CN104253207A - 压电材料、压电元件、液体喷射头、液体喷射装置、超声波传感器、压电电机以及发电装置 - Google Patents
压电材料、压电元件、液体喷射头、液体喷射装置、超声波传感器、压电电机以及发电装置 Download PDFInfo
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- CN104253207A CN104253207A CN201410120033.XA CN201410120033A CN104253207A CN 104253207 A CN104253207 A CN 104253207A CN 201410120033 A CN201410120033 A CN 201410120033A CN 104253207 A CN104253207 A CN 104253207A
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- piezoelectric
- piezoelectric element
- tio
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 39
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- DJSWDXUOSQTQCP-UHFFFAOYSA-N 2-ethylhexanoic acid;titanium Chemical compound [Ti].CCCCC(CC)C(O)=O DJSWDXUOSQTQCP-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
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- 239000010931 gold Substances 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- JGUAIAMPONKRLK-UHFFFAOYSA-N 2-ethylhexanoic acid;niobium Chemical compound [Nb].CCCCC(CC)C(O)=O JGUAIAMPONKRLK-UHFFFAOYSA-N 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- MERVPLTULGFPOE-UHFFFAOYSA-N 2-ethylhexanoic acid;iron Chemical compound [Fe].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O MERVPLTULGFPOE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 230000003534 oscillatory effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000003826 uniaxial pressing Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
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- B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
- B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
- B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
- B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
- B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
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- B41J2/04—Ink jet characterised by the jet generation process generating single droplets or particles on demand
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Abstract
本发明提供一种压电材料及使用它的压电元件、液体喷射头、液体喷射装置、超声波传感器、压电电机以及发电装置,上述压电材料可减少环境负担,在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高。上述压电材料含有:第1成分,由为菱面体晶且居里温度为Tc1的具有钙钛矿型结构的复合氧化物构成;第2成分,由为菱面体以外的晶体的且居里温度为Tc2的具有钙钛矿型结构的复合氧化物构成;第3成分,由为与上述第2成分相同的晶系且居里温度为Tc3的具有钙钛矿型结构的复合氧化物构成,上述Tc1比上述Tc2高,上述Tc3为上述Tc1以上。
Description
技术领域
本发明涉及在致动器、超声波振荡器等的超声波器件、超声波电机、压力传感器、IR传感器等热释电元件等其他装置上搭载的压电元件等所使用的压电材料、使用它的压电元件、液体喷射头、液体喷射装置、超声波传感器、压电电机以及发电装置。
背景技术
以往,对作为构成致动器、超声波振荡器等的超声波器件、超声波电机、压力传感器、IR传感器等热释电元件等其他装置上搭载的压电元件等的压电体层(压电陶瓷)所使用的压电材料要求高的压电特性,作为代表例,可举出锆钛酸铅(PZT)。
然而,从环境问题的观点考虑,需求一种抑制铅的含量的压电材料。作为这样的非铅系压电材料,有KxNa(1-x)NbO3、(Ba,Na)TiO3等含碱金属的压电材料、BiFeO3-BaTiO3等压电材料。
作为这样的压电材料,已知通过使用准同型相界(MPB:Morphotoropic Phase Boundary)附近的组成,得到大的压电特性。然而,在横轴表示组成、纵轴表示温度的相图中,对于锆钛酸铅(PZT)而言,MPB线与温度轴几乎平行或者与组成轴垂直,但对于非铅系压电材料而言,通常,其MPB相对于温度轴倾斜(例如,参照专利文献1的图1等)。这样MBP线倾斜的情况下,即便根据要求特性选择在特定的温度例如室温下位于MPB上的组成,但若使用环境温度变化则在组成-温度状态图上也会从MPB偏离,所以有如下问题:存在因使用环境温度的变化、使用中的发热等而引起元件的压电特性、介电特性降低的温度区域。
因此,出于在上述相图中使MPB线尽量竖立而使在常温附近压电 特性、介电特性大,并且尽量在高的温度下也可使用的期望,要求一般与压电特性呈反比关系的居里温度(Tc)尽量高的压电材料。
因此,提出了通过层叠多个不同组成的压电材料来改善温度依赖性的技术(参照专利文献2、3等),但存在必须使用多个不同的压电材料这样的问题。
专利文献1:日本特开2009-215111号公报
专利文献2:日本特开2003-277143号公报
专利文献3:日本特开2011-181764号公报
发明内容
如上所述,现在,不存在与PZT相当的非铅系压电材料,迫切期望在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的非铅系压电材料的出现。
应予说明,这样的问题不仅存在于喷墨式记录喷头,同样也存在于喷出油墨以外的液滴的其他液体喷射头,另外,也同样存在于在液体喷射头以外使用的压电元件。
本发明鉴于这样的情况,以提供一种减少环境负担,在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料及使用它的压电元件、液体喷射头、液体喷射装置、超声波传感器、压电电机以及发电装置为目的。
解决上述课题的本发明的方式涉及一种压电材料,其特征在于,含有:第1成分,由为菱面体晶且居里温度为Tc1的具有钙钛矿型结构的复合氧化物构成;第2成分,由为菱面体以外的晶体且居里温度为Tc2的具有钙钛矿型结构的复合氧化物构成;第3成分,由为菱面体以外的晶体但与上述第2成分不同、居里温度为Tc3的具有钙钛矿型结构的复合氧化物构成,上述Tc1比上述Tc2高,上述Tc3为上述Tc1以上。
上述方式中形成的压电材料,其由于不含铅所以能够减少环境负担,在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度 也高。
在此,优选(0.9×Tc1+0.1×Tc2)的值为280℃以下,具有在相图中的MPB线附近的组成,所述相图的横轴表示上述第1成分与上述第1成分和上述第2成分的组成比、纵轴表示温度,该组成的居里温度Tc4为280℃以上。由此,更可靠地形成在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
在此,优选(第2成分+第3成分)相对于(第1成分+第2成分+第3成分)的摩尔比率为0.1~0.9。由此,通过选定各成分,从而能够在广泛的组成范围内实现在使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
另外,优选第3成分相对于(第2成分+第3成分)的摩尔比率为0.05~0.49。由此,通过选定各成分,从而能够在广泛的组成范围内实现在使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
另外,优选上述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,上述第2成分为BaTiO3,上述第3成分为KNbO3。由此,能够更可靠地实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
另外,优选上述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,上述第2成分为(Ba,Ca)TiO3,上述第3成分为(Bi,K)TiO3。由此,能够更可靠地实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
另外,优选上述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,上述第2成分为(Ba,Ca)TiO3,上述第3成分为NaNbO3。由此,能够更可靠地实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
本发明的其他方式涉及一种压电元件,其特征在于,具备由上述方式的压电材料构成的压电体层和设置于上述压电体层的电极。
由此,能够实现因不含铅而可减少环境负担的、在宽的使用环境温度范围内可维持优异的特性的压电元件。
另外,本发明的其他方式涉及一种液体喷射头,其特征在于,具备与喷嘴开口连通的压力产生室以及具备压电体层和设置于该压电体层的电极的压电元件,上述压电体层由上述方式的压电材料构成。
由此,能够实现具备因不含铅而可减少环境负担的、在宽的使用环境温度范围内可维持优异的特性的压电元件的液体喷射头。
另外,本发明的其他方式涉及一种液体喷射装置,其特征在于,具备上述方式的液体喷射头。
由此,能够实现具备下述液体喷射头的液体喷射装置,所述液体喷射头具备因不含铅而可减少环境负担的、在宽的使用环境温度范围内可维持优异的特性的压电元件。
另外,本发明的其他的方式是一种超声波传感器,其特征在于,具备:将通过驱动上述的压电元件而产生的位移向外部传递的振动部和将产生的压力波向外部传递的匹配层。
由此,能够实现具备因不含铅而可减少环境负担的、可在宽的使用环境温度范围内维持优异的特性的压电元件的超声波传感器。
另外,本发明的其他的方式是一种压电电机,其特征在于,至少具备:配置有上述的压电元件的振动体和进行接触的移动体。
由此,能够实现具备因不含铅而可减少环境负担的、可在宽的使用环境温度范围内维持优异的特性的压电元件的压电电机。
另外,本发明的其他的方式是一种发电装置,其特征在于,具备将通过上述的压电元件而生成的电荷从所述电极取出的电极。
由此,能够实现具备因不含铅而可减少环境负担的、可在宽的使用环境温度范围内维持优异的特性的压电元件的发电装置。
附图说明
图1是表示说明本发明的压电材料的相图的一个例子的图。
图2是表示说明本发明的压电材料的相图的一个例子的图。
图3是表示说明本发明的压电材料的相图的一个例子的图。
图4是表示实施方式1涉及的记录喷头的简要构成的分解立体图。
图5是实施方式1涉及的记录喷头的俯视图。
图6是实施方式1涉及的记录喷头的截面图。
图7是表示本发明一个实施方式涉及的记录装置的简要构成的图。
具体实施方式
以下,基于实施方式对本发明进行详细说明。
压电材料
本发明的压电材料含有:第1成分,由在单独组成时为菱面体晶且居里温度为Tc1的具有钙钛矿型结构的复合氧化物构成;第2成分,由单独组成时位菱面体以外的晶体且居里温度为Tc2的具有钙钛矿型结构的复合氧化物构成;第3成分,由具有与上述第2成分相同的钙钛矿型结构的复合氧化物构成且具有由居里温度为Tc3的钙钛矿型结构的复合氧化物构成,上述Tc1比上述Tc2高,上述Tc3为上述Tc1以上,(0.9×Tc1+0.1×Tc2)的值为280℃以下。
本发明通过制成使满足上述条件的第1成分、第2成分、第3成分固溶而成的压电材料,从而能够使在横轴表示上述第1成分相对于上述第1成分和上述第2成分之和的组成比(第1成分/(第1成分+第2成分))、纵轴表示温度的相图中的MPB线几乎垂直地竖立。
在此,第1成分是在单独成分时为菱面体的、居里温度较高的具有钙钛矿型结构的复合氧化物,例如,可以举出添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3、(Bi,La)(Zn,Ti)O3等。
第2成分是菱形以外的晶体即正方晶或斜方晶的、居里温度较低的具有钙钛矿型结构的复合氧化物,可以举出BaTiO3、(Ba,Ca)TiO3、添加了Sr、Li、Sb、Ta中的至少一个元素的(K,Na)NbO3等。
第3成分是在单独成分时为菱面体以外的晶体即正方晶或斜方晶,但与第2成分不同,具有居里温度Tc3为Tc2以上的钙钛矿型结构的复合氧化物,可以举出KNbO3、(Bi,K)TiO3、NaNbO3、NaTaO3等。
在此,在以上述第1成分相对于上述第1成分和上述第2成分的总量的比例(第1成分/(第1成分+第2成分))为横轴、以温度为纵轴的相图中,连接菱面体晶的第1成分的Tc1与菱面体以外例如正方晶的第2成分的Tc2而成的线倾斜,MPB线也倾斜。另外,由于(0.9×Tc1+0.1×Tc2)的值为280℃以下,所以全体的Tc也为280℃以下。因此,对于这样的组成而言,Tc低于与PZT相当的280℃,压电特性、介电特性等随周围的温度大幅度变动,即所谓的温度依赖性变大。
通过在这样的体系中添加满足上述条件的与第2成分晶系相同的菱面体以外的第3成分,从而使第2成分和第3成分的混合体系组成的Tc上升,进而,使在以上述第1成分相对于上述第1成分和上述第2成分的总量的比例(第1成分/(第1成分+第2成分))为横轴、以温度为纵轴的相图中的MPB线成为基本垂直地竖立的状态。因此,通过使用沿MPB线的组成,从而使该组成的居里温度Tc4为280℃以上,能够实现即便使用环境温度变化也能基本恒定地维持特性的压电材料。
因此,本发明的压电材料的组成为使上述第1成分、第2成分和第3成分固溶的组成,具有在横轴表示第1成分与第1成分和第2成分的组成比、纵轴表示温度的相图中的MPB线附近的组成,该组成的居里温度Tc4为280℃以上。
在此,MPB线是不同晶系形成的边界,晶系具有组成依赖性,介电常数、压电常数、杨氏模量具有组成依赖性。因此,对于形成MPB线的组成而言,介电常数、压电常数成为极大值,杨氏模量成为极小值。在本发明中,将介电常数、压电常数的特性在峰值(MPB上的值)的70%以上的范围内的组成区域、杨氏模量的特性在极小值的130%以内的组成区域定义为MPB附近的组成。
在此,优选(第2成分+第3成分)相对于(第1成分+第2成分+第3成分)的摩尔比率为0.1~0.9。这样,通过适当地选定第1成分、第2成分、第3成分,从而能够在广泛的组成范围内发挥上述的效果。
另外,优选第3成分相对于(第2成分+第3成分)的摩尔比率为0.05~0.49。上述第3成分通过添加到居里温度Tc较高的第1成分和居里温度较低的第2成分的组合中而有效发挥作用,从而使全体组成的居里温度Tc4提高到280℃以上且使MPB线几乎垂直地竖立,实现即便使用环境温度变化特性也不会大幅度变化的压电材料。因此,虽然根据组合的组成而添加量会变化,但只要在上述范围内添加,就能发挥有效的作用。
以下示出可适用于本发明的压电材料的第1成分、第2成分以及第3成分的例子。
例如,第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,第2成分为BaTiO3,第3成分为KNbO3。
另外,第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,第2成分为(Ba,Ca)TiO3,第3成分为(Bi,K)TiO3。
另外,第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,第2成分为(Ba,Ca)TiO3,第3成分为NaNbO3。
以下,举出具体例,进一步进行详细说明。
图1中,示出第1成分为添加了Sr的(Bi,Na)TiO3、第2成分为BaTiO3时的以上述第1成分相对于上述第1成分和上述第2成分的总量的比例(第1成分/(第1成分+第2成分))为横轴、以温度为纵轴的相图。此时,作为第1成分的添加了Sr的(Bi,Na)TiO3的居里温度Tc为268℃,作为第2成分的BaTiO3的居里温度为123℃,MPB线m1在添加了Sr的(Bi,Na)TiO3的组成比为0.33~0.70的范围内倾斜。如果将作为第3成分的KNbO3(居里温度Tc3=435℃)以相对于第2成分和第3成分总量为0.40的比例混合到上述体系中,则第2成分和第3成分的组成的居里温度变为310℃。在第1成分相对于第1成分和第2成分总量的比例为横轴的相图中的MPB线M1近乎垂直地竖立,第1 成分仅在0.50~0.70的范围变化。另外,相对于MPB线m1的顶点的居里温度为170℃,MPB线M1的顶点的居里温度Tc4为300℃。由此,能够实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。在此,相图由以菱面体晶构成的组成范围(图中表示为R的范围)和以正方晶(图中表示为T)或斜方晶(图中表示为O)构成的组成范围以及以立方晶构成的组成范围(图中表示为C)构成。
图2中,示出第1成分为添加了Sr的(Bi,Na)TiO3、第2成分为(Ba,Ca)TiO3时的以上述第1成分相对于上述第1成分和上述第2成分的总量的比例(第1成分/(第1成分+第2成分))为横轴、以温度为纵轴的相图。此时,作为第1成分的添加了Sr的(Bi,Na)TiO3为268℃,作为第2成分的(Ba,Ca)TiO3的居里温度为70℃,MPB线m2在添加了Sr的(Bi,Na)TiO3的组成比为0.47~0.80的范围内倾斜。如果将作为第3成分的(Bi,K)TiO3(居里温度Tc3=380℃)以相对于第2成分和第3成分的总量为0.25的比例混合到这样的体系中,则第2成分和第3成分的组成的居里温度变成302℃,在用第2成分和第3成分代替第2成分作为横轴的相图中的MPB线M2近乎垂直地竖立,第1成分的组成比仅在0.57~0.80的范围变化。另外,相对于MPB线m2的顶点的居里温度为110℃,MPB线M1的顶点的居里温度Tc4为285℃。由此,能够实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
图3中,示出第1成分为添加了Sr的(Bi,Na)TiO3、第2成分为(Ba,Ca)TiO3时的以上述第1成分相对于上述第1成分和上述第2成分的总量的比例(第1成分/(第1成分+第2成分))为横轴、以温度为纵轴的相图。此时,作为第1成分的添加了Sr的(Bi,Na)TiO3的居里温度Tc为268℃,作为第2成分的(Ba,Ca)TiO3的居里温度为70℃,MPB线m3在添加了Sr的(Bi,Na)TiO3的组成比为0.4~0.6的范围内倾斜。如果将作为第3成分的NaNbO3(居里温度Tc3=360℃)以相对于第2成分和第3成分的总量为0.2的比例混合到这样的体系中,则第2成分和第3成分的组成的居里温度变成302℃,在以第1成分相对于第1成分和第2成分的总量的比例为横轴的相图中的MPB线M3近乎垂直地竖立,第1成分的组成比仅在0.45~0.60的范围内变化。另 外,相对于MPB线m3的顶点的居里温度为130℃,MPB线M3的顶点的居里温度Tc4为291℃。由此,能够实现在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高的压电材料。
即,作为致动器使用时,压电特性d33的优选范围为100~300pC/N,更优选范围为150~300pC/N。并且,此时,杨氏模量的优选范围为30~80GPa,居里温度Tc的优选范围为70~350℃,更优选范围为100~300℃。并且,介电常数的优选范围为2000以下,更优选范围为100~1000。
另外,作为传感器使用时,e常数的优选范围为3~15C/m2,更优选范围为5~15C/m2。并且,此时,杨氏模量的优选范围为70~150GPa,更优选范围为80~130GPa。并且,居里温度Tc的优选范围为100~350℃,更优选范围为120~300℃。并且,介电常数的优选范围为2000以下,更优选范围为100~800。
压电元件、液体喷射头
图4是表示作为具备本发明的一个实施方式涉及的压电元件的液体喷射头的一个例子的喷墨式记录喷头的简要构成的分解立体图,图5是图4的俯视图,图6是图5的A-A′线截面图。如图4~图6所示,本实施方式的流路形成基板10由单晶硅基板构成,在其一侧的面上形成有由二氧化硅构成的弹性膜50。
在流路形成基板10上沿其宽方向并列设有多个压力产生室12。另外,在流路形成基板10的压力产生室12长度方向外侧的区域形成有连通部13,连通部13与各压力产生室12介由设置于各压力产生室12每个上的油墨供给流路14和连通流路15进行连通。连通部13与后述的保护基板的歧管部31连通从而构成作为各压力产生室12共通的油墨室的歧管的一部分。油墨供给流路14以比压力产生室12更窄的宽度形成,将由连通部13流入压力产生室12的油墨的流路阻力保持恒定。应予说明,本实施方式中,通过从一侧收紧流路的宽度而形成了油墨供给流路14,但也可以从两侧收紧流路的宽度而形成油墨供给流路。另外,也可以不收紧流路的宽度,而是通过从厚度方向收紧而形成油墨供给流路。本实施方式中,在流路形成基板10上设有由压力产生室12、连通部13、油墨供给流路14以及连通流路15形成的液体流路。
另外,在流路形成基板10的开口面侧上通过粘接剂或热熔膜等固定有喷嘴板20,在该喷嘴板20上穿设有与各压力产生室12的与油墨供给流路14相反侧的端部附近连通的喷嘴开口21。应予说明,喷嘴板20例如由玻璃陶瓷、单晶硅基板、不锈钢等形成。
另一方面,在这样的流路形成基板10的与开口面相反的一侧,如上所述形成有弹性膜50,在该弹性膜50上设有由氧化钛等形成的、用来提高弹性膜50等与第1电极60的衬底间的密合性的密合层56。应予说明,在弹性膜50与密合层56之间,根据需要也可以形成由氧化锆等构成的绝缘体膜。
此外,在该密合层56上,层叠形成有第1电极60、作为厚度为2μm以下、优选为0.3~1.5μm的薄膜的压电体层70以及第2电极80,从而构成压电元件300。在此,压电元件300是指包含第1电极60、压电体层70和第2电极80的部分。通常是将压电元件300的任一个电极作为共用电极,将另一个电极和压电体层70在每个压力产生室12中进行图案化而构成。在本实施方式中,将第1电极60作为压电元件300的共用电极,将第2电极80作为压电元件300的独立电极,但根据驱动电路、配线的情况即使将它们相反地设置也没有问题。另外,在此,将压电元件300和通过该压电元件300的驱动而产生位移的振动板合起来称为致动器装置。应予说明,上述的例子中,弹性膜50、密合层56、第1电极60以及根据需要设置的绝缘膜作为振动板发挥作用,但自然不限定于这些,例如也可以不设置弹性膜50、密合层56。另外,也可以压电元件300本身实质上兼作振动板。
在本实施方式中,压电体层70由上述的本发明的压电材料构成。由于上述压电材料在宽的使用环境温度范围内压电特性、介电特性高,并且居里温度也高,所以能够实现在宽的使用环境温度内显示优异的位移特性的压电元件。另外,由于压电材料不含铅,所以能够减少对环境的负担。
在作为这样的压电元件300的独立电极的各第2电极80上连接有例如由金(Au)等形成的引出电极90,该引出电极90从油墨供给流路14侧的端部附近被引出,延伸设置到密合层56上。
在形成有这样的压电元件300的流路形成基板10上,即在第1电极60、密合层56及引出电极90上,介由粘接剂35接合具有构成歧管100的至少一部分的歧管部31的保护基板30。在本实施方式中,该歧管部31在厚度方向贯通保护基板30且在压力产生室12的宽度方向上形成,如上所述,与流路形成基板10的连通部13连通,构成成为各压力产生室12的共通的油墨室的歧管100。另外,也可以将流路形成基板10的连通部13按照每个压力产生室12分割成多个,仅将歧管部31作为歧管。此外,例如也可以在流路形成基板10上仅设置压力产生室12,在介于流路形成基板10和保护基板30之间的部件(例如,弹性膜50、密合层56等)上设置连通歧管100和各压力产生室12的油墨供给流路14。
另外,在保护基板30的与压电元件300对置的区域设置具有不阻碍压电元件300的运动程度的空间的压电元件保持部32。压电元件保持部32只要具有不阻碍压电元件300的运动程度的空间即可,该空间可以被密封也可以不被密封。
作为这样的保护基板30,优选使用与流路形成基板10的热膨胀率大致相同的材料,例如玻璃、陶瓷材料等,在本实施方式中,使用与流路形成基板10相同材料的单晶硅基板来形成。
另外,在保护基板30上设置有在厚度方向贯通保护基板30的贯通孔33。并且,以在贯通孔33内露出从各压电元件300中引出的引出电极90的端部附近的方式设置。
另外,在保护基板30上固定有用于驱动并列设置的压电元件300的驱动电路120。作为该驱动电路120,例如可以使用电路基板、半导体集成电路(IC)等。并且,驱动电路120和引出电极90介由以接合引线等导电性线形成的连接配线121进行电连接。
另外,在这样的保护基板30上接合有由密封膜41和固定板42形成的柔性基板40。在此,密封膜41由刚性低且具有可挠性的材料形成,利用该密封膜41将歧管部31的一个面密封。另外,固定板42由较硬的材料形成。该固定板42的与歧管100对置的区域是在厚度方向完全被除去的开口部43,因此歧管100的一个面仅由具有可挠性的密封膜 41所密封。
在这样的本实施方式的喷墨式记录喷头I中,从与未图示的外部油墨供给装置连接的油墨导入口导入油墨,由油墨填满从歧管100至喷嘴开口21都的内部后,根据来自驱动电路120的记录信号,在与压力产生室12对应的各第1电极60和第2电极80之间施加电压,使弹性膜50、密合层56、第1电极60以及压电体层70发生挠曲变形,从而升高各压力产生室12内的压力,使墨滴从喷嘴开口21喷出。
接下来,对本实施方式的喷墨式记录喷头的压电元件的制造方法的一个例子进行说明。
首先,用热氧化等,在属于硅晶片的流路形成基板用晶片110的表面形成由构成弹性膜50的二氧化硅(SiO2)等构成的二氧化硅膜。接着,用反应性溅射法、热氧化等在弹性膜50(二氧化硅膜)上形成由氧化钛等构成的密合层56。
接下来,在密合层56上形成第1电极60。具体而言,在密合层56上形成由铂、铱、氧化铱或者它们的层叠结构等构成的第1电极60。应予说明,密合层56和第1电极60例如可以采用溅射法、蒸镀法形成。
接着,在第1电极60上层叠压电体层70。压电体层70的制造方法没有特别限定,例如可以使用以下方法来形成压电体层70,即,将使有机金属化合物溶解·分散于溶剂中而成的溶液涂布干燥,再以高温煅烧得到由金属氧化物形成的压电体层70的MOD(Metal-Organic Decomposition)法、溶胶-凝胶法等化学溶液法。另外,压电体层70也可以由其他激光烧蚀法、溅射法、脉冲激光沉积法(PLD法)、CVD法、气溶胶沉积法等形成。
将压电体层70用例如化学涂布法形成时,使用含所希望的元素的2-乙基己酸盐、醋酸盐等作为起始原料。例如,2-乙基己酸铋、2-乙基己酸钡、2-乙基己酸铁、2-乙基己酸钛等。混合各自的正辛烷溶液,以与化学计量比一致的方式调整金属元素的摩尔比,制成前体溶液。接着,将上述前体溶液滴加到事先制成的下部电极上,以500rpm旋转6秒钟后,以3000rpm使基板旋转20秒,利用旋涂法形成压电体膜。接下来, 将基板载置于热板上,在180℃下干燥2分钟。接着,将基板载置于热板上,在350℃下进行2分钟脱脂。反复进行2次该溶液涂布~脱脂工序后,在氧气氛中,用RTA装置,在750℃下进行5分钟煅烧。接着,可以反复进行5次上述工序,利用总计10次的涂布,从而可形成压电体层70。
在这样形成压电体层70后,在压电体层70上,用溅射法等形成由铂等形成的第2电极80,在与各压力产生室12对置的区域将压电体层70和第2电极80同时进行图案化,形成由第1电极60、压电体层70和第2电极80构成的压电元件300。应予说明,压电体层70和第2电极80的图案化,可以通过介由已形成为规定形状的抗蚀剂(未图示)进行干式蚀刻而一并实施。其后,也可以根据需要例如在600℃~800℃的温度区域进行退火。由此,可以形成压电体层70与第1电极60、第2电极80的良好界面,且可以改善压电体层70的结晶性。
接下来,在流路形成基板用晶片的整个面上形成例如由金(Au)等形成的引出电极90后,例如介由以抗蚀剂等形成的掩模图案对每个压电元件300图案化。
接下来,在流路形成基板用晶片的压电元件300侧,介由粘接剂35接合多个属于硅晶片的成为保护基板30的保护基板用晶片,然后将流路形成基板用晶片薄化到规定厚度。
接下来,在流路形成基板用晶片上,重新形成掩模膜,以规定形状进行图案化。
然后,通过将流路形成基板用晶片,介由掩模膜使用KOH等碱溶液进行各向异性蚀刻(湿式蚀刻),从而形成与压电元件300对应的压力产生室12、连通部13、油墨供给流路14以及连通路15等。
其后,例如利用划片机等将流路形成基板用晶片和保护基板用晶片的外边缘部的不需要部分切断而除去。接着,除去流路形成基板用晶片的与保护基板用晶片相反侧的面上的掩模膜后,接合穿设有喷嘴开口21的喷嘴板20,并且在保护基板用晶片上接合柔性基板40,将流路形成基板用晶片等分割成如图4所示的一个芯片尺寸的流路形成基板10等, 由此得到本实施方式的喷墨式记录喷头I。
实施例1
选定添加了Sr的(Bi0.5,Na0.5)TiO3作为第1成分,选定BaTiO3作为第2成分,选定KNbO3作为第3成分,如下形成三者的摩尔比为0.56:0.39:0.26的组成的压电材料。
作为起始原料,将2-乙基己酸铋、2-乙基己酸钠、2-乙基己酸钛、2-乙基己酸钡、2-乙基己酸钾、2-乙基己酸铌、2-乙基己酸锶各自的正辛烷溶液以与上述组成的化学计量比一致的方式调整金属元素的摩尔比而混合,制成前体溶液。
将这样的前体溶液滴加到事先制成的下部电极上,以500rpm旋转6秒钟后,以3000rpm使基板旋转20秒,利用旋涂法形成压电体膜。接下来,将基板载置于热板上,在180℃下干燥2分钟。接着,将基板载置于热板上,在350℃下进行2分钟脱脂。反复2次该溶液涂布~脱脂工序后,在氧气氛中,用RTA装置,在750℃下进行5分钟煅烧。接着,反复5次上述的工序,利用总计10次的涂布形成压电体层。
采用使用了这样的压电体层的压电元件构成上述结构的喷头。上述压电元件的d33为300pC/N,杨氏模量为55GPa。另外,居里温度为290℃。与此相对,不添加第3成分时,d33为100pC/N,杨氏模量为100GPa左右。另外,居里温度为190℃。因此,可容易预料到构成使用了这样的压电材料的压电元件,特别是构成致动器时,获得大的位移。
如图1明确所示,通过加入第3成分而居里温度从170℃上升到300℃。该300℃的值与被称为所谓硬质材料的PZT系的居里温度的值相等。以往一直认为高的居里温度和高的压电特性无法兼得,但根据本发明,能够兼得与Pb系同样高的居里温度和高的压电特性。通常环境温度位于居里温度附近时,压电特性、介电特性的温度依赖性急剧升高,随着环境温度从居里温度附近移至低温侧,压电特性和介电特性的温度依赖性通常变缓慢。因此,对于一般在室温附近具有驱动环境温度的装置而言,由于具有高的居里温度的压电材料能保障稳定的特性,所以适合。
实施例2
选定添加了Sr的(Bi0.5,Na0.5)TiO3作为第1成分,选定(Ba0.8,Ca0.2)TiO3作为第2成分,选定(Bi0.5,K0.5)TiO3作为第3成分,如下形成三者的摩尔比为0.53:0.32:0.21的组成的压电材料。
作为起始原料,将2-乙基己酸铋、2-乙基己酸钠、2-乙基己酸钛、2-乙基己酸钡、2-乙基己酸钙、2-乙基己酸钾、2-乙基己酸锶各自的正辛烷溶液以与上述组成的化学计量比一致的方式调整金属元素的摩尔比而混合,制成前体溶液。
将这样的前体溶液滴加到事先制成的下部电极上,以500rpm旋转6秒钟后,以3000rpm使基板旋转20秒,利用旋涂法形成压电体膜。接下来,将基板载置于热板上,在180℃下干燥2分钟。接着,将基板载置于热板上,在350℃下进行2分钟脱脂。反复2次该溶液涂布~脱脂工序后,在氧气氛中,用RTA装置,在750℃下进行5分钟煅烧。接着,反复5次上述的工序,利用总计10次的涂布形成压电体层。
采用使用了这样的压电体层的压电元件构成上述结构的喷头。上述压电元件的d33为250pC/N,杨氏模量为70GPa。另外,居里温度为285℃。与此相对,不添加第3成分时,d33为150pC/N,杨氏模量为97GPa左右。另外,居里温度为110℃。因此,可容易预料到构成使用了这样的压电材料的压电元件,特别是构成致动器时,获得大的位移。
实施例3
选定添加了Sr的(Bi0.5,Na0.5)TiO3作为第1成分,选定(Ba0.8,Ca0.2)TiO3作为第2成分,选定NaNbO3作为第3成分,如下形成三者的摩尔比为0.40:0.48:0.12的组成的压电材料。
作为起始原料,将2-乙基己酸铋、2-乙基己酸钠、2-乙基己酸钛、2-乙基己酸钡、2-乙基己酸钙、2-乙基己酸铌、2-乙基己酸锶各自的正辛烷溶液以与上述组成的化学计量比一致的方式调整金属元素的摩尔比而混合,制成前体溶液。
将这样的前体溶液滴加到事先制成的下部电极上,以500rpm旋转 6秒钟后,以3000rpm使基板旋转20秒,利用旋涂法形成压电体膜。接下来,将基板载置于热板上,在180℃下干燥2分钟。接着,将基板载置于热板上,在350℃下进行2分钟脱脂。反复2次该溶液涂布~脱脂工序后,在氧气氛中,用RTA装置,在750℃下进行5分钟煅烧。接着,反复5次上述的工序,利用总计10次的涂布形成压电体层。
采用使用了这样的压电体层的压电元件构成上述结构的喷头。上述压电元件的d33为235pC/N,杨氏模量为75GPa。另外,居里温度为291℃。与此相对,不添加第3成分时,d33为150pC/N,杨氏模量为97GPa左右。另外,居里温度为130℃。因此,可容易预料到构成使用了这样的压电材料的压电元件,特别是构成致动器时,获得大的位移。
关于压电材料的其他的实施方式
以上,说明了关于本发明的压电材料的一个实施方式,但本发明的压电材料的基本构成不限于上述实施方式。
表1记载了构成钙钛矿型结晶(ABO3:A和B为金属元素)的组成(A位和B位)和其晶系及其居里温度Tc。由于MPB能够以不同晶系的组合来形成,所以即便是以下的组合也能够获得压电性能的提高和居里温度Tc的提高。
I 正方晶系和斜方晶系
II 正方晶系和单斜晶系
III 斜方晶系和单斜晶系
因此,以能够实现不同晶系的组合的方式,可以从表1中任意选择。此时,通过调整添加剂及其添加量,能够将Tc1、Tc2、Tc3包括在技术方案的范围内。以下列举作为添加剂适当的元素且表1中记载的元素以外的元素。
Mn、Ge、Si、B、Cu、Ag。
表1组成和Tc、晶系
*T:Tetragonal正方晶系 *M:Monoclinic单斜晶系
*R:Rhombohedral菱面体晶系 *O:Orthorhombic斜方晶系
其他的实施方式
以上,说明了本发明的一个实施方式,但本发明的基本的构成不限于上述实施方式。例如,在上述实施方式中,作为流路形成基板10,例示了单晶硅基板,但没有特别限定,例如,可以使用SOI基板、玻璃等材料。
此外,在上述实施方式中,例示了在基板(流路形成基板10)上依次层叠第1电极60、压电体层70以及第2电极80而成的压电元件300,但没有特别限定,例如,也可以将本发明应用于使压电材料和电极形成 材料交互层叠而在轴向伸缩的纵振动型的压电元件。
压电体层可以不是如上所述的薄膜,可以形成为块体。由块体形成时,作为起始原料,使用碳酸盐或氧化物。例如,K2CO3、Na2CO3、以及Nb2O5等。将这些起始原料以与化学计量比一致的方式称取,使用球磨机在乙醇中进行湿式混合。将得到的混合物干燥后,在700℃下焙烧3h。向这些焙烧粉中适量加入作为粘结剂的PVA,使用乳钵粉碎混合,通过150目的筛进行粒度调整,用单轴冲压装置将得到的粉体成形为圆板状的颗粒。接下来,将成型的颗粒和剩余的焙烧粉放入坩埚中在1100℃下烧结3h,得到圆板状的氧化物。接着,对得到的圆板状氧化物的两面进行研磨调整表面,在其上涂布银浆料并烧结,从而能够得到具备银电极的压电体。应予说明,在这样的块体的制造中,作为起始原料,可以举出碳酸钡、氧化钛、氧化铋、氧化锡、氧化铁、氧化锆、氧化镧、碳酸锂等。
另外,这些实施方式的喷墨式记录喷头构成具备与墨盒等连通的油墨流路的记录喷头单元的一部分,搭载于喷墨式记录装置。图7是表示该喷墨式记录装置的一个例子的示意图。
如图7所示,具有喷墨式记录喷头I的记录喷头单元1A和1B可装卸地设置有构成油墨供给装置的墨盒2A和2B并搭载有该记录喷头单元1A和1B的托架3被设置成在安装于装置主体4的托架轴5上沿轴向自由移动。该记录喷头单元1A和1B例如分别喷出黑色油墨组合物和彩色油墨组合物。
而且,驱动电机6的驱动力介由未图示的多个齿轮和同步带7传递到托架3上,从而搭载记录喷头单元1A和1B的托架3沿托架轴5移动。另一方面,在装置主体4上沿托架轴5设有压板8,利用未图示的供纸辊等将供纸的纸等作为记录介质的记录片S卷挂输送至压板8。
在图7所示的例子中,喷墨式记录喷头单元1A、1B分别具有1个喷墨式记录喷头I,但没有特别限定,例如,1个喷墨式记录喷头单元1A或1B可以具有2个以上的喷墨式记录喷头。
应予说明,在上述的实施方式中,举出喷墨式记录喷头作为液体喷 射头的一个例子进行了说明,但本发明广泛地将全部液体喷射头作为对象,因此自然也适用于喷射油墨以外液体的液体喷射头。作为其他的液体喷射头,例如可举出打印机等图像记录装置所使用的各种记录喷头,制造液晶显示器等的滤色器时使用的色料喷射头,有机EL显示器、FED(场致电子发射显示器)等的电极形成中所使用的电极材料喷射头,生物芯片制造中所使用的生物体有机物喷射头等。
(超声波传感器和压电电机)
本发明的压电元件因显示良好的绝缘性和压电特性,所以如上所述可应用于以喷墨式记录喷头为代表的液体喷射头的压电元件,但并不局限于此。本发明涉及的压电元件因表示优异的位移特性,所以并不局限于以喷墨式记录喷头为代表的液体喷射头,可搭载于液体喷射装置、超声波传感器、压电电机、超音波电机、压电变压器、振动式除尘装置、压力-电转换机、超音波发射机、压力传感器、加速度传感器等中而很好地使用。
(发电装置)
另外,本发明涉及的压电元件显示良好的能量-电转换能力,所以可以搭载于发电装置中而很好地使用。作为发电装置可举出利用压力-电转换效果的发电装置、使用基于光的电子激发(光电动势)的发电装置、使用基于热的电子激发(热电动势)的发电装置、利用振动的发电装置等。
并且,本发明涉及压电元件还可以很好地应用于红外线检测器、太赫兹检测器、温度传感器、热敏传感器等的热释电设备、铁电体存储器等的铁电体元件中。
符号说明
I 喷墨式记录喷头(液体喷射头)、10 流路形成基板、12 压力产生室、13 连通部、14 油墨供给流路、20 喷嘴板、21 喷嘴开口、30 保护基板、31 歧管部、32 压电元件保持部、40 柔性基板、50弹性膜、60 第1电极、70 压电体层、80 第2电极、90 引出电极、100 歧管、120 驱动电路、300 压电元件
Claims (13)
1.一种压电材料,其特征在于,含有:
第1成分,由为菱面体晶且居里温度为Tc1的具有钙钛矿型结构的复合氧化物构成;
第2成分,由为菱面体以外的晶体且居里温度为Tc2的具有钙钛矿型结构的复合氧化物构成;
第3成分,由为与所述第2成分相同的晶系且居里温度为Tc3的具有钙钛矿型结构的复合氧化物构成,
所述Tc1比所述Tc2高,所述Tc3为所述Tc1以上。
2.根据权利要求1所述的压电材料,其特征在于,
(0.9×Tc1+0.1×Tc2)的值为280℃以下,
具有在以所述第1成分与所述第1成分和所述第2成分的组成比即第1成分/(第1成分+第2成分)为横轴、以温度为纵轴的相图中位于MPB线附近的组成,该组成的居里温度Tc4为280℃以上。
3.根据权利要求1或2所述的压电材料,其特征在于,(第2成分+第3成分)相对于(第1成分+第2成分+第3成分)的摩尔比率为0.1~0.9。
4.根据权利要求1~3中任一项所述的压电材料,其特征在于,第3成分相对于(第2成分+第3成分)的摩尔比率为0.05~0.49。
5.根据权利要求1~4中任一项所述的压电材料,其特征在于,所述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,所述第2成分为BaTiO3,所述第3成分为KNbO3。
6.根据权利要求1~4中任一项所述的压电材料,其特征在于,所述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,所述第2成分为(Ba,Ca)TiO3,所述第3成分为(Bi,K)TiO3。
7.根据权利要求1~4中任一项所述的压电材料,其特征在于,所述第1成分为添加了选自Sr、Li和Ca中的至少1种的(Bi,Na)TiO3,所述第2成分为(Ba,Ca)TiO3,所述第3成分为NaNbO3。
8.一种压电元件,其特征在于,具备由权利要求1~7中任一项所述的压电材料构成的压电体层和设置于所述压电体层的电极。
9.一种液体喷射头,其特征在于,具备压电元件和与喷嘴开口连通的压力产生室,所述压电元件具备压电体层和设置于该压电体层的电极,所述压电体层由权利要求1~7中任一项所述的压电材料构成。
10.一种液体喷射装置,其特征在于,具备权利要求9所述的液体喷射头。
11.一种超声波传感器,其特征在于,具备:将通过驱动权利要求8所述的压电元件而产生的位移向外部传递的振动部和将产生的压力波向外部传递的匹配层。
12.一种压电电机,其特征在于,至少具备:配置有权利要求8所述的压电元件的振动体和进行接触的移动体。
13.一种发电装置,其特征在于,具备将通过权利要求8所述的压电元件而生成的电荷从所述电极取出的电极。
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