JPH09228036A - Production of target for ito sputtering - Google Patents
Production of target for ito sputteringInfo
- Publication number
- JPH09228036A JPH09228036A JP8039701A JP3970196A JPH09228036A JP H09228036 A JPH09228036 A JP H09228036A JP 8039701 A JP8039701 A JP 8039701A JP 3970196 A JP3970196 A JP 3970196A JP H09228036 A JPH09228036 A JP H09228036A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- particle size
- sintering
- temp
- target
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、スパッタリングに
よりＩＴＯ膜（Indium Tin Oxide膜）を形成させる際に
使用するＩＴＯスパッタリング用ターゲットの製造方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an ITO sputtering target used when forming an ITO film (Indium Tin Oxide film) by sputtering.
【０００２】[0002]
【従来の技術】ＩＴＯ膜は高い導電性と可視光透過性を
併せ持つため、液晶表示デバイスや、窓ガラス用結露防
止発熱膜等、様々な用途に広く用いられている。ＩＴＯ
膜の形成方法としてＣＶＤ法、真空蒸着法、スパッタリ
ング法等が知られているが、この中でも特に、スパッタ
リング法は大面積の成膜が可能である、成膜速度が
速い、低抵抗の膜を再現性よく形成できる、等の利点
から広く採用されている。2. Description of the Related Art Since an ITO film has both high conductivity and visible light transmittance, it is widely used in various applications such as a liquid crystal display device and a dew condensation preventing heat generating film for window glass. ITO
As a method for forming a film, a CVD method, a vacuum vapor deposition method, a sputtering method and the like are known. Among them, the sputtering method can form a large area film, has a high film formation rate, and has a low resistance film. It is widely used because it can be formed with good reproducibility.
【０００３】ＩＴＯターゲットの焼結密度は、スパッタ
リング法によるＩＴＯ成膜に大きな影響を与えることが
知られている。ＩＴＯターゲットの焼結密度が高いもの
程、成膜速度が速い、ターゲット寿命が長い、Ｉ
ＴＯ特有の表面黒色化が少ない、基板上のゴミ（パー
ティクル）が減少する等の利点がある。このため、より
高い密度のＩＴＯターゲットが求められているが、ＩＴ
Ｏは焼結性が悪く、また高温に加熱すると不安定化する
性質があるため、一般的な焼成方法では、焼結後の密度
が４．２〜５．０ｇ／ｃｍ3 （理論密度の６０〜７０
％）の低いものしか得られない。It is known that the sintering density of the ITO target has a great influence on the ITO film formation by the sputtering method. The higher the sintered density of the ITO target, the faster the film formation rate, the longer the target life, I
There are advantages such as less surface blackening peculiar to TO and less dust (particles) on the substrate. For this reason, a higher density ITO target is required.
O has a poor sinterability and has a property of becoming unstable when heated to a high temperature. Therefore, in a general firing method, the density after sintering is 4.2 to 5.0 g / cm 3 (the theoretical density of 60). ~ 70
You can only get the ones with low%).
【０００４】そこで、より高密度のＩＴＯターゲットを
製造するために通常の焼結法に替えて、ホットプレス法
が用いられている。これにより、密度６．８ｇ／ｃｍ3
（理論密度の９５％）程度のものが製造されているが、
この方法には、設備のイニシャルコストが高い、ラ
ンニングコストが高い、同時に多数のターゲットを焼
結することが困難である、等の難点がある。Therefore, in order to manufacture a higher density ITO target, the hot pressing method is used instead of the usual sintering method. This gives a density of 6.8 g / cm 3.
Although about 95% of theoretical density is manufactured,
This method has disadvantages such as high initial cost of equipment, high running cost, and difficulty in sintering a large number of targets at the same time.
【０００５】また、焼成時の雰囲気を１気圧以上の加圧
酸素雰囲気とすることにより理論密度の９５％以上の高
密度ＩＴＯターゲットを得る方法（特開平３−２０７８
５８号公報）が開示されている。ここでは、「焼結雰囲
気の酸素分圧が１気圧（ゲージ圧）を下回ると焼結体の
密度向上効果が小さい」、および「より優れた効果を確
保するためには焼結雰囲気の酸素分圧を３気圧以上に設
定するのが望ましい」としている。しかしながら、酸素
ガスは助燃性を持つため、このように圧力の高い酸素ガ
スを必要とする製造方法は、操作上危険が伴うという問
題点を有している。Further, a method for obtaining a high density ITO target having a density of 95% or more of the theoretical density by setting a pressurized oxygen atmosphere having a pressure of 1 atmosphere or more during firing (Japanese Patent Laid-Open No. 3-2078).
No. 58) is disclosed. Here, "if the oxygen partial pressure of the sintering atmosphere is less than 1 atm (gauge pressure), the effect of improving the density of the sintered body is small", and "to ensure a more excellent effect, the oxygen content of the sintering atmosphere is reduced. It is desirable to set the pressure to 3 atmospheres or more. " However, since oxygen gas has an auxiliary combustion property, the manufacturing method which requires oxygen gas having such a high pressure has a problem in that it is dangerous in operation.
【０００６】本発明者らは、上述した従来技術の問題点
を解決するため、高い圧力の酸素雰囲気を必要とせず、
安全かつ低コストで理論密度の９５％を超える高密度Ｉ
ＴＯを高い生産性で製造する方法（特開平６−２９９３
４４号公報）を既に開発し、提案している。しかしなが
ら、現状においては、より成膜速度が速く、ターゲット
寿命が長く、更にＩＴＯ特有の表面黒色化が少ないＩＴ
Ｏターゲットが要求されていることから、ＩＴＯ焼結体
ターゲットの密度は、理論密度の９５％程度では十分と
は言えず、更なる高密度化が求められている。In order to solve the above-mentioned problems of the prior art, the present inventors did not need an oxygen atmosphere of high pressure,
Safe and low cost, high density I exceeding 95% of theoretical density
Method for producing TO with high productivity (Japanese Patent Laid-Open No. 6-2993)
No. 44) has already been developed and proposed. However, under the present circumstances, IT has a higher film formation rate, a longer target life, and less surface blackening peculiar to ITO.
Since the O target is required, the density of the ITO sintered body target cannot be said to be sufficient at about 95% of the theoretical density, and further densification is required.
【０００７】一方で近年、より欠陥の少ない良質の膜が
高歩留りで得られること等から、ＩＴＯ成膜に用いられ
るスパッタ装置も変りつつある。すなわち、ターゲット
と基板を相対運動させながら成膜を行う従来インライン
型の装置から、ターゲットと基板を互いに固定した状態
で成膜を行う枚葉式の装置へと移行しつつある。従来の
インライン型の装置は、基板とトレイと呼ばれる搬送台
車に乗せた状態で、ターゲット前面を低速で移動させな
がら連続的に成膜を行っていた。このため、基板の移動
方向にたいして垂直方向の幅と同程度のサイズを持つタ
ーゲットを用いて成膜を行えば、基板の移動方向に沿っ
たターゲットのサイズはあまり問題にならず、均一な膜
厚が得られていた。このため、インライン型装置では、
例えば１３０ｍｍ×５００ｍｍ程度の、細長いターゲッ
トが一般的であった。しかしながら、インライン型の装
置は大型になることが避けられない点や、トレイの移動
機構から発生するパーティクルが膜の欠陥を引き起こす
問題点があった。そのため、上記のようなトレイを使用
せず、基板のみを搬送し、ターゲット前面で基板が停止
した状態で成膜を行う枚葉式の装置が用いられるように
なってきている。この枚葉式のスパッタ装置では、基板
上に均一な膜厚になるよう成膜するために、基板とほぼ
同等の形状を持つ大面積のターゲットが要求される。従
来のインライン型装置に比べ大面積のＩＴＯターゲッ
ト、（例えば、５００ｍｍ×６００ｍｍ程度）が求めら
れるようになってきている。On the other hand, in recent years, a sputtering apparatus used for forming an ITO film is changing because a high-quality film with fewer defects can be obtained with a high yield. In other words, the conventional in-line type apparatus that performs film formation while moving the target and the substrate relative to each other is shifting to a single-wafer type apparatus that performs the film formation with the target and the substrate fixed to each other. In the conventional in-line type apparatus, film formation is continuously performed while the front surface of the target is moved at a low speed while being placed on a carrier truck called a substrate and a tray. For this reason, if a target having a size similar to the width in the vertical direction with respect to the moving direction of the substrate is used for film formation, the size of the target along the moving direction of the substrate does not matter so much and a uniform film thickness is obtained. Was obtained. Therefore, in the in-line type device,
For example, a slender target having a size of about 130 mm × 500 mm was common. However, the in-line type device has problems in that it is inevitable that the device becomes large in size, and particles generated from the moving mechanism of the tray cause defects in the film. Therefore, a single-wafer type apparatus has been used in which only the substrate is transported without using the tray as described above, and film formation is performed in a state where the substrate is stopped at the front surface of the target. In this single-wafer type sputtering apparatus, a large-area target having a shape substantially similar to that of the substrate is required in order to form a film having a uniform film thickness on the substrate. An ITO target having a large area (for example, about 500 mm × 600 mm) is required in comparison with the conventional in-line type device.
【０００８】従来、大面積のＩＴＯ焼結体ターゲットを
得るために、幾つかのＩＴＯ焼結体の小片をバッキング
プレート上に並べてボンディングして用いていた。しか
し、小片同士の継ぎ目部分がスパッタリング時にエロー
ジョン領域にかかるために、ここからゴミ（パーティク
ル）が発生し、ＩＴＯ膜のピンポール等の欠陥を引き起
こすという問題点を有していた。このことから、継ぎ目
のない一体品の大面積ＩＴＯ焼結体ターゲットが求めら
れている。Conventionally, in order to obtain a large-area ITO sintered body target, several small pieces of ITO sintered body have been arranged and bonded on a backing plate. However, since the seam portion between the small pieces is applied to the erosion area during sputtering, dust (particles) is generated from this area, which causes a defect such as a pin pole of the ITO film. Therefore, there is a demand for a large-area ITO sintered body target that is a seamless and integrated product.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上述した従
来技術の問題点を解決するためのものであって、枚葉式
スパッタ装置に使用するのに好適な、理論密度の９７％
を超える十分に高密度で、かつ継ぎ目のない一体品の大
面積ＩＴＯ焼結ターゲットを安定して製造する方法を提
供することを目的としている。SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of the prior art and is suitable for use in a single-wafer sputtering apparatus, and has a theoretical density of 97%.
It is an object of the present invention to provide a method for stably manufacturing a large-area ITO sintered target of a one-piece, which has a sufficiently high density and is seamless and has a seamlessness.
【００１０】[0010]
【課題を解決するための手段】本発明は、下記の通りの
ものである。 （１） 酸化インジウムと酸化すずを主成分とするＩＴ
Ｏスパッタリング用ターゲットを製造するに際し、粒度
分布から求めた平均粒径が０．８〜２μｍ、ＢＥＴ表面
積が３〜５ｍ2 ／ｇである酸化インジウム粉末と粒度分
布から求めた平均粒径が２μｍ以下の酸化すず粉末を用
い、原料粉末を混合した後、乾式ボールミル処理を行
い、次いでバインダーを添加してプレス成形を行い、得
られた成形体を再び粉砕して粒度を整え、この粉末を用
いてプレス成形を行い、得られた成形体を加圧酸素雰囲
気中で１５５０℃以上１７００℃までの焼結温度で焼結
し、この時成形体を焼結温度にまで加熱・昇温するに際
し、室温〜８００℃まで昇温した後、一旦昇温を停止し
て８００℃に保持し、その後、８００℃〜焼結温度にま
で昇温する速度を１時間に３５０℃以上とすることを特
徴とする、ＩＴＯスパッタリング用ターゲットの製造方
法。 （２） 乾式ボールミル処理において、ＺｒＯ2 製また
はＡｌ2 Ｏ3 製ボールを用いることを特徴とする前項
（１）に記載のＩＴＯスパッタリング用ターゲットの製
造方法。 （３） プレス成形により得られた成形体を脱脂して
後、加圧酸素雰囲気中で焼結することを特徴とする前項
（１）に記載のＩＴＯスパッタリング用ターゲットの製
造方法。 （４） 焼結雰囲気がゲージ圧で１気圧以下の加圧酸素
雰囲気であることを特徴とする前項（１）に記載のＩＴ
Ｏスパッタリング用ターゲットの製造方法。 （５） 成形体を焼結温度にまで加熱・昇温する速度が
１時間に３５０℃〜８００℃であることを特徴とする前
項（１）に記載のＩＴＯスパッタリング用ターゲットの
製造方法。Means for Solving the Problems The present invention is as follows. (1) IT containing indium oxide and tin oxide as main components
When manufacturing a target for O sputtering, the average particle diameter obtained from the particle size distribution is 0.8 to 2 μm, the BET surface area is 3 to 5 m 2 / g, and the average particle diameter obtained from the particle size distribution is 2 μm or less. After mixing the raw material powders with the tin oxide powder of, the dry ball mill treatment was performed, then the binder was added and press molding was performed, and the obtained molded body was pulverized again to adjust the particle size, and this powder was used. Press molding is performed, and the obtained compact is sintered at a sintering temperature of 1550 ° C. or higher and 1700 ° C. in a pressurized oxygen atmosphere. At this time, when heating / heating the compact to the sintering temperature, room temperature is applied. After the temperature is raised to ˜800 ° C., the temperature is temporarily stopped and kept at 800 ° C., and then the rate of raising the temperature from 800 ° C. to the sintering temperature is set to 350 ° C. or more per hour. , ITO Spa A method for manufacturing a target for tattering. (2) The method for producing an ITO sputtering target according to item (1), wherein ZrO 2 or Al 2 O 3 balls are used in the dry ball mill treatment. (3) The method for producing an ITO sputtering target according to the above item (1), which comprises degreasing a molded body obtained by press molding and then sintering the molded body in a pressurized oxygen atmosphere. (4) IT according to (1) above, wherein the sintering atmosphere is a pressurized oxygen atmosphere with a gauge pressure of 1 atm or less.
Method for manufacturing O sputtering target. (5) The method for producing an ITO sputtering target according to item (1), wherein the rate of heating / heating the compact to the sintering temperature is 350 ° C. to 800 ° C. per hour.
【００１１】以下、本発明を詳細に説明する。本発明に
おいて、加圧酸素雰囲気とは、純酸素雰囲気、即ち酸素
ガス及び不可避に含まれる不純物ガスを、大気圧よりも
高い圧力とした雰囲気のことをさす。ただし、高い圧力
の酸素ガスを扱う操業には危険が伴うため、加圧の圧力
はゲージ圧で１気圧以下とすることが好ましい。Hereinafter, the present invention will be described in detail. In the present invention, the pressurized oxygen atmosphere refers to a pure oxygen atmosphere, that is, an atmosphere in which oxygen gas and unavoidably contained impurity gas have a pressure higher than atmospheric pressure. However, since there is a danger in the operation of handling oxygen gas having a high pressure, it is preferable that the pressure for pressurization be 1 atm or less in gauge pressure.
【００１２】本発明において、使用する原料の酸化イン
ジウム粉末と酸化すず粉末の粒度分布から求めた平均粒
径及びＢＥＴ表面積を限定した理由について述べる。酸
化インジウム粉末の平均粒径を０．８〜２μｍ、ＢＥＴ
表面積を３〜５ｍ2／ｇ、酸化すず粉末の平均粒径を２
μｍ以下に規定したが、この範囲外の粉末を原料として
用いた場合には、十分な高密度焼結体が得られなかった
り、焼結体に反りやクラックが発生したり、あるいは酸
化インジウムと酸化すずの混合が不均一になる等の問題
が生じる。In the present invention, the reason for limiting the average particle size and the BET surface area obtained from the particle size distribution of the raw material indium oxide powder and tin oxide powder will be described. Indium oxide powder has an average particle size of 0.8 to 2 μm, BET
The surface area is 3 to 5 m 2 / g, and the average particle size of tin oxide powder is 2
However, if a powder outside this range is used as a raw material, a sufficient high density sintered body cannot be obtained, warpage or cracks occur in the sintered body, or indium oxide is used. Problems such as non-uniform mixing of tin oxide occur.
【００１３】本発明において使用される乾式ボールミル
処理は、ボールからの汚染がないように耐磨耗性の高い
ＺｒＯ２製またはＡｌ２Ｏ３製ボールを用いることが好
ましい。In the dry ball mill treatment used in the present invention, it is preferable to use ZrO 2 or Al 2 O 3 balls having high wear resistance so that the balls are not contaminated.
【００１４】本発明の特徴である、原料混合粉末にバイ
ンダーを添加して一度プレス成形を行い、得られた成形
体を再び粉砕して粒度を整え、この粉砕を用いてプレス
成形を行う理由は次の通りである。すなわち、添加され
たバインダーの分散を均一化し、同時に、プレス成形に
より原料混合粉末が圧密された粒子を造粒し、これを用
いて再度プレス成形を行うことで、成形体の密度ムラを
低減することができる。The feature of the present invention is that the binder is added to the raw material mixed powder and press-molding is once performed, and the obtained compact is crushed again to adjust the particle size, and the reason why press-molding is performed using this crushing is performed. It is as follows. That is, the dispersion of the added binder is made uniform, and at the same time, particles of which the raw material mixed powder is compacted by press molding are granulated, and press molding is performed again using this, thereby reducing the density unevenness of the molded body. be able to.
【００１５】本発明の特徴である、昇温に際して、室温
〜８００℃まで昇温した後、一旦昇温を停止して８００
℃に保持する理由は、次の段階で８００℃〜焼結温度の
間を１時間に３５０℃以上の速さで昇温するに先立ち、
焼結体全体の温度を均一にしておくためである。保持時
間は、使用する炉の大きさにもよるが、１〜６時間程度
が好ましい。When the temperature is raised, which is a feature of the present invention, the temperature is raised from room temperature to 800 ° C., and then the temperature is temporarily stopped to 800
The reason for holding the temperature at 0 ° C. is to raise the temperature between 800 ° C. and the sintering temperature at a rate of 350 ° C. or more per hour in the next stage,
This is to keep the temperature of the whole sintered body uniform. The holding time depends on the size of the furnace used, but is preferably about 1 to 6 hours.
【００１６】昇温速度を、８００℃〜焼結温度の間で、
１時間に３５０℃以上に限定したのは、これより遅い昇
温速度では十分に高密度なＩＴＯターゲットが得られな
いからである。昇温速度は特に上限はないが、好ましく
は８００℃／時程度以下とする。なぜなら、急激な昇温
に伴って加熱が不均一になると熱歪みにより焼結体にク
ラック等が生じる恐れがあるためである。ただし加熱の
均一性が十分保たれる場合にはこの限りではない。The temperature rising rate is from 800 ° C. to the sintering temperature,
The reason why the temperature is limited to 350 ° C. or higher for one hour is that a sufficiently high density ITO target cannot be obtained at a heating rate slower than this. The rate of temperature increase has no particular upper limit, but is preferably about 800 ° C./hour or less. This is because if the heating becomes non-uniform due to the rapid temperature rise, cracks or the like may occur in the sintered body due to thermal strain. However, this is not the case when heating uniformity is sufficiently maintained.
【００１７】また、焼結温度を１５５０℃以上に限定す
る理由は、これより低い焼結温度では十分に高密度なＩ
ＴＯターゲットが得られないからである。一方、１７０
０℃を超えると炉の発熱体の消耗が激しく、経済的でな
くなる。The reason for limiting the sintering temperature to 1550 ° C. or higher is that the sufficiently high density I is obtained at a lower sintering temperature.
This is because the TO target cannot be obtained. On the other hand, 170
If the temperature exceeds 0 ° C, the heating element of the furnace will be consumed so heavily that it becomes uneconomical.
【００１８】[0018]
【発明の実施の形態】以下、本発明の実施例を比較例と
共に挙げ、本発明をより詳細に説明する。実施例１ 粒度分布から求めた平均粒径が１．２μｍ、ＢＥＴ表面
積が４ｍ2 ／ｇである酸化インジウム粉末と粒度分布か
ら求めた平均粒径が０．８μｍの酸化すず粉末を、酸化
すずの組成が１０ｗｔ％となるように秤量・混合した
後、ＺｒＯ２ボールを用いて乾式ボールミル処理（２１
時間）を行った。次いで、バインダーを添加した撹拌擂
潰機により混合後、２００ｋｇｆ／ｃｍ2 の圧力でプレ
ス成形を行い、得られた成形体をハンマーミルを用いて
再び粉砕して３ｍｍΦの篩目を通過させ、この粉末を用
いて１０００ｋｇｆ／ｃｍ2 の圧力でプレス成形を行
い、３００ｍｍ×８００ｍｍ、厚さ８ｍｍ、成形体密度
４．３８ｇ／ｃｍ3 の成形体を得た。この成形体を８０
℃で１５時間乾燥し、脱脂炉を用いて大気中で６００℃
で６時間脱脂した後、ゲージ圧で０．９気圧の加圧酸素
雰囲気中で１５５０℃で８時間焼結した。この成形体を
焼結温度にまで加熱・昇温するに際しては、室温〜８０
０℃まで８０℃／時で昇温した後、一旦昇温を停止して
８００℃に４時間保持し、その後、８００℃〜焼結温度
にまで昇温する速度を１時間に４００℃とした。この結
果、得られたＩＴＯ焼結体ターゲットの密度は７．０８
ｇ／ｃｍ3 （理論密度の９９．０％）であった。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention together with Comparative Examples. Example 1 An indium oxide powder having an average particle size of 1.2 μm determined from the particle size distribution and a BET surface area of 4 m 2 / g and a tin oxide powder having an average particle size of 0.8 μm determined from the particle size distribution were used for the composition of tin oxide. Is weighed and mixed so as to be 10% by weight, and then dry ball mill treatment is performed using ZrO 2 balls (21
Time). Then, after mixing with a stirring and crushing machine to which a binder was added, press molding was performed at a pressure of 200 kgf / cm 2 , and the obtained molded body was pulverized again using a hammer mill and passed through a 3 mmΦ sieve mesh. Press molding was performed using the powder at a pressure of 1000 kgf / cm 2 to obtain a molded body having a size of 300 mm × 800 mm, a thickness of 8 mm and a molded body density of 4.38 g / cm 3 . 80 this molded body
Dry for 15 hours at ℃, 600 ℃ in the air using a degreasing furnace
After degreasing for 6 hours, it was sintered at 1550 ° C. for 8 hours in a pressurized oxygen atmosphere with a gauge pressure of 0.9 atm. When heating and raising the temperature of this molded body to the sintering temperature, the temperature is from room temperature to 80
After raising the temperature to 0 ° C. at 80 ° C./hour, the temperature raising was stopped once, the temperature was kept at 800 ° C. for 4 hours, and then the rate of raising the temperature from 800 ° C. to the sintering temperature was 400 ° C. per hour. . As a result, the density of the obtained ITO sintered body target was 7.08.
It was g / cm 3 (99.0% of theoretical density).
【００１９】比較例１−１ バインダー添加後の原料混合粉末を１０００ｋｇｆ／ｃ
ｍ2 の圧力でプレス成形し、次いで得られた成形体を再
粉砕することを省略したこと以外は、実施例１とまった
く同様にしてＩＴＯ焼結体ターゲットを製造した。焼結
後のＩＴＯ焼結体ターゲットにはクラックが生じた。こ
のことから、バインダーを添加してプレス成形を行い、
得られた成形体を再び粉砕して粒度を整え、この粉末を
用いてプレス成形を行う工程が、クラック発生の防止に
効果があることがわかる。 Comparative Example 1-1 1000 kgf / c of raw material mixed powder after addition of binder
An ITO sintered body target was manufactured in exactly the same manner as in Example 1 except that press molding was performed at a pressure of m 2 and then re-pulverization of the obtained molded body was omitted. Cracks were generated in the ITO sintered body target after sintering. From this, a binder is added and press molding is performed,
It can be seen that the step of crushing the obtained molded body again to adjust the particle size and press-molding using this powder is effective in preventing the occurrence of cracks.
【００２０】比較例１−２ 焼結温度を１５００℃とすること以外は、実施例１とま
ったく同様にしてＩＴＯ焼結体ターゲットを製造した。
焼結後の密度が６．８２ｇ／ｃｍ3 （理論密度の９５．
４％）であった。このことから、理論密度の９７％を超
える十分に高密度なＩＴＯ焼結体ターゲットを得るため
には、１５５０℃以上の焼結温度が必要であることがわ
かる。 Comparative Example 1-2 An ITO sintered body target was manufactured in exactly the same manner as in Example 1 except that the sintering temperature was 1500 ° C.
The density after sintering was 6.82 g / cm 3 (the theoretical density of 95.
4%). From this, it is understood that a sintering temperature of 1550 ° C. or higher is necessary in order to obtain a sufficiently high density ITO sintered body target that exceeds 97% of the theoretical density.
【００２１】実施例２ 粒度分布から求めた平均粒径が１．２μｍ、ＢＥＴ表面
積が４ｍ2 ／ｇである酸化インジウム粉末と粒度分布か
ら求めた平均粒径が０．８μｍの酸化すず粉末を、酸化
すずの組成が１０ｗｔ％となるように秤量・混合した
後、ＺｒＯ２ボールを用いて乾式ボールミル処理（２１
時間）を行った。次いで、バインダーを添加した撹拌擂
潰機により混合後、２００ｋｇｆ／ｃｍ2 の圧力でプレ
ス成形を行い、得られた成形体をハンマーミルを用いて
再び粉砕して３ｍｍΦの篩目を通過させ、この粉末を用
いて４００ｋｇｆ／ｃｍ2 の圧力でプレス成形を行い、
７００ｍｍ×８００ｍｍ、厚さ８ｍｍ、成形体密度４．
３２ｇ／ｃｍ3 の成形体を得た。この成形体を８０℃で
１５時間乾燥した後、ゲージ圧で０．９気圧の加圧酸素
雰囲気中で１５５０℃で８時間焼結した。この成形体を
焼結温度にまで加熱・昇温するに際しては、室温〜４０
０℃まで２０℃／時で昇温し、この間に脱脂を行い、引
き続き８００℃まで５０℃／時で昇温し、一旦昇温を停
止して８００℃に４時間保持し、その後、８００℃〜焼
結温度にまで昇温する速度を１時間に４００℃とした。
この結果、得られたＩＴＯ焼結体ターゲットの密度は
７．０６ｇ／ｃｍ3 （理論密度の９８．７％）であっ
た。 Example 2 Indium oxide powder having an average particle size of 1.2 μm determined from the particle size distribution and BET surface area of 4 m 2 / g and tin oxide powder having an average particle size of 0.8 μm determined from the particle size distribution were prepared. After weighing and mixing so that the composition of tin oxide is 10 wt%, dry ball mill treatment using a ZrO 2 ball (21
Time). Then, after mixing with a stirring and crushing machine to which a binder was added, press molding was performed at a pressure of 200 kgf / cm 2 , and the obtained molded body was pulverized again using a hammer mill and passed through a 3 mmΦ sieve mesh. Press molding is performed using a powder at a pressure of 400 kgf / cm 2 ,
700 mm × 800 mm, thickness 8 mm, compact density 4.
A molded body of 32 g / cm 3 was obtained. This molded body was dried at 80 ° C. for 15 hours and then sintered at 1550 ° C. for 8 hours in a pressurized oxygen atmosphere having a gauge pressure of 0.9 atm. When heating and raising the temperature of this molded body to the sintering temperature, the temperature is from room temperature to 40
The temperature was raised to 0 ° C at 20 ° C / hour, degreasing was performed during this period, the temperature was raised to 800 ° C at 50 ° C / hour, the temperature was temporarily stopped and kept at 800 ° C for 4 hours, and then 800 ° C. ~ The rate of raising the temperature to the sintering temperature was 400 ° C per hour.
As a result, the density of the obtained ITO sintered body target was 7.06 g / cm 3 (98.7% of the theoretical density).
【００２２】比較例２−１ 粒度分布から求めた平均粒径が２．９μｍ、ＢＥＴ表面
積が２ｍ2 ／ｇである酸化インジウム粉末と粒度分布か
ら求めた平均粒計が２．２μｍの酸化すず粉末を用いる
こと以外は、実施例２と全く同様にしてＩＴＯ焼結体タ
ーゲットを製造した。プレス成形後の成形体密度が４．
３６ｇ／ｃｍ3 、焼結後の密度が６．８２ｇ／ｃｍ
3 （理論密度の９５．４％）であった。このことから、
粒度分布から求めた平均粒径とＢＥＴ表面積が本発明の
範囲外である原料粉末を用いた場合、十分な高密度のＩ
ＴＯ焼結体ターゲットは得られないことがわかる。 Comparative Example 2-1 Indium oxide powder having an average particle size determined from the particle size distribution of 2.9 μm and BET surface area of 2 m 2 / g and tin oxide powder having an average particle size determined from the particle size distribution of 2.2 μm. An ITO sintered body target was manufactured in exactly the same manner as in Example 2 except that was used. 3. The compact density after press molding is 4.
36 g / cm 3 , density after sintering is 6.82 g / cm
3 (95.4% of theoretical density). From this,
When a raw material powder having an average particle size and BET surface area determined from the particle size distribution is outside the range of the present invention, a sufficiently high density I
It can be seen that the TO sintered body target cannot be obtained.
【００２３】比較例２−２ 粒度分布から求めた平均粒径が０．３μｍ、ＢＥＴ表面
積が６ｍ2 ／ｇである酸化インジウム粉末と粒度分布か
ら求めた平均粒計が０．８μｍの酸化すず粉末を用いる
こと以外は、実施例２と全く同様にしてＩＴＯ焼結体タ
ーゲットを製造した。プレス成形後の成形体密度が４．
１４ｇ／ｃｍ3 、焼結後の密度が６．８０ｇ／ｃｍ
3 （理論密度の９５．１％）であった。このことから、
本発明の範囲外の粒度分布から求めた平均粒径とＢＥＴ
表面積を有する原料粉末を用いた場合、十分に高密度の
ＩＴＯ焼結体ターゲットは得られないことがわかる。 Comparative Example 2-2 Indium oxide powder having an average particle size determined from the particle size distribution of 0.3 μm and BET surface area of 6 m 2 / g and tin oxide powder having an average particle size determined from the particle size distribution of 0.8 μm An ITO sintered body target was manufactured in exactly the same manner as in Example 2 except that was used. 3. The compact density after press molding is 4.
14 g / cm 3 , density after sintering 6.80 g / cm
3 (95.1% of theoretical density). From this,
Average particle size and BET determined from particle size distribution outside the range of the present invention
It is understood that when the raw material powder having a surface area is used, an ITO sintered body target having a sufficiently high density cannot be obtained.
【００２４】実施例１〜２および比較例１〜２における
ＩＴＯ焼結体の製造条件および焼結体の特性値の測定結
果を、表１に示す。Table 1 shows the manufacturing conditions of the ITO sintered bodies and the measurement results of the characteristic values of the sintered bodies in Examples 1 and 2 and Comparative Examples 1 and 2.
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明によれば、高い圧力の酸素雰囲気
を用いることなく、安全かつ低コストで、枚葉式スパッ
タ装置に使用するのに好適な、理論密度の９８％を超え
る十分に高密度で、かつ継ぎ目のない一体品の大面積Ｉ
ＴＯ焼結ターゲットを安定して製造することができる。
従来は２００ｍｍ×５００ｍｍ程度が限度であったが、
本発明により７００ｍｍ×８００ｍｍ程度の大型サイズ
のＩＴＯ焼結体ターゲットが得られることとなった。EFFECTS OF THE INVENTION According to the present invention, it is possible to safely and inexpensively use a high-pressure oxygen atmosphere, and to use it in a single-wafer sputtering apparatus. Large area I of high density and seamless
The TO sintering target can be stably manufactured.
Conventionally, the limit was about 200 mm x 500 mm,
According to the present invention, a large-sized ITO sintered body target of about 700 mm × 800 mm can be obtained.
Claims (5)
ＩＴＯスパッタリング用ターゲットを製造するに際し、
粒度分布から求めた平均粒径が０．８〜２μｍ、ＢＥＴ
表面積が３〜５ｍ2 ／ｇである酸化インジウム粉末と粒
度分布から求めた平均粒径が２μｍ以下の酸化すず粉末
を用い、原料粉末を混合した後、乾式ボールミル処理を
行い、次いでバインダーを添加してプレス成形を行い、
得られた成形体を再び粉砕して粒度を整え、この粉末を
用いてプレス成形を行い、得られた成形体を加圧酸素雰
囲気中で１５５０℃以上１７００℃までの焼結温度で焼
結し、この時成形体を焼結温度にまで加熱・昇温するに
際し、室温から８００℃まで昇温した後、一旦昇温を停
止して８００℃に保持し、その後、８００℃から焼結温
度にまで昇温する速度を１時間に３５０℃以上とするこ
とを特徴とする、ＩＴＯスパッタリング用ターゲットの
製造方法。In producing an ITO sputtering target containing indium oxide and tin oxide as main components,
Average particle size obtained from particle size distribution is 0.8-2 μm, BET
Using indium oxide powder having a surface area of 3 to 5 m 2 / g and tin oxide powder having an average particle size of 2 μm or less obtained from the particle size distribution, after mixing the raw material powders, dry ball mill treatment was performed, and then a binder was added. Press molding,
The obtained molded body is pulverized again to adjust the grain size, press molding is performed using this powder, and the obtained molded body is sintered in a pressurized oxygen atmosphere at a sintering temperature of 1550 ° C to 1700 ° C. At this time, when heating and raising the temperature of the compact to the sintering temperature, after raising the temperature from room temperature to 800 ° C., the temperature rise is stopped once and kept at 800 ° C., and then from 800 ° C. to the sintering temperature. A method for manufacturing an ITO sputtering target, characterized in that the temperature rising rate is set to 350 ° C. or higher for 1 hour.
またはＡｌ2 Ｏ3 製ボールを用いることを特徴とする請
求項１に記載のＩＴＯスパッタリング用ターゲットの製
造方法。2. The method for producing an ITO sputtering target according to claim 1, wherein ZrO 2 or Al 2 O 3 balls are used in the dry ball mill treatment.
て後、加圧酸素雰囲気中で焼結することを特徴とする請
求項１に記載のＩＴＯスパッタリング用ターゲットの製
造方法。3. The method for producing an ITO sputtering target according to claim 1, wherein the molded body obtained by press molding is degreased and then sintered in a pressurized oxygen atmosphere.
酸素雰囲気であることを特徴とする請求項１に記載のＩ
ＴＯスパッタリング用ターゲットの製造方法。4. The I according to claim 1, wherein the sintering atmosphere is a pressurized oxygen atmosphere having a gauge pressure of 1 atm or less.
A method for manufacturing a target for TO sputtering.
・昇温する速度が１時間に３５０℃〜８００℃であるこ
とを特徴とする請求項１に記載のＩＴＯスパッタリング
用ターゲットの製造方法。5. The production of an ITO sputtering target according to claim 1, wherein the rate of heating / heating the compact from 800 ° C. to the sintering temperature is 350 ° C. to 800 ° C. per hour. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03970196A JP3444713B2 (en) | 1996-02-27 | 1996-02-27 | Method for manufacturing ITO sputtering target |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03970196A JP3444713B2 (en) | 1996-02-27 | 1996-02-27 | Method for manufacturing ITO sputtering target |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09228036A true JPH09228036A (en) | 1997-09-02 |
| JP3444713B2 JP3444713B2 (en) | 2003-09-08 |
Family
ID=12560327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03970196A Expired - Fee Related JP3444713B2 (en) | 1996-02-27 | 1996-02-27 | Method for manufacturing ITO sputtering target |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3444713B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100492290B1 (en) * | 1996-12-20 | 2005-09-02 | 도소 가부시키가이샤 | Manufacture method of sintered thio sinter |
| JP2007113051A (en) * | 2005-10-19 | 2007-05-10 | Mitsui Mining & Smelting Co Ltd | Manufacturing method of target material for sputtering target, and box used therefor |
| JP5704571B2 (en) * | 2010-01-15 | 2015-04-22 | 株式会社アルバック | Method for producing LiCoO2 sintered body |
| CN114068945A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Tin alloy cathode target material for preparing thin film lithium battery and preparation method thereof |
| CN114853467A (en) * | 2022-05-24 | 2022-08-05 | 先导薄膜材料（广东）有限公司 | ITO (indium tin oxide) planar target material and preparation method thereof |
| CN115482965A (en) * | 2022-09-16 | 2022-12-16 | 北京高压科学研究中心 | Method for improving conductivity of transparent conductive oxide and blue light filtering efficiency |
-
1996
- 1996-02-27 JP JP03970196A patent/JP3444713B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100492290B1 (en) * | 1996-12-20 | 2005-09-02 | 도소 가부시키가이샤 | Manufacture method of sintered thio sinter |
| JP2007113051A (en) * | 2005-10-19 | 2007-05-10 | Mitsui Mining & Smelting Co Ltd | Manufacturing method of target material for sputtering target, and box used therefor |
| JP5704571B2 (en) * | 2010-01-15 | 2015-04-22 | 株式会社アルバック | Method for producing LiCoO2 sintered body |
| CN114068945A (en) * | 2021-11-17 | 2022-02-18 | 鄂尔多斯市紫荆创新研究院 | Tin alloy cathode target material for preparing thin film lithium battery and preparation method thereof |
| CN114068945B (en) * | 2021-11-17 | 2023-08-29 | 鄂尔多斯市紫荆创新研究院 | Tin alloy negative electrode target material for preparing thin film lithium battery and preparation method thereof |
| CN114853467A (en) * | 2022-05-24 | 2022-08-05 | 先导薄膜材料（广东）有限公司 | ITO (indium tin oxide) planar target material and preparation method thereof |
| CN114853467B (en) * | 2022-05-24 | 2023-05-26 | 先导薄膜材料（广东）有限公司 | ITO planar target and preparation method thereof |
| CN115482965A (en) * | 2022-09-16 | 2022-12-16 | 北京高压科学研究中心 | Method for improving conductivity of transparent conductive oxide and blue light filtering efficiency |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3444713B2 (en) | 2003-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20200019654A (en) | Indium zinc oxide (izo) based sputtering target, and method for producing same | |
| JPH0971860A (en) | Target and its production | |
| JP2000144393A (en) | Ito sputtering target and its production | |
| JP3444713B2 (en) | Method for manufacturing ITO sputtering target | |
| JP2000281431A (en) | Tin dioxide-based sintered compact, material for thin film formation and electroconductive film | |
| JP6293359B2 (en) | Oxide sintered body and sputtering target comprising the oxide sintered body | |
| WO2016152349A1 (en) | Oxide sintered body, and sputtering target comprising the oxide sintered body | |
| US6500225B2 (en) | Method for producing high density indium-tin-oxide sintered body | |
| JP2001098359A (en) | MANUFACTURE OF Mg-CONTAINING ITO SPUTTERING TARGET AND Mg-CONTAINING ITO EVAPORATION MATERIAL | |
| JPH04228466A (en) | Production of sintered material of tin oxide | |
| JP2020164930A (en) | Ito sputtering target, method for manufacturing the same, ito transparent conductive film and method for manufacturing the same | |
| JP4733930B2 (en) | Method for producing composite oxide sintered body and sputtering target comprising the sintered body | |
| TW201910539A (en) | Oxide sintered body and sputtering target | |
| CN114853467A (en) | ITO (indium tin oxide) planar target material and preparation method thereof | |
| JP2612807B2 (en) | Method for manufacturing ITO sputtering target | |
| JP4904645B2 (en) | Method for producing Mg-containing ITO sputtering target | |
| JPH10158826A (en) | Mgo target and its production | |
| JP4000813B2 (en) | Sputtering target | |
| CN1203026C (en) | Tool for heat treating silicon carbide material | |
| KR101135732B1 (en) | Fluorine-Containing Indium-Tin-Oxide Sintered Body and the Method of Preparation of the Same | |
| JPH11100660A (en) | Ito pellet for vapor deposition and its production | |
| JPH10330169A (en) | Production of ceramic sintered compact | |
| JP2001072470A (en) | Production of ito sintered compact | |
| JPH0940460A (en) | Production of titanic acid based sintered body | |
| JPH03153570A (en) | Polycrystalline spinel sintered body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080627 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090627 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |