JP2007266346A - Piezoelectric thin film, piezoelectric element, liquid droplet injection head, liquid droplet injection apparatus, and manufacturing method of the liquid droplet injection head - Google Patents

Piezoelectric thin film, piezoelectric element, liquid droplet injection head, liquid droplet injection apparatus, and manufacturing method of the liquid droplet injection head Download PDF

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JP2007266346A
JP2007266346A JP2006089997A JP2006089997A JP2007266346A JP 2007266346 A JP2007266346 A JP 2007266346A JP 2006089997 A JP2006089997 A JP 2006089997A JP 2006089997 A JP2006089997 A JP 2006089997A JP 2007266346 A JP2007266346 A JP 2007266346A
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piezoelectric
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Shoko O
小興 王
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Seiko Epson Corp
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<P>PROBLEM TO BE SOLVED: To provide a non-lead based piezoelectric element (piezoelectric thin film), and to improve the characteristics of the same. <P>SOLUTION: An ink jet type recording head, including a piezoelectric element PE, comprises a substrate 1 having a plurality of pressure chambers 1a; a vibrating plate 3 formed thereabove; a first electrode 5 formed thereabove; a first piezoelectric film 7 formed thereabove; a second electrode 9 formed thereabove; a second piezoelectric film 11 formed thereabove; and a third electrode 13 formed thereabove. The first and second piezoelectric films 7, 11 comprise a BNT film ((Bi, Na, Ba)TiO<SB>3</SB>). More preferably, Li or K is doped to the BNT film. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、圧電薄膜、圧電素子、液滴噴射ヘッド、液滴噴射装置および液滴噴射ヘッドの製造方法、特に、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3よりなる圧電薄膜を有する圧電素子等に関するものである。 The present invention relates to a piezoelectric thin film, a piezoelectric element, a droplet ejecting head, a droplet ejecting apparatus, and a manufacturing method of the droplet ejecting head, and more particularly to a piezoelectric element having a piezoelectric thin film made of (Bi, Na, Ba) TiO 3. It is.

圧電素子とは、結晶を歪ませると帯電したり、電界中に置くと歪んだりする現象を利用した素子であり、インクジェットプリンタ等の液滴噴射装置に使用されている。   A piezoelectric element is an element that utilizes a phenomenon in which a crystal is charged when it is distorted or is distorted when placed in an electric field, and is used in a droplet ejecting apparatus such as an ink jet printer.

追って詳細に説明するように、インクジェットプリンタに用いられる圧電素子は、例えば、圧力発生室の上部に振動板、下部電極、圧電体膜および上部電極を順次形成した構成を有する。これら電極部への電位の印加によって圧電体膜を歪ませ、圧力発生室を加圧することで、その内部の液体を圧力発生室底部のノズル孔から外部に噴射させる。   As will be described in detail later, a piezoelectric element used in an ink jet printer has, for example, a configuration in which a diaphragm, a lower electrode, a piezoelectric film, and an upper electrode are sequentially formed on the upper part of a pressure generating chamber. By applying a potential to these electrode portions, the piezoelectric film is distorted and the pressure generating chamber is pressurized, whereby the liquid inside thereof is ejected from the nozzle hole at the bottom of the pressure generating chamber.

このような圧電素子には、ＰＺＴ膜（チタン酸ジルコン酸鉛、Ｐｂ（Ｚｒ1-xＴｉx）Ｏ3）等の圧電薄膜が用いられる。 For such a piezoelectric element, a piezoelectric thin film such as a PZT film (lead zirconate titanate, Pb (Zr 1-x Ti x ) O 3 ) is used.

例えば、下記特許文献１には、ペロブスカイト型酸化物薄膜を圧電部材とする圧電素子において、圧電部材を、組成が異なるいくつかの層からなる多層構造、もしくは、組成が連続して変化する傾斜組成構造とすることで、多素子化（小型化や高解像度）を容易にする技術が開示されている。   For example, in the following Patent Document 1, in a piezoelectric element using a perovskite oxide thin film as a piezoelectric member, the piezoelectric member has a multilayer structure composed of several layers having different compositions, or a gradient composition in which the composition changes continuously. A technique for facilitating the increase in the number of elements (miniaturization and high resolution) by using a structure is disclosed.

しかしながら、かかる技術では、圧電素子の変位量に限界があり、さらに大きな変位量を有する素子開発が求められる。   However, in such a technique, there is a limit to the amount of displacement of the piezoelectric element, and development of an element having a larger amount of displacement is required.

また、上記技術では、圧電素子の動作時において、その内部応力により圧電薄膜等にクラックが生じる恐れがあり、このようなクラックの発生を防止するため、圧電薄膜を薄くせざるを得ず、所望の特性を得ることが困難であった。   Further, in the above technique, there is a possibility that the piezoelectric thin film or the like may crack due to the internal stress during the operation of the piezoelectric element. In order to prevent the occurrence of such a crack, the piezoelectric thin film has to be thinned and desired. It was difficult to obtain the characteristics.

このクラックの防止に関しては、例えば、下記特許文献２に記載があり、圧電体層（４０１、４０２）間に応力緩和層（４０３）を形成することで、クラックの発生を防止する技術が開示されている。なお、括弧内は当該文献中の符号である。
特許公報３６６６１７７号公報 特開平１１−８７７９１号公報 Regarding prevention of this crack, for example, there is a description in Patent Document 2 below, and a technique for preventing the occurrence of cracks by forming a stress relaxation layer (403) between the piezoelectric layers (401, 402) is disclosed. ing. In addition, the code | symbol in the said literature is a parenthesis.
Japanese Patent Publication No. 3666177 JP-A-11-87791

しかしながら、上記特許文献等に記載される従来の圧電素子には、ＰＺＴ膜等の鉛系の圧電薄膜が用いられている。鉛（Ｐｂ）に関しては、環境汚染物質としてその環境への影響が懸念され、環境保全のため、各国においてその使用を種々の方面から規制する傾向にある。   However, lead-type piezoelectric thin films such as PZT films are used in conventional piezoelectric elements described in the above-mentioned patent documents. Regarding lead (Pb), there is a concern about its environmental impact as an environmental pollutant, and there is a tendency to restrict its use in various countries in various countries in order to preserve the environment.

従って、非鉛系の圧電素子の開発が急がれるとともに、従来のＰＺＴ膜等と同等、もしくはそれ以上の特性を確保できる、代替膜や素子構成の検討が必要である。   Accordingly, development of lead-free piezoelectric elements is urgently required, and it is necessary to study alternative films and element configurations that can ensure characteristics equivalent to or higher than those of conventional PZT films.

そこで、本発明は、非鉛系の圧電素子（圧電薄膜）を提供することを目的とする。また、非鉛系の圧電素子（圧電薄膜）の特性の向上を図ることを目的とする。   Therefore, an object of the present invention is to provide a lead-free piezoelectric element (piezoelectric thin film). It is another object of the present invention to improve the characteristics of a lead-free piezoelectric element (piezoelectric thin film).

（１）本発明に係る圧電薄膜は、圧電素子に用いられる圧電薄膜であって、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする。 (1) A piezoelectric thin film according to the present invention is a piezoelectric thin film used for a piezoelectric element, and is characterized by containing (Bi, Na, Ba) TiO 3 .

より好ましくは、上記圧電薄膜を、さらに、Ｌｉを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3とする。 More preferably, the piezoelectric thin film is further made of (Bi, Na, Ba, Li) TiO 3 containing Li.

より好ましくは、上記圧電薄膜を、さらに、Ｋを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3とする。 More preferably, the piezoelectric thin film is further made of (Bi, Na, Ba, K) TiO 3 containing K.

かかる構成によれば、非鉛系の圧電薄膜として、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を採用したので、鉛汚染を低減でき、環境問題を改善することができる。また、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3に、さらに、Ｌｉ（リチウム）もしくはＫ（カリウム）を含有させることで、退分極温度を上昇させることができ、圧電薄膜の特性を向上させることができる。 According to such a configuration, since (Bi, Na, Ba) TiO 3 is adopted as the lead-free piezoelectric thin film, lead contamination can be reduced and environmental problems can be improved. Further, by adding Li (lithium) or K (potassium) to (Bi, Na, Ba) TiO 3 , the depolarization temperature can be increased and the characteristics of the piezoelectric thin film can be improved. .

（２）本発明に係る圧電素子は、第１および第２電極との間に形成された圧電体膜を有する圧電素子であって、上記圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする。 (2) A piezoelectric element according to the present invention is a piezoelectric element having a piezoelectric film formed between first and second electrodes, wherein the piezoelectric film is made of (Bi, Na, Ba) TiO 3 . It is characterized by containing.

また、本発明に係る圧電素子は、基板と、基板の上方に形成された第１電極と、上記第１電極の上方に形成された圧電体膜と、上記圧電体膜の上方に形成された第２電極とその上部に形成された第２圧電体膜とからなる積層膜と、を有する圧電素子であって、上記積層膜を複数有し、上記圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする。 The piezoelectric element according to the present invention is formed on a substrate, a first electrode formed above the substrate, a piezoelectric film formed above the first electrode, and above the piezoelectric film. A piezoelectric element having a laminated film comprising a second electrode and a second piezoelectric film formed on the second electrode, the piezoelectric element having a plurality of the laminated films, wherein the piezoelectric film is (Bi, Na, Ba) It contains TiO 3 .

より好ましくは、上記圧電体膜を、さらに、Ｌｉを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3とする。 More preferably, the piezoelectric film is further made of (Bi, Na, Ba, Li) TiO 3 containing Li.

より好ましくは、上記圧電体膜を、さらに、Ｋを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3とする。 More preferably, the piezoelectric film is further made of (Bi, Na, Ba, K) TiO 3 containing K.

かかる構成によれば、非鉛系の圧電体膜として、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を採用したので、鉛汚染を低減でき、環境問題を改善することができる。また、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3に、さらに、Ｌｉ（リチウム）もしくはＫ（カリウム）を含有させることで、退分極温度を上昇させることができ、素子特性を向上させることができる。また、圧電体膜を電極を介して積層させることにより圧電常数を向上することができ、また、変異量を増加させることができる。その結果、素子特性を向上させることができる。 According to this configuration, since (Bi, Na, Ba) TiO 3 is employed as the lead-free piezoelectric film, lead contamination can be reduced and environmental problems can be improved. Further, by adding Li (lithium) or K (potassium) to (Bi, Na, Ba) TiO 3 , the depolarization temperature can be increased, and the device characteristics can be improved. In addition, the piezoelectric constant can be improved by laminating the piezoelectric film through the electrode, and the amount of variation can be increased. As a result, element characteristics can be improved.

（３）本発明に係る液滴噴射ヘッドは、複数の圧力室を有する基板と、基板の上方に形成された振動板と、上記振動板の上方に形成された第１電極と、上記第１電極の上方に形成された第１圧電体膜と、上記第１圧電体膜の上方に形成された第２電極と、上記第２電極の上方に形成された第２圧電体膜と、上記第２圧電体膜の上方に形成された第３電極と、を有し、上記第１および第２圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする。 (3) A liquid droplet ejecting head according to the present invention includes a substrate having a plurality of pressure chambers, a diaphragm formed above the substrate, a first electrode formed above the diaphragm, and the first electrode. A first piezoelectric film formed above the electrode; a second electrode formed above the first piezoelectric film; a second piezoelectric film formed above the second electrode; And a third electrode formed above the two piezoelectric films, wherein the first and second piezoelectric films contain (Bi, Na, Ba) TiO 3 .

例えば、上記第２圧電体膜、第３および第２電極は、上記複数の圧力室毎に分離して形成され、上記第１圧電体膜および第１電極は、上記複数の圧力室の上方に連続して配置されている。   For example, the second piezoelectric film, the third and second electrodes are formed separately for each of the plurality of pressure chambers, and the first piezoelectric film and the first electrode are above the plurality of pressure chambers. It is arranged continuously.

かかる構成によれば、非鉛系の圧電体膜として、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を採用したので、鉛汚染を低減でき、環境問題を改善することができる。また、圧電体膜を電極を介して積層させることにより圧電常数を向上することができ、また、変異量を増加させることができる。その結果、液滴噴射ヘッドの特性を向上させることができる。 According to this configuration, since (Bi, Na, Ba) TiO 3 is employed as the lead-free piezoelectric film, lead contamination can be reduced and environmental problems can be improved. In addition, the piezoelectric constant can be improved by laminating the piezoelectric film through the electrode, and the amount of variation can be increased. As a result, the characteristics of the droplet ejecting head can be improved.

（４）本発明に係る液滴噴射ヘッドは、圧電素子を有する液滴噴射ヘッドであって、上記圧電素子を有することを特徴とする。   (4) A liquid droplet ejecting head according to the present invention is a liquid droplet ejecting head having a piezoelectric element, and has the piezoelectric element.

（５）本発明に係る液滴噴射装置は、液滴噴射ヘッドを有する液滴噴射装置であって、上記液滴噴射ヘッドを有することを特徴とする。   (5) A liquid droplet ejecting apparatus according to the present invention is a liquid droplet ejecting apparatus having a liquid droplet ejecting head, and includes the liquid droplet ejecting head.

（６）本発明に係る液滴噴射ヘッドの形成方法は、基板の上方に振動板を形成する工程と、上記振動板の上方に第１電極を形成する工程と、上記第１電極の上方に、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する第１圧電体膜を形成する工程と、上記第１圧電体膜の上方に第２電極を形成する工程と、上記第２電極の上方に、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する第２圧電体膜を形成する工程と、上記第２圧電体膜の上方に第３電極を形成する工程と、上記第３電極、第２圧電体膜および第２電極を上記基板に形成される圧力室の上方に配置されるよう上記第１圧電体膜が露出するまでエッチングする工程と、を有する。 (6) A method of forming a liquid droplet ejecting head according to the present invention includes a step of forming a diaphragm above a substrate, a step of forming a first electrode above the diaphragm, and a position above the first electrode. , Forming a first piezoelectric film containing (Bi, Na, Ba) TiO 3 , forming a second electrode above the first piezoelectric film, and above the second electrode, Forming a second piezoelectric film containing (Bi, Na, Ba) TiO 3 ; forming a third electrode above the second piezoelectric film; and the third electrode and the second piezoelectric body. Etching the film and the second electrode until the first piezoelectric film is exposed so as to be disposed above the pressure chamber formed on the substrate.

かかる方法によれば、非鉛系の圧電体膜として、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を採用したので、鉛汚染を低減でき、環境問題を改善することができる。また、圧電体膜を電極を介して積層させることにより圧電常数を向上することができ、また、変異量を増加させることができる。その結果、素子特性を向上させることができる。また、第３電極、第２圧電体膜および第２電極のみをエッチングすることで、効率良くエッチングを行なうことができる。また、効率よく液滴噴射ヘッドを製造することができる。 According to this method, since (Bi, Na, Ba) TiO 3 is used as the lead-free piezoelectric film, lead contamination can be reduced and environmental problems can be improved. In addition, the piezoelectric constant can be improved by laminating the piezoelectric film through the electrode, and the amount of variation can be increased. As a result, element characteristics can be improved. Moreover, etching can be efficiently performed by etching only the third electrode, the second piezoelectric film, and the second electrode. In addition, the droplet ejecting head can be manufactured efficiently.

以下、本発明の実施の形態を図面を参照しながら詳細に説明する。なお、同一の機能を有するものには同一もしくは関連の符号を付し、その繰り返しの説明を省略する。   Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same or related code | symbol is attached | subjected to what has the same function, and the repeated description is abbreviate | omitted.

本実施の形態の圧電素子およびその製造方法について図１および図２を参照しながら説明する。図１および図２は、本実施の形態のインクジェット記録式ヘッド（液滴噴射ヘッド、液滴吐出ヘッド）の製造工程を示す工程断面図である。   A piezoelectric element and a manufacturing method thereof according to the present embodiment will be described with reference to FIGS. FIG. 1 and FIG. 2 are process cross-sectional views showing the manufacturing process of the ink jet recording head (droplet ejection head, droplet discharge head) of the present embodiment.

まず、本実施の形態の圧電素子を有するインクジェット記録式ヘッド構成について説明する。なお、詳細な構成は、後述する製造工程においても明確となると思われるため、ここでは、その特徴的な部分について説明する。   First, an ink jet recording head configuration having the piezoelectric element of the present embodiment will be described. In addition, since it seems that a detailed structure becomes clear also in the manufacturing process mentioned later, the characteristic part is demonstrated here.

最終工程断面図である図２（Ｂ）に示すように、インクジェット記録式ヘッドは、ノズルプレート２０と、その上部に形成され、圧力室（キャビティー、圧力発生室）１ａを有する基板１と、その上部に形成された振動板（弾性膜、硬質膜）３と、その上部に形成された圧電素子ＰＥとを有する。   As shown in FIG. 2B, which is a final process cross-sectional view, the ink jet recording head includes a nozzle plate 20 and a substrate 1 formed on the nozzle plate 20 and having a pressure chamber (cavity, pressure generation chamber) 1a, It has a diaphragm (elastic film, hard film) 3 formed on the upper part and a piezoelectric element PE formed on the upper part.

圧力室１ａは、基板（例えば、シリコン基板）１に形成された凹部であり、その底部にはノズルプレート２０に形成されたノズル孔２０ａが位置する。振動板３は、例えば、酸化シリコン（ＳｉＯ2）膜３ａと酸化ジルコニウム（ＺｒＯ2）膜３ｂとの積層膜よりなる。 The pressure chamber 1a is a recess formed in the substrate (for example, a silicon substrate) 1, and a nozzle hole 20a formed in the nozzle plate 20 is located at the bottom thereof. The diaphragm 3 is made of, for example, a laminated film of a silicon oxide (SiO 2 ) film 3a and a zirconium oxide (ZrO 2 ) film 3b.

また、圧電素子ＰＥは、圧力室１ａ側から、第１電極５、第１圧電体膜（圧電薄膜、圧電膜）７、第２電極９、第２圧電体膜１１および第３電極１３の積層構造を有する。ここで、第２電極９、第２圧電体膜１１および第３電極１３は、圧力室１ａ毎に分離されているが、第１電極５および第１圧電体膜７は、各圧力室１ａに共通して、即ち、連続して配置されている。このように、第２電極９、第２圧電体膜１１および第３電極１３を、圧力室１ａ毎に分離することで、圧力室１ａからの液滴の噴射（吐出）を選択的に行なうことができる。なお、第１電極５および第１圧電体膜７を、各圧力室１ａに共通して形成しても、第２電極９および第３電極１３を制御することで、圧力室１ａからの選択的な噴射が可能である。もちろん、第１電極５のみならず、第２電極９および第３電極１３に共通に電位を印加し、各圧力室１ａから同時に液滴を噴射させてもよい。   In addition, the piezoelectric element PE includes a first electrode 5, a first piezoelectric film (piezoelectric thin film, piezoelectric film) 7, a second electrode 9, a second piezoelectric film 11, and a third electrode 13 stacked from the pressure chamber 1 a side. It has a structure. Here, the second electrode 9, the second piezoelectric film 11 and the third electrode 13 are separated for each pressure chamber 1a, but the first electrode 5 and the first piezoelectric film 7 are provided in each pressure chamber 1a. They are arranged in common, that is, continuously. In this way, by separating the second electrode 9, the second piezoelectric film 11 and the third electrode 13 for each pressure chamber 1a, it is possible to selectively eject (discharge) droplets from the pressure chamber 1a. Can do. Even if the first electrode 5 and the first piezoelectric film 7 are formed in common to the respective pressure chambers 1a, the second electrode 9 and the third electrode 13 are controlled so as to be selectively selected from the pressure chamber 1a. Injection is possible. Of course, not only the first electrode 5 but also the second electrode 9 and the third electrode 13 may be applied with a common potential, and droplets may be ejected simultaneously from the pressure chambers 1a.

ここで、本実施の形態の第１の特徴は、第１圧電体膜７および第２圧電体膜１１が、いわゆるＢＮＴ膜で構成されていることである。このＢＮＴ膜は、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3で表せる。なお、（Ｂｉ，Ｎａ）ＢａＴｉＯ3と表されることもある。また、ＢＮＴ−ＢＴ（（Ｂｉ0.5Ｎａ0.5）ＴｉＯ3−ＢａＴｉＯ3）と呼ばれることもある。 Here, the first feature of the present embodiment is that the first piezoelectric film 7 and the second piezoelectric film 11 are formed of a so-called BNT film. This BNT film can be expressed by (Bi, Na, Ba) TiO 3 . It may be expressed as (Bi, Na) BaTiO 3 . It may also be called BNT-BT ((Bi 0.5 Na 0.5 ) TiO 3 —BaTiO 3 ).

このように、本実施の形態によれば、圧電体膜として、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を採用したので鉛フリーとすることができ、ＰＺＴ膜を用いる場合のような鉛汚染がなく、環境問題を改善することができる。 Thus, according to the present embodiment, since (Bi, Na, Ba) TiO 3 is adopted as the piezoelectric film, it can be made lead-free, and there is no lead contamination as in the case of using the PZT film. , Can improve environmental problems.

但し、ＢＮＴ膜を用いた場合には、退分極温度が低下し、１５０℃程度となってしまう。退分極温度とは、分極特性を維持できる温度であり、かかる温度が低下すると当該温度以上の使用に耐えることができなくなる。   However, when the BNT film is used, the depolarization temperature is lowered to about 150 ° C. The depolarization temperature is a temperature at which the polarization characteristics can be maintained. When the temperature decreases, the depolarization temperature cannot withstand use above the temperature.

そこで、退分極温度を向上させるため、ＢＮＴ膜にＬｉ（リチウム）もしくはＫ（カリウム）を添加することが好ましい。即ち、圧電体膜（７、１１）として、Ｌｉを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3や、Ｋを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3を用いることが好ましい。 Therefore, in order to improve the depolarization temperature, it is preferable to add Li (lithium) or K (potassium) to the BNT film. That is, it is preferable to use (Bi, Na, Ba, Li) TiO 3 containing Li or (Bi, Na, Ba, K) TiO 3 containing K as the piezoelectric film (7, 11).

このように、ＬｉやＫの添加によりペロブスカイト構造の相転移が抑圧でき、退分極温度が向上する。   Thus, the addition of Li or K can suppress the phase transition of the perovskite structure and improve the depolarization temperature.

一方、圧電体膜（７、１１）としてＢＮＴ膜を使用した場合、ＰＺＴ膜と比較し、圧電常数や変異量が低くなってしまう。圧電常数とは、機械量と電気量の変換の程度を示すもので、加える機械量（力）によって生じる発生電気が大きい方が圧電常数は高くなる。また、加える電気量によって生じる機械量（変位量）が大きい方が圧電常数は高くなる。   On the other hand, when a BNT film is used as the piezoelectric film (7, 11), the piezoelectric constant and the amount of variation are reduced as compared with the PZT film. The piezoelectric constant indicates the degree of conversion between the mechanical quantity and the electrical quantity, and the piezoelectric constant increases as the electricity generated by the applied mechanical quantity (force) increases. In addition, the piezoelectric constant increases as the mechanical amount (displacement amount) generated by the amount of electricity applied increases.

そこで、本実施の形態の第２の特徴は、前述した通り、圧電体膜（７、１１）を電極（９）を介して積層させる構成としたことにある。その結果、変位量を大きくすることができる。また、一の圧電体膜の膜厚を低減することができ、変位の際の応力を緩和でき、クラックの発生を低減することができる。   Therefore, the second feature of the present embodiment is that the piezoelectric films (7, 11) are laminated via the electrodes (9) as described above. As a result, the amount of displacement can be increased. In addition, the film thickness of one piezoelectric film can be reduced, the stress at the time of displacement can be relaxed, and the occurrence of cracks can be reduced.

次いで、本実施の形態のインクジェット記録式ヘッドの製造方法を図１および図２を参照しながら順を追って説明するとともに、その構造を明確化する。   Next, a method for manufacturing the ink jet recording head according to the present embodiment will be described step by step with reference to FIGS. 1 and 2, and the structure will be clarified.

まず、図１（Ａ）に示すように、基板１として例えばシリコン基板を準備し、その表面に振動板３として酸化シリコン膜３ａを形成する。この酸化シリコン膜３ａは、例えば、基板１を熱酸化することにより形成する。次いで、酸化シリコン膜３ａ上に、例えば、酸化ジルコニウム膜３ｂを形成する。この膜は、例えば、スパッタリング法等によりジルコニウム（Ｚｒ）層を形成し、このジルコニウム層を、熱酸化することにより形成する。この酸化ジルコニウム膜３ｂは、酸化シリコン膜３ａの硬さを調節するために形成する。従って、酸化シリコン膜３ａおよび酸化ジルコニウム膜３ｂの積層膜を振動板３としてとらえてもよい。なお、酸化ジルコニウム膜３ｂは振動板として必須のものではない。   First, as shown in FIG. 1A, for example, a silicon substrate is prepared as the substrate 1, and a silicon oxide film 3a is formed as a vibration plate 3 on the surface. The silicon oxide film 3a is formed, for example, by thermally oxidizing the substrate 1. Next, for example, a zirconium oxide film 3b is formed on the silicon oxide film 3a. This film is formed, for example, by forming a zirconium (Zr) layer by sputtering or the like and thermally oxidizing the zirconium layer. The zirconium oxide film 3b is formed in order to adjust the hardness of the silicon oxide film 3a. Therefore, the laminated film of the silicon oxide film 3 a and the zirconium oxide film 3 b may be regarded as the diaphragm 3. The zirconium oxide film 3b is not essential as a diaphragm.

次いで、第１電極（導電性膜）５として、例えば、白金（Ｐｔ）膜をスパッタリング法を用いて、１００〜２００ｎｍ程度、振動板（酸化ジルコニウム膜３ｂ）３上に堆積する。かかる電極としては、Ｐｔの他、ＺｒとＰｔの積層膜、Ｎｉ（ニッケル）、Ｉｒ（イリジウム）等の金属膜や後述するＬＮＯ膜等の導電性を有する金属酸化物を用いてもよい。   Next, as the first electrode (conductive film) 5, for example, a platinum (Pt) film is deposited on the vibration plate (zirconium oxide film 3 b) 3 to a thickness of about 100 to 200 nm using a sputtering method. As such an electrode, a conductive metal oxide such as a laminated film of Zr and Pt, a metal film such as Ni (nickel) or Ir (iridium), or an LNO film described later may be used in addition to Pt.

次いで、図１（Ｂ）に示すように、第１電極５上に第１圧電体膜（圧電体、圧電体層）７としてＢＮＴ膜を４００〜８００ｎｍ程度形成する。このＢＮＴ膜は、例えば、Ｂｉ（ビスマス）、Ｎａ（ナトリウム）、Ｂａ（バリウム）およびＴｉ（チタン）をそれぞれ含有する金属化合物を溶媒に溶解させた溶液を基板上に塗布した後、熱処理（乾燥、脱脂、焼成）を施すことにより形成する。   Next, as shown in FIG. 1B, a BNT film is formed on the first electrode 5 as a first piezoelectric film (piezoelectric body, piezoelectric layer) 7 to a thickness of about 400 to 800 nm. This BNT film is formed by, for example, applying a solution in which a metal compound containing Bi (bismuth), Na (sodium), Ba (barium) and Ti (titanium) is dissolved in a solvent on a substrate, followed by heat treatment (drying). , Degreasing, and firing).

塗布は、例えば、スピンコート法を用いて行なう。スピンの回転数は、初期においては、５００ｒｐｍ程度とし、続いて塗布ムラが起こらないように回転数を上昇させ、例えば２５００ｒｐｍとする。   The application is performed using, for example, a spin coating method. The rotation speed of the spin is initially set to about 500 rpm, and then the rotation speed is increased so as not to cause coating unevenness, for example, 2500 rpm.

熱処理は、例えば、大気雰囲気下でホットプレートに上記溶液塗布基板を搭載し、上記溶液に用いた溶媒の沸点よりも例えば１０℃程度高い温度（例えば１５０℃程度）で第１熱処理（乾燥）を行う。次いで、原料溶液を分解すべく、ホットプレート温度を３００〜４００℃程度とし、第２熱処理（脱脂）を行う。なお、塗布および熱処理工程を複数回、繰り返し所望の膜厚を確保してもよい。次いで、第３熱処理（結晶化アニール、焼成）として、例えばＲＴＡ（Rapid Thermal Annealing）等により、酸素雰囲気中で６００℃〜７５０℃程度の熱処理を施し、結晶化を行う。   The heat treatment is performed by, for example, mounting the solution-coated substrate on a hot plate in an air atmosphere, and performing the first heat treatment (drying) at a temperature (for example, about 150 ° C.) higher than the boiling point of the solvent used in the solution, for example. Do. Next, in order to decompose the raw material solution, the hot plate temperature is set to about 300 to 400 ° C., and the second heat treatment (degreasing) is performed. Note that a desired film thickness may be ensured by repeating the coating and heat treatment steps a plurality of times. Next, as a third heat treatment (crystallization annealing, firing), for example, by RTA (Rapid Thermal Annealing) or the like, heat treatment is performed at about 600 ° C. to 750 ° C. in an oxygen atmosphere to perform crystallization.

上記工程により形成されたＢＮＴ膜は、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する。 The BNT film formed by the above process contains (Bi, Na, Ba) TiO 3 .

ここで、上記溶液中にさらに、Ｌｉを含有する金属化合物を添加することによりＬｉを含有するＢＮＴ膜、即ち、（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3とすることができる。 Here, a BNT film containing Li, that is, (Bi, Na, Ba, Li) TiO 3 , can be obtained by further adding a metal compound containing Li to the solution.

また、上記溶液中にさらに、Ｋを含有する金属化合物を添加することによりＬｉを含有するＢＮＴ膜、即ち、（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3とすることができる。 Further, by adding a metal compound containing K to the solution, a BNT film containing Li, that is, (Bi, Na, Ba, K) TiO 3 can be obtained.

また、ＢＮＴ膜に上記ＬｉおよびＫの化合物を添加し、（Ｂｉ，Ｎａ，Ｂａ，Ｋ，Ｌｉ）ＴｉＯ3としてもよい。このようなＢＮＴ系の圧電体膜の組成式は、（Ｂｉ0.5Ｎａ0.5-x-yＫxＬｉy）1-zＢａzＴｉＯ3（但し、０．０５≦ｘ≦０．１５、０．００５≦ｙ≦０．０３、０．０２≦ｚ≦０．１）で表される。例えば、（Ｂｉ0.5Ｎａ0.39Ｋ0.1Ｌｉ0.01）0.95Ｂａ0.05ＴｉＯ3などがある。 Alternatively, the above Li and K compounds may be added to the BNT film to form (Bi, Na, Ba, K, Li) TiO 3 . Formula of the piezoelectric film having such a BNT system, (Bi 0.5 Na 0.5-xy K x Li y) 1-z Ba z TiO 3 ( where, 0.05 ≦ x ≦ 0.15,0.005 ≦ y ≦ 0.03, 0.02 ≦ z ≦ 0.1). For example, there is (Bi 0.5 Na 0.39 K 0.1 Li 0.01 ) 0.95 Ba 0.05 TiO 3 .

これらの金属を含有する金属化合物としては、Ｂｉについては、硝酸ビスマス、Ｌｉについては、硝酸リチウム、Ｎａについては、酢酸ナトリウム、Ｋについては、酢酸カリウム、Ｔｉについては、チタンイソプロポキシド、Ｂａについては、酢酸バリウムなどが挙げられる。これらの材料の他、各種金属の有機化合物を用いて塗布溶液を調整してもよい。このような液体溶液を用いた成膜方法は、ゾルゲル法もしくはＭＯＤ（Metal Organic Decomposition）法と呼ばれる。なお、ＢＮＴ膜の形成方法としては、この他、スパッタリング法やＭＯＣＶＤ（有機金属気相成長法）法などを用いて形成してもよい。但し、液体溶液を用いた成膜方法によれば、それぞれの金属化合物（溶液）の添加量（混合比率）を調整することで、ＢＮＴ膜の金属組成を容易に制御でき、また、ＬｉやＫの添加等も比較的容易に行うことができるので、本実施の形態に適用して好適である。   As the metal compounds containing these metals, Bi for bismuth nitrate, Li for lithium nitrate, Na for sodium acetate, K for potassium acetate, Ti for titanium isopropoxide, Ba Includes barium acetate. In addition to these materials, coating solutions may be prepared using organic compounds of various metals. A film forming method using such a liquid solution is called a sol-gel method or a MOD (Metal Organic Decomposition) method. In addition, as a method for forming the BNT film, a sputtering method, a MOCVD (metal organic chemical vapor deposition) method, or the like may be used. However, according to the film forming method using a liquid solution, the metal composition of the BNT film can be easily controlled by adjusting the addition amount (mixing ratio) of each metal compound (solution), and Li or K Since the addition of can be performed relatively easily, it is suitable to be applied to this embodiment mode.

なお、第１電極５上に、バッファ層として面方位（１００）の層、例えば、ＬＮＯ膜やＳＲＯ膜等を形成し、このバッファ層上にＢＮＴ膜を形成してもよい。このバッファ層を用いることで、ＢＮＴ膜を面方位（１００）に主に配向した膜とすることができ、圧電特性を向上させることができる。ＬＮＯ膜は、ニッケル酸ランタン（ＬａＮｉＯ3）膜であり、ＳＲＯ膜は、ルテニウム酸ストロンチウム（ＳｒＲｕＯ3）である。 Note that a surface orientation (100) layer such as an LNO film or an SRO film may be formed on the first electrode 5 as a buffer layer, and a BNT film may be formed on the buffer layer. By using this buffer layer, the BNT film can be a film mainly oriented in the plane direction (100), and the piezoelectric characteristics can be improved. The LNO film is a lanthanum nickelate (LaNiO 3 ) film, and the SRO film is strontium ruthenate (SrRuO 3 ).

次いで、第１圧電体膜７上に第２電極９として例えばＰｔ膜を例えば１５０〜３００ｎｍ程度、第１電極７と同様に形成する。   Next, a Pt film, for example, about 150 to 300 nm is formed on the first piezoelectric film 7 as the second electrode 9 in the same manner as the first electrode 7.

次いで、第２電極９上に第２圧電体膜１１としてＢＮＴ膜を４００〜８００ｎｍ程度、例えば、第１圧電体膜７と同様に形成する。その結果、第２圧電体膜１１は、第１圧電体膜７と同様に、ＢＮＴ膜となる。即ち、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する膜となる。第２圧電体膜１１においても、Ｌｉを含有するＢＮＴ膜、即ち、（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3とすることができ、また、Ｌｉを含有するＢＮＴ膜、即ち、（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3とすることができる。また、ＢＮＴ膜にＬｉおよびＫを添加し、（Ｂｉ，Ｎａ，Ｂａ，Ｋ，Ｌｉ）ＴｉＯ3としてもよい。 Next, a BNT film is formed on the second electrode 9 as the second piezoelectric film 11 to a thickness of about 400 to 800 nm, for example, in the same manner as the first piezoelectric film 7. As a result, the second piezoelectric film 11 becomes a BNT film in the same manner as the first piezoelectric film 7. That is, the film contains (Bi, Na, Ba) TiO 3 . The second piezoelectric film 11 can also be a BNT film containing Li, that is, (Bi, Na, Ba, Li) TiO 3, and a BNT film containing Li, ie, (Bi, Na). , Ba, K) TiO 3 . Further, Li and K may be added to the BNT film to form (Bi, Na, Ba, K, Li) TiO 3 .

また、この際も前述したように、第２電極９上にバッファ層としてＬＮＯ膜もしくはＳＲＯ膜を形成した後、ＢＮＴ膜（第２圧電体膜１１）を形成してもよい。   Also at this time, as described above, after forming the LNO film or the SRO film as the buffer layer on the second electrode 9, the BNT film (second piezoelectric film 11) may be formed.

次いで、第２圧電体膜１１上に第３電極１３として例えばＰｔ膜を第１電極７と同様に形成する。   Next, for example, a Pt film is formed on the second piezoelectric film 11 as the third electrode 13 in the same manner as the first electrode 7.

次いで、図２（Ａ）に示すように、後述する圧力室（１ａ）形成予定領域上にのみ、第３電極１３、第２圧電体膜１１および第２電極９を残存させるべく、これらの積層膜をエッチングする。即ち、これらの膜を第１圧電体膜７が露出するまでエッチングする。このエッチングは、例えば、ドライエッチング法やイオンリミング法を用いて行う。なお、前述したように、第１圧電体膜７や第１電極５をエッチングしなくてもインクジェット記録式ヘッドの動作上の問題は生じない。   Next, as shown in FIG. 2A, the third electrode 13, the second piezoelectric film 11 and the second electrode 9 are left only on the region where the pressure chamber (1 a) to be described later is to be formed. Etch the film. That is, these films are etched until the first piezoelectric film 7 is exposed. This etching is performed using, for example, a dry etching method or an ion rimming method. As described above, the operation problem of the ink jet recording head does not occur even if the first piezoelectric film 7 and the first electrode 5 are not etched.

このように、本実施の形態においは、第１圧電体膜７や第１電極５を残存させたので、エッチング時間を短縮することができる。特に、ＢＮＴ膜は、ＰＺＴ膜と比較し、エッチング速度が小さいと考えられるため、第１圧電体膜７や第１電極５を残存させることによる、エッチング時間の短縮効果が大きい。また、本実施の形態においては、圧電体膜（７、１１）を電極（９）を介して積層させる構成を有しているため、電極→圧電体膜→電極と、異なる材料を順次エッチングする必要がある。従って、エッチングの制御が重要となり、例えば、電極材料や電極と圧電体膜のエッチング比によっては、エッチング対象膜が変わる毎にエッチング条件を変化させる必要がある。従って、第１圧電体膜７や第１電極５のエッチングを回避することで、エッチングを効率良く行なうことができる。   Thus, in the present embodiment, the first piezoelectric film 7 and the first electrode 5 are left, so that the etching time can be shortened. In particular, since the BNT film is considered to have a lower etching rate than the PZT film, the effect of shortening the etching time by leaving the first piezoelectric film 7 and the first electrode 5 is great. In the present embodiment, since the piezoelectric films (7, 11) are stacked via the electrode (9), different materials are sequentially etched in the order of electrode → piezoelectric film → electrode. There is a need. Therefore, it is important to control the etching. For example, depending on the electrode material and the etching ratio between the electrode and the piezoelectric film, it is necessary to change the etching conditions every time the etching target film changes. Therefore, the etching can be performed efficiently by avoiding the etching of the first piezoelectric film 7 and the first electrode 5.

次いで、図２（Ｂ）に示すように、基板１の裏面（圧電素子ＰＥ形成側と逆側の面）にマスク膜として例えば窒化シリコン膜（図示せず）を堆積し、所望の形状にパターニングする。次いで、このマスク膜をマスクに、基板１を振動板（酸化シリコン膜３ａ）３が露出するまでエッチングすることにより、基板１中に圧力室（凹部、開口部）１ａを形成する。次いで、圧力室１ａに対応する位置にノズル孔（ノズル開口）２０ａを有するノズルプレート２０を基板１の裏面に例えば接着剤等を用いて接合する。次いで、圧電素子（基板１）ＰＥ上に、保護基板（基体）３０を搭載し、接合する（図３参照）。この保護基板３０は、圧電素子ＰＥに対応する部分に凹部を有する。以上の工程により、複数の圧電素子ＰＥを有するインクジェット式記録ヘッドが略完成する。   Next, as shown in FIG. 2B, for example, a silicon nitride film (not shown) is deposited as a mask film on the back surface (the surface opposite to the piezoelectric element PE formation side) of the substrate 1 and patterned into a desired shape. To do. Next, using this mask film as a mask, the substrate 1 is etched until the vibration plate (silicon oxide film 3 a) 3 is exposed, thereby forming a pressure chamber (recess, opening) 1 a in the substrate 1. Next, a nozzle plate 20 having a nozzle hole (nozzle opening) 20a at a position corresponding to the pressure chamber 1a is bonded to the back surface of the substrate 1 using, for example, an adhesive. Next, a protective substrate (base) 30 is mounted on the piezoelectric element (substrate 1) PE and bonded (see FIG. 3). The protective substrate 30 has a recess in a portion corresponding to the piezoelectric element PE. Through the above steps, an ink jet recording head having a plurality of piezoelectric elements PE is substantially completed.

図３は、インクジェット記録式ヘッドの分解斜視図であり、図１および図２と対応する部分については同じ符号を付してある。図示するように、基板１には、圧力室１ａと同時にリザーバ１ｂや複数の供給口１ｃが設けられており、これらを介して圧力室１ａにインク（液滴）が供給される。   FIG. 3 is an exploded perspective view of the ink jet recording head. Parts corresponding to those in FIGS. 1 and 2 are denoted by the same reference numerals. As shown in the figure, the substrate 1 is provided with a reservoir 1b and a plurality of supply ports 1c simultaneously with the pressure chamber 1a, and ink (droplets) is supplied to the pressure chamber 1a through these.

圧電素子ＰＥの駆動により振動板３が変位し、圧力室１ａが加圧され、ノズル孔２０ａからインクが噴射される。圧電素子ＰＥおよび振動板３を合わせてアクチュエータ装置と言うこともある。なお、図３は、インクジェット記録式ヘッドの構成の一例に過ぎず、圧電素子ＰＥの形状や配列方向等、その構成が適宜変更可能であることは言うまでもない。   The diaphragm 3 is displaced by driving the piezoelectric element PE, the pressure chamber 1a is pressurized, and ink is ejected from the nozzle hole 20a. The piezoelectric element PE and the diaphragm 3 may be collectively referred to as an actuator device. Note that FIG. 3 is only an example of the configuration of the ink jet recording head, and it goes without saying that the configuration of the piezoelectric elements PE, such as the shape and arrangement direction, can be changed as appropriate.

また、図４は、インクジェットプリンタ装置（液体噴射装置、液滴吐出装置）１０４の概略を示す要部斜視図であり、図示するように、前述のインクジェット記録式ヘッドは、噴射ヘッドユニット１０１Ａおよび１０１Ｂ中に組み込まれている。また、噴射ヘッドユニット１０１Ａおよび１０１Ｂには、インク供給手段を構成するカートリッジ１０２Ａおよび１０２Ｂが着脱可能に設けられている。   FIG. 4 is a perspective view showing a main part of an outline of the ink jet printer apparatus (liquid ejecting apparatus, liquid droplet ejecting apparatus) 104. As shown in the figure, the above-described ink jet recording type head is composed of ejecting head units 101A and 101B. Built in. The ejection head units 101A and 101B are detachably provided with cartridges 102A and 102B that constitute ink supply means.

また、この噴射ヘッドユニット１０１Ａ、１０１Ｂ自身は、キャリッジ１０３に搭載され、装置本体１０４に取り付けられている。また、このキャリッジ１０３は、キャリッジ軸１０５の軸方向に対し、移動可能に配置されている。   The ejection head units 101 </ b> A and 101 </ b> B themselves are mounted on the carriage 103 and attached to the apparatus main body 104. The carriage 103 is arranged so as to be movable with respect to the axial direction of the carriage shaft 105.

駆動モータ１０６の駆動力が、タイミングベルト１０７を介してキャリッジ１０３に伝達されることで、噴射ヘッドユニット１０１Ａおよび１０１Ｂがキャリッジ軸１０５に沿って移動する。また、当該装置１０４には、キャリッジ軸１０５に沿ってテプラン１０８が設けられ、記録シート（例えば、紙）Ｓが当該テプラン１０８上に搬送される。この記録シートＳに対し、噴射ヘッドユニット１０１Ａ、１０１Ｂからインクを噴射することで印刷がなされる。   When the driving force of the driving motor 106 is transmitted to the carriage 103 via the timing belt 107, the ejection head units 101 </ b> A and 101 </ b> B move along the carriage shaft 105. Further, the apparatus 104 is provided with a Teplan 108 along the carriage shaft 105, and a recording sheet (for example, paper) S is conveyed onto the Teplan 108. Printing is performed on the recording sheet S by ejecting ink from the ejection head units 101A and 101B.

なお、上記実施の形態においては、第１圧電体膜７や第１電極５を残存させたが、これらの膜を第３電極１３等と同様にエッチングしてもよい。   In the above embodiment, the first piezoelectric film 7 and the first electrode 5 are left, but these films may be etched in the same manner as the third electrode 13 and the like.

また、上記実施の形態においては、第１圧電体膜７上に第２電極９とその上部に形成された第２圧電体膜１１とからなる積層膜を形成したが、さらに、この積層膜を複数層配置してもよい。このように、圧電体膜を電極を介して複数積層させる構成とすることで、変位量を大きくすることができる。また、一の圧電体膜の膜厚を低減することができ、変位の際の応力を緩和でき、クラックの発生を低減することができる。   In the above embodiment, the laminated film including the second electrode 9 and the second piezoelectric film 11 formed on the second electrode 9 is formed on the first piezoelectric film 7. Multiple layers may be arranged. Thus, the displacement amount can be increased by adopting a configuration in which a plurality of piezoelectric films are stacked via electrodes. In addition, the film thickness of one piezoelectric film can be reduced, the stress at the time of displacement can be relaxed, and the occurrence of cracks can be reduced.

また、上記実施の形態においては、インクジェット式記録ヘッドを例に説明したが、本発明は広く液体噴射ヘッドに適用可能であり、例えば、液晶ディスプレイ等のカラーフィルタの製造に用いられる色材噴射ヘッド、有機ＥＬディスプレイ、ＦＥＤ（面発光ディスプレイ）等の液体電極材料を噴射する液体噴射ヘッド、バイオチップの製造に用いられる生体有機物噴射ヘッド等にも用いることができる。   In the above embodiment, the ink jet recording head has been described as an example. However, the present invention is widely applicable to a liquid ejecting head. For example, a color material ejecting head used for manufacturing a color filter such as a liquid crystal display. Further, it can be used for a liquid ejecting head for ejecting a liquid electrode material such as an organic EL display and FED (surface emitting display), a bio-organic matter ejecting head used for manufacturing a biochip, and the like.

また、上記発実施の形態を通じて説明された実施例や応用例は、用途に応じて適宜に組み合わせて、又は変更若しくは改良を加えて用いることができ、本発明は上述した実施形態の記載に限定されるものではない。そのような組み合わせ又は変更若しくは改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。   In addition, the examples and application examples described through the above-described embodiments can be used in combination as appropriate according to the application, or can be used with modifications or improvements, and the present invention is limited to the description of the above-described embodiments. Is not to be done. It is apparent from the description of the scope of claims that the embodiments added with such combinations or changes or improvements can be included in the technical scope of the present invention.

本実施の形態のインクジェット記録式ヘッドの製造工程を示す工程断面図である。It is process sectional drawing which shows the manufacturing process of the inkjet recording head of this Embodiment. 本実施の形態のインクジェット記録式ヘッドの製造工程を示す工程断面図である。It is process sectional drawing which shows the manufacturing process of the inkjet recording head of this Embodiment. インクジェット記録式ヘッドの分解斜視図である。It is a disassembled perspective view of an inkjet recording head. インクジェットプリンタ装置の概略を示す要部斜視図である。It is a principal part perspective view which shows the outline of an inkjet printer apparatus.

符号の説明Explanation of symbols

１…基板、１ａ…圧力室、１ｂ…リザーバ、１ｃ…供給口、３…振動板、３ａ…酸化シリコン膜、３ｂ…酸化ジルコニウム膜、５…第１電極、７…第１圧電体膜、９…第２電極、１１…第２圧電体膜、１３…第３電極、２０…ノズルプレート、２０ａ…ノズル孔、３０…保護基板、１０１Ａ、１０１Ｂ…噴射ヘッドユニット、１０２Ａ、１０２Ｂ…カートリッジ、１０３…キャリッジ、１０４…インクジェットプリンタ装置、１０５…キャリッジ軸、１０６…駆動モータ、１０７…タイミングベルト、１０８テプラン、ＰＥ…圧電素子、Ｓ…記録シート   DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 1a ... Pressure chamber, 1b ... Reservoir, 1c ... Supply port, 3 ... Diaphragm, 3a ... Silicon oxide film, 3b ... Zirconium oxide film, 5 ... 1st electrode, 7 ... 1st piezoelectric film, 9 2nd electrode, 11 ... 2nd piezoelectric film, 13 ... 3rd electrode, 20 ... Nozzle plate, 20a ... Nozzle hole, 30 ... Protection substrate, 101A, 101B ... Ejection head unit, 102A, 102B ... Cartridge, 103 ... Carriage, 104 ... Inkjet printer device, 105 ... Carriage shaft, 106 ... Drive motor, 107 ... Timing belt, 108 Teplan, PE ... Piezoelectric element, S ... Recording sheet

Claims (12)

圧電素子に用いられる圧電薄膜であって、
（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする圧電薄膜。 A piezoelectric thin film used for a piezoelectric element,
A piezoelectric thin film containing (Bi, Na, Ba) TiO 3 . 前記圧電薄膜は、さらに、Ｌｉを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3であることを特徴とする請求項１記載の圧電薄膜。 2. The piezoelectric thin film according to claim 1, wherein the piezoelectric thin film is (Bi, Na, Ba, Li) TiO 3 containing Li. 前記圧電薄膜は、さらに、Ｋを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3であることを特徴とする請求項１記載の圧電薄膜。 2. The piezoelectric thin film according to claim 1, wherein the piezoelectric thin film is (Bi, Na, Ba, K) TiO 3 further containing K. 3 . 第１および第２電極との間に形成された圧電体膜を有する圧電素子であって、
前記圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする圧電素子。 A piezoelectric element having a piezoelectric film formed between first and second electrodes,
The piezoelectric element characterized in that the piezoelectric film contains (Bi, Na, Ba) TiO 3 . 基板と、
基板の上方に形成された第１電極と、
前記第１電極の上方に形成された圧電体膜と、
前記圧電体膜の上方に形成された第２電極とその上部に形成された第２圧電体膜とからなる積層膜と、を有する圧電素子であって、
前記積層膜を複数有し、
前記圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする圧電素子。 A substrate,
A first electrode formed above the substrate;
A piezoelectric film formed above the first electrode;
A piezoelectric element having a laminated film comprising a second electrode formed above the piezoelectric film and a second piezoelectric film formed thereon;
A plurality of the laminated films;
The piezoelectric element characterized in that the piezoelectric film contains (Bi, Na, Ba) TiO 3 . 前記圧電体膜は、さらに、Ｌｉを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｌｉ）ＴｉＯ3であることを特徴とする請求項４又は５記載の圧電素子。 6. The piezoelectric element according to claim 4, wherein the piezoelectric film is (Bi, Na, Ba, Li) TiO 3 containing Li. 前記圧電体膜は、さらに、Ｋを含有する（Ｂｉ，Ｎａ，Ｂａ，Ｋ）ＴｉＯ3であることを特徴とする請求項４又は５記載の圧電素子。 6. The piezoelectric element according to claim 4, wherein the piezoelectric film is (Bi, Na, Ba, K) TiO 3 further containing K. 複数の圧力室を有する基板と、
基板の上方に形成された振動板と、
前記振動板の上方に形成された第１電極と、
前記第１電極の上方に形成された第１圧電体膜と、
前記第１圧電体膜の上方に形成された第２電極と、
前記第２電極の上方に形成された第２圧電体膜と、
前記第２圧電体膜の上方に形成された第３電極と、を有し、
前記第１および第２圧電体膜が（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有することを特徴とする液滴噴射ヘッド。 A substrate having a plurality of pressure chambers;
A diaphragm formed above the substrate;
A first electrode formed above the diaphragm;
A first piezoelectric film formed above the first electrode;
A second electrode formed above the first piezoelectric film;
A second piezoelectric film formed above the second electrode;
A third electrode formed above the second piezoelectric film,
The liquid droplet ejecting head, wherein the first and second piezoelectric films contain (Bi, Na, Ba) TiO 3 . 前記第２圧電体膜、第３および第２電極は、前記複数の圧力室毎に分離して形成され、
前記第１圧電体膜および第１電極は、前記複数の圧力室の上方に連続して配置されていることを特徴とする請求項８記載の液滴噴射ヘッド。 The second piezoelectric film, the third and second electrodes are formed separately for each of the plurality of pressure chambers,
The liquid droplet ejecting head according to claim 8, wherein the first piezoelectric film and the first electrode are continuously arranged above the plurality of pressure chambers. 圧電素子を有する液滴噴射ヘッドであって、請求項４乃至７のいずれか一項に記載の圧電素子を有することを特徴とする液滴噴射ヘッド。   A liquid droplet ejecting head having a piezoelectric element, wherein the liquid droplet ejecting head includes the piezoelectric element according to claim 4. 液滴噴射ヘッドを有する液滴噴射装置であって、請求項８乃至１０のいずれか一項に記載の液滴噴射ヘッドを有することを特徴とする液滴噴射装置。   A droplet ejecting apparatus having a droplet ejecting head, wherein the droplet ejecting apparatus includes the droplet ejecting head according to claim 8. 基板の上方に振動板を形成する工程と、
前記振動板の上方に第１電極を形成する工程と、
前記第１電極の上方に、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する第１圧電体膜を形成する工程と、
前記第１圧電体膜の上方に第２電極を形成する工程と、
前記第２電極の上方に、（Ｂｉ，Ｎａ，Ｂａ）ＴｉＯ3を含有する第２圧電体膜を形成する工程と、
前記第２圧電体膜の上方に第３電極を形成する工程と、
前記第３電極、第２圧電体膜および第２電極を前記基板に形成される圧力室の上方に配置されるよう前記第１圧電体膜が露出するまでエッチングする工程と、
を有することを特徴とする液滴噴射ヘッドの形成方法。

Forming a diaphragm above the substrate;
Forming a first electrode above the diaphragm;
Forming a first piezoelectric film containing (Bi, Na, Ba) TiO 3 above the first electrode;
Forming a second electrode above the first piezoelectric film;
Forming a second piezoelectric film containing (Bi, Na, Ba) TiO 3 above the second electrode;
Forming a third electrode above the second piezoelectric film;
Etching the third electrode, the second piezoelectric film, and the second electrode until the first piezoelectric film is exposed so as to be disposed above a pressure chamber formed on the substrate;
A method for forming a liquid droplet ejecting head, comprising:

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