JPH05170513A - Production of high-density ito sintered compact - Google Patents
Production of high-density ito sintered compactInfo
- Publication number
- JPH05170513A JPH05170513A JP3353102A JP35310291A JPH05170513A JP H05170513 A JPH05170513 A JP H05170513A JP 3353102 A JP3353102 A JP 3353102A JP 35310291 A JP35310291 A JP 35310291A JP H05170513 A JPH05170513 A JP H05170513A
- Authority
- JP
- Japan
- Prior art keywords
- ito
- sintering
- density
- atmosphere
- sintered body
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高密度なＩＴＯ焼結体を
熱間等方圧プレス（以下、ＨＩＰと略する）焼結によっ
て製造する方法に関する。本発明で得られる焼結体は、
特に高密度でかつ還元されにくいのでＩＴＯスパッタリ
ングタ−ゲットとして有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high density ITO sintered body by hot isostatic pressing (hereinafter abbreviated as HIP) sintering. The sintered body obtained in the present invention is
It is particularly useful as an ITO sputtering target because it has a high density and is difficult to reduce.
【０００２】[0002]
【従来の技術】近年、ＩＴＯ透明導電膜の製膜方法とし
てスパッタリング法が広く用いられている。この様なス
パッタリングで高性能な透明導電膜を形成するタ−ゲッ
トとしては高密度なＩＴＯ焼結体が優れていることが知
られている。これまで高密度なＩＴＯ焼結体を製造する
方法が幾つか提案されている。例えば常圧焼結では、原
料粉末に極めて微細なＩＴＯ粉末を用いたり、焼結雰囲
気を酸素雰囲気とする方法があり、一方加圧焼結では熱
間一軸方向プレス（ホットプレス：ＨＰ）、ＨＩＰ等が
知られている。2. Description of the Related Art In recent years, a sputtering method has been widely used as a method for forming an ITO transparent conductive film. It is known that a high-density ITO sintered body is excellent as a target for forming a high-performance transparent conductive film by such sputtering. Up to now, several methods for producing a high density ITO sintered body have been proposed. For example, in the normal pressure sintering, there is a method of using extremely fine ITO powder as a raw material powder or setting an oxygen atmosphere as a sintering atmosphere, while in the pressure sintering, hot uniaxial pressing (hot press: HP), HIP Etc. are known.
【０００３】前者の常圧焼結では、ＩＴＯ焼結体の密度
は原料粉末の粒度に大きく依存し、高密度焼結体を得る
には極めて高度な粉末調製技術が必要であった。一方後
者の加圧焼結では、焼結が還元雰囲気あるいは脱気雰囲
気であったため、焼結体密度は向上するが焼結体が還元
され、タ−ゲットとしての性能は必ずしも十分なものと
は言えなかった。In the former pressureless sintering, the density of the ITO sintered body largely depends on the particle size of the raw material powder, and an extremely advanced powder preparation technique was required to obtain a high density sintered body. On the other hand, in the latter pressure sintering, since the sintering was performed in a reducing atmosphere or a degassing atmosphere, the density of the sintered body was improved, but the sintered body was reduced, and the performance as a target is not always sufficient. I could not say.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、ＩＴＯをＨ
ＩＰによって焼結させる際、焼結雰囲気を酸素雰囲気と
することにより、還元がない高性能な高密度ＩＴＯ焼結
体を製造する方法を提供することにある。DISCLOSURE OF THE INVENTION The present invention uses ITO as an H
An object of the present invention is to provide a method for producing a high-performance high-density ITO sintered body that is not reduced by setting the sintering atmosphere to an oxygen atmosphere when sintering by IP.
【０００５】[0005]
【課題を解決するための手段】本発明者等はＨＩＰによ
ってＩＴＯを焼結させる際、焼結雰囲気を酸素雰囲気と
し、用いる缶体にＩＴＯと反応しにくいアルミナもしく
は窒化硼素等をコ−ティングした缶体を用い、さらに比
較的低温（１１００℃以下）、高圧（１００ｋｇ／ｃｍ
２以上）で焼結させることにより、理論密度の９０％以
上の高密度で、還元されないＩＴＯ焼結体が容易に得ら
れることを見出し本発明を完成するに至ったものであ
る。Means for Solving the Problems When the ITO is sintered by HIP, the present inventors set the sintering atmosphere to an oxygen atmosphere, and coated alumina or boron nitride, which is difficult to react with ITO, on the can body used. Using a can, relatively low temperature (1100 ° C or less), high pressure (100 kg / cm)
The present invention has been completed by finding that an unreduced ITO sintered body having a high density of 90% or more of the theoretical density can be easily obtained by sintering ( 2 or more).
【０００６】以下、本発明に関して詳細に説明する。The present invention will be described in detail below.
【０００７】本発明の焼結ではＨＩＰを用いて焼結する
が、その焼結雰囲気としては酸素雰囲気でなくてはなら
ない。従来のＨＩＰ焼結では焼結雰囲気は脱気状態ある
いは、不活性ガス雰囲気が一般的であるが、その様な条
件では得られる焼結体が還元され好ましくない。本発明
のＨＩＰ焼結では焼結容器内に酸素を導入し、焼結体、
特に焼結体表面の還元を抑制することが可能である。酸
素の導入量は缶体の初期の圧力が数ｍｍＨｇから１気圧
を用いるのが好ましい。In the sintering of the present invention, HIP is used for sintering, but the sintering atmosphere must be an oxygen atmosphere. In the conventional HIP sintering, the sintering atmosphere is generally in a degassed state or an inert gas atmosphere, but under such conditions, the obtained sintered body is reduced, which is not preferable. In the HIP sintering of the present invention, oxygen is introduced into the sintering container,
In particular, it is possible to suppress the reduction of the surface of the sintered body. The amount of oxygen introduced is preferably such that the initial pressure of the can body is from several mmHg to 1 atm.
【０００８】本発明の焼結に用いる容器としては、ニッ
ケル又は銅の缶体が適当である。特にこれらの缶体内部
に、アルミナコ−ティング、窒化硼素（ＢＮ）コ−ティ
ング、それらの多層コ−ティングを用いることにより、
缶体とＩＴＯとの反応を抑えることが可能である。特に
アルミナのコ−ティングはプラズマ溶射によるものの性
能が良い。コ−ティング層の厚さとしては、全体として
数十μｍ〜１０００μｍ、好ましくは、１００〜８００
μｍである。As the container used for the sintering of the present invention, a nickel or copper can body is suitable. In particular, by using alumina coating, boron nitride (BN) coating, and their multi-layer coating inside these cans,
It is possible to suppress the reaction between the can body and ITO. Particularly, the coating of alumina has good performance though it is formed by plasma spraying. The coating layer has a total thickness of several tens of μm to 1000 μm, preferably 100 to 800.
μm.
【０００９】本発明の焼結温度としては、１１００℃以
下、１００ｋｇ／ｃｍ２以上の比較的低温、高圧条件が
好ましい。焼結温度が１１００℃を越えると、缶体とＩ
ＴＯとの反応が進行するため、好ましくない。一方、７
００℃未満では焼結密度が向上しないため好ましくない
場合があり、従って、焼結温度は７００℃〜１１００℃
が特に好ましい。The sintering temperature of the present invention is preferably 1100 ° C. or lower and 100 kg / cm 2 or higher at a relatively low temperature and high pressure. If the sintering temperature exceeds 1100 ° C, the
It is not preferable because the reaction with TO proceeds. On the other hand, 7
If it is less than 00 ° C, the sintered density may not be improved, which may not be preferable. Therefore, the sintering temperature is 700 ° C to 1100 ° C.
Is particularly preferable.
【００１０】本発明の焼結圧力としては高いほうが好ま
しく、１００ｋｇ／ｃｍ２以上であることが好ましい。
１００ｋｇ／ｃｍ２未満の圧力では焼結密度が向上しに
くい。一方圧力の上限は特に規定されないが、２５０ｋ
ｇ／ｃｍ２程度までが一般的に上げられる圧力の上限で
ある。The sintering pressure of the present invention is preferably as high as possible, and is preferably 100 kg / cm 2 or more.
If the pressure is less than 100 kg / cm 2 , it is difficult to improve the sintered density. On the other hand, the upper limit of pressure is not specified, but 250k
The upper limit of the pressure that can be generally raised is up to about g / cm 2 .
【００１１】本発明の加圧焼結の時間は特に限定されな
いが、一般的に１時間から１０時間、特に２時間から４
時間で十分である。The time for pressure sintering of the present invention is not particularly limited, but is generally 1 hour to 10 hours, particularly 2 hours to 4 hours.
Time is enough.
【００１２】本発明で焼結させるＩＴＯ粉末は特に限定
されないが、酸化インジウムに対し、酸化錫を５％から
１５％含んだ混合粉末あるいは共沈粉末を用いることが
可能である。焼結用の缶体に充填する形態としては粉体
のままでも良いが、静水圧プレス（ＣＩＰ）等により予
備成型した粉体を用いることも可能である。さらに１０
００℃以下の低温で熱処理したＩＴＯ仮焼結体を用いる
ことにより、缶体とＩＴＯの反応をさらに抑制すること
が可能である。The ITO powder to be sintered in the present invention is not particularly limited, but it is possible to use a mixed powder or a coprecipitated powder containing 5% to 15% of tin oxide with respect to indium oxide. Although the powder may be used as it is in the form of filling the can body for sintering, it is also possible to use powder preformed by isostatic pressing (CIP) or the like. 10 more
It is possible to further suppress the reaction between the can body and the ITO by using the ITO pre-sintered body that is heat-treated at a low temperature of 00 ° C. or less.
【００１３】この様にして得られるＩＴＯ焼結体は理論
密度の９０％から１００％（理論密度７．１５ｇ／ｃｍ
２）であり、多くは９５％から９９％の極めて高密度な
焼結体となる。The ITO sintered body thus obtained has a theoretical density of 90% to 100% (theoretical density of 7.15 g / cm3).
2 ), and most of them are extremely dense sintered bodies of 95% to 99%.
【００１４】[0014]
【実施例】以下実施例に基づき本発明を説明するが、本
発明は実施例になんら限定されるものではない。EXAMPLES The present invention will be described below based on examples, but the present invention is not limited to the examples.
【００１５】実施例１ 酸化錫を１０重量％混合した酸化インジウム粉末を金型
プレスで予備成型し、缶体内面よりプラズマ溶射アルミ
ナ−窒化硼素−プラズマ溶射アルミナの順で各２００μ
ｍずつ３層コ−ティングした銅缶体に充填した。缶体内
部を脱気した後、酸素ガスを０．５気圧で封入し、９５
０℃、２００ｋｇ／ｃｍ３で２時間ＨＩＰ焼結させた。
得られたＩＴＯ焼結体は密度９８％（７．０１ｇ／ｃｍ
３）の高密度であった。Example 1 Indium oxide powder mixed with 10% by weight of tin oxide was preformed by a die press, and plasma sprayed alumina-boron nitride-plasma sprayed alumina in the order of 200 μm from the inside of the can.
Each layer was filled in a copper can body coated with 3 layers of m. After degassing the inside of the can, fill it with oxygen gas at 0.5 atm.
HIP sintering was performed at 0 ° C. and 200 kg / cm 3 for 2 hours.
The obtained ITO sintered body had a density of 98% (7.01 g / cm
3 ) High density.
【００１６】得られた高密度ＩＴＯ焼結体をタ−ゲット
として用い、ＤＣマグネトロンスパッタリングにより透
明導電膜を成膜した。スパッタ条件は、１％酸素導入ア
ルゴン雰囲気、圧力０．５Ｐａ、基板温度３００℃のガ
ラス基板上に２Ｗ／ｃｍ２で２０００オングストロ−ム
の膜厚で成膜した。A transparent conductive film was formed by DC magnetron sputtering using the obtained high density ITO sintered body as a target. As the sputtering conditions, a film having a film thickness of 2000 angstrom was formed at 2 W / cm 2 on a glass substrate having a 1% oxygen introduced argon atmosphere, a pressure of 0.5 Pa and a substrate temperature of 300 ° C.
【００１７】得られた膜の比抵抗は１．４×１０−４Ω
・ｃｍの低抵抗で、膜の可視光透過率８０％以上の透明
性に優れた透明導電膜が得られた。The specific resistance of the obtained film is 1.4 × 10 −4 Ω.
A transparent conductive film having a low resistance of cm and a visible light transmittance of 80% or more and excellent transparency was obtained.
【００１８】比較例１ 酸化錫を１０重量％混合した酸化インジウム粉末を金型
プレスで予備成型し、ステンレス缶体に充填した。次に
缶体内部を脱気封入した後、１１５０℃、１５０ｋｇ／
ｃｍ３で２時間ＨＩＰ焼結させた。得られたＩＴＯ焼結
体は密度９５％（６．７９ｇ／ｃｍ３）の高密度であっ
たが、焼結体と缶体が反応し、溶着しており、焼結体表
面が著しく還元され、缶の腐食が著しく一部ピンホ−ル
が発生した。Comparative Example 1 Indium oxide powder mixed with 10% by weight of tin oxide was preformed by a die press and filled in a stainless steel can body. Next, after degassing and filling the inside of the can, 1150 ° C., 150 kg /
HIP sintering was performed at cm 3 for 2 hours. The obtained ITO sintered body had a high density of 95% (6.79 g / cm 3 ), but the sintered body and the can body reacted and welded, and the surface of the sintered body was significantly reduced. , The can was remarkably corroded, and some pinholes were generated.
【００１９】得られた高密度ＩＴＯ焼結体をタ−ゲット
として用い、ＤＣマグネトロンスパッタリングにより透
明導電膜を成膜した。スパッタ条件は、実施例１と同様
とした。得られた膜の比抵抗は２．５×１０−４Ω・ｃ
ｍで、膜の可視光透過率７５％程度の比較的導電性、透
明性に劣った透明導電膜しか得られなかった。A transparent conductive film was formed by DC magnetron sputtering using the obtained high density ITO sintered body as a target. The sputtering conditions were the same as in Example 1. The specific resistance of the obtained film is 2.5 × 10 −4 Ω · c.
In m, only a transparent conductive film having relatively low conductivity and transparency with a visible light transmittance of about 75% was obtained.
【００２０】[0020]
【発明の効果】以上説明したように本発明の製造方法に
より、原料粉末の粒度等に依存せず、高密度で還元され
ないＩＴＯ焼結体を得ることが可能となり、この様な焼
結体はをタ−ゲットとして用いることにより極めて低抵
抗な透明導電膜を形成することが可能である。As described above, according to the production method of the present invention, it becomes possible to obtain an ITO sintered body which is not reduced at a high density and does not depend on the particle size of the raw material powder. It is possible to form a transparent conductive film having an extremely low resistance by using as a target.
Claims (2)
に充填し、熱間等方圧プレスによって焼結させる際、雰
囲気を酸素雰囲気とすることを特徴とする高密度ＩＴＯ
焼結体の製造方法。1. A high-density ITO, characterized in that when an ITO powder or an ITO powder molded body is filled in a can and is sintered by hot isostatic pressing, the atmosphere is an oxygen atmosphere.
Manufacturing method of sintered body.
させる際、焼結雰囲気を酸素導入雰囲気とし、内面にア
ルミナ及び／又は窒化硼素をコ−ティングした容器を用
い、１１００℃以下、１００ｋｇ／ｃｍ２以上で焼結さ
せることを特徴とする高密度ＩＴＯ焼結体の製造方法。2. When sintering ITO by hot isostatic pressing, a sintering atmosphere is an oxygen-introduced atmosphere, and a container having an inner surface coated with alumina and / or boron nitride is used, and the temperature is 1100 ° C. or less and 100 kg. A method for producing a high-density ITO sintered body, which comprises sintering at a density of not less than 1 cm 2 / cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03353102A JP3079724B2 (en) | 1991-12-18 | 1991-12-18 | Method for producing high-density ITO sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03353102A JP3079724B2 (en) | 1991-12-18 | 1991-12-18 | Method for producing high-density ITO sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05170513A true JPH05170513A (en) | 1993-07-09 |
| JP3079724B2 JP3079724B2 (en) | 2000-08-21 |
Family
ID=18428582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03353102A Expired - Fee Related JP3079724B2 (en) | 1991-12-18 | 1991-12-18 | Method for producing high-density ITO sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3079724B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0694507A1 (en) * | 1994-07-29 | 1996-01-31 | W.C. Heraeus GmbH | Indium-tin oxide component and process for its production |
| WO1997008358A1 (en) * | 1995-08-31 | 1997-03-06 | Innovative Sputtering Technology | A process for manufacturing ito alloy articles |
| EP0959055A1 (en) * | 1998-05-20 | 1999-11-24 | W.C. Heraeus GmbH & Co. KG | Process for manufacturing indium tin oxide articles |
-
1991
- 1991-12-18 JP JP03353102A patent/JP3079724B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0694507A1 (en) * | 1994-07-29 | 1996-01-31 | W.C. Heraeus GmbH | Indium-tin oxide component and process for its production |
| WO1997008358A1 (en) * | 1995-08-31 | 1997-03-06 | Innovative Sputtering Technology | A process for manufacturing ito alloy articles |
| US6123787A (en) * | 1995-08-31 | 2000-09-26 | Innovative Sputtering Technology | Process for manufacturing ITO alloy articles |
| EP0959055A1 (en) * | 1998-05-20 | 1999-11-24 | W.C. Heraeus GmbH & Co. KG | Process for manufacturing indium tin oxide articles |
| US6080341A (en) * | 1998-05-20 | 2000-06-27 | W.C. Heraeus Gmbh & Co. Kg | Process for making an indium-tin-oxide shaped body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3079724B2 (en) | 2000-08-21 |
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