JPH0849070A - Ito sintered compact and its production - Google Patents
Ito sintered compact and its productionInfo
- Publication number
- JPH0849070A JPH0849070A JP6202910A JP20291094A JPH0849070A JP H0849070 A JPH0849070 A JP H0849070A JP 6202910 A JP6202910 A JP 6202910A JP 20291094 A JP20291094 A JP 20291094A JP H0849070 A JPH0849070 A JP H0849070A
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- Prior art keywords
- powder
- particle size
- sintered body
- tin
- ito
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、透明導電膜をスパッタ
リングにより形成する際に蒸着材として使用するＩＴＯ
焼結体およびその製造方法に関する。The present invention relates to an ITO used as a vapor deposition material when forming a transparent conductive film by sputtering.
The present invention relates to a sintered body and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】ＩＴＯ焼結体から蒸着、スパッタリン
グ、イオンプレーティング等により得られる透明導電膜
は、その比抵抗値の低さから有望な膜として注目されて
いる。たとえば、電子ビーム加熱（以下、ＥＢ蒸着とい
う）により適当な条件のもとでＩＴＯ焼結体から成膜す
ることにより、透明性が高く、良好な膜のシート抵抗値
が得られている。2. Description of the Related Art A transparent conductive film obtained from an ITO sintered body by vapor deposition, sputtering, ion plating or the like has been attracting attention as a promising film because of its low specific resistance value. For example, by forming a film from an ITO sintered body under appropriate conditions by electron beam heating (hereinafter referred to as EB vapor deposition), high transparency and a good sheet resistance value of the film are obtained.
【０００３】このようなＩＴＯ焼結体は次のようにして
製造されている。すなわち、所望の組成に配合された、
実質的にインジウム、錫および酸素からなる粉末を成形
した後、大気中もしくは真空中、酸素雰囲気中で１５０
０〜１６００℃程度の温度で焼結する等の方法がとられ
ている。Such an ITO sintered body is manufactured as follows. That is, blended in the desired composition,
After forming a powder consisting essentially of indium, tin, and oxygen, the powder is heated to 150 in air or in an oxygen atmosphere.
A method such as sintering at a temperature of about 0 to 1600 ° C. is used.
【０００４】[0004]
【発明が解決しようとする課題】近年のカラー液晶ディ
スプレイを中心とする液晶業界の急速な発展に伴い、デ
ィスプレイの電極に用いられるＩＴＯ薄膜の需要は拡大
している。それを受けて、ＩＴＯ薄膜には、高い膜特性
の他に低コスト化が要求されている。また、焼結体の使
用効果を高める方法としては、焼結体に照射する電子線
の走査など成膜装置の改良が行われてきたが、電子線を
移動する距離に限界があったり、装置が高いなどの理由
により改良されるまでには至っていない。With the rapid development of the liquid crystal industry centering on color liquid crystal displays in recent years, the demand for ITO thin films used for display electrodes is expanding. In response, ITO thin films are required to have low cost in addition to high film characteristics. Further, as a method for enhancing the effect of using the sintered body, the film forming apparatus has been improved by scanning the electron beam with which the sintered body is irradiated. It has not been improved because of high cost.
【０００５】一方、ＩＴＯ薄膜の原料となるＩＴＯ焼結
体への要求も利用効率に優れたものが求められている。On the other hand, there is also a demand for an ITO sintered body which is a raw material for an ITO thin film, which has excellent utilization efficiency.
【０００６】前述の先行技術に開示されたＩＴＯ焼結体
においては、基板加熱によるＥＢ蒸着によれば比抵抗値
の低い膜は得られるが、集束させた電子線をＩＴＯ焼結
体に照射し、ごく一部分を加熱蒸発させるために、ＩＴ
Ｏ焼結体の表面と内部に温度差が生じ、熱膨張の違いに
よりＩＴＯ焼結体に割れ（熱衝撃による割れ）が発生す
る。特に、ＩＴＯ焼結体に割れが発生すると放電状態が
不安定になったり、使用不可能になることが知られてい
る。In the ITO sintered body disclosed in the above-mentioned prior art, although a film having a low specific resistance value can be obtained by EB vapor deposition by heating the substrate, the ITO sintered body is irradiated with a focused electron beam. , To heat and evaporate a small part of the IT
A temperature difference occurs between the surface and the inside of the O sintered body, and the ITO sintered body is cracked (cracked by thermal shock) due to the difference in thermal expansion. In particular, it is known that when the ITO sintered body is cracked, the discharge state becomes unstable or unusable.
【０００７】再利用の問題を解決するために、ＥＢ蒸着
で使いきった後のＩＴＯ焼結体を手粉砕にて粉末状にし
て再度ＥＢ蒸着に供する方法が提案されている。しか
し、従来公知の焼結体においては、使いきった後のＩＴ
Ｏ焼結体自体が固いために粉砕による粉末化ができず、
ＩＴＯ焼結体の利用効率は上がっていない。In order to solve the problem of reuse, there has been proposed a method in which an ITO sintered body that has been used up by EB vapor deposition is powdered by hand pulverization and subjected to EB vapor deposition again. However, in the case of the conventionally known sintered body, the IT after being used up
Since the O sintered body itself is hard, it cannot be pulverized by crushing,
The utilization efficiency of the ITO sintered body has not improved.
【０００８】したがって本発明は、比抵抗値の良好なＩ
ＴＯ膜が成膜できるばかりでなく、耐熱衝撃性に優れ、
かつ手による粉砕が容易であるために、最終的には粉末
としても使用でき、作業性がよく利用効率に優れたＩＴ
Ｏ焼結体を提供することを目的とする。Therefore, according to the present invention, I having a good specific resistance value is used.
Not only can a TO film be formed, but it also has excellent thermal shock resistance,
And since it can be easily crushed by hand, it can be used as a powder in the end, and it has good workability and excellent utilization efficiency.
The object is to provide an O sintered body.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するため
に、本発明のＩＴＯ焼結体の製造方法は、主としてイン
ジウム、錫および酸素からなる粉末を成形して焼結を行
うＩＴＯ焼結体の製造方法において、酸化インジウム粉
末と酸化錫粉末を混合して熱処理することにより粒度調
整粉を得て、酸化インジウム粉末を主とする原料粉中に
前記粒度調整粉を添加して造粒粉末とし、該造粒粉末を
成形、焼結することを特徴とする。In order to solve the above problems, the method for producing an ITO sintered body of the present invention is an ITO sintered body in which a powder mainly composed of indium, tin and oxygen is molded and sintered. In the manufacturing method, the indium oxide powder and the tin oxide powder are mixed and heat-treated to obtain a particle size adjusting powder, and the particle size adjusting powder is added to a raw material powder mainly containing indium oxide powder to obtain a granulated powder. It is characterized in that the granulated powder is molded and sintered.
【００１０】一面からみれば、錫組成が１〜５０重量％
となるように酸化インジウム粉末と酸化錫粉末とを混合
し熱処理して粒度調整粉を生成し、酸化インジウム粉末
を主とする原料粉中に前記粒度調整粉を添加し混合して
造粒粉末とし、該造粒粉末を成形、焼結する。From one aspect, the tin composition is 1 to 50% by weight.
Indium oxide powder and tin oxide powder are mixed and heat treated to produce a particle size adjusting powder, and the particle size adjusting powder is added to a raw material powder mainly containing indium oxide powder and mixed to form a granulated powder. , Molding and sintering the granulated powder.
【００１１】他の一面からみれば、錫組成が１〜５０重
量％となるように酸化インジウムと酸化錫を配合し熱処
理した粒度調整粉末を酸化インジウムや酸化錫からなる
原料粉末中に混合し成形した後、大気中、真空中、もし
くは酸素雰囲気中にて焼結する。そして、これにより、
３０〜８０ｋｇ／ｃｍ2 以下の圧縮強度で粉砕可能なＩ
ＴＯ焼結体が得られる。本発明のＩＴＯ焼結体は、Ｉｎ
2Ｏ3−ＳｎＯ2 系で、実質的にインジウム、錫および酸
素からなり、ＩＴＯ焼結体の錫組成は２０重量％以下で
あることが望ましい。From another aspect, indium oxide and tin oxide are mixed so as to have a tin composition of 1 to 50% by weight and heat-treated, and the particle size adjusting powder is mixed with a raw material powder made of indium oxide or tin oxide and molded. After that, sintering is performed in the air, a vacuum, or an oxygen atmosphere. And this
I that can be crushed with a compressive strength of 30 to 80 kg / cm 2 or less
A TO sintered body is obtained. The ITO sintered body of the present invention is
The 2 O 3 —SnO 2 system is substantially composed of indium, tin and oxygen, and the tin composition of the ITO sintered body is preferably 20% by weight or less.
【００１２】さらに他の一面からみれば、実質的にイン
ジウム、錫、および酸素からなり、錫成分を所望の組成
および粒度分布に配合された粉末を成形し、大気中、真
空中もしくは酸素雰囲気中にて焼結しＩＴＯ焼結体を製
造する。これにより、３０〜８０ｋｇ／ｃｍ2 以下の圧
縮強度で粉砕可能で、また６００℃からの水中急冷にお
いて割れの生じることのないＩＴＯ焼結体が得られる。[0012] From still another aspect, a powder consisting essentially of indium, tin, and oxygen, in which a tin component is mixed in a desired composition and particle size distribution, is molded, and the powder is molded in the air, a vacuum, or an oxygen atmosphere. And sintered to produce an ITO sintered body. This makes it possible to obtain an ITO sintered body that can be crushed with a compressive strength of 30 to 80 kg / cm 2 or less and that does not crack when quenched in water from 600 ° C.
【００１３】本発明によって得られたＩＴＯ焼結体は、
耐熱衝撃性が高く、成膜中における割れが有効的に抑制
され、したがって良質なＩＴＯ膜を安定して得られる。
また、手による粉砕が容易であるために、ＥＢ蒸着で使
いきった後のＩＴＯ焼結体を最終的には粉末として再度
ＥＢ蒸着により成膜できる。The ITO sintered body obtained according to the present invention is
The thermal shock resistance is high, cracking during film formation is effectively suppressed, and therefore a good quality ITO film can be stably obtained.
Further, since it is easy to pulverize by hand, the ITO sintered body that has been used up by EB evaporation can be finally formed into a film by EB evaporation again as a powder.
【００１４】[0014]
【作用】前述のように、従来公知の方法で製造されたＩ
ＴＯ焼結体を用いてＥＢ蒸着を行った場合に生じる割れ
は、集束させた電子線を焼結体に当て、ごく一部分を加
熱蒸着させるために、ＩＴＯ焼結体の表面と内部に生じ
る温度差によって起こる熱膨張の違いが原因である。熱
膨張差が生じて割れる原因は、焼結が進行する際の粒同
士の結合具合の影響が大きく、強いては粒同士の密着度
に起因していると思われる。As described above, I produced by a conventionally known method
The cracks that occur when EB vapor deposition is performed using a TO sintered body are the temperatures generated on the surface and inside of the ITO sintered body in order to apply a focused electron beam to the sintered body and heat-deposit only a small portion. This is due to the difference in thermal expansion caused by the difference. It is considered that the cause of the difference in thermal expansion and cracking is largely due to the degree of bonding between the particles during the progress of sintering, and is strongly due to the degree of adhesion between the particles.
【００１５】本発明者は、粒同士の密着度を制御するこ
とにより、成膜中の割れを有効的に抑制するばかりでな
く、成膜後の手粉砕作業を容易にすることができること
に注目し、前述した製造条件により、粒同士の密着度を
制御することで、ＩＴＯ焼結体の成膜中の割れ、成膜後
の粉砕具合を解決することに成功した。The inventor of the present invention has noticed that not only can the cracks during film formation be effectively suppressed by controlling the degree of adhesion between the grains, but also the manual crushing work after film formation can be facilitated. Then, by controlling the degree of adhesion between the particles based on the above-mentioned manufacturing conditions, it has succeeded in solving cracks during film formation of the ITO sintered body and crushing conditions after film formation.
【００１６】粒同士の密着度は、圧縮試験機によりＩＴ
Ｏ焼結体の圧縮強度を測定することにより求められ、８
０ｋｇ／ｃｍ2 以下、好ましくは４０〜６０ｋｇ／ｃｍ
2 の範囲が手でも粉砕しやすく、また耐熱衝撃性に対し
ても効果が大きい。The degree of adhesion between the particles is determined by IT using a compression tester.
The value obtained by measuring the compressive strength of the O sintered body was 8
0 kg / cm 2 or less, preferably 40 to 60 kg / cm
The range of 2 is easy to pulverize even by hand, and has a great effect on thermal shock resistance.
【００１７】圧縮強度が８０ｋｇ／ｃｍ2 を越える場
合、成膜のためにＥＢ照射する時に局所的な加熱によっ
て起こる熱膨張差により、ＩＴＯ焼結体は割れてしまう
ばかりでなく、手粉砕が容易でなくなるために粉末化作
業に手間取り、利用効率に優れたＩＴＯ焼結体を提供す
ることは難しい。When the compressive strength exceeds 80 kg / cm 2 , the ITO sintered body is not only cracked due to the difference in thermal expansion caused by local heating at the time of EB irradiation for film formation, but also easy to crush by hand. Therefore, it is difficult to provide an ITO sintered body which is time-consuming for powdering work and has excellent utilization efficiency.
【００１８】逆に、圧縮強度が３０ｋｇ／ｃｍ2 以下で
あると、粒同士の密着度が逆に弱くなりすぎるために、
ＥＢ照射直後にビームがＩＴＯ焼結体を貫通してしまっ
たり、膜特性にも問題が生じたりする。On the other hand, when the compressive strength is 30 kg / cm 2 or less, the adhesion between the grains becomes too weak, and
The beam may penetrate the ITO sintered body immediately after the EB irradiation, or a problem may occur in the film characteristics.
【００１９】なお、耐熱衝撃性は、ＩＴＯ焼結体を６０
０℃にて１時間加熱後、水中に投入し割れ具合を調べる
ことにより求められる。The thermal shock resistance of the ITO sintered body is 60
After heating for 1 hour at 0 ° C., it is placed in water and examined for cracks.
【００２０】以下に、本発明に係わる他の各要素に基づ
いて説明する。The following is a description based on each of the other elements relating to the present invention.
【００２１】（原料粉末）原料粉末として用いる粉末は
酸化インジウム粉末の他に、酸化インジウム−酸化錫の
複合粉末、酸化インジウム−酸化錫複合粉末と酸化錫粉
末との混合粉末などを用いることもできる。(Raw Material Powder) As the raw material powder, indium oxide powder, indium oxide-tin oxide composite powder, mixed powder of indium oxide-tin oxide composite powder and tin oxide powder, and the like can be used. .
【００２２】（粒度調整粉） 粒度調整粉（Ａ）：酸化インジウム粉末中に酸化錫を所
望の組成に配合（好ましくは錫組成が１〜５０重量％の
組成となるように酸化錫粉末を配合）し、混合した後、
該粉末をガスフロー型大気炉もしくは真空加熱炉により
大気中、真空中もしくは酸素雰囲気中にて、１３００℃
以上（好ましくは１３００〜１６００℃）の温度で１〜
１５時間の熱処理を行い、平均粒径を５〜３０μｍまで
粒成長させて粒度調整粉とする。(Particle size adjusting powder) Particle size adjusting powder (A): Indium oxide powder is compounded with tin oxide in a desired composition (preferably tin oxide powder is compounded so that the tin composition is 1 to 50% by weight). ), And after mixing
The powder is heated to 1300 ° C. in an atmosphere, a vacuum or an oxygen atmosphere by a gas flow type atmospheric furnace or a vacuum heating furnace.
1 to above (preferably 1300 to 1600 ° C)
Heat treatment is carried out for 15 hours, and grains are grown to an average grain size of 5 to 30 μm to obtain grain size adjusting powder.
【００２３】粒度調整粉（Ｂ）：酸化インジウム粉末の
みをガスフロー型大気炉もしくは真空加熱炉により大気
中、真空中もしくは酸素雰囲気中にて、１３００℃以上
（好ましくは１３００〜１６００℃）の温度で１〜１５
時間の熱処理を行い、平均粒径を５〜３０μｍまで粒成
長させて粒度調整粉とする。Particle size adjusting powder (B): Indium oxide powder alone is heated in a gas flow type atmospheric furnace or a vacuum heating furnace in the atmosphere, in a vacuum or in an oxygen atmosphere at a temperature of 1300 ° C. or higher (preferably 1300 to 1600 ° C.). 1 to 15
Heat treatment is performed for a period of time to grow the particles to an average particle size of 5 to 30 μm to obtain a particle size adjusting powder.
【００２４】熱処理温度が１３００℃未満の場合、不純
物ガスの抜けが不十分であったり、熱処理粉末中にＳｎ
Ｏ2 相が存在するなどのために、成膜時に良好な、すな
わちきれいなＩＴＯ膜を得ることが難しくなる。さらに
熱処理温度が１６００℃を越える場合、錫の粗大化によ
り錫分散性が低下し、成膜中の放電状態に支障を来す。When the heat treatment temperature is lower than 1300 ° C., the escape of the impurity gas is insufficient, or Sn is contained in the heat treated powder.
Due to the presence of the O 2 phase, it is difficult to obtain a good ITO film, that is, a clean ITO film. Further, when the heat treatment temperature exceeds 1600 ° C., the tin dispersibility deteriorates due to the coarsening of tin, and the discharge state during film formation is hindered.
【００２５】（造粒粉末）上記のようにして得た粒度調
整粉を原料粉末に配合した後、混合・粉砕を行い造粒粉
末とする。ただし、その配合量は、粒度調整粉（Ａ）の
み、もしくは粒度調整粉（Ａ）と酸化インジウム粉末の
みの粒度調整粉（Ｂ）の合計量を原料粉末に対し、４０
重量％以上、好ましくは５０〜７０重量％とする。あら
かじめ熱処理により、平均粒径を５〜３０μｍにまで粒
成長させた粒度調整粉を原料粉末に対し５０〜７０重量
％添加することで粒度分布を広げ、成形し易くするばか
りでなく、焼結時に生じる粒同士の密着度を緩和させ、
成膜する際の割れを抑制することができる。(Granulated powder) The particle size-adjusted powder obtained as described above is mixed with the raw material powder, and then mixed and pulverized to obtain a granulated powder. However, the compounding amount of the particle size adjusting powder (A) alone or the total amount of the particle size adjusting powder (A) and the particle size adjusting powder (B) of only indium oxide powder is 40% with respect to the raw material powder.
The amount is not less than wt%, preferably 50 to 70 wt%. 50% to 70% by weight of the raw material powder is added to the raw material powder by the heat treatment so that the average particle size is grown to 5 to 30 μm to broaden the particle size distribution and facilitate molding, and at the time of sintering. Relaxes the adhesion between the generated particles,
It is possible to suppress cracking during film formation.
【００２６】（混合・粉砕）混合・粉砕を行う方法とし
ては、たとえばボールミル混合がある。ボールミル混合
を行う場合、混合時間は、好ましくは１２時間以上、さ
らに好ましくは２４時間以上である。パラフィンワック
ス、ポリビニルアルコールなどのバインダーは混合・粉
砕時などに１〜４重量％添加することができる。(Mixing / Pulverizing) As a method for performing mixing / pulverization, there is, for example, ball mill mixing. When performing ball mill mixing, the mixing time is preferably 12 hours or longer, more preferably 24 hours or longer. A binder such as paraffin wax or polyvinyl alcohol can be added in an amount of 1 to 4% by weight when mixing and pulverizing.
【００２７】（成形）造粒粉末の成形は、コールドプレ
スにて行う。この際、焼結による収縮はほとんどなくＩ
ＴＯ焼結体の寸法は成形時に決まってしまうため、ＩＴ
Ｏ焼結体の仕様を考えて成形しなければならない。たと
えばＩＴＯ焼結体の相対密度を４．３ｇ／ｃｍ3 にする
ためには１ｔｏｎ／ｃｍ2 前後の成形圧力が好ましい。(Molding) The granulated powder is molded by cold pressing. At this time, there was almost no shrinkage due to sintering.
Since the dimensions of the TO sintered body are determined at the time of molding, IT
It must be formed by considering the specifications of the O sintered body. For example, a molding pressure of about 1 ton / cm 2 is preferable in order to make the relative density of the ITO sintered body 4.3 g / cm 3 .
【００２８】（焼結−昇温速度）焼結は、ガスフロー型
大気炉もしくは真空加熱炉により、大気中、真空中もし
くは酸素雰囲気中にて行うが、大気中による方法が安価
にできて最も好ましい。昇温速度は脱バインダーが容易
に行える範囲とし、たとえば室温から脱バインダー終了
温度４００℃までの昇温時間を１３時間程度とする。(Sintering-heating rate) Sintering is carried out in a gas flow type atmospheric furnace or a vacuum heating furnace in the air, in a vacuum or in an oxygen atmosphere, but the method in the air is the cheapest method. preferable. The temperature rising rate is set within a range where debinding can be easily performed, and for example, the heating time from room temperature to the debinding completion temperature of 400 ° C. is set to about 13 hours.
【００２９】（焼結−焼結温度）焼結温度は、５００℃
〜１１００℃とする。５００℃未満では、焼結が進行し
ないために非常に脆いＩＴＯ焼結体となり作業性が低下
してしまう。１１００℃を越えると、焼結が強固になり
すぎて、圧縮強度が６０ｋｇ／ｃｍ2 以上になり、成膜
時にＩＴＯ焼結体が割れてしまうばかりでなく、手粉砕
が困難となる。(Sintering-Sintering temperature) The sintering temperature is 500.degree.
~ 1100 ° C. If the temperature is lower than 500 ° C., the sintering does not proceed, resulting in a very brittle ITO sintered body, which lowers the workability. If it exceeds 1100 ° C., the sintering becomes too strong and the compressive strength becomes 60 kg / cm 2 or more, so that not only the ITO sintered body is cracked during film formation but also hand grinding becomes difficult.
【００３０】（焼結−保持時間）焼結温度に達した際に
保持する時間を制御してやることも重要である。焼結温
度に達した際に保持する時間は１〜５時間程度が好まし
い。保持期間が１時間未満であると、焼結炉内の均熱に
不具合が生じて安定した生産ができない。(Sintering-holding time) It is also important to control the holding time when the sintering temperature is reached. The holding time when reaching the sintering temperature is preferably about 1 to 5 hours. If the holding period is less than 1 hour, a problem occurs in soaking in the sintering furnace and stable production cannot be performed.
【００３１】[0031]
【実施例】以下に、実施例を用いて本発明を説明する。EXAMPLES The present invention will be described below with reference to examples.
【００３２】（実施例１）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が１０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した。その後、大気中に
て１５００℃で１５時間の熱処理を行い、平均粒径３０
μｍの粒度調整粉（Ａ）とした。Example 1 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
Mix for 8 hours, dry and grind. After that, heat treatment is performed in the air at 1500 ° C. for 15 hours to obtain an average particle size of 30
The particle size-adjusted powder (A) having a particle size of μm was used.
【００３３】平均粒径１μｍ以下の酸化インジウム粉末
を主とする原料粉中に粒度調整粉（Ａ）を５０重量％添
加して混合した後、造粒粉末とした。さらに、造粒粉末
を所定の形状に成形した後、大気中で焼結を行った。焼
結工程は室温から４００℃までを１３時間にて昇温し、
６００℃まで３時間にて温度上昇させた。そして６００
℃にて３時間保持し２５ｍｍφ、厚さ１５ｍｍの大きさ
のＩＴＯ焼結体を得た。粒度調整粉の熱処理条件、配合
率および焼結条件を表１に示す。50% by weight of the particle size adjusting powder (A) was added to and mixed with a raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, to obtain a granulated powder. Further, the granulated powder was molded into a predetermined shape and then sintered in the atmosphere. In the sintering process, the temperature is raised from room temperature to 400 ° C in 13 hours,
The temperature was raised to 600 ° C. in 3 hours. And 600
The temperature was kept at 3 ° C. for 3 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００３４】このようにして得られたＩＴＯ焼結体の相
対密度は４．４ｇ／ｃｍ3 、化学分析による錫組成（平
均組成）は、４．８重量％であった。また、焼結体の圧
縮強度をＲＵ型万能材料試験機にて求め、さらに熱衝撃
性は、焼結体を６００℃にて１時間加熱後、水中に投入
し割れ具合を調べた。これらの結果を表２に示す。The ITO sintered body thus obtained had a relative density of 4.4 g / cm 3 and a tin composition (average composition) by chemical analysis of 4.8% by weight. Further, the compressive strength of the sintered body was determined with a RU type universal material testing machine, and the thermal shock resistance was examined by heating the sintered body at 600 ° C. for 1 hour and then pouring it into water. Table 2 shows the results.
【００３５】（実施例２）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が１０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した。その後、大気中に
て１５００℃で１０時間の熱処理を行い、平均粒径２４
μｍの粒度調整粉（Ａ）とした。さらに、平均粒径１μ
ｍの酸化インジウム粉末および３重量％の酢酸ビニール
系バインダーを添加した後、湿式ボールミル中で１８時
間混合し、乾燥および粉砕にて平均粒径を１０μｍ以下
にして、大気中にて１５００℃で３時間の熱処理を行
い、平均粒径１５μｍの粒度調整粉（Ｂ）とした。そし
て、平均粒径１μｍ以下の酸化インジウム粉末を主とす
る原料粉中に粒度調整粉（Ａ）を５０重量％、粒度調整
粉（Ｂ）を２０重量％添加して混合した後、造粒粉末と
した。さらに、造粒粉末を所定の形状に成形した後、大
気中で焼結を行った。焼結工程は室温から４００℃まで
を１３時間にて昇温し、６００℃まで３時間にて温度上
昇させた。そして６００℃にて３時間保持し２５ｍｍ
φ、厚さ１５ｍｍの大きさのＩＴＯ焼結体を得た。粒度
調整粉の熱処理条件、配合率および焼結条件を表１に示
す。Example 2 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition would be 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
Mix for 8 hours, dry and grind. After that, heat treatment is performed in the air at 1500 ° C. for 10 hours to obtain an average particle size of 24
The particle size-adjusted powder (A) having a particle size of μm was used. Furthermore, average particle size 1μ
m indium oxide powder and 3% by weight of vinyl acetate binder were added, mixed in a wet ball mill for 18 hours, dried and pulverized to have an average particle size of 10 μm or less, and dried at 1500 ° C. in the atmosphere at 3 ° C. for 3 hours. Heat treatment was performed for a time to obtain a particle size-adjusted powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 20% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Further, the granulated powder was molded into a predetermined shape and then sintered in the atmosphere. In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And hold at 600 ℃ for 3 hours 25mm
An ITO sintered body having a size of φ and a thickness of 15 mm was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００３６】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００３７】（実施例３）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が５０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、流量１０リット
ル／分のＯ2 を流した酸素雰囲気中にて１５００℃で１
０時間の熱処理を行い、平均粒径２５μｍの粒度調整粉
（Ａ）とした。また、平均粒径１μｍ以下の酸化インジ
ウム粉末に３重量％の酢酸ビニール系バインダーを添加
した後、湿式ボールミル中で１８時間混合し、乾燥およ
び粉砕にて平均粒径を１０μｍ以下にして、大気中にて
１３００℃で１５時間の熱処理を行い、平均粒径１５μ
ｍとした粒度調整粉（Ｂ）とした。そして、平均粒径１
μｍ以下の酸化インジウム粉末を主とする原料粉中に粒
度調整粉（Ａ）を１０重量％、粒度調整粉（Ｂ）を３０
重量％添加して混合した後、造粒粉末とした。さらに、
造粒粉末を用いて成形した後、大気中で焼結を行った。
焼結工程は室温から４００℃までを１３時間にて昇温
し、６００℃まで３時間にて温度上昇させた。そして、
５００℃にて５時間保持し２５ｍｍφ、厚さ１５ｍｍの
大きさのＩＴＯ焼結体を得た。粒度調整粉の熱処理条
件、配合率および焼結条件を表１に示す。Example 3 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 50% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and pulverizing, the mixture was dried at 1500 ° C. for 1 hour in an oxygen atmosphere containing O 2 at a flow rate of 10 l / min.
Heat treatment was performed for 0 hours to obtain a particle size-adjusted powder (A) having an average particle size of 25 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Heat treatment at 1300 ℃ for 15 hours at
The particle size-adjusted powder (B) was set to m. And the average particle size 1
10% by weight of the particle size adjusting powder (A) and 30% by weight of the particle size adjusting powder (B) in the raw material powder mainly composed of indium oxide powder having a particle size of μm or less
After adding by weight% and mixing, a granulated powder was obtained. further,
After molding using the granulated powder, sintering was performed in the atmosphere.
In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And
It was kept at 500 ° C. for 5 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００３８】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００３９】（実施例４）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が２０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、大気中にて１４
００、１５００、１６００℃の温度で各１時間の熱処理
を行い、各々の平均粒径を５、８、１４μｍの粒度調整
粉（Ａ）とした。また、平均粒径１μｍ以下の酸化イン
ジウム粉末に３重量％の酢酸ビニール系バインダーを添
加した後、湿式ボールミル中で１８時間混合し、乾燥お
よび粉砕にて平均粒径を１０μｍ以下にして、大気中に
て１５００℃で３時間の熱処理を行い、平均粒径１５μ
ｍとした粒度調整粉（Ｂ）とした。そして、平均粒径１
μｍ以下の酸化インジウム粉末を主とする原料粉中に粒
度調整粉（Ａ）を２５重量％、粒度調整粉（Ｂ）を２０
重量％添加して混合した後、造粒粉末とした。さらに、
造粒粉末を用いて成形した後、大気中で焼結を行った。
焼結工程は室温から４００℃までを１３時間にて昇温
し、６００℃まで３時間にて温度上昇させた。そして６
００℃にて３時間保持し２５ｍｍφ、厚さ１５ｍｍの大
きさのＩＴＯ焼結体を得た。粒度調整粉の熱処理条件、
配合率および焼結条件を表１に示す（実施例４−１、４
−２、４−３）。Example 4 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and pulverizing,
Heat treatment was performed at a temperature of 00, 1500, 1600 ° C. for 1 hour each to obtain a particle size adjusting powder (A) having an average particle size of 5, 8, 14 μm. Further, after adding 3% by weight of a vinyl acetate-based binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Heat treatment at 1500 ℃ for 3 hours, average particle size 15μ
The particle size-adjusted powder (B) was set to m. And the average particle size 1
25% by weight of the particle size adjusting powder (A) and 20% of the particle size adjusting powder (B) in the raw material powder mainly composed of indium oxide powder having a particle size of μm or less
After adding by weight% and mixing, a granulated powder was obtained. further,
After molding using the granulated powder, sintering was performed in the atmosphere.
In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. And 6
The temperature was maintained at 00 ° C. for 3 hours to obtain an ITO sintered body having a size of 25 mmφ and a thickness of 15 mm. Heat treatment conditions for the particle size adjusted powder,
The compounding ratio and sintering conditions are shown in Table 1 (Examples 4-1 and 4).
-2, 4-3).
【００４０】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す（実施例４−１、４−
２、４−３）。The ITO sintered body thus obtained was evaluated in the same manner as in Example 1, and the results are shown in Table 2 (Examples 4-1 and 4-).
2, 4-3).
【００４１】（実施例５）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が５０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、大気中にて１５
００℃の温度で１５時間の熱処理を行い、各々の平均粒
径を３０μｍとした粒度調整粉（Ａ）とした。また、平
均粒径１μｍ以下の酸化インジウム粉末に３重量％の酢
酸ビニール系バインダーを添加した後、湿式ボールミル
中で１８時間混合し、乾燥および粉砕にて平均粒径を１
０μｍ以下にして、大気中にて１４００℃で３時間の熱
処理を行い、平均粒径７μｍとした粒度調整粉（Ｂ）と
した。そして、平均粒径１μｍ以下の酸化インジウム粉
末を主とする原料粉中に粒度調整粉（Ａ）を１０重量
％、粒度調整粉（Ｂ）を４０重量％添加して混合した
後、造粒粉末とした。さらに、造粒粉末を用いて成形し
た後、大気中で焼結を行った。焼結工程は室温から４０
０℃までを１３時間にて昇温し、６００℃まで３時間に
て温度上昇させた。そして、６００℃にて３時間保持し
２５ｍｍφ、厚さ１５ｍｍの大きさのＩＴＯ焼結体を得
た。粒度調整粉の熱処理条件、配合率および焼結条件を
表１に示す。Example 5 Tin oxide powder having an average particle size of 3 μm was mixed in indium oxide powder having an average particle size of 1 μm or less so that the tin composition was 50% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 15 in the air
Heat treatment was carried out at a temperature of 00 ° C. for 15 hours to obtain a particle size adjusting powder (A) having an average particle size of 30 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, and drying and pulverizing to obtain an average particle size of 1
The particle size was adjusted to 0 μm or less and heat-treated in the atmosphere at 1400 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 7 μm. Then, 10% by weight of the particle size adjusting powder (A) and 40% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. Sintering process from room temperature to 40
The temperature was raised to 0 ° C. in 13 hours, and was raised to 600 ° C. in 3 hours. And it hold | maintained at 600 degreeC for 3 hours, and obtained the ITO sintered compact of 25 mm (phi) and the thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００４２】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００４３】（実施例６）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が２０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、大気中にて１５
００℃で１０時間の熱処理を行い、平均粒径２４μｍと
した粒度調整粉（Ａ）とした。また、平均粒径１μｍ以
下の酸化インジウム粉末に３重量％の酢酸ビニール系バ
インダーを添加した後、湿式ボールミル中で１８時間混
合し、乾燥および粉砕にて平均粒径を１０μｍ以下にし
て、大気中にて１５００℃で３時間の熱処理を行い、平
均粒径１５μｍとした粒度調整粉（Ｂ）とした。そし
て、平均粒径１μｍ以下の酸化インジウム粉末を主とす
る原料粉中に粒度調整粉（Ａ）を５０重量％、粒度調整
粉（Ｂ）を３０重量％添加して混合した後、造粒粉末と
した。さらに、造粒粉末を用いて成形した後、大気中で
焼結を行った。焼結工程は室温から４００℃までを１３
時間にて昇温し、１１００℃まで１１時間にて温度上昇
させた。そして、１１００℃にて１時間保持し２５ｍｍ
φ、厚さ１５ｍｍの大きさのＩＴＯ焼結体を得た。粒度
調整粉の熱処理条件、配合率および焼結条件を表１に示
す。Example 6 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 15 in the air
Heat treatment was carried out at 00 ° C. for 10 hours to obtain a particle size adjusting powder (A) having an average particle size of 24 μm. In addition, after adding 3% by weight of a vinyl acetate binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Was heat-treated at 1500 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 30% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. 13 steps from room temperature to 400 ℃
The temperature was raised over time, and the temperature was raised to 1100 ° C. over 11 hours. Then, hold at 1100 ° C for 1 hour and 25 mm
An ITO sintered body having a size of φ and a thickness of 15 mm was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００４４】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００４５】（実施例７）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が２０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、大気中にて１３
００℃で１５時間の熱処理を行い、平均粒径１２μｍと
した粒度調整粉（Ａ）とした。また、平均粒径１μｍ以
下の酸化インジウム粉末に３重量％の酢酸ビニール系バ
インダーを添加した後、湿式ボールミル中で１８時間混
合し、乾燥および粉砕にて平均粒径を１０μｍ以下にし
て、大気中にて１５００℃で３時間の熱処理を行い、平
均粒径１５μｍとした粒度調整粉（Ｂ）とした。そし
て、平均粒径１μｍ以下の酸化インジウム粉末を主とす
る原料粉中に粒度調整粉（Ａ）を５０重量％、粒度調整
粉（Ｂ）を２０重量％添加して混合した後、造粒粉末と
した。さらに、造粒粉末を用いて成形した後、大気中で
焼結を行った。焼結工程は室温から４００℃までを１３
時間にて昇温し、６００℃まで３時間にて温度上昇させ
た。そして、６００℃にて３時間保持し２５ｍｍφ、厚
さ１５ｍｍの大きさのＩＴＯ焼結体を得た。粒度調整粉
の熱処理条件、配合率および焼結条件を表１に示す。Example 7 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 20% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 13 in the air
Heat treatment was carried out at 00 ° C. for 15 hours to obtain a particle size adjusting powder (A) having an average particle size of 12 μm. Further, after adding 3% by weight of a vinyl acetate-based binder to indium oxide powder having an average particle size of 1 μm or less, mixing in a wet ball mill for 18 hours, drying and pulverizing to make the average particle size 10 μm or less, and then in air. Was heat-treated at 1500 ° C. for 3 hours to obtain a particle size adjusting powder (B) having an average particle size of 15 μm. Then, 50% by weight of the particle size adjusting powder (A) and 20% by weight of the particle size adjusting powder (B) are added to and mixed with the raw material powder mainly composed of indium oxide powder having an average particle size of 1 μm or less, and then the granulated powder. And Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. 13 steps from room temperature to 400 ℃
The temperature was raised over time, and the temperature was raised to 600 ° C. over 3 hours. And it hold | maintained at 600 degreeC for 3 hours, and obtained the ITO sintered compact of 25 mm (phi) and the thickness of 15 mm. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００４６】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表１に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
【００４７】（比較例１）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が５重量％となるように配合し、３重量％の酢酸ビニー
ル系バインダーを添加した後、湿式ボールミル中で１８
時間混合し、乾燥および粉砕して造粒粉末とした。さら
に、造粒粉末を用いて成形した後、大気中で焼結を行っ
た。焼結工程は室温から４００℃までを１３時間にて昇
温し、６００℃まで３時間にて温度上昇させた。そし
て、６００、８００、１０００℃にて３時間保持し２５
ｍｍφ、厚さ１５ｍｍの大きさのＩＴＯ焼結体を得た。
焼結条件を表１に示す（比較例１−１、１−２、１−
３）。(Comparative Example 1) Tin oxide powder having an average particle diameter of 3 μm was mixed in indium oxide powder having an average particle diameter of 1 μm or less so that the tin composition was 5% by weight, and 3% by weight of a vinyl acetate binder was added. 18 in a wet ball mill after addition
It was mixed for time, dried and pulverized to obtain a granulated powder. Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. In the sintering step, the temperature was raised from room temperature to 400 ° C in 13 hours, and the temperature was raised to 600 ° C in 3 hours. Then, hold at 600, 800, 1000 ° C. for 3 hours to obtain 25
An ITO sintered body having a size of mmφ and a thickness of 15 mm was obtained.
The sintering conditions are shown in Table 1 (Comparative Examples 1-1, 1-2, 1-
3).
【００４８】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す（比較例１−１、１−
２、１−３）。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2 (Comparative Examples 1-1, 1-
2, 1-3).
【００４９】（比較例２）平均粒径１μｍ以下の酸化イ
ンジウム粉末中に平均粒径３μｍの酸化錫粉末を錫組成
が１０重量％となるように配合し、３重量％の酢酸ビニ
ール系バインダーを添加した後、湿式ボールミル中で１
８時間混合し、乾燥および粉砕した後、大気中にて１２
００℃で３時間の熱処理を行い、平均粒径４μｍの粒度
調整粉とした。この粒度調整粉を平均粒径１μｍ以下の
酸化インジウム粉末を主とする原料粉中に３０重量％添
加して混合した後、造粒粉末とした。さらに、造粒粉末
を用いて成形した後、大気中で焼結を行った。焼結工程
は室温から４００℃までを１３時間にて昇温し、６００
℃まで３時間にて温度上昇させた。そして、６００℃に
て３時間保持し２５ｍｍφ、厚さ１５ｍｍの大きさのＩ
ＴＯ焼結体を得た。粒度調整粉の熱処理条件、配合率お
よび焼結条件を表１に示す。Comparative Example 2 Indium oxide powder having an average particle size of 1 μm or less was mixed with tin oxide powder having an average particle size of 3 μm so that the tin composition was 10% by weight, and 3% by weight of a vinyl acetate binder was added. 1 in the wet ball mill after addition
After mixing for 8 hours, drying and crushing, 12 in the air
Heat treatment was performed at 00 ° C. for 3 hours to obtain a particle size-adjusted powder having an average particle size of 4 μm. 30% by weight of this particle size adjusting powder was added to and mixed with a raw material powder mainly containing indium oxide powder having an average particle size of 1 μm or less, and then a granulated powder was obtained. Furthermore, after molding using the granulated powder, sintering was performed in the atmosphere. In the sintering process, the temperature is raised from room temperature to 400 ° C in 13 hours, and 600
The temperature was raised to 3 ° C. in 3 hours. Then, it was held at 600 ° C. for 3 hours, and the size of I of 25 mmφ and thickness of 15 mm was used.
A TO sintered body was obtained. Table 1 shows the heat treatment conditions, the compounding ratio, and the sintering conditions of the particle size adjusting powder.
【００５０】得られたＩＴＯ焼結体を実施例１と同様な
評価を行い、結果を表２に示す。The obtained ITO sintered body was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
【００５１】[0051]
【表１】 ［粒度調整粉（Ａ）］ 熱処理温度 時間 平均粒径 配合割合 雰囲気 （℃） （ｈｒ） （μｍ） （％） 実施例１ １５００ １５ ３０ ５０ ａｉｒ 実施例２ １５００ １０ ２４ ５０ ａｉｒ 実施例３ １５００ １０ ２５ １０ Ｏ2 実施例４−１ １４００ １ ５ ２５ ａｉｒ 実施例４−２ １５００ １ ８ ２５ ａｉｒ 実施例４−３ １６００ １ １４ ２５ ａｉｒ 実施例５ １５００ １５ ３０ １０ ａｉｒ 実施例６ １５００ １０ ２４ ５０ ａｉｒ 実施例７ １３００ １５ １２ ５０ ａｉｒ 比較例１ − − − − − 比較例１−２ − − − − − 比較例１−３ − − − − − 比較例２ １２００ ３ ４ ３０ ａｉｒ ［粒度調整粉（Ｂ）］ 熱処理温度 時間 平均粒径 配合割合 雰囲気 （℃） （ｈｒ） （μｍ） （％） 実施例１ − − − − ａｉｒ 実施例２ １５００ ３ １５ ２０ ａｉｒ 実施例３ １３００ １５ ２１ ３０ ａｉｒ 実施例４−１ １５００ ３ １５ ２０ ａｉｒ 実施例４−２ １５００ ３ １５ ２０ ａｉｒ 実施例４−３ １５００ ３ １５ ２０ ａｉｒ 実施例５ １４００ ３ ７ ４０ ａｉｒ 実施例６ １５００ ３ １５ ３０ ａｉｒ 実施例７ １５００ ３ １５ ２０ ａｉｒ 比較例１−１ − − − − − 比較例１−２ − − − − − 比較例１−３ − − − − − 比較例２ − − − − − [Table 1] [Particle size control powder (A)] Heat treatment temperature Time Average particle size Blending ratio Atmosphere (° C) (hr) (μm) (%) Example 1 1500 15 30 50 50 air Example 2 1500 10 24 50 air Example 3 1500 10 25 10 O 2 Example 4-1 1400 1 525 25 air Example 4-2 1500 1 8 25 air Example 4-3 1600 1 14 25 air Example 5 1500 1500 15 30 10 air Example 6 1500 10 24 50 air Example 7 1300 15 12 50 air Comparative example 1 --- --- Comparative example 1-2 --- --- Comparative example 1-3 --- --- Comparative example 2 1200 3 4 30 air [Particle size Conditioning powder (B)] Heat treatment temperature Time Average particle size Blending ratio Atmosphere (° C) (hr) (μm) (%) Example 1 ----- air Example 2 1500 3 15 20 air Example 3 1300 15 21 30 air Example 4-1 1500 3 15 20 air Example 4-2 1500 3 15 20 air Example 4-3 1500 3 15 20 air Example 5 1400 3 7 40 air Example 6 1500 3 15 30 30 air Example 7 1500 3 15 20 20 air Comparative example 1-1 − − − − − Comparative example 1-2 − − − − − Comparative example 1-3 − − − − − Comparative Example 2 − − − − −
【００５２】[0052]
【表２】 相対密度 錫平均組成 圧縮強度 熱衝撃性 （g/cm3 ） （重量％） （kg/cm2） （目視観察） 実施例１ ４．４ ４．８ ６４ ○ 実施例２ ４．２ ５．０ ４５ ○ 実施例３ ３．８ ４．９ ５７ ○ 実施例４−１ ４．６ ５．１ ７６ ○ 実施例４−２ ４．５ ４．８ ６３ ○ 実施例４−３ ４．２ ４．８ ５２ ○ 実施例５ ４．３ ４．９ ４７ ○ 実施例６ ４．０ ９．８ ５６ ○ 実施例７ ４．０ ９．７ ３２ ○ 比較例１−１ ４．８ ９．８ ８１ × 比較例１−２ ５．１ ９．９ ９７ × 比較例１−３ ５．４ ９．８ １１２ × 比較例２ ４．３ ９．８ ８６ ×[Table 2] Relative density Tin average composition Compressive strength Thermal shock resistance (g / cm 3 ) (wt%) (kg / cm 2 ) (Visual observation) Example 1 4.4 4.8 64 ○ Example 2 4. 2 5.0 45 ○ Example 3 3.8 4.9 57 ○ Example 4-1 4.6 5.1 5.1 76 ○ Example 4-2 4.5 4.8 63 ○ Example 4-3 4. 2 4.8 52 ○ Example 5 4.3 4.9 47 ○ Example 6 4.0 9.8 56 ○ Example 7 4.0 9.7 32 ○ Comparative example 1-1 4.8 9.8 81 x Comparative example 1-2 5.1 9.9 97 x Comparative example 1-3 5.4 9.8 112 x Comparative example 2 4.3 9.8 86 x
【００５３】表２中、熱衝撃性の○は割れが観察されな
かったことを、また×は割れが観察されたことを示す。In Table 2, ◯ of thermal shock resistance indicates that no crack was observed, and x indicates that crack was observed.
【００５４】[0054]
【発明の効果】本発明のＩＴＯ焼結体は以上のように構
成させているので、耐熱衝撃性が高いことで、ＥＢ蒸着
中における焼結体の割れが有効的に抑制され、良質なＩ
ＴＯ膜を安定して得られる。また手による粉砕が容易で
あるために、ＥＢ蒸着で使いきった後の焼結体を最終的
には粉末として再度ＥＢ蒸着により使用できる利用効率
に優れ、安価に製造可能なＩＴＯ焼結体を提供すること
ができる。EFFECTS OF THE INVENTION Since the ITO sintered body of the present invention is configured as described above, it has high thermal shock resistance, so that cracking of the sintered body during EB vapor deposition is effectively suppressed, and good quality I
A TO film can be obtained stably. In addition, since it is easy to pulverize by hand, the sintered body that has been used up by EB vapor deposition can be finally used as a powder again by EB vapor deposition, and an ITO sintered body that has excellent utilization efficiency and can be manufactured at low cost can be obtained. Can be provided.
Claims (12)
なる粉末を成形して焼結を行うＩＴＯ焼結体の製造方法
において、酸化インジウム粉末と酸化錫粉末を混合して
熱処理することにより粒度調整粉を得て、酸化インジウ
ム粉末を主とする原料粉中に前記粒度調整粉を添加して
造粒粉末とし、該造粒粉末を成形、焼結するＩＴＯ焼結
体の製造方法。1. A method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the mixture, wherein the indium oxide powder and the tin oxide powder are mixed and heat-treated to obtain a particle size adjusting powder. A method for producing an ITO sintered body, comprising the step of adding the particle size adjusting powder to a raw material powder mainly composed of indium oxide powder to obtain a granulated powder, and molding and sintering the granulated powder.
なる粉末を成形して焼結を行うＩＴＯ焼結体の製造方法
において、錫組成が１〜５０重量％となるように酸化イ
ンジウム粉末と酸化錫粉末とを混合し熱処理して粒度調
整粉を生成し、酸化インジウム粉末を主とする原料粉中
に前記粒度調整粉を添加し混合して造粒粉末とし、該造
粒粉末を成形、焼結するＩＴＯ焼結体の製造方法。2. An indium oxide powder and a tin oxide powder having a tin composition of 1 to 50% by weight in a method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the powder. Are mixed and heat-treated to generate a particle size adjusting powder, and the particle size adjusting powder is added to and mixed with a raw material powder mainly containing indium oxide powder to form a granulated powder, and the granulated powder is molded and sintered. Manufacturing method of ITO sintered body.
なる粉末を成形して焼結を行うＩＴＯ焼結体の製造方法
において、錫組成が１〜５０重量％となるように酸化イ
ンジウム粉末と酸化錫粉末とを混合し熱処理して第１の
粒度調整粉を生成し、さらに酸化インジウム粉のみを熱
処理して第２の粒度調整粉を生成し、酸化インジウム粉
末を主とする原料粉中に前記第１の粒度調整粉と第２の
粒度調整粉とを添加し混合して造粒粉末とし、該造粒粉
末を成形、焼結するＩＴＯ焼結体の製造方法。3. A method for producing an ITO sintered body, which comprises forming a powder of mainly indium, tin and oxygen and sintering the powder, wherein the indium oxide powder and the tin oxide powder have a tin composition of 1 to 50% by weight. Are mixed and heat-treated to generate a first particle size adjusting powder, and further only the indium oxide powder is heat-treated to generate a second particle size adjusting powder, and the first powder is mainly added to the raw material powder mainly containing indium oxide powder. 2. A method for producing an ITO sintered body, comprising adding the particle size-adjusted powder and the second particle size-adjusted powder to a mixture to form a granulated powder, and molding and sintering the granulated powder.
整粉の平均一次粒子径が５〜３０μｍからなるＩＴＯ焼
結体の製造方法。4. A method for producing an ITO sintered body, wherein the particle size-adjusted powder according to claim 1 has an average primary particle diameter of 5 to 30 μm.
中に添加する粒度調整粉の総量が原料粉に対し、４０重
量％以上であるＩＴＯ焼結体の製造方法。5. A method for producing an ITO sintered body, wherein the total amount of the grain size adjusting powder added to the raw material powder according to claim 1 is 40% by weight or more based on the raw material powder.
整粉の平均一次粒子径を５〜３０μｍとするため、１３
００〜１６００℃の温度で１〜１５時間の熱処理するＩ
ＴＯ焼結体の製造方法。6. The average primary particle diameter of the particle size adjusting powder according to claim 1, which is 5 to 30 μm,
Heat treatment at a temperature of 00 to 1600 ° C. for 1 to 15 hours I
Method of manufacturing TO sintered body.
整粉の平均一次粒子径を５〜３０μｍとするため、１３
００〜１６００℃の温度で１〜１５時間の熱処理し、か
つ原料粉中に添加する粒度調整粉の総量が原料粉に対
し、４０重量％以上であるＩＴＯ焼結体の製造方法。7. The average primary particle diameter of the particle size-adjusted powder according to claim 1 is set to 5 to 30 μm.
A method for producing an ITO sintered body, wherein heat treatment is performed at a temperature of 00 to 1600 ° C. for 1 to 15 hours, and the total amount of grain size adjusting powder added to the raw material powder is 40% by weight or more based on the raw material powder.
末を成形した後、５００〜１１００℃の温度で１〜５時
間の焼結を行うＩＴＯ焼結体の製造方法。8. A method for producing an ITO sintered body, which comprises molding the granulated powder according to any one of claims 1 to 3 and then sintering at a temperature of 500 to 1100 ° C. for 1 to 5 hours.
インジウム−酸化錫の複合粉末、または酸化インジウム
−酸化錫の複合粉末と酸化錫粉末との混合粉末からなる
請求項１〜３のいずれかに記載のＩＴＯ焼結体の製造方
法。9. The method according to claim 1, wherein the raw material powder is indium oxide powder, indium oxide-tin oxide composite powder, or a mixed powder of indium oxide-tin oxide composite powder and tin oxide powder. A method for producing an ITO sintered body as described above.
０ｋｇ／ｃｍ2 の圧縮強度で粉砕可能な、請求項１〜９
に記載の製造方法で作られた焼結体からなるＩＴＯ蒸着
材。10. A tin composition of 20% by weight or less and 30 to 8
Grinding with a compressive strength of 0 kg / cm 2 is possible.
An ITO vapor deposition material comprising a sintered body produced by the production method described in 1.
からの水中急冷でも割れの生じることのない、請求項１
〜９に記載の製造方法で作られた焼結体からなるＩＴＯ
蒸着材。11. A tin composition of 20% by weight or less at 600 ° C.
Claim 1 which does not cause a crack even if it is rapidly cooled in water.
To ITO made of a sintered body manufactured by the manufacturing method described in
Evaporation material.
度が３．８〜４．６ｇ／ｃｍ3 である、請求項１〜９に
記載の製造方法で作られた焼結体からなるＩＴＯ蒸着
材。12. A sintered body produced by the manufacturing method according to claim 1, which has a tin composition of 20% by weight or less and a sintered body density of 3.8 to 4.6 g / cm 3. ITO vapor deposition material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20291094A JP3269272B2 (en) | 1994-08-05 | 1994-08-05 | ITO sintered body and method of manufacturing the same |
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| Publication Number | Publication Date |
|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010037197A (en) * | 2009-09-25 | 2010-02-18 | Murata Mfg Co Ltd | Method for producing glass ceramic substrate |
| JP2013184840A (en) * | 2012-03-06 | 2013-09-19 | Sumitomo Metal Mining Co Ltd | Tablet for vapor deposition and method for producing the same |
| JP2014141375A (en) * | 2013-01-24 | 2014-08-07 | Ulvac Japan Ltd | Method for producing sintered compact powder, sintered compact powder, sputtering target, method for producing sputtering target and apparatus for producing sintered compact powder |
| CN104507888A (en) * | 2012-07-31 | 2015-04-08 | 住友金属矿山株式会社 | Oxide sintered body and tablet obtained by processing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007077781A1 (en) * | 2005-12-28 | 2007-07-12 | Mitsui Mining & Smelting Co., Ltd. | Indium oxide powder |
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1994
- 1994-08-05 JP JP20291094A patent/JP3269272B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010037197A (en) * | 2009-09-25 | 2010-02-18 | Murata Mfg Co Ltd | Method for producing glass ceramic substrate |
| JP2013184840A (en) * | 2012-03-06 | 2013-09-19 | Sumitomo Metal Mining Co Ltd | Tablet for vapor deposition and method for producing the same |
| CN104507888A (en) * | 2012-07-31 | 2015-04-08 | 住友金属矿山株式会社 | Oxide sintered body and tablet obtained by processing same |
| EP2881379A4 (en) * | 2012-07-31 | 2016-03-02 | Sumitomo Metal Mining Co | Oxide sintered body and tablet obtained by processing same |
| JP2014141375A (en) * | 2013-01-24 | 2014-08-07 | Ulvac Japan Ltd | Method for producing sintered compact powder, sintered compact powder, sputtering target, method for producing sputtering target and apparatus for producing sintered compact powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3269272B2 (en) | 2002-03-25 |
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