JP2017160103A - Sn-Zn-O-BASED OXIDE SINTERED BODY AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Sn-Zn-O-based oxide sintered body which has excellent mechanical strength, machining performance, a high density, and a low resistance; and to provide a method for producing such a Sn-Zn-O-based oxide sintered body.SOLUTION: The Sn-Zn-O-based oxide sintered body including a ZnO phase or a SnOphase as well as a ZnSnOphase includes Sn at an atomic number ratio Sn/(Sn+Zn) of 0.1 or more and 0.9 or less, includes a first addition element M selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga at an atomic number ratio M/(Sn+Zn+M+X) of 0.001 or more and 0.04 or less with respect to the total amount of all metal elements, includes a second addition element X selected from Nb, Ta, W, and Mo at an atomic number ratio X/(Sn+Zn+M+X) of 0.0001 or more and 0.1 or less with respect to the total amount of all the metal elements, includes an M-containing compound that contains the first addition element M and is different from the ZnO phase, the SnOphase, and the ZnSnOphase, has a relative density of 90% or more, and has a specific resistance of 1 Ω cm or less.SELECTED DRAWING: None

Description

  The present invention is a Sn—Zn—O-based oxide sintered material used as a sputtering target when a transparent conductive film applied to a solar cell, a liquid crystal surface element, a touch panel or the like is manufactured by a sputtering method such as direct current sputtering or high frequency sputtering. In particular, it prevents clogging of the grindstone when grinding a sintered body to prevent damage to the sintered body during processing, and also causes damage to the sputtering target and generation of cracks during sputtering film formation. The present invention relates to a high-density, low-resistance Sn—Zn—O-based oxide sintered body and a method for producing the same.

  A transparent conductive film having high conductivity and high transmittance in the visible light region is used for surface elements such as solar cells, liquid crystal display elements, organic electroluminescence and inorganic electroluminescence, electrodes for touch panels, etc. It is also used as various antifogging transparent heating elements such as automobile windows, heat ray reflective films for buildings, antistatic films, and refrigerated showcases.

Examples of the transparent conductive film include tin oxide (SnO ₂ ) containing antimony or fluorine as a dopant, zinc oxide (ZnO) containing aluminum or gallium as a dopant, and indium oxide (In ₂ O ₃ ) containing tin as a dopant. Are known. In particular, an indium oxide (In ₂ O ₃ ) film containing tin as a dopant, that is, an In—Sn—O-based film is called an ITO (Indium tin oxide) film, and a low resistance film can be easily obtained. Widely used.

  As a method for producing the transparent conductive film, sputtering methods such as direct current sputtering and high frequency sputtering are often used. The sputtering method is an effective method when film formation of a material having a low vapor pressure or precise film thickness control is required, and since the operation is very simple, it is widely used industrially.

  This sputtering method uses a sputtering target as a thin film material. The sputtering target is an individual containing a metal element constituting a thin film to be formed, and a sintered body such as a metal, a metal oxide, a metal nitride, and a metal carbide, or a single crystal depending on the case is used. In the sputtering method, generally, an apparatus having a vacuum chamber in which a substrate and a sputtering target can be arranged is used. After the substrate and the sputtering target are arranged, the vacuum chamber is set to a high vacuum, and then a rare gas such as argon is introduced. Then, the inside of the vacuum chamber is brought to a gas pressure of about 10 Pa or less. Then, the substrate is an anode, the sputtering target is a cathode, a glow discharge is generated between the two to generate argon plasma, and the argon cation in the plasma collides with the cathode sputtering target, thereby repelling the target. The component particles are deposited on the substrate to form a film.

  And in order to manufacture the said transparent conductive film, conventionally, indium oxide type materials, such as ITO, are used extensively. However, since indium metal is a rare metal on the earth and has toxicity, there are concerns about adverse effects on the environment and the human body, and non-indium materials are required.

As the non-indium material, as described above, a zinc oxide (ZnO) material containing aluminum or gallium as a dopant and a tin oxide (SnO ₂ ) material containing antimony or fluorine as a dopant are known. . And although the transparent conductive film of the said zinc oxide (ZnO) type | system | group material is manufactured industrially by sputtering method, it has faults, such as being poor in chemical resistance (alkali resistance, acid resistance). On the other hand, although the transparent conductive film of tin oxide (SnO ₂ ) -based material is excellent in chemical resistance, it is difficult to produce a tin oxide-based sintered target having high density, durability, and excellent processing efficiency. It has a drawback that it is difficult to produce a transparent conductive film by a sputtering method.

Therefore, as a material for improving these disadvantages, a sintered body mainly composed of zinc oxide and tin oxide has been proposed. For example, Patent Document 1 describes a sintered body composed of a SnO ₂ phase and a Zn ₂ SnO ₄ phase, and the average crystal grain size of the Zn ₂ SnO ₄ phase is in the range of 1 to 10 μm.

Patent Document 2 discloses that the integrated intensity of the (222) plane and the (400) plane in the Zn ₂ SnO ₄ phase by X-ray diffraction using CuKα rays with an average crystal grain size of 4.5 μm or less is I _{(222 ) And} I ₍₄₀₀₎ , the degree of orientation represented by I ₍₂₂₂₎ / [I ₍₂₂₂₎ + I ₍₄₀₀₎ ] is set to 0.52 or more, which is larger than the standard (0.44). The body is listed. Furthermore, in Patent Document 2, as a method for producing a sintered body having the above characteristics, the sintered body production process is performed under the conditions of 800 ° C. to 1400 ° C. in an atmosphere containing oxygen in a firing furnace. And a method of cooling the inside of the firing furnace to an inert atmosphere such as Ar gas after holding at the maximum firing temperature is also described.

  However, in these methods, although the Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components can obtain a sintered body strength that can withstand the mechanical strength, There has been a problem that the grinding stone is clogged during grinding and the processing efficiency is lowered. Furthermore, it is difficult to obtain a sufficient density and conductivity, and the characteristics required for sputtering film formation at the mass production site are not satisfactory. That is, in the normal pressure sintering method, problems remain in terms of increasing the density of the sintered body, conductivity, and processing performance.

JP 2010-037161 A (refer to claim 13) JP 2013-036073 A (refer to claims 1 and 3)

  The present invention has been made paying attention to such demands, and has Sn and Sn as main components, excellent mechanical performance in addition to mechanical strength (that is, high processing efficiency), high density and low resistance Sn. An object is to provide a —Zn—O-based oxide sintered body and a method for producing the same.

A Sn—Zn—O-based oxide sintered body mainly composed of Zn and Sn is a material that is difficult to have both high density and low resistance, and has high density and conductivity even when the composition is changed. It is difficult to produce an excellent oxide sintered body. In the sintered body density, although the density is somewhat higher and lower depending on the blending ratio, the conductivity is very high, such as 1 × 10 ⁶ Ω · cm or more, and the conductivity is poor.

In the production of a Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components, a compound called Zn ₂ SnO ₄ starts to be generated around 1100 ° C., and the volatilization of Zn becomes remarkable around 1450 ° C. When burning at a high temperature to increase the density of the Sn—Zn—O-based oxide sintered body, the volatilization of Zn proceeds, so that the grain boundary diffusion and the bonding between the grains are weakened to obtain a high-density oxide sintered body. I can't.

As for conductivity, Zn ₂ SnO ₄ , ZnO, and SnO ₂ are substances having poor conductivity. Therefore, even if the compounding ratio is adjusted to adjust the amount of the compound phase and ZnO, SnO ₂ Cannot be improved significantly. As a result, the Sn—Zn—O-based oxide sintered body mainly composed of Zn and Sn has the high density and high conductivity of the sintered body, which are characteristics required for sputtering film formation at the mass production site. Can't get.

  On the other hand, regarding the processing efficiency (that is, processing performance) of the sintered body, the Sn-Zn-O-based oxide sintered body has high toughness, so that the grindstone is easily clogged during the grinding process, and the processing performance is improved. There was a problem that it was inferior (processing efficiency was low).

  That is, the subject of the present invention is that an oxide sintered body that promotes grain boundary diffusion and strengthens bonding between grains while suppressing volatilization of Zn is provided with a means for improving conductivity and is appropriate. By forming a compound structure, it is to provide a Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components, which are dense and excellent in electrical conductivity and have high processing efficiency as described above.

Therefore, in order to solve the above-mentioned problems, the present inventors searched for manufacturing conditions that achieve both the density and conductivity characteristics of the sintered body, and started the formation of a compound called Zn ₂ SnO ₄ from 1100 ° C. In the temperature range of 1450 ° C. in which the volatilization of N is remarkable, a method for producing a Sn—Zn—O-based oxide sintered body mainly composed of Zn and Sn having high density and high conductivity was studied. As a result, at least selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga under the condition that Sn is contained at a ratio of 0.1 to 0.9 as the atomic ratio Sn / (Sn + Zn). An oxide sintered body having a relative density of 90% could be obtained by adding one type (that is, the first additive element M) as a dopant. However, although the density has been improved, the conductivity has not been improved. Therefore, in order to improve the conductivity, by further adding any one of Nb, Ta, W, and Mo (that is, the second additive element X), An oxide sintered body excellent in conductivity can be produced while maintaining a high density. In the Sn—Zn—O-based oxide sintered body, when the concentration of Sn in the sintered body is low, the main component is a ZnO phase having a wurtzite crystal structure and a Zn ₂ SnO ₄ phase having a spinel crystal structure. Thus, when Sn is high in concentration, the main component is a Zn ₂ SnO ₄ phase having a spinel crystal structure and a SnO ₂ phase having a rutile crystal structure.

Furthermore, when the structure of the oxide sintered body excellent in processing efficiency was investigated, it was selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga in the Sn—Zn—O-based oxide sintered body. In the case where a compound phase different from the ZnO phase, SnO ₂ phase and Zn ₂ SnO ₄ phase is generated, the sintered body is ground. In this case, it was found that clogging of the grindstone was difficult to occur, and this led to the finding that the processing efficiency of the sintered body was improved. The present invention has been completed by such technical discovery.

That is, the first invention according to the present invention is:
In a Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components and containing at least one of a ZnO phase and a SnO ₂ phase and a Zn ₂ SnO ₄ phase,
Sn is contained in an atomic ratio Sn / (Sn + Zn) at a ratio of 0.1 to 0.9.
At least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga is used as the first additive element M, and at least one selected from Nb, Ta, W, and Mo is added as the second additive In the case of element X,
The first additive element M is contained at a ratio of 0.001 or more and 0.04 or less as an atomic ratio M / (Sn + Zn + M + X) with respect to the total amount of all metal elements,
Containing the second additive element X in a ratio of 0.0001 to 0.1 as an atomic ratio X / (Sn + Zn + M + X) to the total amount of all metal elements, and
A compound phase different from the ZnO phase, SnO ₂ phase, Zn ₂ SnO ₄ phase and the compound phase contains the first additive element M;
The relative density is 90% or more and the specific resistance is 1 Ω · cm or less.

Further, the second invention according to the present invention is:
In the method for producing a Sn—Zn—O-based oxide sintered body according to the first invention,
ZnO powder and SnO ₂ powder, oxide powder containing at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga, from Nb, Ta, W and Mo A slurry obtained by mixing the selected oxide powder containing at least one second additive element X with pure water, an organic binder, and a dispersant is dried and granulated to produce a granulated powder. Granule powder manufacturing process,
A molded body manufacturing process for obtaining a molded body by pressure molding the granulated powder; and
A sintering step in which the molded body is fired under conditions of 1200 ° C. or higher and 1450 ° C. or lower and 10 hours or longer and 30 hours or shorter in an atmosphere having an oxygen concentration of 70% by volume or higher in the firing furnace
A post-sintering holding step of holding the obtained sintered body under the conditions of 800 ° C. or higher and 1100 ° C. or lower and 1 hour or longer and 10 hours or shorter;
It is characterized by comprising.

According to the present invention, Sn is contained at a ratio of 0.1 to 0.9 as the atomic ratio Sn / (Sn + Zn), the first additive element M (Si, Ti, Ge, In, Bi, Ce , At least one selected from Al and Ga) at a ratio of 0.001 to 0.04 as the atomic ratio M / (Sn + Zn + M + X) to the total amount of all metal elements, the second additive element X ( A condition of containing at least one selected from Nb, Ta, W and Mo in an atomic ratio X / (Sn + Zn + M + X) of 0.0001 or more and 0.1 or less with respect to the total amount of all metal elements, and ZnO A phase that further includes a compound phase different from the phase, the SnO ₂ phase, and the Zn ₂ SnO ₄ phase, and the compound phase contains the first additive element M;
Sn-Zn-O-based oxide sintering with high density, low resistance, and excellent processing efficiency, which is excellent in mass production by the atmospheric pressure sintering method at any mixing ratio of Sn and Zn The body can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, Sn is included at a ratio of 0.1 to 0.9 as the atomic ratio Sn / (Sn + Zn), and at least one first selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga. 1 addition element M is included in a ratio of 0.001 or more and 0.04 or less as atomic ratio M / (Sn + Zn + M + X) with respect to the total amount of all metal elements, and at least one selected from Nb, Ta, W and Mo A raw material powder containing the second additive element X in a ratio of 0.0001 or more and 0.1 or less as an atomic ratio X / (Sn + Zn + M + X) with respect to the total amount of all metal elements was prepared and obtained by granulating the raw material powder. The molded product is produced by molding the granulated powder, and in the atmosphere in the firing furnace having an oxygen concentration of 70% by volume or higher, and the temperature is 1200 ° C. or higher and 1450 ° C. or lower and 10 hours or longer and 30 hours or shorter. After firing (sintering step), the sintered body obtained is held under conditions of 800 ° C. or higher and 1100 ° C. or lower and 1 hour or longer and 10 hours or shorter (holding step after sintering), and then cooled, thereby processing performance It is possible to produce a Sn—Zn—O-based oxide sintered body according to the present invention which has an excellent relative density of 90% or more and a specific resistance of 1 Ω · cm or less.

  Hereinafter, the manufacturing method of the Sn—Zn—O-based oxide sintered body according to the present invention will be described.

[Additive elements]
The first additive element M and the second additive element X are required under the condition that Sn is contained at a ratio of 0.1 to 0.9 as the atomic ratio Sn / (Sn + Zn). In the case of M alone, the density is improved, but the low resistance characteristic cannot be obtained. On the other hand, when only the second additive element X is used, the resistance becomes low, but a high density cannot be obtained.

  That is, by adding the first additive element M and the second additive element X, it is possible to obtain a Sn—Zn—O-based oxide sintered body with high density and low resistance.

(First additive element M)
The densification of the oxide sintered body is achieved by adding at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga, thereby increasing the density. Can be obtained. In the sintering step, it is considered that the first additive element M promotes grain boundary diffusion, helps neck growth between grains, strengthens the bond between grains, and contributes to densification. Further, in the post-sintering holding step, a phase containing the first additive element M and different from the above-described ZnO phase, SnO ₂ phase, and Zn ₂ SnO ₄ phase (hereinafter sometimes abbreviated as M-containing compound) Therefore, the compound phase has the effect of suppressing clogging of the grindstone during cutting and improving the machining performance.

  Here, the first additive element is M, and the atomic ratio M / (Sn + Zn + M + X) of the first additive element M to the total amount of all metal elements is 0.001 or more and 0.04 or less. This is because, when the atomic ratio M / (Sn + Zn + M + X) is less than 0.001, even if the post-sintering holding step is performed, an M-containing compound is not generated, and an improvement effect on processing performance does not appear (Comparative Example). 9). On the other hand, when the atomic ratio M / (Sn + Zn + M + X) exceeds 0.04, the conductivity of the oxide sintered body does not increase even when a second additive element X described later is added (see Comparative Example 10).

The M-containing compound itself, which contains the first additive element M and is different from the ZnO phase, SnO ₂ phase, and Zn ₂ SnO ₄ phase, is brittle. There is an effect of suppressing clogging. Examples of such a compound containing the first additive element M include SiO ₂ , TiO ₂ , GeO ₂ , In ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ , Al ₂ O ₃ , Ga ₂ O ₃ , and Zn. ₂ SiO ₄ , ZnSiO ₃ , Zn ₂ TiO ₄ , Ti _0.5 Sn _0.5 O ₂ , Zn ₂ GeO ₄ , Zn ₂ In ₂ O ₅ , In ₂ Sn ₂ O ₇ , ZnBi ₁₂ O ₁₉ , Zn _0.5 Ce _0.5 O _1.75 , There are oxides such as ZnAl ₂ O ₄ and ZnGa ₂ O ₄ .

  By the way, only by adding the first additive element M, the density of the oxide sintered body is improved, but the conductivity is not improved.

(Second additive element)
The Sn—Zn—O-based oxide sintered body to which the first additive element M is added under the condition that Sn is contained at a ratio of 0.1 to 0.9 as the atomic ratio Sn / (Sn + Zn) is described above. As described above, although the density is improved, a problem remains in conductivity.

  Therefore, at least one second additive element X selected from Nb, Ta, W and Mo is added. The addition of the second additive element X improves the conductivity while maintaining the high density of the oxide sintered body. The second additive element X is a pentavalent or higher element such as Nb, Ta, W, or Mo.

The amount to be added requires that the atomic ratio X / (Sn + Zn + M + X) of the second additive element X to the total amount of all metal elements be 0.0001 or more and 0.1 or less. When the atomic ratio X / (Sn + Zn + M + X) is less than 0.0001, the conductivity does not increase (see Comparative Example 7). On the other hand, when the atomic ratio X / (Sn + Zn + M + X) exceeds 0.1, another compound phase, for example, Nb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , MoO ₃ , ZnTa ₂ O ₆ , ZnWO ₄ , ZnMoO _{4 and} other compound phases are produced, so that the conductivity is deteriorated (see Comparative Example 8).

  In this way, by adding appropriate amounts of the first additive element M and the second additive element X and generating the M-containing compound, high density, excellent conductivity, and high processing efficiency (excellent processing performance) ) A Sn—Zn—O-based oxide sintered body can be obtained.

[Conditions for firing compacts]
(Furnace atmosphere)
The molded body is preferably fired in an atmosphere having an oxygen concentration of 70% by volume or more in the sintering furnace. This is because the diffusion of ZnO, SnO ₂ and Zn ₂ SnO ₄ compound is promoted to improve the sinterability and improve the conductivity. In the high temperature range, there is also an effect of suppressing volatilization of ZnO and Zn ₂ SnO ₄ .

On the other hand, when the oxygen concentration in the sintering furnace is less than 70% by volume, the diffusion of ZnO, SnO ₂ or Zn ₂ SnO ₄ compound declines. Furthermore, in the high temperature range, the volatilization of the Zn component is promoted and a dense sintered body cannot be produced (see Comparative Example 3).

(Sintering process temperature)
It is preferable to set it as 1200 degreeC or more and 1450 degrees C or less. When the sintering temperature is less than 1200 ° C. (see Comparative Example 4), the temperature is too low and the grain boundary diffusion of sintering in the ZnO, SnO ₂ , Zn ₂ SnO ₄ compound does not proceed. On the other hand, when the temperature exceeds 1450 ° C. (see Comparative Example 5), the grain boundary diffusion is promoted and the sintering proceeds, but the Zn component volatilizes even if fired in a furnace having an oxygen concentration of 70% by volume or more. Can not be suppressed, leaving large pores inside the sintered body.

(Sintering process holding time)
It is preferable to set it to 10 hours or more and 30 hours or less. When the time is less than 10 hours, sintering is incomplete, resulting in a sintered body having large distortion and warpage, and grain boundary diffusion does not proceed and sintering does not proceed. As a result, a dense sintered body cannot be produced. On the other hand, when it exceeds 30 hours, the effect of time is not particularly obtained, resulting in deterioration of work efficiency and high cost.

(Temperature of holding process after sintering)
The temperature condition for holding the sintered body obtained after the sintering step is preferably 800 ° C. or higher and 1100 ° C. or lower. When the temperature is less than 800 ° C., the temperature is too low to generate an M-containing compound (compound containing the first additive element M and different from ZnO, SnO ₂ , Zn ₂ SnO ₄ ). On the other hand, when the temperature exceeds 1100 ° C., all of the added first additive element M remains in solid solution in the ZnO phase, SnO ₂ phase, and Zn ₂ SnO ₄ phase in the oxide sintered body and contains M. Does not produce compounds.

(Holding time of holding process after sintering)
The time for holding the sintered body obtained after the sintering step is preferably 10 hours or more and 30 hours or less. If it is less than 10 hours, the production of the M-containing compound becomes insufficient, clogging of the grindstone is not suppressed, and the processing efficiency does not increase. On the other hand, when it exceeds 30 hours, the crystal grain size of the oxide sintered body becomes large and becomes brittle, the mechanical strength is lowered, and cracks occur during processing.

The Sn—Zn—O-based oxide sintered body mainly composed of ZnO and SnO ₂ obtained under the above-described conditions has improved conductivity in addition to high density, so that film formation by DC sputtering is performed. Is possible. Moreover, since a special manufacturing method is not used, it can be applied to a cylindrical target.

  Hereinafter, examples of the present invention will be specifically described with reference to comparative examples. However, the technical scope according to the present invention is not limited to the description of the following examples, and changes are made within the scope suitable for the present invention. Of course, it is also possible to carry out by adding.

[Example 1]
SnO ₂ powder with an average particle diameter of 10 μm or less, ZnO powder with an average particle diameter of 10 μm or less, Bi ₂ O ₃ powder with an average particle diameter of 20 μm or less as the first additive element M, and an average particle diameter as the second additive element X A Ta ₂ O ₅ powder of 20 μm or less was prepared.

The SnO ₂ powder and the ZnO powder were prepared so that the atomic ratio Sn / (Sn + Zn) of Sn and Zn was 0.5, and the atomic ratio Bi / (Sn + Zn + Bi + Ta) of the first additive element M was 0.01, Bi ₂ O ₃ powder and Ta ₂ O ₅ powder were prepared so that the atomic ratio Ta / (Sn + Zn + Bi + Ta) of the two additive elements X was 0.001.

  Then, the prepared raw material powder, pure water, an organic binder, and a dispersant were mixed in a mixing tank so that the raw material powder concentration was 60% by mass.

Next, using a bead mill apparatus (manufactured by Ashizawa Finetech Co., Ltd., LMZ type) charged with hard ZrO ₂ balls, wet grinding is performed until the average particle size of the raw material powder becomes 1 μm or less, and then 10 hours. The mixture was stirred as above to obtain a slurry. In addition, a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD-2200) was used to measure the average particle size of the raw material powder.

  Next, the obtained slurry was sprayed and dried with a spray dryer apparatus (Okawara Chemical Co., Ltd., ODL-20 type) to obtain granulated powder.

Next, the obtained granulated powder is filled into a rubber mold and molded by applying a pressure of 294 MPa (3 ton / cm ² ) with a cold isostatic press, and the molded product having a diameter of about 250 mm is fired at normal pressure. The furnace was charged and air (oxygen concentration 21 vol%) was introduced into the sintering furnace up to 700 ° C. After confirming that the temperature in the firing furnace has reached 700 ° C., as a “sintering step”, oxygen is introduced so that the oxygen concentration becomes 80% by volume, the temperature is raised to 1400 ° C., and 1400 ° C. For 15 hours.

  Next, as a “post-sintering holding step”, the temperature was lowered to 1000 ° C. while maintaining the oxygen concentration at 80% by volume, and held at 1000 ° C. for 15 hours.

  After the holding time was completed, the introduction of oxygen was stopped and cooling was performed to obtain a Sn—Zn—O-based oxide sintered body according to Example 1.

  Next, the Sn—Zn—O-based oxide sintered body according to Example 1 was ground to a diameter of 200 mm and a thickness of 5 mm using a surface grinder (GHL manufactured by Hitachi Via Mechanics). As the grinding wheel, a resin bond diamond wheel with a grain size of # 140 was used. As a result of grinding under the conditions of a cutting depth of 0.015 mm and a table speed of 25 m / min, clogging of the grindstone did not occur.

  When the density of this processed body was measured by the Archimedes method, the relative density was 97.9%. The specific resistance was measured by a 4-probe method and found to be 0.09 Ω · cm.

Next, a part of this processed body was pulverized with a mortar to form a powder and analyzed using an X-ray diffractometer (X'Pert-PRO manufactured by PANalytical). As a result, in addition to SnO ₂ and Zn ₂ SnO ₄ , It was confirmed that Bi ₂ O ₃ as the M-containing compound was generated. The results are shown in Table 1.

[Example 2]
The Sn—Zn—O-based oxide sintered body according to Example 2 was obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) between Sn and Zn was adjusted to a ratio of 0.1. Obtained.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 96.4% and the specific resistance value was 0.23 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 3]
The Sn—Zn—O-based oxide sintered body according to Example 3 was obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn and Zn was adjusted to a ratio of 0.9. Obtained.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 95.2% and the specific resistance value was 0.33 Ω · cm.

Furthermore, was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 4]
The Sn—Zn—O-based oxide sintering according to Example 4 is performed in the same manner as in Example 1, except that the atomic ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X is 0.0001. Got the body.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 97.5% and the specific resistance value was 0.21 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 5]
A Sn—Zn—O-based oxide sintered body according to Example 5 was obtained in the same manner as in Example 1 except that the oxygen concentration was 100% by volume.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 98.8%, and the specific resistance value was 0.022 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 6]
The second additive element X was prepared in such a ratio that the atomic ratio Ta / (Sn + Zn + Bi + Ta) was 0.1, the “sintering step” was held for 10 hours, the oxygen concentration was 70% by volume, A Sn—Zn—O-based oxide sintered body according to Example 6 was obtained in the same manner as in Example 1 except that the holding time of “Step” was 10 hours and the oxygen concentration was 70% by volume.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 95.3% and the specific resistance value was 0.15 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 7]
Except that the atomic ratio Bi / (Sn + Zn + Bi + Ta) of the first additive element M was adjusted to 0.001, the sintering temperature was 1450 ° C., and the temperature of the “holding step after sintering” was 1100 ° C. In the same manner as in Example 1, a Sn—Zn—O-based oxide sintered body according to Example 7 was obtained.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 97.1%, and the specific resistance value was 0.060 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Example 8]
Except that the atomic ratio Bi / (Sn + Zn + Bi + Ta) of the first additive element M is 0.04, the sintering temperature is 1200 ° C., and the temperature of the “holding step after sintering” is 800 ° C. The Sn—Zn—O-based oxide sintered body according to Example 8 was obtained in the same manner as Example 1.

  As a result of grinding this oxide sintered body in the same manner as in Example 1, clogging of the grindstone did not occur. The relative density was 96.2% and the specific resistance value was 0.17 Ω · cm.

Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, were produced a Bi ₂ O ₃ is the M-containing compound. The results are shown in Table 1.

[Examples 9 to 15]
As the first additive element M, SiO ₂ powder (Example 9), TiO ₂ powder (Example 10), GeO ₂ powder (Example 11), In ₂ O ₃ powder (Example 12), CeO ₂ powder (Implementation) Example 13), Al ₂ O ₃ powder (Example 14), Ga ₂ O ₃ powder (Example 15), the atomic ratio M / (Sn + Zn + M + Ta) of the first additive element M was set to 0.04, and the second The same Ta ₂ O ₅ powder as in Example 1 was used as the additive element X, and the same as in Example 1 except that the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additive element X was 0.1. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 9 to 15 were obtained.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 95.1%, 0.10 Ω · cm (Example 9), 94.2%, 0, respectively. .26 Ω · cm (Example 10), 96.8%, 0.031 Ω · cm (Example 11), 97.2%, 0.090 Ω · cm (Example 12), 98.3%, 0.11Ω • cm (Example 13), 92.2%, 0.45 Ω · cm (Example 14), 96.1%, 0.16 Ω · cm (Example 15).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, the above M-containing compounds, SiO ₂ (Example 9), TiO ₂ (implementation). Example 10), GeO ₂ (Example 11), In ₂ O ₃ (Example 12), CeO ₂ (Example 13), Al ₂ O ₃ (Example 14), and Ga ₂ O ₃ (Example 15) ) Respectively. The results are shown in Table 2.

[Examples 16 to 22]
As the first additive element M, SiO ₂ powder (Example 16), TiO ₂ powder (Example 17), GeO ₂ powder (Example 18), In ₂ O ₃ powder (Example 19), CeO ₂ powder (Implementation) Example 20), Al ₂ O ₃ powder (Example 21), Ga ₂ O ₃ powder (Example 22), the atomic ratio M / (Sn + Zn + M + Ta) of the first additive element M was set to 0.001, and the second The same Ta ₂ O ₅ powder as in Example 1 was used as the additive element X, and the same as in Example 1 except that the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additive element X was 0.1. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 16 to 22 were obtained.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 91.8%, 0.022 Ω · cm (Example 16), 94.4%, and 0, respectively. .25 Ω · cm (Example 17), 95.3%, 0.016 Ω · cm (Example 18), 93.3%, 0.061 Ω · cm (Example 19), 96.6%, 0.053 Ω • cm (Example 20), 94.8%, 0.079 Ω · cm (Example 21), 95.8%, 0.052 Ω · cm (Example 22).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, SiO ₂ (Example 16), TiO ₂ ( Example 17), GeO ₂ (Example 18), In ₂ O ₃ (Example 19), CeO ₂ (Example 20), Al ₂ O ₃ (Example 21), and Ga ₂ O ₃ (Example) 22) respectively. The results are shown in Table 2.

[Examples 23 to 29]
As the first additive element M, SiO ₂ powder (Example 23), TiO ₂ powder (Example 24), GeO ₂ powder (Example 25), In ₂ O ₃ powder (Example 26), CeO ₂ powder (Implementation) Example 27), Al ₂ O ₃ powder (Example 28), Ga ₂ O ₃ powder (Example 29), the atomic ratio M / (Sn + Zn + M + Ta) of the first additive element M was set to 0.04, and the second As the additive element X, the same Ta ₂ O ₅ powder as in Example 1 was used, and the same as in Example 1 except that the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additive element X was 0.0001. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 23 to 29 were obtained.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 96.6%, 0.31 Ω · cm (Example 23), 95.5%, and 0, respectively. 0.098 Ω · cm (Example 24), 97.7%, 0.0096 Ω · cm (Example 25), 97.2%, 0.02 Ω · cm (Example 26), 98.5%, 0.0081 Ω • cm (Example 27), 95.2%, 0.023 Ω · cm (Example 28), 96.0%, 0.014 Ω · cm (Example 29).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, SiO ₂ (Example 23), TiO ₂ ( Example 24), GeO ₂ (Example 25), In ₂ O ₃ (Example 26), CeO ₂ (Example 27), Al ₂ O ₃ (Example 28), and Ga ₂ O ₃ (Example) 29) respectively. The results are shown in Table 2.

[Examples 30 to 36]
As the first additive element M, SiO ₂ powder (Example 30), TiO ₂ powder (Example 31), GeO ₂ powder (Example 32), In ₂ O ₃ powder (Example 33), CeO ₂ powder (Implementation) Example 34), Al ₂ O ₃ powder (Example 35), Ga ₂ O ₃ powder (Example 36), the atomic ratio M / (Sn + Zn + M + Ta) of the first additive element M was set to 0.001, and the second As the additive element X, the same Ta ₂ O ₅ powder as in Example 1 was used, and the same as in Example 1 except that the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additive element X was 0.0001. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 30 to 36 were obtained.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 96.3%, 0.19 Ω · cm (Example 30), 95.5%, 0, respectively. 0.041 Ω · cm (Example 31), 96.9%, 0.0077 Ω · cm (Example 32), 94.4%, 0.010 Ω · cm (Example 33), 96.0%, 0.055Ω • cm (Example 34), 97.6%, 0.014 Ω · cm (Example 35), 92.2%, 0.0077 Ω · cm (Example 36).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, SiO ₂ (Example 30), TiO ₂ ( Example 31), GeO ₂ (Example 32), In ₂ O ₃ (Example 33), CeO ₂ (Example 34), Al ₂ O ₃ (Example 35), and Ga ₂ O ₃ (Example) 36) respectively. The results are shown in Table 2.

[Examples 37 to 39]
The same Bi ₂ O ₃ powder as in Example 1 was used as the first additive element M, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M was 0.04, and the second additive element X was Nb ₂ O _{Using 5} powders (Example 37), WO ₃ powder (Example 38), and MoO ₃ powder (Example 39), the atomic ratio X / (Sn + Zn + Bi + X) of the second additive element X is 0.1. Sn-Zn-O-based oxide sintered bodies according to Examples 37 to 39 were obtained in the same manner as Example 1 except that the preparations were made.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 95.4%, 0.13 Ω · cm (Example 37), 95.2%, 0, respectively. 0.088 Ω · cm (Example 38), 93.3%, and 0.33 Ω · cm (Example 39).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, Bi ₂ O ₃ which was the M-containing compound was generated. The results are shown in Table 3.

[Examples 40 to 42]
As the first additive element M, the same Bi ₂ O ₃ powder as in Example 1 was used, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M was 0.001, and the second additive element X was Nb ₂ O _{Using 5} powders (Example 40), WO ₃ powder (Example 41), and MoO ₃ powder (Example 42), the atomic ratio X / (Sn + Zn + Bi + X) of the second additive element X is 0.1. Sn-Zn-O-based oxide sintered bodies according to Examples 40 to 42 were obtained in the same manner as Example 1 except that the preparations were made.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 96.5%, 0.068 Ω · cm (Example 40), 94.7%, 0, respectively. They were 0.17 Ω · cm (Example 41), 96.5%, and 0.096 Ω · cm (Example 42).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, Bi ₂ O ₃ which was the M-containing compound was generated. The results are shown in Table 3.

[Examples 43 to 45]
The same Bi ₂ O ₃ powder as in Example 1 was used as the first additive element M, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M was 0.04, and the second additive element X was Nb ₂ O _{Using 5} powders (Example 43), WO ₃ powder (Example 44), and MoO ₃ powder (Example 45), the atomic ratio X / (Sn + Zn + Bi + X) of the second additive element X is 0.0001. Sn-Zn-O-based oxide sintered bodies according to Examples 43 to 45 were obtained in the same manner as Example 1 except that the preparations were made.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 97.3%, 0.25 Ω · cm (Example 43), 94.4%, and 0, respectively. It was .28 Ω · cm (Example 44), 92.8%, 0.76 Ω · cm (Example 45).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, Bi ₂ O ₃ which was the M-containing compound was generated. The results are shown in Table 3.

[Examples 46 to 48]
As the first additive element M, the same Bi ₂ O ₃ powder as in Example 1 was used, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M was 0.001, and the second additive element X was Nb ₂ O _{Using 5} powders (Example 46), WO ₃ powder (Example 47), and MoO ₃ powder (Example 48), the atomic ratio X / (Sn + Zn + Bi + X) of the second additive element X is 0.0001. Sn-Zn-O-based oxide sintered bodies according to Examples 46 to 48 were obtained in the same manner as Example 1 except that the preparations were made.

  And like Example 1, as a result of grinding the Sn—Zn—O-based oxide sintered body according to each Example, clogging of the grindstone did not occur.

  Moreover, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example were 97.7%, 0.041 Ω · cm (Example 46), 91.6%, 0, respectively. 0.085 Ω · cm (Example 47), 92.9%, and 0.036 Ω · cm (Example 48).

Further, when the Sn—Zn—O-based oxide sintered body according to each example was subjected to X-ray diffraction analysis in the same manner as in Example 1, Bi ₂ O ₃ which was the M-containing compound was generated. The results are shown in Table 3.

[Comparative Example 1]
An Sn—Zn—O-based oxide sintered body according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn and Zn was adjusted to a ratio of 0.05. .

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 1 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value are measured, the relative density is 87.0%, the specific resistance value is 600 Ω · cm, and it is impossible to achieve the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less. confirmed. The results are shown in Table 4.

[Comparative Example 2]
An Sn—Zn—O-based oxide sintered body according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the compound was prepared at a ratio where the atomic ratio Sn / (Sn + Zn) of Sn and Zn was 0.95. It was.

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 2 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value are measured, the relative density is 85.0%, the specific resistance value is 1000 Ω · cm, and the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less cannot be achieved. confirmed. The results are shown in Table 4.

[Comparative Example 3]
A Sn—Zn—O-based oxide sintered body according to Comparative Example 3 was obtained in the same manner as in Example 1 except that the oxygen concentration in the furnace was set to 68% by volume during sintering at 1400 ° C.

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 3 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value are measured, the relative density is 86.5%, the specific resistance value is 47000 Ω · cm, and it is impossible to achieve the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less. confirmed. The results are shown in Table 4.

[Comparative Example 4]
The Sn—Zn—O according to Comparative Example 4 was the same as Example 1 except that the sintering temperature of the “sintering process” was 1170 ° C. and the holding temperature of the “post-sintering holding process” was 700 ° C. A system oxide sintered body was obtained.

  As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 4 in the same manner as in Example 1, clogging of the grindstone occurred. Moreover, when the X-ray-diffraction analysis was carried out similarly to Example 1, the said M containing compound was not detected.

  Furthermore, when the relative density and the specific resistance value were measured, the relative density was 81.4%, the specific resistance value was 94000 Ω · cm, and it was impossible to achieve the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less. confirmed. The results are shown in Table 4.

[Comparative Example 5]
The Sn—Zn—O according to Comparative Example 5 was the same as Example 1 except that the sintering temperature of the “sintering step” was 1500 ° C. and the holding temperature of the “post-sintering holding step” was 1200 ° C. A system oxide sintered body was obtained.

  As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 5 in the same manner as in Example 1, clogging of the grindstone occurred. Moreover, when the X-ray-diffraction analysis was carried out similarly to Example 1, the said M containing compound was not detected.

  Furthermore, when the relative density and the specific resistance value were measured, the relative density was 86.9%, the specific resistance value was 12 Ω · cm, and it was impossible to achieve the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less. confirmed. The results are shown in Table 4.

[Comparative Example 6]
A Sn—Zn—O-based oxide sintered body according to Comparative Example 6 was obtained in the same manner as in Example 1 except that the “sintering process” was followed by cooling without performing the “post-sintering holding process”. . The time required to lower the temperature from 1100 ° C. to 800 ° C. was 7 hours.

  As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 6 in the same manner as in Example 1, clogging of the grindstone occurred. Moreover, when the X-ray-diffraction analysis was carried out similarly to Example 1, the said M containing compound was not detected.

  Furthermore, when the relative density and the specific resistance value were measured, the relative density was 82.0%, the specific resistance value was 730000 Ω · cm, and it was impossible to achieve the characteristics of the relative density of 90% or more and the specific resistance of 1 Ω · cm or less. confirmed. The results are shown in Table 4.

[Comparative Example 7]
The Sn—Zn—O-based oxide sintering according to Comparative Example 7 was performed in the same manner as in Example 1 except that the atomic ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X was adjusted to 0.00009. Got the body.

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 7 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value were measured, the relative density was 93.5%, the specific resistance value was 260 Ω · cm, and a characteristic with a relative density of 90% or more was achieved, but the specific resistance was 1 Ω · cm or less. It was confirmed that this characteristic cannot be achieved. The results are shown in Table 4.

[Comparative Example 8]
The Sn—Zn—O-based oxide sintering according to Comparative Example 8 is performed in the same manner as in Example 1 except that the atomic ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X is 0.15. Got the body.

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 8 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value were measured, the relative density was 92.2%, the specific resistance value was 110 Ω · cm, and a characteristic with a relative density of 90% or more was achieved, but the specific resistance was 1 Ω · cm or less. It was confirmed that this characteristic cannot be achieved. The results are shown in Table 4.

[Comparative Example 9]
The Sn—Zn—O-based oxide sintering according to Comparative Example 9 was performed in the same manner as in Example 1, except that the atomic ratio Bi / (Sn + Zn + Bi + Ta) of the first additive element M was adjusted to 0.0009. Got the body.

  As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 9 in the same manner as in Example 1, clogging of the grindstone occurred. Moreover, when the X-ray-diffraction analysis was carried out similarly to Example 1, the said M containing compound was not detected.

  Furthermore, when the relative density and the specific resistance value were measured, the relative density was 85.0%, the specific resistance value was 0.889 Ω · cm, and a characteristic with a specific resistance of 1 Ω · cm or less was achieved. It was confirmed that more than% characteristics could not be achieved. The results are shown in Table 4.

[Comparative Example 10]
The Sn—Zn—O-based oxide sintering according to Comparative Example 10 was performed in the same manner as in Example 1 except that the atomic ratio Bi / (Sn + Zn + Bi + Ta) of the first additive element M was adjusted to 0.05. Got the body.

As a result of grinding the Sn—Zn—O-based oxide sintered body according to Comparative Example 10 in the same manner as in Example 1, clogging of the grindstone did not occur. Furthermore, it was X-ray diffraction analysis in the same manner as in Example 1, generation of Bi ₂ O ₃ is the M-containing compounds was observed.

  However, when the relative density and the specific resistance value were measured, the relative density was 96.9%, the specific resistance value was 5500 Ω · cm, and a characteristic with a relative density of 90% or more was achieved, but the specific resistance was 1 Ω · cm or less. It was confirmed that this characteristic cannot be achieved. The results are shown in Table 4.

  The Sn—Zn—O-based oxide sintered body according to the present invention has mechanical strength and excellent processing performance, and additionally has characteristics such as high density and low resistance. It has industrial applicability as a sputtering target for forming electrodes.

Claims (2)

In a Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components and containing at least one of a ZnO phase and a SnO ₂ phase and a Zn ₂ SnO ₄ phase,
Sn is contained in an atomic ratio Sn / (Sn + Zn) at a ratio of 0.1 to 0.9.
At least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga is used as the first additive element M, and at least one selected from Nb, Ta, W, and Mo is added as the second additive In the case of element X,
The first additive element M is contained at a ratio of 0.001 or more and 0.04 or less as an atomic ratio M / (Sn + Zn + M + X) with respect to the total amount of all metal elements,
Containing the second additive element X in a ratio of 0.0001 to 0.1 as an atomic ratio X / (Sn + Zn + M + X) to the total amount of all metal elements, and
A compound phase different from the ZnO phase, SnO ₂ phase, Zn ₂ SnO ₄ phase and the compound phase contains the first additive element M;
A Sn—Zn—O-based oxide sintered body having a relative density of 90% or more and a specific resistance of 1 Ω · cm or less. In the manufacturing method of the Sn-Zn-O type oxide sintered compact according to claim 1,
ZnO powder and SnO ₂ powder, oxide powder containing at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga, from Nb, Ta, W and Mo A slurry obtained by mixing the selected oxide powder containing at least one second additive element X with pure water, an organic binder, and a dispersant is dried and granulated to produce a granulated powder. Granule powder manufacturing process,
A molded body manufacturing process for obtaining a molded body by pressure molding the granulated powder; and
A sintering step in which the molded body is fired under conditions of 1200 ° C. or higher and 1450 ° C. or lower and 10 hours or longer and 30 hours or shorter in an atmosphere having an oxygen concentration of 70% by volume or higher in the firing furnace
A post-sintering holding step of holding the obtained sintered body under the conditions of 800 ° C. or higher and 1100 ° C. or lower and 1 hour or longer and 10 hours or shorter;
The manufacturing method of the Sn-Zn-O type oxide sintered compact characterized by comprising.