TW201731799A - Sn-Zn-O-based oxide sintered body and method for producing same - Google Patents

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

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TW201731799A
TW201731799A TW105141143A TW105141143A TW201731799A TW 201731799 A TW201731799 A TW 201731799A TW 105141143 A TW105141143 A TW 105141143A TW 105141143 A TW105141143 A TW 105141143A TW 201731799 A TW201731799 A TW 201731799A
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based oxide
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TWI748971B (en
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安東勳雄
小澤誠
五十嵐茂
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住友金屬鑛山股份有限公司
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Abstract

To provide: a Sn-Zn-O-based oxide sintered body with a high Sn concentration that is used as a sputtering target, and has mechanical strength and properties of high density and low resistance; and a method for producing the Sn-Zn-O based oxide sintered body. This Sn-Zn-O-based oxide sintered body with a high Sn concentration is characterized by including 0.75 to 0.9 of Sn in the Sn/(Zn+Sn) atomic ratio, by including 0.001 to 0.1 of at least one type of additional element (X) selected from Nb, Ta, W, and Mo in the X/(Sn+Zn+X) atomic ratio, which is relative to the total amount of Sn, Zn, and the additional element (X), and in having a relative density of 95% or more and a specific resistance of 1 [Omega].cm or less. The Sn-Zn-O-based oxide sintered body with a high Sn concentration is also characterized by being produced by being fired under conditions where a heating rate from 700 DEG C to a sintering temperature is 0.4 DEG C/min to 0.8 DEG C/min in an atmosphere of oxygen concentration in a furnace of 70 volume% or higher, the sintering temperature is 1300 DEG C to 1460 DEG C, and the firing time is 10 to 30 hours.

Description

Sn-Zn-O系氧化物燒結體及其製造方法 Sn-Zn-O based oxide sintered body and method for producing same

本發明係關於一種在以直流濺鍍、射頻濺鍍等濺鍍法製造應用於太陽能電池、液晶表面元件、觸控面板等的透明導電膜時作為濺鍍靶材使用之Sn-Zn-O系氧化物燒結體，尤其是關於一種可抑制燒結體之加工中的破損、及濺鍍成膜中之濺鍍靶材的破損或裂痕的產生等之Sn-Zn-O系氧化物燒結體及其製造方法。 The present invention relates to a Sn-Zn-O system used as a sputtering target when a transparent conductive film applied to a solar cell, a liquid crystal surface element, a touch panel or the like is manufactured by a sputtering method such as direct current sputtering or radio frequency sputtering. An oxide sintered body, in particular, a Sn-Zn-O-based oxide sintered body capable of suppressing breakage during processing of a sintered body and occurrence of breakage or cracking of a sputtering target in sputter deposition, and the like Production method.

具有高導電性與在可見光區域之高穿透率的透明導電膜係利用於太陽能電池、液晶顯示元件、有機電致發光及無機電致發光等的表面元件、或觸控面板用電極等，此外亦利用作為汽車車窗或建築用的熱射線反射膜、抗靜電膜、冷凍展示櫃等的各種的防霧用透明發熱體。 A transparent conductive film having high conductivity and high transmittance in a visible light region is used for surface elements such as solar cells, liquid crystal display elements, organic electroluminescence, and inorganic electroluminescence, or electrodes for touch panels, and the like. Various anti-fog transparent heat generating bodies such as a heat ray reflection film, an antistatic film, and a refrigerating display case for automobile windows or buildings are also used.

就透明導電膜而言，已知有包含銻或氟作為摻雜物之氧化錫(SnO2)、包含鋁或鎵作為摻雜物之氧化鋅(ZnO)、及包含錫作為摻雜物之氧化銦(In2O3)等。尤其，包含錫作為摻雜物之氧化銦(In2O3)膜，亦即In-Sn-O系膜係稱為ITO(銦錫氧化物(Indium tin oxide))膜，由於可容易獲得低電阻的膜而被廣泛使用。 As the transparent conductive film, tin oxide (SnO 2 ) containing germanium or fluorine as a dopant, zinc oxide (ZnO) containing aluminum or gallium as a dopant, and oxidation containing tin as a dopant are known. Indium (In 2 O 3 ) or the like. In particular, an indium oxide (In 2 O 3 ) film containing tin as a dopant, that is, an In-Sn-O film, is called an ITO (Indium Tin Oxide) film, which is easily available because it can be easily obtained. A film of a resistor is widely used.

就上述透明導電膜之製造方法而言，常使用直流濺鍍、射頻濺鍍等濺鍍法。濺鍍法係在需要低蒸氣壓之材料的成膜或精密的膜厚控制時有效的手法，由於操作極為簡便，而於工業上廣泛利用。 In the method for producing the above transparent conductive film, sputtering such as DC sputtering or RF sputtering is often used. The sputtering method is effective in film formation or precise film thickness control of a material requiring a low vapor pressure, and is widely used industrially because of its extremely simple operation.

該濺鍍法係使用濺鍍靶材作為薄膜的原料。濺鍍靶材為包含構成欲成膜之薄膜的金屬元素之固體，係使用金屬、金屬氧化物、金屬氮化物、金屬碳化物等的燒結體、或視情況使用單晶。在濺鍍法中，通常使用在其內部具有變成可配置基板與濺鍍靶材的真空室之裝置，配置基板與濺鍍靶材後，使真空室成為高真空，其後導入氬氣等的稀有氣體，將真空室內設成約10Pa以下的氣壓。然後，以基板為陽極，以濺鍍靶材為陰極，在兩者之間引起輝光放電而使氬電漿產生，使電漿中的氬陽離子對陰極之濺鍍靶材碰撞，藉此使被彈飛的靶材之成分粒子堆積於基板上而形成膜。 This sputtering method uses a sputtering target as a raw material of a film. The sputtering target is a solid containing a metal element constituting a film to be formed into a film, and a sintered body of a metal, a metal oxide, a metal nitride, a metal carbide or the like, or a single crystal is used as the case may be. In the sputtering method, a device having a vacuum chamber which becomes a configurable substrate and a sputtering target is usually used, and after the substrate and the sputtering target are placed, the vacuum chamber is made to have a high vacuum, and then argon gas or the like is introduced. For a rare gas, the vacuum chamber is set to a pressure of about 10 Pa or less. Then, using the substrate as the anode and the sputtering target as the cathode, a glow discharge is caused between the two to generate argon plasma, and the argon cation in the plasma collides with the sputtering target of the cathode, thereby The constituent particles of the target of the flying fly are deposited on the substrate to form a film.

而且，為了製造上述透明導電膜，以往廣泛使用ITO等之氧化銦系的材料。然而，由於銦金屬在地球上為稀少金屬且具有毒性，因此對環境及人體有造成不良影響之虞，而要求非銦系的材料。 Further, in order to produce the above transparent conductive film, an indium oxide-based material such as ITO has been widely used. However, since indium metal is a rare metal on the earth and is toxic, it has a bad influence on the environment and the human body, and requires a non-indium material.

就上述非銦系的材料而言，已知有如上所述的包含鋁或鎵作為摻雜物之氧化鋅(ZnO)系材料、及包含銻或氟作為摻雜物之氧化錫(SnO2)系材料。而且，上述氧化鋅(ZnO)系材料的透明導電膜雖在工業上以濺鍍法製造，但有缺乏耐化學性(耐鹼性、耐酸性)等的缺點。另一方面，氧化錫(SnO2)系材料的透明導電膜雖耐化學 性優良，但不易製造高密度且具耐久性的氧化錫系燒結體靶材，因此有以濺鍍法製造上述透明導電膜會伴有困難之缺點。 As the non-indium-based material, a zinc oxide (ZnO)-based material containing aluminum or gallium as a dopant, and tin oxide (SnO 2 ) containing germanium or fluorine as a dopant are known. Department of materials. Further, although the transparent conductive film of the above zinc oxide (ZnO)-based material is industrially produced by a sputtering method, 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 body target. Therefore, the transparent conductive material is produced by sputtering. The film will be accompanied by the disadvantages of difficulty.

因此，作為改善此等缺點之材料，有提案一種以氧化鋅與氧化錫為主成分的燒結體。例如，專利文獻1中記載一種燒結體，其包含SnO2相與Zn2SnO4相，且該Zn2SnO4相的平均結晶粒徑為1~10μm之範圍。 Therefore, as a material for improving these disadvantages, a sintered body mainly composed of zinc oxide and tin oxide has been proposed. For example, Patent Document 1 describes a sintered body comprising a SnO 2 phase and a Zn 2 SnO 4 phase, and an average crystal grain size of the Zn 2 SnO 4 phase is in the range of 1 to 10 μm.

又，專利文獻2中記載一種燒結體，其平均結晶粒徑為4.5μm以下，且將基於使用CuKα線之X光繞射之Zn2SnO4相中之(222)面、(400)面的積分強度設為I(222)、I(400)時，以I(222)/[I(222)+I(400)]表示之配向度為大於標準(0.44)的0.52以上。再者，專利文獻2中，作為製造具備上述特性的燒結體之方法，亦記載一種以下述步驟構成該燒結體製造步驟的方法：在燒製爐內包含氧的氣體環境中以800℃~1400℃的條件將成形體進行燒製之步驟、及保持在最高燒製溫度結束後使燒製爐內成為Ar氣等的惰性氣體環境而予以冷卻之步驟。 Further, Patent Document 2 describes a sintered body having an average crystal grain size of 4.5 μm or less and having (222) planes and (400) planes in a Zn 2 SnO 4 phase which is diffracted by X-rays using CuKα lines. When the integral intensity is set to I (222) or I (400) , the degree of alignment expressed by I (222) / [I (222) + I (400) ] is 0.52 or more larger than the standard (0.44). Further, in Patent Document 2, as a method of producing a sintered body having the above-described characteristics, a method of constituting the sintered body production step in a gas atmosphere containing oxygen in a firing furnace at 800 ° C to 1400 is also described. The condition of °C is a step of firing the formed body and maintaining the inert gas atmosphere such as Ar gas in the firing furnace after the completion of the maximum firing temperature.

然而，專利文獻1~2記載之方法作為製造以Zn為主成分之Zn-Sn-O系氧化物燒結體之方法為有效，但是作為製造由於耐化學性高而需求多之以Sn為主成分之Sn-Zn-O系氧化物燒結體、尤其為原子數比Sn/(Zn+Sn)為0.75以上0.9以下之高Sn濃度的Sn-Zn-O系氧化物燒結體之方法難謂有效。的確，藉由採用專利文獻1~2之方法，雖然可獲得可耐受機械強度的燒結體強度，但難以獲得充分的密度及導電性，就在量產現場 之濺鍍成膜所需之特性而言無法令人滿足。亦即，在常壓燒結法中，達到燒結體的高密度化及導電性方面尚留有課題。 However, the method described in Patent Documents 1 to 2 is effective as a method of producing a Zn-Sn-O-based oxide sintered body containing Zn as a main component, but Sn is mainly used as a component because of high chemical resistance. The Sn-Zn-O-based oxide sintered body, in particular, a sintered Sn-Zn-O-based oxide sintered body having an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less is difficult to be effective. Indeed, by using the methods of Patent Documents 1 to 2, although the strength of the sintered body which can withstand mechanical strength can be obtained, it is difficult to obtain sufficient density and conductivity, and it is at the mass production site. The properties required for sputter deposition are not satisfactory. In other words, in the normal pressure sintering method, there is still a problem in achieving high density and conductivity of the sintered body.

先前技術文獻Prior technical literature 專利文獻Patent literature

專利文獻1 日本特開2010-037161號公報(參照請求項1、13~14) Patent Document 1 Japanese Laid-Open Patent Publication No. 2010-037161 (refer to claims 1 and 13 to 14)

專利文獻2 日本特開2013-036073號公報(參照請求項1、3) Japanese Patent Laid-Open Publication No. 2013-036073 (see claims 1 and 3)

發明之概要Summary of invention

本發明係著眼於此種要求而完成者，以提供Sn-Zn-O系氧化物燒結體及其製造方法作為課題，該Sn-Zn-O系氧化物燒結體係以Sn為主成分，且除了具機械強度以外，亦具高密度且低電阻。 The present invention has been made in view of such a demand, and provides a sintered body of a Sn-Zn-O-based oxide and a method for producing the same, and the Sn-Zn-O-based oxide sintering system contains Sn as a main component, and In addition to mechanical strength, it also has high density and low resistance.

如上所述以Sn為主成分之Sn-Zn-O系氧化物燒結體、尤其為原子數比Sn/(Zn+Sn)為0.75以上0.9以下之高Sn濃度的Sn-Zn-O系氧化物燒結體，係不易具備高密度且低電阻之兩特性的材料。 The Sn-Zn-O-based oxide sintered body containing Sn as a main component as described above, in particular, a Sn-Zn-O-based oxide having a high Sn concentration of 0.75 or more and an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less. A sintered body is a material which is difficult to provide both high density and low electrical resistance.

作為其主要原因，可舉出Sn-Zn-O系氧化物燒結體的主成分之Sn的燒結性差之點，並可舉出在Sn-Zn-O系氧化物燒結體中，於1000℃左右所生成之所謂Zn2SnO4之化合物與Sn皆容易揮發之點。其理由在 於：雖然通常提高燒製溫度對於燒結材料的高密度化為有效的，但是因Zn2SnO4相與Sn的揮發性而無法提高燒製溫度。另外，專利文獻1之方法中，於900℃~1100℃之溫度下進行燒製而製造煆燒粉末，使用所得之煆燒粉末，於1300℃~1600℃之溫度下進行正式燒製，藉此製造高密度的Sn-Zn-O系氧化物燒結體。 The reason for this is that the Sn of the main component of the Sn—Zn—O-based oxide sintered body is inferior in sinterability, and it is about 1000° C. in the Sn—Zn—O-based oxide sintered body. The so-called Zn 2 SnO 4 compound and Sn which are formed are easily volatilized. The reason for this is that although the firing temperature is generally increased to increase the density of the sintered material, the firing temperature cannot be increased due to the volatility of the Zn 2 SnO 4 phase and Sn. Further, in the method of Patent Document 1, the calcined powder is produced by firing at a temperature of from 900 ° C to 1100 ° C, and the calcined powder obtained is used to be fired at a temperature of from 1300 ° C to 1600 ° C. A high-density sintered body of Sn-Zn-O-based oxide is produced.

然而，即使在專利文獻1之方法中亦無法完全抑制Sn及Zn等的揮發，而難以得到高的密度。又，由於在超過1500℃之高溫進行燒製，晶粒會變大，對於燒結體強度尚存不安。再者，關於導電性亦顯示高達1×106Ω‧cm以上的比電阻值，而缺乏導電性。 However, even in the method of Patent Document 1, volatilization of Sn, Zn, or the like cannot be completely suppressed, and it is difficult to obtain a high density. Further, since the firing is performed at a high temperature exceeding 1500 ° C, the crystal grains become large, and the strength of the sintered body is still uncomfortable. Further, the conductivity also shows a specific resistance value of up to 1 × 10 6 Ω ‧ cm or more, and lacks conductivity.

因此，本發明之課題在於以Sn為主成分之Sn-Zn-O系氧化物燒結體、尤其為原子數比Sn/(Zn+Sn)為0.75以上0.9以下之高Sn濃度的Sn-Zn-O系氧化物燒結體作為前提，藉由在該氧化物燒結體製造時施用適當的燒製步驟並且添加有效的添加物，而提供量產性優異之高密度且低電阻的Sn-Zn-O系氧化物燒結體。 Therefore, the subject of the present invention is a sintered Sn-Zn-O-based oxide containing Sn as a main component, in particular, a Sn-Zn having a high Sn concentration of 0.75 or more and an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less. On the premise of the O-based oxide sintered body, a high-density and low-resistance Sn-Zn-O excellent in mass productivity is provided by applying an appropriate firing step at the time of production of the oxide sintered body and adding an effective additive. It is an oxide sintered body.

為了解決上述課題，本發明人等針對原子數比Sn/(Zn+Sn)為0.75以上0.9以下之高Sn濃度的Sn-Zn-O系氧化物燒結體，探索兼具其密度(相對密度95%以上)與導電性(比電阻1Ω‧cm以下)之製造條件，並且進行昇溫過程(燒製過程)與添加物之研討。 In order to solve the problem, the present inventors have searched for a Sn-Zn-O-based oxide sintered body having a high Sn concentration of an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less, and has a density (relative density of 95). % or more) and the manufacturing conditions of electrical conductivity (specific resistance 1 Ω ‧ cm or less), and the temperature rising process (firing process) and additives were investigated.

其結果，可知：即使為以原子數比Sn/(Sn+Zn)為0.75以上0.9以下的比例之條件所製造之高Sn濃度 的Sn-Zn-O系氧化物燒結體，藉由適當地設定昇溫過程(燒製過程)，亦可謀求氧化物燒結體的緻密化。具體而言，確認：在燒製爐內的氧濃度為70體積%以上的氣體環境下，以將去黏結劑(debinder)以後的昇溫過程，亦即，將700℃至燒結溫度為止的昇溫速度設定為0.4℃/min以上0.8℃/min以下、且將燒結溫度設定為1300℃以上1460℃以下、並且10小時以上30小時以內之條件進行燒製，藉此可製造經緻密化的Sn-Zn-O系氧化物燒結體。 As a result, it is understood that the high Sn concentration is produced under the condition that the atomic ratio Sn/(Sn+Zn) is 0.75 or more and 0.9 or less. The Sn-Zn-O-based oxide sintered body can be densified by an appropriate temperature setting process (firing process). Specifically, it was confirmed that in the gas atmosphere in which the oxygen concentration in the firing furnace is 70% by volume or more, the temperature rising process after the debonding agent is performed, that is, the temperature rising rate from 700 ° C to the sintering temperature It is set to 0.4 ° C / min or more and 0.8 ° C / min or less, and the sintering temperature is set to 1300 ° C or more and 1460 ° C or less, and firing is performed for 10 hours or more and 30 hours or less, whereby the densified Sn-Zn can be produced. -O-based oxide sintered body.

再者，確認：在上述製造條件下，藉由將選自Nb、Ta、W、Mo的至少1種作為添加元素(X)而加入，可製造在維持高密度下導電性亦優異的Sn-Zn-O系氧化物燒結體。 In addition, it is confirmed that by adding at least one selected from the group consisting of Nb, Ta, W, and Mo as the additive element (X) under the above-described production conditions, it is possible to produce Sn-which is excellent in conductivity while maintaining high density. Zn-O based oxide sintered body.

另外，亦確認：在伴隨添加元素(X)的增量而有氧化物燒結體的密度降低之傾向之情形，藉由將選自Si、Ge、Ce、In、Bi、Ga的至少1種作為添加元素(M)而追加，可抑制上述密度降低傾向，並且，可藉由添加元素(M)的添加而更提高相對密度。 In addition, it is also confirmed that at least one selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga is used as the density of the oxide sintered body tends to decrease with an increase in the additive element (X). Addition of the element (M) is added to suppress the above-described tendency to decrease in density, and the relative density can be further increased by the addition of the additive element (M).

本發明係根據這樣的技術上的分析與發現所完成者。 The present invention has been accomplished in accordance with such technical analysis and findings.

亦即，本發明之第1發明係以Sn為主成分的Sn-Zn-O系氧化物燒結體，其特徵為：以原子數比Sn/(Zn+Sn)為0.75以上0.9以下的比例含有Sn，且以相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下的比例含有選自Nb、Ta、W、Mo的至少1種添加元素(X)，並且 其相對密度為95%以上且比電阻為1Ω‧cm以下；第2發明係如第1發明所記載的Sn-Zn-O系氧化物燒結體，其特徵為：以相對於Sn、Zn與添加元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下的比例含有選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)，且氧化物燒結體的相對密度為98%以上。 In the first aspect of the invention, the Sn-Zn-O-based oxide sintered body containing Sn as a main component is characterized in that the atomic ratio Sn/(Zn+Sn) is 0.75 or more and 0.9 or less. Sn is at least a ratio selected from Nb, Ta, W, and Mo in a ratio of an atomic ratio X/(Sn+Zn+X) of the total amount of Sn, Zn, and the additive element (X) of 0.001 or more and 0.1 or less. 1 addition element (X), and The Sn-Zn-O-based oxide sintered body according to the first aspect of the present invention is characterized in that the relative density is 95% or more and the specific resistance is 1 Ω ‧ cm or less. The ratio of the atomic ratio of the total amount of the element (M) to M/(Sn+Zn+M) is 0.0001 or more and 0.04 or less, and at least one additive element (M) selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga is contained. And the relative density of the oxide sintered body is 98% or more.

接著，本發明之第3發明係以Sn為主成分的Sn-Zn-O系氧化物燒結體之製造方法，其特徵為具備：造粒粉末製造步驟，其係將以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末，與純水、有機黏結劑、分散劑混合，將所得之漿液進行乾燥且造粒，而製造造粒粉末；成形體製造步驟，其係將上述造粒粉末進行加壓成形而得到成形體；及燒結體製造步驟，其係在燒製爐內的氧濃度為70體積%以上的氣體環境下，以700℃至燒結溫度為止的昇溫速度為0.4℃/min以上0.8℃/min以下、且燒結溫度為1300℃以上1460℃以下、10小時以上30小時以內的條件，將上述成形體進行燒製，而製造燒結體； 又，第4發明係如第3發明所記載的Sn-Zn-O系氧化物燒結體之製造方法，其特徵為：除了以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末以外，進一步添加以選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)所構成且以使相對於Sn、Zn與添加元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下之方式所摻合的添加元素(M)的氧化物粉末。 According to a third aspect of the invention, there is provided a method for producing a sintered Sn-Zn-O-based oxide containing Sn as a main component, comprising the step of producing a granulated powder, which is such that an atomic ratio Sn/ (Zn+Sn) is a tin oxide (SnO 2 ) powder and a zinc oxide (ZnO) powder blended in a manner of 0.75 or more and 0.9 or less, and at least one element (X) selected from the group consisting of Nb, Ta, W, and Mo Oxidation of the additive element (X) blended so as to be 0.001 or more and 0.1 or less with respect to the atomic ratio X/(Sn+Zn+X) of the total amount of Sn, Zn and the additive element (X) The powder is mixed with pure water, an organic binder, a dispersing agent, and the obtained slurry is dried and granulated to produce a granulated powder; and the shaped body is produced by subjecting the granulated powder to press forming to obtain a shaped powder And a sintered body production step in which the temperature increase rate from 700 ° C to the sintering temperature is 0.4 ° C / min or more and 0.8 ° C / min or less in a gas atmosphere in which the oxygen concentration in the firing furnace is 70% by volume or more. The sintered body is fired under the conditions of a sintering temperature of 1300 ° C or more and 1460 ° C or less for 10 hours or more and 30 hours or less. The method of producing a sintered body of a Sn-Zn-O-based oxide according to the third aspect of the invention, characterized in that the atomic ratio Sn/(Zn+Sn) is a tin oxide (SnO 2 ) powder and a zinc oxide (ZnO) powder blended in a form of 0.75 or more and 0.9 or less, and at least one element (X) selected from the group consisting of Nb, Ta, W, and Mo, and Further, in addition to the oxide powder of the additive element (X) blended in such a manner that the atomic ratio X/(Sn+Zn+X) of the total amount of the additive element (X) is 0.001 or more and 0.1 or less, An atomic ratio M/(Sn) composed of at least one additive element (M) selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga so as to be relative to the total amount of Sn, Zn, and the additive element (M) +Zn+M) is an oxide powder of the additive element (M) blended in a form of 0.0001 or more and 0.04 or less.

在本發明中，藉由具備以原子數比Sn/(Sn+Zn)為0.75以上0.9以下的比例含有Sn之條件、與將選自Nb、Ta、W、Mo的至少1種作為添加元素(X)而添加之條件，可藉由常壓燒結法獲得量產性優異之高密度且低電阻的Sn-Zn-O系氧化物燒結體。 In the present invention, a condition in which Sn is contained in a ratio of an atomic ratio of Sn/(Sn+Zn) of 0.75 or more and 0.9 or less, and at least one selected from the group consisting of Nb, Ta, W, and Mo are added as an additive element ( The conditions of addition of X) can obtain a high-density and low-resistance Sn-Zn-O-based oxide sintered body excellent in mass productivity by a normal pressure sintering method.

用以實施發明之形態Form for implementing the invention

以下，詳細說明本發明之實施形態。 Hereinafter, embodiments of the present invention will be described in detail.

首先，調製包含以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末 與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末之原料粉末，且使將該粉末進行造粒而製造之造粒粉末進行成形而得到成形體，並且在燒製爐內的氧濃度為70體積%以上的氣體環境下，以700℃至燒結溫度為止的昇溫速度為0.4℃/min以上0.8℃/min以下、且燒結溫度為1300℃以上1460℃以下、10小時以上30小時以內的條件，將上述成形體進行燒製，藉此可製造相對密度為95%以上且比電阻為1Ω‧cm以下之高Sn濃度的Sn-Zn-O系氧化物燒結體。 First, a tin oxide (SnO 2 ) powder and a zinc oxide (ZnO) powder blended so as to have an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less, and a selected from Nb, Ta, and the like are prepared. At least one element (X) of W and Mo is formed so that the atomic ratio X/(Sn+Zn+X) with respect to the total amount of Sn, Zn, and the additive element (X) is 0.001 or more and 0.1 or less. The raw material powder of the oxide powder of the additive element (X) to be blended, and the granulated powder produced by granulating the powder is molded to obtain a shaped body, and the oxygen concentration in the firing furnace is 70 vol. In a gas atmosphere of at least 100%, the temperature increase rate from 700 ° C to the sintering temperature is 0.4 ° C / min or more and 0.8 ° C / min or less, and the sintering temperature is 1300 ° C or higher and 1460 ° C or lower, and the temperature is within 10 hours and 30 hours. The molded body is fired, whereby a sintered Sn-Zn-O-based oxide having a high density of 95% or more and a specific electric resistance of 1 Ω‧cm or less can be produced.

又，為了維持高密度化的效果且更提高上述效果，亦可連同添加元素(X)一起加入添加元素(M)。亦即，調製除了以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末以外亦包含以選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)所構成且以使相對於Sn、Zn與添加元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下之方式所摻合的添加元素(M)的氧化物粉末之原料粉末，且使將該粉末進行造粒而製造之造粒粉末進行成形而得到成形體，並且在 燒製爐內的氧濃度為70體積%以上的氣體環境下，以700℃至燒結溫度為止的昇溫速度為0.4℃/min以上0.8℃/min以下、且燒結溫度為1300℃以上1460℃以下、10小時以上30小時以內的條件，將上述成形體進行燒製，藉此可製造相對密度為98%以上且比電阻為1Ω‧cm以下之高Sn濃度的Sn-Zn-O系氧化物燒結體。 Further, in order to maintain the effect of increasing the density and to further enhance the above effects, the additive element (M) may be added together with the additive element (X). That is, the tin oxide (SnO 2 ) powder and the zinc oxide (ZnO) powder blended in such a manner that the atomic ratio Sn/(Zn+Sn) is 0.75 or more and 0.9 or less, and the selected one is selected from Nb and Ta. At least one element (X) of W and Mo is formed so that the atomic ratio X/(Sn+Zn+X) with respect to the total amount of Sn, Zn, and the additive element (X) is 0.001 or more and 0.1 or less. The oxide powder of the additive element (X) to be blended by the method further comprises at least one additive element (M) selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga so as to be relative to Sn and Zn. a raw material powder of an oxide powder of the additive element (M) blended in such a manner that the atomic ratio M/(Sn+Zn+M) of the total amount of the additive element (M) is 0.0001 or more and 0.04 or less, and The granulated powder produced by granulating the powder is molded to obtain a molded body, and in a gas atmosphere having an oxygen concentration of 70% by volume or more in the firing furnace, the temperature rising rate from 700 ° C to the sintering temperature is 0.4 ° C / The molded body is fired under conditions of a temperature of 0.8 ° C/min or less and a sintering temperature of 1300 ° C or more and 1460 ° C or less and 10 hours or more and 30 hours or less, whereby the phase can be produced. Density of 98% or more and a specific resistance based Sn-Zn-O oxide sintered body 1Ω‧cm high Sn concentration in the following.

以下，說明本發明之Sn-Zn-O系氧化物燒結體之製造方法。 Hereinafter, a method for producing the sintered Sn-Zn-O-based oxide of the present invention will be described.

[摻合比] [ blending ratio]

(1)Zn與Sn元素 (1) Zn and Sn elements

在原子比數Sn/(Zn+Sn)為0.75以上0.9以下之高Sn濃度的Sn-Zn-O系氧化物燒結體之製造中難以獲得高密度之主要原因係由於：Sn及Zn易揮發之點、與燒製時所生成之Zn2SnO4相也易揮發。因此，不僅會影響燒製溫度，也會影響昇溫速度、燒結時間(保持時間)。 The reason why it is difficult to obtain a high density in the production of a Sn-Zn-O-based oxide sintered body having a high Sn concentration of an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9 or less is due to the fact that Sn and Zn are volatile. The point and the Zn 2 SnO 4 phase formed during firing are also volatile. Therefore, not only the firing temperature but also the heating rate and the sintering time (holding time) are affected.

據此，在燒製爐內的氧濃度為70體積%以上的氣體環境下，將去黏結劑以後之昇溫步驟，亦即，將700℃至燒結溫度之昇溫速度設定為0.4℃/min以上0.8℃/min以下、且將燒結溫度設定為1300℃以上1460℃以下、並且10小時以上30小時以內的條件下進行燒製，藉此可得到經緻密化的Sn-Zn-O系氧化物燒結體。 According to this, in the gas atmosphere in which the oxygen concentration in the firing furnace is 70% by volume or more, the temperature increasing step after the debonding agent, that is, the temperature rising rate from 700 ° C to the sintering temperature is set to 0.4 ° C / min or more. The sintered Sn-Zn-O-based oxide sintered body can be obtained by setting the sintering temperature to 1300 ° C or higher and 1460 ° C or lower and firing for 10 hours or longer and 30 hours or less. .

(2)添加元素 (2) Adding elements

(2-1)添加元素(X) (2-1) Adding elements (X)

以原子數比Sn/(Sn+Zn)為0.75以上0.9以下的比例含有Sn，在燒結爐內的氧濃度為70體積%以上的氣體環 境下，將從700℃至燒結溫度為止的昇溫速度設定為0.4℃/min以上0.8℃/min以下，並且將燒結溫度設定為1300℃以上1460℃以下，同時以10小時以上30小時以內的條件所製造之Sn-Zn-O系氧化物燒結體係如上述，雖提升密度但留有導電性之課題。因此，添加選自Nb、Ta、W及Mo的至少1種添加元素(X)。藉由添加元素(X)的添加，可在維持氧化物燒結體的高密度下改善導電性。另外，添加元素(X)為上述的Nb、Ta、W、Mo等五價以上的元素。 a gas ring containing Sn in a ratio of atomic ratio Sn/(Sn+Zn) of 0.75 or more and 0.9 or less, and an oxygen concentration in the sintering furnace of 70% by volume or more The temperature increase rate from 700 ° C to the sintering temperature is set to 0.4 ° C / min or more and 0.8 ° C / min or less, and the sintering temperature is set to 1300 ° C or higher and 1460 ° C or lower, and the conditions are within 10 hours and 30 hours. As described above, the sintered Sn-Zn-O-based oxide system has a problem of increasing the density but leaving conductivity. Therefore, at least one additive element (X) selected from Nb, Ta, W, and Mo is added. By adding the addition of the element (X), the conductivity can be improved while maintaining the high density of the oxide sintered body. Further, the additive element (X) is an element having a pentavalent or higher value such as Nb, Ta, W or Mo described above.

又，添加元素(X)的添加量需設定為使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下。在原子數比X/(Sn+Zn+X)小於0.001時，由於添加量少，而未改善導電性。另一方面，在原子數比X/(Sn+Zn+X)超過0.1時，由於會生成與Zn2SnO4相不同的化合物相，例如Nb2O5、Ta2O5、WO3、MoO3、ZnTa2O6、ZnWO4、ZnMoO4等的化合物相，而有會使導電性惡化，甚至使相對密度降低的情形。 In addition, the addition amount of the additive element (X) is set so that the atomic ratio X/(Sn+Zn+X) with respect to the total amount of Sn, Zn, and the additive element (X) is 0.001 or more and 0.1 or less. When the atomic ratio X/(Sn+Zn+X) is less than 0.001, the amount of addition is small, and the conductivity is not improved. On the other hand, when the atomic ratio X/(Sn+Zn+X) exceeds 0.1, a compound phase different from the Zn 2 SnO 4 phase is formed, for example, Nb 2 O 5 , Ta 2 O 5 , WO 3 , MoO. 3. A compound phase such as ZnTa 2 O 6 , ZnWO 4 or ZnMoO 4 may deteriorate conductivity or even lower the relative density.

(2-2)添加元素(M) (2-2) Adding elements (M)

為了維持高密度化的效果且更提高上述效果，亦可連同添加元素(X)一起加入添加元素(M)。藉由添加元素(X)的添加，會改善氧化物燒結體的導電性，但有伴隨添加元素(X)的增量而相對密度降低之傾向。為了抑制此密度降低傾向，可添加選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)。另外，添加元素(M)係以氧化物的形態添加，所添加之量係設定為使相對於Sn、Zn與添加 元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下。在原子數比M/(Sn+Zn+M)小於0.0001之情形，由於添加量少，而無法提高抑制密度降低傾向之效果。另一方面，在原子數比M/(Sn+Zn+M)超過0.04之情形，由於會生成其他的化合物相，例如SiO2、GeO2、CeO2、In2O3、Bi2O3、Ga2O3、ZnSiO4等的化合物相，而變成使導電性惡化。 In order to maintain the effect of increasing the density and to further enhance the above effects, the additive element (M) may be added together with the additive element (X). The addition of the element (X) improves the conductivity of the oxide sintered body, but the relative density tends to decrease as the additive element (X) increases. In order to suppress this tendency of density reduction, at least one additive element (M) selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga may be added. Further, the additive element (M) is added in the form of an oxide, and the amount added is set so as to make the atomic ratio M/(Sn+Zn+M) with respect to the total amount of Sn, Zn, and the additive element (M). It is 0.0001 or more and 0.04 or less. When the atomic ratio M/(Sn+Zn+M) is less than 0.0001, since the amount of addition is small, the effect of suppressing the decrease in density cannot be improved. On the other hand, in the case where the atomic ratio M/(Sn+Zn+M) exceeds 0.04, other compound phases are formed, for example, SiO 2 , GeO 2 , CeO 2 , In 2 O 3 , Bi 2 O 3 , A compound phase such as Ga 2 O 3 or ZnSiO 4 deteriorates conductivity.

[燒製條件] [Burning conditions]

(1)爐內氣體環境 (1) Gas environment in the furnace

需要在燒結爐內中的氧濃度為70體積%以上的氣體環境下將成形體進行燒製。這是因為有促進ZnO、SnO2或Zn2SnO4化合物的擴散，使燒結性提升且使導電性提升之效果。在高溫區域，亦有抑制Sn及Zn或Zn2SnO4的揮發之效果。不僅有該等效果，進一步亦有抑制Zn2SnO4與SnO2的揮發之效果。 It is necessary to fire the molded body in a gas atmosphere in which the oxygen concentration in the sintering furnace is 70% by volume or more. This is because it promotes the diffusion of ZnO, SnO 2 or Zn 2 SnO 4 compound, improves the sinterability, and enhances the conductivity. In the high temperature region, there is also an effect of suppressing the volatilization of Sn and Zn or Zn 2 SnO 4 . Not only these effects, but also the effect of suppressing the volatilization of Zn 2 SnO 4 and SnO 2 .

另一方面，在燒結爐內的氧濃度小於70體積%之情形，ZnO、SnO2或Zn2SnO4化合物的擴散會減緩，再者，在高溫區域，會促進Sn及Zn成分的揮發，而難以製作緻密的燒結體。 On the other hand, in the case where the oxygen concentration in the sintering furnace is less than 70% by volume, the diffusion of the ZnO, SnO 2 or Zn 2 SnO 4 compound is slowed down, and further, in the high temperature region, the volatilization of the Sn and Zn components is promoted, and It is difficult to produce a dense sintered body.

因此，爐內氣體環境需要氧濃度為70體積%以上。 Therefore, the gas atmosphere in the furnace requires an oxygen concentration of 70% by volume or more.

(2)700℃以後的昇溫速度 (2) Heating rate after 700 °C

為了以Sn為主成分之Sn-Zn-O系氧化物燒結體的高密度化，重要的是從去黏結劑結束之700℃至燒結溫度之1300℃~1460℃為止的昇溫速度。從去黏結劑結束後 至燒結溫度為止，進行化合物之Zn2SnO4的生成、粒界擴散，此溫度區域的燒製時間會對燒結體的高密度化產生影響。此溫度區域中，較佳為在燒製上不花費所需以上的時間。此係因為有需要使化合物相之Zn2SnO4相的粒界擴散暫時延遲而抑制過度的粒界擴散。 In order to increase the density of the sintered Sn-Zn-O-based oxide containing Sn as a main component, it is important to increase the temperature from 700 ° C to the sintering temperature of 1300 ° C to 1460 ° C from the end of the debonding agent. From the end of the debonding agent to the sintering temperature, the formation of the compound Zn 2 SnO 4 and the grain boundary diffusion are performed, and the firing time in this temperature region affects the density of the sintered body. In this temperature region, it is preferred that it does not take more than the time required for firing. This is because it is necessary to temporarily delay the grain boundary diffusion of the Zn 2 SnO 4 phase of the compound phase to suppress excessive grain boundary diffusion.

粒界擴散中有開始擴散之「初期」、與固溶、擴散之「中期」、擴散結束而轉變至晶粒成長之「後期」，通常固溶、擴散所進行之「中期」因為有需要給予用來進行固溶、擴散之充分的時間，所以施加設置有保持時間等之過程為有效的。 In the grain boundary diffusion, there is a "initial" of the beginning of diffusion, a "medium term" with solid solution and diffusion, and a "late period" when the diffusion is over and the growth of the grain is usually carried out. Since it is sufficient time for solid solution and diffusion, it is effective to apply a process in which a holding time or the like is applied.

然而，在以Sn為主成分的Sn-Zn-O系氧化物燒結體之情形，自生成Zn2SnO4相起至粒界擴散、晶粒成長、揮發的時間短。例如，若在1100℃中設置保持時間，則由於進行所需以上的粒界擴散或晶粒成長，所以花費時間反而會導致低密度化，因此較佳為不給予多餘之暴露於熱的時間。 However, in the case of a sintered Sn-Zn-O-based oxide containing Sn as a main component, the time from the formation of the Zn 2 SnO 4 phase to the grain boundary diffusion, grain growth, and volatilization is short. For example, when the holding time is set at 1100 ° C, since the grain boundary diffusion or the grain growth of more than necessary is performed, it takes time to cause a lower density, and therefore it is preferable not to give an extra time of exposure to heat.

因此，有需要自低於化合物之Zn2SnO4所生成之1000℃區域之溫度起加速昇溫速度，去黏結劑以後的昇溫速度較佳為0.4℃/min~0.8℃/min，更佳為0.5℃/min~0.7℃/min。然而，在700℃以後的昇溫速度小於0.4℃/min之情形，按昇溫花費的時間所增長的量而能得到進行粒界擴散之充分的時間，因此，雖進行Sn的燒結，但是會產生Zn2SnO4相的揮發。另一方面，在700℃以後的昇溫速度超過0.8℃/min之情形，雖然按昇溫花費的時間所縮短的量而可抑制Zn2SnO4與Sn的揮發， 但是進行Sn的粒界擴散之時間變短，例如，在燒結溫度區域中即使確實地進行燒結，也難以成為高密度。 Therefore, it is necessary to accelerate the temperature rise rate from a temperature lower than the temperature of the 1000 ° C region formed by the Zn 2 SnO 4 of the compound, and the temperature increase rate after the debonding agent is preferably 0.4 ° C / min to 0.8 ° C / min, more preferably 0.5. °C/min~0.7°C/min. However, in the case where the temperature increase rate after 700 ° C is less than 0.4 ° C / min, a sufficient time for grain boundary diffusion can be obtained in accordance with the amount of time taken for the temperature rise, and therefore, sintering of Sn is performed, but Zn is generated. 2 Volatilization of SnO 4 phase. On the other hand, in the case where the temperature increase rate after 700 ° C exceeds 0.8 ° C / min, the volatilization of Zn 2 SnO 4 and Sn can be suppressed by the amount shortened by the time taken for the temperature rise, but the grain boundary diffusion time of Sn is performed. It is shortened. For example, even if sintering is surely performed in the sintering temperature region, it is difficult to achieve high density.

因此，從去黏結劑結束之700℃至燒結溫度之1300℃~1460℃為止的昇溫速度需設定為0.4℃/min以上0.8℃/min以下。 Therefore, the temperature increase rate from 700 ° C to the sintering temperature of 1300 ° C to 1460 ° C from the end of the debonding agent should be set to 0.4 ° C / min or more and 0.8 ° C / min or less.

(3)燒結溫度 (3) sintering temperature

燒結溫度需設定為1300℃以上1460℃以下。在燒結溫度小於1300℃之情形，溫度過低而變得難以充分進行SnO2、Zn2SnO4化合物的晶粒成長，導致低密度化。另一方面，在超過1460℃之情形，雖然進行晶粒成長，但是，即使在例如氧濃度為70體積%以上的爐內進行燒製，也無法抑制Zn2SnO4化合物或Sn成分的揮發，而變成在燒結體內部殘留大的空孔。 The sintering temperature needs to be set to 1300 ° C or more and 1460 ° C or less. When the sintering temperature is less than 1300 ° C, the temperature is too low, and it becomes difficult to sufficiently carry out grain growth of the SnO 2 and Zn 2 SnO 4 compound, resulting in a decrease in density. On the other hand, in the case of exceeding 1460 ° C, grain growth is performed, but even if it is fired in a furnace having an oxygen concentration of 70% by volume or more, volatilization of the Zn 2 SnO 4 compound or the Sn component cannot be suppressed. On the other hand, a large void remains in the inside of the sintered body.

(4)保持時間 (4) Hold time

燒製時的保持時間需設定為10小時以上30小時以內。在保持時間為小於10小時之情形，由於燒結不完全，而形成變形或翹曲大的燒結體，並且，未增進粒界擴散、未增進燒結。其結果，無法製作緻密的燒結體。另一方面，若超過30小時，尤其由於無法獲得保持時間的效果，而導致作業效率的惡化、成本高之結果。 The holding time at the time of firing needs to be set to be 10 hours or more and 30 hours or less. In the case where the holding time is less than 10 hours, since the sintering is incomplete, a sintered body having a large deformation or warpage is formed, and the grain boundary diffusion is not promoted, and sintering is not promoted. As a result, a dense sintered body cannot be produced. On the other hand, if it exceeds 30 hours, especially because the effect of holding time is not obtained, the work efficiency is deteriorated and the cost is high.

在此種條件下所製造之高Sn濃度的Sn-Zn-O系氧化物燒結體由於為高密度且改善導電性，而能夠以DC濺鍍實施成膜。又，由於未使用特別的製造方法，故亦容易應用於圓筒形靶材。 The Sn-Zn-O-based oxide sintered body having a high Sn concentration produced under such conditions can be formed into a film by DC sputtering because of its high density and improved conductivity. Moreover, since a special manufacturing method is not used, it is easy to apply to a cylindrical target.

[實施例] [Examples]

以下，針對本發明之實施例舉出比較例具體加以說明，惟本發明技術範圍不限定於下述實施例之記載內容，理當亦可在符合本發明的範圍添加變更而實施。 In the following, the comparative examples are specifically described in the examples of the present invention, but the technical scope of the present invention is not limited to the description of the following examples, and it is also possible to carry out the modifications within the scope of the present invention.

[實施例1] [Example 1]

準備平均粒徑10μm以下的SnO2粉、平均粒徑10μm以下的ZnO粉、與作為添加元素X之平均粒徑20μm以下的Ta2O5粉。 SnO 2 powder having an average particle diameter of 10 μm or less, ZnO powder having an average particle diameter of 10 μm or less, and Ta 2 O 5 powder having an average particle diameter of 20 μm or less as the additive element X are prepared.

然後，以使Sn與Zn的原子數比Sn/(Sn+Zn)成為0.8、添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.01之方式來調合SnO2粉、ZnO粉、及Ta2O5粉，將所得之原料粉末與純水、有機黏結劑、分散劑在混合槽中混合，使原料粉末濃度成為60質量%。 Then, the SnO 2 powder and the ZnO powder are blended so that the atomic ratio of Sn to Zn is Sn/(Sn+Zn) is 0.8, and the atomic ratio Ta/(Sn+Zn+Ta) of the additive element X is 0.01. And the Ta 2 O 5 powder, the raw material powder obtained was mixed with pure water, an organic binder, and a dispersing agent in a mixing tank, and the raw material powder concentration was 60 mass %.

接著，使用投入有硬質ZrO2球的珠磨機裝置(Ashizawa Finetech股份有限公司製，LMZ型)，進行濕式粉碎至原料粉末的平均粒徑成為1μm以下為止後，混合攪拌10小時以上，而得到漿液。另外，原料粉末的平均粒徑之測定係使用雷射繞射式粒度分布測定裝置(島津製作所製，SALD-2200)。 Then, the bead mill apparatus (LMZ type, manufactured by Ashizawa Finetech Co., Ltd.) to which the hard ZrO 2 balls were placed was wet-pulverized until the average particle diameter of the raw material powder became 1 μm or less, and then the mixture was stirred for 10 hours or more. A slurry is obtained. In addition, the average particle diameter of the raw material powder was measured using a laser diffraction type particle size distribution measuring apparatus (SALD-2200, manufactured by Shimadzu Corporation).

接著，將所得之漿液以噴霧乾燥裝置(大川原化工機股份有限公司製，ODL-20型)進行噴霧及乾燥而得到造粒粉。 Then, the obtained slurry was sprayed and dried by a spray drying apparatus (manufactured by Okawara Chemical Co., Ltd., ODL-20 type) to obtain a granulated powder.

接著，將所得造粒粉末填充於橡膠模，以冷均壓法施加294MPa(3ton/cm2)的壓力進行成形，將所 得之直徑約250mm的成形體投入至常壓燒製爐，將空氣(氧濃度21體積%)導入燒結爐內直到700℃。確認燒製爐內的溫度成為700℃後，以氧濃度成為80體積%的方式導入氧，以昇溫速度0.5℃/min的條件使其昇溫至1400℃，並且在1400℃保持15小時。 Next, the obtained granulated powder was filled in a rubber mold, and a pressure of 294 MPa (3 ton/cm 2 ) was applied by cold pressure equalization, and the obtained molded body having a diameter of about 250 mm was placed in an atmospheric pressure firing furnace to carry out air ( The oxygen concentration of 21% by volume was introduced into the sintering furnace up to 700 °C. After confirming that the temperature in the firing furnace was 700 ° C, oxygen was introduced so that the oxygen concentration became 80 vol%, and the temperature was raised to 1400 ° C under the conditions of a temperature increase rate of 0.5 ° C/min, and held at 1400 ° C for 15 hours.

保持時間結束後停止導入氧，進行冷卻，得到實施例1之Sn-Zn-O系氧化物燒結體。 After the completion of the holding time, the introduction of oxygen was stopped, and cooling was performed to obtain a sintered Sn-Zn-O-based oxide of Example 1.

接著，使用平面磨機與研磨中心機(grinding center)，將實施例1之Sn-Zn-O系氧化物燒結體實施加工成直徑200mm、厚度5mm。 Next, the sintered Sn-Zn-O-based oxide of Example 1 was processed into a diameter of 200 mm and a thickness of 5 mm using a surface grinder and a grinding center.

以阿基米德法測定該加工體的密度之結果，相對密度為99.5%。又，以4探針法測定氧化物燒結體的比電阻之結果為0.03Ω‧cm。將此條件與結果示於表1-1、表1-2。 As a result of measuring the density of the processed body by the Archimedes method, the relative density was 99.5%. Further, the specific resistance of the oxide sintered body was measured by a 4-probe method and found to be 0.03 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例2] [Embodiment 2]

除了使用Nb2O5粉作為上述添加元素X、且以使添加元素X的原子數比Nb/(Sn+Zn+Nb)成為0.01之方式來調合SnO2粉、ZnO粉、及Nb2O5粉以外，係以與實施例1同樣的方式，製造實施例2之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.3%、比電阻值為0.09Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the Nb 2 O 5 are blended in such a manner that the Nb 2 O 5 powder is used as the additive element X and the atomic ratio of the additive element X is Nb/(Sn+Zn+Nb) is 0.01. A sintered Sn-Zn-O-based oxide of Example 2 was produced in the same manner as in Example 1 except for the powder. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.3%, and the specific resistance was 0.09 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例3] [Example 3]

除了使用WO3粉作為上述添加元素X、且以使添加元素X的原子數比W/(Sn+Zn+W)成為0.01之方式來調 合SnO2粉、ZnO粉、及WO3粉以外，係以與實施例1同樣的方式，製造實施例3之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.0%、比電阻值為0.11Ω‧cm。將此條件與結果示於表1-1、表1-2。 In addition to using the WO 3 powder as the additive element X and blending the SnO 2 powder, the ZnO powder, and the WO 3 powder so that the atomic ratio W/(Sn+Zn+W) of the additive element X is 0.01, A sintered Sn-Zn-O-based oxide of Example 3 was produced in the same manner as in Example 1. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.0%, and the specific resistance was 0.11 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例4] [Example 4]

除了使用MoO3粉作為上述添加元素X、且以使添加元素X的原子數比Mo/(Sn+Zn+Mo)成為0.01之方式來調合SnO2粉、ZnO粉、及MoO3粉以外，係以與實施例1同樣的方式，製造實施例4之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.7%、比電阻值為0.16Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the MoO 3 powder are blended in such a manner that the MoO 3 powder is used as the additive element X and the atomic ratio of the additive element X is 0.01 or less. The Sn-Zn-O-based oxide sintered body of Example 4 was produced in the same manner as in Example 1. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 98.7%, and the specific resistance was 0.16 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例5] [Example 5]

除了使用Ta2O5粉作為上述添加元素X、且以使添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.1之方式來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例1同樣的方式，製造實施例5之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.5%、比電阻值為0.10Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the Ta 2 O 5 are blended in such a manner that the Ta 2 O 5 powder is used as the additive element X and the atomic ratio of the additive element X is Ta/(Sn+Zn+Ta) is 0.1. A sintered Sn-Zn-O-based oxide of Example 5 was produced in the same manner as in Example 1 except for the powder. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 98.5%, and the specific resistance was 0.10 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例6] [Embodiment 6]

除了使用Ta2O5粉作為上述添加元素X、且以使添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.001之方式來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例 1同樣的方式，製造實施例6之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.3%、比電阻值為0.009Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the Ta 2 O 5 are blended in such a manner that the Ta 2 O 5 powder is used as the additive element X and the atomic ratio of the additive element X is Ta/(Sn+Zn+Ta) is 0.001. A sintered Sn-Zn-O-based oxide of Example 6 was produced in the same manner as in Example 1 except for the powder. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 99.3%, and the specific resistance was 0.009 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例7] [Embodiment 7]

除了以使Sn與Zn的原子數比Sn/(Sn+Zn)成為0.9、添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.05之方式來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例1同樣的方式，製造實施例7之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.0%、比電阻值為0.7Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the SnO 2 powder are blended so that the atomic ratio of Sn to Zn is Sn/(Sn+Zn) is 0.9 and the atomic ratio Ta/(Sn+Zn+Ta) of the additive element X is 0.05. A sintered Sn-Zn-O-based oxide of Example 7 was produced in the same manner as in Example 1 except for the Ta 2 O 5 powder. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 99.0%, and the specific resistance was 0.7 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例8] [Embodiment 8]

除了以使Sn與Zn的原子數比Sn/(Sn+Zn)成為0.75、添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.05之方式來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例1同樣的方式，製造實施例8之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.5%、比電阻值為0.02Ω‧cm。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the SnO 2 powder are blended so that the atomic ratio Sn/(Sn+Zn) of Sn and Zn is 0.75 and the atomic ratio Ta/(Sn+Zn+Ta) of the additive element X is 0.05. A sintered Sn-Zn-O-based oxide of Example 8 was produced in the same manner as in Example 1 except for the Ta 2 O 5 powder. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 98.5%, and the specific resistance was 0.02 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例9] [Embodiment 9]

除了將700℃至燒結溫度為止的昇溫速度設為0.4℃/min以外，係以與實施例1同樣的方式，製造實施例9之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度 為97.0%、比電阻值為0.35Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 9 was produced in the same manner as in Example 1 except that the temperature increase rate from 700 ° C to the sintering temperature was changed to 0.4 ° C / min. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was measured. It was 97.0% and the specific resistance value was 0.35 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例10] [Embodiment 10]

除了將700℃至燒結溫度為止的昇溫速度設為0.8℃/min以外，係以與實施例1同樣的方式，製造實施例10之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為95.9%、比電阻值為0.62Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 10 was produced in the same manner as in Example 1 except that the temperature increase rate from 700 ° C to the sintering temperature was 0.8 ° C / min. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 95.9%, and the specific resistance was 0.62 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例11] [Example 11]

除了將爐內的氧濃度設為70體積%以外，係以與實施例1同樣的方式，製造實施例11之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為95.8%、比電阻值為0.83Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 11 was produced in the same manner as in Example 1 except that the oxygen concentration in the furnace was changed to 70% by volume. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 95.8%, and the specific resistance was 0.83 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例12] [Embodiment 12]

除了將爐內的氧濃度設為99體積%以外，係以與實施例1同樣的方式，製造實施例12之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.5%、比電阻值為0.03Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 12 was produced in the same manner as in Example 1 except that the oxygen concentration in the furnace was changed to 99% by volume. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 99.5%, and the specific resistance was 0.03 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例13] [Example 13]

除了將燒結溫度設為1300℃以外，係以與實施例1同樣的方式，製造實施例13之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度 與比電阻值之結果，相對密度為95.4%、比電阻值為0.34Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 13 was produced in the same manner as in Example 1 except that the sintering temperature was 1300 °C. The relative density of the processed body was measured in the same manner as in Example 1. As a result of the specific resistance value, the relative density was 95.4%, and the specific resistance value was 0.34 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例14] [Embodiment 14]

除了將燒結溫度設為1460℃以外，係以與實施例1同樣的方式，製造實施例14之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為97.2%、比電阻值為0.22Ω‧cm。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Example 14 was produced in the same manner as in Example 1 except that the sintering temperature was changed to 1460 °C. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 97.2%, and the specific resistance was 0.22 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例15] [Example 15]

除了將燒結溫度下的保持時間設為10小時以外，係以與實施例1同樣的方式，製造實施例15之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為96.0%、比電阻值為0.18Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 15 was produced in the same manner as in Example 1 except that the holding time at the sintering temperature was changed to 10 hours. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 96.0%, and the specific resistance was 0.18 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例16] [Example 16]

除了將燒結溫度下的保持時間設為30小時以外，係以與實施例1同樣的方式，製造實施例16之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.5%、比電阻值為0.03Ω‧cm。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O-based oxide sintered body of Example 16 was produced in the same manner as in Example 1 except that the holding time at the sintering temperature was 30 hours. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1, and the relative density was 99.5%, and the specific resistance was 0.03 Ω·cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例1] [Comparative Example 1]

除了使用Ta2O5粉作為上述添加元素X、且以使添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.0001之方式 來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例1同樣的方式，製造比較例1之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.4%、比電阻值為190Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the Ta 2 O 5 are blended in such a manner that the Ta 2 O 5 powder is used as the additive element X and the atomic ratio Ta/(Sn+Zn+Ta) of the additive element X is 0.0001. A sintered Sn-Zn-O-based oxide of Comparative Example 1 was produced in the same manner as in Example 1 except for the powder. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.4%, and the specific resistance was 190 Ω ‧ cm. It was confirmed that the relative density was 95% or more, but it was not possible. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例2] [Comparative Example 2]

除了使用Ta2O5粉作為上述添加元素X、且以使添加元素X的原子數比Ta/(Sn+Zn+Ta)成為0.00009之方式來調合SnO2粉、ZnO粉、及Ta2O5粉以外，係以與實施例1同樣的方式，製造比較例2之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.3%、比電阻值為1600Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The SnO 2 powder, the ZnO powder, and the Ta 2 O 5 are blended in such a manner that the Ta 2 O 5 powder is used as the additive element X and the atomic ratio Ta/(Sn+Zn+Ta) of the additive element X is 0.00009. A sintered Sn-Zn-O-based oxide of Comparative Example 2 was produced in the same manner as in Example 1 except for the powder. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.3%, and the specific resistance was 1600 Ω·cm. It was confirmed that the relative density was 95% or more, but it was not possible. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例3] [Comparative Example 3]

除了應用未摻合上述添加元素X之原料粉末以外，係以與實施例1同樣的方式，製造比較例3之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.3%、比電阻值為1000Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Comparative Example 3 was produced in the same manner as in Example 1 except that the raw material powder in which the above-mentioned additive element X was not blended was used. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.3%, and the specific resistance was 1000 Ω·cm. It was confirmed that the relative density was 95% or more, but it was impossible to achieve The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例4] [Comparative Example 4]

除了應用未摻合上述添加元素X之原料粉末、且將700℃以後的昇溫速度設為0.4℃/min以外，係以與實施例1同樣的方式，製造比較例4之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.0%、比電阻值為1100Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A Sn-Zn-O system of Comparative Example 4 was produced in the same manner as in Example 1 except that the raw material powder to which the above-mentioned additive element X was not blended was applied, and the temperature increase rate after 700 ° C was 0.4 ° C / min. Oxide sintered body. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 98.0%, and the specific resistance was 1100 Ω·cm. It was confirmed that the relative density was 95% or more, but it was not possible. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例5] [Comparative Example 5]

除了應用未摻合上述添加元素X之原料粉末、且將700℃以後的昇溫速度設為0.8℃/min以外，係以與實施例1同樣的方式，製造比較例5之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.9%、比電阻值為1160Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O system of Comparative Example 5 was produced in the same manner as in Example 1 except that the raw material powder to which the above-mentioned additive element X was not blended was applied, and the temperature increase rate after 700 ° C was 0.8 ° C / min. Oxide sintered body. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 98.9%, and the specific resistance was 1160 Ω·cm. It was confirmed that the relative density was 95% or more, but it was not possible. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例6] [Comparative Example 6]

除了應用未摻合上述添加元素X之原料粉末、且將氧濃度設為99.0體積%以外，係以與實施例1同樣的方式，製造比較例6之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.9%、比電阻值為1160Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電 阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Comparative Example 6 was produced in the same manner as in Example 1 except that the raw material powder of the above-mentioned additive element X was not added and the oxygen concentration was changed to 99.0% by volume. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 98.9%, and the specific resistance was 1160 Ω·cm. It was confirmed that the relative density was 95% or more, but it was not possible. Specific electricity The resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例7] [Comparative Example 7]

除了應用未摻合上述添加元素X之原料粉末、且將燒結溫度設為1300℃以外，係以與實施例1同樣的方式，製造比較例7之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為98.1%、比電阻值為1500Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Comparative Example 7 was produced in the same manner as in Example 1 except that the raw material powder of the additive element X was not blended and the sintering temperature was 1300 °C. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 98.1%, and the specific resistance was 1500 Ω·cm. It was confirmed that the relative density was 95% or more, but it was impossible to achieve the same. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例8] [Comparative Example 8]

除了應用未摻合上述添加元素X之原料粉末、且將燒結溫度設為1460℃以外，係以與實施例1同樣的方式，製造比較例8之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為99.2%、比電阻值為1200Ω‧cm，確認可達成相對密度95%以上之特性，但無法達成比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Comparative Example 8 was produced in the same manner as in Example 1 except that the raw material powder of the additive element X was not blended and the sintering temperature was changed to 1460 °C. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 99.2%, and the specific resistance was 1200 Ω·cm. It was confirmed that the relative density was 95% or more, but it was impossible to achieve the same. The specific resistance is less than 1 Ω ‧ cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例9] [Comparative Example 9]

除了應用以Sn與Zn的原子數比Sn/(Sn+Zn)成為0.7的比例調合SnO2粉與ZnO粉、且未摻合上述添加元素X之原料粉末以外，係以與實施例1同樣的方式，製造比較例9之Sn-Zn-O系氧化物燒結體。以與實施例1同樣 的方法測定該加工體的相對密度與比電阻值之結果，相對密度為94.5%、比電阻值為10000Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The same applies to Example 1, except that the SnO 2 powder and the ZnO powder were blended in a ratio of the atomic ratio of Sn to Zn to 0.7, and the raw material powder of the additive element X was not blended. In the manner of producing a sintered Sn-Zn-O-based oxide of Comparative Example 9. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 94.5%, and the specific resistance was 10000 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例10] [Comparative Example 10]

除了應用以Sn與Zn的原子數比Sn/(Sn+Zn)成為0.95的比例調合SnO2粉與ZnO粉、且未摻合上述添加元素X之原料粉末以外，係以與實施例1同樣的方式，製造比較例10之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為88.3%、比電阻值為10000Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The same applies to Example 1 except that the SnO 2 powder and the ZnO powder were blended in such a ratio that the atomic ratio of Sn to Zn was 0.95, and the raw material powder of the additive element X was not blended. In the manner of producing a sintered Sn-Zn-O-based oxide of Comparative Example 10. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 88.3%, and the specific resistance was 10000 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例11] [Comparative Example 11]

除了應用未摻合上述添加元素X之原料粉末、且將700℃以後的昇溫速度設為0.38℃/min以外，係以與實施例1同樣的方式，製造比較例11之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為93.0%、比電阻值為1400Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The Sn-Zn-O system of Comparative Example 11 was produced in the same manner as in Example 1 except that the raw material powder to which the above-mentioned additive element X was not blended was applied, and the temperature increase rate after 700 ° C was 0.38 ° C / min. Oxide sintered body. The relative density and specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 93.0%, and the specific resistance was 1400 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例12] [Comparative Example 12]

除了應用未摻合上述添加元素X之原料粉末、且將700℃以後的昇溫速度設為1.0℃/min以外，係以與實施 例1同樣的方式，製造比較例12之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為93.8%、比電阻值為1500Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 In addition to the application of the raw material powder which is not blended with the above-mentioned additive element X, and the temperature increase rate after 700 ° C is set to 1.0 ° C / min, In the same manner as in Example 1, a sintered Sn-Zn-O-based oxide of Comparative Example 12 was produced. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 93.8%, and the specific resistance was 1500 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例13] [Comparative Example 13]

除了應用未摻合上述添加元素X之原料粉末、且將氧濃度設為68體積%以外，係以與實施例1同樣的方式，製造比較例13之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為90.1%、比電阻值為10000Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A Sn-Zn-O-based oxide sintered body of Comparative Example 13 was produced in the same manner as in Example 1 except that the raw material powder of the additive element X was not blended and the oxygen concentration was 68% by volume. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 90.1%, and the specific resistance was 10000 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例14] [Comparative Example 14]

除了應用未摻合上述添加元素X之原料粉末、且將燒結溫度設為1250℃以外，係以與實施例1同樣的方式，製造比較例14之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為85.0%、比電阻值為10000Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 A sintered Sn-Zn-O-based oxide of Comparative Example 14 was produced in the same manner as in Example 1 except that the raw material powder of the above-mentioned additive element X was not used and the sintering temperature was changed to 1,250 °C. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 85.0%, and the specific resistance was 10000 Ω·cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[比較例15] [Comparative Example 15]

除了應用未摻合上述添加元素X之原料粉末、且將燒結溫度設為1490℃以外，係以與實施例1同樣的方 式，製造比較例15之Sn-Zn-O系氧化物燒結體。以與實施例1同樣的方法測定該加工體的相對密度與比電阻值之結果，相對密度為94.1%、比電阻值為1800Ω‧cm，確認無法達成相對密度95%以上且比電阻值1Ω‧cm以下之特性。將此條件與結果示於表1-1、表1-2。 The same method as in Example 1 was used except that the raw material powder to which the above-mentioned additive element X was not blended was applied, and the sintering temperature was set to 1490 °C. A sintered Sn-Zn-O-based oxide of Comparative Example 15 was produced. The relative density and the specific resistance of the processed body were measured in the same manner as in Example 1. The relative density was 94.1%, and the specific resistance was 1800 Ω ‧ cm. It was confirmed that the relative density was 95% or more and the specific resistance was 1 Ω. Features below cm. The conditions and results are shown in Table 1-1 and Table 1-2.

[實施例17] [Example 17]

除了以平均粒徑為1μm以下的鍺的氧化物粉末作為添加元素M並以使添加元素M的原子比Ge/(Sn+Zn+Ge)成為0.01的方式進行以外，係以與實施例5同樣的方式，製造實施例17之Sn-Zn-O系氧化物燒結體。 The same procedure as in Example 5 was carried out except that the oxide powder of cerium having an average particle diameter of 1 μm or less was used as the additive element M and the atomic ratio Ge/(Sn+Zn+Ge) of the additive element M was 0.01. The Sn-Zn-O-based oxide sintered body of Example 17 was produced.

以阿基米德法測定該加工體的密度的結果，相對密度為99.3%(實施例5之相對密度為98.5%)，且氧化物燒結體的比電阻為0.07Ω‧cm(實施例5之比電阻為0.1Ω‧cm)，確認：與實施例5相比，更改善相對密度與比電阻。將此條件與結果示於表2-1、表2-2。 As a result of measuring the density of the processed body by the Archimedes method, the relative density was 99.3% (the relative density of Example 5 was 98.5%), and the specific resistance of the oxide sintered body was 0.07 Ω ‧ cm (Example 5) The specific resistance was 0.1 Ω ‧ cm), and it was confirmed that the relative density and specific resistance were improved as compared with Example 5. The conditions and results are shown in Table 2-1 and Table 2-2.

[實施例18~22] [Examples 18 to 22]

除了將添加元素M設為鈰(實施例18)、矽(實施例19)、鉍(實施例20)、銦(實施例21)、鎵(實施例22)以外，係以與實施例17同樣的方式，製造實施例18~22之Sn-Zn-O系氧化物燒結體。 The same applies to Example 17 except that the additive element M is 铈 (Example 18), 矽 (Example 19), 铋 (Example 20), Indium (Example 21), and Gallium (Example 22). The Sn-Zn-O-based oxide sintered bodies of Examples 18 to 22 were produced.

以阿基米德法測定該等加工體的密度。 The density of the processed bodies was measured by the Archimedes method.

各相對密度與比電阻分別為99.2%、0.08Ω‧cm(實施例18)、99.2%、0.2Ω‧cm(實施例19)、99.4%、0.6Ω‧cm(實施例20)、99.0%、0.3Ω‧cm(實施例21)、99.1%、0.4Ω‧cm(實施例22)，確認：與實施例5(相對密度為98.5%)相比，更改善相對密度。將該等條件與結果示於表2-1、表2-2。 The relative density and specific resistance were respectively 99.2%, 0.08 Ω ‧ cm (Example 18), 99.2%, 0.2 Ω ‧ cm (Example 19), 99.4%, 0.6 Ω ‧ cm (Example 20), 99.0%, 0.3 Ω ‧ cm (Example 21), 99.1%, 0.4 Ω ‧ cm (Example 22), it was confirmed that the relative density was improved as compared with Example 5 (relative density: 98.5%). These conditions and results are shown in Table 2-1 and Table 2-2.

[實施例23] [Example 23]

除了以使添加元素M的原子比Ge/(Sn+Zn+Ge)成為0.0001之方式進行以外，係以與實施例17同樣的方式，製造實施例23之Sn-Zn-O系氧化物燒結體。 The Sn-Zn-O-based oxide sintered body of Example 23 was produced in the same manner as in Example 17 except that the atomic ratio Ge/(Sn+Zn+Ge) of the additive element M was 0.0001. .

以阿基米德法測定該加工體的密度的結果，相對密度為98.9%、氧化物燒結體的比電阻為0.09Ω‧cm，確認：與實施例5(相對密度為98.5%、比電阻為0.1Ω‧cm)相比，更改善相對密度與比電阻。將此條件與結果示於表2-1、表2-2。 As a result of measuring the density of the processed body by the Archimedes method, the relative density was 98.9%, and the specific resistance of the oxide sintered body was 0.09 Ω ‧ cm. It was confirmed that it was the same as Example 5 (relative density was 98.5%, and specific resistance was Compared with 0.1 Ω ‧ cm), the relative density and specific resistance are improved. The conditions and results are shown in Table 2-1 and Table 2-2.

[實施例24] [Example 24]

除了以使添加元素M的原子比Ge/(Sn+Zn+Ge)成為0.04之方式進行以外，係以與實施例17同樣的方式，製造實施例24之Sn-Zn-O系氧化物燒結體。 The Sn-Zn-O-based oxide sintered body of Example 24 was produced in the same manner as in Example 17 except that the atomic ratio Ge/(Sn+Zn+Ge) of the additive element M was 0.04. .

以阿基米德法測定該加工體的密度的結果，相對密度為99.4%，且氧化物燒結體的比電阻為0.14Ω‧cm，確認：與實施例5(相對密度 98.5%)相比，更改善相對密度。將此條件與結果示於表2-1、表2-2。 As a result of measuring the density of the processed body by the Archimedes method, the relative density was 99.4%, and the specific resistance of the oxide sintered body was 0.14 Ω ‧ cm, confirming: and Example 5 (relative density) Compared with 98.5%), the relative density is improved. The conditions and results are shown in Table 2-1 and Table 2-2.

[實施例25] [Example 25]

除了以平均粒徑為1μm以下的鍺的氧化物粉末作為添加元素M之並以使添加元素M的原子比Ge/(Sn+Zn+Ge)成為0.01的方式進行以外，係以與實施例1同樣的方式，製造實施例25之Sn-Zn-O系氧化物燒結體。 Except that the oxide powder of cerium having an average particle diameter of 1 μm or less is used as the additive element M, and the atomic ratio Ge/(Sn+Zn+Ge) of the additive element M is 0.01, In the same manner, the sintered Sn-Zn-O-based oxide of Example 25 was produced.

以阿基米德法測定該加工體的密度的結果，相對密度為99.5%，且氧化物燒結體的比電阻為0.06Ω‧cm。將此條件與結果示於表2-1、表2-2。 As a result of measuring the density of the processed body by the Archimedes method, the relative density was 99.5%, and the specific resistance of the oxide sintered body was 0.06 Ω‧ cm. The conditions and results are shown in Table 2-1 and Table 2-2.

[產業上可利用性] [Industrial availability]

本發明之Sn-Zn-O系氧化物燒結體，由於除了機械強度以外，亦具備高密度且低電阻等特性，故具有作為用於形成太陽能電池或觸控面板等的透明電極之濺鍍靶材利用的產業上可利用性。 The Sn-Zn-O-based oxide sintered body of the present invention has characteristics such as high density and low electrical resistance in addition to mechanical strength, and thus has a sputtering target as a transparent electrode for forming a solar cell or a touch panel. Industrial availability of materials utilization.

Claims (4)

一種Sn-Zn-O系氧化物燒結體，其係以Sn為主成分的Sn-Zn-O系氧化物燒結體，其特徵為：以原子數比Sn/(Zn+Sn)為0.75以上0.9以下的比例含有Sn，且以相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下的比例含有選自Nb、Ta、W、Mo的至少1種添加元素(X)，並且其相對密度為95%以上且比電阻為1Ω‧cm以下。 A sintered Sn-Zn-O-based oxide which is a sintered Sn-Zn-O-based oxide containing Sn as a main component, and has an atomic ratio of Sn/(Zn+Sn) of 0.75 or more and 0.9. The following ratio contains Sn, and is selected from Nb, Ta, and W in a ratio of 0.001 or more and 0.1 or less to the atomic ratio X/(Sn+Zn+X) of the total amount of Sn, Zn, and the additive element (X). At least one additive element (X) of Mo, and a relative density of 95% or more and a specific resistance of 1 Ω‧cm or less. 如請求項1之Sn-Zn-O系氧化物燒結體，其中以相對於Sn、Zn與添加元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下的比例含有選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)，且氧化物燒結體的相對密度為98%以上。 The Sn-Zn-O-based oxide sintered body of claim 1, wherein the atomic ratio M/(Sn+Zn+M) with respect to the total amount of Sn, Zn and the additive element (M) is 0.0001 or more and 0.04 or less. The ratio includes at least one additive element (M) selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga, and the relative density of the oxide sintered body is 98% or more. 一種Sn-Zn-O系氧化物燒結體之製造方法，其特徵為具備：造粒粉末製造步驟，其係將以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末，與純水、有機黏結劑、分散劑混合，將所得之漿液進行乾燥且造粒，而製造造粒粉末；成形體製造步驟，其係將上述造粒粉末進行加壓成形而得到成形體；及 燒結體製造步驟，其係在燒製爐內的氧濃度為70體積%以上的氣體環境下，以700℃至燒結溫度為止的昇溫速度為0.4℃/min以上0.8℃/min以下、且燒結溫度為1300℃以上1460℃以下、10小時以上30小時以內的條件，將上述成形體進行燒製，而製造燒結體。 A method for producing a sintered body of a Sn-Zn-O-based oxide, comprising: a step of producing a granulated powder, which is prepared by mixing an atomic ratio Sn/(Zn+Sn) of 0.75 or more and 0.9 or less a tin oxide (SnO 2 ) powder and a zinc oxide (ZnO) powder, and at least one element (X) selected from the group consisting of Nb, Ta, W, and Mo, so as to be relative to Sn, Zn, and an additive element ( The oxide powder of the additive element (X) blended in such a manner that the atomic ratio of X/(Sn+Zn+X) is 0.001 or more and 0.1 or less, and is mixed with pure water, an organic binder, and a dispersant. The obtained slurry is dried and granulated to produce a granulated powder; the molded body is produced by subjecting the granulated powder to press molding to obtain a molded body; and the sintered body producing step is carried out in a firing furnace In a gas atmosphere having an oxygen concentration of 70% by volume or more, the temperature increase rate from 700 ° C to the sintering temperature is 0.4 ° C / min or more and 0.8 ° C / min or less, and the sintering temperature is 1300 ° C or higher and 1460 ° C or lower for 10 hours or longer. The molded body was fired under the conditions of 30 hours or less to produce a sintered body. 如請求項3之Sn-Zn-O系氧化物燒結體之製造方法，其中，除了以使原子數比Sn/(Zn+Sn)為0.75以上0.9以下之方式所摻合的氧化錫(SnO2)粉末與氧化鋅(ZnO)粉末、及以選自Nb、Ta、W、Mo的至少1種元素(X)所構成且以使相對於Sn、Zn與添加元素(X)的總量之原子數比X/(Sn+Zn+X)為0.001以上0.1以下之方式所摻合的添加元素(X)的氧化物粉末以外，進一步添加以選自Si、Ge、Ce、In、Bi、Ga的至少1種添加元素(M)所構成且以使相對於Sn、Zn與添加元素(M)的總量之原子數比M/(Sn+Zn+M)為0.0001以上0.04以下之方式所摻合的添加元素(M)的氧化物粉末。 The method for producing a sintered Sn-Zn-O-based oxide according to claim 3, wherein the tin oxide (SnO 2 ) is blended in such a manner that the atomic ratio Sn/(Zn+Sn) is 0.75 or more and 0.9 or less. a powder and a zinc oxide (ZnO) powder, and an atom composed of at least one element (X) selected from the group consisting of Nb, Ta, W, and Mo so as to be relative to the total amount of Sn, Zn, and the additive element (X) The oxide powder of the additive element (X) to be blended in a ratio of X/(Sn+Zn+X) of 0.001 or more and 0.1 or less is further added to be selected from the group consisting of Si, Ge, Ce, In, Bi, and Ga. At least one additive element (M) is formed so as to be blended in such a manner that the atomic ratio M/(Sn+Zn+M) of the total amount of Sn, Zn, and the additive element (M) is 0.0001 or more and 0.04 or less. An oxide powder of the added element (M).
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