WO2019097959A1 - Oxide sintered body and sputtering target - Google Patents

Oxide sintered body and sputtering target Download PDF

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WO2019097959A1
WO2019097959A1 PCT/JP2018/039241 JP2018039241W WO2019097959A1 WO 2019097959 A1 WO2019097959 A1 WO 2019097959A1 JP 2018039241 W JP2018039241 W JP 2018039241W WO 2019097959 A1 WO2019097959 A1 WO 2019097959A1
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oxide
sintered body
sno
oxide sintered
mol
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PCT/JP2018/039241
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French (fr)
Japanese (ja)
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俊亮 竹谷
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三井金属鉱業株式会社
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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
    • C04B35/457—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 based on tin oxides or stannates
    • 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

  • Embodiments of the disclosure relate to an oxide sintered body and a sputtering target.
  • GTO Gallium Tin Oxide
  • tin oxide SnO 2
  • gallium oxide Ga 2 O 3
  • One aspect of the embodiment is made in view of the above, and it is an object of the present invention to provide an oxide sintered body for a GTO sputtering target that can perform DC sputtering even if the concentration of gallium oxide is higher than 20 mol%. I assume.
  • the oxide sintered body according to one aspect of the embodiment is an oxide sintered body containing tin oxide and gallium oxide, and the content of gallium oxide is 20 mol% ⁇ Ga 2 O 3 ⁇ 90 mol%.
  • the specific resistance is 1 ⁇ 10 3 ⁇ ⁇ cm or less.
  • an oxide sintered body for a GTO sputtering target which can perform DC sputtering even when the concentration of gallium oxide is higher than 20 mol%.
  • FIG. 1 is a SEM observation photograph of the oxide sintered body in Example 4.
  • FIG. 2 is a schematic diagram showing the measurement location of the bulk resistance of oxide sinter.
  • FIG. 3 is an X-ray diffraction chart of the oxide sintered body in Examples 4 to 8.
  • FIG. 4 is an X-ray diffraction chart of the oxide sintered body in Comparative Example 1.
  • Oxide sinter 1 of an embodiment contains tin oxide and gallium oxide, and can be used as a sputtering target.
  • Oxide sinter 1 of an embodiment consists of tin oxide, gallium oxide, and an unavoidable impurity, for example, and can be used as a GTO target.
  • the GTO target of the embodiment is allowed to contain a small amount of other elements as long as the advantageous effects of the embodiment are not impaired.
  • the content of gallium oxide is 20 mol% ⁇ Ga 2 O 3 ⁇ 90 mol%, and the specific resistance is 1 ⁇ 10 3 ⁇ ⁇ cm or less.
  • the oxide sinter 1 of the embodiment preferably has a gallium oxide content of more than 20 mol% (typically 20.5 mol% or more) and 90 mol% or less.
  • the content of gallium oxide is 90 mol% or less, the contribution of Ga 2 O 3 having a large specific resistance is smaller than that of SnO 2 , which is preferable because the specific resistance of the sputtering target is low.
  • the content of gallium oxide is preferably 85 mol% or less, more preferably 75 mol% or less, still more preferably 65 mol% or less, and still more preferably 50 mol% or less.
  • the content of gallium oxide is preferably 45 mol% or less, more preferably 40 mol% or less.
  • the oxide sintered body 1 of the embodiment has a specific resistance of 1 ⁇ 10 3 ⁇ ⁇ cm or less. Therefore, when this oxide sinter 1 is used as a sputtering target, sputtering using an inexpensive DC power supply becomes possible, and the film forming rate can be improved.
  • the oxide sintered body 1 of the embodiment preferably has a specific resistance of 5 ⁇ 10 2 ⁇ ⁇ cm or less, and more preferably 1 ⁇ 10 2 ⁇ ⁇ cm or less.
  • a gallium stannate compound (Ga 4 SnO 8 ) is not generated as much as possible. Although the specific resistance becomes reason is not clear low by stannate gallium compound (Ga 4 SnO 8) is not generated, the resistivity of stannate gallium compound (Ga 4 SnO 8) is considered or not for high.
  • the oxide sintered body 1 of the embodiment is the (111) of the gallium stannate compound (Ga 4 SnO 8 ) phase with respect to the peak of the (110) plane of the tin oxide (SnO 2 ) phase in the X-ray diffraction measurement.
  • the peak intensity ratio I of the surface is preferably 0.15 or less. That is, in the oxide sintered body 1 of the embodiment, the ratio of the gallium stannate compound (Ga 4 SnO 8 ) phase to the tin oxide (SnO 2 ) phase is a predetermined ratio defined by the above peak intensity ratio I. It is preferable to be small.
  • oxide sinter 1 with a small specific resistance can be formed. Therefore, according to the embodiment, DC sputtering is facilitated when the oxide sintered body 1 is used as a sputtering target.
  • the above-mentioned peak intensity ratio I is preferably 0.10 or less, more preferably 0.05 or less, and still more preferably 0.03 or less. Preferably, it is more preferably 0.01 or less.
  • the oxide sintered body 1 of the embodiment preferably has a relative density of 90% or more. Thereby, when this oxide sinter 1 is used as a sputtering target, the discharge state of DC sputtering can be stabilized. From this viewpoint, the oxide sintered body 1 of the embodiment more preferably has a relative density of 95% or more.
  • the oxide sintered body 1 When the oxide sintered body 1 is used as a sputtering target, if the relative density is 90% or more, voids can be reduced in the sputtering target, and it is easy to prevent uptake of gas components in the atmosphere. In addition, abnormal discharge starting from the gap, cracking of the sputtering target, and the like are less likely to occur.
  • the oxide sintered body 1 of the embodiment can be manufactured, for example, by the following method.
  • the raw material powders are Ga 2 O 3 powder and SnO 2 powder.
  • the average particle size of each raw material powder is preferably 2 ⁇ m or less. If the average particle diameter of each raw material powder is 2 ⁇ m or less, a high density sintered body can be easily obtained even if the sintering temperature is lowered. From such a viewpoint, the average particle diameter of each raw material powder is more preferably 1.5 ⁇ m or less, and still more preferably 1 ⁇ m or less.
  • the lower limit value of the average particle diameter of each raw material powder is not particularly limited, but is preferably 0.1 ⁇ m or more from the viewpoint of preventing aggregation of the raw material.
  • 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.
  • Various mixing means can be used for mixing of raw material powder.
  • media stirring type mills such as bead mills, sand mills, attritors (registered trademark) and ball mills can be used.
  • the obtained mixed powder may be sieved.
  • the oxide sintered body 1 of the embodiment is preferably sintered by a spark plasma sintering (SPS) method or a hot press (HP) method.
  • SPS spark plasma sintering
  • HP hot press
  • the mixed powder is filled in a sintering die having a shaped concave portion of a predetermined shape.
  • a sintering die for example, one made of graphite can be used.
  • the oxide sintered body 1 of the embodiment is preferably sintered at a relatively low temperature of 1200 ° C. or less. By sintering at a low temperature of 1200 ° C. or less, the formation of a gallium stannate compound (Ga 4 SnO 8 ) can be suppressed, and the specific resistance of the oxide sintered body 1 can be lowered.
  • a gallium stannate compound Ga 4 SnO 8
  • the sintering temperature of the embodiment is preferably 1100 ° C. or less, more preferably 1000 ° C. or less, and still more preferably 950 ° C. or less.
  • the lower limit value of the firing temperature is preferably 500 ° C. or more from the viewpoint of sufficient sintering.
  • the mixed powder was sieved with a sieve having an opening of 710 ⁇ m to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 ⁇ m.
  • the sieved mixed powder was filled into a graphite sintering die with an inner diameter of 120 mm.
  • the sintered die filled with the mixed powder was sintered by a spark plasma sintering (SPS) apparatus to produce a sintered body.
  • Sintering with this SPS device is performed under vacuum (15 Pa or less), pressure 20 MPa, sintering temperature 600 ° C., temperature rising rate 20 ° C./min, holding time at sintering temperature 30 min, temperature lowering is natural furnace cooling.
  • the obtained sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
  • the ratio (mol%) of each oxide contained in the mixed powder of SnO 2 powder and Ga 2 O 3 powder is the oxide sintered body 1 finally obtained. It can be regarded as the ratio (mol%) of each oxide contained in.
  • the mixed powder was sieved with a sieve having an opening of 710 ⁇ m to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 ⁇ m.
  • the sieved mixed powder was filled into a graphite sintering die with an inner diameter of 120 mm.
  • the sintered die filled with the mixed powder was sintered by a hot press (HP) device to produce a sintered body.
  • Sintering with this HP apparatus was carried out in an argon atmosphere at a pressure of 17 MPa, a sintering temperature of 920 ° C., a temperature rising rate of 60 ° C./min, a holding time of 180 minutes at the sintering temperature, and a temperature lowering by natural furnace cooling.
  • the obtained sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
  • Ga 2 O 3 powder having an average particle diameter (volume cumulative particle diameter D 50) is 1 [mu] m, an average particle diameter (volume cumulative particle diameter D 50) is a SnO 2 powder is 0.5 ⁇ m, Ga 2 O 3: SnO 2 30.0: were weighed so as to 70.0 (mol%). Next, it mixed using a ball mill for 24 hours, and obtained mixed powder.
  • the mixed powder was sieved with a sieve having an opening of 710 ⁇ m to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 ⁇ m.
  • the obtained mixed powder 6% by mass of polyvinyl alcohol diluted to 4% by mass was added with respect to the mixed powder, and the polyvinyl alcohol was made to conform well to the powder using a mortar. Then, the obtained powder was temporarily pressed under the condition of 200 kg / cm 2 , and the obtained temporary formed body was crushed in a mortar to obtain a crushed powder. Next, the obtained pulverized powder was filled in a press die, and molded for 60 seconds under a press pressure of 1 t / cm 2 to obtain a molded body.
  • the obtained compact is put into a sintering furnace, oxygen is allowed to flow in the furnace at 1 L / h, and the sintering atmosphere is made an oxygen flow atmosphere, and the temperature rising rate is 5.83 ° C./min (350 ° C./min. h)
  • the sintering temperature was 1500 ° C.
  • the holding time at the sintering temperature was set to 540 minutes (9 h).
  • the obtained sintered body was cooled at a temperature lowering rate of 100 ° C./h.
  • the cooled sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
  • the air mass of the oxide sintered body 1 is divided by the volume (mass of the sintered body in water / specific gravity of water at the measurement temperature), and the percentage value relative to the theoretical density ⁇ (g / cm 3 ) is a relative density (Unit:%).
  • C 1 and C 2 and ⁇ ⁇ ⁇ 1 and ⁇ 2 in the above formula indicate the following values, respectively.
  • C 1 :% by mass of SnO 2 powder used for the production of oxide sintered body 1 ⁇ ⁇ 1 density of SnO 2 (6.95 g / cm 3 )
  • C 2 :% by mass of Ga 2 O 3 powder used in the production of oxide sintered body 1 ⁇ ⁇ 2 density of Ga 2 O 3 (5.95 g / cm 3 )
  • FIG. 1 is a SEM observation photograph of the oxide sintered body 1 in Example 4.
  • a dark gallium oxide (Ga 2 O 3 ) phase is dispersed in a light tin oxide (SnO 2 ) phase.
  • a gallium stannate compound (Ga 4 SnO 8 ) phase which is a compound of tin oxide and gallium oxide, was not observed in the oxide sintered bodies 1 of Examples 1 to 8.
  • the concentration of Zr impurities contained in each of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above was measured. Specifically, it was measured by an acid decomposition ICP-OES method using ICP emission spectrometer 720 ICP-OES manufactured by Agilent Technologies. As a result, in all the oxide sintered bodies 1, the Zr concentration was less than 50 ppm.
  • FIG. 2 is a schematic view showing measurement points of bulk resistance of the oxide sintered body 1.
  • the specific resistance was 1 ⁇ 10 3 ⁇ ⁇ cm or less, and it was possible to measure the specific resistance
  • Comparative Example 1 was an insulator (That is, the specific resistance was larger than 1 ⁇ 10 7 ⁇ ⁇ cm), and the measurement of the specific resistance (bulk resistance) could not be performed.
  • Comparative Example 2 has a specific resistance of 2.4 ⁇ 10 3 ⁇ ⁇ cm, which is higher than those of Examples 1 to 8. It is considered that this is because the proportion of tin oxide which is considered to be responsible for conductivity decreases and it becomes difficult to form a conductive path in the target.
  • sputtering targets of Examples 1 to 8 and Comparative Examples 1 and 2 were produced from the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above.
  • the sputtering target was manufactured by using indium as a low melting point solder as a bonding material, and bonding the oxide sintered body 1 obtained above to a copper base.
  • Film forming apparatus DC magnetron sputtering apparatus
  • Exhaust system cryopump
  • rotary pump Sputtering power 150 W (1.85 W / cm 2 )
  • the ultimate pressure 1.0 ⁇ 10-4 Pa
  • Sputtering pressure 0.4 Pa -Oxygen partial pressure: O 2 2.0%
  • the content of gallium oxide 90 mol% or less By making the content of gallium oxide 90 mol% or less according to the comparison between Examples 1 to 8 in which the content of gallium oxide is 90 mol% or less and the comparative example 2 in which the content of gallium oxide is 95 mol% or more.
  • the specific resistance can be reduced to 1 ⁇ 10 3 ⁇ ⁇ cm or less.
  • Examples 1-8 specific resistance 1 ⁇ 10 3 ⁇ ⁇ cm or less by comparison with Comparative Examples 1 and 2 the resistivity is 1 ⁇ 10 3 ⁇ ⁇ cm or more, the resistivity 1 ⁇ It is understood that a sputtering target capable of DC sputtering can be realized by reducing it to 10 3 ⁇ ⁇ cm or less.
  • the discharge state of DC sputtering can be stabilized. Furthermore, by making the relative density 95% or more, the discharge state of DC sputtering is made by comparing the examples 4 to 8 having a relative density of less than 95% and the examples 1 to 3 having a relative density of 95% or more. It turns out that it is stabilized further.
  • X-Ray Diffraction (XRD) measurement is performed on each of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above, and X-ray diffraction charts Obtained. Then, the structures of oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 were identified from the obtained X-ray diffraction chart.
  • XRD X-Ray Diffraction
  • FIG. 3 is an X-ray diffraction chart of the oxide sintered body 1 in Examples 4 to 8.
  • FIG. 3 also shows the positions of peaks appearing due to various planes present in each oxide in the X-ray diffraction chart.
  • the peak of the (110) plane of tin oxide (SnO 2) phase is the main peak of the tin oxide (SnO 2) phases, the diffraction angle (2 [Theta]) appears to 26.58 ° It is a peak.
  • the peak of the (111) plane of stannate gallium compound (Ga 4 SnO 8) phase is the main peak of stannate gallium compound (Ga 4 SnO 8) phase, diffraction angle (2 [Theta]) is the 34.81 ° It is a peak that appears.
  • the peak intensity ratio I in Example 4 is 0.03, the peak intensity ratio I in Example 5 is 0.03, and the peak intensity ratio I in Example 6 is 0.04.
  • the peak intensity ratio I in Example 7 was 0.09, and the peak intensity ratio I in Example 8 was 0.13.
  • the peak intensity ratio I in Example 1 is 0.01
  • the peak intensity ratio I in Example 2 is 0.01
  • the peak intensity in Example 3 The ratio I was 0.01.
  • FIG. 4 is an X-ray diffraction chart of the oxide sintered body 1 in Comparative Example 1. As in FIG. 3, FIG. 4 also shows the positions of peaks appearing in the X-ray diffraction chart due to various planes present in each oxide.
  • Example 1 sintered at a relatively low temperature of 1200 ° C. or lower using the SPS method or the HP method, and Comparative Example 1 sintered at a temperature higher than 1200 ° C.
  • the peak intensity ratio I can be reduced to 0.05 or less by bonding. That is, in the embodiment, the formation of the gallium stannate compound (Ga 4 SnO 8 ) phase can be suppressed by sintering at a relatively low temperature.
  • the gallium stannate compound (Ga 4 SnO 8 ) phase has a high ratio It is considered to have resistance. That is, according to the embodiment, the specific resistance can be reduced to 1 ⁇ 10 3 ( ⁇ ⁇ cm) or less by suppressing the formation of the gallium stannate compound (Ga 4 SnO 8 ) phase by low temperature sintering. .
  • the SPS method and the HP method are used is described as a method capable of performing sintering at a relatively low temperature of 1200 ° C. or less.
  • the low temperature sintering method includes the SPS method and the HP method It is not limited to.
  • the shape of the oxide sintered body 1 is not limited to the disc shape, and may be cylindrical or the like. It may have any shape.

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Abstract

The oxide sintered body according to one aspect of an embodiment of the present invention contains a tin oxide and a gallium oxide, wherein the content of the gallium oxide satisfies 20 mol% < Ga2O3 ≤ 90 mol%, and the oxide sintered body has a specific resistance of 1 × 103 Ω·cm or less.

Description

酸化物焼結体およびスパッタリングターゲットOxide sinter and sputtering target
　開示の実施形態は、酸化物焼結体およびスパッタリングターゲットに関する。 Embodiments of the disclosure relate to an oxide sintered body and a sputtering target.
　従来、酸化物半導体薄膜を成膜するスパッタリングターゲットとして、酸化スズ（ＳｎＯ2）と酸化ガリウム（Ｇａ2Ｏ3）とを含んだＧＴＯ（Gallium　Tin　Oxide）ターゲットが知られている（たとえば、特許文献１参照）。 Conventionally, a GTO (Gallium Tin Oxide) target including tin oxide (SnO 2 ) and gallium oxide (Ga 2 O 3 ) is known as a sputtering target for forming an oxide semiconductor thin film (for example, patent documents 1).
特開２０１３－４０３９４号公報JP, 2013-40394, A
　しかしながら、従来のＧＴＯターゲットでは、酸化ガリウムの濃度を２０ｍｏｌ％より高くした場合、ターゲットの比抵抗が大きくなりＤＣ（直流）電源を用いたスパッタリング（以下、ＤＣスパッタリングとも呼称する。）ができないという問題があった。 However, in the conventional GTO target, when the concentration of gallium oxide is higher than 20 mol%, the specific resistance of the target is increased, and sputtering using a DC (direct current) power source can not be performed (hereinafter also referred to as DC sputtering). was there.
　実施形態の一態様は、上記に鑑みてなされたものであって、酸化ガリウムの濃度が２０ｍｏｌ％より高くてもＤＣスパッタリングが可能であるＧＴＯスパッタリングターゲット用酸化物焼結体を提供することを目的とする。 One aspect of the embodiment is made in view of the above, and it is an object of the present invention to provide an oxide sintered body for a GTO sputtering target that can perform DC sputtering even if the concentration of gallium oxide is higher than 20 mol%. I assume.
　実施形態の一態様に係る酸化物焼結体は、酸化スズと、酸化ガリウムとを含む酸化物焼結体であって、酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦９０ｍｏｌ％であり、比抵抗が１×１０3Ω・ｃｍ以下である。 The oxide sintered body according to one aspect of the embodiment is an oxide sintered body containing tin oxide and gallium oxide, and the content of gallium oxide is 20 mol% <Ga 2 O 3 ≦ 90 mol%. The specific resistance is 1 × 10 3 Ω · cm or less.
　実施形態の一態様によれば、酸化ガリウムの濃度が２０ｍｏｌ％より高くてもＤＣスパッタリングが可能であるＧＴＯスパッタリングターゲット用酸化物焼結体を提供することができる。 According to one aspect of the embodiment, it is possible to provide an oxide sintered body for a GTO sputtering target, which can perform DC sputtering even when the concentration of gallium oxide is higher than 20 mol%.
図１は、実施例４における酸化物焼結体のＳＥＭ観察写真である。FIG. 1 is a SEM observation photograph of the oxide sintered body in Example 4. 図２は、酸化物焼結体のバルク抵抗の測定箇所を表す模式図である。FIG. 2: is a schematic diagram showing the measurement location of the bulk resistance of oxide sinter. 図３は、実施例４～８における酸化物焼結体のＸ線回折チャートである。FIG. 3 is an X-ray diffraction chart of the oxide sintered body in Examples 4 to 8. 図４は、比較例１における酸化物焼結体のＸ線回折チャートである。FIG. 4 is an X-ray diffraction chart of the oxide sintered body in Comparative Example 1.
　以下、添付図面を参照して、本願の開示する酸化物焼結体およびスパッタリングターゲットの実施形態について説明する。なお、以下に示す実施形態によりこの発明が限定されるものではない。 Hereinafter, embodiments of the oxide sintered body and the sputtering target disclosed in the present application will be described with reference to the attached drawings. Note that the present invention is not limited by the embodiments described below.
　実施形態の酸化物焼結体１（図２参照）は、酸化スズと酸化ガリウムとを含み、スパッタリングターゲットとして用いることができる。実施形態の酸化物焼結体１は、たとえば、酸化スズと、酸化ガリウムと、不可避不純物とからなり、ＧＴＯターゲットとして用いることができる。なお、実施形態のＧＴＯターゲットは、実施形態の有利な効果を損なわない範囲において、他元素を少量含むことが許容される。 Oxide sinter 1 of an embodiment (refer to Drawing 2) contains tin oxide and gallium oxide, and can be used as a sputtering target. Oxide sinter 1 of an embodiment consists of tin oxide, gallium oxide, and an unavoidable impurity, for example, and can be used as a GTO target. The GTO target of the embodiment is allowed to contain a small amount of other elements as long as the advantageous effects of the embodiment are not impaired.
　実施形態の酸化物焼結体１は、酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦９０ｍｏｌ％であり、比抵抗が１×１０3Ω・ｃｍ以下である。 In the oxide sintered body 1 of the embodiment, the content of gallium oxide is 20 mol% <Ga 2 O 3 ≦ 90 mol%, and the specific resistance is 1 × 10 3 Ω · cm or less.
　実施形態の酸化物焼結体１は、酸化ガリウムの含有量が２０ｍｏｌ％を超える（典型的には２０．５ｍｏｌ％以上）一方で、９０ｍｏｌ％以下であることが好ましい。酸化ガリウムの含有量が９０ｍｏｌ％以下であると、ＳｎＯ2と比べて比抵抗が大きいＧａ2Ｏ3の寄与が小さくなることからスパッタリングターゲットの比抵抗が低くなり好ましい。この観点から酸化ガリウムの含有量は８５ｍｏｌ％以下が好ましく、７５ｍｏｌ％以下がより好ましく、６５ｍｏｌ％以下がさらに好ましく、５０ｍｏｌ％以下が一層好ましい。また、酸化ガリウムの含有量が５０ｍｏｌ％以下の場合、酸化ガリウムの含有量は４５ｍｏｌ％以下が好ましく、４０ｍｏｌ％以下がより好ましい。 The oxide sinter 1 of the embodiment preferably has a gallium oxide content of more than 20 mol% (typically 20.5 mol% or more) and 90 mol% or less. When the content of gallium oxide is 90 mol% or less, the contribution of Ga 2 O 3 having a large specific resistance is smaller than that of SnO 2 , which is preferable because the specific resistance of the sputtering target is low. From this viewpoint, the content of gallium oxide is preferably 85 mol% or less, more preferably 75 mol% or less, still more preferably 65 mol% or less, and still more preferably 50 mol% or less. When the content of gallium oxide is 50 mol% or less, the content of gallium oxide is preferably 45 mol% or less, more preferably 40 mol% or less.
　また、実施形態の酸化物焼結体１は、比抵抗が１×１０3Ω・ｃｍ以下である。これにより、かかる酸化物焼結体１をスパッタリングターゲットとして用いた場合に、安価なＤＣ電源を用いたスパッタリングが可能となり、成膜レートを向上させることができる。 The oxide sintered body 1 of the embodiment has a specific resistance of 1 × 10 3 Ω · cm or less. Thereby, when this oxide sinter 1 is used as a sputtering target, sputtering using an inexpensive DC power supply becomes possible, and the film forming rate can be improved.
　なお、実施形態の酸化物焼結体１は、比抵抗が５×１０2Ω・ｃｍ以下であるのが好ましく、比抵抗が１×１０2Ω・ｃｍ以下であるのがさらに好ましい。 The oxide sintered body 1 of the embodiment preferably has a specific resistance of 5 × 10 2 Ω · cm or less, and more preferably 1 × 10 2 Ω · cm or less.
　実施形態の酸化物焼結体１は、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）がなるべく生成されないことが好ましい。スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）が生成されないことにより比抵抗が低くなる理由は定かではないが、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）の比抵抗が高いためではないかと考えられる。 In the oxide sintered body 1 of the embodiment, it is preferable that a gallium stannate compound (Ga 4 SnO 8 ) is not generated as much as possible. Although the specific resistance becomes reason is not clear low by stannate gallium compound (Ga 4 SnO 8) is not generated, the resistivity of stannate gallium compound (Ga 4 SnO 8) is considered or not for high.
　この観点から実施形態の酸化物焼結体１は、Ｘ線回折測定において、酸化スズ（ＳｎＯ2）相の（１１０）面のピークに対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比Ｉが０．１５以下であることが好ましい。すなわち、実施形態の酸化物焼結体１は、酸化スズ（ＳｎＯ2）相に対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の割合が、上述のピーク強度比Ｉで規定される所定の割合より小さいことが好ましい。 From this viewpoint, the oxide sintered body 1 of the embodiment is the (111) of the gallium stannate compound (Ga 4 SnO 8 ) phase with respect to the peak of the (110) plane of the tin oxide (SnO 2 ) phase in the X-ray diffraction measurement. The peak intensity ratio I of the surface is preferably 0.15 or less. That is, in the oxide sintered body 1 of the embodiment, the ratio of the gallium stannate compound (Ga 4 SnO 8 ) phase to the tin oxide (SnO 2 ) phase is a predetermined ratio defined by the above peak intensity ratio I. It is preferable to be small.
　これにより、比抵抗の小さい酸化物焼結体１を形成することができる。したがって、実施形態によれば、かかる酸化物焼結体１をスパッタリングターゲットとして用いた場合に、ＤＣスパッタリングが容易になる。 Thereby, oxide sinter 1 with a small specific resistance can be formed. Therefore, according to the embodiment, DC sputtering is facilitated when the oxide sintered body 1 is used as a sputtering target.
　なお、実施形態の酸化物焼結体１は、上述のピーク強度比Ｉが０．１０以下であることが好ましく、０．０５以下であることがより好ましく、０．０３以下であることがさらに好ましく、０．０１以下であるのが一層好ましい。 In the oxide sintered body 1 of the embodiment, the above-mentioned peak intensity ratio I is preferably 0.10 or less, more preferably 0.05 or less, and still more preferably 0.03 or less. Preferably, it is more preferably 0.01 or less.
　実施形態の酸化物焼結体１は、相対密度が９０％以上であることが好ましい。これにより、かかる酸化物焼結体１をスパッタリングターゲットとして用いた場合に、ＤＣスパッタリングの放電状態を安定させることができる。この観点から、実施形態の酸化物焼結体１は、相対密度が９５％以上であるのがさらに好ましい。 The oxide sintered body 1 of the embodiment preferably has a relative density of 90% or more. Thereby, when this oxide sinter 1 is used as a sputtering target, the discharge state of DC sputtering can be stabilized. From this viewpoint, the oxide sintered body 1 of the embodiment more preferably has a relative density of 95% or more.
　相対密度が９０％以上であると、かかる酸化物焼結体１をスパッタリングターゲットとして用いた場合に、スパッタリングターゲット中に空隙を少なくでき、大気中のガス成分の取り込みを防止しやすい。また、かかる空隙を起点とした異常放電やスパッタリングターゲットの割れ現象等が生じにくくなる。 When the oxide sintered body 1 is used as a sputtering target, if the relative density is 90% or more, voids can be reduced in the sputtering target, and it is easy to prevent uptake of gas components in the atmosphere. In addition, abnormal discharge starting from the gap, cracking of the sputtering target, and the like are less likely to occur.
　実施形態の酸化物焼結体１は、たとえば以下に示すような方法により製造することができる。まず、原料粉末を混合する。原料粉末としては、Ｇａ2Ｏ3粉末およびＳｎＯ2粉末である。各原料粉末の平均粒径は２μｍ以下であることが好ましい。各原料粉末の平均粒径が２μｍ以下であると焼結温度を低くしても高密度な焼結体が得られやすくなる。このような観点から、各原料粉末の平均粒径は１．５μｍ以下がより好ましく、１μｍ以下がさらに好ましい。各原料粉末の平均粒径の下限値は特に定めるものではないが、原料の凝集を防ぐ観点から０．１μｍ以上が好ましい。なお、原料粉末の平均粒径はレーザー回折散乱式粒度分布測定法による累積体積５０容量％における体積累積粒径Ｄ50である。 The oxide sintered body 1 of the embodiment can be manufactured, for example, by the following method. First, the raw material powder is mixed. The raw material powders are Ga 2 O 3 powder and SnO 2 powder. The average particle size of each raw material powder is preferably 2 μm or less. If the average particle diameter of each raw material powder is 2 μm or less, a high density sintered body can be easily obtained even if the sintering temperature is lowered. From such a viewpoint, the average particle diameter of each raw material powder is more preferably 1.5 μm or less, and still more preferably 1 μm or less. The lower limit value of the average particle diameter of each raw material powder is not particularly limited, but is preferably 0.1 μm or more from the viewpoint of preventing aggregation of the raw material. 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.
　原料粉末の混合には種々の混合手段を用いることができる。例えばビーズミル、サンドミル、アトライタ（登録商標）及びボールミルなどの媒体攪拌型ミルなどを用いることができる。また、得られた混合粉をふるい分けしてもよい。 Various mixing means can be used for mixing of raw material powder. For example, media stirring type mills such as bead mills, sand mills, attritors (registered trademark) and ball mills can be used. In addition, the obtained mixed powder may be sieved.
　次に得られた混合粉の焼結を行う。実施形態の酸化物焼結体１は、放電プラズマ焼結（Spark　Plasma　Sintering：ＳＰＳ）法やホットプレス（Hot　Press：ＨＰ）法で焼結を行うことが好ましい。ＳＰＳ法やＨＰ法で焼結を行う場合、混合粉は、所定形状の成形凹部を有する焼結ダイ内に充填される。焼結ダイとしては例えばグラファイト製のものを用いることができる。焼結ダイに混合粉を充填したら、ＳＰＳ法やＨＰ法で焼結を行う。 Next, sintering of the obtained mixed powder is performed. The oxide sintered body 1 of the embodiment is preferably sintered by a spark plasma sintering (SPS) method or a hot press (HP) method. When sintering is performed by the SPS method or the HP method, the mixed powder is filled in a sintering die having a shaped concave portion of a predetermined shape. As a sintering die, for example, one made of graphite can be used. After the mixed powder is filled in the sintering die, sintering is performed by the SPS method or the HP method.
　実施形態の酸化物焼結体１は、１２００℃以下の比較的低温で焼結されることが好ましい。１２００℃以下の低温で焼結することにより、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）の生成を抑制することができ、酸化物焼結体１の比抵抗を低くすることができる。 The oxide sintered body 1 of the embodiment is preferably sintered at a relatively low temperature of 1200 ° C. or less. By sintering at a low temperature of 1200 ° C. or less, the formation of a gallium stannate compound (Ga 4 SnO 8 ) can be suppressed, and the specific resistance of the oxide sintered body 1 can be lowered.
　この観点から、実施形態の焼結温度は、１１００℃以下が好ましく、１０００℃以下がより好ましく、９５０℃以下がさらに好ましい。焼成温度の下限値は焼結を十分に行う観点から５００℃以上が好ましい。 From this viewpoint, the sintering temperature of the embodiment is preferably 1100 ° C. or less, more preferably 1000 ° C. or less, and still more preferably 950 ° C. or less. The lower limit value of the firing temperature is preferably 500 ° C. or more from the viewpoint of sufficient sintering.
［実施例１］
　平均粒径（体積累積粒径Ｄ50）が１μｍであるＧａ2Ｏ3粉末と、平均粒径（体積累積粒径Ｄ50）が０．５μｍであるＳｎＯ2粉末とを、Ｇａ2Ｏ3：ＳｎＯ2＝２１．１：７８．９（ｍｏｌ％）となるように秤量した。次に、ボールミルを用いて２４時間混合し、混合粉を得た。 Example 1
And Ga 2 O 3 powder having an average particle diameter (volume cumulative particle diameter D 50) is 1 [mu] m, an average particle diameter (volume cumulative particle diameter D 50) is a SnO 2 powder is 0.5μm, Ga 2 O 3: SnO 2 = 21.1: 78.9 were weighed so that (mol%). Next, it mixed using a ball mill for 24 hours, and obtained mixed powder.
　次に、かかる混合粉を、目開き７１０μｍのふるいでふるい分けし、平均粒径（体積累積粒径Ｄ50）が０．８μｍである混合粉を得た。 Next, the mixed powder was sieved with a sieve having an opening of 710 μm to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 μm.
　次に、ふるい分けした混合粉を内径１２０ｍｍのグラファイト製の焼結ダイに充填した。そして、混合粉が充填された焼結ダイを放電プラズマ焼結（ＳＰＳ）装置で焼結して焼結体を作製した。かかるＳＰＳ装置による焼結は、真空中（１５Ｐａ以下)、加圧圧力２０ＭＰａ、焼結温度６００℃、昇温速度２０℃／ｍｉｎ、焼結温度での保持時間３０ｍｉｎ、降温は自然炉冷で行った。 Next, the sieved mixed powder was filled into a graphite sintering die with an inner diameter of 120 mm. Then, the sintered die filled with the mixed powder was sintered by a spark plasma sintering (SPS) apparatus to produce a sintered body. Sintering with this SPS device is performed under vacuum (15 Pa or less), pressure 20 MPa, sintering temperature 600 ° C., temperature rising rate 20 ° C./min, holding time at sintering temperature 30 min, temperature lowering is natural furnace cooling The
　次に、得られた焼結体を切削加工し、直径１０１．６ｍｍ、厚さ６ｍｍの酸化物焼結体１を得た。 Next, the obtained sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
　なお、実施例に用いられる製造方法において、ＳｎＯ2粉末と、Ｇａ2Ｏ3粉末との混合粉に含まれる各酸化物の比率（ｍｏｌ％）は、最終的に得られる酸化物焼結体１に含まれる各酸化物の比率（ｍｏｌ％）と同視することができる。 In the manufacturing method used in the examples, the ratio (mol%) of each oxide contained in the mixed powder of SnO 2 powder and Ga 2 O 3 powder is the oxide sintered body 1 finally obtained. It can be regarded as the ratio (mol%) of each oxide contained in.
［実施例２］
　実施例１と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例２では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝３０．０：７０．０（ｍｏｌ％）となるように各原料粉を秤量した。 Example 2
The oxide sintered body 1 was obtained in the same manner as in Example 1. In Example 2, when the weighing of the powder mixture, Ga 2 O 3: SnO 2 = 30.0: they were weighed each raw material powder so as to 70.0 (mol%).
［実施例３］
　実施例１と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例３では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝３５．０：６５．０（ｍｏｌ％）となるように各原料粉を秤量した。 [Example 3]
The oxide sintered body 1 was obtained in the same manner as in Example 1. In Example 3, each raw material powder was weighed so that Ga 2 O 3 : SnO 2 = 35.0: 65.0 (mol%) when weighing the mixed powder.
［実施例４］
　平均粒径（体積累積粒径Ｄ50）が１μｍであるＧａ2Ｏ3粉末と、平均粒径（体積累積粒径Ｄ50）が０．５μｍであるＳｎＯ2粉末とを、Ｇａ2Ｏ3：ＳｎＯ2＝２１．１：７８．９（ｍｏｌ％）となるように秤量した。次に、ボールミルを用いて２４時間混合し、混合粉を得た。 Example 4
And Ga 2 O 3 powder having an average particle diameter (volume cumulative particle diameter D 50) is 1 [mu] m, an average particle diameter (volume cumulative particle diameter D 50) is a SnO 2 powder is 0.5μm, Ga 2 O 3: SnO 2 = 21.1: 78.9 were weighed so that (mol%). Next, it mixed using a ball mill for 24 hours, and obtained mixed powder.
　次に、かかる混合粉を、目開き７１０μｍのふるいでふるい分けし、平均粒径（体積累積粒径Ｄ50）が０．８μｍである混合粉を得た。 Next, the mixed powder was sieved with a sieve having an opening of 710 μm to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 μm.
　次に、ふるい分けした混合粉を内径１２０ｍｍのグラファイト製の焼結ダイに充填した。そして、混合粉が充填された焼結ダイをホットプレス（ＨＰ）装置で焼結して焼結体を作製した。かかるＨＰ装置による焼結は、アルゴン雰囲気中、加圧圧力１７ＭＰａ、焼結温度９２０℃、昇温速度６０℃／ｍｉｎ、焼結温度での保持時間１８０ｍｉｎ、降温は自然炉冷で行った。 Next, the sieved mixed powder was filled into a graphite sintering die with an inner diameter of 120 mm. Then, the sintered die filled with the mixed powder was sintered by a hot press (HP) device to produce a sintered body. Sintering with this HP apparatus was carried out in an argon atmosphere at a pressure of 17 MPa, a sintering temperature of 920 ° C., a temperature rising rate of 60 ° C./min, a holding time of 180 minutes at the sintering temperature, and a temperature lowering by natural furnace cooling.
　次に、得られた焼結体を切削加工し、直径１０１．６ｍｍ、厚さ６ｍｍの酸化物焼結体１を得た。 Next, the obtained sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
［実施例５］
　実施例４と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例５では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝３０．０：７０．０（ｍｏｌ％）となるように各原料粉を秤量した。 [Example 5]
The oxide sintered body 1 was obtained in the same manner as in Example 4. In Example 5, when the weighing of the powder mixture, Ga 2 O 3: SnO 2 = 30.0: they were weighed each raw material powder so as to 70.0 (mol%).
［実施例６］
　実施例４と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例６では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝３５．０：６５．０（ｍｏｌ％）となるように各原料粉を秤量した。 [Example 6]
The oxide sintered body 1 was obtained in the same manner as in Example 4. In Example 6, when weighing the mixed powder, each raw material powder was weighed such that Ga 2 O 3 : SnO 2 = 35.0: 65.0 (mol%).
［実施例７］
　実施例４と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例７では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝７０.０：３０．０（ｍｏｌ％）となるように各原料粉を秤量した。 [Example 7]
The oxide sintered body 1 was obtained in the same manner as in Example 4. In Example 7, each raw material powder was weighed so that Ga 2 O 3 : SnO 2 = 70.0: 30.0 (mol%) when weighing the mixed powder.
［実施例８］
　実施例４と同様な方法を用いて、酸化物焼結体１を得た。なお、実施例８では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝８０.０：２０．０（ｍｏｌ％）となるように各原料粉を秤量した。 [Example 8]
The oxide sintered body 1 was obtained in the same manner as in Example 4. In Example 8, when weighing the mixed powder, each raw material powder was weighed such that Ga 2 O 3 : SnO 2 = 80.0: 20.0 (mol%).
［比較例１］
　平均粒径（体積累積粒径Ｄ50）が１μｍであるＧａ2Ｏ3粉末と、平均粒径（体積累積粒径Ｄ50）が０．５μｍであるＳｎＯ2粉末とを、Ｇａ2Ｏ3：ＳｎＯ2＝３０．０：７０．０（ｍｏｌ％）となるように秤量した。次に、ボールミルを用いて２４時間混合し、混合粉を得た。 Comparative Example 1
And Ga 2 O 3 powder having an average particle diameter (volume cumulative particle diameter D 50) is 1 [mu] m, an average particle diameter (volume cumulative particle diameter D 50) is a SnO 2 powder is 0.5μm, Ga 2 O 3: SnO 2 = 30.0: were weighed so as to 70.0 (mol%). Next, it mixed using a ball mill for 24 hours, and obtained mixed powder.
　次に、かかる混合粉を、目開き７１０μｍのふるいでふるい分けし、平均粒径（体積累積粒径Ｄ50）が０．８μｍである混合粉を得た。 Next, the mixed powder was sieved with a sieve having an opening of 710 μm to obtain a mixed powder having an average particle size (volume cumulative particle size D 50 ) of 0.8 μm.
　次に、得られた混合粉に、４質量％に希釈したポリビニルアルコールを混合粉に対して６質量％添加し、乳鉢を用いてポリビニルアルコールを粉末によく馴染ませた。そして、得られた粉末を２００ｋｇ/ｃｍ2の条件で仮プレスし、得られた仮成形体を乳鉢で粉砕して粉砕粉を得た。次に、得られた粉砕粉をプレス用の型に充填し、プレス圧１ｔ/ｃｍ2で６０秒間成形して、成形体を得た。 Next, to the obtained mixed powder, 6% by mass of polyvinyl alcohol diluted to 4% by mass was added with respect to the mixed powder, and the polyvinyl alcohol was made to conform well to the powder using a mortar. Then, the obtained powder was temporarily pressed under the condition of 200 kg / cm 2 , and the obtained temporary formed body was crushed in a mortar to obtain a crushed powder. Next, the obtained pulverized powder was filled in a press die, and molded for 60 seconds under a press pressure of 1 t / cm 2 to obtain a molded body.
　次に、得られた成形体を焼結炉に入れ、炉内に１Ｌ／ｈで酸素をフローさせ、焼結雰囲気を酸素フロー雰囲気とし、昇温速度を５．８３℃／ｍｉｎ（３５０℃／ｈ）、焼結温度を１５００℃、焼結温度での保持時間を５４０ｍｉｎ（９ｈ）として焼結した。その後、得られた焼結体を降温速度１００℃／ｈで冷却した。 Next, the obtained compact is put into a sintering furnace, oxygen is allowed to flow in the furnace at 1 L / h, and the sintering atmosphere is made an oxygen flow atmosphere, and the temperature rising rate is 5.83 ° C./min (350 ° C./min. h) The sintering temperature was 1500 ° C., and the holding time at the sintering temperature was set to 540 minutes (9 h). Thereafter, the obtained sintered body was cooled at a temperature lowering rate of 100 ° C./h.
　次に、冷却した焼結体を切削加工し、直径１０１．６ｍｍ、厚さ６ｍｍの酸化物焼結体１を得た。 Next, the cooled sintered body was cut to obtain an oxide sintered body 1 having a diameter of 101.6 mm and a thickness of 6 mm.
［比較例２］
　実施例４と同様な方法を用いて、酸化物焼結体１を得た。なお、比較例２では、混合粉の秤量の際、Ｇａ2Ｏ3：ＳｎＯ2＝９５．０：５．０（ｍｏｌ％）となるように各原料粉を秤量した。 Comparative Example 2
The oxide sintered body 1 was obtained in the same manner as in Example 4. In Comparative Example 2, each raw material powder was weighed so that Ga 2 O 3 : SnO 2 = 95.0: 5.0 (mol%) when weighing the mixed powder.
　つづいて、上記にて得られた実施例１～８および比較例１、２の酸化物焼結体１について、相対密度の測定を行った。かかる相対密度は、アルキメデス法に基づき測定した。 Subsequently, the relative density of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above was measured. The relative density was measured based on the Archimedes method.
　具体的には、酸化物焼結体１の空中質量を体積（焼結体の水中質量／計測温度における水比重）で除し、理論密度ρ（ｇ／ｃｍ3）に対する百分率の値を相対密度（単位：％）とした。 Specifically, the air mass of the oxide sintered body 1 is divided by the volume (mass of the sintered body in water / specific gravity of water at the measurement temperature), and the percentage value relative to the theoretical density ρ (g / cm 3 ) is a relative density (Unit:%).
　また、かかる理論密度ρ（ｇ／ｃｍ3）は、酸化物焼結体１の製造に用いた原料粉の質量％および密度から算出した。具体的には、下記の式により算出した。
ρ＝｛（Ｃ1／１００）／ρ1＋（Ｃ2／１００）／ρ2｝-1 The theoretical density ρ (g / cm 3 ) was calculated from the mass% and density of the raw material powder used for producing the oxide sintered body 1. Specifically, it was calculated by the following equation.
ρ = {(C 1/100 ) / ρ 1 + (C 2/100) / ρ 2} -1
　なお、上記式中のＣ1、Ｃ2およびρ1、ρ2は、それぞれ以下の値を示している。
・Ｃ1：酸化物焼結体１の製造に用いたＳｎＯ2粉末の質量％
・ρ1：ＳｎＯ2の密度（６．９５ｇ／ｃｍ3）
・Ｃ2：酸化物焼結体１の製造に用いたＧａ2Ｏ3粉末の質量％
・ρ2：Ｇａ2Ｏ3の密度（５．９５ｇ／ｃｍ3） Note that C 1 and C 2 and お よ び1 and ρ 2 in the above formula indicate the following values, respectively.
C 1 :% by mass of SnO 2 powder used for the production of oxide sintered body 1
· Ρ 1 : density of SnO 2 (6.95 g / cm 3 )
C 2 :% by mass of Ga 2 O 3 powder used in the production of oxide sintered body 1
· Ρ 2 : density of Ga 2 O 3 (5.95 g / cm 3 )
　つづいて、上記にて得られた実施例１～８の酸化物焼結体１の表面を、走査型電子顕微鏡（ＳＥＭ：Scanning　Electron　Microscope）を用いて観察するとともに、観察された表面における各相の詳細について調査した。かかる観察結果について以下に示す。 Continuing, while observing the surface of oxide sinter 1 of Examples 1-8 obtained above using a scanning electron microscope (SEM: Scanning Electron Microscope), each phase in the observed surface is observed. We investigated about the details of. The observation results are shown below.
　図１は、実施例４における酸化物焼結体１のＳＥＭ観察写真である。図１に示すように、実施例１～８の酸化物焼結体１では、色の薄い酸化スズ（ＳｎＯ2）相の中に、色の濃い酸化ガリウム（Ｇａ2Ｏ3）相が分散していることがわかった。また、ＳＥＭ観察において、実施例１～８の酸化物焼結体１には、酸化スズと酸化ガリウムとの化合物であるスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相は観察されなかった。 FIG. 1 is a SEM observation photograph of the oxide sintered body 1 in Example 4. As shown in FIG. 1, in the oxide sintered bodies 1 of Examples 1 to 8, a dark gallium oxide (Ga 2 O 3 ) phase is dispersed in a light tin oxide (SnO 2 ) phase. I found that. In SEM observation, a gallium stannate compound (Ga 4 SnO 8 ) phase, which is a compound of tin oxide and gallium oxide, was not observed in the oxide sintered bodies 1 of Examples 1 to 8.
　つづいて、上記にて得られた実施例１～８および比較例１、２の酸化物焼結体１について、それぞれ含有するＺｒ不純物の濃度測定を行った。具体的には、Agilent　Technologies社製ＩＣＰ発光分光分析装置　720　ICP-OESを使用して、酸分解ＩＣＰ-ＯＥＳ法にて測定した。その結果、すべての酸化物焼結体１で、Ｚｒ濃度は５０ｐｐｍ未満であった。 Subsequently, the concentration of Zr impurities contained in each of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above was measured. Specifically, it was measured by an acid decomposition ICP-OES method using ICP emission spectrometer 720 ICP-OES manufactured by Agilent Technologies. As a result, in all the oxide sintered bodies 1, the Zr concentration was less than 50 ppm.
　つづいて、上記にて得られた実施例１～８および比較例１、２の酸化物焼結体１について、それぞれ比抵抗（バルク抵抗）の測定を行った。 Subsequently, the specific resistance (bulk resistance) of each of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above was measured.
　具体的には、三菱化学社製ロレスタ（登録商標）ＨＰ　ＭＣＰ－Ｔ４１０（直列４探針プローブ　ＴＹＰＥ　ＥＳＰ）を用いて、加工後の酸化物焼結体１の表面にプローブをあてて、ＡＵＴＯ　ＲＡＮＧＥモードで測定した。測定箇所は、図２に示すように、酸化物焼結体１の中央部１ａ、および外周部１ｂを均等に４箇所の計５か所とし、各測定値の平均値をその酸化物焼結体１のバルク抵抗値とした。図２は、酸化物焼結体１のバルク抵抗の測定箇所を表す模式図である。 Specifically, a probe is placed on the surface of the oxide sintered body 1 after processing using Lorester (registered trademark) HP MCP-T410 (series 4-probe probe TYPE ESP) manufactured by Mitsubishi Chemical Corporation, and AUTO RANGE Measured in mode. As shown in FIG. 2, the central portion 1a and the outer peripheral portion 1b of the oxide sintered body 1 are equally divided into four locations, as shown in FIG. 2, and the average value of each measured value is sintered The bulk resistance value of body 1 was used. FIG. 2 is a schematic view showing measurement points of bulk resistance of the oxide sintered body 1.
　その結果、実施例１～８では、いずれも比抵抗（バルク抵抗）が１×１０3Ω・ｃｍ以下であり、比抵抗の測定が可能であったのに対し、比較例１は絶縁体（すなわち、比抵抗が１×１０7Ω・ｃｍより大きい）となっており、比抵抗（バルク抵抗）の測定ができなかった。比較例２は、比抵抗が２．４×１０３Ω・ｃｍであり、実施例１～８と比較すると高い。これは導電性を担うとされる酸化スズの割合が減少し、ターゲット中において導電パスが形成されにくくなったためと考えられる。 As a result, in all of Examples 1 to 8, the specific resistance (bulk resistance) was 1 × 10 3 Ω · cm or less, and it was possible to measure the specific resistance, while Comparative Example 1 was an insulator ( That is, the specific resistance was larger than 1 × 10 7 Ω · cm), and the measurement of the specific resistance (bulk resistance) could not be performed. Comparative Example 2 has a specific resistance of 2.4 × 10 3 Ω · cm, which is higher than those of Examples 1 to 8. It is considered that this is because the proportion of tin oxide which is considered to be responsible for conductivity decreases and it becomes difficult to form a conductive path in the target.
　つづいて、上記にて得られた実施例１～８および比較例１、２の酸化物焼結体１から、実施例１～８および比較例１、２のスパッタリングターゲットを作製した。かかるスパッタリングターゲットは、低融点半田であるインジウムを接合材として使用し、上記にて得られた酸化物焼結体１を銅製の基材に接合して作製した。 Subsequently, sputtering targets of Examples 1 to 8 and Comparative Examples 1 and 2 were produced from the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above. The sputtering target was manufactured by using indium as a low melting point solder as a bonding material, and bonding the oxide sintered body 1 obtained above to a copper base.
　つづいて、作製された実施例１～８および比較例１、２のスパッタリングターゲットを用いて、下記の条件でＤＣ電源を用いたスパッタリングを試み、作製されたスパッタリングターゲットによるＤＣスパッタリングの可否を評価した。
・成膜装置：ＤＣマグネトロンスパッタリング装置
・排気系：クライオポンプ、ロータリーポンプ
・スパッタリング電力：１５０Ｗ（１．８５Ｗ／ｃｍ2）
・到達真空度：１．０×１０-4Ｐａ
・スパッタリング圧力：０．４Ｐａ
・酸素分圧：Ｏ2２．０％ Subsequently, sputtering was performed using a DC power supply under the following conditions, using the sputtering targets of Examples 1 to 8 and Comparative Examples 1 and 2 manufactured, and the propriety of DC sputtering by the sputtering targets manufactured was evaluated. .
Film forming apparatus: DC magnetron sputtering apparatus Exhaust system: cryopump, rotary pump Sputtering power: 150 W (1.85 W / cm 2 )
・ The ultimate pressure: 1.0 × 10-4 Pa
Sputtering pressure: 0.4 Pa
-Oxygen partial pressure: O 2 2.0%
　なお、かかるＤＣスパッタリングの可否評価における基準は次の通りである。
　Ａ（良）：良好にＤＣスパッタリングができる
　Ｂ（可）：ＤＣスパッタリングができる
　Ｃ（不可）：ＤＣスパッタリングができない In addition, the reference | standard in the propriety evaluation of this DC sputtering is as follows.
A (good): good DC sputtering possible B (good): DC sputtering possible C (not good): DC sputtering impossible
　ここで、上述の実施例１～８および比較例１、２について、酸化物焼結体１の製造条件と、酸化物焼結体１における各種特性の評価結果とを表１に示す。 Here, for the above-described Examples 1 to 8 and Comparative Examples 1 and 2, the production conditions of the oxide sintered body 1 and the evaluation results of various characteristics of the oxide sintered body 1 are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　ＳＰＳ法やＨＰ法を用いて、１２００℃以下の比較的低温で焼結される実施例１～８と、１２００℃より高温で焼結される比較例１との比較により、比較的低温で焼結することによって、比抵抗を１×１０3Ω・ｃｍ以下に低減できることがわかる。 According to comparison with Examples 1 to 8 sintered at a relatively low temperature of 1200 ° C. or lower using the SPS method or the HP method, and Comparative Example 1 sintered at a temperature higher than 1200 ° C. By bonding, it is understood that the specific resistance can be reduced to 1 × 10 3 Ω · cm or less.
　酸化ガリウムの含有量が９０ｍｏｌ％以下である実施例１～８と、酸化ガリウムの含有量が９５ｍｏｌ％以上である比較例２との比較により、酸化ガリウムの含有量を９０ｍｏｌ％以下にすることによって、比抵抗を１×１０3Ω・ｃｍ以下に低減できることがわかる。 By making the content of gallium oxide 90 mol% or less according to the comparison between Examples 1 to 8 in which the content of gallium oxide is 90 mol% or less and the comparative example 2 in which the content of gallium oxide is 95 mol% or more. The specific resistance can be reduced to 1 × 10 3 Ω · cm or less.
　そして、比抵抗が１×１０3Ω・ｃｍ以下である実施例１～８と、比抵抗が１×１０3Ω・ｃｍ以上である比較例１、２との比較により、比抵抗を１×１０3Ω・ｃｍ以下に低減させることによって、ＤＣスパッタリングが可能なスパッタリングターゲットを実現できることがわかる。 Then, as in Examples 1-8 is specific resistance 1 × 10 3 Ω · cm or less by comparison with Comparative Examples 1 and 2 the resistivity is 1 × 10 3 Ω · cm or more, the resistivity 1 × It is understood that a sputtering target capable of DC sputtering can be realized by reducing it to 10 3 Ω · cm or less.
　また、相対密度を９０％以上にすることにより、ＤＣスパッタリングの放電状態を安定させることができる。さらに、相対密度が９５％未満の実施例４～８と、相対密度が９５％以上の実施例１～３との比較により、相対密度を９５％以上にすることによって、ＤＣスパッタリングの放電状態をさらに安定させられることがわかる。 Further, by setting the relative density to 90% or more, the discharge state of DC sputtering can be stabilized. Furthermore, by making the relative density 95% or more, the discharge state of DC sputtering is made by comparing the examples 4 to 8 having a relative density of less than 95% and the examples 1 to 3 having a relative density of 95% or more. It turns out that it is stabilized further.
　つづいて、上記にて得られた実施例１～８および比較例１、２の酸化物焼結体１について、それぞれＸ線回折（X-Ray　Diffraction：ＸＲＤ）測定を行い、Ｘ線回折チャートを得た。そして、得られたＸ線回折チャートから実施例１～８および比較例１、２の酸化物焼結体１の構造を同定した。 Subsequently, X-Ray Diffraction (XRD) measurement is performed on each of the oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 obtained above, and X-ray diffraction charts Obtained. Then, the structures of oxide sintered bodies 1 of Examples 1 to 8 and Comparative Examples 1 and 2 were identified from the obtained X-ray diffraction chart.
　具体的な測定条件は以下の通りであった。
・装置：ＳｍａｒｔＬａｂ（株式会社リガク製）
・線源：ＣｕＫα線
・管電圧：４０ｋＶ
・管電流：３０ｍＡ
・スキャン速度：５ｄｅｇ／ｍｉｎ
・ステップ：０．０２ｄｅｇ
・スキャン範囲：２θ＝２０度～８０度 The specific measurement conditions were as follows.
-Device: SmartLab (manufactured by Rigaku Corporation)
・ Source: CuKα ray ・ Tube voltage: 40kV
・ Tube current: 30 mA
・ Scan speed: 5deg / min
・ Step: 0.02 deg
・ Scan range: 2θ = 20 degrees to 80 degrees
　図３は、実施例４～８における酸化物焼結体１のＸ線回折チャートである。なお、図３には、Ｘ線回折チャートにおいて、各酸化物中に存在する様々な面に起因して現れるピークの位置も示している。 FIG. 3 is an X-ray diffraction chart of the oxide sintered body 1 in Examples 4 to 8. FIG. 3 also shows the positions of peaks appearing due to various planes present in each oxide in the X-ray diffraction chart.
　図３に示すように、実施例４～８のＸ線回折チャートでは、酸化スズ（ＳｎＯ2）相に起因するピークと酸化ガリウム（Ｇａ2Ｏ3）相に起因するピークとが現れている。一方で、実施例４～８のＸ線回折チャートでは、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相に起因するピークはほとんど現れていない。 As shown in FIG. 3, in the X-ray diffraction charts of Examples 4 to 8, a peak attributable to the tin oxide (SnO 2 ) phase and a peak attributable to the gallium oxide (Ga 2 O 3 ) phase appear. On the other hand, in the X-ray diffraction charts of Examples 4 to 8, almost no peak attributable to the gallium stannate compound (Ga 4 SnO 8 ) phase appears.
　ここで、図３に示す実施例４～８のＸ線回折チャートに基づいて、酸化スズ（ＳｎＯ2）相の（１１０）面のピーク強度に対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比Ｉを同定した。 Here, based on the X-ray diffraction charts of Examples 4 to 8 shown in FIG. 3, the peak intensity of the (110) plane of the tin oxide (SnO 2 ) phase with respect to the peak intensity of the gallium stannate compound (Ga 4 SnO 8 ) phase The peak intensity ratio I of the 111) plane was identified.
　なお、図３に示すように、酸化スズ（ＳｎＯ2）相の（１１０）面のピークは、酸化スズ（ＳｎＯ2）相のメーンピークであり、回折角（２θ）が２６．５８°に現れるピークである。また、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピークは、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相のメーンピークであり、回折角（２θ）が３４．８１°に現れるピークである。 As shown in FIG. 3, the peak of the (110) plane of tin oxide (SnO 2) phase is the main peak of the tin oxide (SnO 2) phases, the diffraction angle (2 [Theta]) appears to 26.58 ° It is a peak. The peak of the (111) plane of stannate gallium compound (Ga 4 SnO 8) phase is the main peak of stannate gallium compound (Ga 4 SnO 8) phase, diffraction angle (2 [Theta]) is the 34.81 ° It is a peak that appears.
　その結果、実施例４でのピーク強度比Ｉは０．０３であり、実施例５でのピーク強度比Ｉは０．０３であり、実施例６でのピーク強度比Ｉは０．０４であり、実施例７でのピーク強度比Ｉは０．０９であり、実施例８でのピーク強度比Ｉは０．１３であった。なお、図３には示していないが、実施例１でのピーク強度比Ｉは０．０１であり、実施例２でのピーク強度比Ｉは０．０１であり、実施例３でのピーク強度比Ｉは０．０１であった。 As a result, the peak intensity ratio I in Example 4 is 0.03, the peak intensity ratio I in Example 5 is 0.03, and the peak intensity ratio I in Example 6 is 0.04. The peak intensity ratio I in Example 7 was 0.09, and the peak intensity ratio I in Example 8 was 0.13. Although not shown in FIG. 3, the peak intensity ratio I in Example 1 is 0.01, the peak intensity ratio I in Example 2 is 0.01, and the peak intensity in Example 3 The ratio I was 0.01.
　図４は、比較例１における酸化物焼結体１のＸ線回折チャートである。なお、図４にも、図３と同様に、Ｘ線回折チャートにおいて各酸化物中に存在する様々な面に起因して現れるピークの位置を示している。 FIG. 4 is an X-ray diffraction chart of the oxide sintered body 1 in Comparative Example 1. As in FIG. 3, FIG. 4 also shows the positions of peaks appearing in the X-ray diffraction chart due to various planes present in each oxide.
　図４に示すように、比較例１のＸ線回折チャートでは、酸化スズ（ＳｎＯ2）相に起因するピークと、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相に起因するピークとが現れている。 As shown in FIG. 4, in the X-ray diffraction chart of Comparative Example 1, a peak attributable to the tin oxide (SnO 2 ) phase and a peak attributable to the gallium stannate compound (Ga 4 SnO 8 ) phase appear .
　ここで、図４に示す比較例１のＸ線回折チャートに基づいて、酸化スズ（ＳｎＯ2）相の（１１０）面のピーク強度に対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比Ｉを同定した。その結果、比較例１でのピーク強度比Ｉは０．１６であった。なお、図４には示していないが、比較例２でのピーク強度比Ｉは０．２１であった。 Here, based on the X-ray diffraction chart of Comparative Example 1 shown in FIG. 4, (111) of the gallium stannate compound (Ga 4 SnO 8 ) phase with respect to the peak intensity of the (110) plane of the tin oxide (SnO 2 ) phase. The peak intensity ratio I of the surface was identified. As a result, the peak intensity ratio I in Comparative Example 1 was 0.16. Although not shown in FIG. 4, the peak intensity ratio I in Comparative Example 2 was 0.21.
　ＳＰＳ法やＨＰ法を用いて、１２００℃以下の比較的低温で焼結される実施例１～６と、１２００℃より高温で焼結される比較例１との比較により、比較的低温で焼結することによって、ピーク強度比Ｉを０．０５以下に低減することができる。すなわち、実施形態では、比較的低温で焼結することによって、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の生成を抑制することができる。 According to comparison with Examples 1 to 6 sintered at a relatively low temperature of 1200 ° C. or lower using the SPS method or the HP method, and Comparative Example 1 sintered at a temperature higher than 1200 ° C. The peak intensity ratio I can be reduced to 0.05 or less by bonding. That is, in the embodiment, the formation of the gallium stannate compound (Ga 4 SnO 8 ) phase can be suppressed by sintering at a relatively low temperature.
　ここで、酸化スズ（ＳｎＯ2）相および酸化ガリウム（Ｇａ2Ｏ3）相は、酸素欠損により比抵抗を小さくすることができる一方で、スズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相は高い比抵抗を有すると考えられる。すなわち、実施形態によれば、低温焼結でスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の生成を抑制することにより、比抵抗を１×１０3（Ω・ｃｍ）以下に低減させることができる。 Here, while the tin oxide (SnO 2 ) phase and the gallium oxide (Ga 2 O 3 ) phase can reduce the specific resistance due to oxygen deficiency, the gallium stannate compound (Ga 4 SnO 8 ) phase has a high ratio It is considered to have resistance. That is, according to the embodiment, the specific resistance can be reduced to 1 × 10 3 (Ω · cm) or less by suppressing the formation of the gallium stannate compound (Ga 4 SnO 8 ) phase by low temperature sintering. .
　以上、本発明の実施形態について説明したが、本発明は上述の実施形態に限定されるものではなく、その趣旨を逸脱しない限りにおいて種々の変更が可能である。たとえば、実施形態では、１２００℃以下の比較的低温で焼結を行うことができる手法として、ＳＰＳ法およびＨＰ法が用いられた例について示したが、低温焼結手法は、ＳＰＳ法およびＨＰ法に限られない。 As mentioned above, although embodiment of this invention was described, this invention is not limited to the above-mentioned embodiment, A various change is possible unless it deviates from the meaning. For example, in the embodiment, an example in which the SPS method and the HP method are used is described as a method capable of performing sintering at a relatively low temperature of 1200 ° C. or less. However, the low temperature sintering method includes the SPS method and the HP method It is not limited to.
　また、実施形態では、円板状の酸化物焼結体１を用いてスパッタリングターゲットが作製された例について示したが、酸化物焼結体１の形状は円板状に限られず、円筒状など、どのような形状であってもよい。 In the embodiment, although the example in which the sputtering target is manufactured using the disc-shaped oxide sintered body 1 is described, the shape of the oxide sintered body 1 is not limited to the disc shape, and may be cylindrical or the like. It may have any shape.
　さらなる効果や変形例は、当業者によって容易に導き出すことができる。このため、本発明のより広範な態様は、以上のように表しかつ記述した特定の詳細および代表的な実施形態に限定されるものではない。したがって、添付の請求の範囲およびその均等物によって定義される総括的な発明の概念の精神または範囲から逸脱することなく、様々な変更が可能である。 Further effects and modifications can be easily derived by those skilled in the art. Thus, the broader aspects of the invention are not limited to the specific details and representative embodiments represented and described above. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
　１　　酸化物焼結体
　１ａ　中央部
　１ｂ　外周部 1 Oxide sinter 1a central part 1b outer peripheral part

Claims (10)

  1. 　酸化スズと、酸化ガリウムとを含む酸化物焼結体であって、
    　酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦９０ｍｏｌ％であり、
    　比抵抗が１×１０3Ω・ｃｍ以下である
    　酸化物焼結体。     An oxide sintered body containing tin oxide and gallium oxide,
    The content of gallium oxide is 20 mol% <Ga 2 O 3 ≦ 90 mol%,
    An oxide sintered body having a specific resistance of 1 × 10 3 Ω · cm or less.
  2. 　酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦８５ｍｏｌ％である
    　請求項１に記載の酸化物焼結体。     The oxide sintered body according to claim 1, wherein the content of gallium oxide is 20 mol% <Ga 2 O 3 85 85 mol%.
  3. 　酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦７５ｍｏｌ％である
    　請求項１に記載の酸化物焼結体。     The oxide sintered body according to claim 1, wherein the content of gallium oxide is 20 mol% <Ga 2 O 3 ≦ 75 mol%.
  4. 　酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦６５ｍｏｌ％である
    　請求項１に記載の酸化物焼結体。     The oxide sintered body according to claim 1, wherein the content of gallium oxide is 20 mol% <Ga 2 O 3 65 65 mol%.
  5. 　酸化ガリウムの含有量が２０ｍｏｌ％＜Ｇａ2Ｏ3≦５０ｍｏｌ％である
    　請求項１に記載の酸化物焼結体。     The oxide sintered body according to claim 1, wherein the content of gallium oxide is 20 mol% <Ga 2 O 3 ≦ 50 mol%.
  6. 　酸化スズ（ＳｎＯ2）相と酸化ガリウム（Ｇａ2Ｏ3）相とを含む酸化物焼結体であって、
    　Ｘ線回折測定において、前記酸化スズ（ＳｎＯ2）相の（１１０）面のピークに対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比が０．１５以下である
    　請求項１～５のいずれか一つに記載の酸化物焼結体。     An oxide sintered body containing a tin oxide (SnO 2 ) phase and a gallium oxide (Ga 2 O 3 ) phase,
    In the X-ray diffraction measurement, the peak intensity ratio of the (111) plane of the gallium stannate compound (Ga 4 SnO 8 ) phase to the peak of the (110) plane of the tin oxide (SnO 2 ) phase is 0.15 or less. The oxide sintered body according to any one of Items 1 to 5.
  7. 　酸化スズ（ＳｎＯ2）相と酸化ガリウム（Ｇａ2Ｏ3）相とを含む酸化物焼結体であって、
    　Ｘ線回折測定において、前記酸化スズ（ＳｎＯ2）相の（１１０）面のピークに対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比が０．１０以下である
    　請求項１～６のいずれか一つに記載の酸化物焼結体。     An oxide sintered body containing a tin oxide (SnO 2 ) phase and a gallium oxide (Ga 2 O 3 ) phase,
    In the X-ray diffraction measurement, the peak intensity ratio of the (111) plane of the gallium stannate compound (Ga 4 SnO 8 ) phase to the peak of the (110) plane of the tin oxide (SnO 2 ) phase is 0.10 or less. The oxide sintered body according to any one of Items 1 to 6.
  8. 　酸化スズ（ＳｎＯ2）相と酸化ガリウム（Ｇａ2Ｏ3）相とを含む酸化物焼結体であって、
    　Ｘ線回折測定において、前記酸化スズ（ＳｎＯ2）相の（１１０）面のピークに対するスズ酸ガリウム化合物（Ｇａ4ＳｎＯ8）相の（１１１）面のピーク強度比が０．０５以下である
    　請求項１～７のいずれか一つに記載の酸化物焼結体。     An oxide sintered body containing a tin oxide (SnO 2 ) phase and a gallium oxide (Ga 2 O 3 ) phase,
    In the X-ray diffraction measurement, the peak intensity ratio of the (111) plane of the gallium stannate compound (Ga 4 SnO 8 ) phase to the peak of the (110) plane of the tin oxide (SnO 2 ) phase is 0.05 or less. The oxide sintered body according to any one of Items 1 to 7.
  9. 　相対密度が９０％以上である
    　請求項１～８のいずれか一つに記載の酸化物焼結体。     The oxide sintered body according to any one of claims 1 to 8, which has a relative density of 90% or more.
  10. 　請求項１～９のいずれか一つに記載の酸化物焼結体をターゲット材として用いる
    　スパッタリングターゲット。     A sputtering target using the oxide sintered body according to any one of claims 1 to 9 as a target material.
PCT/JP2018/039241 2017-11-15 2018-10-22 Oxide sintered body and sputtering target WO2019097959A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000077358A (en) * 1998-08-27 2000-03-14 Asahi Glass Co Ltd Transparent conductive film, sputtering target and basic body with transparent conductive film
JP2015166305A (en) * 2014-02-14 2015-09-24 株式会社コベルコ科研 Sintered oxide and sputtering target
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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WO2010018707A1 (en) * 2008-08-11 2010-02-18 出光興産株式会社 Gallium oxide-tin oxide based oxide sintered body and oxide film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000077358A (en) * 1998-08-27 2000-03-14 Asahi Glass Co Ltd Transparent conductive film, sputtering target and basic body with transparent conductive film
JP2015166305A (en) * 2014-02-14 2015-09-24 株式会社コベルコ科研 Sintered oxide and sputtering target
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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