KR20200006534A - Sn-Zn-O-based oxide sintered body and its manufacturing method - Google Patents

Abstract

The present invention provides a Sn-Zn-O-based oxide sintered body of high density and low resistance that can also be used for a barrier film, a protective film, and the like, and a method of manufacturing the same. Sn-Zn-O-based oxide sintered body having zinc (Zn) and tin (Sn) as components, and at least, containing germanium (Ge), tantalum (Ta), and gallium (Ga) as components, and containing a metal atom Sn / (Zn + Sn) is 0.1 or more and 0.3 or less, Ge / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less, Ta / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more 0.01 or less, Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less, specific resistance is 5 ohm * cm or more and 12000 ohm * cm or less, and relative density is 94% or more.

Description

Sn-Zn-O-based oxide sintered body and its manufacturing method

The present invention relates to a Sn-Zn-O-based oxide sintered body used as a sputtering target when a transparent conductive film applied to a solar cell, a liquid crystal display device, a touch panel, or the like by a sputtering method such as direct current sputtering or high frequency sputtering, and a method for producing the same. will be. This application claims priority based on Japanese Patent Application No. 2017-095982 for which it applied to Japan on May 12, 2017, and this application is integrated in this application by reference.

The transparent conductive film which has high electroconductivity and high transmittance | permeability in visible region is used for display elements, such as a solar cell, a liquid crystal display element, organic electroluminescence, and inorganic electroluminescence, an electrode for touch panels, etc. It is also used as various antifogging transparent heating elements, such as a heat ray reflecting film, an antistatic film, a frozen showcase, and a protective film for windows and a building.

As the transparent conductive film, tin oxide (SnO ₂ ) containing antimony or fluorine as dopant, zinc oxide (ZnO) containing aluminum or gallium as dopant, and indium oxide (In ₂ O ₃ ) containing tin as 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 called an indium tin oxide (ITO) film, and is widely used because a low resistance film is easily obtained. It is becoming.

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

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

As the non-indium materials, zinc oxide (ZnO) materials containing aluminum and gallium as dopants as described above, and tin oxide (SnO ₂ ) materials containing antimony or fluorine as dopants are known. In addition, although the transparent conductive film of the zinc oxide (ZnO) -based material is industrially produced by sputtering, it has disadvantages such as lack of chemical resistance (alkali resistance, acid resistance). On the other hand, the transparent conductive film of the tin oxide (SnO ₂ ) -based material is excellent in chemical resistance, but it is difficult to produce a high density and durable tin oxide-based sintered compact target, which makes it difficult to produce the transparent conductive film by sputtering. Had a flaw.

Then, as a material which improves these faults, the sintered compact which has zinc oxide and tin oxide as a main component is proposed. For example, Patent Literature 1 does not contain a crystal phase of tin oxide or a crystal phase of tin oxide in which zinc is dissolved, and is composed of a zinc oxide phase and a zinc stannate compound phase, or a zinc stannate compound phase. The Zn-Sn-O type oxide sintered compact comprised is described.

In addition, Patent Document 2 has an average grain size of 4.5 µm or less, and indicates the integrated strength of the (222) plane and the (400) plane on the Zn ₂ SnO ₄ phase by X-ray diffraction using CuKα rays _. , I ₍₄₀₀₎ , the sintered compact whose orientation degree represented by I ₍₂₂₂₎ / [I ₍₂₂₂₎ + I ₍₄₀₀₎ ] is 0.52 or more whose standard degree is larger than the standard (0.44) is described. In addition, Patent Literature 2 discloses a step of firing a molded product under conditions of 800 ° C to 1400 ° C in an atmosphere containing oxygen in the firing furnace as a method for producing a sintered compact having the above characteristics, and the highest firing. Also described is a method in which the inside of the kiln is cooled to an inert atmosphere such as Ar gas and cooled after the holding at the temperature is finished.

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-277075 Patent Document 2: Japanese Patent Application Laid-Open No. 2013-036073

However, in these methods, in the Sn-Zn-O-based oxide sintered body containing Zn and Sn as main components, the sintered body strength that withstands mechanical strength is obtained, but it is difficult to obtain sufficient density and conductivity, so that sputtering film formation on a mass production site ( The characteristics required for the formation were not satisfactory. That is, in the atmospheric pressure sintering method, the problem remains in the point of densification of a sintered compact and electroconductivity.

A Sn-Zn-O-based oxide sintered body containing Zn and Sn as a main component is a material that is difficult to have both characteristics such as high density and low resistance, and produces an oxide sintered body having high density and excellent conductivity even if the compounding ratio of Sn and Zn is changed. It is difficult to do. In the density of the sintered compact, there are some rises and decreases in density depending on the blending ratio. However, the conductivity exhibits a very high specific resistance value of 1 × 10 ⁶ Ω · cm or more, resulting in insufficient conductivity.

In the preparation of the Sn-Zn-O-based oxide sintered body containing Zn and Sn as main components, a compound called Zn ₂ SnO ₄ starts to form from around 1100 ° C, and volatilization of Zn begins after exceeding 1400 ° C. The volatilization of Zn becomes remarkable from around 1450 degreeC. In order to increase the density of the Sn-Zn-O-based oxide sintered compact, when the calcination is carried out at high temperature, volatilization of Zn proceeds, so that grain boundary diffusion and bonding of particles are weakened, and a high-density oxide sintered compact cannot be obtained.

With respect to conductivity, Zn ₂ SnO _4, ZnO, SnO ₂ is not able to even if since the lack of conductive material, to adjust the mixing ratio by adjusting the amount of a compound phase or ZnO, SnO _2, to improve the conductivity significantly.

Resistivity of a sintered body of ITO, which is conventionally used, and 2~3 × 10 ^-4 Ω · ㎝, by sputtering with the sinter as the target is preferably used as a transparent conductive film such as a liquid crystal or a solar cell. On the other hand, in recent years, as compared to ITO but poor conductivity, gas barrier film, can also be used for applications such as the protective film for protection from a barrier film or a scratch or impact, such as water vapor barrier film, and the specific resistance value of 10 Ω · ㎝~ × 10 ⁴ There is a request that it is desired to be about Ω · cm. Therefore, the Sn-Zn-O type oxide sintered compact suitable for these conditions is calculated | required.

Then, the subject of this invention is providing the high density, low resistance Sn-Zn-O type oxide sintered compact and its manufacturing method which can be used also for uses, such as a barrier film and a protective film.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this inventor included Sn in the ratio of 0.1 or more and 0.3 or less as atomic ratio Sn / (Sn + Zn), and added three types of Ge, Ta, and Ga as a predetermined element. By containing it in ratio, it discovered that the specific-resistance value suitable for the use of a barrier film, a protective film, etc. is 10 ohm * cm-x10 <^4> ohm * cm, and can obtain Sn-Zn-O type oxide sintered compact of high density, The present invention has been completed.

That is, one aspect of the present invention is a Sn-Zn-O-based oxide sintered body having zinc (Zn) and tin (Sn) as components, and, at least, germanium (Ge), tantalum (Ta), and gallium (Ga). ) As a component, and the metal atomic ratio is Sn / (Zn + Sn) of 0.1 or more and 0.3 or less, Ge / (Zn + Sn + Ge + Ta + Ga) of 0.0005 or more and 0.01 or less and Ta / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less, Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less, specific resistance is 5 Ω · cm or more and 12000 Ω · cm or less, and relative density is 94% That's it.

According to one aspect of the present invention, Sn / (Zn + Sn) is in a ratio of 0.1 to 0.3 or less, and three kinds of germanium (Ge), tantalum (Ta), and gallium (Ga) as additional elements. By using this, it can be used also for uses, such as a barrier film and a protective film, and it can be set as the Sn-Zn-O type oxide sintered compact of high density and low resistance.

At this time, in one aspect of the present invention, the ratio of metal atoms to Sn / (Zn + Sn) is 0.16 or more and 0.23 or less, the specific resistance is 5 Ω · cm or more and 110 Ω · cm or less, and the relative density is 98% or more. have.

Thus, by further limiting Sn / (Zn + Sn), a higher density and lower resistance Sn-Zn-O-based oxide sintered body can be realized.

In addition, in one aspect of the present invention, in the Sn-Zn-O-based oxide sintered body, the ZnO phase of the wurtzite crystal structure is 5 to 70% of the total (in the present specification, "to" refers to a lower limit or more and an upper limit or less). The same), or the Zn ₂ SnO ₄ phase of the spinel crystal structure may be comprised in the range of 30 to 95% of the total.

By setting it as a metal atomic ratio like one aspect of this invention, it becomes the Sn-Zn-O type oxide sintered compact comprised by the said crystal structure.

Moreover, another aspect of this invention is a manufacturing method of the Sn-Zn-O-type oxide sintered compact which has zinc (Zn) and tin (Sn) as a component, and contains zinc oxide powder, oxide powder of tin, and an additional element. The addition element which has the granulation process which mixes the oxide powder to produce granulated powder, the shaping | molding process which press-forms the said granulated powder, and obtains a molded object, and the baking process which calcinates the said molded object and obtains an oxide sintered compact, The said addition element Is at least germanium (Ge), tantalum (Ta), and gallium (Ga), and the metal atom ratio is Sn / (Zn + Sn) of 0.1 or more and 0.3 or less and Ge / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less, Ta / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less, and Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less, so that An oxide powder, an oxide powder of tin and an oxide powder containing the additive element are mixed.

According to another aspect of the present invention, Sn / (Zn + Sn) is in a ratio of 0.1 or more and 0.3 or less, and three kinds of germanium (Ge), tantalum (Ta), and gallium (Ga) as additional elements. By mixing at a predetermined ratio, the Sn-Zn-O-based oxide sintered compact of high density and low resistance can be produced.

At this time, in another aspect of the present invention, in the firing step, the temperature rising rate is set to 0.3 to 1.0 ° C / min in the atmosphere in the firing furnace in the air, and the temperature is raised to 1300 ° C or more and 1400 ° C or less, under conditions of 15 hours or more and 25 hours or less. It is preferable to fire the said molded object.

By firing the molded body under the above conditions, a denser Sn-Zn-O-based oxide sintered body of higher density can be produced.

ADVANTAGE OF THE INVENTION According to this invention, it can be used also for uses, such as a barrier film and a protective film, and it becomes possible to set it as the high density, low resistance Sn-Zn-O type oxide sintered compact.

BRIEF DESCRIPTION OF THE DRAWINGS It is process drawing which shows the outline of the process in the manufacturing method of the Sn-Zn-O type oxide sintered compact which concerns on one Embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the Sn-Zn-O type oxide sintered compact which concerns on this invention, and its manufacturing method are demonstrated in the following order, referring drawings. In addition, this invention is not limited to the following examples, It can change arbitrarily in the range which does not deviate from the summary of this invention.

1.Sn-Zn-O type oxide sintered body

2. Manufacturing method of Sn-Zn-O type oxide sintered body

  2-1. Assembly process

  2-2. Molding process

  2-3. Firing process

<1. Sn-Zn-O-based Oxide Sintered Body>

First, the Sn-Zn-O type oxide sintered compact of this invention is demonstrated. The Sn-Zn-O-based oxide sintered compact according to one embodiment of the present invention contains Sn in an amount of 0.1 or more and 0.3 or less as an atomic ratio Sn / (Sn + Zn), and includes Ge of the first additive element as a whole metal element. An atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) with respect to the total amount of is contained in a ratio of 0.0005 or more and 0.01 or less, and the second addition element Ta is an atomic ratio Ta / (to the total amount of all metal elements; Sn + Zn + Ge + Ta + Ga), and the ratio of 0.0005 or more and 0.01 or less, and the atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) with respect to the total amount of all metal elements of a 3rd additional element Ga It is contained in a ratio of 0.001 or more and 0.1 or less. The Sn-Zn-O-based oxide sintered compact according to one embodiment of the present invention has a specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less and a relative density of 94% or more.

Tin oxide and zinc oxide, which are the main raw materials of the Sn-Zn-O-based oxide sintered body according to one embodiment of the present invention, include a raw material powder containing only a zinc tin oxide compound or a mixed powder of tin oxide and zinc oxide. Is contained in an atomic ratio Sn / (Sn + Zn) at a ratio of 0.1 or more and 0.3 or less.

The content of Sn shows a difference in the crystal structure of the sintered body after sintering. When Sn is contained in the ratio of 0.1 or more and 0.3 or less as atomic ratio Sn / (Sn + Zn), the ZnO phase of a wurtzite crystal structure and the Zn ₂ SnO ₄ phase of a spinel crystal structure become main components. When contained in a ratio of more than 0.3 and 0.9 or less, the Zn ₂ SnO ₄ phase of the spinel crystal structure and the SnO ₂ phase of the rutile crystal structure are the main components. When the main component of the SnO ₂ phase of the rutile crystal structure increases, the resistance value increases. In addition, the transmittance is also lowered.

The atomic ratio Sn / (Sn + Zn) is more preferably 0.16 or more and 0.23 or less. If it is this range, it will become desired resistance value, and also it is 98% or more with respect to density, and it is more preferable.

When manufacturing the Sn-Zn-O-based oxide sintered body, as described above, upon sintering, Zn ₂ SnO ₄ compound starts to form from around 1100 ° C., and Zn volatilization starts after exceeding 1400 ° C., The volatilization of Zn becomes remarkable from around 1450 degreeC. In order to increase the density of the Sn-Zn-O-based oxide sintered compact, when the calcination is carried out at high temperature, volatilization of Zn proceeds, so that grain boundary diffusion and bonding of particles are weakened, and a high-density oxide sintered compact cannot be obtained. On the other hand, as for the conductive, Zn ₂ SnO _4, ZnO, SnO ₂ is not able to even if since the lack of conductive material, to adjust the mixing ratio by adjusting the amount of a compound phase or ZnO, SnO _2, to improve the conductivity significantly.

(Additional element)

Therefore, in this invention, in order to improve the said electroconductivity, 1st thru | or 3rd addition element is added. That is, Sn-Zn-O-based oxide sintered compact having high density and low resistance by adding germanium (Ge) as the first addition element, tantalum (Ta) as the second addition element, and gallium (Ga) as the third addition element. It becomes possible to obtain.

[First Additive Element]

The densification effect of an oxide sintered compact can be obtained by adding the first addition element Ge. The first additive element Ge promotes grain boundary diffusion, aids neck growth between the particles, strengthens the bonding between the particles, and contributes to densification. Here, the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) with respect to the total amount of all metal elements of the 1st addition element Ge is made into 0.0005 or more and 0.01 or less, The said atomic ratio Ge / (Sn + Zn + It is because the effect of densification does not appear when Ge + Ta + Ga) is less than 0.0005 (refer comparative example 10). Even when the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) exceeds 0.01, the effect of densification does not appear (see Comparative Example 9). This is because other compounds such as Zn ₂ Ge ₃ O ₈ are produced.

However, only by adding Ge of a 1st addition element, although the density of an oxide sintered compact improves, electroconductivity does not improve.

[Second additional element]

The Sn-Zn-O-based oxide sintered body to which the first additive element Ge is added under conditions containing Sn in an atomic ratio Sn / (Sn + Zn) at a ratio of 0.1 to 0.3, but the density is improved as described above. The problem remains in conductivity.

Thus, the second additional element Ta is added. By adding the second additional element Ta, the conductivity is improved while maintaining the high density of the oxide sintered body. On the other hand, the second additional element Ta is a pentavalent or higher element.

The amount to add requires that atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) with respect to the total amount of all the metal elements of 2nd addition element Ta shall be 0.0005 or more and 0.01 or less. When the atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) is less than 0.0005, the conductivity does not increase (see Comparative Example 12). On the other hand, when the atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) exceeds 0.01, other compound phases, such as Ta ₂ O ₅ and ZnTa ₂ O ₆ , form a compound phase, so that conductivity Worsen (see Comparative Example 11).

[Third additional element]

As described above, the conductivity is improved by the addition of the second additional element Ta. However, since Ta is dissolved and replaced with Sn and SnO ₂ in the Zn ₂ SnO ₄ phase, the resistance may not be able to obtain a desired conductivity.

Thus, the third additional element Ga is added. First by the addition of a third additional element Ga, an improvement in the conductivity of the Zn, Zn ₂ SnO ₄ of the Zn is expected.

The amount to add requires that atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) with respect to the total amount of all the metal elements of 3rd addition element Ga shall be 0.001 or more and 0.1 or less. When the atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) is less than 0.001, the conductivity does not increase (see Comparative Example 14). On the other hand, when the atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) exceeds 0.1, another compound phase, for example, a compound phase such as Ga ₂ O ₃ , is produced, thereby deteriorating conductivity (comparatively). See Example 13).

On the other hand, it can be used for applications such as a barrier film and a protective film, which is a feature of the Sn-Zn-O-based oxide sintered body according to one embodiment of the present invention, and has a high density (relative density of 94% or more) and low resistance (resistance of 5). Additional elements may be further included as long as it does not impair the properties of Ω · cm or more and 12000 Ω · cm or less). As an additional addition element, Si, Ti, Bi, Ce, Al, Nb, W, Mo etc. are mentioned, for example.

(X-ray diffraction peak)

In the Sn-Zn-O-based oxide sintered body according to one embodiment of the present invention, when the atomic ratio Sn / (Sn + Zn) is 0.1 or more and 0.3 or less, the ZnO phase of the wurtzite crystal structure and the Zn of the spinel crystal structure _{The 2} SnO ₄ phase is a main component, and an appropriate amount of the first addition element Ge, the second addition element Ta, and the third addition element Ga are Zn in the ZnO phase, Zn in the Zn ₂ SnO ₄ phase, or Sn, SnO ₂ phase Since it is substituted with Sn in solid solution, the compound phase other than the ZnO phase of a wurtzite crystal structure and the Zn ₂ SnO ₄ phase of a spinel type crystal structure is not formed.

(Resistance)

The specific resistance of Sn-Zn-O type oxide sintered compact which concerns on one Embodiment of this invention is 5 ohm * cm or more and 12000 ohm * cm or less. As described above, the resistivity of the oxide sintered body of Sn—Zn—O is a very high resistivity value of 1 × 10 ⁶ Ω · cm or more. In this invention, specific resistance value is reduced by mix | blending Ge, Ta, and Ga as 1st-3rd addition element.

Resistivity of a sintered body of ITO, which is conventionally used, and 2~3 × 10 ^-4 Ω · ㎝, by sputtering with the sinter as the target is preferably used as a transparent conductive film such as a liquid crystal or a solar cell. The transparent conductive film obtained by sputtering using the Sn-Zn-O type | system | group oxide sintered compact which concerns on one Embodiment of this invention has a specific resistance of about 10 ohm * cm-1 * 10 <^4> ohm * cm, and electroconductivity compared with ITO Although it is inferior, it can be used also for uses, such as a barrier film, such as a gas barrier film and a water vapor barrier film, and a protective film which protects from a wound and an impact. Sn-Zn-O oxide sintered compact which concerns on one Embodiment of this invention is a specific resistance suitable for the sputtering of the film of about 10 ohm * cm-about ¹ * 10 <^4> ohm * cm.

The specific resistance value of the film of sputtering is also influenced by the film formation conditions at the time of sputtering, especially the oxygen concentration at the time of sputtering. However, in consideration of productivity during sputtering, film uniformity, and the like, it is preferable to match the resistivity of the film with the resistivity of the crystal.

In addition, since a specific resistance value depends on the film-forming speed | rate at the time of sputtering, it is more preferable that a specific resistance value is small. Since the specific resistance of the Sn-Zn-O type oxide sintered compact which concerns on one Embodiment of this invention is 5 ohm * cm or more and 12000 ohm * cm or less, it becomes an oxide sintered compact suitable for sputtering. When the specific resistance is less than 5 Ω · cm, the resistance value of the obtained film is lowered, so that leakage from an adjacent electrode is a problem. In addition, when the specific resistance exceeds 12000 Ω · cm, it becomes difficult to discharge, which is a problem because film formation cannot be performed stably with respect to direct current sputtering.

In addition, in one embodiment of the present invention, the resistivity value can be in the range of 5 Ω · cm or more and 110 Ω · cm or less by setting the ratio of metal atoms to Sn / (Zn + Sn) of 0.16 or more and 0.23 or less. (See Examples 1, 8, 9). When the specific resistance value is 5 Ω · cm or more and 110 Ω · cm or less, the deposition rate is improved, which is more preferable.

(Relative density)

The relative density of the Sn-Zn-O type oxide sintered compact which concerns on one Embodiment of this invention is 94% or more. As shown in Patent Literature 1, in the oxide sintered body of Sn-Zn-O compounded in an atomic ratio Sn / (Sn + Zn) at a ratio of 0.23 or more and 0.5 or less, the relative density is relative by volatilization of Zn during sintering. Dense crystals could not be obtained. In this invention, relative density can be improved by mix | blending predetermined amount with the above-mentioned addition element.

On the other hand, by making metal atomic ratio Sn / (Zn + Sn) into 0.16 or more and 0.23 or less, the said relative density can be improved to 98% or more. When the relative density is 98% or more, the target strength is improved, the film formation rate at the time of sputtering is improved, and the out gas due to the target is reduced, which enables stable film formation.

<2. Manufacturing Method of Sn-Zn-O Oxide Sintered Body>

Next, the manufacturing method of the Sn-Zn-O type oxide sintered compact of this invention is demonstrated. One embodiment of the present invention is a method for producing a Sn-Zn-O-based oxide sintered body having zinc (Zn) and tin (Sn) as components, comprising zinc oxide powder, oxide powder of tin, and an additive element. A granulation step S1 for mixing granulated powder to produce granulated powder, a molding step S2 for press molding the granulated powder to obtain a molded article, and a firing step S3 for firing the molded article to obtain an oxide sintered body. For example, the Sn-Zn-O-based oxide sintered body according to one embodiment of the present invention is a germanium oxide of a first additive element in a raw material powder containing only a zinc tin oxide compound or a mixed powder of tin oxide and zinc oxide, Tantalum oxide of the second additional element and gallium oxide of the third additional element are blended in a predetermined ratio, granulated, and the granulated powder is molded by a cold constant pressure press or the like, and the molded body is fired in a firing furnace to obtain a sintered body. Hereinafter, each process is demonstrated individually.

(2-1.Assembling Process)

First, in the assembling step S1, a main raw material is prepared. The tin oxide and zinc oxide which are the main raw materials are a raw material powder containing only a zinc oxide compound or a mixed powder of tin oxide and zinc oxide, and the ratio of Sn is 0.1 to 0.3 or less as the atomic ratio Sn / (Sn + Zn). It is contained as. It is preferable to use a mixture of tin oxide and zinc oxide because the main raw material can easily adjust the blending ratio. For example, the raw material powder, and a SnO ₂ powder and ZnO powder. Further, oxides containing the first to third additional elements are prepared, added to the main raw material, and combined. For example, GeO ₂ powder as the first addition element Ge, Ta ₂ O ₅ powder as the second addition element Ta, and Ga ₂ O ₃ powder as the third addition element Ga are prepared, added to the main raw material, and combined.

In the assembling step S1, the metal atomic ratio is Sn / (Zn + Sn) of 0.1 or more and 0.3 or less, Ge / (Zn + Sn + Ge + Ta + Ga) of 0.0005 or more and 0.01 or less and Ta / (Zn + Sn + Ge An oxide powder containing zinc oxide powder, tin oxide powder, and additive elements so that + Ta + Ga) is 0.0005 or more and 0.01 or less and Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less. Mix. Thus, the ratio is such that Sn / (Zn + Sn) is 0.1 or more and 0.3 or less, and as mentioned above, three kinds of germanium (Ge), tantalum (Ta), and gallium (Ga) are added as additional elements. By mixing in a predetermined ratio, it can be used also for uses, such as a barrier film and a protective film, and can manufacture Sn-Zn-O type oxide sintered compact of high density and low resistance.

Next, the combined raw material powder is mixed with pure water or ultrapure water, an organic binder, a dispersant, and an antifoamer in a mixing tank so that the raw material powder concentration becomes a predetermined concentration. Then, the wet powder is wet-pulverized using a bead mill or the like into which hard ZrO ₂ balls are added, followed by mixing and stirring to obtain a slurry. A granulated powder can be obtained by spraying and drying the obtained slurry with a spray dryer apparatus or the like.

(2-2. Molding process)

Molding process S2 is a process of press-molding the granulated powder obtained by granulation process S1, and obtaining a molded object. In shaping | molding process S2, in order to remove the space | gap between the particle | grains of granulated powder, press molding is performed by the pressure of about 294 Mpa (3.0 ton / cm <2>), for example. Although it does not specifically limit about the method of pressure shaping | molding, For example, it is preferable to use the cold isostatic press (CIP: Cold Isostatic Press) which can fill the rubber frame with the granulated powder obtained by granulation process S1, and can apply a high pressure.

(2-3.Sintering process)

Firing process S3 is a process of baking the molded object obtained by said shaping | molding process S2 on predetermined temperature and predetermined | prescribed time conditions at the predetermined temperature increase rate in a kiln, and obtaining a sintered compact. Firing process S3 is performed in the atmosphere in the kiln in air | atmosphere, for example. In the manufacturing method of Sn-Zn-O-type oxide sintered compact which concerns on one Embodiment of this invention, these baking conditions also have characteristics, and it demonstrates in detail below.

[Raising rate]

It is preferable that the temperature increase rate from 700 degreeC in a sintering furnace to predetermined | prescribed sintering temperature bakes a molded object at the speed | rate of 0.3-1.0 degreeC / min. This is because the diffusion of ZnO, SnO ₂ or Zn ₂ SnO ₄ compounds is promoted, and the sinterability is improved and the conductivity is improved. Further, by using this type the rate of temperature rise, the high-temperature region, it has an effect of suppressing the volatilization of the ZnO and Zn ₂ SnO _4.

On the other hand, in the production method of the Sn-Zn-O type oxide sintered body of the embodiment of the present invention, SnO _2, but also when present in the (relatively low-temperature region) of the sintering, Sn / (Zn + Sn) of 0.1 it is also not more than 0.3, when the specified temperature of the sintering is completed, SnO ₂ phase is lost, and no diffraction peak in the SnO ₂ in the X-ray diffraction analysis are not measured.

When the temperature increase rate in a sintering furnace is less than 0.3 degree-C / min, the diffusion of a compound will decline. In addition, when exceeding 1.0 degree-C / min, since a temperature increase rate is high, compound formation becomes incomplete and a compact sintered compact cannot be manufactured (refer comparative example 3, 4).

[Sintering temperature]

It is preferable to make sintering temperature 1300 degreeC or more and 1400 degrees C or less. When the sintering temperature is less than 1300 ° C. (see Comparative Example 5), the temperature is too low, and the grain boundary diffusion of the sintering in the ZnO, SnO ₂ , and Zn ₂ SnO ₄ compounds does not proceed. On the other hand, even when it exceeds 1400 degreeC (refer comparative example 6), although grain boundary diffusion is accelerated | stimulated and sintering advances, volatilization of a Zn component cannot be suppressed and it will leave a big void inside a sintered compact.

[Holding time]

The holding time is preferably 15 hours or more and less than 25 hours. If less than 15 hours, since sintering is incomplete, it becomes a sintered compact with large distortion and curvature, and grain boundary diffusion does not progress and sintering does not advance. As a result, a dense sintered body cannot be produced (see Comparative Example 7). On the other hand, when exceeding 25 hours, the volatilization of the ZnO and Zn ₂ SnO ₄ becomes large, results in deterioration of one of the low work efficiency of the density, and high cost (see Comparative Example 8).

Since Sn-Zn-O type oxide sintered compact which concerns on one Embodiment of this invention which has Zn and Sn obtained as such a main component is improved in electroconductivity, film formation by DC sputtering becomes possible. In addition, since no special manufacturing method is used, it is possible to apply to a cylindrical target.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited to a following example at all.

(Example 1)

In Example 1, as the SnO ₂ powder, the ZnO powder, the GeO ₂ powder as the first additional element Ge, the Ta ₂ O ₅ powder as the second additional element Ta, and the Ga ₂ O ₃ powder as the third additional element Ga Was prepared.

Next, the SnO ₂ powder and the ZnO powder are combined so that the atomic ratio Sn / (Sn + Zn) of Sn and Zn is 0.2, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga of the first additional element Ge is added. ) Is 0.004, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.002, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga GeO ₂ powder, Ta ₂ O ₅ powder, and Ga ₂ O ₃ powder were combined so as to be 0.02.

And the combined raw material powder, pure water or ultrapure water, an organic binder, a dispersing agent, and an antifoamer were mixed in the mixing tank so that raw material powder concentration might be 55-65 mass%. Next, after wet grinding is performed using a bead mill apparatus (manufactured by Ashizawa Fine Tech Co., Ltd., LMZ type) into which hard ZrO ₂ balls are added, until the average particle diameter of the raw material powder is 1 μm or less, The mixture was stirred for 10 hours or more to obtain a slurry. In addition, the laser diffraction type particle size distribution measuring apparatus (The Shimadzu Corporation make, SALD-2200) was used for the measurement of the average particle diameter of raw material powder.

The resulting slurry was sprayed and dried with a spray dryer device (manufactured by Okawara Kakouki Co., Ltd., ODL-20 type) to obtain a granulated powder.

Next, the obtained granulated powder was filled into a rubber mold, and molded by applying a pressure of 294 MPa (3 ton / cm 2) by a cold hydrostatic press, and the obtained molded article having a diameter of about 250 mm was put into an atmospheric pressure firing furnace and sintered up to 700 ° C. Air was introduced into the furnace. After confirming that the temperature in the calcination furnace became 700 ° C, oxygen was introduced, the temperature was raised to 1350 ° C, and further maintained at 1350 ° C for 20 hours. The temperature increase rate at this time was 0.7 degreeC / min.

After the holding time had ended, oxygen introduction 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 have a diameter of 200 mm and a thickness of 5 mm using a planar grinding mill and a grinding center.

The relative density was 99.0% when the density of this workpiece was measured by the Archimedes method. Moreover, it was 5.5 ohm * cm when the specific resistance was measured by the four probe method.

In addition, a part of this processed body was cut | disconnected and it was set as the powder by trigger grinding. The powder was analyzed by an X-ray diffractometer [X 'Pert-PRO (manufactured by PANalytical)] using CuKα rays to find that the Zn ₂ SnO ₄ phase of the spinel crystal structure was 66%, and that the wurtzite crystal structure The ZnO phase was diffracted at 34% of the total and no diffraction peaks on other compound phases were measured. These results are shown in Table 1.

(Example 2)

In Example 2, the Sn-Zn-O-based oxide sintered body according to Example 2 was prepared in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) between Sn and Zn was 0.1. Got it. As in Example 1, X-ray diffraction analysis of the powder showed that the wurtzite ZnO phase was diffracted at 70% and the spinel crystal structure at 30% at Zn ₂ SnO ₄ . Diffraction peaks on other compounds were not measured. The relative density was 96.0% and the specific resistance value was 1780 Ω · cm. These results are shown in Table 1.

(Example 3)

In Example 3, the Sn-Zn-O-based oxide sintered body according to Example 3 was prepared in the same manner as in Example 1 except that the atomic ratio Sn / (Sn + Zn) of Sn and Zn was combined at 0.3. Got it. As in Example 1, X-ray diffraction analysis of the powder revealed that the wurtzite ZnO phase was 5%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure was diffracted at 95%. Diffraction peaks on other compounds were not measured. The relative density was 95.5% and the specific resistance value was 7100 Ω · cm. These results are shown in Table 1.

(Example 4)

In Example 4, the atomic ratio Sn / (Sn + Zn) of Sn and Zn is combined at a ratio of 0.1, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge is 0.0005, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.0005, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.001 A Sn-Zn-O-based oxide sintered body according to Example 4 was obtained in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined. In the same manner as in Example 2, the wurtzite ZnO phase was diffracted by 70%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 30%. Diffraction peaks on other compounds were not measured. Moreover, the relative density was 95.0% and the specific resistance value was 5300 ohm * cm. These results are shown in Table 1.

(Example 5)

In Example 5, the combination of Sn and Zn in an atomic ratio of Sn / (Sn + Zn) is 0.1, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge is 0.01, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.01, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.1; Sn-Zn-O-based oxide sintered body according to Example 5 was obtained in the same manner as in Example 1 except that the GeO ₂ powder, Ta ₂ O ₅ powder, and Ga ₂ O ₃ powder were combined. In the same manner as in Example 2, the wurtzite ZnO phase was diffracted by 70%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 30%. Diffraction peaks on other compounds were not measured. The relative density was 96.0% and the specific resistance value was 980 Ω · cm. These results are shown in Table 1.

(Example 6)

In Example 6, the atomic ratio Sn / (Sn + Zn) of Sn and Zn was combined at a ratio of 0.3, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge was 0.0005, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.0005, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.001 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 GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined. As in Example 3, the wurtzite ZnO phase was diffracted by 5%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 95%. Diffraction peaks on other compounds were not measured. The relative density was 94.7% and the specific resistance value was 10000 Ω · cm. These results are shown in Table 1.

(Example 7)

In Example 7, the combination of Sn and Zn in an atomic ratio Sn / (Sn + Zn) of 0.3 was obtained, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge was 0.01, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.01, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.1; Sn-Zn-O-based oxide sintered body according to Example 7 was obtained in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined. As in Example 3, the wurtzite ZnO phase was diffracted by 5%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 95%. Diffraction peaks on other compounds were not measured. Moreover, the relative density was 95.0% and the specific resistance value was 9500 ohm * cm. These results are shown in Table 1.

(Example 8)

In Example 8, it carried out similarly to Example 1 except having combined the atomic ratio Sn / (Sn + Zn) of Sn and Zn into 0.16, and setting the sintering holding temperature to 1300 degreeC. A Sn-Zn-O based oxide sintered body was obtained. As in Example 1, X-ray diffraction analysis of the powder showed that the Zn ₂ SnO ₄ phase of the spinel crystal structure was diffracted at 54%, and the ZnO phase of the wurtzite crystal structure was diffracted at 46% of the total. Diffraction peaks on the compound were not measured. The relative density was 98.0% and the specific resistance value was 60 Ω · cm. These results are shown in Table 1.

(Example 9)

In Example 9, it carried out similarly to Example 1 except having combined with the ratio of Sn and Zn in atomic ratio Sn / (Sn + Zn) to 0.23, and setting sintering holding temperature to 1400 degreeC. A Sn-Zn-O based oxide sintered body was obtained. As in Example 1, X-ray diffraction analysis of the powder shows that the Zn ₂ SnO ₄ phase of the spinel crystal structure is diffracted at 74%, and the ZnO phase of the wurtzite crystal structure is diffracted at 26% of the total. Diffraction peaks on the compound were not measured. The relative density was 98.5% and the specific resistance value was 105 Ω · cm. These results are shown in Table 1.

(Example 10)

In Example 10, the atomic ratio Sn / (Sn + Zn) of Sn and Zn combined at a ratio of 0.3, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge are 0.0005, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.0005, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.001 Sn-Zn-O according to Example 10 in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined, and the sintering holding time was 15 hours. A system oxide sintered body was obtained. As in Example 6, the wurtzite ZnO phase was diffracted by 5% and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 95%. Diffraction peaks on other compounds were not measured. Moreover, the relative density was 94.0% and the specific resistance value was 12000 ohm * cm. These results are shown in Table 1.

(Example 11)

In Example 11, the atomic ratio Sn / (Sn + Zn) of Sn and Zn was combined at a ratio of 0.3, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge was 0.01, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.01, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.1; Sn-Zn-O according to Example 11 was carried out in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined to obtain a sintering holding time of 25 hours. A system oxide sintered body was obtained. As in Example 3, the wurtzite ZnO phase was diffracted by 5%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 95%. Diffraction peaks on other compounds were not measured. The relative density was 95.5% and the specific resistance value was 10500 Ω · cm. These results are shown in Table 1.

(Example 12)

In Example 12, the atomic ratio Sn / (Sn + Zn) of Sn and Zn was combined at a ratio of 0.1, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge was 0.01, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.01, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.1; Sn-Zn according to Example 12 was prepared in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined, and the temperature increase rate was 0.3 ° C / min. A -O oxide sintered body was obtained. In the same manner as in Example 2, the wurtzite ZnO phase was diffracted by 70%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 30%. Diffraction peaks on other compounds were not measured. The relative density was 95.0% and the specific resistance value was 1320 Ω · cm. These results are shown in Table 1.

(Example 13)

In Example 13, the atomic ratio Sn / (Sn + Zn) of Sn and Zn was combined at a ratio of 0.1, and the atomic ratio Ge / (Sn + Zn + Ge + Ta + Ga) of the first additional element Ge was 0.0005, atomic ratio Ta / (Sn + Zn + Ge + Ta + Ga) of the second additional element Ta is 0.0005, and atomic ratio Ga / (Sn + Zn + Ge + Ta + Ga) of the third additional element Ga is 0.001 Sn-Zn according to Example 13 was prepared in the same manner as in Example 1 except that the GeO ₂ powder, the Ta ₂ O ₅ powder, and the Ga ₂ O ₃ powder were combined, and the temperature increase rate was 1.0 ° C / min. A -O oxide sintered body was obtained. In the same manner as in Example 2, the wurtzite ZnO phase was diffracted by 70%, and the Zn ₂ SnO ₄ phase of the spinel crystal structure by 30%. Diffraction peaks on other compounds were not measured. The relative density was 94.5%, and the specific resistance value was 6800 Ω · cm. These results are shown in Table 1.

(Comparative Example 1)

In Comparative Example 1, a 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 set to 0.05. . X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 1 showed that 90% of a wurtzite-type ZnO phase and 10% of a Zn ₂ SnO ₄ phase having a spinel crystal structure were found as in X-ray diffraction analysis. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring the relative density and specific resistance value, the relative density was 93.0% and the specific resistance value was 3510 ohm * cm. That is, it was confirmed that the relative density could not achieve 94% or more, and the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less. The results are shown in Table 2.

(Comparative Example 2)

In Comparative Example 2, a 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 and Zn was combined at a ratio of 0.40. . X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 2 showed that, in the same manner as in Example 1, the wurtzite-type ZnO phase was 0%, the rutile SnO ₂ phase was 14%, and the spinel crystal structure. Zn ₂ SnO ₄ phase of was diffracted at 86%. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring the relative density and specific resistance, the relative density was 89.0% and the specific resistance was 597000 ohm * cm. That is, it was confirmed that the relative density is 94% or more, and the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less cannot be achieved. The results are shown in Table 2.

(Comparative Example 3)

In 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 temperature raising rate was 0.2 ° C / min. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered compact according to Comparative Example 3 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 90.0% and the specific resistance value was 15000 ohm * cm. That is, it was confirmed that the relative density of 94% or more and the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less cannot be achieved. The results are shown in Table 2.

(Comparative Example 4)

In Comparative Example 4, a Sn-Zn-O-based oxide sintered body according to Comparative Example 4 was obtained in the same manner as in Example 1 except that the temperature raising rate was 1.2 ° C / min. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered compact according to Comparative Example 4 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 92.0% and the specific resistance value was 12500 ohm * cm. That is, it was confirmed that it is 94% or more of relative density, and cannot achieve a specific resistance of 5 ohm * cm or more and 12000 ohm * cm or less. The results are shown in Table 2.

(Comparative Example 5)

In 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 set to 1280 ° C. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 5 showed that the wurtzite-type ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring the relative density and specific resistance value, the relative density was 91.0% and the specific resistance value was 14000 ohm * cm. That is, it was confirmed that it is 94% or more of relative density, and cannot achieve a specific resistance of 5 ohm * cm or more and 12000 ohm * cm or less. The results are shown in Table 2.

(Comparative Example 6)

In 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 temperature was 1430 ° C. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 6 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 93.0% and the specific resistance value was 12500 ohm * cm. That is, it was confirmed that it is 94% or more of relative density, and cannot achieve a specific resistance of 5 ohm * cm or more and 12000 ohm * cm or less. The results are shown in Table 2.

(Comparative Example 7)

In Comparative Example 7, a Sn-Zn-O-based oxide sintered body according to Comparative Example 7 was obtained in the same manner as in Example 1 except that the holding time of the sintering at 1350 ° C. was 10 hours. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 7 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 90.0% and the specific resistance value was 13500 ohm * cm. That is, it was confirmed that it is 94% or more of relative density, and cannot achieve a specific resistance of 5 ohm * cm or more and 12000 ohm * cm or less. The results are shown in Table 2.

(Comparative Example 8)

In Comparative Example 8, a Sn-Zn-O-based oxide sintered body according to Comparative Example 8 was obtained in the same manner as in Example 1 except that the holding time of the sintering at 1350 ° C. was 30 hours. X-ray diffraction analysis of the Sn-Zn-O based oxide sintered body according to Comparative Example 8 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure, as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Further, in the volatile relative density of the results of measuring the relative density and the specific resistance value, ZnO and Zn ₂ SnO ₄ was 93.0%, the specific resistance values 13000 Ω · ㎝. That is, it was confirmed that it is 94% or more of relative density, and cannot achieve a specific resistance of 5 ohm * cm or more and 12000 ohm * cm or less. The results are shown in Table 2.

(Comparative Example 9)

In Comparative Example 9, a Sn-Zn-O-based oxide sintered body according to Comparative Example 9 was prepared in the same manner as in Example 1 except for combining Ge / (Sn + Zn + Ge + Ta + Ga) at a ratio of 0.03. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 9 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure, as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring the relative density and specific resistance value, the relative density was 93.0% and the specific resistance value was 8500 ohm * cm. That is, it was confirmed that 94% or more of relative density could not be achieved. The results are shown in Table 2.

(Comparative Example 10)

In Comparative Example 10, a Sn-Zn-O-based oxide sintered body according to Comparative Example 10 was prepared in the same manner as in Example 1 except for combining Ge / (Sn + Zn + Ge + Ta + Ga) at a ratio of 0.0001. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 10 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 91.0% and the specific resistance value was 9800 ohm * cm. That is, it was confirmed that 94% or more of relative density could not be achieved. The results are shown in Table 2.

(Comparative Example 11)

In Comparative Example 11, a Sn-Zn-O-based oxide sintered body according to Comparative Example 11 was prepared in the same manner as in Example 1 except that Ta / (Sn + Zn + Ge + Ta + Ga) was combined at a ratio of 0.03. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 11 showed that the wurtzite-type ZnO phase was 34% and the Zn ₂ SnO ₄ phase of the spinel crystal structure was 66% as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 97.0% and the specific resistance value was 16000 ohm * cm. That is, it was confirmed that the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less could not be achieved. The results are shown in Table 2.

(Comparative Example 12)

In Comparative Example 12, the Sn-Zn-O-based oxide sintered body according to Comparative Example 12 was prepared in the same manner as in Example 1 except that Ta / (Sn + Zn + Ge + Ta + Ga) was combined at a ratio of 0.0001. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 12 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 96.7% and the specific resistance value was 25000 ohm * cm. That is, it was confirmed that the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less could not be achieved. The results are shown in Table 2.

(Comparative Example 13)

In Comparative Example 13, the Sn-Zn-O-based oxide sintered body according to Comparative Example 13 was prepared in the same manner as in Example 1 except that Ga / (Sn + Zn + Ge + Ta + Ga) was combined at a ratio of 0.2. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 13 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 97.3% and the specific resistance value was 14800 ohm * cm. That is, it was confirmed that the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less could not be achieved. The results are shown in Table 2.

(Comparative Example 14)

In Comparative Example 14, a Sn-Zn-O-based oxide sintered body according to Comparative Example 14 was prepared in the same manner as in Example 1 except that Ga / (Sn + Zn + Ge + Ta + Ga) was combined at a ratio of 0.0008. Got it. X-ray diffraction analysis of the Sn-Zn-O-based oxide sintered body according to Comparative Example 14 showed that the wurtzite ZnO phase was 34% and the Zn ₂ SnO ₄ phase was 66% in the spinel crystal structure as in Example 1. Diffraction. Diffraction peaks on other compounds were not measured. Moreover, as a result of measuring a relative density and a specific resistance value, the relative density was 97.0% and the specific resistance value was 22000 ohm * cm. That is, it was confirmed that the specific resistance of 5 Ω · cm or more and 12000 Ω · cm or less could not be achieved. The results are shown in Table 2.

On the other hand, while one embodiment and each example of the present invention has been described in detail as described above, it can be easily understood by those skilled in the art that many modifications are possible without departing substantially from the novelty and effects of the present invention. will be. Therefore, all such modifications shall fall within the scope of the present invention.

For example, in a specification or drawing, the term described with the other term of a broader or more synonymous at least once may be substituted with the other term in any place of a specification or drawing. In addition, the structure of Sn-Zn-O type oxide sintered compact and its manufacturing method is not limited to what was demonstrated by one Embodiment of this invention and each Example, and various deformation | transformation is possible.

Claims (6)

As a Sn-Zn-O-based oxide sintered body having zinc (Zn) and tin (Sn) as components,
At least, further containing germanium (Ge), tantalum (Ta), and gallium (Ga) as components,
Metal atomic ratio,
Sn / (Zn + Sn) is 0.1 or more and 0.3 or less,
Ge / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less,
Ta / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less,
Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less
The Sn-Zn-O type oxide sintered compact whose specific resistance is 5 ohm * cm or more and 12000 ohm * cm or less and a relative density is 94% or more. 2. The metal atom ratio of claim 1, wherein Sn / (Zn + Sn) is 0.16 or more and 0.23 or less,
The said resistivity is 5 ohm * cm or more and 110 ohm * cm or less, and said relative density is 98% or more, The Sn-Zn-O-type oxide sintered compact characterized by the above-mentioned. The said Sn-Zn-O type oxide sintered compact of Claim 1,
A Sn-Zn-O type oxide sintered compact in which the ZnO phase of the wurtzite crystal structure is 5 to 70% of the total, or the Zn ₂ SnO ₄ phase of the spinel crystal structure is 30 to 95% of the total. The said Sn-Zn-O type oxide sintered compact of Claim 2,
A Sn-Zn-O type oxide sintered compact in which the ZnO phase of the wurtzite crystal structure is 5 to 70% of the total, or the Zn ₂ SnO ₄ phase of the spinel crystal structure is 30 to 95% of the total. As a manufacturing method of the Sn-Zn-O type oxide sintered compact which has zinc (Zn) and tin (Sn) as a component,
A granulation step of producing a granulated powder by mixing an oxide powder of zinc, an oxide powder of tin, and an oxide powder containing an additive element;
A molding step of press molding the granulated powder to obtain a molded article;
It has a baking process of baking the said molded object and obtaining an oxide sintered compact,
The addition element is at least germanium (Ge), tantalum (Ta), and gallium (Ga),
Metal atomic ratio,
Sn / (Zn + Sn) is 0.1 or more and 0.3 or less,
Ge / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less,
Ta / (Zn + Sn + Ge + Ta + Ga) is 0.0005 or more and 0.01 or less,
Ga / (Zn + Sn + Ge + Ta + Ga) is 0.001 or more and 0.1 or less
The oxide powder of zinc, the oxide powder of tin, and the oxide powder containing the said additive element are mixed so that Sn-Zn-O-type oxide sintered compact may be used. The said firing process WHEREIN: The said baking process WHEREIN: It raises to 1300 degreeC or more and 1400 degrees C or less in the atmosphere inside a kiln in air | atmosphere with the temperature increase rate 0.3-1.0 degreeC / min, The said conditions on 15 hours or more and less than 25 hours. A method for producing a Sn-Zn-O-based oxide sintered body, wherein the molded body is fired.

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