JPH10147861A - Production of indium oxide-tin oxide sintered body - Google Patents
Production of indium oxide-tin oxide sintered bodyInfo
- Publication number
- JPH10147861A JPH10147861A JP30449296A JP30449296A JPH10147861A JP H10147861 A JPH10147861 A JP H10147861A JP 30449296 A JP30449296 A JP 30449296A JP 30449296 A JP30449296 A JP 30449296A JP H10147861 A JPH10147861 A JP H10147861A
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- Japan
- Prior art keywords
- powder
- sintered body
- raw material
- material powder
- diameter
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化インジウム・
酸化錫（以下ＩＴＯと記載する）焼結体、特にスパッタ
リング法により透明導電膜を形成する際のスパッタリン
グ用ターゲットとして極めて優れた性能を有するＩＴＯ
焼結体の製造方法に関する。TECHNICAL FIELD The present invention relates to an indium oxide
Tin oxide (hereinafter referred to as ITO) sintered body, particularly ITO having extremely excellent performance as a sputtering target when forming a transparent conductive film by a sputtering method
The present invention relates to a method for manufacturing a sintered body.
【０００２】[0002]
【従来技術】ＩＴＯ焼結体をターゲットとしてスパッタ
リングにより得られる薄膜は、その比抵抗値の低さから
有望な透明電極膜として注目されている。例えば、３０
０℃程度の高温に加熱された基板上に、適当な条件でＩ
ＴＯを物理蒸着することによって、透明性が良く且つ比
抵抗値が２.０×１０-4Ω・ｃｍ以下の良質なＩＴＯ膜
を形成することができる。2. Description of the Related Art A thin film obtained by sputtering using an ITO sintered body as a target has attracted attention as a promising transparent electrode film because of its low specific resistance. For example, 30
On a substrate heated to a high temperature of about 0 ° C., under appropriate conditions,
By performing physical vapor deposition of TO, a high-quality ITO film having good transparency and a specific resistance of 2.0 × 10 −4 Ω · cm or less can be formed.
【０００３】このような加熱基板上に比抵抗値の低いＩ
ＴＯ膜を成膜するためのスパッタリング用ターゲットと
して、特開昭６２−２１７５１号公報には、Ｉｎ2Ｏ3粉
末とＳｎＯ2粉末を配合し、混合及び粉砕を行い、これ
を成形して仮焼した後、再度粉砕を行って粉末とし、得
られた仮焼済み粉末を、更に成形及び焼結して製造され
たＩＴＯ焼結体が開示されている。また、同公報には、
仮焼済み粉末を成形した後、ホットプレスのような高温
加圧下で焼結する方法も記載されている。更に、特開平
５−１４８６３６号公報には、Ｉｎ2Ｏ3粉末とＳｎＯ2
粉末を配合し、これを成形した後に、酸素加圧法にて１
５５０℃以上で焼結することにより製造されたＩＴＯ焼
結体が開示されている。[0003] On such a heated substrate, I having a low specific resistance value is used.
As a sputtering target for forming a TO film, JP-A-62-21751 discloses that a mixture of In 2 O 3 powder and SnO 2 powder is mixed, pulverized, molded, and calcined. After that, pulverization is again performed to obtain a powder, and the calcined powder obtained is further molded and sintered to disclose an ITO sintered body. The publication also states that
There is also described a method of forming a calcined powder and then sintering it under a high-temperature press such as a hot press. Further, JP-A-5-148636 discloses that In 2 O 3 powder and SnO 2
After mixing the powder and molding it, 1
An ITO sintered body manufactured by sintering at 550 ° C. or higher is disclosed.
【０００４】しかし、このようにして得られたＩＴＯ焼
結体のターゲットを用いてスパッタリングを行うと、異
常放電の発生によりプラズマ状態が不安定になり、安定
した成膜が行われず、得られる膜の構造が悪化し、膜の
特性値が劣化するという不都合が生じていた。また、異
常放電が頻繁に発生する状況下において長時間スパッタ
リングを行うと、ＩＴＯ焼結体からなるターゲット表面
にノジュールと呼ばれる黒色の突起物が生成し、これに
よって成膜速度が低下するという問題も生じていた。[0004] However, when sputtering is performed using the target of the ITO sintered body thus obtained, the plasma state becomes unstable due to the occurrence of abnormal discharge, and stable film formation is not performed. Has deteriorated, and the characteristic value of the film has deteriorated. In addition, when sputtering is performed for a long time in a situation where abnormal discharge frequently occurs, black protrusions called nodules are generated on the surface of the target made of the ITO sintered body, which causes a problem that the film formation rate is reduced. Had occurred.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、このような
従来の事情に鑑み、透明電極膜のスパッタリング用ター
ゲットとして、スパッタリング中の異常放電の発生及び
ノジュールの生成が少なく、特性の優れたＩＴＯ膜を効
率良く成膜することが可能な酸化インジウム・酸化錫焼
結体の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention provides an ITO having excellent characteristics, as a sputtering target for a transparent electrode film, in which the occurrence of abnormal discharge and the generation of nodules during sputtering are reduced. It is an object of the present invention to provide a method for producing an indium oxide / tin oxide sintered body capable of efficiently forming a film.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明が提供する酸化インジウム・酸化錫焼結体の
製造方法は、Ｉｎ2Ｏ3粉末とＳｎＯ2粉末を湿式混合
し、乾燥造粒して成形した後、酸素雰囲気中で焼結する
酸化インジウム・酸化錫焼結体の製造方法において、比
表面積２０ｍ2／ｇ以上のＩｎ2Ｏ3粉末と比表面積５ｍ2
／ｇ以上のＳｎＯ2粉末とを原料粉末とし、原料粉末を
湿式ボールミルにて混合する際に、 (1) 使用するボールの直径が３〜１０ｍｍ、 (2) 原料粉末に対して添加する水分量が重量比で１.８
〜２.０倍 (3) 原料粉末に対して添加するボール量が重量比で３.
０〜５.０倍 (4) 原料粉末と水とボールの合計量がポット容積の４０
〜６０％ (5) 混合時間が１２〜７２時間 の条件で混合することを特徴とするものである。In order to achieve the above object, the present invention provides a method for producing an indium oxide / tin oxide sintered body, which comprises wet mixing an In 2 O 3 powder and a SnO 2 powder and drying the mixture. A method for producing an indium oxide / tin oxide sintered body, which is formed by sintering in an oxygen atmosphere after granulating and shaping, comprises an In 2 O 3 powder having a specific surface area of 20 m 2 / g or more and a specific surface area of 5 m 2.
/ G or more of SnO 2 powder as raw material powder and mixing the raw material powder with a wet ball mill, (1) the diameter of the ball used is 3 to 10 mm, (2) the amount of water added to the raw material powder Is 1.8 by weight
Up to 2.0 times (3) The amount of balls added to the raw material powder is 3.
0 to 5.0 times (4) The total amount of the raw material powder, water and balls is 40 times the pot volume.
６０60% (5) The mixing time is 12 to 72 hours.
【０００７】また、本発明の酸化インジウム・酸化錫焼
結体の製造方法は、その焼結方法の一つとして、酸素雰
囲気中において１３５０〜１５５０℃で１５時間以下の
焼結を行うことを特徴とする。別の焼結方法として、酸
素雰囲気中において１３５０〜１５５０℃で５〜１０時
間の焼結を行った後、更に還元雰囲気中において１３５
０〜１５５０℃で１０時間以下の焼結を行うこともでき
る。The method for producing an indium oxide / tin oxide sintered body of the present invention is characterized in that, as one of the sintering methods, sintering is performed at 1350-1550 ° C. for 15 hours or less in an oxygen atmosphere. And As another sintering method, sintering is performed at 1350 to 1550 ° C. for 5 to 10 hours in an oxygen atmosphere, and then further performed in a reducing atmosphere at 135 ° C.
Sintering at 0 to 1550 ° C. for 10 hours or less can also be performed.
【０００８】[0008]
【発明の実施の形態】本発明者らは、異常放電の発生及
びノジュールの生成原因を調べるために、従来公知の方
法によって得たＩＴＯ焼結体を分析し、詳細に検討し
た。その結果、特開昭６２−２１７５１号公報記載にの
方法で作製されるＩＴＯ焼結体においては、例えば１０
重量％のＳｎＯ2粉末を配合して焼結し、錫分散性をＥ
ＰＭＡ面分析により測定することによって、粒径５μｍ
以上の錫の凝集体が存在していることが判明した。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors analyzed and examined in detail an ITO sintered body obtained by a conventionally known method in order to investigate the occurrence of abnormal discharge and the generation of nodules. As a result, in an ITO sintered body manufactured by the method described in JP-A-62-21751, for example, 10
Wt% SnO 2 powder is blended and sintered, and the tin dispersibility is
The particle size was 5 μm as measured by PMA surface analysis.
It turned out that the above-mentioned tin aggregate exists.
【０００９】また、このＩＴＯ焼結体では、ＥＰＭＡ線
分析及びＸ線回析により、Ｉｎ2Ｏ3相中に固溶される錫
原子は３重量％前後であり、残りの錫は錫濃度の高いＩ
ｎ2Ｏ3とＳｎＯ2との中間化合物相として存在してい
た。更に、この焼結体は低密度であるために、内部に大
きな空孔部が点在していた。ホットプレスを用いれば大
きな空孔部は消失するが、６００〜８００℃程度の低温
処理であるため錫原子は殆ど固溶されず、錫は全てＳｎ
Ｏ2相として存在した。In this ITO sintered body, tin atoms dissolved in the In 2 O 3 phase are about 3% by weight by EPMA ray analysis and X-ray diffraction, and the remaining tin has a tin concentration of High i
It was present as an intermediate compound phase between n 2 O 3 and SnO 2 . Further, since this sintered body has a low density, large pores are scattered inside. If a hot press is used, large pores disappear, but since the low-temperature treatment is performed at about 600 to 800 ° C., tin atoms hardly form a solid solution, and all tin is Sn.
Present as O 2 phase.
【００１０】一方、特開平５−１４８６３６号公報に記
載の方法でＩＴＯ焼結体を作製した場合には、ＳｎＯ2
相が存在せず且つ緻密な焼結体が得られる。しかし、１
５５０℃以上での高温処理によって製造されるために、
焼結体中に粒径１０μｍ以上の錫の凝集体が存在した。
更に、Ｉｎ2Ｏ3相の結晶粒径又はＩｎ2Ｏ3相中に錫原子
が固溶された相の結晶粒径が、１０μｍ以上と粗大であ
った。On the other hand, when an ITO sintered body is manufactured by the method described in JP-A-5-148636, SnO 2
A dense sintered body having no phase is obtained. However, 1
To be manufactured by high temperature processing at 550 ° C. or higher,
Aggregates of tin having a particle size of 10 μm or more were present in the sintered body.
Further, the crystal grain diameter or In 2 O 3 phase crystal grain size of the phases in which the tin atoms were solid-dissolved In 2 O 3 phase was a 10μm or more and coarse.
【００１１】そして、これら従来のＩＴＯ焼結体をター
ゲットとしたとき、高電圧をかけてのスパッタリングが
できず、従って成膜速度を上げることができず、良質な
ＩＴＯ膜も得られない。また、高電圧をかければ異常放
電及びノジュールが多発するばかりでなく、焼結体の結
晶粒径が粗大化しているために熱衝撃に弱く、焼結体の
ターゲットに割れが発生することが分かった。When these conventional ITO sintered bodies are used as targets, sputtering at a high voltage cannot be performed, so that the film forming speed cannot be increased and a high quality ITO film cannot be obtained. It is also found that when a high voltage is applied, not only abnormal discharge and nodules occur frequently, but also because the crystal grain size of the sintered body is large, it is susceptible to thermal shock and cracks occur in the target of the sintered body. Was.
【００１２】以上のことから、スパッタリング用ターゲ
ットとしてのＩＴＯ焼結体における異常放電の発生及び
ノジュールの生成という問題点は、 (１) 比抵抗値の低いＳｎＯ2相、錫の凝集体又は錫濃
度の高い中間化合物相 (２) 焼結体内にある大きな空孔部 (３) 粗大化されたＩｎ2Ｏ3相又はＩｎ2Ｏ3相中に錫元
素が固溶された相 の３点が主な原因であると判断された。From the above, the problems of the occurrence of abnormal discharge and the generation of nodules in an ITO sintered body as a sputtering target are as follows: (1) SnO 2 phase having low specific resistance, aggregate of tin or tin concentration. (2) Large pores in the sintered body (3) Coarse In 2 O 3 phase or phase in which tin element is dissolved in In 2 O 3 phase Was determined to be the cause.
【００１３】本発明は、ＩＴＯ焼結体の製造方法を改良
し、上記３点を解決することによって、スパッタリング
用ターゲットとして使用したときの異常放電の発生及び
ノジュールの生成を防止し又は低減することのできるＩ
ＴＯ焼結体を提供するものである。An object of the present invention is to improve or reduce the above three points of the method for producing an ITO sintered body to prevent or reduce the occurrence of abnormal discharge and the generation of nodules when used as a sputtering target. I can do
A TO sintered body is provided.
【００１４】本発明が対象とするＩＴＯ焼結体は、イン
ジウム、錫及び酸素を主成分とするＩｎ2Ｏ3−ＳｎＯ2
系の焼結体であって、その組成自体は公知のＩＴＯ焼結
体と同様であり、一般に錫の平均組成は３〜１２重量
％、及びインジウムの平均組成は７０〜７８重量％の範
囲にある。The ITO sintered body to which the present invention is directed is an In 2 O 3 —SnO 2 containing indium, tin and oxygen as main components.
This is a sintered body of a system, and the composition itself is the same as that of a known ITO sintered body. Generally, the average composition of tin is in the range of 3 to 12% by weight, and the average composition of indium is in the range of 70 to 78% by weight. is there.
【００１５】本発明のＩＴＯ焼結体の製造方法において
は、Ｉｎ2Ｏ3粉末とＳｎＯ2粉末とを原料粉末とし、こ
れに水と、酢酸ビニル、ポリビニルアルコール等からな
るバインダーを添加して、湿式混合を行う。混合後に得
られたスラリーを乾燥造粒した後、コールドプレス若し
くは冷間静水圧プレスによって成形する。得られた成形
体を、Ｉｎ2Ｏ3及びＳｎＯ２の蒸発を抑制するため酸素
雰囲気中にて焼結することによって、ＩＴＯ焼結体を得
ることができる。In the method for producing an ITO sintered body of the present invention, In 2 O 3 powder and SnO 2 powder are used as raw material powders, and water and a binder composed of vinyl acetate, polyvinyl alcohol or the like are added thereto. Perform wet mixing. After the slurry obtained after mixing is dried and granulated, it is formed by a cold press or a cold isostatic press. By sintering the obtained molded body in an oxygen atmosphere in order to suppress the evaporation of In 2 O 3 and SnO 2 , an ITO sintered body can be obtained.
【００１６】原料粉末としては、平均一次粒径が共に
０.１μｍ以下のＩｎ2Ｏ3粉末とＳｎＯ2粉末とを使用す
る。これらの原料粉末は、例えば、インジウム又は錫の
金属水酸化物を加水分解又は熱分解して得ることができ
る。Ｉｎ2Ｏ3粉末とＳｎＯ2粉末は、ＩｎとＳｎの組成
が前記した通常の範囲となるように混合して使用され
る。As the raw material powder, an In 2 O 3 powder and an SnO 2 powder each having an average primary particle size of 0.1 μm or less are used. These raw material powders can be obtained, for example, by hydrolyzing or thermally decomposing a metal hydroxide of indium or tin. The In 2 O 3 powder and the SnO 2 powder are mixed and used so that the composition of In and Sn falls within the above-mentioned normal range.
【００１７】原料粉末のＢＥＴ法により測定される比表
面積は、Ｉｎ2Ｏ3粉末では２０ｍ2／ｇ以上であるが、
余り微細なものは凝集が激しいので３０〜４０ｍ2／ｇ
が好ましい。ＳｎＯ2粉末では５ｍ2／ｇ以上であり、同
じく５〜８ｍ2／ｇが好ましい。しかし、これらの原料
粉末は微細であるために凝集し易く、凝集によって局部
的に焼結速度の異なる場所が生じ、収縮が不均一に起こ
って大きな空孔ができたり、空孔径分布が広くなり易
い。また、粒子によって粒成長する速度が異なるので、
不均一な微細構造になり易い。従って、本発明のＩＴＯ
焼結体を得るためには、凝集している原料粉末を一次粒
子に解砕することが重要である。The specific surface area of the raw material powder measured by the BET method is 20 m 2 / g or more for In 2 O 3 powder,
Very fine ones are intensely agglomerated, so 30-40 m 2 / g
Is preferred. The SnO 2 powder is a 5 m 2 / g or more, likewise 5~8m 2 / g are preferred. However, since these raw material powders are fine, they tend to agglomerate, and agglomeration may cause local differences in sintering speed, causing non-uniform shrinkage to form large pores or a wide pore size distribution. easy. Also, since the speed of grain growth differs depending on the particles,
It tends to have an uneven microstructure. Therefore, the ITO of the present invention
In order to obtain a sintered body, it is important to crush the agglomerated raw material powder into primary particles.
【００１８】この凝集している原料粉末の解砕は、以下
に説明する粉末の粉砕混合方法により行う。即ち、原料
粉末の粉砕混合は、湿式法又は乾式法によるボールミ
ル、振動ミル等を用いることができるが、均一微細な結
晶粒及び空孔を得るには湿式法によるボールミル混合が
最も好ましい。その理由は、乾式ボールミルや振動ミル
にて長時間の粉砕混合を行うと、不純物の混入が多くな
るからである。また、微粉砕にはボールの落下による衝
撃よりも、ボールとボール又はボールとポット内壁との
間における摩擦力の方が大きな役割を果たしていること
から、ボールミルによる粉砕混合が最も効果的である。The agglomeration of the agglomerated raw material powder is carried out by the method of pulverizing and mixing the powder described below. That is, for the pulverization and mixing of the raw material powder, a ball mill or a vibration mill by a wet method or a dry method can be used, but the ball mill mixing by a wet method is most preferable in order to obtain uniformly fine crystal grains and pores. The reason is that if pulverization and mixing are performed for a long time in a dry ball mill or a vibration mill, the amount of impurities increases. Further, since the frictional force between the ball and the ball or between the ball and the inner wall of the pot plays a greater role in the fine pulverization than the impact due to the drop of the ball, the pulverization and mixing using a ball mill is most effective.
【００１９】湿式のボールミル混合は、樹脂性ポットの
容器内に原料粉末、ボール、水、及びバインダーを任意
の量だけ添加して行う。スラリー濃度が高い場合には、
ボールが浮き上がって互いに接触し難くなり、逆にスラ
リー濃度が低い場合には、ボールに滑りが生じて十分な
高さにまで到達することができないため、添加する水分
量やボール量等を調整する必要がある。添加する水分量
は原料粉末に対して重量で１.８〜２.０倍の範囲とし、
ボール量は原料粉末に対して重量で３.０〜５.０倍の範
囲とする。また、ポット内に添加する原料粉末、ボー
ル、及び水の全体量は、ポット容積に対して４０％〜６
０％の範囲内に納まるようにしなければならない。The wet ball mill mixing is performed by adding raw material powder, balls, water, and a binder in arbitrary amounts into a container of a resin pot. If the slurry concentration is high,
When the ball is lifted and it is difficult to contact each other, and when the slurry concentration is low, the ball slides and cannot reach a sufficient height. Therefore, the amount of water to be added and the amount of the ball are adjusted. There is a need. The amount of water to be added is in the range of 1.8 to 2.0 times the weight of the raw material powder,
The amount of the ball is in the range of 3.0 to 5.0 times the weight of the raw material powder. The total amount of the raw material powder, balls, and water to be added to the pot is 40% to 6% based on the pot volume.
It must be within the 0% range.
【００２０】使用するボールは、摩耗の少ない硬質ジル
コニアボールが好ましく、そのボール径が小さいほど表
面積が大きくなるので粉砕効果は高くなる。しかし、ボ
ール径が小さ過ぎると、ボールの摩耗が激しくなるため
不純物の混入量が多くなる。従って、ボール径は３〜１
０ｍｍの範囲とする。ボールミル混合では、ポットの回
転によってボールが到達した最高の高さから４５°の角
度で流れ落ちるのが理想的な回転数であり、この状態が
達成されると高い粉砕効果が得られる。この理想的な回
転数はポットの直径にもよるが、例えばポットの直径が
１００ｍｍであれば、その回転数は４０〜６０ｒｐｍが
好ましい。The ball to be used is preferably a hard zirconia ball with little wear. The smaller the ball diameter, the larger the surface area, so that the pulverizing effect is enhanced. However, if the ball diameter is too small, wear of the ball becomes severe, so that the amount of mixed impurities increases. Therefore, the ball diameter is 3 to 1
The range is 0 mm. In ball mill mixing, the ideal rotation speed is for the ball to flow down at an angle of 45 ° from the highest height reached by the rotation of the pot, and when this state is achieved, a high crushing effect is obtained. The ideal rotation speed depends on the diameter of the pot. For example, if the diameter of the pot is 100 mm, the rotation speed is preferably 40 to 60 rpm.
【００２１】ボールミル混合における混合時間は、１２
時間〜７２時間の範囲とする。混合時間が１２時間未満
であると、微細な原料粉末の凝集を十分に解砕すること
ができず、結晶粒径が小さく且つ空孔径並びに錫の凝集
径が小さいＩＴＯ焼結体を得ることが困難となる。ま
た、混合時間が７２時間を越えると、混合粉末中に不純
物が多く混入するため好ましくない。The mixing time in ball mill mixing is 12
Hours to 72 hours. If the mixing time is less than 12 hours, the agglomeration of the fine raw material powder cannot be sufficiently disintegrated, and an ITO sintered body having a small crystal grain size, a small pore diameter, and a small agglomeration diameter of tin may be obtained. It will be difficult. On the other hand, if the mixing time exceeds 72 hours, it is not preferable because many impurities are mixed in the mixed powder.
【００２２】上記の湿式混合により得られたスラリー
は、乾燥造粒した後、コールドプレス若しくは冷間静水
圧プレスにより３ｔｏｎ／ｃｍ2以上で成形し、成形体
を酸素雰囲気中にて１３５０℃〜１５５０℃、好ましく
は１４５０℃〜１５００℃の温度範囲で、１５時間以下
の焼結を行う。この焼結条件の範囲内であれば、酸素雰
囲気中で焼結を行うことによって、前記した中間化合物
相の粗大化等の弊害を阻止できる。しかし、焼結温度が
１５５０℃を越えるか又は焼結時間が１５時間を越える
と、粗大化された錫原子の凝集体が形成されるか、若し
くは結晶粒成長による粒径の粗大化と共に空孔径も粗大
化するため、スパッタリング時の異常放電やノジュール
が多発する原因となる。The slurry obtained by the above wet mixing is dried and granulated, and then molded at a pressure of 3 ton / cm 2 or more by a cold press or a cold isostatic press. Sintering is performed at a temperature in the range of 1450C to 1500C for 15 hours or less. Within the range of the sintering conditions, sintering in an oxygen atmosphere can prevent the above-mentioned adverse effects such as coarsening of the intermediate compound phase. However, if the sintering temperature exceeds 1550 ° C. or the sintering time exceeds 15 hours, agglomerates of coarsened tin atoms are formed, or the pore size increases due to the coarsening of the grain size due to crystal grain growth. Is also coarsened, which causes abnormal discharge and nodules during sputtering.
【００２３】このようにして得られたＩＴＯ焼結体は、
実質的にＩｎ2Ｏ3相と、Ｉｎ2Ｏ3相中に錫元素が固溶さ
れた相とから構成され、これらＩｎ2Ｏ3相及びＩｎ2Ｏ3
相中に錫元素が固溶された相の平均結晶粒径が３〜８μ
ｍと微細に制御されている。また、焼結体内部に存在す
る最大空孔径が１μｍ以下、錫原子の最大凝集径も３μ
ｍ以下となり、ＩＴＯ焼結体の密度は６.８ｇ／ｃｍ3以
上である。The ITO sintered body thus obtained is
Substantially In 2 O 3 phase, tin element is composed of a solid-dissolved phase in the In 2 O 3 phase, they In 2 O 3 phase and In 2 O 3
The average crystal grain size of the phase in which tin element is dissolved in the phase is 3 to 8μ.
m is finely controlled. Further, the maximum pore diameter existing in the sintered body is 1 μm or less, and the maximum aggregation diameter of tin atom is 3 μm.
m or less, and the density of the ITO sintered body is 6.8 g / cm 3 or more.
【００２４】また、このＩＴＯ焼結体では、錫は大部分
がＩｎ2Ｏ3相中に固溶され、Ｉｎ2Ｏ3相中に固溶される
錫原子は２重量％以上であることが好ましい。更に、Ｉ
ｎ2Ｏ3とＳｎＯ2との中間化合物相として、主に(Ｉｎ60
Ｓｎ40)2Ｏ3などが形成されることがあるが、この中間
化合物相の量は少ないほど好ましい。この中間化合物相
の量としては、Ｘ線回析において２θ＝３０.２°に現
れる上記組成の中間化合物相の回析ピーク強度が、Ｉｎ
2Ｏ3相の（２２２）面の回析ピーク強度の１０％以下で
あることが好ましい。Further, in this ITO sintered body, tin largely been solved in In 2 O 3 phase, it tin atoms solid-dissolved in the In 2 O 3 phase is 2 wt% or more preferable. Furthermore, I
As an intermediate compound phase between n 2 O 3 and SnO 2 , mainly (In 60
Although Sn 40 ) 2 O 3 and the like may be formed, the amount of the intermediate compound phase is preferably as small as possible. As the amount of the intermediate compound phase, the diffraction peak intensity of the intermediate compound phase having the above composition which appears at 2θ = 30.2 ° in the X-ray diffraction is In.
It is preferably 10% or less of the diffraction peak intensity of the (222) plane of the 2 O 3 phase.
【００２５】本発明における別の焼結方法として、最初
に酸素雰囲気中にて１３５０℃〜１５５０℃、好ましく
は１４５０℃〜１５００℃の温度範囲で１５時間以下の
焼結を行い、続いて窒素ガス又はＡｒ等の不活性ガス若
しくは真空雰囲気のような還元雰囲気中において、１３
５０〜１５５０℃の温度範囲で１０時間以下の焼結を行
うこともできる。この１次焼結と２次焼結によって得ら
れるＩＴＯ焼結体は、上記した特徴のほかに、焼結体内
の酸欠により酸素空孔が導入されて空孔拡散が行われる
ので、密度が容易に上昇して７.０ｇ／ｃｍ3以上に緻密
化でき、更に０.１オーム・ｃｍ以下のバルク抵抗値を容
易に達成することができる。As another sintering method in the present invention, sintering is first performed in an oxygen atmosphere at a temperature in the range of 1350 ° C. to 1550 ° C., preferably 1450 ° C. to 1500 ° C. for 15 hours or less. Or, in a reducing atmosphere such as an inert gas such as Ar or a vacuum atmosphere, 13
Sintering at a temperature in the range of 50 to 1550 ° C. for 10 hours or less can also be performed. The ITO sintered body obtained by the primary sintering and the secondary sintering has, in addition to the above-mentioned features, oxygen vacancies are introduced due to lack of oxygen in the sintered body and vacancy diffusion is performed. It can easily rise to a density of 7.0 g / cm 3 or more, and can easily achieve a bulk resistance value of 0.1 ohm · cm or less.
【００２６】上記ＩＴＯ焼結体の各特性の測定方法は以
下の通りである。即ち、結晶粒径及び空孔径は、焼結体
断面を研磨した後、熱腐食によって粒界を析出させ、Ｓ
ＥＭ観察することで測定する。中間化合物相の存在は、
焼結体を粉末化した試料をＸ線回析法にて測定し、その
量は上記のごとく中間化合物相の上記回析ピークの積分
強度とＩｎ2Ｏ3相の（２２２）面の回析ピークの積分強
度との強度比から求める。また、Ｉｎ2Ｏ3相中に固溶さ
れる錫量、及び錫原子の凝集径は、焼結体断面を研磨
し、ビーム径１μｍのＥＰＭＡ線分析及び面分析によっ
て測定することができる。The measuring method of each property of the above-mentioned ITO sintered body is as follows. That is, the crystal grain size and the pore size are determined by polishing the cross section of the sintered body, then precipitating a grain boundary by hot corrosion,
It is measured by EM observation. The presence of the intermediate compound phase
A powdered sample of the sintered body was measured by an X-ray diffraction method, and the amount was determined by the integrated intensity of the diffraction peak of the intermediate compound phase and the diffraction of the (222) plane of the In 2 O 3 phase as described above. It is determined from the intensity ratio with the integrated intensity of the peak. In addition, the amount of tin dissolved in the In 2 O 3 phase and the aggregation diameter of tin atoms can be measured by polishing the cross section of the sintered body and performing EPMA line analysis and surface analysis with a beam diameter of 1 μm.
【００２７】[0027]
【実施例】実施例１ 比表面積３０ｍ2／ｇ、平均粒径０.０８μｍのＩｎ2Ｏ3
粉末に、比表面積７ｍ2／ｇ、平均粒径０.０８μｍのＳ
ｎＯ2粉末を、錫組成が７.８重量％になるように配合
し、これを原料粉末とした。この原料粉末を硬質ジルコ
ニアボール及び水と共に樹脂製ポットに入れ、原料粉
末：ボール：水分の重量比を１.０：３.０：１.８とす
ると共に、その全体量をポット容積に対して６０％とし
た。次に、バインダーとしてポリビニルアルコールを１
重量％加え、ボールミルで２４時間混合した。尚、使用
したボールの直径は３ｍｍ、ポットの直径は１５０ｍ
ｍ、ボールミルの回転数は５０ｒｐｍとした。EXAMPLES Example 1 In 2 O 3 having a specific surface area of 30 m 2 / g and an average particle size of 0.08 μm
A powder having a specific surface area of 7 m 2 / g and an average particle size of 0.08 μm was added to the powder.
The nO 2 powder was blended so that the tin composition became 7.8% by weight, and this was used as a raw material powder. The raw material powder is put into a resin pot together with hard zirconia balls and water, and the weight ratio of the raw material powder: ball: water is set to 1.0: 3.0: 1.8, and the whole amount is based on the pot volume. 60%. Next, 1 polyvinyl alcohol was used as a binder.
% By weight and mixed with a ball mill for 24 hours. The diameter of the ball used was 3 mm, and the diameter of the pot was 150 m.
m, and the rotation speed of the ball mill was 50 rpm.
【００２８】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を冷間静水圧プレスによって３ｔ
ｏｎ／ｃｍ2の圧力で成形した。得られた成形体は、１
０リットル／ｍｉｎで酸素ガスを導入しながら昇温速度
５℃／ｍｉｎにて１５００℃に昇温させ、この温度で１
５時間の焼結を行った。得られたＩＴＯ焼結体は、直径
１２７ｍｍ×厚さ６ｍｍの円盤状の焼結体である。Thereafter, the slurry was taken out, dried and granulated, and the obtained granulated powder was subjected to cold isostatic pressing for 3 tons.
It was molded at a pressure of on / cm 2 . The obtained molded body is 1
The temperature was raised to 1500 ° C. at a rate of 5 ° C./min while introducing oxygen gas at 0 liter / min.
Sintering was performed for 5 hours. The obtained ITO sintered body is a disc-shaped sintered body having a diameter of 127 mm and a thickness of 6 mm.
【００２９】得られたＩＴＯ焼結体の密度を求めた後、
焼結体の一部を切断して粉砕し、Ｘ線回析測定を２θ＝
２５°〜３７°の角度範囲で行って１０回積算し、その
結果から中間化合物相(Ｉｎ60Ｓｎ40)2Ｏ3の回折ピーク
の強度比を求めた。また、焼結体の一部を切断して切断
面を研磨した後、試料をＥＰＭＡ線分析及び面分析によ
り測定し、Ｉｎ2Ｏ3相中に固溶された錫量、及び錫原子
の凝集径を求めた。更に、この試料を用いて熱腐食によ
り粒界を析出させ、ＳＥＭ観察によって平均結晶粒径と
空孔径を測定した。得られた各測定値を下記表１に示し
た。After determining the density of the obtained ITO sintered body,
A part of the sintered body was cut and pulverized, and X-ray diffraction measurement was performed at 2θ =
The measurement was performed in an angle range of 25 ° to 37 ° and integrated 10 times, and the intensity ratio of the diffraction peak of the intermediate compound phase (In 60 Sn 40 ) 2 O 3 was determined from the result. Further, after cutting a part of the sintered body and polishing the cut surface, the sample was measured by EPMA linear analysis and surface analysis, and the amount of tin dissolved in the In 2 O 3 phase and the aggregation of tin atoms were measured. The diameter was determined. Further, a grain boundary was precipitated by thermal corrosion using this sample, and the average crystal grain size and the pore size were measured by SEM observation. The measured values obtained are shown in Table 1 below.
【００３０】また、得られたＩＴＯ焼結体を直径１００
ｍｍ×厚さ６ｍｍの円盤状に加工してスパッタリング用
ターゲットを形成し、このターゲットを用いてＤＣマグ
ネトロンスパッタ法によりスパッタリングを行った。ス
パッタリング条件は、投入電力２Ｗ／ｃｍ2、ガス圧０.
５Ｐａ、Ｏ2分圧２％に固定した。実験開始から２０時
間経過後に投入電力の変化から異常放電回数を１０分間
測定すると同時に、４０時間経過後のターゲット表面に
生成したノジュールの状況を目視観察した。得られた結
果を下記表２に示した。Further, the obtained ITO sintered body was made to have a diameter of 100
A target for sputtering was formed by processing into a disk having a size of 6 mm x 6 mm, and sputtering was performed using this target by a DC magnetron sputtering method. The sputtering conditions were as follows: input power 2 W / cm 2 , gas pressure 0.
The pressure was fixed at 5 Pa and the O 2 partial pressure was 2%. Twenty hours after the start of the experiment, the number of abnormal discharges was measured for 10 minutes from the change in the supplied power, and at the same time, the state of nodules generated on the target surface after the lapse of 40 hours was visually observed. The results obtained are shown in Table 2 below.
【００３１】実施例２ 比表面積３４ｍ2／ｇ、平均粒径０.０７μｍのＩｎ2Ｏ3
粉末に、比表面積７ｍ2／ｇ、平均粒径０.０８μｍのＳ
ｎＯ2粉末を、錫組成が７.８重量％になるように配合し
て、原料粉末とした。この原料粉末を硬質ジルコニアボ
ール及び水と共に樹脂製ポットに入れ、原料粉末：ボー
ル：水分の重量比を１.０：５.０：１.８とし、その全
体量をポット容積に対して４０％とした。更にバインダ
ーとしてポリビニルアルコールを１重量％加え、ボール
ミルで２４時間混合した。使用したボールの直径は１０
ｍｍ、ポットの直径は１５０ｍｍ、ボールミルの回転数
は５０ｒｐｍとした。 Example 2 In 2 O 3 having a specific surface area of 34 m 2 / g and an average particle size of 0.07 μm
A powder having a specific surface area of 7 m 2 / g and an average particle size of 0.08 μm was added to the powder.
The nO 2 powder was blended so as to have a tin composition of 7.8% by weight to obtain a raw material powder. This raw material powder is put into a resin pot together with hard zirconia balls and water, and the weight ratio of the raw material powder: ball: water is 1.0: 5.0: 1.8, and the total amount is 40% with respect to the pot volume. And Further, 1% by weight of polyvinyl alcohol was added as a binder, and the mixture was mixed by a ball mill for 24 hours. The diameter of the ball used is 10
mm, the diameter of the pot was 150 mm, and the rotation speed of the ball mill was 50 rpm.
【００３２】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を冷間静水圧プレスにより３ｔｏ
ｎ／ｃｍ2で成形した。この成形体は、１０リットル／
ｍｉｎで酸素ガスを導入しながら昇温速度５℃／ｍｉｎ
で１５００℃まで昇温させ、この温度で１０時間の焼結
を行った。得られたＩＴＯ焼結体について実施例１と同
様の測定及び試験を行い、その結果を下記表１及び表２
に示した。Thereafter, the slurry was taken out, dried and granulated, and the obtained granulated powder was subjected to cold isostatic pressing for 3 tons.
Molded at n / cm 2 . This molded body is 10 liters /
min while introducing oxygen gas, heating rate 5 ° C / min
And sintering was performed at this temperature for 10 hours. The same measurement and test as in Example 1 were performed on the obtained ITO sintered body, and the results were shown in Tables 1 and 2 below.
It was shown to.
【００３３】実施例３ 上記実施例２と同じＩｎ2Ｏ3粉末とＳｎＯ2粉末を同様
に配合し、これを原料粉末とした。この原料粉末を硬質
ジルコニアボール及び水と共に樹脂製ポットに入れ、原
料粉末：ボール：水分の重量比を１.０：３.０：２.０
とし、その全体量をポット容積に対して４０％とした。
更にバインダーとしてポリビニルアルコールを１重量％
加え、ボールミルで１８時間混合した。使用したボール
の直径は５ｍｍ、ポットの直径は１５０ｍｍ、ボールミ
ルの回転数は５０ｒｐｍとした。 Example 3 The same In 2 O 3 powder and SnO 2 powder as in Example 2 were blended in the same manner and used as a raw material powder. This raw material powder is put into a resin pot together with hard zirconia balls and water, and the weight ratio of the raw material powder: ball: water is 1.0: 3.0: 2.0.
And the total amount was set to 40% with respect to the pot volume.
1% by weight of polyvinyl alcohol as a binder
In addition, the mixture was mixed in a ball mill for 18 hours. The diameter of the ball used was 5 mm, the diameter of the pot was 150 mm, and the rotation speed of the ball mill was 50 rpm.
【００３４】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を冷間静水圧プレスにより３ｔｏ
ｎ／ｃｍ2で成形した。この成形体は、１０リットル／
ｍｉｎで酸素ガスを導入しながら昇温速度１℃／ｍｉｎ
で１５００℃まで昇温させ、この温度で１０時間の１次
焼結を行った。次に、酸素ガスを窒素ガスに切り換えて
同一流速で導入しながら１５００℃で５時間の２次焼結
を行った。得られたＩＴＯ焼結体について実施例１と同
様の測定及び試験を行い、その結果を下記表１及び表２
に示した。Thereafter, the slurry was taken out, dried and granulated, and the obtained granulated powder was subjected to cold isostatic pressing for 3 tons.
Molded at n / cm 2 . This molded body is 10 liters /
min while introducing oxygen gas, heating rate 1 ° C / min
And primary sintering was performed at this temperature for 10 hours. Next, secondary sintering was performed at 1500 ° C. for 5 hours while switching the oxygen gas to nitrogen gas and introducing the gas at the same flow rate. The same measurement and test as in Example 1 were performed on the obtained ITO sintered body, and the results were shown in Tables 1 and 2 below.
It was shown to.
【００３５】比較例１ 上記実施例２と同じＩｎ2Ｏ3粉末とＳｎＯ2粉末を同様
に配合し、これを原料粉末とした。この原料粉末を硬質
ジルコニアボール及び水と共に樹脂製ポットに入れ、原
料粉末：ボール：水分の重量比を１.０：３.０：１.２
とし、その全体量をポット容積に対して６０％とした。
更に、バインダーとしてポリビニルアルコールを１重量
％加え、ボールミルで２４時間混合した。使用したボー
ルの直径は２０ｍｍ、ポットの直径は１５０ｍｍ、ボー
ルミルの回転数は５０ｒｐｍとした。 Comparative Example 1 The same In 2 O 3 powder and SnO 2 powder as in Example 2 were mixed in the same manner, and this was used as a raw material powder. This raw material powder is put into a resin pot together with hard zirconia balls and water, and the weight ratio of the raw material powder: ball: water is 1.0: 3.0: 1.2.
And the total amount was set to 60% of the pot volume.
Further, 1% by weight of polyvinyl alcohol was added as a binder, and the mixture was mixed in a ball mill for 24 hours. The diameter of the ball used was 20 mm, the diameter of the pot was 150 mm, and the rotation speed of the ball mill was 50 rpm.
【００３６】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を冷間静水圧プレスにより３ｔｏ
ｎ／ｃｍ2で成形した。この成形体は、１０リットル／
ｍｉｎにて酸素ガスを導入しながら昇温速度１℃／ｍｉ
ｎにて１５００℃に昇温させ、この温度で１５時間の焼
結を行った。得られたＩＴＯ焼結体について実施例１と
同様の測定及び試験を行い、その結果を下記表１及び表
２に示した。Thereafter, the slurry was taken out and dried and granulated, and the obtained granulated powder was subjected to cold isostatic pressing for 3 tons.
Molded at n / cm 2 . This molded body is 10 liters /
min while introducing oxygen gas, heating rate 1 ° C / mi
Then, the temperature was raised to 1500 ° C. and sintering was performed at this temperature for 15 hours. The same measurement and test as in Example 1 were performed for the obtained ITO sintered body, and the results are shown in Tables 1 and 2 below.
【００３７】比較例２ 上記実施例１と同様に、比表面積３０ｍ2／ｇ、平均粒
径０.０８μｍのＩｎ2Ｏ3粉末に、比表面積７ｍ2／ｇ、
平均粒径０.０８μｍのＳｎＯ2粉末を、錫組成が７.８
重量％になるように配合し、これを原料粉末とした。こ
の原料粉末を硬質ジルコニアボール及び水と共に樹脂製
ポットに入れ、原料粉末：ボール：水分の重量比を１.
０：３.０：２.５とし、その全体量をポット容積に対し
て６０％とした。更に、バインダーとしてポリビニルア
ルコールを１重量％加え、ボールミルで２４時間混合し
た。使用したボールの直径は１０ｍｍ、ポットの直径は
１５０ｍｍ、ボールミルの回転数は３５ｒｐｍとした。COMPARATIVE EXAMPLE 2 In the same manner as in Example 1 described above, In 2 O 3 powder having a specific surface area of 30 m 2 / g and an average particle size of 0.08 μm was added to a specific surface area of 7 m 2 / g.
SnO 2 powder with an average particle size of 0.08 μm
% By weight, and this was used as a raw material powder. This raw material powder was put into a resin pot together with hard zirconia balls and water, and the weight ratio of raw material powder: ball: water was 1.
0: 3.0: 2.5, and the total amount was 60% of the pot volume. Further, 1% by weight of polyvinyl alcohol was added as a binder, and the mixture was mixed in a ball mill for 24 hours. The diameter of the ball used was 10 mm, the diameter of the pot was 150 mm, and the rotation speed of the ball mill was 35 rpm.
【００３８】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を比較例１と同様に成形した。得
られた成形体は、１０リットル／ｍｉｎにて酸素ガスを
導入しながら昇温速度１℃／ｍｉｎにて１５００℃に昇
温させ、この温度で１５時間の焼結を行った。得られた
ＩＴＯ焼結体について実施例１と同様の測定及び試験を
行い、その結果を下記表１及び表２に示した。Thereafter, the slurry was taken out and dried and granulated, and the obtained granulated powder was molded in the same manner as in Comparative Example 1. The obtained molded body was heated to 1500 ° C. at a rate of 1 ° C./min while introducing oxygen gas at 10 liter / min, and sintered at this temperature for 15 hours. The same measurement and test as in Example 1 were performed for the obtained ITO sintered body, and the results are shown in Tables 1 and 2 below.
【００３９】比較例３ 上記実施例１と同じＩｎ2Ｏ3粉末とＳｎＯ2粉末を同様
に配合し、これを原料粉末とした。この原料粉末を硬質
ジルコニアボール及び水と共に樹脂製ポットに入れ、原
料粉末：ボール：水分の重量比を１.０：１.０：２.０
とし、その全体量をポット容積に対して６０％とした。
更に、バインダーとしてポリビニルアルコールを１重量
％加え、ボールミルで２４時間混合した。使用したボー
ルの直径は１０ｍｍ、ポットの直径は１５０ｍｍ、ボー
ルミルの回転数は４０ｒｐｍとした。 Comparative Example 3 The same In 2 O 3 powder and SnO 2 powder as in Example 1 were mixed in the same manner to obtain a raw material powder. This raw material powder is put into a resin pot together with hard zirconia balls and water, and the weight ratio of the raw material powder: ball: water is 1.0: 1.0: 2.0.
And the total amount was set to 60% of the pot volume.
Further, 1% by weight of polyvinyl alcohol was added as a binder, and the mixture was mixed in a ball mill for 24 hours. The diameter of the ball used was 10 mm, the diameter of the pot was 150 mm, and the rotation speed of the ball mill was 40 rpm.
【００４０】その後、スラリーを取り出して乾燥造粒し
た後、得られた造粒粉を油圧プレスにより１ｔｏｎ／ｃ
ｍ2で成形した。得られた成形体は、３気圧の酸素ガス
雰囲気中で昇温速度１℃／ｍｉｎにて１６００℃まで昇
温させ、この温度で１０時間の焼結を行った。得られた
ＩＴＯ焼結体について実施例１と同様の測定及び試験を
行い、その結果を下記表１及び表２に示した。Thereafter, the slurry was taken out, dried and granulated, and the obtained granulated powder was subjected to 1 ton / c by a hydraulic press.
It was molded in m 2. The obtained compact was heated to 1600 ° C. at a rate of 1 ° C./min in an oxygen gas atmosphere at 3 atm, and sintered at this temperature for 10 hours. The same measurement and test as in Example 1 were performed for the obtained ITO sintered body, and the results are shown in Tables 1 and 2 below.
【００４１】[0041]
【表１】 密 度 中間化合物相 錫固溶量 最大錫凝集 平均粒径 最大空孔焼結体試料 (g/cm3) 強度比 (％) (重量％) 径 (μm) (μm) 径(μm) 実施例 1 6.9 9 4 2 7 1 実施例 2 7.0 8 4 2 6 1 実施例 3 7.1 8 5 3 8 1 比較例 1 6.7 8 4 12 8 8 比較例 2 6.6 7 4 8 8 5 比較例 3 6.5 7 4 10 7 6[Table 1] Density Intermediate compound phase Tin solid solution amount Maximum tin agglomeration Average particle size Maximum pore sintered body sample (g / cm 3 ) Strength ratio (%) (% by weight) Diameter (μm) (μm) Diameter ( [mu] m) example 1 6.9 9 4 2 7 1 example 2 7.0 8 4 2 6 1 example 3 7.1 8 5 3 8 1 Comparative example 1 6.7 8 4 12 8 8 Comparative example 2 6.6 7 4 8 8 5 Comparative example 3 6.5 7 4 10 7 6
【００４２】[0042]
【表２】 [Table 2]
【００４３】以上の結果から分かるように、本発明の実
施例１〜３のＩＴＯ焼結体においては、平均結晶粒径や
錫の最大凝集径並びに最大空孔径がいずれも小さく、ス
パッタリングにおける異常放電及びノジュールの生成を
少なくすることができた。これに対して比較例１〜３の
焼結体では、湿式ボールミルでの混合条件が適切でない
ため錫の凝集径及び空孔径が粗大化した。また、比較例
２の焼結体では、更に焼結温度が高過ぎるため、錫の凝
集径や空孔径に加えて平均結晶粒径も大きくなった。そ
の結果、比較例の各焼結体はいずれも異常放電が多発
し、ノジュールの生成も多かった。As can be seen from the above results, in the ITO sintered bodies of Examples 1 to 3 of the present invention, the average crystal grain size, the maximum aggregation diameter of tin, and the maximum pore diameter are all small, and abnormal discharge during sputtering is And the production of nodules could be reduced. On the other hand, in the sintered bodies of Comparative Examples 1 to 3, the agglomerated diameter and the pore diameter of tin were coarsened because the mixing conditions in the wet ball mill were not appropriate. In the sintered body of Comparative Example 2, the sintering temperature was too high, so that the average crystal grain size was increased in addition to the tin agglomeration diameter and the pore diameter. As a result, in each of the sintered bodies of the comparative examples, abnormal discharge frequently occurred, and nodules were also frequently generated.
【００４４】[0044]
【発明の効果】本発明によれば、スパッタリング用ター
ゲットとして、長時間の使用後であっても、異常放電の
発生及びノジュールの発生が極めて少ない酸化インジウ
ム・酸化錫焼結体を製造することができる。従って、本
発明により得られた酸化インジウム・酸化錫焼結体をス
パッタリング用ターゲットとして使用すれば、優れた特
性のＩＴＯ透明電極膜を安定して効率良く成膜すること
が可能である。According to the present invention, it is possible to produce an indium oxide / tin oxide sintered body as a sputtering target, in which abnormal discharge and nodule generation are extremely small even after long-time use. it can. Therefore, if the indium oxide / tin oxide sintered body obtained according to the present invention is used as a sputtering target, it is possible to stably and efficiently form an ITO transparent electrode film having excellent characteristics.
Claims (3)
し、乾燥造粒して成形した後、酸素雰囲気中で焼結する
酸化インジウム・酸化錫焼結体の製造方法において、比
表面積２０ｍ2／ｇ以上のＩｎ2Ｏ3粉末と比表面積５ｍ2
／ｇ以上のＳｎＯ2粉末とを原料粉末とし、原料粉末を
湿式ボールミルにて混合する際に、 (1) 使用するボールの直径が３〜１０ｍｍ、 (2) 原料粉末に対して添加する水分量が重量比で１.８
〜２.０倍 (3) 原料粉末に対して添加するボール量が重量比で３.
０〜５.０倍 (4) 原料粉末と水とボールの合計量がポット容積の４０
〜６０％ (5) 混合時間が１２〜７２時間 の条件で混合することを特徴とする酸化インジウム・酸
化錫焼結体の製造方法。In a method for producing an indium oxide / tin oxide sintered body, In 2 O 3 powder and SnO 2 powder are wet-mixed, dried, granulated, and then sintered in an oxygen atmosphere. In 2 O 3 powder of 20 m 2 / g or more and specific surface area of 5 m 2
/ G or more of SnO 2 powder as raw material powder and mixing the raw material powder with a wet ball mill, (1) the diameter of the ball used is 3 to 10 mm, (2) the amount of water added to the raw material powder Is 1.8 by weight
Up to 2.0 times (3) The amount of balls added to the raw material powder is 3.
0 to 5.0 times (4) The total amount of the raw material powder, water and balls is 40 times the pot volume.
(5) A method for producing an indium oxide / tin oxide sintered body, wherein the mixing is performed under the conditions of a mixing time of 12 to 72 hours.
０℃で１５時間以下の焼結を行うことを特徴とする、請
求項１に記載の酸化インジウム・酸化錫焼結体の製造方
法。2. In an oxygen atmosphere, 1350 to 155
The method for producing an indium oxide / tin oxide sintered body according to claim 1, wherein sintering is performed at 0 ° C for 15 hours or less.
０℃で５〜１０時間の焼結を行った後、更に還元雰囲気
中において１３５０〜１５５０℃で１０時間以下の焼結
を行うことを特徴とする、請求項１に記載の酸化インジ
ウム・酸化錫焼結体の製造方法。3. The method according to claim 1, wherein the temperature is 1350 to 155 in an oxygen atmosphere.
The indium oxide / tin oxide according to claim 1, wherein after sintering at 0 ° C for 5 to 10 hours, sintering is further performed at 1350 to 1550 ° C for 10 hours or less in a reducing atmosphere. A method for manufacturing a sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30449296A JPH10147861A (en) | 1996-11-15 | 1996-11-15 | Production of indium oxide-tin oxide sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30449296A JPH10147861A (en) | 1996-11-15 | 1996-11-15 | Production of indium oxide-tin oxide sintered body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10147861A true JPH10147861A (en) | 1998-06-02 |
Family
ID=17933693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30449296A Pending JPH10147861A (en) | 1996-11-15 | 1996-11-15 | Production of indium oxide-tin oxide sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10147861A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030429A (en) * | 2000-07-18 | 2002-01-31 | Tosoh Corp | Ito sputtering target and manufacturing method |
| JP2002047562A (en) * | 2000-07-28 | 2002-02-15 | Sumitomo Metal Mining Co Ltd | Method for manufacturing ito target |
| JP2002302761A (en) * | 2001-04-06 | 2002-10-18 | Tosoh Corp | Ito sputtering target and production method therefor |
| WO2003014409A1 (en) * | 2001-08-02 | 2003-02-20 | Idemitsu Kosan Co., Ltd. | Sputtering target, transparent conductive film, and their manufacturing method |
| JP2009029706A (en) * | 2001-03-12 | 2009-02-12 | Nikko Kinzoku Kk | Tin oxide powder for ito sputtering target, production method of the powder, sintered body sputtering target for ito film formation and production method of the target |
| KR101010563B1 (en) | 2003-04-24 | 2011-01-24 | 토소가부시키가이샤 | Transparent conductive film and sputtering target |
| JP2011202276A (en) * | 2011-04-19 | 2011-10-13 | Jx Nippon Mining & Metals Corp | Transparent electrode film |
-
1996
- 1996-11-15 JP JP30449296A patent/JPH10147861A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002030429A (en) * | 2000-07-18 | 2002-01-31 | Tosoh Corp | Ito sputtering target and manufacturing method |
| JP2002047562A (en) * | 2000-07-28 | 2002-02-15 | Sumitomo Metal Mining Co Ltd | Method for manufacturing ito target |
| JP2009029706A (en) * | 2001-03-12 | 2009-02-12 | Nikko Kinzoku Kk | Tin oxide powder for ito sputtering target, production method of the powder, sintered body sputtering target for ito film formation and production method of the target |
| JP2002302761A (en) * | 2001-04-06 | 2002-10-18 | Tosoh Corp | Ito sputtering target and production method therefor |
| WO2003014409A1 (en) * | 2001-08-02 | 2003-02-20 | Idemitsu Kosan Co., Ltd. | Sputtering target, transparent conductive film, and their manufacturing method |
| KR101010563B1 (en) | 2003-04-24 | 2011-01-24 | 토소가부시키가이샤 | Transparent conductive film and sputtering target |
| JP2011202276A (en) * | 2011-04-19 | 2011-10-13 | Jx Nippon Mining & Metals Corp | Transparent electrode film |
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