  • the oxide sintered body of Example 1 is composed of a single-phase crystal phase.
  • FIG. 3 is an SEM image of the oxide sintered body in Comparative Example 2.
  • the portion that appears black is a phase in which indium is reduced (In poor phase).
  • the oxide sintered body of Comparative Example 2 is composed of a multiphase crystal phase.
  • X-ray diffraction (XRD) measurement was performed on the oxide sintered bodies of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above to obtain an X-ray diffraction chart. It was.
  • FIG. 4 is an X-ray diffraction chart of the oxide sintered body in Example 1.
  • diffraction peaks are observed in the following areas A to P when the diffraction angle 2 ⁇ is in the range of 20 ° to 70 °.
  • the oxide sintered body of Example 1 is composed of a single-phase crystal phase
  • the diffraction peak observed in the above-described regions A to P is such a single-phase crystal phase. It turns out that it originates in. In other words, it is possible to identify the single-phase crystal phase constituting the oxide sintered body of Example 1 by using the chart obtained by the X-ray diffraction measurement.
  • FIG. 5 is a diagram comparing the X-ray diffraction chart of the oxide sintered body in Example 1 and the peak positions in the X-ray diffraction charts of InGaZnO 4 , In 2 Ga 2 ZnO 7 and Ga 2 ZnO 4 .
  • the single-phase crystal phase constituting the oxide sintered body of Example 1 is a known crystal phase (here, InGaZnO 4 , In 2 Ga 2 ZnO 7, and Ga 2 ZnO 4 ). It can be seen that diffraction peaks are observed at different peak positions.
  • the “known crystal phase” means “a crystal phase in which a peak position of an X-ray diffraction chart is registered in a JCPDS (Joint Committee of Powder Diffraction Standards) card”.
  • the single-phase crystal phase constituting the oxide sintered body of Example 1 is a crystal phase that has not been known so far.
  • the maximum height Ry of the surface roughness was measured for each of the sputtering targets of Examples 1 to 3 and Comparative Examples 1 to 3 obtained above. Specifically, the maximum height Ry of the sputtering surface was measured using a surface roughness measuring instrument (SJ-210 / manufactured by Mitutoyo Corporation). Ten locations on the sputtering surface were measured, and the maximum value was defined as the maximum height Ry of the sputtering target. The measurement results are shown in Table 2.
  • the “color difference ⁇ E * ” is an index obtained by quantifying the difference between two colors.
  • the maximum color difference ⁇ E * in the depth direction is measured by using a color difference meter at each depth to the center of the sputtering target by cutting 0.5 mm at an arbitrary position of the cut sputtering target, The L value, a value, and b value of each measured point were evaluated in the CIE 1976 space. Then, a color difference ⁇ E * is obtained from a combination of all two points from the differences ⁇ L, ⁇ a, ⁇ b between the L value, a value, and b value of two measured points, and a plurality of obtained color differences ⁇ E * are obtained. The maximum value was defined as the maximum color difference ⁇ E * in the depth direction.
  • the sputtering targets obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were used indium as a low melting point solder as a bonding material. Bonded to a copper substrate.
  • the oxide sintered bodies of Examples 1 to 3 are all composed of a single phase. Therefore, according to the embodiment, as can be seen from the results of arcing evaluation, when such an oxide sintered body is used as a sputtering target, sputtering can be performed stably.
  • the oxide sintered bodies of Examples 1 to 3 all have an average particle size of 15.0 ⁇ m or less. Therefore, according to the embodiment, when the oxide sintered body is ground, it is possible to prevent the surface from becoming rough due to peeling of large crystal grains from the surface.
  • the sputtering targets of Examples 1 to 3 all have a maximum height Ry of the surface roughness of the oxide sintered body of 15.0 ⁇ m or less. Therefore, according to the embodiment, it is possible to suppress generation of nodules on the target surface during sputtering.
  • the maximum color difference ⁇ E * in the in-plane direction and the depth direction is 10 or less. Therefore, according to the embodiment, since there is no bias in the crystal grain size and composition, it is suitable as a sputtering target.
  • the shape of the oxide sintered body is not limited to a plate shape, and may be any shape such as a cylindrical shape. It may be a shape.

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PCT/JP2018/032028 2018-04-18 2018-08-29 酸化物焼結体、スパッタリングターゲットおよび酸化物薄膜の製造方法 WO2019202753A1 (ja)

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