JPH06211523A - Production of composite body containing film of titanium metal and lead titanate zirconate and composite body - Google Patents
Production of composite body containing film of titanium metal and lead titanate zirconate and composite bodyInfo
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- JPH06211523A JPH06211523A JP2214693A JP2214693A JPH06211523A JP H06211523 A JPH06211523 A JP H06211523A JP 2214693 A JP2214693 A JP 2214693A JP 2214693 A JP2214693 A JP 2214693A JP H06211523 A JPH06211523 A JP H06211523A
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- film
- substrate
- metal
- composite body
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Abstract
(57)【要約】
【目的】 低温で、後処理工程を必要とすることなく、
Ｔｉ金属上にＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜を容易かつ確実
に形成する。
【構成】 Ｔｉ基板または、Ｔｉ金属膜をその表面に形
成した基板を、０．１mol／l 以上の鉛（Ｐｂ）化学種
と０．０５mol／l 以上のジルコニウム（Ｚｒ）化学種
とを含有するｐＨが１４以上のアルカリ性水溶液中に浸
漬し、２００℃以上の温度で水熱処理を施すことによ
り、前記Ｔｉ基板上、または、前記基板の表面に形成さ
れたＴｉ金属膜上にチタン酸ジルコン酸鉛（Ｐｂ（Ｚ
ｒ，Ｔｉ）Ｏ3）膜を形成する。
(57) [Summary] [Purpose] At low temperature, without the need for post-treatment,
A Pb (Zr, Ti) O 3 film is easily and reliably formed on Ti metal. A Ti substrate or a substrate having a Ti metal film formed on its surface contains 0.1 mol / l or more lead (Pb) chemical species and 0.05 mol / l or more zirconium (Zr) chemical species. Lead zirconate titanate is deposited on the Ti substrate or on the Ti metal film formed on the surface of the substrate by immersing in an alkaline aqueous solution having a pH of 14 or more and performing hydrothermal treatment at a temperature of 200 ° C. or more. (Pb (Z
An r, Ti) O 3 ) film is formed.
Description
【０００１】[0001]
【産業上の利用分野】本願発明は、Ｐｂ（Ｚｒ，Ｔｉ）
Ｏ3膜を含む複合体に関し、詳しくは、Ｔｉ基板上、ま
たは、基板の表面に形成されたＴｉ金属膜上にチタン酸
ジルコン酸鉛（Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3）膜を形成する
方法と、Ｔｉ基板とＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜、あるい
はＴｉ金属膜を表面に形成した基板と該Ｔｉ金属膜上に
形成されたＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜からなる複合体に
関する。BACKGROUND OF THE INVENTION The present invention relates to Pb (Zr, Ti)
Regarding a composite including an O 3 film, in detail, a method of forming a lead zirconate titanate (Pb (Zr, Ti) O 3 ) film on a Ti substrate or on a Ti metal film formed on the surface of the substrate. And a composite comprising a Ti substrate and a Pb (Zr, Ti) O 3 film, or a substrate having a Ti metal film formed on its surface and a Pb (Zr, Ti) O 3 film formed on the Ti metal film.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】チタン
酸ジルコン酸鉛（Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3）は、圧電体
材料、焦電体材料、強誘電体材料として優れた性質を有
し、超音波センサ、焦電型赤外線センサ、不揮発性メモ
リー、コンデンサ、アクチュエータ、などの種々のデバ
イスに幅広く利用されており、さらに多くの分野への応
用が試みられている。2. Description of the Related Art Lead zirconate titanate (Pb (Zr, Ti) O 3 ) has excellent properties as a piezoelectric material, a pyroelectric material, and a ferroelectric material. , Ultrasonic sensors, pyroelectric infrared sensors, non-volatile memories, capacitors, actuators, and various other devices, and are being applied to various fields.
【０００３】そして、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3をこれら
のデバイスに応用する場合、その特性を有効に利用する
ために、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3を薄膜として用いるこ
とが一般的である。When Pb (Zr, Ti) O 3 is applied to these devices, it is common to use Pb (Zr, Ti) O 3 as a thin film in order to effectively utilize its characteristics. .
【０００４】従来の、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜の製造
方法としては、主として、スパッタリング法やイオン
プレーティング法などの物理蒸着法（ＰＶＤ法）、薄
膜材料である有機金属気体の熱分解，酸化，還元，重合
などにより、薄膜組成を基材上に沈着させて薄膜を形成
する化学蒸着法（ＣＶＤ法）、有機金属を基材に塗布
し、これを焼成して酸化物膜を形成する、いわゆる、ゾ
ル・ゲル法などの有機金属塗布法などの方法が用いられ
ている。As a conventional method for producing a Pb (Zr, Ti) O 3 film, a physical vapor deposition method (PVD method) such as a sputtering method or an ion plating method, or a thermal decomposition of an organic metal gas which is a thin film material is mainly used. , Chemical vapor deposition method (CVD method) of forming a thin film by depositing a thin film composition on a base material by oxidation, reduction, polymerization, or the like, applying an organic metal to the base material, and baking this to form an oxide film The so-called sol-gel method and other organic metal coating methods are used.
【０００５】しかし、の物理蒸着法においては、一般
に、結晶質の膜を得るために、基板などの基材の温度を
５００℃以上にすることが必要であり、基材を冷却する
工程で熱歪が蓄積され、形成されたＰｂ（Ｚｒ，Ｔｉ）
Ｏ3膜にクラックや剥離が生じやすいという問題点があ
る。また、蒸着物質の蒸発は低酸素分圧下で行われるた
め、生成したＰｂ（Ｚｒ，Ｔｉ）Ｏ3は酸素欠陥を有す
ることが多く、特性の劣化やばらつきが生じるという問
題点がある。However, in the physical vapor deposition method, it is generally necessary to raise the temperature of the base material such as the substrate to 500 ° C. or higher in order to obtain a crystalline film, and heat is applied in the step of cooling the base material. Strain accumulated and formed Pb (Zr, Ti)
There is a problem that cracks and peeling are likely to occur in the O 3 film. In addition, since evaporation of the vapor deposition material is performed under a low oxygen partial pressure, the generated Pb (Zr, Ti) O 3 often has oxygen defects, which causes a problem that characteristics are deteriorated or varied.
【０００６】さらに、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3のような
複合酸化物の薄膜を形成する場合には、元素によって蒸
発速度が異なるため、膜の組成を制御して目標とする組
成の複合酸化物を得ることが困難であるという問題点が
ある。また、膜の成長が遅いということもこの方法の重
大な欠点である。Further, when a thin film of a complex oxide such as Pb (Zr, Ti) O 3 is formed, the evaporation rate varies depending on the element. Therefore, the composition of the film is controlled to obtain a complex oxide having a target composition. There is a problem that it is difficult to get things. The slow growth of the film is also a serious drawback of this method.
【０００７】一方、の化学蒸着法においては、有機金
属の蒸発温度が比較的高く、大掛かりな設備が必要にな
るという問題点があり、また、上記の物理蒸着法の場合
と同様に、膜の組成を制御することが困難で、目標とす
る組成の膜を形成することが容易ではないという問題点
がある。さらに、原料である有機金属化合物が極めて高
価であるという欠点がある。On the other hand, in the chemical vapor deposition method, there is a problem that the evaporation temperature of the organic metal is relatively high and a large-scale equipment is required. Further, as in the case of the physical vapor deposition method described above, there is a problem. There is a problem that it is difficult to control the composition and it is not easy to form a film having a target composition. Further, there is a drawback that the organometallic compound as a raw material is extremely expensive.
【０００８】また、の有機金属塗布法においては、基
材に塗布された有機金属を酸化して酸化物膜を形成する
のに５００℃以上の高温で焼成を行うことが必要であ
り、乾燥及び焼成の工程で塗布膜に大きな収縮が生じ、
形成される膜にクラックや剥離が生じやすいという問題
点がある。また、焼成工程中の有機物質の蒸発や燃焼に
よって、ポーラスになり、緻密な膜を得ることが困難で
あるという問題点がある。Further, in the organometallic coating method, it is necessary to carry out baking at a high temperature of 500 ° C. or higher in order to oxidize the organometallic coated on the base material to form an oxide film. A large shrinkage occurs in the coating film during the firing process,
There is a problem that cracks and peeling easily occur in the formed film. In addition, there is a problem that it becomes difficult to obtain a dense film that becomes porous due to evaporation and combustion of the organic substance during the firing process.
【０００９】本願発明は、上記の問題点を解決するもの
であり、低温で、かつ、後処理工程を必要とせずに、Ｐ
ｂ（Ｚｒ，Ｔｉ）Ｏ3膜をＴｉ金属上に形成することが
可能な、Ｔｉ金属とＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜を含む複
合体の製造方法及びＴｉ金属上にＰｂ（Ｚｒ，Ｔｉ）Ｏ
3膜を形成してなる複合体を提供することを目的とす
る。The present invention is intended to solve the above-mentioned problems, in which P is used at a low temperature and without requiring a post-treatment process.
A method of manufacturing a composite containing a Ti metal and a Pb (Zr, Ti) O 3 film capable of forming a b (Zr, Ti) O 3 film on a Ti metal, and Pb (Zr, Ti on the Ti metal. ) O
It is intended to provide a composite formed by forming three films.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するため
に、本願発明のチタン金属とチタン酸ジルコン酸鉛膜を
含む複合体の製造方法は、チタン（Ｔｉ）金属からなる
Ｔｉ基板を、０．１mol／l 以上の鉛（Ｐｂ）化学種と
０．０５mol／l 以上のジルコニウム（Ｚｒ）化学種と
を含有するｐＨが１４以上のアルカリ性の処理水溶液中
に浸漬し、２００℃以上の温度で水熱処理を施すことに
より、前記Ｔｉ基板上にチタン酸ジルコン酸鉛（Ｐｂ
（Ｚｒ，Ｔｉ）Ｏ3）膜を形成することを特徴とする。In order to achieve the above object, a method for producing a composite containing a titanium metal and a lead zirconate titanate film according to the present invention comprises a Ti substrate made of titanium (Ti) metal Immersing in an alkaline treatment aqueous solution containing 1 mol / l or more of lead (Pb) species and 0.05 mol / l or more of zirconium (Zr) species and having a pH of 14 or more, and at a temperature of 200 ° C. or more By performing hydrothermal treatment, lead zirconate titanate (Pb
It is characterized in that a (Zr, Ti) O 3 ) film is formed.
【００１１】また、本願発明の複合体は、上記の方法に
より形成される複合体であって、Ｔｉ基板と、該Ｔｉ基
板上に形成されたＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜とを具備す
ることを特徴とする。Further, the composite body of the present invention is a composite body formed by the above method and comprises a Ti substrate and a Pb (Zr, Ti) O 3 film formed on the Ti substrate. It is characterized by
【００１２】また、本願発明の他のＴｉ金属とチタン酸
ジルコン酸鉛膜を含む複合体の製造方法は、Ｔｉ金属膜
をその表面に形成した基板を、０．１mol／l 以上の鉛
（Ｐｂ）化学種と、０．０５mol／l 以上のジルコニウ
ム（Ｚｒ）化学種とを含有するｐＨが１４以上のアルカ
リ性の処理水溶液中に浸漬し、２００℃以上の温度で水
熱処理を施すことにより、基板の表面に形成された前記
Ｔｉ金属膜上にＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜を形成するこ
とを特徴とする。Further, according to another method for producing a composite containing a Ti metal and a lead zirconate titanate film according to the present invention, a substrate having a Ti metal film formed on the surface thereof is coated with 0.1 mol / l or more of lead (Pb). ) The substrate is immersed in an alkaline treatment aqueous solution containing a chemical species and a zirconium (Zr) chemical species of 0.05 mol / l or more and having a pH of 14 or more, and subjected to hydrothermal treatment at a temperature of 200 ° C. or more to obtain a substrate. The Pb (Zr, Ti) O 3 film is formed on the Ti metal film formed on the surface of the.
【００１３】また、本願発明の他の複合体は、上記の方
法により形成される複合体であって、Ｔｉ金属膜を表面
に形成した基板と、該Ｔｉ金属膜上に形成されたＰｂ
（Ｚｒ，Ｔｉ）Ｏ3膜とを具備することを特徴とする。Another composite of the present invention is a composite formed by the above method, which comprises a substrate having a Ti metal film formed on its surface and a Pb film formed on the Ti metal film.
And a (Zr, Ti) O 3 film.
【００１４】[0014]
【実施例】以下に、本願発明の実施例を比較例とともに
示して、その特徴をさらに詳しく説明する。EXAMPLES The features of the present invention will be described in more detail below by showing examples of the present invention together with comparative examples.
【００１５】まず、厚さ約０．５mmの平板状のチタン
（Ｔｉ）金属板を２０mm×５０mmの寸法に切断した後、
その表面を鏡面に研磨し、アセトン及び酸で十分に洗浄
してＴｉ基板とする。First, after a flat titanium (Ti) metal plate having a thickness of about 0.5 mm is cut into a size of 20 mm × 50 mm,
The surface is polished to a mirror surface and sufficiently washed with acetone and acid to obtain a Ti substrate.
【００１６】次に、所定のＰｂ濃度及びＺｒ濃度を与え
る量の硝酸鉛（Ｐｂ（ＮＯ3）2）とオキシ硝酸ジルコニ
ウム（ＺｒＯ（ＮＯ3）2・２Ｈ2Ｏ）を水に溶解し、水
酸化ナトリウム（ＮａＯＨ）を用いてｐＨを所定の値に
調整する。なお、出発水溶液のＰｂ及びＺｒ化学種は、
イオンとして存在する場合に限らず、例えば、サスペン
ジョンとして存在していてもよく、また、イオンとサス
ペンジョンの混合物として存在していてもよい。Next, an amount of lead nitrate (Pb (NO 3 ) 2 ) and zirconium oxynitrate (ZrO (NO 3 ) 2 .2H 2 O) that give a predetermined Pb concentration and Zr concentration are dissolved in water, and water is added. The pH is adjusted to the desired value with sodium oxide (NaOH). The Pb and Zr chemical species of the starting aqueous solution are
The present invention is not limited to the case of being present as ions, but may be present as a suspension, or may be present as a mixture of ions and suspensions.
【００１７】そして、この処理水溶液をオートクレーブ
に入れ、上記Ｔｉ基板を処理水溶液に浸漬して加熱し、
オートクレーブ内の処理水溶液及びＴｉ基板を所定の温
度にまで昇温する。その後、一定時間この温度に保持し
て水熱合成を行い、処理水溶液中のＰｂ，ＺｒとＴｉ基
板とを反応させて、Ｔｉ基板の表面にチタン酸ジルコン
酸鉛（Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3）膜を生成させる。それ
から、Ｔｉ基板を取り出し、蒸留水を用いて十分に超音
波洗浄し、１２０℃で６０分間乾燥する。Then, the treated aqueous solution is placed in an autoclave, the Ti substrate is immersed in the treated aqueous solution and heated,
The treatment aqueous solution and the Ti substrate in the autoclave are heated to a predetermined temperature. After that, hydrothermal synthesis is carried out by maintaining this temperature for a certain period of time to react Pb, Zr in the treatment aqueous solution with the Ti substrate, and lead zirconate titanate (Pb (Zr, Ti) O is formed on the surface of the Ti substrate. 3 ) Form a film. Then, the Ti substrate is taken out, sufficiently ultrasonically cleaned with distilled water, and dried at 120 ° C. for 60 minutes.
【００１８】そして、このようにして得られた実施例
（及び比較例）の試料について、その表面に形成された
薄膜の評価を行った。Then, with respect to the samples of Examples (and Comparative Examples) thus obtained, the thin film formed on the surface thereof was evaluated.
【００１９】反応温度（水熱合成温度）、反応時間、Ｐ
ｂ濃度、Ｚｒ濃度、ｐＨなどをパラメータとする種々の
条件下で形成した薄膜について測定した、Ｐｂ（Ｚｒ
1-X，ＴｉX）Ｏ3相の生成量、組成Ｘ、及び未知相を含
むＰｂ（Ｚｒ1-X，ＴｉX）Ｏ3相以外の相（異相）の生
成量を表１に示す。Reaction temperature (hydrothermal synthesis temperature), reaction time, P
Pb (Zr concentration measured on thin films formed under various conditions with parameters such as b concentration, Zr concentration and pH.
Table 1 shows the production amount of the 1-X , Ti X ) O 3 phase, the composition X, and the production amount of the phase (heterogeneous phase) other than the Pb (Zr 1 -X , Ti X ) O 3 phase including the unknown phase.
【００２０】[0020]
【表１】 [Table 1]
【００２１】但し、表１において、試料番号に＊印を付
したものは、本願発明の範囲外の膜（比較例）を示す。However, in Table 1, the sample numbers marked with * indicate films (comparative examples) outside the scope of the present invention.
【００２２】表１において、Ｐｂ（Ｚｒ1-X，ＴｉX）Ｏ
3相及び異相の生成量の値は、ＣｕＫα線（４０ｋＶ，
１００ｍＡ）を用いたＸ線回折法により、Ｐｂ（Ｚｒ
1-X，ＴｉX）Ｏ3相及び異相による回折Ｘ線の積分強度
を測定し、その値をそれぞれの全測定値の中の最大値で
規格化した値である。In Table 1, Pb (Zr 1-x , Ti x ) O
The values of the amounts of the three phases and the different phases produced are CuKα rays (40 kV,
By the X-ray diffraction method using 100 mA, Pb (Zr
It is a value obtained by measuring the integrated intensity of diffracted X-rays due to the 1-X , Ti x ) O 3 phase and the different phase, and standardizing the value with the maximum value of all the measured values.
【００２３】また、Ｐｂ（Ｚｒ1-X，ＴｉX）Ｏ3膜につ
いては、その格子定数の最適推定値からその組成Ｘを見
積もった。The composition X of the Pb (Zr 1-x , Ti x ) O 3 film was estimated from the optimum estimated value of its lattice constant.
【００２４】なお、Ｐｂと（Ｚｒ＋Ｔｉ）の比率（Ｐｂ
／（Ｚｒ＋Ｔｉ））は、０．９４〜０．９８であり、実
施例の全試料で略一定であった。The ratio of Pb to (Zr + Ti) (Pb
/ (Zr + Ti)) was 0.94 to 0.98 and was substantially constant in all the samples of the examples.
【００２５】表１より、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜の水
熱合成においては、Ｐｂ濃度及びＺｒ濃度，ｐＨ，反応
温度が、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜の生成に影響を与え
る因子であることがわかる。すなわち、Ｐｂ濃度が０．
１mol／l 、Ｚｒ濃度が０．０５mol／l より低い場合、
Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜が生成せず、また、ｐＨが１
４未満の場合にも、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜が生成し
ない。From Table 1, in the hydrothermal synthesis of the Pb (Zr, Ti) O 3 film, the Pb concentration, the Zr concentration, the pH and the reaction temperature influence the formation of the Pb (Zr, Ti) O 3 film. It turns out that it is a factor. That is, the Pb concentration is 0.
1 mol / l, when Zr concentration is lower than 0.05 mol / l,
No Pb (Zr, Ti) O 3 film was formed, and the pH was 1
Even if it is less than 4, no Pb (Zr, Ti) O 3 film is formed.
【００２６】また、Ｐｂ濃度が０．１mol／l 、Ｚｒ濃
度が０．０５mol／l 以上で、かつ、ｐＨが１４以上の
場合には、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜が生成する。しか
し、反応温度が２００℃以下（例えば１７５℃）の場
合、いくらかのＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜の生成は認め
られるが、Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3相の生成量よりも異
相の生成量の方が多くなる。If the Pb concentration is 0.1 mol / l, the Zr concentration is 0.05 mol / l or more, and the pH is 14 or more, a Pb (Zr, Ti) O 3 film is formed. However, when the reaction temperature is 200 ° C. or lower (for example, 175 ° C.), although some Pb (Zr, Ti) O 3 film formation is recognized, the Pb (Zr, Ti) O 3 phase has a different phase than the production amount. The amount produced is greater.
【００２７】なお、Ｐｂ濃度及びＺｒ濃度がそれぞれ、
０．１mol／l ，０．０５mol／l 以上の場合、Ｐｂ（Ｚ
ｒ，Ｔｉ）Ｏ3相の生成量及び組成は反応時間にはあま
り依存しない。The Pb concentration and the Zr concentration are respectively
In the case of 0.1 mol / l, 0.05 mol / l or more, Pb (Z
The amount and composition of the r, Ti) O 3 phase do not depend much on the reaction time.
【００２８】なお、図１に、異相を含まずに合成された
Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3膜のＸ線回折パターンを示す。
なお、このＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜の合成条件は、Ｐ
ｂ濃度：０．５０mol／l ，Ｚｒ濃度：０．２５mol／l
，ｐＨ：１４．５，合成時間：６０分である。Incidentally, FIG. 1 shows an X-ray diffraction pattern of the Pb (Zr, Ti) O 3 film synthesized without containing a heterogeneous phase.
The synthesis condition of this Pb (Zr, Ti) O 3 film is P
b concentration: 0.50 mol / l, Zr concentration: 0.25 mol / l
, PH: 14.5, synthesis time: 60 minutes.
【００２９】なお、上記実施例では、Ｔｉ金属からなる
基板をＴｉ金属（基体）として用いた場合について説明
したが、蒸着などの公知の方法により、その表面にＴｉ
金属膜を形成した任意の基板を用いることも可能であ
る。例えば、清浄で平滑な面を有する厚さ１．０mmのガ
ラス基板上に、公知の高周波スパッタリング法によって
Ｔｉ金属膜を約１μmの厚さに形成し、これを上記実施
例のＴｉ基板の代りに使用した場合にも全く同様の結果
が得られることが確認されている。In the above embodiments, the case where the substrate made of Ti metal is used as the Ti metal (base) has been described. However, the surface of Ti is formed on the surface by a known method such as vapor deposition.
It is also possible to use any substrate on which a metal film is formed. For example, a Ti metal film having a thickness of about 1 μm is formed by a known high frequency sputtering method on a glass substrate having a clean and smooth surface and a thickness of 1.0 mm, and this is used in place of the Ti substrate of the above embodiment. It has been confirmed that exactly the same results are obtained when used.
【００３０】また、上記実施例では、Ｐｂ源及びＺｒ源
として硝酸鉛（Ｐｂ（ＮＯ3）2）及び、オキシ硝酸ジル
コニウム（ＺｒＯ（ＮＯ3）2・２Ｈ2Ｏ）を用い、ｐＨ
調整用のアルカリ源としてＮａＯＨを用いたが、その目
的を達成することが可能な他の物質、例えば、塩化鉛
（ＰｂＣｌ2），オキシ塩化ジルコニウム（ＺｒＯＣｌ2
・８Ｈ2Ｏ）及び水酸化カリウム（ＫＯＨ）を用いても
よい。In the above embodiment, lead nitrate (Pb (NO 3 ) 2 ) and zirconium oxynitrate (ZrO (NO 3 ) 2 .2H 2 O) were used as the Pb source and the Zr source, and the pH was adjusted.
Although NaOH was used as the alkali source for adjustment, other substances that can achieve the purpose, for example, lead chloride (PbCl 2 ), zirconium oxychloride (ZrOCl 2
8H 2 O) and potassium hydroxide (KOH) may be used.
【００３１】また、上記実施例では、平板状のＴｉ基板
を用いた場合について説明したが、この発明の方法によ
れば、平板状ではない複雑な形状のＴｉ金属（基体）の
表面にＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜を形成することも可能
である。Further, in the above embodiment, the case where the flat Ti substrate is used has been described, but according to the method of the present invention, Pb (Pb) is formed on the surface of the Ti metal (base) having a complicated shape other than the flat shape. It is also possible to form a Zr, Ti) O 3 film.
【００３２】[0032]
【発明の効果】上述のように、本願発明のチタン金属と
チタン酸ジルコン酸鉛膜を含む複合体の製造方法は、Ｔ
ｉ基板または、表面にＴｉ金属膜を形成した基板を、
０．１mol／l 以上の鉛（Ｐｂ）化学種と０．０５mol／
l 以上のジルコニウム（Ｚｒ）化学種とを含有するｐＨ
が１４以上のアルカリ性の処理水溶液中に浸漬し、２０
０℃以上の温度で水熱処理を施すことにより、Ｔｉ金属
上にチタン酸ジルコン酸鉛（Ｐｂ（Ｚｒ，Ｔｉ）Ｏ3）
膜を形成するようにしているので、後処理工程を必要と
することなく、２００〜２５０℃の低温で均一なＰｂ
（Ｚｒ，Ｔｉ）Ｏ3膜を容易かつ確実に形成することが
できる。As described above, the method for producing a composite containing the titanium metal and the lead zirconate titanate film according to the present invention is not limited to T.
i substrate or a substrate having a Ti metal film formed on its surface,
0.1 mol / l or more lead (Pb) species and 0.05 mol / l
pH containing at least l zirconium (Zr) species
Is immersed in an alkaline treatment aqueous solution of 14 or more for 20
Lead zirconate titanate (Pb (Zr, Ti) O 3 ) is deposited on Ti metal by hydrothermal treatment at a temperature of 0 ° C. or higher.
Since the film is formed, uniform Pb can be obtained at a low temperature of 200 to 250 ° C. without requiring a post-treatment process.
The (Zr, Ti) O 3 film can be formed easily and surely.
【００３３】また、本願発明によれば、バルクからフォ
イルまでの、種々の形状のＴｉ金属（基体）や任意のパ
ターンのＴｉ金属膜の表面にＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜
を形成した複合体を製造することが可能になる。したが
って、この複合体においては、優れた加工性を有するチ
タン金属（基体）を電極として利用することにより、Ｐ
ｂ（Ｚｒ，Ｔｉ）Ｏ3膜の圧電性，焦電性，強誘電性な
どの特性を利用した各種のデバイスの形状を、その用途
や特性上の必要に応じて任意に制御することができる。Further, according to the present invention, a composite in which a Pb (Zr, Ti) O 3 film is formed on the surface of a Ti metal (substrate) of various shapes from the bulk to the foil or a Ti metal film of an arbitrary pattern. Allows the body to be manufactured. Therefore, in this composite, by using the titanium metal (base) having excellent workability as an electrode, P
The shape of various devices utilizing the characteristics of the b (Zr, Ti) O 3 film, such as piezoelectricity, pyroelectricity, and ferroelectricity, can be arbitrarily controlled according to the application and characteristics. .
【図１】本願発明のチタン金属とチタン酸ジルコン酸鉛
膜を含む複合体の製造方法により、水熱合成温度２５０
℃で形成したチタン酸ジルコン酸鉛膜のＸ線回折パター
ンを示す図である。FIG. 1 shows a hydrothermal synthesis temperature of 250 according to the method for producing a composite containing titanium metal and a lead zirconate titanate film according to the present invention.
It is a figure which shows the X-ray-diffraction pattern of the lead zirconate titanate film | membrane formed in ° C.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浜地 幸生 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 (72)発明者 伴野 国三郎 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 (72)発明者 吉村 昌弘 神奈川県綾瀬市寺尾中一丁目６番12 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Hamachi 2 26-10 Tenjin Tenjin, Nagaokakyo City, Kyoto Prefecture Murata Manufacturing Co., Ltd. (72) Inventor Kunisaburo Banno 2 26-10 Tenjin, Nagaokakyo, Kyoto Stock Murata Manufacturing Co., Ltd. (72) Inventor Masahiro Yoshimura 1-6-12 Terao Naka, Ayase City, Kanagawa Prefecture
Claims (4)
を、０．１mol／l 以上の鉛（Ｐｂ）化学種と０．０５m
ol／l 以上のジルコニウム（Ｚｒ）化学種とを含有する
ｐＨが１４以上のアルカリ性の処理水溶液中に浸漬し、
２００℃以上の温度で水熱処理を施すことにより、前記
Ｔｉ基板上にチタン酸ジルコン酸鉛（Ｐｂ（Ｚｒ，Ｔ
ｉ）Ｏ3）膜を形成することを特徴とするＴｉ金属とＰ
ｂ（Ｚｒ，Ｔｉ）Ｏ3膜を含む複合体の製造方法。1. A Ti substrate made of titanium (Ti) metal and a lead (Pb) species of 0.1 mol / l or more and 0.05 m
immersing in an alkaline treatment aqueous solution containing ol / l or more zirconium (Zr) species and having a pH of 14 or more,
By performing hydrothermal treatment at a temperature of 200 ° C. or higher, lead zirconate titanate (Pb (Zr, T
i) Ti metal and P characterized by forming an O 3 ) film
A method for producing a composite containing a b (Zr, Ti) O 3 film.
Ｔｉ基板と、該Ｔｉ基板上に形成されたＰｂ（Ｚｒ，Ｔ
ｉ）Ｏ3膜とを具備することを特徴とする複合体。2. Manufactured by the method according to claim 1,
Ti substrate and Pb (Zr, T formed on the Ti substrate
i) A composite comprising an O 3 film.
を、０．１mol／l 以上の鉛（Ｐｂ）化学種と、０．０
５mol／l 以上のジルコニウム（Ｚｒ）化学種とを含有
するｐＨが１４以上のアルカリ性の処理水溶液中に浸漬
し、２００℃以上の温度で水熱処理を施すことにより、
基板の表面に形成された前記Ｔｉ金属膜上にＰｂ（Ｚ
ｒ，Ｔｉ）Ｏ3膜を形成することを特徴とするＴｉ金属
とＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜を含む複合体の製造方法。3. A substrate having a Ti metal film formed on its surface is treated with 0.1 mol / l or more of lead (Pb) species and 0.0
By immersing in an alkaline treatment aqueous solution containing 5 mol / l or more of zirconium (Zr) species and having a pH of 14 or more, and subjecting to hydrothermal treatment at a temperature of 200 ° C. or more,
On the Ti metal film formed on the surface of the substrate, Pb (Z
A method for producing a composite containing a Ti metal and a Pb (Zr, Ti) O 3 film, which comprises forming an r, Ti) O 3 film.
Ｔｉ金属膜を表面に形成した基板と、該Ｔｉ金属膜上に
形成されたＰｂ（Ｚｒ，Ｔｉ）Ｏ3膜とを具備すること
を特徴とする複合体。4. Produced by the method of claim 3,
A composite comprising a substrate having a Ti metal film formed on its surface and a Pb (Zr, Ti) O 3 film formed on the Ti metal film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214693A JPH06211523A (en) | 1993-01-13 | 1993-01-13 | Production of composite body containing film of titanium metal and lead titanate zirconate and composite body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214693A JPH06211523A (en) | 1993-01-13 | 1993-01-13 | Production of composite body containing film of titanium metal and lead titanate zirconate and composite body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06211523A true JPH06211523A (en) | 1994-08-02 |
Family
ID=12074729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2214693A Pending JPH06211523A (en) | 1993-01-13 | 1993-01-13 | Production of composite body containing film of titanium metal and lead titanate zirconate and composite body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06211523A (en) |
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| WO1997003834A1 (en) * | 1995-07-14 | 1997-02-06 | Seiko Epson Corporation | Laminated head for ink jet recording, production method thereof, and printer equipped with the recording head |
| WO2007013596A1 (en) * | 2005-07-29 | 2007-02-01 | Showa Denko K. K. | Complex oxide film and method for producing same, dielectric material including complex oxide film, piezoelectric material, capacitor, piezoelectric element, and electronic device |
| US8486493B2 (en) | 2005-12-28 | 2013-07-16 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor and electronic device |
| US8486492B2 (en) | 2005-12-28 | 2013-07-16 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic device |
-
1993
- 1993-01-13 JP JP2214693A patent/JPH06211523A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997003834A1 (en) * | 1995-07-14 | 1997-02-06 | Seiko Epson Corporation | Laminated head for ink jet recording, production method thereof, and printer equipped with the recording head |
| WO2007013596A1 (en) * | 2005-07-29 | 2007-02-01 | Showa Denko K. K. | Complex oxide film and method for producing same, dielectric material including complex oxide film, piezoelectric material, capacitor, piezoelectric element, and electronic device |
| JPWO2007013596A1 (en) * | 2005-07-29 | 2009-02-12 | 昭和電工株式会社 | Composite oxide film and manufacturing method thereof, dielectric material including composite oxide film, piezoelectric material, capacitor, piezoelectric element, and electronic device |
| JP4652406B2 (en) * | 2005-07-29 | 2011-03-16 | 昭和電工株式会社 | Composite oxide film and manufacturing method thereof, dielectric material including composite oxide film, piezoelectric material, capacitor, piezoelectric element, and electronic device |
| US8524324B2 (en) | 2005-07-29 | 2013-09-03 | Showa Denko K.K. | Complex oxide film and method for producing same, dielectric material including complex oxide film, piezoelectric material, capacitor, piezoelectric element, and electronic device |
| US8486493B2 (en) | 2005-12-28 | 2013-07-16 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor and electronic device |
| US8486492B2 (en) | 2005-12-28 | 2013-07-16 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic device |
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