JP2903575B2 - Method for producing Pb-Zr-Ti oxide-based target material - Google Patents
Method for producing Pb-Zr-Ti oxide-based target materialInfo
- Publication number
- JP2903575B2 JP2903575B2 JP1306291A JP30629189A JP2903575B2 JP 2903575 B2 JP2903575 B2 JP 2903575B2 JP 1306291 A JP1306291 A JP 1306291A JP 30629189 A JP30629189 A JP 30629189A JP 2903575 B2 JP2903575 B2 JP 2903575B2
- Authority
- JP
- Japan
- Prior art keywords
- target material
- lead
- oxide
- powder
- producing
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は、スパッタリング法に用いられるターゲット
材の製造方法に関し、特に酸化鉛を過剰に添加したPb−
Zr−Ti酸化物系ターゲット材を製造する方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a target material used for a sputtering method, and in particular, to a method for producing Pb-containing excessively added lead oxide.
The present invention relates to a method for producing a Zr—Ti oxide-based target material.
＜従来の技術＞ 光メモリ、半導体メモリ等に用いられる強誘電体薄膜
は主にスパッタリング法により製造されている。<Prior Art> Ferroelectric thin films used for optical memories, semiconductor memories, and the like are mainly manufactured by a sputtering method.
このスパッタリング法に用いられるターゲット材は、
PbTiO3粉末、PbZrO3粉末、PbO粉末をそれぞれ所定量に
秤量して混合し、この混合粉末を所定のターゲット材形
状にプレス成形した後、焼結処理を施して製造してい
る。The target material used in this sputtering method is
PbTiO3 powder, PbZrO3 powder, and PbO powder are each weighed to a predetermined amount, mixed, press-molded into a predetermined target material shape, and then subjected to a sintering process.
ここで、スパッタリング法によって薄膜を形成する際
にPbの蒸発が生ずるため、形成された薄膜中にPb成分が
欠乏してしまう。このようなPb成分の欠乏を防止するた
め、従来より、ターゲット材にPbOという形でPb成分を
過剰に添加している。Here, when a thin film is formed by a sputtering method, Pb is evaporated, so that a Pb component is deficient in the formed thin film. In order to prevent such a deficiency of the Pb component, an excessive amount of the Pb component has been conventionally added to the target material in the form of PbO.
＜発明が解決しようとする課題＞ しかしながら従来にあっては、ターゲット材にPb成分
を過剰に添加しようとした場合、ターゲット材の密度を
高めることができないという問題があった。<Problems to be Solved by the Invention> However, conventionally, there has been a problem that the density of the target material cannot be increased when the Pb component is excessively added to the target material.
すなわち、通常用いられるプレス圧１〜3ton/cm2程度
のプレス装置を用いる場合にはプレス成形体の密度は理
論密度に対して55〜60％程度しか得られないため、これ
を補うため比較的高温で焼結処理を行わなければならな
いが、PbOの融点が比較的低温（約880℃）であるため、
焼結処理中にターゲット内のPb成分が蒸発してしまう。
このため、Pb成分の添加量を維持しようとする場合に
は、ターゲット材の密度を高めることができなかった。That is, when using a normally used press machine having a press pressure of about 1 to 3 ton / cm 2 , the density of the press-formed body can be obtained only about 55 to 60% of the theoretical density. Sintering must be performed at a high temperature, but the melting point of PbO is relatively low (about 880 ° C).
The Pb component in the target evaporates during the sintering process.
For this reason, when trying to maintain the added amount of the Pb component, the density of the target material could not be increased.
また、ホットプレスを用いる場合にあっても、上記と
同様な理由から、比較的低温な温度条件しか設定するこ
とができず、ターゲット材の十分な密度を得ることがで
きなかった。Further, even when a hot press is used, only a relatively low temperature condition can be set for the same reason as described above, and a sufficient density of the target material cannot be obtained.
本発明は上記従来の事情に鑑みなされたもので、製造
容易にして高密度なターゲット材を得ることができるPb
−Zr−Ti酸化物系ターゲット材の製造方法を提供するこ
とを目的とする。The present invention has been made in view of the above-described conventional circumstances, and can be easily manufactured to obtain a high-density target material.
An object of the present invention is to provide a method for producing a -Zr-Ti oxide-based target material.
＜課題を解決するための手段＞ 本発明に係るPb−Zr−Ti酸化物系ターゲット材の製造
方法は、所定量のチタン、ジルコニウム、鉛の酸化物の
粉末に金属鉛の粉末を混合する工程と、この混合粉末を
300℃〜400℃の条件下でターゲット材の形状にプレス成
形する工程と、金属鉛を酸化させるべくこの成形体を酸
素雰囲気中で600℃〜1000℃に加熱してこの成形体を焼
結体とする工程とを有することを特徴とし、酸化鉛を過
剰に添加したPb−Zr−Ti酸化物系ターゲット材を製造す
る。<Means for Solving the Problems> A method for producing a Pb-Zr-Ti oxide-based target material according to the present invention comprises a step of mixing a predetermined amount of titanium, zirconium, and lead oxide powder with metal lead powder. And this mixed powder
Press forming into the shape of the target material under the condition of 300 ° C to 400 ° C, and heating the formed body to 600 ° C to 1000 ° C in an oxygen atmosphere to oxidize metallic lead And producing a Pb-Zr-Ti oxide-based target material to which lead oxide is excessively added.
ここに、下表の実施データNo1〜No7から判るように、
本発明は次の条件を満たすのが好ましい。Here, as can be seen from the execution data No1 to No7 in the table below,
The present invention preferably satisfies the following conditions.
プレス成形時の温度は金属鉛の融点温度（300℃〜400
℃まで、すなわち100℃）の温度範囲であることが好ま
しい。The temperature during press molding is the melting point of metallic lead (300 ° C to 400 ° C).
C., ie 100 ° C.).
なぜならば、300℃以下では金属鉛が溶融しないので
期待される（成形体密度の向上という）効果が得られな
い（比較データNo I参照）。一方、400℃以上になると
金属鉛の流動性が非常に良くなるため、プレス時に成形
体から溶融した金属鉛がしみ出し、金属鉛がモールドに
付着して成形体が取り出せないことによる（比較データ
No V参照）。This is because at temperatures of 300 ° C. or lower, the expected effect (improvement of the compact density) cannot be obtained because the metallic lead does not melt (see comparative data No. I). On the other hand, when the temperature exceeds 400 ° C, the flowability of metallic lead becomes extremely good, so molten lead melts out of the compact during pressing, and the metallic lead adheres to the mold and the compact cannot be taken out (comparative data).
No V).
また、含有する金属鉛の量は５重量％〜40重量％と限
定される。The amount of metallic lead contained is limited to 5% by weight to 40% by weight.
なぜならば、金属鉛が５重量％以下では、成形体中に
溶融鉛の量が少なすぎて、プレス時所定の密度をもつ成
形体を作ることができない（比較データNo III参照）。
一方、40重量％以上ではプレス中に成形体から溶融した
金属鉛がしみ出てしまい組成が変動する（比較データNo
IV参照）。This is because when the amount of metallic lead is 5% by weight or less, the amount of molten lead in the molded body is too small to produce a molded body having a predetermined density at the time of pressing (see Comparative Data No. III).
On the other hand, when the content is 40% by weight or more, molten lead is exuded from the compact during pressing and the composition fluctuates (Comparative Data No.
IV).
金属鉛を酸化させる温度範囲は、600℃〜1000℃の温
度範囲が好ましい。The temperature range in which the metal lead is oxidized is preferably in the range of 600 ° C to 1000 ° C.
なぜならば、600℃以下の温度では酸化させるのに長
い時間（20時間以上）を必要とし、実用的ではない。一
方、1000℃以上では、生成した酸化鉛の蒸発によるロス
が大きくなり、組成変化をもたらすため好ましくない
（比較データNo II参照）。Because, at a temperature of 600 ° C. or less, a long time (20 hours or more) is required for oxidation, which is not practical. On the other hand, at a temperature of 1000 ° C. or higher, the loss due to evaporation of the generated lead oxide is increased, which causes a change in composition, which is not preferable (see Comparative Data No. II).
＜作用＞ 本発明では、金属鉛の融点（約330℃）付近の温度条
件下でプレス成形することにより、融点直下で塑性変形
が非常に容易となった、あるいは液相となった金属鉛が
粒子間で潤滑剤として働き、低圧のプレスによってもプ
レス成形体の密度をかなり高めることができる。 <Effect> In the present invention, by performing press molding under a temperature condition near the melting point of metallic lead (about 330 ° C.), plastic deformation becomes very easy immediately below the melting point, or metallic lead in a liquid phase becomes It acts as a lubricant between the particles and can significantly increase the density of the pressed body even with low pressure pressing.
そして、これに続く焼結処理においては密度を高める
ためにあまり高温で行う必要がなくなり、金属鉛を酸化
させる程度の比較的低温（700〜1000℃）で行えば済む
こととなる。In the subsequent sintering, it is not necessary to perform the sintering at a very high temperature in order to increase the density, and the sintering may be performed at a relatively low temperature (700 to 1000 ° C.) enough to oxidize the metal lead.
ここで、金属鉛はかなり低温で液相化して反応性が高
まっているため、これによっても酸化温度はかなり低く
抑えられる。また、液相化した金属鉛が酸化物粒子の拡
散を助けることとなり、粒成長が促進されて焼結体の密
度がこれによっても向上する。Here, since the metallic lead is liquefied at a relatively low temperature and has increased reactivity, the oxidation temperature can be suppressed to a considerably low temperature. In addition, the liquid-phased metallic lead helps the diffusion of the oxide particles, and the grain growth is promoted, whereby the density of the sintered body is also improved.
そして、上記のようにしてターゲット材中の金属鉛が
酸化鉛へ酸化されると、モル体積が18.3cm3の金属鉛（P
b）がモル体積27.9cm3の酸化鉛（PbO）となって体積が
約1.5倍となるので、この酸化鉛によってターゲット材
中の酸化物粒子間の隙間が埋められると共に酸化物粒子
同士の結び付けが図られ、これによっても高密度な緻密
ターゲット材が得られる。Then, when the metal lead in the target material is oxidized to lead oxide as described above, a metal lead (P) having a molar volume of 18.3 cm 3 is obtained.
Since b) becomes lead oxide (PbO) with a molar volume of 27.9 cm 3 and the volume becomes about 1.5 times, this lead oxide fills the gaps between the oxide particles in the target material and binds the oxide particles. Thus, a dense target material with high density can be obtained.
＜実施例＞ 本発明を実施例に基づいて更に具体的に説明する。<Examples> The present invention will be described more specifically based on examples.
まず、純度99.99％のPbTiO3粉末（粒径３μｍ）、純
度99.99％のPbZrO3粉末（粒径４μｍ）、純度99.99％の
Pb粉末（粒径約15μｍ）を、それぞれ41.4重量％、47.3
重量％、11.3重量％に秤量し、これら粉末をヘキサンを
混合溶媒として、ジルコニア混合ボールを用いて３時間
ボールミル混合した。First, 99.99% pure PbTiO3 powder (3μm particle size), 99.99% PbZrO3 powder (4μm particle size), 99.99% pure
41.4% by weight of Pb powder (particle size: about 15 μm)
The powder was weighed to 11.3% by weight, and these powders were ball-milled for 3 hours using zirconia mixed balls with hexane as a mixed solvent.
次いで、上記の混合粉末を乾燥させた後に100mmφの
金型中に充填し、これを350℃に加熱した熱板間に挟ん
で100kg/cm2の圧力でプレスした。尚、このプレスは大
気中でも、真空中でもかまわない。Next, after drying the above mixed powder, it was filled in a 100 mmφ mold, and was pressed between hot plates heated to 350 ° C. at a pressure of 100 kg / cm 2 . This press may be performed in the air or in a vacuum.
このようにして得られたプレス成形体の密度は、真密
度を7.7g/cm3とすると、5.5g/cm3であった。The density of the thus obtained press-molded body, a true density When 7.7 g / cm 3, was 5.5 g / cm 3.
次いで、上記プレス成形体を、O2ガス気流中で950℃
にて５時間熱処理したところ、密度7.2g/cm3の焼結体と
してのターゲット材が得られた。Next, the above press-formed body was heated at 950 ° C. in an O2 gas stream.
For 5 hours, a target material as a sintered body having a density of 7.2 g / cm 3 was obtained.
尚、金属鉛の混合量は５重量％〜40重量％が好まし
い。これは、５重量％未満の量ではではプレス成形体中
の金属鉛の量が少なすぎて、350〜400℃程度の温度条件
下における100kg/cm2程度の低圧力では良好なプレス成
形ができず、また、40重量％を上回る量では溶融した金
属鉛がプレス成形中に成形体からしみだして、良好なプ
レス成形ができないからである。In addition, the mixing amount of metallic lead is preferably 5% by weight to 40% by weight. This is because if the amount is less than 5% by weight, the amount of metallic lead in the pressed body is too small, and good press forming can be performed at a low pressure of about 100 kg / cm 2 under the temperature condition of about 350 to 400 ° C. On the other hand, if the amount exceeds 40% by weight, the molten metal lead oozes out of the molded body during press molding, and good press molding cannot be performed.
＜効果＞ 本発明によれば、チタン、ジルコニウム、鉛の酸化物
の粉末に金属鉛の粉末を混合し、該混合粉末を金属鉛の
融点以上の温度条件下でターゲット材の形状にプレス成
形し、金属鉛を酸化させるべく該成形体を酸素雰囲気中
で加熱して当該成形体を焼結体とするようにしたため、
Pb成分を過剰に含みながらも密度の高い（相対密度80％
程度）緻密なPb−Zr−Ti酸化物系ターゲット材を得るこ
とができる。そして特に、プレス成形は比較的低温（35
0℃程度）条件にて比較的低プレス圧（ほぼ100kg/cm2）
で行えるため、製造装置が簡素化できるとともに、大型
のターゲット材も容易に製造することができる。<Effects> According to the present invention, powder of metal lead is mixed with powder of oxides of titanium, zirconium and lead, and the mixed powder is pressed into a target material under a temperature condition not lower than the melting point of metal lead. Since the molded body was heated in an oxygen atmosphere to oxidize metallic lead, and the molded body was made into a sintered body,
High density despite containing excess Pb component (relative density 80%
Degree) A dense Pb-Zr-Ti oxide-based target material can be obtained. In particular, press forming is relatively cool (35
(Approximately 100kg / cm 2 )
Therefore, the manufacturing apparatus can be simplified, and a large-sized target material can be easily manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大内 幸弘 埼玉県大宮市北袋町１丁目297番地 三 菱金属株式会社中央研究所内 (56)参考文献 特開 昭53−116499（ＪＰ，Ａ) 特開 平１−96368（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 14/34 C04B 35/49 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yukihiro Ouchi 1-297 Kitabukuro-cho, Omiya-shi, Saitama Mitsui Kinzoku Co., Ltd. Central Research Laboratory (56) References JP-A-53-116499 (JP, A) 1-96368 (JP, A) (58) Field surveyed (Int. Cl. 6 , DB name) C23C 14/34 C04B 35/49
Claims (1)
物の粉末に金属鉛の粉末を混合する工程と、 この混合粉末を300℃〜400℃の条件下でターゲット材の
形状にプレス成形する工程と、 金属鉛を酸化させるべくこの成形体を酸素雰囲気中で60
0℃〜1000℃に加熱してこの成形体を焼結体とする工程
とを有し、 酸化鉛を過剰に添加したターゲット材を製造するPb−Zr
−Ti酸化物系ターゲット材の製造方法。1. A step of mixing a predetermined amount of titanium, zirconium and lead oxide powder with metal lead powder, and press-forming the mixed powder into a target material in a temperature range of 300 ° C. to 400 ° C. Process, and heat the compact in an oxygen atmosphere to oxidize metallic lead.
Heating the molded body to a sintered body by heating to 0 ° C. to 1000 ° C., and producing a target material to which lead oxide is excessively added.
-A method for producing a Ti oxide-based target material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1306291A JP2903575B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing Pb-Zr-Ti oxide-based target material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1306291A JP2903575B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing Pb-Zr-Ti oxide-based target material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03166368A JPH03166368A (en) | 1991-07-18 |
| JP2903575B2 true JP2903575B2 (en) | 1999-06-07 |
Family
ID=17955328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1306291A Expired - Fee Related JP2903575B2 (en) | 1989-11-24 | 1989-11-24 | Method for producing Pb-Zr-Ti oxide-based target material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2903575B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676304B2 (en) * | 1992-06-03 | 1997-11-12 | アネルバ株式会社 | Ferroelectric thin film manufacturing method |
| JP3821524B2 (en) * | 1996-12-16 | 2006-09-13 | 株式会社ルネサステクノロジ | Sputtering target for dielectric thin film formation |
| US6277254B1 (en) | 1999-12-16 | 2001-08-21 | Honeywell International Inc. | Ceramic compositions, physical vapor deposition targets and methods of forming ceramic compositions |
| JP2013100565A (en) * | 2010-03-03 | 2013-05-23 | Mitsui Mining & Smelting Co Ltd | Gallium oxide-zinc oxide sputtering target and aluminum oxide-zinc oxide sputtering target |
-
1989
- 1989-11-24 JP JP1306291A patent/JP2903575B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03166368A (en) | 1991-07-18 |
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