WO2017086016A1

WO2017086016A1 - SINTERED Sn-Zn-O OXIDE AND PROCESS FOR PRODUCING SAME

Info

Publication number: WO2017086016A1
Application number: PCT/JP2016/077670
Authority: WO
Inventors: 誠小沢; 茂五十嵐; 勲雄安東
Original assignee: 住友金属鉱山株式会社
Priority date: 2015-11-20
Filing date: 2016-09-20
Publication date: 2017-05-26

Abstract

[Problem] To provide a sintered Sn-Zn-O oxide which has mechanical strength, a high density, and a low resistance and is for use as a sputtering target and a process for producing the sintered oxide. [Solution] This sintered oxide is characterized by containing Sn in a proportion of 0.1-0.9 in terms of atomic ratio Sn/(Sn+Zn), containing at least one first additive element M selected from among Si, Ti, Ge, In, Bi, Ce, Al, and Ga, and containing at least one second additive element X selected from among Nb, Ta, W, and Mo, the first additive element M being contained in a proportion of 0.0001-0.04 in terms of atomic ratio to the sum of all the metallic elements, M/(Sn+Zn+M+X), and the second additive element X being contained in a proportion of 0.0001-0.1 in terms of atomic ratio to the sum of all the metallic elements, X/(Sn+Zn+M+X), and by having a relative density of 90% or higher and a resistivity of 1 Ω·cm or less.

Description

Sn-Zn-O-based oxide sintered body and method for producing the same

The present invention relates to a sintered Sn—Zn—O-based oxide used as a sputtering target when producing a transparent conductive film applied to a solar cell, a liquid crystal surface element, a touch panel or the like by a sputtering method such as direct current sputtering or high frequency sputtering. In particular, damage to the sintered body during processing, damage to the sputtering target during sputtering film formation, cracks and the like can be suppressed, and a high-density, low-resistance Sn-Zn-O-based oxide The present invention relates to a sintered body and a method of manufacturing the same.

A transparent conductive film having high conductivity and high transmittance in the visible light region is used for solar cells, liquid crystal display elements, surface elements such as organic electroluminescence and inorganic electroluminescence, and electrodes for touch panels, etc. It is also used as various anti-fogging transparent heating elements such as automobile window and heat ray reflective film for building, antistatic film, frozen showcase and the like.

As the transparent conductive film, tin oxide (SnO ₂ ) containing antimony or fluorine as a dopant, zinc oxide (ZnO) containing aluminum or gallium as a dopant, indium oxide (In ₂ O ₃ ) containing tin as a dopant, etc. 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 referred to as an ITO (Indium tin oxide) film, and a low resistance film is easily obtained. It is 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 and precise film thickness control are required, and its operation is very simple, so 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 into a film, and a sintered body of metal, metal oxide, metal nitride, metal carbide or the like, or in some cases, a single crystal is used. In the sputtering method, generally, after using an apparatus having a vacuum chamber capable of disposing a substrate and a sputtering target therein, the substrate and the sputtering target are disposed, then the vacuum chamber is evacuated to a high vacuum and then a rare gas such as argon is used. It introduce | transduces and sets the inside of a vacuum chamber to about 10 Pa or less gas pressure. Then, the substrate is an anode, the sputtering target is a cathode, glow discharge is caused between the two to generate argon plasma, argon positive ions in the plasma are made to collide with the sputtering target of the cathode, and the target is thereby repelled. Component particles are deposited on a substrate to form a film.

And in order to manufacture the said transparent conductive film, the material of indium oxide types, such as ITO, is used widely widely conventionally. However, since indium metal is a rare metal and toxic on the earth, there is concern about adverse effects on the environment and human body, and non-indium-based materials are required.

As the non-indium-based materials, as described above, zinc oxide (ZnO) -based materials containing aluminum or gallium as a dopant, and tin oxide (SnO ₂ ) -based materials containing antimony or fluorine as a dopant are known. . And although the transparent conductive film of the said zinc oxide (ZnO) type-material is manufactured industrially by sputtering method, it has defects, such as poor 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 manufacture a high density and durable tin oxide based sintered compact target, so the above transparent conductive film is sputtered It has the disadvantages associated with difficulties in manufacturing by the method.

Then, as a material which ameliorates these defects, the sintered compact which makes zinc oxide and tin oxide the main ingredients is proposed. For example, Patent Document 1 describes a sintered body composed of a SnO ₂ phase and a Zn ₂ SnO ₄ phase, and having an average crystal grain size of 1 to 10 μm in the Zn ₂ SnO ₄ phase.

In Patent Document 2, the integrated intensity of (222) plane and (400) plane in Zn ₂ SnO ₄ phase by X-ray diffraction using CuKα ray 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 greater than or equal to the standard (0.44) by 0.52 or more The body is described. Furthermore, in Patent Document 2, as a method of producing a sintered body having the above-mentioned characteristics, the step of producing the sintered body is carried out under the conditions of 800 ° C. to 1400 ° C. in an atmosphere containing oxygen in a firing furnace. There is also described a method comprising the steps of: firing and cooling after making the inside of the firing furnace inert atmosphere such as Ar gas after the holding at the highest firing temperature is finished.

However, in these methods, in the Sn-Zn-O-based oxide sintered body containing Zn and Sn as main components, although the sintered body strength that can endure mechanical strength can be obtained, sufficient density and conductivity can be obtained. It was difficult to obtain, and it was not satisfactory as a characteristic required for sputtering deposition in a mass production site. That is, in the pressureless sintering method, there remain problems in terms of densification and conductivity of the sintered body.

JP, 2010-037161, A (refer to claim 13 and claim 14) JP, 2013-036073, A (refer to claim 1 and claim 3)

The present invention was made in view of such a demand, and is mainly composed of Zn and Sn and has high mechanical strength and high density and low resistance Sn-Zn-O based oxide sintered body and its production The task is to provide a method.

A Sn-Zn-O-based oxide sintered body mainly composed of Zn and Sn is a material which is difficult to have both properties such as high density and low resistance, and can be made dense and conductive even if the composition is changed It is difficult to produce an excellent oxide sintered body. In the sintered body density, although there are some density ups and downs depending on the compounding ratio, the conductivity shows a very high specific resistance value of 1 × 10 ⁶ Ω · cm or more and the conductivity is poor.

In the preparation of a Sn-Zn-O-based oxide sintered body containing Zn and Sn as main components, a compound of Zn ₂ SnO ₄ starts to be formed at about 1100 ° C., and volatilization of Zn becomes remarkable from about 1450 ° C. When firing at a high temperature to increase the density of the Sn-Zn-O-based oxide sintered body, volatilization of Zn proceeds so that grain boundary diffusion and bonding between grains weaken to obtain a high-density oxide sintered body I can not

On the other hand, with regard to the conductivity, since Zn ₂ SnO ₄ , ZnO, and SnO ₂ are substances having poor conductivity, even if the compounding ratio and the amounts of the compound phase and ZnO and SnO ₂ are adjusted, the conductivity is adjusted. Can not be significantly improved. As a result, the Sn-Zn-O-based oxide sintered body mainly composed of Zn and Sn has high density and high conductivity of the sintered body, which is a characteristic required for sputtering film formation at mass production sites. I can not get it.

That is, the object of the present invention is to suppress the volatilization of Zn, promote grain boundary diffusion, and apply a means for improving conductivity to an oxide sintered body in which bonding between grains is strengthened. It is an object of the present invention to provide a Sn—Zn—O-based oxide sintered body mainly composed of Zn and Sn which is dense and excellent in conductivity as described above.

To solve the above problems, the present inventors have, Zn with searching the manufacturing conditions to achieve both characteristics of both density and conductivity of the sintered body, from 1100 ° C. to initiate the compound produced as Zn ₂ SnO ₄ In a temperature range of 1450 ° C., where volatilization of is remarkable, a method of manufacturing a Sn—Zn—O-based oxide sintered body having Zn and Sn as main components excellent in high density and high conductivity was examined.

As a result, at least at least one selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga under the condition that Sn is contained at a ratio of 0.1 or more and 0.9 or less as an atomic ratio Sn / (Sn + Zn). By adding one type (that is, the first additional element M) as a dopant, an oxide sintered body having a relative density of 90% could be obtained. However, although the density has been improved, the conductivity has not been improved, the addition of one of Nb, Ta, W, and Mo additive elements (that is, the second additive element X) is further performed to improve the conductivity. It has become possible to produce an oxide sintered body having excellent conductivity while maintaining high density. When Sn is contained in a ratio of 0.1 or more and 0.33 or less as an atomic ratio Sn / (Sn + Zn), the ZnO phase of wurtzite crystal structure and the Zn ₂ SnO ₄ phase of spinel crystal structure are main components If Sn is contained in a ratio of more than 0.33 and 0.9 or less as atomic ratio Sn / (Sn + Zn), Zn ₂ SnO ₄ phase of spinel type crystal structure and SnO ₂ phase of rutile type crystal structure are mainly It becomes an ingredient. In addition, when the first additive element M and the second additive element X in appropriate amounts are added, the first additive element M and the second additive element X are contained in Zn, Zn ₂ SnO ₄ phase in the ZnO phase. In order to substitute for Sn in the Zn or Sn, SnO ₂ phase, and form a solid solution, the ZnO phase of wurtzite crystal structure, the Zn ₂ SnO ₄ phase of spinel crystal structure, and the SnO ₂ phase of rutile crystal structure No other compound phase is formed. The present invention has been completed by such technical discovery.

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

The second invention according to the present invention is
In the Sn—Zn—O-based oxide sintered body according to the first invention,
The X-ray diffraction peak position of the (101) plane in the ZnO phase by X-ray diffraction using CuKα rays is 36.25 degrees to 36.31 degrees, and the X-ray diffraction peak of the (311) plane in the Zn ₂ SnO ₄ phase The position is characterized by 34.32 degrees to 34.42 degrees,
The third invention is
In the Sn—Zn—O-based oxide sintered body according to the first invention,
The X-ray diffraction peak position of the (311) plane in the Zn ₂ SnO ₄ phase by the X-ray diffraction using CuKα ray is 34.32 degrees to 34.42 degrees, and the X-ray diffraction of the (101) plane in the SnO ₂ phase The peak position is characterized by being 33.86 degrees to 33.91 degrees.

Next, a fourth invention according to the present invention is
In the method of producing a Sn—Zn—O-based oxide sintered body according to any one of the first to third inventions,
Oxide powder containing ZnO powder and SnO ₂ powder, at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga, Nb, Ta, W and Mo A powder obtained by mixing an oxide powder containing at least one selected second additive element X with pure water, an organic binder, and a dispersant, and drying and granulating a slurry to produce a granulated powder Grain powder production process,
A molded body manufacturing process for obtaining a molded body by pressure molding the granulated powder.
A sintered body manufacturing process for forming a sintered body by firing the above-mentioned molded body under the conditions of 1200 ° C. or more and 1450 ° C. or less and 10 hours or more and 30 hours or less in an atmosphere having an oxygen concentration of 70 vol% or more in a firing furnace.
It is characterized by having.

In the Sn—Zn—O-based oxide sintered body according to the present invention, any condition can be satisfied as long as Sn is contained at a ratio of 0.1 or more and 0.9 or less as an atomic ratio Sn / (Sn + Zn). Even with the compounding ratio, it is possible to obtain a high density and low resistance Sn—Zn—O based oxide sintered body excellent in mass productivity by pressureless sintering.

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

First, at least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga containing Sn in a ratio of 0.1 or more and 0.9 or less as an atomic ratio Sn / (Sn + Zn) (1) At least one selected from Nb, Ta, W and Mo, containing the additive element M at a ratio of 0.0001 or more and 0.04 or less as an atomic ratio M / (Sn + Zn + M + X) to the total amount of all metal elements Raw material powder containing the second additive element X at a ratio of 0.0001 or more and 0.1 or less as atomic ratio X / (Sn + Zn + M + X) to total amount of all metal elements was prepared, and obtained by granulating the raw material powder The granulated powder is molded to produce a molded body, and the above-mentioned growth is performed under the conditions of 1200 ° C. or more and 1450 ° C. or less and 10 hours or more and 30 hours or less in an atmosphere in a baking furnace having an oxygen concentration of 70 volume% or more. By firing the body, the relative density it is possible to manufacture a Sn-Zn-O type oxide-sintered body of the present invention is and resistivity at 90% or less 1 [Omega · cm.

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

[Additive element]
The first additive element M and the second additive element X are required under the conditions that Sn is contained in the atomic ratio Sn / (Sn + Zn) in a ratio of 0.1 or more and 0.9 or less. In the case of M alone, although the density is improved, the low resistance characteristic can not be obtained. On the other hand, in the case of only the second additive element X, although the resistance is low, a high density can not be obtained.

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

(First additive element M)
The effect of densification is achieved by adding at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga for densification of the oxide sintered body It is possible to obtain It is thought that the first additive element M promotes grain boundary diffusion, promotes neck growth between grains, strengthens bonding between grains, and contributes to densification. Here, the atomic number ratio M / (Sn + Zn + M + X) relative to the total amount of all the metal elements of the first additive element M is 0.0001 or more and 0.04 or less, where M is the first additive element. It is because the effect of densification does not appear when / (Sn + Zn + M + X) is less than 0.0001 (see 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 if a second additional element X described later is added (see Comparative Example 10). Furthermore, another compound, for example, a compound such as SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZnAl ₂ O ₄ , ZnSiO ₄ , Zn ₂ Ge ₃ O ₈ , ZnTa ₂ O ₆ , Ti _0.5 Sn _0.5 O ₂ is formed. When the film is formed, desired film characteristics can not be obtained.

Thus, the addition of the first additive element M improves the density of the oxide sintered body but does not improve the conductivity.

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

Therefore, at least one second additional 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 is required to make the atomic ratio X / (Sn + Zn + M + X) to the total amount of all the metal elements of the second additive element X be 0.0001 or more and 0.1 or less. If 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 above atomic number 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 The conductivity is deteriorated because a compound phase such as ZnMoO ₄ is generated (see Comparative Example 8).

(X-ray diffraction peak)
In the Sn—Zn—O-based oxide sintered body according to the present invention, when the atomic ratio Sn / (Sn + Zn) is 0.1 or more and 0.33 or less, the ZnO phase and spinel of wurtzite crystal structure as described above -Type Zn ₂ SnO ₄ phase is the main component, and if the atomic ratio Sn / (Sn + Zn) is more than 0.33 and 0.9 or less, Zn ₂ SnO ₄ phase of spinel type crystal structure and SnO of rutile type crystal structure _Two phases are the main components. In addition, since the proper amounts of the first additive element M and the second additive element X are substituted for Zn in the ZnO phase, Zn in the Zn ₂ SnO ₄ phase, or Sn in the Sn phase, or Sn in the SnO ₂ phase. Other compound phases than the ZnO phase of wurtzite crystal structure, the Zn ₂ SnO ₄ phase of spinel crystal structure, and the SnO ₂ phase of rutile crystal structure are not formed.

The crystal structure can be known by X-ray diffraction analysis of a powder obtained by crushing a part of the oxide sintered body and analyzing the obtained diffraction peak. For example, in X-ray diffraction analysis using CuKα radiation, the standard diffraction peak position on the wurtzite ZnO (101) plane is 36.253 degrees according to the ICDD reference code 00-036-1451. The standard diffraction peak position in the Zn ₂ SnO ₄ (311) plane of the spinel crystal structure is 34.291 degrees according to the ICDD reference code 00-041-1470, and the standard in the rutile SnO ₂ (101) plane. The diffraction peak position is 33.893 degrees according to ICDD reference code 00-041-1445.

By the way, the position of the diffraction peak is affected by the kind and amount of the additive element, the sintering temperature, the atmosphere, the holding time, etc., and the crystal structure is It changes due to expansion, contraction or distortion.

Then, in the Sn—Zn—O-based oxide sintered body according to the present invention, the diffraction peak position of the ZnO (101) plane by X-ray diffraction using CuKα rays is the standard diffraction peak position 36.253 degrees Preferably, the temperature is 36.25 degrees to 36.31 degrees, inclusive. Further, the above-mentioned diffraction peak position of the Zn ₂ SnO ₄ (311) plane is preferably 34.32 to 34.42 degrees on the high angle side of the standard diffraction peak position 34.291 degrees, and SnO ₂ ( The diffraction peak position on the 101) plane is preferably 33.86 degrees to 33.91 degrees including a standard diffraction peak position of 33.893 degrees. Outside this range, the expansion, contraction or strain of ZnO, Zn ₂ SnO ₄ and SnO ₂ crystals may become large, which may cause cracking of the oxide sintered body, reduction of sintering density, and reduction of conductivity. .

Thus, by adding appropriate amounts of the first additive element M and the second additive element X, it is possible to obtain a Sn-Zn-O-based oxide sintered body having high density and excellent conductivity. Become.

[Firing conditions of molded body]
(Atmosphere in the furnace)
The formed 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 or Zn ₂ SnO ₄ compound is promoted to improve the sinterability and the conductivity. In the high temperature range, it also has the effect of suppressing the 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, volatilization of the Zn component is promoted and a dense sintered body can not be produced (see Comparative Example 3).

(Sintering 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 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), grain boundary diffusion is promoted and sintering proceeds, but even if it is fired in a furnace having an oxygen concentration of 70 volume% or more, volatilization of Zn component Can not be suppressed, and a large void will be left inside the sintered body.

(Retention time)
It is preferable to set it as 10 hours or more and 30 hours or less. If the heat treatment time is less than 10 hours, the sintering is incomplete, resulting in a sintered body having a large amount of distortion and warpage, diffusion of grain boundaries does not proceed, and sintering does not proceed. As a result, a dense sintered body can not be produced (see Comparative Example 6). On the other hand, when it exceeds 30 hours, the effect of time is not obtained in particular, which results in deterioration of work efficiency and high cost.

The conductivity of the Sn—Zn—O-based oxide sintered body obtained mainly under the conditions described above is also improved, and therefore, film formation by DC sputtering becomes possible. In addition, since no special manufacturing method is used, application to a cylindrical target is possible.

Examples of the present invention will be specifically described below with reference to comparative examples, but the technical scope of the present invention is not limited to the contents of the following examples, and changes are possible as long as they are compatible with the present invention. It is also possible naturally to carry out by adding.

Example 1
SnO ₂ powder having an average particle size of 10 μm or less, ZnO powder having an average particle size of 10 μm or less, Bi ₂ O ₃ powder having an average particle size of 20 μm or less as the first additional element M, and an average particle size as the second additional element X Ta ₂ O ₅ powder of 20 μm or less was prepared.

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

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

Next, using a bead mill apparatus (Ashizawa Finetech Co., Ltd., LMZ type) loaded 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 above mixture was mixed and stirred to obtain a slurry. A laser diffraction particle size distribution measuring apparatus (SALD-2200, manufactured by Shimadzu Corporation) was used to measure the average particle size of the raw material powder.

Next, the obtained slurry was sprayed and dried by means of a spray dryer (manufactured by Ogawara Kakohki Co., Ltd., ODL-20 type) to obtain granulated powder.

Next, the obtained granulated powder is filled into a rubber mold and molded by a cold isostatic press under a pressure of 294 MPa (3 ton / cm ² ), and the obtained compact having a diameter of about 250 mm is pressure-baked The furnace was introduced, and air (oxygen concentration: 21% by volume) was introduced into the sintering furnace up to 700 ° C. After confirming that the temperature in the firing furnace had reached 700 ° C., oxygen was introduced so that the oxygen concentration was 80 vol%, the temperature was raised to 1400 ° C., and the temperature was maintained at 1400 ° C. for 15 hours.

After the holding time ended, 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 processed to a diameter of 200 mm and a thickness of 5 mm using a surface grinder and a gliding center.

The density of this processed body was measured by the Archimedes method, and the relative density was 99.7%. Moreover, it was 0.003 ohm * cm when specific resistance was measured by 4 probe method.

Next, a part of this processed body was cut and ground into a powder by mortar grinding. As a result of analyzing this powder with an X-ray diffraction apparatus [X'Pert-PRO (manufactured by PANalytical)] using CuKα rays, diffraction of Zn ₂ SnO ₄ phase of spinel crystal structure and SnO ₂ phase of rutile crystal structure Only the peak was measured, the diffraction peaks of the other separate compound phases were not measured. The diffraction peak of the Zn ₂ SnO ₄ (311) plane was 34.39 °, and the diffraction peak position of the SnO ₂ (101) plane was 33.89 °, which confirmed that the diffraction peak position was appropriate.

The results are shown in Tables 1-1, 1-2, and 1-3.

Example 2
A Sn—Zn—O-based oxide sintered body according to Example 2 is prepared in the same manner as Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn to Zn is 0.1. Obtained. When powder X-ray diffraction analysis is carried out in the same manner as in Example 1, only diffraction peaks of wurtzite type ZnO phase and Zn ₂ SnO ₄ phase of spinel type crystal structure are measured, and diffraction peaks of other compound phases are It was not measured. The diffraction peak position of the ZnO (101) plane was 36.28 degrees, and the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.34 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 93.0%, and the specific resistance value was 0.57 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 3]
A Sn—Zn—O-based oxide sintered body according to Example 3 is obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn to Zn is 0.3. The When powder X-ray diffraction analysis is carried out in the same manner as in Example 1, only diffraction peaks of wurtzite type ZnO phase and Zn ₂ SnO ₄ phase of spinel type crystal structure are measured, and diffraction peaks of other compound phases are It was not measured. The diffraction peak position of the ZnO (101) plane was 36.26 degrees, and the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.41 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 94.2%, and the specific resistance value was 0.042 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

Example 4
A Sn—Zn—O-based oxide sintered body according to Example 4 is obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn to Zn is 0.7. The The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.36 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.87 degrees, which confirmed that the diffraction peak position was appropriate. Further, the relative density was 99.7%, and the specific resistance value was 0.006 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 5]
A Sn—Zn—O-based oxide sintered body according to Example 5 is obtained in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn to Zn is 0.9. The The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.40 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.90 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 92.7%, and the specific resistance value was 0.89 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 6]
The Sn—Zn—O-based oxide according to Example 6 is the same as Example 1, except that the atomic number ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X is prepared to be a ratio of 0.0001. An object sintered body was obtained. The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.33 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.87 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 98.5%, and the specific resistance value was 0.085 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 7]
A Sn—Zn—O-based oxide sintered body according to Example 7 was obtained in the same manner as Example 1, except that the oxygen concentration was 100 vol%. The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.42 °, and the diffraction peak position of the SnO ₂ (101) plane was 33.90 °, which confirmed that the diffraction peak position was appropriate. The relative density was 99.6%, and the specific resistance value was 0.013 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 8]
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 0.1, the holding time is 10 hours, and the oxygen concentration is 70% by volume. A Sn—Zn—O-based oxide sintered body according to Example 8 was obtained. The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.37 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.87 degrees, which confirmed that the diffraction peak position was appropriate. Further, the relative density was 94.6%, and the specific resistance value was 0.023 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 9]
The Sn according to Example 9 was prepared in the same manner as Example 1, except that the atomic number ratio Bi / (Sn + Zn + Bi + Ta) of the first additional element M was prepared to be 0.0001, and the sintering temperature was 1450 ° C. A -Zn-O-based oxide sintered body was obtained. The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.35 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.91 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 97.3%, and the specific resistance value was 0.08 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Example 10]
The Sn according to Example 10 was prepared in the same manner as Example 1, except that the atomic number ratio Bi / (Sn + Zn + Bi + Ta) of the first additional element M was prepared to be 0.04, and the sintering temperature was 1200 ° C. A -Zn-O-based oxide sintered body was obtained. The powder was subjected to X-ray diffraction analysis in the same manner as in Example 1. As a result, only the diffraction peaks of the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks were not measured. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.36 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.88 degrees, which confirmed that the diffraction peak position was appropriate. The relative density was 96.4%, and the specific resistance value was 0.11 Ω · cm. The results are shown in Tables 1-1, 1-2, and 1-3.

[Examples 11 to 17]
As the first additive element M, SiO ₂ powder (Example 11), TiO ₂ powder (Example 12), GeO ₂ powder (Example 13), In ₂ O ₃ powder (Example 14), CeO ₂ powder (implementation Example 15) Using Al ₂ O ₃ powder (Example 16) and Ga ₂ O ₃ powder (Example 17), the atomic number ratio M / (Sn + Zn + M + Ta) of the first additional element M is 0.04, and the second Same as Example 1 except that the same Ta ₂ O ₅ powder as Example 1 was used as the additional element X, and the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additional element X was prepared at a ratio of 0.1. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 11 to 17 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.32 degrees and 33.87 degrees, respectively. (Example 11), 34.36 degrees, 33.90 degrees (Example 12), 34.40 degrees, 33.86 degrees (Example 13), 34.32 degrees, 33.88 degrees (Example 14) , 34.34 degrees, 33.91 degrees (Example 15), 34.35 degrees, 33.86 degrees (Example 16), and 34.38 degrees, 33.91 degrees (Example 17), It was confirmed that this was the proper diffraction peak position. The results are shown in Table 2-1, Table 2-2 and Table 2-3.

Further, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example are 94.5%, 0.08 Ω · cm (Example 11), 95.1%, 0, respectively. .21 Ω · cm (Example 12), 97.0%, 0.011 Ω · cm (Example 13), 96.1%, 0.40 Ω · cm (Example 14), 94.8%, 0.013 Ω Cm (Example 15), 94.6%, 0.18 Ω · cm (Example 16), and 95.3%, 0.48 Ω · cm (Example 17). The results are shown in Table 2-1, Table 2-2 and Table 2-3.

[Examples 18 to 24]
As the first additive element M, SiO ₂ powder (Example 18), TiO ₂ powder (Example 19), GeO ₂ powder (Example 20), In ₂ O ₃ powder (Example 21), CeO ₂ powder (implementation example 22), Al ₂ O ₃ powder (example 23), Ga ₂ O ₃ using the powder (example 24), the atomic ratio of the first additive element M M / a (Sn + Zn + M + Ta ) and 0.0001, second Same as Example 1 except that the same Ta ₂ O ₅ powder as Example 1 was used as the additional element X, and the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additional element X was prepared at a ratio of 0.1. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 18 to 24 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.33 degrees and 33.89 degrees, respectively. (Example 18), 34.32 degrees, 33.90 degrees (Example 19), 34.41 degrees, 33.88 degrees (Example 20), 34.39 degrees, 33.87 degrees (Example 21) 34.42 degrees, 33.89 degrees (Example 22), 34.37 degrees, 33.89 degrees (Example 23), and 34.38 degrees, 33.88 degrees (Example 24), It was confirmed that this was the proper diffraction peak position. The results are shown in Table 2-1, Table 2-2 and Table 2-3.

Further, the relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example are 93.3%, 0.011 Ω · cm (Example 18), 96.1%, 0, respectively. .07 Ω · cm (Example 19), 95.0%, 0.021 Ω · cm (Example 20), 94.6%, 0.053 Ω · cm (Example 21), 96.1%, 0.08 Ω Cm (Example 22), 95.2%, 0.14 Ω · cm (Example 23), and 96.0%, 0.066 Ω · cm (Example 24). The results are shown in Table 2-1, Table 2-2 and Table 2-3.

[Examples 25 to 31]
As the first additive element M, SiO ₂ powder (Example 25), TiO ₂ powder (Example 26), GeO ₂ powder (Example 27), In ₂ O ₃ powder (Example 28), CeO ₂ powder (implementation example 29), Al ₂ O ₃ powder (example 30), Ga ₂ O ₃ using the powder (example 31), the atomic ratio of the first additive element M M / a (Sn + Zn + M + Ta ) was 0.04, the second Same as Example 1 except that the same Ta ₂ O ₅ powder as Example 1 was used as the additional element X, and the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additional element X was prepared at a ratio of 0.0001. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 25 to 31 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.32 degrees and 33.91 degrees, respectively. (Example 25), 34.37 degrees, 33.86 degrees (Example 26), 34.42 degrees, 33.91 degrees (Example 27), 34.34 degrees, 33.88 degrees (Example 28) , 34.40 degrees, 33.91 degrees (Example 29), 34.34 degrees, 33.86 degrees (Example 30), and 34.38 degrees, 33.90 degrees (Example 31), It was confirmed that this was the proper diffraction peak position. The results are shown in Table 2-1, Table 2-2 and Table 2-3.

The relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example are 97.6%, 0.092 Ω · cm (Example 25), 97.9%, 0%, respectively. .0082 Ω · cm (Example 26), 97.9%, 0.0033 Ω · cm (Example 27), 97.5%, 0.000032 Ω · cm (Example 28), 98.7%, 0.009 Ω Cm (Example 29), 97.0%, 0.0054 Ω · cm (Example 30), and 99.1%, 0.009 Ω · cm (Example 31). The results are shown in Table 2-1, Table 2-2 and Table 2-3.

[Examples 32 to 38]
As the first additive element M, SiO ₂ powder (Example 32), TiO ₂ powder (Example 33), GeO ₂ powder (Example 34), In ₂ O ₃ powder (Example 35), CeO ₂ powder (Implementation example 36), Al ₂ O ₃ powder (example 37), Ga ₂ O ₃ using the powder (example 38), the atomic ratio of the first additive element M M / a (Sn + Zn + M + Ta ) and 0.0001, second Same as Example 1 except that the same Ta ₂ O ₅ powder as Example 1 was used as the additional element X, and the atomic ratio Ta / (Sn + Zn + M + Ta) of the second additional element X was prepared at a ratio of 0.0001. Thus, Sn—Zn—O-based oxide sintered bodies according to Examples 32 to 38 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. The diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.36 ° and 33.91 °, respectively. (Example 32), 34.35 degrees, 33.87 degrees (Example 33), 34.42 degrees, 33.87 degrees (Example 34), 34.42 degrees, 33.86 degrees (Example 35) 34.41 degrees, 33.90 degrees (Example 36), 34.32 degrees, 33.87 degrees (Example 37), and 34.40 degrees, 33.88 degrees (Example 38), It was confirmed that this was the proper diffraction peak position. The results are shown in Table 2-1, Table 2-2 and Table 2-3.

Further, the relative density and specific resistance value of the Sn-Zn-O-based oxide sintered body according to each example are 98.0%, 0.013 Ω · cm (Example 32), 97.5%, 0%, respectively. .0021 Ω · cm (Example 33), 97.8%, 0.012 Ω · cm (Example 34), 97.9%, 0.027 Ω · cm (Example 35), 98.0%, 0.0053 Ω Cm (Example 36), 98.5%, 0.0066 Ω · cm (Example 37), 98.8%, 0.0084 Ω · cm (Example 38). The results are shown in Table 2-1, Table 2-2 and Table 2-3.

[Examples 39 to 41]
The same Bi ₂ O ₃ powder as in Example 1 is used as the first additive element M, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M is 0.04, and Nb ₂ O _{5 is used} as the second additive element X. Formula (Example 39), WO ₃ powder (Example 40), MoO ₃ powder (Example 41) were used to prepare the ratio of the atomic number ratio X / (Sn + Zn + Bi + X) of the second additional element X to 0.1. In the same manner as in Example 1 except for the above, Sn—Zn—O-based oxide sintered bodies according to Examples 39 to 41 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.40 degrees and 33.89 degrees, respectively. (Example 39) 34.35 degrees, 33.90 degrees (Example 40), and 34.39 degrees, 33.86 degrees (Example 41), confirming that the diffraction peak position is appropriate. It was done. The results are shown in Table 3-1, Table 3-2 and Table 3-3.

Further, the relative density and specific resistance value of the Sn-Zn-O-based oxide sintered body according to each example are 97.7%, 0.029 Ω · cm (Example 39), 95.9%, 0%, respectively. It was .069 Ω · cm (Example 40), and 96.9%, 0.19 Ω · cm (Example 41). The results are shown in Table 3-1, Table 3-2 and Table 3-3.

[Examples 42 to 44]
The same Bi ₂ O ₃ powder as in Example 1 is used as the first additive element M, the atomic number ratio Bi / (Sn + Zn + Bi + X) of the first additive element M is 0.0001, and Nb ₂ O _{5 is used} as the second additive element X. Formula (Example 42), WO ₃ powder (Example 43) and MoO ₃ powder (Example 44) were used to prepare the ratio of the atomic number ratio X / (Sn + Zn + Bi + X) of the second additional element X to 0.1. In the same manner as in Example 1 except for the above, Sn—Zn—O-based oxide sintered bodies according to Examples 42 to 44 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.32 degrees and 33.89 degrees, respectively. (Example 42) 34.34 degrees, 33.87 degrees (Example 43), and 34.39 degrees, 33.90 degrees (Example 44), confirming that the diffraction peak position is appropriate. It was done. The results are shown in Table 3-1, Table 3-2 and Table 3-3.

The relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example are 94.8%, 0.021 Ω · cm (Example 42), 96.6%, 0%, respectively. It was .0096 Ω · cm (Example 43), and 95.6%, 0.0092 Ω · cm (Example 44). The results are shown in Table 3-1, Table 3-2 and Table 3-3.

[Examples 45 to 47]
The same Bi ₂ O ₃ powder as in Example 1 is used as the first additive element M, the atomic ratio Bi / (Sn + Zn + Bi + X) of the first additive element M is 0.04, and Nb ₂ O _{5 is used} as the second additive element X. Formula (Example 45), WO ₃ powder (Example 46), and MoO ₃ powder (Example 47) were used to prepare an atomic ratio X / (Sn + Zn + Bi + X) of the second additional element X at a ratio of 0.0001 In the same manner as in Example 1 except for the above, Sn—Zn—O-based oxide sintered bodies according to Examples 45 to 47 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. In addition, the diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.36 degrees and 33.86 degrees, respectively. (Example 45), 34.42 degrees, 33.88 degrees (Example 46), and 34.34 degrees, 33.90 degrees (Example 47), confirming that the diffraction peak position is appropriate. It was done. The results are shown in Table 3-1, Table 3-2 and Table 3-3.

The relative density and specific resistance value of the Sn—Zn—O-based oxide sintered body according to each example are 98.1%, 0.022 Ω · cm (Example 45), 97.6%, 0, respectively. It was .0066 Ω · cm (Example 46), and 97.7%, 0.0077 Ω · cm (Example 47). The results are shown in Table 3-1, Table 3-2 and Table 3-3.

[Examples 48 to 50]
The same Bi ₂ O ₃ powder as in Example 1 is used as the first additive element M, the atomic number ratio Bi / (Sn + Zn + Bi + X) of the first additive element M is 0.0001, and Nb ₂ O _{5 is used} as the second additive element X. Formula (Example 48), WO ₃ powder (Example 49), MoO ₃ powder (Example 50) were used to prepare the ratio of the atomic number ratio X / (Sn + Zn + Bi + X) of the second additional element X to be 0.0001. In the same manner as in Example 1 except for the above, Sn—Zn—O-based oxide sintered bodies according to Examples 48 to 50 were obtained.

And as for X-ray diffraction analysis of the Sn-Zn-O type oxide sintered compact concerning each example, all are only the diffraction peaks of Zn ₂ SnO ₄ phase of spinel type crystal structure, and SnO ₂ phase of rutile type crystal structure. Was measured, and the diffraction peak of the other separate compound phase was not measured. The diffraction peak positions of the Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane of the Sn—Zn—O-based oxide sintered body according to each example are 34.35 degrees and 33.88 degrees, respectively. (Example 48), 34.41 degrees, 33.87 degrees (Example 49), and 34.33 degrees, 33.88 degrees (Example 50), and it is confirmed that the diffraction peak position is appropriate. It was done. The results are shown in Table 3-1, Table 3-2 and Table 3-3.

Further, the relative density and specific resistance value of the Sn-Zn-O-based oxide sintered body according to each example are 95.5%, 0.0099 Ω · cm (Example 48), 97.3%, 0%, respectively. It was .0074 Ω · cm (Example 49), and 97.4%, 0.009 Ω · cm (Example 50). The results are shown in Table 3-1, Table 3-2 and Table 3-3.

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

The Sn—Zn—O-based oxide sintered body according to Comparative Example 1 was subjected to X-ray diffraction analysis as in Example 1. As a result, diffraction of only the wurtzite type ZnO phase and the Zn ₂ SnO ₄ phase of the spinel type crystal structure The peak was measured and the diffraction peak of another compound phase was not measured, but the diffraction peak position of the ZnO (101) surface is 36.24 degrees, and the diffraction peak position of the Zn ₂ SnO ₄ (311) surface is 34.33. Degree, and the diffraction peak position on the ZnO (101) plane was out of the proper position. When the relative density and the specific resistance value were measured, the relative density was 88.0%, the specific resistance value was 500 Ω · cm, and the characteristic that the relative density was 90% or more and the specific resistance 1 Ω · cm or less could not be achieved. confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

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 atomic ratio Sn / (Sn + Zn) of Sn to Zn was 0.95. .

The Sn—Zn—O-based oxide sintered body according to Comparative Example 2 was subjected to X-ray diffraction analysis as in Example 1. As a result, Zn ₂ SnO ₄ phase of spinel type crystal structure and SnO ₂ phase of rutile type crystal structure Although the diffraction peak of only the compound phase was measured, and the diffraction peak of another compound phase was not measured, the diffraction peak position of the Zn ₂ SnO ₄ (311) plane is 34.33 degrees, and the diffraction peak position of the SnO ₂ (101) plane Was 33.92 degrees, and the diffraction peak position on the SnO ₂ (101) plane was out of the proper position. When the relative density and the specific resistance value were measured, the relative density was 86.0%, the specific resistance value was 700 Ω · cm, and the characteristic that the relative density was 90% or more and the specific resistance 1 Ω · cm or less could not be achieved. confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 3
At the time of sintering at 1400 ° C., a Sn—Zn—O-based oxide sintered body according to Comparative Example 3 was obtained in the same manner as Example 1, except that the oxygen concentration in the furnace was 68 vol%.

The X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 3 revealed that the diffraction peaks of only the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks of another compound phase were not measured, but the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.39 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.93 degrees. The diffraction peak position of the SnO ₂ (101) plane was out of the proper position. When the relative density and the specific resistance value were measured, the relative density was 87.3%, the specific resistance value was 53000 Ω · cm, and the characteristic that the relative density was 90% or more and the specific resistance 1 Ω · cm or less could not be achieved. confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 4
A Sn—Zn—O-based oxide sintered body according to Comparative Example 4 was obtained in the same manner as Example 1, except that the sintering temperature was 1170 ° C.

The X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 4 shows that the diffraction peaks of only the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure are measured. Although the diffraction peak of another compound phase was not measured, the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.29 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.88 degrees. The diffraction peak position of the Zn ₂ SnO ₄ (311) plane was out of the proper position. When the relative density and the specific resistance value are measured, the relative density is 82.2%, the specific resistance value is 61000 Ω · cm, and the characteristic that the relative density is 90% or more and the specific resistance 1 Ω · cm or less can not be achieved. confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 5
A Sn—Zn—O-based oxide sintered body according to Comparative Example 5 was obtained in the same manner as in Example 1 except that the sintering temperature was 1500 ° C.

The Sn-Zn-O-based oxide sintered body according to Comparative Example 5 was subjected to X-ray diffraction analysis, and the diffraction peaks of only the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure were measured. Diffraction peaks of another compound phase were not measured, but the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.34 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.95 degrees. The diffraction peak position of the SnO ₂ (101) plane was out of the proper position. In addition, when relative density and specific resistance value are measured, relative density is 88.6%, specific resistance value is 6 Ω · cm, and it can not achieve the characteristics of relative density 90% or more and specific resistance 1 Ω · cm or less confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 6
A Sn—Zn—O-based oxide sintered body according to Comparative Example 6 was obtained in the same manner as Example 1, except that the holding time of sintering at 1400 ° C. was 8 hours.

The X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 6 shows that the diffraction peaks of only the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure are measured. Diffraction peaks of other compound phases were not measured, but the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.33 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.83 degrees. The diffraction peak position of the SnO ₂ (101) plane was out of the proper position. When the relative density and the specific resistance value were measured, the relative density was 80.6%, the specific resistance value was 800000 Ω · cm, and the characteristic that the relative density was 90% or more and the specific resistance 1 Ω · cm or less could not be achieved. confirmed. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 7
Sn—Zn—O-based oxide sintering according to Comparative Example 7 in the same manner as in Example 1 except that the atomic number ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X is prepared in a proportion of 0.00009 I got a body.

The X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 7 shows that the diffraction peaks of only the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure are measured. Diffraction peaks of other compound phases were not measured, but the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.30 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.84 degrees. The Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane both deviated from the position of the proper diffraction peak. Moreover, when relative density and specific resistance value were measured, relative density was 98.3%, specific resistance value was 120 Ω · cm, and characteristics of relative density 90% or more could be achieved, but specific resistance 1 Ω · cm or less It has been confirmed that the characteristics of can not be achieved. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 8
Sn—Zn—O-based oxide sintering according to Comparative Example 8 in the same manner as in Example 1 except that the atomic number ratio Ta / (Sn + Zn + Bi + Ta) of the second additive element X was prepared in a ratio of 0.15. I got a body.

Then, was X-ray diffraction analysis of Sn-Zn-O type oxide-sintered body according to Comparative Example 8, the diffraction peak position of Zn ₂ SnO ₄ (311) plane is 34.37 °, SnO ₂ (101) plane The diffraction peak position of the crystal was 33.88 degrees, which is the position of the appropriate diffraction peak, but in addition to the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure, Ta ₂ O ₅ The diffraction peaks of the phase were measured. Moreover, when relative density and specific resistance value were measured, relative density was 94.4%, specific resistance value was 86 Ω · cm, and characteristics of relative density 90% or more could be achieved, but specific resistance 1 Ω · cm or less It has been confirmed that the characteristics of can not be achieved. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 9
Sn—Zn—O-based oxide sintering according to Comparative Example 9 in the same manner as in Example 1 except that the atomic number ratio Bi / (Sn + Zn + Bi + Ta) of the first additional element M is prepared in a proportion of 0.00009 I got a body.

According to X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 9, diffraction peaks of only Zn ₂ SnO ₄ phase of spinel type crystal structure and SnO ₂ phase of rutile type crystal structure are measured. Diffraction peaks of other compound phases were not measured, but the diffraction peak position of the Zn ₂ SnO ₄ (311) plane was 34.26 degrees, and the diffraction peak position of the SnO ₂ (101) plane was 33.85 degrees. The Zn ₂ SnO ₄ (311) plane and the SnO ₂ (101) plane both deviated from the position of the proper diffraction peak. When the relative density and the specific resistance value were measured, the relative density was 86.7%, the specific resistance value was 0.13 Ω · cm, and the characteristics with a specific resistance of 1 Ω · cm or less could be achieved, but the relative density 90 It was confirmed that the characteristics of more than% could not be achieved. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

Comparative Example 10
Sn-Zn-O-based oxide sintering according to Comparative Example 10 in the same manner as in Example 1 except that the atomic number ratio Bi / (Sn + Zn + Bi + Ta) of the first additional element M was prepared in a ratio of 0.05. I got a body.

Then, was X-ray diffraction analysis of Sn-Zn-O type oxide-sintered body according to Comparative Example 10, the diffraction peak position of Zn ₂ SnO ₄ (311) plane is 34.36 °, SnO ₂ (101) plane The diffraction peak position of is 33.89 degrees, which is the position of a proper diffraction peak, but it can not be identified in addition to Zn ₂ SnO ₄ phase of spinel crystal structure and SnO ₂ phase of rutile crystal structure. Diffraction peaks of the compound phase were measured. Moreover, when relative density and specific resistance value were measured, relative density was 97.2%, specific resistance value was 4700 Ω · cm, and characteristics of relative density 90% or more could be achieved, but specific resistance 1 Ω · cm or less It has been confirmed that the characteristics of can not be achieved. The results are shown in Table 4-1, Table 4-2 and Table 4-3.

The Sn—Zn—O-based oxide sintered body according to the present invention has characteristics such as high density and low resistance in addition to mechanical strength, so sputtering for forming a transparent electrode such as a solar cell or a touch panel It has industrial applicability to be used as a target.

Claims

In an Sn—Zn—O-based oxide sintered body containing Zn and Sn as main components,
Sn is contained at a ratio of 0.1 or more and 0.9 or less as an atomic ratio Sn / (Sn + Zn),
At least one selected from Si, Ti, Ge, In, Bi, Ce, Al, and Ga is used as a first additive element M, and at least one selected from Nb, Ta, W, and Mo is added as a second addition In the case of element X,
The first additive element M is contained at a ratio of 0.0001 or more and 0.04 or less as an atomic ratio M / (Sn + Zn + M + X) to a total amount of all the metal elements,
The second additive element X is contained at a ratio of 0.0001 or more and 0.1 or less as an atomic ratio X / (Sn + Zn + M + X) to the total amount of all the metal elements,
A Sn-Zn-O-based oxide sintered body characterized by having a relative density of 90% or more and a specific resistance of 1 Ω · cm or less.
The X-ray diffraction peak position of the (101) plane in the ZnO phase by X-ray diffraction using CuKα rays is 36.25 degrees to 36.31 degrees, and the X-ray diffraction peak of the (311) plane in the Zn 2 SnO 4 phase The Sn—Zn—O-based oxide sintered body according to claim 1, wherein the position is 34.32 degrees to 34.42 degrees.
The X-ray diffraction peak position of the (311) plane in the Zn 2 SnO 4 phase by the X-ray diffraction using CuKα ray is 34.32 degrees to 34.42 degrees, and the X-ray diffraction of the (101) plane in the SnO 2 phase The Sn—Zn—O-based oxide sintered body according to claim 1, wherein the peak position is 33.86 degrees to 33.91 degrees.
In the method for producing a Sn—Zn—O-based oxide sintered body according to any one of claims 1 to 3,
Oxide powder containing ZnO powder and SnO 2 powder, at least one first additive element M selected from Si, Ti, Ge, In, Bi, Ce, Al and Ga, Nb, Ta, W and Mo A powder obtained by mixing an oxide powder containing at least one selected second additive element X with pure water, an organic binder, and a dispersant, and drying and granulating a slurry to produce a granulated powder Grain powder production process,
A molded body manufacturing process for obtaining a molded body by pressure molding the granulated powder.
A sintered body manufacturing process for forming a sintered body by firing the above-mentioned molded body under the conditions of 1200 ° C. or more and 1450 ° C. or less and 10 hours or more and 30 hours or less in an atmosphere having an oxygen concentration of 70 vol% or more in a firing furnace.
A method for producing a Sn-Zn-O-based oxide sintered body, comprising: