JP2004134768A - Composition for forming piezoelectric film, method of manufacturing piezoelectric film, piezoelectric element, and ink jet recording head - Google Patents

Composition for forming piezoelectric film, method of manufacturing piezoelectric film, piezoelectric element, and ink jet recording head Download PDF

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JP2004134768A
JP2004134768A JP2003312958A JP2003312958A JP2004134768A JP 2004134768 A JP2004134768 A JP 2004134768A JP 2003312958 A JP2003312958 A JP 2003312958A JP 2003312958 A JP2003312958 A JP 2003312958A JP 2004134768 A JP2004134768 A JP 2004134768A
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piezoelectric film
diazabicyclo
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JP3955001B2 (en
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Shinji Eritate
襟立　信二
Motokazu Kobayashi
小林　本和
Jun Kubota
久保田　純
Fumio Uchida
内田　文生
Chiemi Shimizu
清水　千恵美
Kenji Maeda
前田　憲二
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Canon Inc
Fuji Chemical Co Ltd
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    • 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
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a piezoelectric film, which can allow the manufacture of an element having a large quantity of displacement and small nonuniformity of piezoelectric property, and to provide a method of manufacturing a piezoelectric film, and also to provide a piezoelectric element and an ink jet recording head. <P>SOLUTION: The composition for forming a piezoelectric film, which contains dispersoid obtained from a metal chemical compound contains at least one kind of substance from among 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]non-5-en, and 1,4-diazabicyclo[2.2.2]octane. A composition for forming a piezoelectric element, which has little heterogeneity in surface topography, even if it is formed thick and which can provide superior piezoelectric properties, a method of manufacturing a piezoelectric film, a piezoelectric element, and an ink jet recording head are provided. <P>COPYRIGHT: (C)2004,JPO

Description

　本発明は、圧電体膜形成用組成物、圧電体膜の製造方法、圧電体素子及びインクジェット式記録ヘッドに関する。 The present invention relates to a composition for forming a piezoelectric film, a method for manufacturing a piezoelectric film, a piezoelectric element, and an ink jet recording head.

　圧電体素子は、強誘電性あるいは常誘電性の結晶化した圧電性セラミックスにより構成されている。圧電性セラミックスの組成は一般にチタン酸ジルコニウム酸鉛（以下「ＰＺＴ」という）を主成分とする二成分系、またはこの二成分系のＰＺＴに第三成分を加えた三成分系からなる。二成分系ＰＺＴを用いた強誘電体が、[非特許文献１]に記載されている。これら金属酸化物型の圧電体薄膜の製法としては、スパッタリング法、ＭＯＣＶＤ法、ゾルゲル法などが挙げられる。 The piezoelectric element is made of crystallized ferroelectric or paraelectric piezoelectric ceramics. The composition of the piezoelectric ceramic is generally composed of a binary system containing lead zirconate titanate (hereinafter referred to as "PZT") as a main component, or a ternary system obtained by adding a third component to this binary PZT. A ferroelectric using binary PZT is described in [Non-Patent Document 1]. Examples of a method for producing these metal oxide type piezoelectric thin films include a sputtering method, a MOCVD method, and a sol-gel method.

　またゾルゲル法により成膜された圧電体素子を用いたインクジェット式プリンターヘッドが開示されている。たとえば[特許文献１]、[特許文献２]、[特許文献３]などには、ゾルゲル法を利用し、下部電極上に圧電体材料を含むゾルを複数回に分けて塗布し加熱処理を繰り返すことにより、インクジェット式プリンターヘッドに用いられる圧電体素子の圧電体薄膜を形成する方法が開示されている。 Also, an ink jet printer head using a piezoelectric element formed by a sol-gel method is disclosed. For example, in [Patent Literature 1], [Patent Literature 2], and [Patent Literature 3], a sol containing a piezoelectric material is applied to a lower electrode in a plurality of times by using a sol-gel method, and a heat treatment is repeated. Accordingly, a method for forming a piezoelectric thin film of a piezoelectric element used in an ink jet printer head has been disclosed.

特開平９−９２８９７号公報JP-A-9-92797 特開平１０−１３９５９４号公報JP-A-10-139594 特開平１０−２９００３５号公報JP-A-10-290035 Applied PhysicsLetters 1991.vol58 No11 pp1161-1163Applied PhysicsLetters 1991.vol58 No11 pp1161-1163

　しかし、ゾルゲル法による圧電体素子形成用組成物として、通常の金属錯体や有機酸金属塩をそのまま溶剤に溶解して用いるだけでは、有機金属化合物の加水分解速度が違うため、それぞれが単独の金属酸化物を生成することにより、均一な組成になりにくい。また、焼成時には、それらの金属酸化物の固相反応で複合化するが、それぞれの揮発性の違いから、その薄膜の組成を均一に制御することが困難であった。また、成膜時には微細な粉状の膜となり易く、導通を生じ易い等の問題があるなど、目的とする性能の圧電体素子の作製は困難であった。 However, if a conventional metal complex or metal salt of an organic acid is simply dissolved in a solvent as it is as a composition for forming a piezoelectric element by a sol-gel method, the hydrolysis rate of the organic metal compound is different. By generating an oxide, it is difficult to obtain a uniform composition. At the time of firing, these metal oxides are complexed by a solid-phase reaction. However, it is difficult to uniformly control the composition of the thin film due to the difference in volatility. In addition, it has been difficult to produce a piezoelectric element having the desired performance, for example, there is a problem that a fine powder film is easily formed at the time of film formation, and there is a problem that conduction is easily caused.

　これらの問題に関して、急速な加水分解をコントロールするために安定剤を添加することが知られており、塗布液の安定化に寄与し、成膜の安定化につながるとされている。 に 関 し て Regarding these problems, it is known to add a stabilizer in order to control rapid hydrolysis, which is said to contribute to the stabilization of the coating solution and to the stabilization of the film formation.

　従来、安定化剤として、β−ジケトン類、ケトン酸類、これらのケトン酸の低級アルキルエステル類、オキシ酸類、これらのオキシ酸の低級アルキルエステル類、オキシケトン類、α−アミノ酸類、アルカノールアミン類等が使用されている。例えば、上記安定化剤は金属アルコキシドおよび／または金属塩をキレート化して安定化し、加水分解反応速度を遅くするものである。例えば、Ti、Zrなどのアルコキシドをアセチルアセトンと反応させ、加水分解反応速度を遅くすることにより、緻密な膜を得ることを目的に添加される。 Conventionally, as stabilizers, β-diketones, ketone acids, lower alkyl esters of these ketone acids, oxy acids, lower alkyl esters of these oxy acids, oxyketones, α-amino acids, alkanolamines, etc. Is used. For example, the stabilizer stabilizes the metal alkoxide and / or the metal salt by chelating, and reduces the rate of the hydrolysis reaction. For example, it is added for the purpose of obtaining a dense film by reacting an alkoxide such as Ti or Zr with acetylacetone to reduce the rate of the hydrolysis reaction.

　しかし、上記の安定化剤を使用しても、焼成時にアルコキシドから酸化物への転化が不完全で、微細な小粒子からなる緻密化の不完全な膜が生成し、より揮発性の金属成分の損失による組成変動や、圧電性にばらつきが起こる原因となるなど、なお満足できる結果が得られていない場合がある。また、上記の安定化剤を使用して成膜すると薄膜形成粒子の粒径が不均一であるという欠点がある。このように表面形態が不均一な薄膜では、圧電性も場所により不均一なものとなる場合がある。 However, even when the above-mentioned stabilizer is used, the conversion of the alkoxide to the oxide is incomplete at the time of calcination, and an incompletely densified film composed of fine small particles is formed, and the more volatile metal component In some cases, satisfactory results have not been obtained, for example, such as a change in the composition due to the loss of the material or a variation in the piezoelectricity. Further, when the film is formed using the above-mentioned stabilizer, there is a disadvantage that the particle size of the thin film forming particles is not uniform. In such a thin film having a non-uniform surface morphology, the piezoelectricity may be non-uniform depending on the location.

　また、圧電体素子を製造する観点から、形成される一層の膜厚は大きい方が効率がよく、そのための工夫が必要であるとされている。アクチュエータとして使用するためには、膜の表面で圧電体素子としての特性を均一に示し、さらに耐久性の優れた、緻密な膜が求められている。さらに、厚膜を成膜すると、膜内にクラックが発生するといった欠陥も生じ、アクチュエータとしての特性も不十分であった。また、従来の圧電体素子形成用組成物の製造方法では、長期間保存した場合、液中の重合反応等により、沈殿の発生の問題などがあり、長期的に安定して使用することができない場合がある。 From the viewpoint of manufacturing the piezoelectric element, it is said that the larger the thickness of the layer formed, the higher the efficiency is, and it is necessary to devise a device for that. In order to be used as an actuator, a dense film exhibiting uniform characteristics as a piezoelectric element on the surface of the film and having excellent durability is required. Further, when a thick film is formed, defects such as cracks are generated in the film, and the characteristics as an actuator are insufficient. Further, in the conventional method for producing a composition for forming a piezoelectric element, when stored for a long period of time, there is a problem of generation of a precipitate due to a polymerization reaction or the like in a liquid, and cannot be used stably for a long period of time. There are cases.

　本発明は、表面形態の不均一部分が少なく、かつ良好な圧電特性を得られる圧電体素子形成用組成物、圧電体膜の製造方法、圧電体素子及びインクジェット式記録ヘッドを提供することを目的としている。 SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for forming a piezoelectric element, a method for manufacturing a piezoelectric film, a piezoelectric element, and an ink jet recording head, which have less uneven portions in the surface morphology and can obtain good piezoelectric characteristics. And

　本発明は、安定化剤として、1,8-ジアザビシクロ[5.4.0]-７−ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種を用いる。これは、1,8-ジアザビシクロ[5.4.0]-７-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンからの電子供与により、金属アルコキシドおよび／または金属塩を安定化させるものである。同時に金属アルコキシドおよび／または金属塩の反応性、溶解度を変化させ、ゾル合成時の加水分解、縮重合反応の速度、それによる反応生成物の構造の制御を狙ったものである。これにより、圧電体素子の特性向上、圧電体素子形成用組成物の保存性の改善、インクジェット式記録ヘッドの性能向上が認められることを見出し、本発明に到達した。 The present invention provides 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] as a stabilizer. Use at least one of octane. This is due to electron donation from 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,4-diazabicyclo [2.2.2] octane. , Metal alkoxides and / or metal salts. At the same time, the reactivity and solubility of the metal alkoxide and / or metal salt are changed to control the rate of hydrolysis and polycondensation during sol synthesis, and to control the structure of the reaction product. As a result, it has been found that the improvement of the characteristics of the piezoelectric element, the improvement of the preservability of the composition for forming the piezoelectric element, and the improvement of the performance of the ink jet recording head have been achieved, and the present invention has been achieved.

　本発明の圧電体素子形成用組成物は、圧電体素子を形成するための有機金属化合物から得られる分散質を含む圧電体素子形成用組成物において、該溶液中に安定化剤として、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種を含有することを特徴とする。 The composition for forming a piezoelectric element of the present invention is a composition for forming a piezoelectric element containing a dispersoid obtained from an organometallic compound for forming a piezoelectric element. Containing at least one of 8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,4-diazabicyclo [2.2.2] octane. Features.

　本発明の圧電体素子形成用組成物は、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの含有量を、圧電体素子組成物中の総金属原子のモル数に対し、０．００５倍モル以上、５．０倍モル以下の含有量であることを特徴とする。 The composition for forming a piezoelectric element of the present invention comprises 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2 .2] The octane content is not less than 0.005 times and not more than 5.0 times the mole number of the total metal atoms in the piezoelectric element composition.

　本発明の圧電体素子形成用組成物は、Pb及びLa、Zr、Tiの元素から少なくとも1種類以上を構成元素として含むことを特徴とする。 圧 電 The composition for forming a piezoelectric element of the present invention is characterized by containing at least one or more of Pb, La, Zr, and Ti as constituent elements.

　本発明の圧電体素子の製造方法は、前述の圧電体素子形成用組成物を耐熱性基板に塗布し、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱する工程を所望の厚さの膜が得られるまで繰り返し、少なくとも最終工程における加熱中或いは加熱後に該膜を結晶化温度以上で焼成することを特徴とする。 The method for producing a piezoelectric element of the present invention includes a step of applying the composition for forming a piezoelectric element described above to a heat-resistant substrate, and heating the composition in air, an oxidizing atmosphere, or a water-containing atmosphere to a film having a desired thickness. Is repeated until ら れ る is obtained, and the film is fired at a crystallization temperature or higher at least during or after heating in the final step.

　本発明のインクジェット式記録ヘッドは、前述の圧電体素子の製造方法により製造された圧電体素子を備えたインクジェット式記録ヘッドにおいて、圧力室が形成された圧力室基板と、前記圧力室の一方の面に設けられた振動板と、前記振動板の前記圧力室に対応する位置に設けられ、当該圧力室に体積変化を及ぼすことが可能に構成された前記圧電体素子と、を備えたことを特徴とする。 An ink jet recording head of the present invention is an ink jet recording head including a piezoelectric element manufactured by the method for manufacturing a piezoelectric element described above, wherein a pressure chamber substrate in which a pressure chamber is formed, and one of the pressure chambers A vibration plate provided on a surface, and the piezoelectric element provided at a position of the vibration plate corresponding to the pressure chamber, and configured to be able to apply a volume change to the pressure chamber. Features.

　本発明によれば、厚膜で形成されても、表面形態の不均一部分が少なく、かつ良好な圧電特性を得られる圧電体素子形成用組成物、圧電体膜の製造方法、圧電体素子及びインクジェット式記録ヘッドを提供することができる。 Advantageous Effects of Invention According to the present invention, a composition for forming a piezoelectric element, a method for producing a piezoelectric film, a method for producing a piezoelectric film, a piezoelectric element, An ink jet recording head can be provided.

　以下、本発明を実施するための形態について説明する。 Hereinafter, embodiments for carrying out the present invention will be described.

　図１は、本発明の圧電体素子の一実施形態の構成を示す図である。同図において、１は基板である。 FIG. 1 is a diagram showing a configuration of one embodiment of the piezoelectric element of the present invention. In FIG. 1, reference numeral 1 denotes a substrate.

　シリコン（Ｓｉ）やタングステン（Ｗ）などからなる半導体基板が好ましく用いられるが、ジルコニアやアルミナ、シリカなどのセラミックを用いても構わない。また最表面に酸化物層、窒化物層などが形成されていても構わない。 半導体 A semiconductor substrate made of silicon (Si) or tungsten (W) is preferably used, but a ceramic such as zirconia, alumina, or silica may be used. Further, an oxide layer, a nitride layer, or the like may be formed on the outermost surface.

　図１において２、４は、それぞれ下部電極、上部電極であり本発明では５〜500nm程度の導電層よりなる。具体的には、Ti、Pt、Ta、Ir、Sr、In、Sn、Au、Al、Fe、Cr、Niなどの金属およびこれらの酸化物が１種あるいは２種以上が積層して用いられる。 に お い て In FIG. 1, reference numerals 2 and 4 denote a lower electrode and an upper electrode, respectively, which are formed of a conductive layer of about 5 to 500 nm in the present invention. Specifically, metals such as Ti, Pt, Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, and Ni and oxides thereof are used alone or in a stack of two or more.

　これらの金属、酸化物は基板上にゾルゲル法などにより塗工、焼成して形成しても良いし、スパッタ、蒸着などにより形成してもよい。また下部電極、上部電極とも所望の形状にパタンニングして用いても良い。 金属 These metals and oxides may be formed on the substrate by coating and baking by a sol-gel method or the like, or may be formed by sputtering, vapor deposition or the like. Further, both the lower electrode and the upper electrode may be patterned into a desired shape and used.

　図１において３は圧電体薄膜であり、本発明ではPb以外に，La、Zr、Tiの元素から少なくとも１種類以上を構成元素として含むものをゾルゲル法により製造し用いる。即ち溶媒にPb、La、Zr、Ti、などのアルコキシド及び／又は金属塩を溶媒に溶解させた後、水を加え加水分解させた塗工液を基板上に塗工し乾燥、及びその後の熱処理工程による焼成を行うことにより得ることができる。 に お い て In FIG. 1, reference numeral 3 denotes a piezoelectric thin film. In the present invention, a material containing at least one of La, Zr, and Ti as a constituent element in addition to Pb is manufactured and used by a sol-gel method. That is, after dissolving an alkoxide and / or a metal salt of Pb, La, Zr, Ti, or the like in a solvent, adding a water-hydrolyzed coating solution onto a substrate, drying, and then performing a heat treatment. It can be obtained by performing firing in the process.

　Pb、La、Zr、Ti以外に微量の元素でドーピングを行っても良い。具体的な例としてはCa,Sr,Ba,Sn,Th,Y,Sm,Ce,Bi,Sb,Nb,Ta,W,Mo,Cr,Co,Ni,Fe,Cu,Si,Ge,Sc,Mg,Mnなどが挙げられる。その含有量は、一般式Pb1-xLax（ＺryTi1-y)O3（式中、０≦x＜１、０≦ｙ≦１）
　における金属原子の原子分率で0.05以下である。 Doping may be performed with a trace element other than Pb, La, Zr, and Ti. As specific examples, Ca, Sr, Ba, Sn, Th, Y, Sm, Ce, Bi, Sb, Nb, Ta, W, Mo, Cr, Co, Ni, Fe, Cu, Si, Ge, Sc, Mg, Mn and the like can be mentioned. Its content is generally formula Pb 1-x La x (Zr y Ti 1-y) O 3 ( where, 0 ≦ x <1,0 ≦ y ≦ 1)
Is 0.05 or less as an atomic fraction of metal atoms.

　圧電体薄膜の各成分金属の原料として使用する有機金属化合物を、適当な有機溶剤に一緒に分散して、圧電体材料である複合有機金属酸化物（２以上の金属を含有する酸化物）の前駆体を含有する原料ゾルを調製する。また、ゾルの溶剤は分散性、塗布性を考慮して、公知の各種溶剤から適宜選択される。 An organometallic compound used as a raw material for each component metal of the piezoelectric thin film is dispersed together in an appropriate organic solvent to form a composite organic metal oxide (an oxide containing two or more metals) which is a piezoelectric material. A raw material sol containing a precursor is prepared. The solvent of the sol is appropriately selected from various known solvents in consideration of dispersibility and coatability.

　用いられる溶媒としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、n−ブタノール、ｓ−ブタノール、ｔ−ブタノール等のアルコール系溶剤、テトラヒドロフラン、１，４−ジオキサン等のエーテル系溶剤、２−メトキシエタノール、２―エトキシエタノール、１−メトキシ−２−プロパノール等のセロソルブ系、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート等の多価アルコール、N,N−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン系などのアミド系溶剤、アセトニトリル等のニトリル系溶剤が挙げられる。これらの中で好ましくはアルコール系溶剤である。本発明におけるゾルゲル法において用いられる溶媒の量は、金属アルコキシドに対して通常５倍モルから２００倍モルであり、好ましくは１０倍モルから１００倍モルである。溶媒の量が多すぎるとゲル化が起こりにくくなり、少なすぎると加水分解時の発熱が激しくなる。 Examples of the solvent used include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol and t-butanol, ether solvents such as tetrahydrofuran and 1,4-dioxane, and 2-methoxyethanol. Cellosolves such as 2,2-ethoxyethanol and 1-methoxy-2-propanol; polyhydric alcohols such as diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether and diethylene glycol monobutyl ether acetate; N, N-dimethylformamide; Examples include amide solvents such as N, N-dimethylacetamide and N-methylpyrrolidone, and nitrile solvents such as acetonitrile. Of these, alcohol solvents are preferred. The amount of the solvent used in the sol-gel method in the present invention is usually 5 to 200 times, preferably 10 to 100 times the mol of the metal alkoxide. If the amount of the solvent is too large, gelation hardly occurs, and if the amount is too small, heat generation during hydrolysis becomes severe.

　またPbのアルコキシド化合物としては鉛２−エトキシエトキシド、鉛メトキシド、鉛エトキシド、鉛n-プロポキシド、鉛ｉ-プロポキシド、鉛n-ブトキシシド、鉛ｉ-ブトキシシド、鉛t-ブトキシシド、などその他各種アルコキシドおよびそのアルキル置換体などが挙げられる。 Pb alkoxide compounds include lead 2-ethoxyethoxide, lead methoxide, lead ethoxide, lead n-propoxide, lead i-propoxide, lead n-butoxyside, lead i-butoxyside, lead t-butoxyside, and various other types. Alkoxides and their alkyl-substituted products.

　またPbの無機塩化合物、具体的には塩化物、硝酸塩、リン酸塩、硫酸塩などまた有機塩化合物は具体的にはギ酸塩、酢酸塩、プロピオン酸塩、シュウ酸塩、クエン酸塩、リンゴ酸塩などの各種カルボン酸塩、ヒドロキシカルボン酸塩、またアセチルアセトナート錯体などを溶媒と混合してアルコキシドをinsitu合成して用いても良い。La、Mg、Zr、Ti、Nbも同様のアルコキシド化合物または無機塩を用いることができる。これらのPb、La、Mg、Zr、Ti、Nbのアルコキシド溶液または無機塩を前記溶媒に溶解し、加水分解を行うことにより高分子化し圧電体薄膜の塗工液を得る。 In addition, inorganic salt compounds of Pb, specifically chlorides, nitrates, phosphates, sulfates, etc.Organic salt compounds are specifically formate, acetate, propionate, oxalate, citrate, The alkoxide may be in situ synthesized by mixing various carboxylate salts such as malate, hydroxycarboxylate, acetylacetonate complex and the like with a solvent. The same alkoxide compound or inorganic salt can be used for La, Mg, Zr, Ti, and Nb. These alkoxide solutions or inorganic salts of Pb, La, Mg, Zr, Ti, and Nb are dissolved in the above-mentioned solvent and hydrolyzed to polymerize to obtain a coating liquid for a piezoelectric thin film.

　なお、原料の有機金属化合物は、上述したような１種類の金属を含有する化合物の他に、２種以上の成分金属を含有する複合化した有機金属化合物であってもよい。かかる複合化有機金属化合物の例としては、ＰｂＯ2［Ｔｉ（ＯＣ3Ｈ7）3］2、ＰｂＯ2［Ｚｒ（ＯＣ4Ｈ9）3］2などが挙げられる。なお、本発明で有機金属化合物とは金属と有機基を含有する広義の意味として用いており、炭素−金属結合を有する狭義の意味で用いていているのではない。 In addition, the organic metal compound of the raw material may be a compounded organic metal compound containing two or more types of component metals in addition to the compound containing one type of metal as described above. Examples of such composite organometallic compounds include PbO 2 [Ti (OC 3 H 7 ) 3 ] 2 and PbO 2 [Zr (OC 4 H 9 ) 3 ] 2 . In the present invention, the organometallic compound is used in a broad sense containing a metal and an organic group, but not in a narrow sense having a carbon-metal bond.

　上記各金属の仕込み比は、例えばPb、La、Zr、Tiを用いる場合、Pb(1-x)Lax(ZryTi1-y)Ｏ3（式中、０≦x＜１、０≦ｙ≦１）でもよいが、成膜時の焼成過程においてＰｂの消失がおこるため、あらかじめ塗工液作製時にＰｂの量を増やしておくことが好ましい。具体的には、Pb(1-x)Lax(ZryTi1-y)Ｏ3（式中、０≦x＜１、０≦ｙ≦１）においてPbのモル比を5%〜30%の範囲で増やして構わない。 Charge ratio of each metal, for example Pb, La, Zr, when using a Ti, Pb in (1-x) La x ( Zr y Ti 1-y) O 3 ( wherein, 0 ≦ x <1,0 ≦ y ≦ 1), but Pb disappears during the baking process during film formation, so it is preferable to increase the amount of Pb in advance when preparing the coating liquid. Specifically, Pb (1-x) La x (Zr y Ti 1-y) O 3 ( where, 0 ≦ x <1,0 ≦ y ≦ 1) the molar ratio of Pb at 5% to 30% You can increase it in the range.

　次に、安定化剤を、上記混合溶液中に添加して安定化する。金属−酸素−金属結合を、全体としてゆるやかに重合させておくものである。なお、安定化剤を多量に供給すると加水分解が適切に行われない場合があり、また溶解度の問題から沈澱が生ずることもある。 Next, a stabilizer is added to the above-mentioned mixed solution to stabilize it. The metal-oxygen-metal bond is gradually polymerized as a whole. When a large amount of the stabilizer is supplied, hydrolysis may not be performed properly, and precipitation may occur due to solubility problems.

　本発明においては、この強誘電体薄膜形成用組成物の有機金属化合物溶液中に、安定化剤として、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種を添加する。有機金属化合物溶液中の上記安定剤の含有量が少な過ぎるとこれらを添加したことによる改善効果が十分に得られず、多過ぎると、粘度が上昇し成膜性が劣るといった問題が生じることから、この含有量は、総金属原子のモル数に対し、０．００５倍モル以上、５．０倍モル以下、特に０.０５倍モル以上、２.５倍モル以下の濃度であることであることが好ましい。1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンは複数種併用して用いても良い。これらは、酸と結合した塩の化合物として用いてもよい。具体的には、ギ酸塩、オクチル酸塩などが知られている。また、他の安定化剤として従来用いられている、β−ジケトン類（例えば、アセチルアセトン、ヘプタフルオロブタノイルピバロイルメタン、ジピバロイルメタン、トリフルオロアセチルアセトン、ベンゾイルアセトン等）、ケトン酸類（例えば、アセト酢酸、プロピオニル酢酸、ベンゾイル酢酸等）、これらのケトン酸のエチル、プロピル、ブチル等の低級アルキルエステル類、オキシ酸類（例えば、乳酸、グリコール酸、α−オキシ酪酸、サリチル酸等）、これらのオキシ酸の低級アルキルエステル類、オキシケトン類（例えば、ジアセトンアルコール、アセトイン等）、α−アミノ酸類（例えば、グリシン、アラニン等）、アルカノールアミン類（例えば、ジエタノールアミン、トリエタノールアミン、モノエタノールアミン）等を併用しても良い。 In the present invention, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3. Are used as stabilizers in the organometallic compound solution of the composition for forming a ferroelectric thin film. 0] Non-5-ene and 1,4-diazabicyclo [2.2.2] octane are added. If the content of the stabilizer in the organometallic compound solution is too small, the effect of adding these stabilizers cannot be sufficiently improved, and if the content is too large, problems such as increased viscosity and poor film formability occur. The content is a concentration of 0.005 to 5.0 times, particularly 0.05 to 2.5 times the molar number of the total metal atoms. Is preferred. 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene and 1,4-diazabicyclo [2.2.2] octane may be used in combination. Is also good. These may be used as salt compounds combined with acids. Specifically, formate, octylate and the like are known. Also, β-diketones (eg, acetylacetone, heptafluorobutanoylpivaloylmethane, dipivaloylmethane, trifluoroacetylacetone, benzoylacetone, etc.), ketone acids (eg, conventionally used as other stabilizers) For example, acetoacetic acid, propionylacetic acid, benzoylacetic acid, etc.), lower alkyl esters of these ketone acids such as ethyl, propyl, butyl, etc., oxyacids (eg, lactic acid, glycolic acid, α-oxybutyric acid, salicylic acid, etc.), Lower alkyl esters of oxy acids, oxyketones (eg, diacetone alcohol, acetoin, etc.), α-amino acids (eg, glycine, alanine, etc.), alkanolamines (eg, diethanolamine, triethanolamine, monoethanolamine) ) Etc. And it may be.

　本発明において用いられる安定化剤の量は、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種と、上記の従来用いられている安定化剤を併用した場合、総金属原子のモル数に対し、通常０.０５倍モルから５倍モルであり、好ましくは０.１倍モルから１.５倍モルである。 The amount of the stabilizer used in the present invention is 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2 .2] When at least one of octane and the above-mentioned conventional stabilizer are used in combination, the molar amount is usually 0.05 to 5 moles, preferably 0.05 moles, per mole of the total metal atoms. It is 0.1 to 1.5 moles.

　その場合の併用する従来の安定剤の添加量は、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンに対して、通常０．０１倍モルから２０倍モルであり、好ましくは０．０５倍モルから１０倍モルである。 In this case, the amount of the conventional stabilizer used together is 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo. [2.2.2] It is usually 0.01 to 20 moles, preferably 0.05 to 10 moles, relative to octane.

　金属アルコキシドおよび／または金属塩を含む溶液の加水分解には、例えば金属アルコキシドおよび／または金属塩の0．05モル倍〜３０モル倍の水が用いられ、より好ましくは0．5モル倍〜１５モル倍の水が用いられる。この加水分解には、酸触媒および／または塩基触媒を用いるようにしてもよい。好ましくは、酸触媒として金属塩、ハロゲン化物、硫酸、硝酸、塩酸などの鉱酸や酢酸などの有機酸が用いられる。また，塩基触媒としては、乾燥、焼成により容易に除去できるアンモニアが用いられることが多い。 For the hydrolysis of the solution containing the metal alkoxide and / or the metal salt, for example, 0.05 to 30 times the water of the metal alkoxide and / or the metal salt is used, and more preferably 0.5 to 15 times the mole of the metal alkoxide and / or the metal salt. Mole-fold water is used. For this hydrolysis, an acid catalyst and / or a base catalyst may be used. Preferably, metal salts, halides, mineral acids such as sulfuric acid, nitric acid and hydrochloric acid and organic acids such as acetic acid are used as the acid catalyst. As the base catalyst, ammonia that can be easily removed by drying and baking is often used.

　この加水分解反応速度は、金属アルコキシドおよび／または金属塩の種類、溶媒の種類、金属アルコキシドおよび／または金属塩に対する水の濃度、金属アルコキシドおよび／または金属塩の濃度、触媒、金属アルコキシドおよび／または金属塩のキレート化による安定化などにより制御することができる。 The hydrolysis reaction rate depends on the type of metal alkoxide and / or metal salt, the type of solvent, the concentration of water relative to metal alkoxide and / or metal salt, the concentration of metal alkoxide and / or metal salt, the catalyst, the metal alkoxide and / or It can be controlled by stabilizing the metal salt by chelation.

　上記金属組成の溶液を加水分解後、沸点１００℃以下の溶媒を完全に除去し、沸点１００℃以上の溶媒を５０％以上の量を加える。用いられる溶媒としては、１−メトキシ−２−プロパノール、２−エトキシエタノール、３−メトキシ−３−メチルブタノールなどのセロソルブ系、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテートなどの多価アルコール、テルピネオール、パイン油、ラベンダー油などの香料油が挙げられる。好ましくは、セロソルブ系溶媒である。また、エチルセルロース、ヒドロキシプロピルセルロースなどのセルロース誘導体、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルピロリドン誘導体等の高分子樹脂、ロジン、ロジン誘導体などを塗布性が向上する目的で用いても良い。 (4) After hydrolyzing the solution of the metal composition, the solvent having a boiling point of 100 ° C. or lower is completely removed, and the solvent having a boiling point of 100 ° C. or higher is added in an amount of 50% or more. Examples of the solvent used include cellosolves such as 1-methoxy-2-propanol, 2-ethoxyethanol and 3-methoxy-3-methylbutanol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, and diethylene glycol monobutyl ether. Examples include polyhydric alcohols such as acetate, and fragrance oils such as terpineol, pine oil and lavender oil. Preferred are cellosolve solvents. Further, cellulose derivatives such as ethylcellulose and hydroxypropylcellulose, polymer resins such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylpyrrolidone derivatives, rosin, and rosin derivatives may be used for the purpose of improving coatability.

　その後、さらに安定剤を所定量添加することにより、塗布性、表面形態の向上効果を損なうことなく、原料溶液の加水分解速度、重縮合速度等を抑え、その経時変化安定性を改善することができる。 Thereafter, by adding a predetermined amount of a stabilizer, the coating rate and the hydrolysis rate of the raw material solution, the polycondensation rate, etc. can be suppressed without impairing the effect of improving the surface morphology, and the aging stability can be improved. it can.

　上記塗工液は、基板上に形成された下部電極の上に塗工し乾燥させる。塗工方法は、スピンコート、ディップコート、バーコート、スプレーコートなど公知の塗工方法を用いることができる。この際の相対湿度は６０％以下が好ましい。６０％以上であると基板上の塗工液の加水分解が速く進行してしまい析出物が見られることがあり好ましくない。 The coating liquid is applied on the lower electrode formed on the substrate and dried. As a coating method, a known coating method such as spin coating, dip coating, bar coating, and spray coating can be used. At this time, the relative humidity is preferably 60% or less. If it is 60% or more, hydrolysis of the coating solution on the substrate proceeds rapidly, and precipitates may be seen, which is not preferable.

　乾燥後の１層あたりの膜厚は特に問わないが、0.01μm〜5μmが好ましい。また総膜厚としては1μm〜30μmあたりが好ましい。 膜厚 The thickness of one layer after drying is not particularly limited, but is preferably 0.01 μm to 5 μm. The total thickness is preferably about 1 μm to 30 μm.

　乾燥は２００℃以下の温度で行う。なお、この際には、２５℃での相対湿度が１０〜７０％の気体の存在下で行う。７０％以上であると基板上の塗工液の加水分解が速く進行してしまいクラックの原因となり好ましくない。また１０％以下であると逆に加水分解が全く進行しなく、後述する焼成時の温度が上昇し好ましくない。この乾燥には、乾燥機、ドライヤー、ホットプレート、管状炉、電気炉などを用いることができる。また２５℃での相対湿度が１０〜７０％の気体は、所望の気体を水中にバブリングさせることにより得られる。また加湿器などを用いて調整した気体を導入しても良い。 Drying is performed at a temperature of 200 ° C or less. In this case, the reaction is performed in the presence of a gas having a relative humidity of 10 to 70% at 25 ° C. If it is 70% or more, the hydrolysis of the coating liquid on the substrate proceeds rapidly, causing cracks, which is not preferable. On the other hand, if it is 10% or less, hydrolysis does not proceed at all, and the temperature during calcination described later rises, which is not preferable. For this drying, a dryer, a dryer, a hot plate, a tubular furnace, an electric furnace, or the like can be used. A gas having a relative humidity of 10 to 70% at 25 ° C. is obtained by bubbling a desired gas in water. Alternatively, a gas adjusted using a humidifier or the like may be introduced.

　続いて２００℃〜５００℃の範囲で仮焼成を行う。この際には、２５℃での相対湿度が７０〜９９％の気体の存在下で行う。７０％以下では加水分解が進行せず好ましくない。この仮焼成には、乾燥機、ドライヤー、ホットプレート、管状炉、電気炉などを用いることができる。また２５℃での相対湿度が７０〜９９％の気体は、所望の気体を水中にバブリングさせることにより得られる。また加湿器などを用いて調整した気体を導入しても良い。 仮 Subsequently, pre-baking is performed in the range of 200 ° C. to 500 ° C. This is performed in the presence of a gas having a relative humidity of 70 to 99% at 25 ° C. If it is less than 70%, hydrolysis does not proceed, which is not preferable. A dryer, a dryer, a hot plate, a tubular furnace, an electric furnace, or the like can be used for the preliminary firing. A gas having a relative humidity of 70 to 99% at 25 ° C. is obtained by bubbling a desired gas into water. Alternatively, a gas adjusted using a humidifier or the like may be introduced.

　更に５００℃〜８００℃の範囲で本焼成を行う。この際には、２５℃での相対湿度が７０〜９９％の気体の存在下で行う。７０％以下では加水分解が進行せず好ましくない。この本焼成には、管状炉、電気炉などを用いることができる。また２５℃での相対湿度が７０〜９９％の気体は、所望の気体を水中にバブリングさせることにより得られる。また加湿器などを用いて調整した気体を導入しても良い。 (4) Main firing is performed in the range of 500 ° C to 800 ° C. This is performed in the presence of a gas having a relative humidity of 70 to 99% at 25 ° C. If it is less than 70%, hydrolysis does not proceed, which is not preferable. For this main firing, a tubular furnace, an electric furnace, or the like can be used. A gas having a relative humidity of 70 to 99% at 25 ° C. is obtained by bubbling a desired gas into water. Alternatively, a gas adjusted using a humidifier or the like may be introduced.

　前記水分を含有した気体は塗工表面を一定の速度で流れていることが好ましい。滞留してしまうと塗工液の加水分解が滞り好ましくない。基板上の好ましい流速は0.5cm／sec〜50cm／secである。但し基板の面積が微少であり水分を含有した気体が大過剰に存在する場合は滞留していても影響ない。 気 体 It is preferable that the gas containing water flows at a constant speed on the coating surface. If it stays, the hydrolysis of the coating solution will be delayed, which is not preferable. The preferred flow rate over the substrate is between 0.5 cm / sec and 50 cm / sec. However, if the area of the substrate is very small and a gas containing water is present in a large excess, even if the gas stays there is no effect.

　上記塗工液により形成される１層あたりの焼成後膜厚は特に問わないが0.01μm〜１μm、好ましくは作業性を考慮して0.02μm〜0.9μmの範囲で選択するのがよい。この操作を繰り返すことにより任意の膜圧の圧電体薄膜を得ることができる。乾燥工程は各層ごとに行わなければならないが、仮焼成、本焼成は各層ごとに行っても良いし数層おきにまとめて行っても良い。また本焼成は一番最後に行うだけでも良い。 膜厚 The thickness of one layer formed by the above-mentioned coating solution after firing is not particularly limited, but is preferably selected from the range of 0.01 μm to 1 μm, preferably from 0.02 μm to 0.9 μm in consideration of workability. By repeating this operation, a piezoelectric thin film having an arbitrary film pressure can be obtained. The drying step must be performed for each layer, but the preliminary firing and the main firing may be performed for each layer, or may be performed for every several layers. Further, the main firing may be performed only last.

　乾燥工程から本焼成までに基板表面に存在する気体は、酸素含有雰囲気が好ましく、酸素濃度としては20％〜100％の間がよい。20%より少ないと焼結が進まずペロブスカイト構造をとらなくなり所望の性能が現れず好ましくない。 (4) The gas existing on the substrate surface from the drying step to the main baking is preferably an oxygen-containing atmosphere, and the oxygen concentration is preferably between 20% and 100%. If it is less than 20%, sintering does not proceed and a perovskite structure is not obtained, and desired performance does not appear, which is not preferable.

　また、焼成の際に、段階的な昇温を行うようにしてもよい。このような焼成により、有機成分がほぼ消失して、緻密な横造の圧電体膜が得られる。 Also, the temperature may be increased stepwise during firing. By such firing, organic components are almost completely eliminated, and a dense horizontal piezoelectric film is obtained.

　図２は、本発明の実施形態の１例を示し、圧電体素子がアクチュエータに用いられたインクジェット式プリンターヘッドの一部を拡大して模式的に示す図である。プリンターヘッドの基本構成は、従来と同様であり、ヘッド基台５と振動板７および圧電体素子とから構成されている。ヘッド基台５には、インクを噴射する多数のインクノズル（図示せず）、それぞれのインクノズルに個別に連通する多数のインク経路（図示せず）、および、それぞれのインク経路に個別に連通する多数のインク室６が形成されており、ヘッド基台５の上面全体を覆うように振動板７が取り付けられ、この振動板７によってヘッド基台５の全てのインク室６の上面開口が閉塞されている。振動板７上には、それぞれのインク室６と個別に対応した位置に、振動板７に振動駆動力を与えるための圧電体素子８が被着形成されている。そして、多数の圧電体素子８を電源9を制御して、所望の選択された圧電体素子８に電圧を印加することにより、圧電体素子８を変位させて、その部分の振動板７を振動させる。これにより、振動板７の振動に対応した部分のインク室６の容積が変化して、インク経路を通ってインクノズルからインクが押し出されて印刷が行われることになる。 FIG. 2 shows an example of an embodiment of the present invention, and is a diagram schematically showing an enlarged part of an ink jet printer head in which a piezoelectric element is used for an actuator. The basic configuration of the printer head is the same as that of the related art, and includes a head base 5, a vibration plate 7, and a piezoelectric element. The head base 5 has a number of ink nozzles (not shown) for ejecting ink, a number of ink paths (not shown) individually communicating with each ink nozzle, and an individual communication with each ink path. A large number of ink chambers 6 are formed, and a vibrating plate 7 is attached so as to cover the entire upper surface of the head base 5, and the upper surfaces of all the ink chambers 6 of the head base 5 are closed by the vibrating plate 7. Have been. Piezoelectric elements 8 for applying a vibration driving force to the vibration plate 7 are formed on the vibration plate 7 at positions individually corresponding to the respective ink chambers 6. By controlling the power supply 9 for a large number of piezoelectric elements 8 and applying a voltage to the desired selected piezoelectric elements 8, the piezoelectric elements 8 are displaced, and the vibrating plate 7 in that portion is vibrated. Let it. As a result, the volume of the ink chamber 6 corresponding to the vibration of the diaphragm 7 changes, and the ink is pushed out of the ink nozzles through the ink path to perform printing.

　以下に実施例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 本 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist.

　(塗工液製造例１〜11)
　本製造例は、表１に示すように圧電体薄膜用の塗工液として金属組成がＰｂ1+x-yＬａyＺｒ0.52Ｔｉ0.48（式中、０≦x≦０．３、０≦ｙ＜１）で表されるの塗工液を以下の通り作製した。 (Coating liquid production examples 1 to 11)
This preparation are listed in Table 1 metal composition as a coating liquid for the piezoelectric thin film as shown in the Pb 1 + xy La y Zr 0.52 Ti 0.48 ( wherein, 0 ≦ x ≦ 0.3,0 ≦ y <1 ) Was prepared as follows.

　酢酸鉛水和物(Pb)および酢酸ランタン水和物(La)を混合し脱水し、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタン、1，8-ジアザビシクロ[5.4.0]-7-ウンデセンのギ酸塩、1，8-ジアザビシクロ[5.4.0]-7-ウンデセンのオクチル酸塩より選ばれる１種および１−メトキシ−２−プロパノール(溶剤１)を混合し反応させる。以後、1，8-ジアザビシクロ[5.4.0]-7-ウンデセンをＤＢＵ、１，５−ジアザビシクロ[4.3.0]ノン-5-エンをＤＢＮ、１，４-ジアザビシクロ[2.2.2]オクタンをＤＡＢＣＯと略記する。その後、ジルコニアテトラｎ−ブトキシド0.52mol、チタンｎ―ブトキシド0.48molを加えて更に加熱し反応させ、原料金属化合物を互いに複合化させた。次に、水、エタノール(溶剤２)を添加し、加水分解反応を行った。その際、酢酸やアセチルアセトンを加えた。また成膜補助剤としてポリビニルピロリドン Ｋ-30（ＰＶＰ）を加えたもの（製造例５，６，７）も用意した。その後、沸点１００℃以下の溶媒をロータリーエバポレーターで完全に取り除き、ジエチレングリコールモノエチルエーテル (溶剤３)を添加して上記組成式に換算した金属酸化物濃度が１０ｗｔ％になるように調製した。 Lead acetate hydrate (Pb) and lanthanum acetate hydrate (La) are mixed and dehydrated to give 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non- 5-ene, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene formate, octyl of 1,8-diazabicyclo [5.4.0] -7-undecene One selected from acid salts and 1-methoxy-2-propanol (solvent 1) are mixed and reacted. Hereinafter, 1,8-diazabicyclo [5.4.0] -7-undecene is DBU, 1,5-diazabicyclo [4.3.0] non-5-ene is DBN, and 1,4-diazabicyclo [2.2.2] octane is DABCO. Abbreviated. Thereafter, 0.52 mol of zirconia tetra n-butoxide and 0.48 mol of titanium n-butoxide were added, and the mixture was further heated and reacted, whereby the starting metal compounds were combined with each other. Next, water and ethanol (solvent 2) were added to carry out a hydrolysis reaction. At that time, acetic acid and acetylacetone were added. Further, those to which polyvinylpyrrolidone K-30 (PVP) was added as a film-forming auxiliary (Production Examples 5, 6, and 7) were also prepared. Thereafter, the solvent having a boiling point of 100 ° C. or less was completely removed by a rotary evaporator, and diethylene glycol monoethyl ether (solvent 3) was added to adjust the metal oxide concentration to 10 wt% as calculated by the above composition formula.

Figure 2004134768
Figure 2004134768

　（製造比較例１）
　本製造例は、ＤＢＵのかわりにジイソプロピルエチルアミンを添加した点を除いて、製造例２と同様にして、圧電体薄膜用の塗工液を作成した。 (Comparative Example 1)
In this Production Example, a coating liquid for a piezoelectric thin film was prepared in the same manner as in Production Example 2, except that diisopropylethylamine was added instead of DBU.

　（製造比較例２）
　本製造例は、酢酸鉛水和物(Pb)および酢酸ランタン水和物(La)を混合し脱水しておいたものに、ジルコニア−イソプロポキシドおよびチタン−イソプロポキシドを加えて反応し、その後ＤＢＵのかわりにジアミノエタノールを添加する点を除いて、製造例５と同様にして、圧電体薄膜用の塗工液を作成した。 (Production Comparative Example 2)
In this production example, lead acetate hydrate (Pb) and lanthanum acetate hydrate (La) were mixed and dehydrated, and zirconia-isopropoxide and titanium-isopropoxide were added and reacted. Thereafter, a coating liquid for a piezoelectric thin film was prepared in the same manner as in Production Example 5, except that diaminoethanol was added instead of DBU.

　（製造比較例３）
　本比較例は、ＤＢＵを添加せずに合成した点を除いて、製造例2と同様にして、圧電体薄膜用の塗工液を作成した。この塗工液を放置すると、白色結晶物が析出した。 (Production Comparative Example 3)
In this comparative example, a coating liquid for a piezoelectric thin film was prepared in the same manner as in Production Example 2, except that the composition was synthesized without adding DBU. When this coating liquid was left, white crystals precipitated.

　（実施例１〜９）
　図３、図４に示すような裏面の一部がくり抜かれたジルコニアの基板（3cm角）の表面に上記塗工液製造例１、３、４、６、７、８，９で得られた塗工液を、スピンコート法によって塗布し、２５℃で相対湿度３５％の空気を、１００℃の温度、空気中において５分間乾燥した（乾燥工程）。その後、直径5cm 長さ100cm（内ヒーター部30cm）の管状炉に２５℃で相対湿度８０％の酸素30%、窒素70%含有気体を流速20cm/secで流しながら４００℃５分（仮焼成工程）、同じ雰囲気下で６５０℃５分間熱処理した（本焼成工程）。この塗布と加熱を３回繰り返した後、最後に、上記管状炉で２５℃で相対湿度７５％の酸素30%、窒素70%含有気体雰囲気下、７００℃にて４０分間焼成し（本焼成工程）、その後同湿度環境下で室温まで冷却し（冷却工程）、本発明の圧電体素子を得た。（図５）圧電体薄膜の中間部の金属組成を分析したところPb1.0Zr0.52Ti0.48であった。 (Examples 1 to 9)
The coating liquid production examples 1, 3, 4, 6, 7, 8, and 9 were obtained on the surface of a zirconia substrate (3 cm square) having a part of the back surface hollowed out as shown in FIGS. The coating liquid was applied by spin coating, and air having a relative humidity of 35% at 25 ° C. was dried at 100 ° C. in air for 5 minutes (drying step). Thereafter, a gas containing 30% oxygen and 70% nitrogen at 25 ° C and a relative humidity of 80% was passed through a tubular furnace having a diameter of 5cm and a length of 100cm (inner heater 30cm) at a flow rate of 20cm / sec at 25 ° C for 5 minutes at 400 ° C. ), And heat-treated at 650 ° C. for 5 minutes in the same atmosphere (final firing step). After repeating this coating and heating three times, finally, the tube is baked at 700 ° C. for 40 minutes in a gas atmosphere containing 30% oxygen and 70% nitrogen at 25 ° C. in the above tubular furnace (main firing step). ) And then cooled to room temperature under the same humidity environment (cooling step) to obtain the piezoelectric element of the present invention. (FIG. 5) When the metal composition of the middle part of the piezoelectric thin film was analyzed, it was Pb 1.0 Zr 0.52 Ti 0.48 .

　３回塗布焼成後の膜厚は次の通りである。 膜厚 The film thickness after three times of application and baking is as follows.

Figure 2004134768
Figure 2004134768

　（実施例１０〜１１）
　実施例１〜４と同様の基板に上記塗工液製造例２、５で得られた塗工液を、スピンコートによって塗布し、２５℃で相対湿度５０％、１００℃、空気中において５分間乾燥した（乾燥工程）。その後、直径5cm 長さ100cm（内ヒーター部30cm）の管状炉に２５℃で相対湿度９０％、酸素30%窒素70%含有気体雰囲気下で３００℃２０分間加熱（仮焼成工程）し、この塗布と加熱を３回繰り返した後、最後に薄膜を結晶化させるために上記管状炉に２５℃で相対湿度７０％の酸素40%、窒素60%含有気体雰囲気下、７５０℃４０分間焼成（本焼成工程）し、その後同湿度環境下で室温まで冷却した（冷却工程）。本発明の圧電体素子を得た。圧電体薄膜の中間部の金属組成を分析したところPb0.99La0.01Zr0.52Ti0.48であった。３回塗布焼成後の膜厚は次の通りである。 (Examples 10 to 11)
The coating liquid obtained in the above-mentioned coating liquid production examples 2 and 5 was applied to the same substrate as in Examples 1 to 4 by spin coating, and the relative humidity was 50% at 25 ° C, 100 ° C, and 5 minutes in the air. It was dried (drying step). Then, it is heated (temporary firing step) at 300 ° C. for 20 minutes at 25 ° C. in a gas atmosphere containing 90% relative humidity and 30% oxygen and 70% nitrogen in a tube furnace having a diameter of 5 cm and a length of 100 cm (inner heater portion 30 cm). And heating are repeated three times. Finally, in order to crystallize the thin film, baking at 750 ° C. for 40 minutes in a gas atmosphere containing 40% oxygen and 60% nitrogen at 25 ° C. in the above-mentioned tube furnace at 25 ° C. (final baking) Step), and then cooled to room temperature under the same humidity environment (cooling step). The piezoelectric element of the present invention was obtained. When the metal composition of the middle part of the piezoelectric thin film was analyzed, it was Pb 0.99 La 0.01 Zr 0.52 Ti 0.48 . The film thickness after three times of application and baking is as follows.

Figure 2004134768
Figure 2004134768

　（実施例１２）
　本実施例は、乾燥時には２５℃で相対湿度６０％の空気を、１５０℃での乾燥において５分間用いたこと、その後、２５℃で相対湿度８０％の空気を、４００℃から６００℃まで昇温速度２℃／ｍｉｎ昇温し、６５０℃に至ったとき１０分間熱処理した際に用いた点を除いて、実施例6と同様にして、本発明の圧電体素子を得た。圧電体薄膜の中間部の金属組成を分析したところPb0.99La0.01Zr0.52Ti0.48であった。10回塗布焼成後の膜厚は2.71μmであった。 (Example 12)
In this embodiment, air having a relative humidity of 60% at 25 ° C. was used for drying for 5 minutes at 150 ° C., and then air having a relative humidity of 80% was increased from 400 ° C. to 600 ° C. at 25 ° C. A piezoelectric element of the present invention was obtained in the same manner as in Example 6, except that the temperature was raised at a rate of 2 ° C./min and a heat treatment was performed for 10 minutes when the temperature reached 650 ° C. When the metal composition of the middle part of the piezoelectric thin film was analyzed, it was Pb 0.99 La 0.01 Zr 0.52 Ti 0.48 . The film thickness after coating and firing 10 times was 2.71 μm.

　（実施例１３）
　実施例１において基板をジルコニア製からＳｉウエハーに変更した以外は同様に製造した。（図５）３回塗布焼成後の膜厚は1.22μmであった。 (Example 13)
Example 1 was repeated except that the substrate was changed from zirconia to Si wafer. (FIG. 5) The film thickness after three coating and firing steps was 1.22 μm.

　（比較例１〜２）
　製造比較例１、２で得られた塗工液を用いて、実施例５、６と同様にして圧電体素子を得た。 (Comparative Examples 1-2)
Piezoelectric elements were obtained in the same manner as in Examples 5 and 6, using the coating liquids obtained in Production Comparative Examples 1 and 2.

　［評価］
　実施例１〜１３、比較例１、２の圧電体素子を各３０個作成し、以下のように評価した。 [Evaluation]
Thirty piezoelectric elements were prepared for Examples 1 to 13 and Comparative Examples 1 and 2, and evaluated as follows.

　上部電極と下部電極間に10Vで10kHzを印加した際の変位量をレーザードップラー法により測定した。各３０個の素子における初期変位量と720時間動作後変位量の平均値および標準偏差の結果を表４に示す。 変 位 Displacement when 10kHz and 10kHz were applied between the upper electrode and the lower electrode was measured by the laser Doppler method. Table 4 shows the results of the average value and the standard deviation of the initial displacement amount and the displacement amount after the operation for 720 hours in each of the 30 devices.

　表４よりわかるように比較例にくらべ変位量が大きいことがわかりかつ７２０時間の耐久試験後も良好に動作していることがわかる。なおかつ比較例に比べ、圧電特性の不均一性の小さい素子が得られた。 (4) As can be seen from Table 4, it can be seen that the displacement amount is larger than that of the comparative example, and that it operates well even after the endurance test for 720 hours. In addition, an element having less non-uniformity of the piezoelectric characteristics as compared with the comparative example was obtained.

Figure 2004134768
Figure 2004134768

　［その他の評価］
　実施例１、比較例1で作製した圧電体素子における印加電界に対する分極特性を測定した。測定はＲａｄｉａｎｔｓ社製ＨＶＳ−６０００を用いて素子に２０Ｖ印加しヒステリシス曲線を得た。これを図８に示す。 [Other evaluations]
The polarization characteristics of the piezoelectric elements manufactured in Example 1 and Comparative Example 1 with respect to an applied electric field were measured. In the measurement, a hysteresis curve was obtained by applying 20 V to the device using HVS-6000 manufactured by Radiants. This is shown in FIG.

　この図より実施例１は比較例１に比べて残留分極が大きいことがわかる。このような顕著なヒステリシス特性は記憶素子となり得るため、複数並べて個別に電圧を印可可能にすることでメモリとして用いることも可能である。即ち記録したい情報にあわせて駆動信号を供給して書き込みを行い、分極方向を検出して読みとりを行うことにより、書き換え可能なメモリとして使用することが可能である。このようなメモリとして用いる場合の圧電体薄膜の膜厚は0.1μm〜2μmが好ましい。 よ り From this figure, it can be seen that Example 1 has larger remanent polarization than Comparative Example 1. Since such a remarkable hysteresis characteristic can serve as a memory element, it is possible to use a memory as a memory by arranging a plurality of them and applying a voltage individually. That is, a drive signal is supplied in accordance with information to be recorded, writing is performed, a polarization direction is detected, and reading is performed, whereby the memory can be used as a rewritable memory. When used as such a memory, the thickness of the piezoelectric thin film is preferably 0.1 μm to 2 μm.

　上記のように本発明で製造した圧電体素子は、インクジェット式記録ヘッドの圧電体素子だけでなく、メモリ、コンデンサ、センサ、光変調器などの装置に用いることが可能である。図６、７は、ノズル６ａが設けられたノズルプレート１０が取り付けられ、さらにインクを導入するための導入路１１が設けられたインクジェット記録ヘッドを示す。この様なインクジェット記録ヘッドを用いて、良好な記録を行うことができた。 The piezoelectric element manufactured by the present invention as described above can be used not only for the piezoelectric element of an ink jet recording head but also for devices such as a memory, a capacitor, a sensor, and an optical modulator. 6 and 7 show an ink jet recording head to which a nozzle plate 10 provided with a nozzle 6a is attached, and further, an introduction path 11 for introducing ink is provided. Good recording could be performed using such an ink jet recording head.

本発明の圧電体素子の概略を示す断面図。FIG. 1 is a cross-sectional view schematically showing a piezoelectric element of the present invention. 本発明の圧電体素子をインクジェット式プリンターヘッドのアクチュエータとした際の概略を示す断面図。FIG. 3 is a cross-sectional view schematically illustrating the piezoelectric element of the present invention when used as an actuator of an ink jet printer head. 実施例１〜１３、比較例１〜３で用いた基板の概略を示す斜視図。The perspective view which shows the outline of the board | substrate used in Examples 1-13 and Comparative Examples 1-3. 実施例１〜１３、比較例１〜３で用いた基板の概略を示す断面図。Sectional drawing which shows the outline of the board | substrate used in Examples 1-13 and Comparative Examples 1-3. 実施例１〜１３、比較例１〜３で作製した圧電体素子の概略を示す断面図。Sectional drawing which shows the outline of the piezoelectric element produced in Examples 1-13 and Comparative Examples 1-3. インクジェット式記録ヘッドの評価で用いたヘッドの概略を示す断面図。FIG. 2 is a cross-sectional view schematically illustrating a head used in the evaluation of the inkjet recording head. インクジェット式記録ヘッドの評価で用いたヘッドの概略を示す斜視図。FIG. 2 is a perspective view schematically showing a head used in the evaluation of the inkjet recording head. 実施例１、比較例１のヒステリシス曲線。3 is a hysteresis curve of Example 1 and Comparative Example 1.

Claims (7)

　金属化合物から得られる分散質を含む圧電体膜形成用組成物において、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種を含有することを特徴とする圧電体膜形成用組成物。 In a composition for forming a piezoelectric film containing a dispersoid obtained from a metal compound, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, A composition for forming a piezoelectric film, comprising at least one of 4,4-diazabicyclo [2.2.2] octane. 　前記金属化合物が、有機金属化合物であることを特徴とする請求項1記載の圧電体膜形成用組成物。 4. The composition for forming a piezoelectric film according to claim 1, wherein the metal compound is an organometallic compound. 　前記少なくとも１種の材料が、圧電体膜組成物中の総金属原子のモル数に対し、０．００５倍モル以上、５．０倍モル以下の量含有されていることを特徴とする請求項１または２に記載の圧電体膜形成用組成物。 The amount of the at least one material is 0.005 times or more and 5.0 times or less the mole number of the total metal atoms in the piezoelectric film composition. 3. The composition for forming a piezoelectric film according to 1 or 2. 　前記圧電体膜形成用組成物が、Pb及びLa、Zr、Tiの元素から少なくとも1種類以上を構成元素として含むことを特徴とする請求項1〜３のいずれかに記載の圧電体膜形成用組成物。 The composition for forming a piezoelectric film according to any one of claims 1 to 3, wherein the composition for forming a piezoelectric film comprises at least one of Pb, La, Zr, and Ti as a constituent element. Composition. 　金属化合物から得られる分散質を含み、1，8-ジアザビシクロ[5.4.0]-7-ウンデセン、１，５-ジアザビシクロ[4.3.0]ノン-5-エン、１，４-ジアザビシクロ[2.2.2]オクタンの内少なくとも１種を含有する圧電体膜形成用組成物を基板に塗布して塗布膜を形成する工程と、
　該塗布膜を乾燥する工程と、
　該乾燥した塗布膜を焼成して、圧電体膜を得る工程と、
を有することを特徴とする圧電体膜の製造方法。 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2, including dispersoids obtained from metal compounds A step of applying a composition for forming a piezoelectric film containing at least one of octane to a substrate to form a coating film;
Drying the coating film;
Baking the dried coating film to obtain a piezoelectric film,
A method for manufacturing a piezoelectric film, comprising: 　下部電極及び上部電極に挟持された圧電体膜を備える圧電体素子において、該圧電体膜が請求項５記載の方法により製造されたものであることを特徴とする圧電体素子。 A piezoelectric element comprising a piezoelectric film sandwiched between a lower electrode and an upper electrode, wherein the piezoelectric film is manufactured by the method according to claim 5. 　インク吐出口に連通する圧力室と、該圧力室に対応して設けられた振動板と、該振動板に対応して設けられた請求項６に記載の圧電体素子とを有し、該圧電体素子により生じる前記圧力室内の体積変化によって該圧力室内のインクを前記インク吐出口から吐出するインクジェット記録ヘッド。 7. A piezoelectric device comprising: a pressure chamber communicating with an ink discharge port; a vibration plate provided corresponding to the pressure chamber; and the piezoelectric element according to claim 6 provided corresponding to the vibration plate. An ink jet recording head that discharges ink in the pressure chamber from the ink discharge port by a volume change in the pressure chamber caused by a body element.
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