JPH10330195A - Piezoelectric crystal film - Google Patents
Piezoelectric crystal filmInfo
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- JPH10330195A JPH10330195A JP9142052A JP14205297A JPH10330195A JP H10330195 A JPH10330195 A JP H10330195A JP 9142052 A JP9142052 A JP 9142052A JP 14205297 A JP14205297 A JP 14205297A JP H10330195 A JPH10330195 A JP H10330195A
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- aqueous solution
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- raw material
- pzt
- film
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- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、圧電アクチュエー
タ、圧電センサー、焦電センサー、誘電体素子等に使用
することができる、水熱法によるＰＺＴ（チタン酸ジル
コン酸鉛）系圧電結晶膜に関するものであり、特に基板
面に接するＰＺＴ系圧電結晶膜の初期結晶層の組成に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrothermal PZT (lead zirconate titanate) -based piezoelectric crystal film which can be used for a piezoelectric actuator, a piezoelectric sensor, a pyroelectric sensor, a dielectric element, and the like. In particular, it relates to the composition of the initial crystal layer of the PZT-based piezoelectric crystal film in contact with the substrate surface.
【０００２】[0002]
【従来の技術】近年、通信機器、情報処理機器、ＡＶ、
家電製品等の高性能化と小型化が進むのと並行して、そ
れらの機器を構成する電子部品の小型化、軽量化が検討
されており、薄膜化による性能向上が試みられている。2. Description of the Related Art In recent years, communication equipment, information processing equipment, AV,
At the same time as high performance and miniaturization of home electric appliances and the like are progressing, miniaturization and weight reduction of electronic components constituting those devices are being studied, and attempts have been made to improve performance by thinning.
【０００３】しかしながら、従来のセラミックス研磨法
による薄膜化では、所望の密度や組成は得られるもの
の、目的とする厚み（３〜５０μｍ）に形成するために
は歩留まりが悪く極度のコストアップとなるという課題
があり、また、曲面状等の自由な形状に圧電結晶膜を形
成するには適していない。However, in conventional thinning by ceramic polishing, although a desired density and composition can be obtained, the yield is low and the cost is extremely increased in order to form a desired thickness (3 to 50 μm). There is a problem, and it is not suitable for forming a piezoelectric crystal film in a free shape such as a curved surface.
【０００４】また、スパッタリング法やＣＶＤ法等の真
空プロセス、ゾル−ゲル法などを用いて薄膜化すること
もできるが、これらの方法の場合、高温での製膜あるい
は製膜後の熱処理が必要であり組成の制御が難しく、基
板の種類が限られ、さらに膜厚を厚くする場合の量産性
に乏しいという課題がある。A thin film can be formed by using a vacuum process such as a sputtering method or a CVD method, or a sol-gel method. However, these methods require film formation at a high temperature or heat treatment after the film formation. However, there is a problem that it is difficult to control the composition, the type of the substrate is limited, and the mass productivity when the film thickness is further increased is poor.
【０００５】[0005]
【発明が解決しようとする課題】前記課題を解決する手
段として、水熱法によるＰＺＴ系圧電結晶膜が開発され
た。水熱法によるＰＺＴ系圧電結晶膜は、大きさや形状
の制限が少なく、膜形成時点で分極しており、さらにチ
タン表面に優先的に結晶成長することを利用したパター
ニングが可能等の特性を有しており、電子材料として幅
広い応用分野を有している。As means for solving the above-mentioned problems, a PZT-based piezoelectric crystal film formed by a hydrothermal method has been developed. The PZT-based piezoelectric crystal film produced by the hydrothermal method has such characteristics that the size and shape are few, the film is polarized at the time of film formation, and that patterning can be performed by utilizing preferential crystal growth on the titanium surface. It has a wide range of application fields as electronic materials.
【０００６】しかし、従来公知の水熱法で得られる膜
は、表面粗さがやや大きいため電極の付与が難しい場合
があるという点や誘電損失等の特性の点で未だ十分では
なく、その改善が種々検討されている。However, a film obtained by a conventionally known hydrothermal method is not sufficient in terms of characteristics such as the fact that it may be difficult to provide an electrode due to a relatively large surface roughness and dielectric loss, etc. Are variously studied.
【０００７】本発明は、上記課題を解決し、さらに各種
デバイスに応用可能な優れた特性を有するＰＺＴ系圧電
結晶膜を提供することを目的とする。An object of the present invention is to solve the above problems and to provide a PZT-based piezoelectric crystal film having excellent characteristics applicable to various devices.
【０００８】[0008]
【課題を解決するための手段】本発明は、基板上に水熱
法により形成されたＰＺＴ系圧電結晶膜において、前記
圧電結晶膜の基板面に接する結晶層が鉛、チタンおよび
ジルコニウムの他にストロンチウムおよび／またはバリ
ウムを含むことを特徴とする圧電結晶膜に関する。According to the present invention, there is provided a PZT-based piezoelectric crystal film formed on a substrate by a hydrothermal method, wherein a crystal layer in contact with the substrate surface of the piezoelectric crystal film is made of lead, titanium and zirconium. The present invention relates to a piezoelectric crystal film containing strontium and / or barium.
【０００９】[0009]
【発明の実施の形態】本発明のＰＺＴ系圧電結晶膜は以
下のような方法により得られる。まず、０．１ｍｏｌ／
ｌ〜８．０ｍｏｌ／ｌのアルカリ溶液中、鉛含有原料化
合物が５０ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／ｌ、ジルコ
ニウム含有原料化合物が１０ｍｍｏｌ／ｌ〜５００ｍｍ
ｏｌ／ｌ、チタン含有原料化合物が０ｍｍｏｌ／ｌ〜５
００ｍｍｏｌ／ｌ、ストロンチウムおよび／またはバリ
ウム含有原料化合物が０．０１ｍｍｏｌ／ｌ〜５００ｍ
ｍｏｌ／ｌとなるように調製された混合溶液中に基板を
設置固定し、８０℃〜２００℃、好ましくは１００℃〜
１６０℃、さらに好ましくは１２０℃〜１６０℃で１分
以上、好ましくは１０分以上反応させ、基板上に初期結
晶層を形成する第１工程、および、０．１ｍｏｌ／ｌ〜
８．０ｍｏｌ／ｌのアルカリ溶液中、鉛含有原料化合物
が５０ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／ｌ、ジルコニウ
ム含有原料化合物が１０ｍｍｏｌ／ｌ〜５００ｍｍｏｌ
／ｌおよびチタン含有原料化合物が１０ｍｍｏｌ／ｌ〜
５００ｍｍｏｌ／ｌの条件で８０℃〜２００℃、好まし
くは１００℃〜１６０℃、さらに好ましくは１２０℃〜
１６０℃で１分以上、好ましくは１０分以上反応させ、
結晶成長層を形成する第２工程とからＰＺＴ系圧電結晶
膜が製造される。DESCRIPTION OF THE PREFERRED EMBODIMENTS The PZT-based piezoelectric crystal film of the present invention is obtained by the following method. First, 0.1mol /
In a 1 to 8.0 mol / l alkaline solution, a lead-containing raw material compound is 50 mmol / l to 500 mmol / l, and a zirconium-containing raw material compound is 10 mmol / l to 500 mm.
ol / l, 0 mmol / l to 5 titanium-containing raw material compounds
00 mmol / l, strontium and / or barium-containing starting compound is 0.01 mmol / l to 500 m
The substrate was placed and fixed in a mixed solution prepared so as to have a mol / l of 80 ° C to 200 ° C, preferably 100 ° C to 200 ° C.
A first step of reacting at 160 ° C., more preferably 120 ° C. to 160 ° C. for 1 minute or more, preferably 10 minutes or more to form an initial crystal layer on a substrate, and 0.1 mol / l to
In an 8.0 mol / l alkaline solution, the lead-containing raw material compound is 50 mmol / l to 500 mmol / l, and the zirconium-containing raw material compound is 10 mmol / l to 500 mmol.
/ L and the titanium-containing raw material compound is 10 mmol / l or more.
80 ° C. to 200 ° C., preferably 100 ° C. to 160 ° C., more preferably 120 ° C. to 500 mmol / l
Reacted at 160 ° C. for 1 minute or more, preferably 10 minutes or more,
From the second step of forming the crystal growth layer, a PZT-based piezoelectric crystal film is manufactured.
【００１０】水熱法によるＰＺＴ系圧電結晶膜は、上記
各原料化合物濃度でまず基板上に水熱法により初期結晶
層を形成し、ついで結晶成長を行うことにより得られ
る。本発明によれば、初期結晶層形成時に鉛成分原料、
ジルコニウム成分原料、微量のチタン成分原料、および
ストロンチウムおよび／またはバリウム成分原料化合物
を存在させて第１工程の水熱反応を行った後、第２工程
の成長反応を行う。本発明における第２工程は繰り返し
行うことにより成長膜の厚みが制御できる。A PZT-based piezoelectric crystal film obtained by a hydrothermal method is obtained by first forming an initial crystal layer on a substrate by the hydrothermal method at the above-mentioned respective raw material compound concentrations, and then performing crystal growth. According to the present invention, a lead component raw material at the time of initial crystal layer formation,
The hydrothermal reaction of the first step is performed in the presence of a zirconium component raw material, a trace amount of a titanium component raw material, and a strontium and / or barium component raw material compound, and then a growth reaction of a second step is performed. By repeating the second step in the present invention, the thickness of the grown film can be controlled.
【００１１】本発明において水熱法により、ストロンチ
ウムおよび／またはバリウムが０．０１ｍｏｌ％〜５０
ｍｏｌ％、好ましくは１．０ｍｏｌ％〜４０ｍｏｌ％、
さらに好ましくは１０ｍｏｌ％〜４０ｍｏｌ％含む初期
結晶層の組成に第２工程の結晶成長を行うことにより、
表面平滑性が良く、電気特性の高いＰＺＴ系圧電結晶膜
が得られる。In the present invention, strontium and / or barium is contained in an amount of 0.01 mol% to 50 mol% by a hydrothermal method.
mol%, preferably 1.0 mol% to 40 mol%,
More preferably, the crystal growth in the second step is performed on the composition of the initial crystal layer containing 10 mol% to 40 mol%,
A PZT-based piezoelectric crystal film having good surface smoothness and high electric characteristics can be obtained.
【００１２】本発明で使用される基板は特に限定されな
いが、結晶核形成時に基板と溶液中の金属イオンとの反
応による初期結晶層と基板との密着力を大きくするため
にＰＺＴ系圧電結晶膜の構成元素を少なくとも１つ以上
含有するような基板が好ましい。また、ＰＺＴ系圧電結
晶膜を構成する元素でコーティングした基板を使用する
こともできる。The substrate used in the present invention is not particularly limited. However, in order to increase the adhesion between the initial crystal layer and the substrate due to the reaction between the substrate and metal ions in the solution at the time of forming the crystal nucleus, a PZT-based piezoelectric crystal film is used. A substrate that contains at least one or more of the constituent elements described above is preferable. Further, a substrate coated with an element constituting the PZT-based piezoelectric crystal film can also be used.
【００１３】本発明において水熱反応に使用される鉛、
ジルコニウム、チタン、ストロンチウム、およびバリウ
ムの構成元素を含有する原料化合物としては塩化物、オ
キシ塩化物、硝酸塩、水酸化物酸化物等が好ましい。ま
た、水熱反応において使用されるアルカリ化合物とし
て、例えば水酸化ナトリウム、水酸化カリウム等のアル
カリ金属の水酸化物を挙げることができる。Lead used in the hydrothermal reaction in the present invention,
As the raw material compound containing the constituent elements of zirconium, titanium, strontium, and barium, chloride, oxychloride, nitrate, hydroxide and the like are preferable. Examples of the alkali compound used in the hydrothermal reaction include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.
【００１４】本発明の製造方法の具体例を以下に詳述す
る。基板としてチタン基板あるいはチタンをコーティン
グしたものを用い、前記基板上に水熱法により、表面
性、電気特性の改善されたＰＺＴ系圧電結晶膜を作製す
る。A specific example of the production method of the present invention will be described in detail below. Using a titanium substrate or a titanium-coated substrate as a substrate, a PZT-based piezoelectric crystal film having improved surface properties and electrical characteristics is formed on the substrate by a hydrothermal method.
【００１５】まず、Ｐｂ（ＮＯ3 ）2 水溶液５０ｍｍｏ
ｌ／ｌ〜５００ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液１０
ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液
０ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／ｌと、それら以外に
Ｓｒ（ＮＯ3 ）2 および／またはＢａ（ＯＨ）2 ０．０
１ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／ｌおよびＫＯＨ水溶
液０．１ｍｏｌ／ｌ〜８．０ｍｏｌ／ｌの混合溶液中
に、前記の基板を任意の場所に設置固定し、８０℃〜２
００℃、好ましくは１００℃〜１６０℃、さらに好まし
くは１２０℃〜１６０℃で１分以上、好ましくは１０分
以上反応させ、表面性の高い、緻密な初期結晶層を形成
する。このときの初期結晶層の厚みは０．０５μｍ〜
２．０μｍとなっている。First, a Pb (NO 3 ) 2 aqueous solution of 50 mmol
l / l to 500 mmol / l, aqueous solution of ZrOCl 2 10
mmol / l to 500 mmol / l, TiCl 4 aqueous solution 0 mmol / l to 500 mmol / l, and Sr (NO 3 ) 2 and / or Ba (OH) 2 0.0
In a mixed solution of 1 mmol / l to 500 mmol / l and an aqueous KOH solution of 0.1 mol / l to 8.0 mol / l, the substrate is set and fixed at an arbitrary place,
The reaction is performed at 00 ° C., preferably 100 ° C. to 160 ° C., more preferably 120 ° C. to 160 ° C. for 1 minute or more, preferably 10 minutes or more, to form a dense initial crystal layer having high surface properties. At this time, the thickness of the initial crystal layer is 0.05 μm or more.
2.0 μm.
【００１６】次に結晶を成長させるため、Ｐｂ（Ｎ
Ｏ3 ）2 水溶液５０ｍｍｏｌ／ｌ〜５００ｍｍｏｌ／
ｌ、ＺｒＯＣｌ2 水溶液１０ｍｍｏｌ／ｌ〜５００ｍｍ
ｏｌ／ｌ、ＴｉＣｌ4 水溶液０．０２ｍｍｏｌ／ｌ〜５
００ｍｍｏｌ／ｌおよびＫＯＨ水溶液０．１ｍｏｌ／ｌ
〜８．０ｍｏｌ／ｌの混合溶液中に、前記の表面性の良
好な初期結晶層が形成された基板を任意の場所に設置固
定し、８０℃〜２００℃、好ましくは１００℃〜１６０
℃、さらに好ましくは１２０℃〜１６０℃で１分以上、
好ましくは１０分以上水熱処理を行う。これにより基板
上にＰＺＴ系圧電結晶膜が形成される。水熱処理におけ
る加熱方法は油浴や電気炉等による。その後、一般的な
洗浄を行う。例えば、純水中で超音波洗浄を行い、１０
０℃〜２００℃で２時間以上乾燥させる。洗浄には酢酸
等の有機酸、硝酸、硫酸等の使用もできる。Next, in order to grow a crystal, Pb (N
O 3) 2 aqueous solution 50mmol / l~500mmol /
1, ZrOCl 2 aqueous solution 10 mmol / l to 500 mm
ol / l, 0.02 mmol / l to 5 TiCl 4 aqueous solution
00 mmol / l and KOH aqueous solution 0.1 mol / l
The substrate on which the initial crystal layer having a good surface property is formed is fixed in an arbitrary place in a mixed solution of up to 8.0 mol / l, and is fixed at 80 to 200 ° C, preferably 100 to 160 ° C.
° C, more preferably at 120 ° C to 160 ° C for 1 minute or more,
Hydrothermal treatment is preferably performed for 10 minutes or more. Thus, a PZT-based piezoelectric crystal film is formed on the substrate. The heating method in the hydrothermal treatment uses an oil bath, an electric furnace, or the like. Thereafter, general cleaning is performed. For example, ultrasonic cleaning in pure water
Dry at 0 ° C to 200 ° C for 2 hours or more. Organic acids such as acetic acid, nitric acid, sulfuric acid and the like can be used for washing.
【００１７】こうして形成された圧電結晶膜の組成は第
１工程による第１層はチタン酸鉛、ジルコン酸鉛、チタ
ン酸ストロンチウムおよび、またはチタン酸バリウム、
ジルコン酸ストロンチウムおよび／またはジルコン酸バ
リウムの固溶体からなる複合酸化物であり、膜厚は０．
０５μｍ〜２．０μｍである。初期結晶層の上に成長し
たＰＺＴ系圧電結晶膜の組成はＰｂＺｒx Ｔｉ1-x Ｏ3
（ただし、０＜ｘ＜１である。）からなっている。The composition of the piezoelectric crystal film thus formed is such that the first layer formed by the first step is composed of lead titanate, lead zirconate, strontium titanate and / or barium titanate;
It is a composite oxide composed of a solid solution of strontium zirconate and / or barium zirconate, and has a thickness of 0.1 μm.
05 μm to 2.0 μm. The composition of the PZT-based piezoelectric crystal film grown on the initial crystal layer is PbZr x Ti 1-x O 3
(However, 0 <x <1).
【００１８】本発明で得られるＰＺＴ系圧電結晶膜を素
子化する場合に使用される電極としては、特に限定され
ないが、コストや量産性を考慮し、最適なものが選定さ
れる。例えば、無電解メッキ法によるニッケル、焼き付
けタイプの銀等がある。その他、蒸着によるアルミニウ
ム、スパッタリング法による白金、あるいはスパッタリ
ング法によるニッケル、金等も用いられる。なお、基板
に樹脂を用いる場合には、高温に加熱できないので焼き
付けタイプの銀電極は温度に注意が必要である。The electrode used when the PZT-based piezoelectric crystal film obtained in the present invention is made into an element is not particularly limited, but an optimum one is selected in consideration of cost and mass productivity. For example, there are nickel by electroless plating, baking silver, and the like. In addition, aluminum by vapor deposition, platinum by sputtering, nickel, gold, or the like by sputtering is also used. When a resin is used for the substrate, it is not possible to heat the substrate to a high temperature.
【００１９】[0019]
【実施例】以下、本発明の具体的実施例についてさらに
詳述する。EXAMPLES Hereinafter, specific examples of the present invention will be described in more detail.
【００２０】実施例１ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
９０ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液１０ｍｍｏ
ｌ／ｌ、ＺｒＯＣｌ2 水溶液５０ｍｍｏｌ／ｌ、ＴｉＣ
ｌ4 水溶液５０ｍｍｏｌ／ｌ、およびＫＯＨ水溶液４．
２ｍｏｌ／ｌとし、該混合溶液中にチタン基板を設置固
定して通常の撹拌操作の下、１５０℃で６時間の水熱処
理を行った。この第１工程で生成した初期結晶層の組成
はＰｂxＳｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ＜
１、０＜ｙ＜１である。）であった。Example 1 The amount of the reactant used in the first step was changed to Pb (NO 3 ) 2 aqueous solution 1
90 mmol / l, Sr (NO 3 ) 2 aqueous solution 10 mmol
1 / l, 50 mmol / l ZrOCl 2 aqueous solution, TiC
3. 4 mmol aqueous solution 50 mmol / l and KOH aqueous solution
The mixture was adjusted to 2 mol / l, and a titanium substrate was placed and fixed in the mixed solution and subjected to a hydrothermal treatment at 150 ° C. for 6 hours under a normal stirring operation. The composition of the first produced in step initial crystal layer Pb x Sr 1-x Zr y Ti 1-y O 3 ( where, 0 <x <
1, 0 <y <1. )Met.
【００２１】このようにして得られた第１工程の初期結
晶層に結晶成長のための第２工程の反応原料投入量をＰ
ｂ（ＮＯ3 ）2 水溶液３３０ｍｍｏｌ／ｌ、ＺｒＯＣｌ
2 水溶液１５０ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液１５０
ｍｍｏｌ／ｌ、およびＫＯＨ水溶液５．０６ｍｏｌ／ｌ
とし、該混合溶液中に結晶核層を形成したチタン基板を
設置固定して通常の撹拌操作の下、１３０℃で４時間の
水熱処理を行い、ＰｂＺｒy Ｔｉ1-y Ｏ3 （但し、０＜
ｙ＜１である。）の膜を形成した。この第２工程を３回
繰り返して膜厚を１０μｍとした。その後、純水中で超
音波洗浄を３分間×２回行い、１００℃で１２時間乾燥
を行った。In the thus obtained initial crystal layer of the first step, the input amount of the reaction material in the second step for crystal growth is P
b (NO 3 ) 2 aqueous solution 330 mmol / l, ZrOCl
2 aqueous solution 150 mmol / l, TiCl 4 aqueous solution 150
mmol / l and KOH aqueous solution 5.06 mol / l
And then, under normal stirring operation titanium substrate with the crystal nucleus layer on the mixed solution was placed stationary, performs hydrothermal treatment of 4 hours at 130 ℃, PbZr y Ti 1- y O 3 ( where, 0 <
y <1. ) Was formed. This second step was repeated three times to obtain a film thickness of 10 μm. Then, ultrasonic cleaning was performed twice in pure water for 3 minutes, and drying was performed at 100 ° C. for 12 hours.
【００２２】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．５μｍと薄く、Ｐ
ｂx Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ＜１、
０＜ｙ＜１である。）の均一な膜となっていた。また、
得られたＰＺＴ系圧電結晶膜の表面粗さはＲmax が２．
０μｍで、膜厚１０．０μｍの２０％であった。得られ
たＰＺＴ系圧電結晶膜にスパッタリング法により、金電
極を付与し、バイモルフ素子の構成で、分極処理を施す
ことなく電圧を印加したところ変位を示し、分極方向が
揃っていることが電気的に確認された。この膜の誘電率
は約９００、誘電損失は約０．００９であった。The initial crystal layer of the PZT-based piezoelectric crystal film thus obtained in the first step is as thin as 0.5 μm.
b x Sr 1-x Zr y Ti 1-y O 3 ( where, 0 <x <1,
0 <y <1. ) Was uniform. Also,
Surface roughness of the obtained PZT piezoelectric crystal film R max is 2.
The thickness was 0 μm, which was 20% of the film thickness of 10.0 μm. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. The dielectric constant of this film was about 900, and the dielectric loss was about 0.009.
【００２３】実施例２ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
５０ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液３０ｍｍｏ
ｌ／ｌ、ＢａＣｌ2 水溶液２０ｍｍｏｌ／ｌ、ＺｒＯＣ
ｌ2 水溶液５０ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液５０ｍ
ｍｏｌ／ｌ、およびＫＯＨ水溶液４．２ｍｏｌ／ｌと
し、該混合溶液中にチタン基板を設置固定して通常の撹
拌操作の下、１５０℃で６時間の水熱処理を行った。こ
の第１工程で生成した初期結晶層の組成はＰｂx （Ｓｒ
v Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3（但し、ｖ＋ｗ＝
１、０＜ｘ＜１、０＜ｙ＜１である。）であった。この
ようにして得られた第１工程の初期結晶層に結晶成長の
ための第２工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水
溶液３３０ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液１５０ｍ
ｍｏｌ／ｌ、ＴｉＣｌ4 水溶液１５０ｍｍｏｌ／ｌ、お
よびＫＯＨ水溶液２．０６ｍｏｌ／ｌとし、該混合溶液
中に結晶核層を形成したチタン基板を設置固定して通常
の撹拌操作の下、１３０℃で１２時間の水熱処理を行
い、ＰｂＺｒy Ｔｉ1-y Ｏ3 （但し、０＜ｙ＜１であ
る。）の膜を形成した。この第２工程を３回繰り返して
膜厚を１０μｍとした。その後、純水中で超音波洗浄を
３分間×２回行い、１５０℃で１２時間乾燥を行った。Example 2 The amount of the reaction raw material charged in the first step was 1% aqueous solution of Pb (NO 3 ) 2.
50 mmol / l, 30 mmol of Sr (NO 3 ) 2 aqueous solution
1 / l, BaCl 2 aqueous solution 20 mmol / l, ZrOC
l 2 aqueous solution 50mmol / l, TiCl 4 aqueous solution 50m
mol / l and 4.2 mol / l of a KOH aqueous solution, and a titanium substrate was placed and fixed in the mixed solution and subjected to hydrothermal treatment at 150 ° C. for 6 hours under a normal stirring operation. The composition of the initial crystal layer generated in the first step is Pb x (Sr
v Ba w) 1-x Zr y Ti 1-y O 3 ( where, v + w =
1, 0 <x <1, 0 <y <1. )Met. In the thus obtained initial crystal layer of the first step, the input amount of the reaction raw material in the second step for crystal growth was 330 mmol / l of a Pb (NO 3 ) 2 aqueous solution and 150 m of a ZrOCl 2 aqueous solution.
mol / l, a TiCl 4 aqueous solution 150 mmol / l, and a KOH aqueous solution 2.06 mol / l, and a titanium substrate having a crystal nucleus layer formed therein was fixed in the mixed solution at 130 ° C. under a normal stirring operation. performs hydrothermal treatment time, PbZr y Ti 1-y O 3 ( provided that 0 <y <1.) to form a film of. This second step was repeated three times to obtain a film thickness of 10 μm. After that, ultrasonic cleaning was performed twice in pure water for 3 minutes and dried at 150 ° C. for 12 hours.
【００２４】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．５μｍと薄く、Ｐ
ｂx （Ｓｒv Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、
ｖ＋ｗ＝１、０＜ｘ＜１、０＜ｙ＜１である。）の均一
な膜となっていた。また、得られたＰＺＴ系圧電結晶膜
の表面粗さはＲmax が２．０μｍで、膜厚１０．０μｍ
の２０％であった。得られたＰＺＴ系圧電結晶膜にスパ
ッタリング法により、金電極を付与し、バイモルフ素子
の構成で、分極処理を施すことなく電圧を印加したとこ
ろ変位を示し、分極方向が揃っていることが電気的に確
認された。この膜の誘電率は約１０００、誘電損失は約
０．００９であった。The initial crystal layer of the PZT-based piezoelectric crystal film obtained in the first step is as thin as 0.5 μm.
b x (Sr v Ba w) 1-x Zr y Ti 1-y O 3 ( where,
v + w = 1, 0 <x <1, 0 <y <1. ) Was uniform. The surface roughness of the obtained PZT-based piezoelectric crystal film was such that R max was 2.0 μm and the film thickness was 10.0 μm.
Was 20%. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 1000 and a dielectric loss of about 0.009.
【００２５】実施例３ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
００ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液１００ｍｍ
ｏｌ／ｌ、ＺｒＯＣｌ2 水溶液５０ｍｍｏｌ／ｌ、Ｔｉ
Ｃｌ4 水溶液５０ｍｍｏｌ／ｌ、およびＫＯＨ水溶液
４．２ｍｏｌ／ｌとし、該混合溶液中にチタン基板を設
置固定して通常の撹拌操作の下、１５０℃で６時間の水
熱処理を行った。この第１工程で生成した初期結晶層の
組成はＰｂ x Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜
ｘ＜１、０＜ｙ＜１である。）であった。Example 3 The amount of the reactant used in the first step was Pb (NOThree)TwoAqueous solution 1
00 mmol / l, Sr (NOThree)TwoAqueous solution 100mm
ol / l, ZrOClTwoAqueous solution 50 mmol / l, Ti
ClFour50 mmol / l aqueous solution and KOH aqueous solution
4.2 mol / l, and a titanium substrate was set in the mixed solution.
6 hours at 150 ° C under normal stirring
Heat treatment was performed. Of the initial crystal layer generated in the first step.
The composition is Pb xSr1-xZryTi1-yOThree(However, 0 <
x <1, 0 <y <1. )Met.
【００２６】このようにして得られた第１工程の初期結
晶層に結晶成長のための第２工程の反応原料投入量をＰ
ｂ（ＮＯ3 ）2 水溶液１１０ｍｍｏｌ／ｌ、ＺｒＯＣｌ
2 水溶液７５ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液２５ｍｍ
ｏｌ／ｌ、およびＫＯＨ水溶液３．９７ｍｏｌ／ｌと
し、該混合溶液中に結晶核層を形成したチタン基板を設
置固定して通常の撹拌操作の下、１３０℃で４時間の水
熱処理を行い、ＰｂＺｒ y Ｔｉ1-y Ｏ3 （但し、０＜ｙ
＜１である。）の膜を形成した。この第２工程を３回繰
り返して膜厚を８μｍとした。その後、純水中で超音波
洗浄を３分間×２回行い、１００℃で１２時間乾燥を行
った。The initial result of the first step thus obtained is
The input amount of the reaction material in the second step for crystal growth is P
b (NOThree)TwoAqueous solution 110 mmol / l, ZrOCl
TwoAqueous solution 75 mmol / l, TiClFourAqueous solution 25mm
ol / l, and 3.97 mol / l of a KOH aqueous solution.
Then, a titanium substrate having a crystal nucleus layer formed in the mixed solution is provided.
Water for 4 hours at 130 ° C under normal stirring operation.
Heat treatment, PbZr yTi1-yOThree(However, 0 <y
<1. ) Was formed. Repeat this second step three times
This was repeated to make the film thickness 8 μm. After that, ultrasonic wave in pure water
Wash twice for 3 minutes and dry at 100 ° C for 12 hours.
Was.
【００２７】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．３μｍと薄く、Ｐ
ｂx Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ＜１、
０＜ｙ＜１である。）の均一な膜となっていた。また、
得られたＰＺＴ系圧電結晶膜の表面粗さはＲmax が１．
５μｍで、膜厚８．０μｍの１８．７５％であった。得
られたＰＺＴ系圧電結晶膜にスパッタリング法により、
金電極を付与し、バイモルフ素子の構成で、分極処理を
施すことなく電圧を印加したところ変位を示し、分極方
向が揃っていることが電気的に確認された。この膜の誘
電率は約９５０、誘電損失は約０．００８であった。The PZT-based piezoelectric crystal film thus obtained has a thin initial crystal layer of 0.3 μm in the first step.
b x Sr 1-x Zr y Ti 1-y O 3 ( where, 0 <x <1,
0 <y <1. ) Was uniform. Also,
Surface roughness of the obtained PZT piezoelectric crystal film R max is 1.
The thickness was 5 μm, which was 18.75% of the film thickness of 8.0 μm. The resulting PZT-based piezoelectric crystal film is formed by sputtering.
In the configuration of the bimorph element provided with a gold electrode, when a voltage was applied without performing polarization processing, displacement was shown, and it was electrically confirmed that the polarization directions were aligned. The dielectric constant of this film was about 950, and the dielectric loss was about 0.008.
【００２８】実施例４ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
００ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液６０ｍｍｏ
ｌ／ｌ、ＢａＣｌ2 水溶液４０ｍｍｏｌ／ｌ、ＺｒＯＣ
ｌ2 水溶液７５ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液２５ｍ
ｍｏｌ／ｌ、およびＫＯＨ水溶液４．１５ｍｏｌ／ｌと
し、該混合溶液中にチタン基板を設置固定して通常の撹
拌操作の下、１５０℃で６時間の水熱処理を行った。こ
の第１工程で生成した初期結晶層の組成はＰｂx （Ｓｒ
v Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ 3 （但し、ｖ＋ｗ＝
１、０＜ｘ＜１、０＜ｙ＜１である。）であった。この
ようにして得られた第１工程の初期結晶層に結晶成長の
ための第２工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水
溶液１１０ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液６０ｍｍ
ｏｌ／ｌ、ＴｉＣｌ4 水溶液４０ｍｍｏｌ／ｌ、および
ＫＯＨ水溶液４．０ｍｏｌ／ｌとし、該混合溶液中に結
晶核層を形成したチタン基板を設置固定して通常の撹拌
操作の下、１３０℃で４時間の水熱処理を行い、ＰｂＺ
ｒyＴｉ1-y Ｏ3 （但し、０＜ｙ＜１である。）の膜を
形成した。この第２工程を３回繰り返して膜厚を９μｍ
とした。その後、純水中で超音波洗浄を３分間×２回行
い、１５０℃で１２時間乾燥を行った。Example 4 The amount of reactant charged in the first step was Pb (NOThree)TwoAqueous solution 1
00 mmol / l, Sr (NOThree)TwoAqueous solution 60mmo
1 / l, BaClTwoAqueous solution 40 mmol / l, ZrOC
lTwoAqueous solution 75 mmol / l, TiClFour25m aqueous solution
mol / l, and 4.15 mol / l of a KOH aqueous solution.
Then, a titanium substrate is placed and fixed in the mixed solution and ordinary stirring is performed.
Under a stirring operation, a hydrothermal treatment was performed at 150 ° C. for 6 hours. This
The composition of the initial crystal layer generated in the first step is Pbx(Sr
vBaw)1-xZryTi1-yO Three(However, v + w =
1, 0 <x <1, 0 <y <1. )Met. this
Of the crystal growth in the initial crystal layer of the first step thus obtained.
For the reaction material input in the second step for Pb (NOThree)Twowater
Solution 110 mmol / l, ZrOClTwoAqueous solution 60mm
ol / l, TiClFourAqueous solution 40 mmol / l, and
A KOH aqueous solution of 4.0 mol / l was added to the mixed solution.
Place the titanium substrate with the crystal nucleus layer on it and fix it normally
Under the operation, a hydrothermal treatment is performed at 130 ° C. for 4 hours, and PbZ
ryTi1-yOThree(However, 0 <y <1)
Formed. This second step is repeated three times to obtain a film thickness of 9 μm.
And After that, ultrasonic cleaning was performed twice in pure water for 3 minutes.
And dried at 150 ° C. for 12 hours.
【００２９】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．４μｍと薄く、Ｐ
ｂx （Ｓｒv Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、
ｖ＋ｗ＝１、０＜ｘ＜１、０＜ｙ＜１である。）の均一
な膜となっていた。また、得られたＰＺＴ系圧電結晶膜
の表面粗さはＲmax が１．８μｍで、膜厚９．０μｍの
２０％であった。得られたＰＺＴ系圧電結晶膜にスパッ
タリング法により、金電極を付与し、バイモルフ素子の
構成で、分極処理を施すことなく電圧を印加したところ
変位を示し、分極方向が揃っていることが電気的に確認
された。この膜の誘電率は約１０００、誘電損失は約
０．００９であった。The initial crystal layer of the PZT-based piezoelectric crystal film thus obtained in the first step is as thin as 0.4 μm.
b x (Sr v Ba w) 1-x Zr y Ti 1-y O 3 ( where,
v + w = 1, 0 <x <1, 0 <y <1. ) Was uniform. Further, the surface roughness of the obtained PZT piezoelectric crystal film in R max is 1.8 .mu.m, was 20% of the thickness of 9.0 .mu.m. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 1000 and a dielectric loss of about 0.009.
【００３０】実施例５ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
５０ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液５０ｍｍｏ
ｌ／ｌ、ＺｒＯＣｌ2 水溶液７５ｍｍｏｌ／ｌ、ＴｉＣ
ｌ4 水溶液２５ｍｍｏｌ／ｌ、およびＫＯＨ水溶液４．
１５ｍｏｌ／ｌとし、該混合溶液中にチタン基板を設置
固定して通常の撹拌操作の下、１５０℃で４時間の水熱
処理を行った。この第１工程で生成した初期結晶層の組
成はＰｂ x Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ
＜１、０＜ｙ＜１である。）であった。Example 5 The amount of the reactant used in the first step was Pb (NOThree)TwoAqueous solution 1
50 mmol / l, Sr (NOThree)TwoAqueous solution 50mmo
1 / l, ZrOClTwoAqueous solution 75 mmol / l, TiC
lFour3. 25 mmol / l aqueous solution and KOH aqueous solution
15 mol / l, titanium substrate placed in the mixed solution
Hydrothermal for 4 hours at 150 ° C under normal stirring operation while fixed
Processing was performed. A set of initial crystal layers generated in the first step
The result is Pb xSr1-xZryTi1-yOThree(However, 0 <x
<1, 0 <y <1. )Met.
【００３１】このようにして得られた第１工程の初期結
晶層に結晶成長のための第２工程の反応原料投入量をＰ
ｂ（ＮＯ3 ）2 水溶液２２０ｍｍｏｌ／ｌ、ＺｒＯＣｌ
2 水溶液６０ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液４０ｍｍ
ｏｌ／ｌ、およびＫＯＨ水溶液４．２２ｍｏｌ／ｌと
し、該混合溶液中に結晶核層を形成したチタン基板を設
置固定して通常の撹拌操作の下、１３０℃で４時間の水
熱処理を行い、ＰｂＺｒ y Ｔｉ1-y Ｏ3 （但し、０＜ｙ
＜１である。）の膜を形成した。この第２工程を３回繰
り返して膜厚を１０μｍとした。その後、純水中で超音
波洗浄を３分間×２回行い、１００℃で１２時間乾燥を
行った。The initial results of the first step thus obtained are
The input amount of the reaction material in the second step for crystal growth is P
b (NOThree)TwoAqueous solution 220 mmol / l, ZrOCl
TwoAqueous solution 60 mmol / l, TiClFourAqueous solution 40mm
ol / l, and 4.22 mol / l of a KOH aqueous solution.
Then, a titanium substrate having a crystal nucleus layer formed in the mixed solution is provided.
Water for 4 hours at 130 ° C under normal stirring operation.
Heat treatment, PbZr yTi1-yOThree(However, 0 <y
<1. ) Was formed. Repeat this second step three times
This was repeated to make the film thickness 10 μm. After that, in super pure water
Perform wave washing twice for 3 minutes and dry at 100 ° C for 12 hours.
went.
【００３２】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．５μｍと薄く、Ｐ
ｂx Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ＜１、
０＜ｙ＜１である。）の均一な膜となっていた。また、
得られたＰＺＴ系圧電結晶膜の表面粗さはＲmax が２．
０μｍで、膜厚１０．０μｍの２０％であった。得られ
たＰＺＴ系圧電結晶膜にスパッタリング法により、金電
極を付与し、バイモルフ素子の構成で、分極処理を施す
ことなく電圧を印加したところ変位を示し、分極方向が
揃っていることが電気的に確認された。この膜の誘電率
は約９５０、誘電損失は約０．００６であった。The initial crystal layer of the PZT-based piezoelectric crystal film obtained in the first step is as thin as 0.5 μm.
b x Sr 1-x Zr y Ti 1-y O 3 ( where, 0 <x <1,
0 <y <1. ) Was uniform. Also,
Surface roughness of the obtained PZT piezoelectric crystal film R max is 2.
The thickness was 0 μm, which was 20% of the film thickness of 10.0 μm. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 950 and a dielectric loss of about 0.006.
【００３３】実施例６ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
５０ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液３０ｍｍｏ
ｌ／ｌ、ＢａＣｌ2 水溶液２０ｍｍｏｌ／ｌ、ＺｒＯＣ
ｌ2 水溶液５０ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液５０ｍ
ｍｏｌ／ｌ、およびＫＯＨ水溶液１．７ｍｏｌ／ｌと
し、該混合溶液中にチタン基板を設置固定して通常の撹
拌操作の下、１５０℃で６時間の水熱処理を行った。こ
の第１工程で生成した初期結晶層の組成はＰｂx （Ｓｒ
v Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3（但し、ｖ＋ｗ＝
１、０＜ｘ＜１、０＜ｙ＜１である。）であった。この
ようにして得られた第１工程の初期結晶層に結晶成長の
ための第２工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水
溶液１１０ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液５０ｍｍ
ｏｌ／ｌ、ＴｉＣｌ4 水溶液５０ｍｍｏｌ／ｌ、および
ＫＯＨ水溶液４．０２ｍｏｌ／ｌとし、該混合溶液中に
結晶核層を形成したチタン基板を設置固定して通常の撹
拌操作の下、１３０℃で４時間の水熱処理を行い、Ｐｂ
Ｚｒ y Ｔｉ1-y Ｏ3 （但し、０＜ｙ＜１である。）の膜
を形成した。この第２工程を４回繰り返して膜厚を１５
μｍとした。その後、純水中で超音波洗浄を３分間×２
回行い、１５０℃で１２時間乾燥を行った。Example 6 The input amount of the reactant in the first step was Pb (NOThree)TwoAqueous solution 1
50 mmol / l, Sr (NOThree)TwoAqueous solution 30mmo
1 / l, BaClTwoAqueous solution 20 mmol / l, ZrOC
lTwoAqueous solution 50 mmol / l, TiClFourAqueous solution 50m
mol / l, and 1.7 mol / l of a KOH aqueous solution.
Then, a titanium substrate is placed and fixed in the mixed solution and ordinary stirring is performed.
Under a stirring operation, a hydrothermal treatment was performed at 150 ° C. for 6 hours. This
The composition of the initial crystal layer generated in the first step is Pbx(Sr
vBaw)1-xZryTi1-yOThree(However, v + w =
1, 0 <x <1, 0 <y <1. )Met. this
Of the crystal growth in the initial crystal layer of the first step thus obtained.
For the reaction material input in the second step for Pb (NOThree)Twowater
Solution 110 mmol / l, ZrOClTwoAqueous solution 50mm
ol / l, TiClFourAqueous solution 50 mmol / l, and
4.02 mol / l of KOH aqueous solution was added to the mixed solution.
Place the titanium substrate on which the crystal nuclei layer is formed
Hydrothermal treatment at 130 ° C. for 4 hours under stirring operation
Zr yTi1-yOThree(However, 0 <y <1)
Was formed. This second step is repeated four times to reduce the film thickness to 15
μm. Then, ultrasonic cleaning in pure water for 3 minutes x 2
And drying at 150 ° C. for 12 hours.
【００３４】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．５μｍと薄く、Ｐ
ｂx （Ｓｒv Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、
ｖ＋ｗ＝１、０＜ｘ＜１、０＜ｙ＜１である。）の均一
な膜となっていた。また、得られたＰＺＴ系圧電結晶膜
の表面粗さはＲmax が３．０μｍで、膜厚１５．０μｍ
の２０％であった。得られたＰＺＴ系圧電結晶膜にスパ
ッタリング法により、金電極を付与し、バイモルフ素子
の構成で、分極処理を施すことなく電圧を印加したとこ
ろ変位を示し、分極方向が揃っていることが電気的に確
認された。この膜の誘電率は約１０００、誘電損失は約
０．００９であった。The PZT-based piezoelectric crystal film thus obtained has a thin initial crystal layer of 0.5 μm in the first step.
b x (Sr v Ba w) 1-x Zr y Ti 1-y O 3 ( where,
v + w = 1, 0 <x <1, 0 <y <1. ) Was uniform. Further, the surface roughness of the obtained PZT-based piezoelectric crystal film was such that R max was 3.0 μm and the film thickness was 15.0 μm.
Was 20%. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 1000 and a dielectric loss of about 0.009.
【００３５】実施例７ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液１
００ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液１００ｍｍ
ｏｌ／ｌ、ＺｒＯＣｌ2 水溶液５０ｍｍｏｌ／ｌ、Ｔｉ
Ｃｌ4 水溶液５０ｍｍｏｌ／ｌ、およびＫＯＨ水溶液
４．２ｍｏｌ／ｌとし、該混合溶液中にチタン基板を設
置固定して通常の撹拌操作の下、１５０℃で５時間の水
熱処理を行った。この第１工程で生成した初期結晶層の
組成はＰｂ x Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜
ｘ＜１、０＜ｙ＜１である。）であった。Example 7 The amount of reactant charged in the first step was Pb (NOThree)TwoAqueous solution 1
00 mmol / l, Sr (NOThree)TwoAqueous solution 100mm
ol / l, ZrOClTwoAqueous solution 50 mmol / l, Ti
ClFour50 mmol / l aqueous solution and KOH aqueous solution
4.2 mol / l, and a titanium substrate was set in the mixed solution.
Water at 150 ° C for 5 hours under normal stirring operation.
Heat treatment was performed. Of the initial crystal layer generated in the first step.
The composition is Pb xSr1-xZryTi1-yOThree(However, 0 <
x <1, 0 <y <1. )Met.
【００３６】このようにして得られた第１工程の初期結
晶層に結晶成長のための第２工程の反応原料投入量をＰ
ｂ（ＮＯ3 ）2 水溶液２２０ｍｍｏｌ／ｌ、ＺｒＯＣｌ
2 水溶液８０ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液２０ｍｍ
ｏｌ／ｌ、およびＫＯＨ水溶液４．１８ｍｏｌ／ｌと
し、該混合溶液中に結晶核層を形成したチタン基板を設
置固定して通常の撹拌操作の下、１３０℃で３時間の水
熱処理を行い、ＰｂＺｒ y Ｔｉ1-y Ｏ3 （但し、０＜ｙ
＜１である。）の膜を形成した。この第２工程を３回繰
り返して膜厚を８μｍとした。その後、純水中で超音波
洗浄を３分間×２回行い、１００℃で１２時間乾燥を行
った。The initial results of the first step thus obtained are as follows.
The input amount of the reaction material in the second step for crystal growth is P
b (NOThree)TwoAqueous solution 220 mmol / l, ZrOCl
TwoAqueous solution 80 mmol / l, TiClFourAqueous solution 20mm
ol / l, and 4.18 mol / l of a KOH aqueous solution.
Then, a titanium substrate having a crystal nucleus layer formed in the mixed solution is provided.
Water for 3 hours at 130 ° C under normal stirring operation.
Heat treatment, PbZr yTi1-yOThree(However, 0 <y
<1. ) Was formed. Repeat this second step three times
This was repeated to make the film thickness 8 μm. After that, ultrasonic wave in pure water
Wash twice for 3 minutes and dry at 100 ° C for 12 hours.
Was.
【００３７】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．８μｍと薄く、Ｐ
ｂx Ｓｒ1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、０＜ｘ＜１、
０＜ｙ＜１である。）の均一な膜となっていた。また、
得られたＰＺＴ系圧電結晶膜の表面粗さはＲmax が１．
６μｍで、膜厚８．０μｍの２０％であった。得られた
ＰＺＴ系圧電結晶膜にスパッタリング法により、金電極
を付与し、バイモルフ素子の構成で、分極処理を施すこ
となく電圧を印加したところ変位を示し、分極方向が揃
っていることが電気的に確認された。この膜の誘電率は
約８８０、誘電損失は約０．００８であった。The initial crystal layer of the PZT-based piezoelectric crystal film thus obtained in the first step is as thin as 0.8 μm.
b x Sr 1-x Zr y Ti 1-y O 3 ( where, 0 <x <1,
0 <y <1. ) Was uniform. Also,
Surface roughness of the obtained PZT piezoelectric crystal film R max is 1.
The thickness was 6 μm, which was 20% of the film thickness of 8.0 μm. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 880 and a dielectric loss of about 0.008.
【００３８】実施例８ 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液５
０ｍｍｏｌ／ｌ、Ｓｒ（ＮＯ3 ）2 水溶液１００ｍｍｏ
ｌ／ｌ、ＢａＣｌ2 水溶液５０ｍｍｏｌ／ｌ、ＺｒＯＣ
ｌ2 水溶液７５ｍｍｏｌ／ｌ、ＴｉＣｌ4 水溶液２５ｍ
ｍｏｌ／ｌ、およびＫＯＨ水溶液４．１５ｍｏｌ／ｌと
し、該混合溶液中にチタン基板を設置固定して通常の撹
拌操作の下、１５０℃で６時間の水熱処理を行った。こ
の第１工程で生成した初期結晶層の組成はＰｂx （Ｓｒ
v Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ 3 （但し、ｖ＋ｗ＝
１、０＜ｘ＜１、０＜ｙ＜１である。）であった。この
ようにして得られた第１工程の初期結晶層に結晶成長の
ための第２工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水
溶液１１０ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液９０ｍｍ
ｏｌ／ｌ、ＴｉＣｌ4 水溶液１０ｍｍｏｌ／ｌ、および
ＫＯＨ水溶液３．９４ｍｏｌ／ｌとし、該混合溶液中に
結晶核層を形成したチタン基板を設置固定して通常の撹
拌操作の下、１４０℃で２時間の水熱処理を行い、Ｐｂ
Ｚｒ y Ｔｉ1-y Ｏ3 （但し、０＜ｙ＜１である。）の膜
を形成した。この第２工程を４回繰り返して膜厚を９μ
ｍとした。その後、純水中で超音波洗浄を３分間×２回
行い、１５０℃で１２時間乾燥を行った。Example 8 The amount of the reactant used in the first step was changed to Pb (NOThree)TwoAqueous solution 5
0 mmol / l, Sr (NOThree)TwoAqueous solution 100mmo
1 / l, BaClTwoAqueous solution 50 mmol / l, ZrOC
lTwoAqueous solution 75 mmol / l, TiClFour25m aqueous solution
mol / l, and 4.15 mol / l of a KOH aqueous solution.
Then, a titanium substrate is placed and fixed in the mixed solution and ordinary stirring is performed.
Under a stirring operation, a hydrothermal treatment was performed at 150 ° C. for 6 hours. This
The composition of the initial crystal layer generated in the first step is Pbx(Sr
vBaw)1-xZryTi1-yO Three(However, v + w =
1, 0 <x <1, 0 <y <1. )Met. this
Of the crystal growth in the initial crystal layer of the first step thus obtained.
For the reaction material input in the second step for Pb (NOThree)Twowater
Solution 110 mmol / l, ZrOClTwoAqueous solution 90mm
ol / l, TiClFourAqueous solution 10 mmol / l, and
3.94 mol / L KOH aqueous solution was added to the mixed solution.
Place the titanium substrate on which the crystal nuclei layer is formed
Hydrothermal treatment at 140 ° C. for 2 hours under stirring operation
Zr yTi1-yOThree(However, 0 <y <1)
Was formed. This second step is repeated four times to reduce the film thickness to 9 μm.
m. Then, ultrasonic cleaning in pure water twice for 3 minutes
The drying was performed at 150 ° C. for 12 hours.
【００３９】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による初期結晶層は０．３μｍと薄く、Ｐ
ｂx （Ｓｒv Ｂａw ）1-x Ｚｒy Ｔｉ1-y Ｏ3 （但し、
ｖ＋ｗ＝１、０＜ｘ＜１、０＜ｙ＜１である。）の均一
な膜となっていた。また、得られたＰＺＴ系圧電結晶膜
の表面粗さはＲmax が１．５μｍで、膜厚９．０μｍの
１７％であった。得られたＰＺＴ系圧電結晶膜にスパッ
タリング法により、金電極を付与し、バイモルフ素子の
構成で、分極処理を施すことなく電圧を印加したところ
変位を示し、分極方向が揃っていることが電気的に確認
された。この膜の誘電率は約１０００、誘電損失は約
０．００５であった。The initial crystal layer of the PZT-based piezoelectric crystal film thus obtained in the first step is as thin as 0.3 μm.
b x (Sr v Ba w) 1-x Zr y Ti 1-y O 3 ( where,
v + w = 1, 0 <x <1, 0 <y <1. ) Was uniform. Further, the surface roughness of the obtained PZT piezoelectric crystal film in R max is 1.5 [mu] m, 17% of the thickness of 9.0 .mu.m. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. Was confirmed. This film had a dielectric constant of about 1000 and a dielectric loss of about 0.005.
【００４０】比較例 第１工程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液３
００ｍｍｏｌ／ｌ、ＺｒＯＣｌ2 水溶液１００ｍｍｏｌ
／ｌ、およびＫＯＨ水溶液３．８ｍｏｌ／ｌとし、該混
合溶液中にチタン基板を設置固定して通常の撹拌操作の
下、１６０℃で１２時間の水熱処理を行った。この第１
工程で精製した膜の組成はＰｂＺｒy Ｔｉ1-y Ｏ3 （但
し、０＜ｙ＜１である。）であった。このようにして得
られた第１工程の初期結晶層に結晶成長のための第２工
程の反応原料投入量をＰｂ（ＮＯ3 ）2 水溶液３３０ｍ
ｍｏｌ／ｌ、ＺｒＯＣｌ２水溶液１５０ｍｍｏｌ／ｌ、
ＴｉＣｌ4 水溶液１５０ｍｍｏｌ／ｌ、およびＫＯＨ水
溶液５．０６ｍｏｌ／ｌとし、該混合溶液中に結晶核層
を形成したチタン基板を設置固定して通常の撹拌操作の
下、１３０℃で４時間の水熱処理を行い、ＰｂＺｒy Ｔ
ｉ1-y Ｏ3 （但し、０＜ｙ＜１である。）の膜を形成し
た。この第２工程を２回繰り返して膜厚を１０μｍとし
た。その後、純水中で超音波洗浄を３分間×２回行い、
１５０℃で１２時間乾燥を行った。COMPARATIVE EXAMPLE The input amount of the reaction raw material in the first step was Pb (NO 3 ) 2 aqueous solution 3
00 mmol / l, 100 mmol ZrOCl 2 aqueous solution
And a KOH aqueous solution of 3.8 mol / l, and a titanium substrate was placed and fixed in the mixed solution and subjected to a hydrothermal treatment at 160 ° C. for 12 hours under a normal stirring operation. This first
The composition of the film was purified by step PbZr y Ti 1-y O 3 ( provided that 0 <y <1.) Was. In the thus obtained initial crystal layer in the first step, the input amount of the reaction raw material in the second step for crystal growth was 330 m of Pb (NO 3 ) 2 aqueous solution.
mol / l, 150 mmol / l ZrOCl2 aqueous solution,
A TiCl 4 aqueous solution of 150 mmol / l and a KOH aqueous solution of 5.06 mol / l, and a titanium substrate having a crystal nucleus layer formed in the mixed solution is fixed, and subjected to a hydrothermal treatment at 130 ° C. for 4 hours under a normal stirring operation. was carried out, PbZr y T
A film of i 1-y O 3 (where 0 <y <1) was formed. This second step was repeated twice to obtain a film thickness of 10 μm. After that, perform ultrasonic cleaning in pure water twice for 3 minutes,
Drying was performed at 150 ° C. for 12 hours.
【００４１】このようにして得られたＰＺＴ系圧電結晶
膜の第１工程による結晶核層は５．０μｍとなってお
り、基板表面にはチタン酸鉛系の結晶層が存在し、徐々
にジルコニウムを多く含む層に変化している。また、第
１工程による結晶核層の表面粗さはＲmax が３．２μｍ
となっており、この影響を受けて、得られたＰＺＴ系圧
電結晶膜の表面粗さはＲmax が５．５μｍで、膜厚１
０．０μｍの５５％であった。得られたＰＺＴ系圧電結
晶膜にスパッタリング法により、金電極を付与し、バイ
モルフ素子の構成で、分極処理を施すことなく電圧を印
加したところ変位を示し、分極方向が揃っていることが
電気的に確認され、この膜の誘電率は約８００を示した
が、誘電損失は約０．０５であった。The PZT-based piezoelectric crystal film thus obtained has a crystal nucleus layer of 5.0 μm in the first step, and a lead titanate-based crystal layer is present on the substrate surface, and zirconium is gradually present. Has been changed to a layer containing a lot of. The surface roughness of the crystal nucleus layer obtained in the first step was R max of 3.2 μm.
Under the influence of this, the surface roughness of the obtained PZT-based piezoelectric crystal film was such that R max was 5.5 μm and the film thickness was 1 μm.
55% of 0.0 μm. A gold electrode was applied to the obtained PZT-based piezoelectric crystal film by a sputtering method, and when a voltage was applied without performing a polarization process in a bimorph element configuration, displacement was exhibited, and it was confirmed that the polarization direction was uniform. The dielectric constant of this film was about 800, but the dielectric loss was about 0.05.
【００４２】[0042]
【発明の効果】以上のように本発明によれば、水熱法に
よるＰＺＴ系圧電結晶膜合成において、第１工程の初期
結晶層の形成時にストロンチウムおよび／またはバリウ
ムを添加することにより、アクチュエータ、センサー等
に用いた場合、誘電損失の少ない、表面性の良い圧電結
晶膜の形成が可能である。As described above, according to the present invention, in the synthesis of a PZT-based piezoelectric crystal film by the hydrothermal method, strontium and / or barium is added at the time of forming the initial crystal layer in the first step, whereby the actuator, When used for a sensor or the like, it is possible to form a piezoelectric crystal film having small dielectric loss and good surface properties.
Claims (1)
系圧電結晶膜において、前記圧電結晶膜の基板面に接す
る結晶層が鉛、チタンおよびジルコニウムの他にストロ
ンチウムおよび／またはバリウムを含む複合酸化物であ
ることを特徴とする圧電結晶膜。1. A PZT formed on a substrate by a hydrothermal method.
A piezoelectric crystal film, wherein the crystal layer in contact with the substrate surface of the piezoelectric crystal film is a composite oxide containing strontium and / or barium in addition to lead, titanium and zirconium.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7009328B2 (en) * | 2003-06-20 | 2006-03-07 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive device made of piezoelectric/electrostrictive film and manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015111425B4 (en) * | 2014-07-18 | 2016-06-30 | Klaus Kürschner | Method and device for electrical force measurement by means of insulating thin film |
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1997
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7009328B2 (en) * | 2003-06-20 | 2006-03-07 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive device made of piezoelectric/electrostrictive film and manufacturing method |
| US7559128B2 (en) | 2003-06-20 | 2009-07-14 | Ngk Insulators, Ltd. | Method of manufacturing a piezoelectric/electrostrictive device |
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