JP2003012371A - Piezoelecrtic ceramic and piezoelectric element - Google Patents
Piezoelecrtic ceramic and piezoelectric elementInfo
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- JP2003012371A JP2003012371A JP2001197120A JP2001197120A JP2003012371A JP 2003012371 A JP2003012371 A JP 2003012371A JP 2001197120 A JP2001197120 A JP 2001197120A JP 2001197120 A JP2001197120 A JP 2001197120A JP 2003012371 A JP2003012371 A JP 2003012371A
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- piezoelectric ceramic
- coupling coefficient
- piezoelectric
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- electromechanical coupling
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、圧電磁器および圧
電素子に関し、特に、圧電共振子および発振子に好適に
用いられる圧電磁器および圧電素子に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic and a piezoelectric element, and more particularly to a piezoelectric ceramic and a piezoelectric element suitable for use in a piezoelectric resonator and an oscillator.
【０００２】[0002]
【従来技術】近年、鉛を含有せず、高い圧電性を示すセ
ラミック材料として、ニオブ酸アルカリ系の圧電磁器が
注目されている。2. Description of the Related Art In recent years, an alkali niobate-based piezoelectric ceramic has attracted attention as a ceramic material that does not contain lead and exhibits high piezoelectricity.
【０００３】このニオブ酸アルカリ系の酸化物の中にお
いて、ニオブ酸ナトリウム（ＮａＮｂＯ3）は、ぺロブ
スカイト（ＡＢＯ3）型に分類される酸化物であるが、
例えば、Ｊａｐａｎ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌ
ｉｅｄ Ｐｈｙｓｉｃｓ， ｐ．３２２１， ｖｏｌ．
３１， １９９２に記載されているように、それ自身で
は、−１３３℃付近よりも低い温度下でのみ強誘電性を
示し、圧電共振子および発振子用材料の一般的な使用温
度である−２０〜８０℃の範囲においては圧電性を示さ
ず、圧電材料としての利用ができない。Among these alkaline niobate oxides, sodium niobate (NaNbO 3 ) is an oxide classified into the perovskite (ABO 3 ) type.
For example, Japan Journal of Appl
ied Physics, p. 3221, vol.
31 and 1992, it exhibits ferroelectricity only at a temperature lower than around -133 ° C, which is a general operating temperature of materials for piezoelectric resonators and oscillators. In the range of -80 ° C, it does not exhibit piezoelectricity and cannot be used as a piezoelectric material.
【０００４】また、Ｊ．Ｐｈｙｓ：Ｃｏｎｄｅｎｓ．Ｍ
ａｔｔｅｒ，ｐ６８３３，ｖｏｌ．６、１９９４．に
は、Ｎａの一部をＭｎで置換したニオブ酸ナトリウム
（ＮａＮｂＯ3）が開示されているが、その組成では圧
電特性を示さないことが開示されている。In addition, J. Phys: Condens. M
atter, p6833, vol. 6, 1994. Discloses sodium niobate (NaNbO 3 ) in which a part of Na is replaced with Mn, but it is disclosed that its composition does not show piezoelectric characteristics.
【０００５】しかし、ＮａＮｂＯ3に対し、Ｂａ0.5Ｎｂ
Ｏ3やＳｒ0.5ＮｂＯ3などの副成分を含有させると、圧
電性を示すようになることが、例えば、特開平９−１６
５２６２号公報の中に記載されている。このようなＮａ
ＮｂＯ3系の圧電セラミックスは、比誘電率が低く、電
気機械結合係数が高く、かつ、機械的品質係数が比較的
高いという特徴を有している。However, with respect to NaNbO 3 , Ba 0.5 Nb
When an auxiliary component such as O 3 or Sr 0.5 NbO 3 is contained, piezoelectric properties may be exhibited, for example, as disclosed in JP-A-9-16.
It is described in Japanese Patent No. 5262. Such Na
NbO 3 -based piezoelectric ceramics are characterized by a low relative permittivity, a high electromechanical coupling coefficient, and a relatively high mechanical quality coefficient.
【０００６】一方、例えば、特開昭５７−２９３９６号
公報に開示されるように、ＫxＮａyＬｉzＮｂＯ3系セラ
ミックスは、キュリー温度が高く、比誘電率が低く、高
い電気機械結合係数を有すると同時に、機械的品質係数
が低いという特徴を示す圧電磁器であり、圧電共振子や
発振子用材料としての利用が考えられている。On the other hand, as disclosed in, for example, Japanese Patent Application Laid-Open No. 57-29396, K x Na y Li z NbO 3 ceramics has a high Curie temperature, a low relative dielectric constant, and a high electromechanical coupling coefficient. It is a piezoelectric ceramic which has the characteristics of low mechanical quality coefficient at the same time, and is considered to be used as a material for piezoelectric resonators and oscillators.
【０００７】[0007]
【発明が解決しようとする課題】しかし、従来のＮａＮ
ｂＯ3を主成分とする圧電セラミックスやＫxＮａyＬｉz
ＮｂＯ3系セラミックスは、キュリー温度が高く、比誘
電率が低く、高い電気機械結合係数を示すものの、共振
周波数の温度依存性が大きいため、高い精度が要求され
るフィルタ・発振子用材料などの用途には不向きである
という問題があった。[Problems to be Solved by the Invention] However, conventional NaN
Piezoelectric ceramics mainly composed of bO 3 and K x Na y Li z
NbO 3 -based ceramics have a high Curie temperature, a low relative permittivity, and a high electromechanical coupling coefficient, but have a large temperature dependence of the resonance frequency, so that high accuracy is required for materials such as filters and resonators. There was a problem that it was not suitable for use.
【０００８】本発明は、特に、厚み滑りモードを用いた
場合において、電気機械結合係数が高く、共振周波数の
温度依存性が小さい圧電磁器および圧電素子を提供する
ことを目的とする。An object of the present invention is to provide a piezoelectric ceramic and a piezoelectric element which have a high electromechanical coupling coefficient and a small temperature dependence of the resonance frequency particularly when the thickness sliding mode is used.
【０００９】[0009]
【課題を解決するための手段】本発明の圧電磁器は、Ｎ
ａＮｂＯ3を主成分とするペロブスカイト型の結晶粒子
からなり、Ａサイトを占めるＮａの一部が、（Ｂｉ1/2
Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）の
うち少なくとも１種とＭｎで置換され、Ｂサイトを占め
るＮｂの一部が少なくともＳｉで置換されていることを
特徴とする。さらには、Ｎｂの一部がＬｉで置換されて
いることが望ましい。The piezoelectric ceramic according to the present invention has an N
Part of Na occupying the A site, which is composed of perovskite type crystal particles containing aNbO 3 as a main component, is (Bi 1/2
At least one of K 1/2 ), (Bi 1/2 Na 1/2 ), and (Bi 1/2 Li 1/2 ) is substituted with Mn, and a part of Nb occupying the B site is at least Si. It is characterized by being replaced. Furthermore, it is desirable that a part of Nb is replaced with Li.
【００１０】また、本発明は、金属元素のモル比による
組成を（１−ｘ）Ｎａy（Ｎｂ1-aＳｉa）Ｏ3＋ｘＭ
y（Ｎｂ1-bＬｉb）Ｏf（ただし、Ｍは（Ｂｉ
1/2Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）
のうち少なくとも１種とＭｎ、ｆは任意）とした時、前
記ａ、ｂ、ｘ，ｙが、
０．００２≦ａ≦０．０５
０≦ｂ≦１
０．００５≦ｘ≦０．０５
０．９５≦ｙ≦１
を満足することが望ましい。In the present invention, the composition based on the molar ratio of metal elements is (1-x) Na y (Nb 1-a Si a ) O 3 + xM.
y (Nb 1-b Li b ) O f (where M is (Bi
1/2 K 1/2 ), (Bi 1/2 Na 1/2 ), (Bi 1/2 Li 1/2 ).
At least one of them and Mn and f are arbitrary), the above a, b, x, y are 0.002 ≦ a ≦ 0.05 0 ≦ b ≦ 1 0.005 ≦ x ≦ 0.05 0 It is desirable to satisfy 0.95 ≦ y ≦ 1.
【００１１】このような構成にすることにより、特に、
厚み滑りモードを用いた場合の電気機械結合係数が高
く、共振周波数の温度依存性が小さい圧電磁器を得るこ
とができる。With this structure, in particular,
It is possible to obtain a piezoelectric ceramic having a high electromechanical coupling coefficient and a small temperature dependence of the resonance frequency when the thickness sliding mode is used.
【００１２】また、本発明の圧電素子は、上記した圧電
磁器の両面に電極を形成してなるものである。そして、
この圧電素子では、厚み滑りモードを用いた場合の電気
機械結合係数が高く、共振周波数の温度依存性が小さい
ことから、圧電共振子や発振子として優れた特性を発揮
できる。Further, the piezoelectric element of the present invention is formed by forming electrodes on both surfaces of the above-mentioned piezoelectric ceramic. And
This piezoelectric element has a high electromechanical coupling coefficient when the thickness-sliding mode is used and has a small temperature dependence of the resonance frequency, and therefore can exhibit excellent characteristics as a piezoelectric resonator or an oscillator.
【００１３】[0013]
【発明の実施の形態】本発明の圧電磁器は、ＮａＮｂＯ
3を主成分とするペロブスカイト型の結晶粒子からな
り、Ａサイトを占めるＮａの一部が、（Ｂｉ
1/2Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）
のうち少なくとも１種とＭｎ、Ｂサイトを占めるＮｂの
一部が、少なくともＳｉで置換されていることを特徴と
する。BEST MODE FOR CARRYING OUT THE INVENTION The piezoelectric ceramic of the present invention is NaNbO.
3 consisting of perovskite type crystal particles as a main component, and a part of Na occupying the A site is (Bi
1/2 K 1/2 ), (Bi 1/2 Na 1/2 ), (Bi 1/2 Li 1/2 ).
Among them, at least one of them, and part of Nb occupying Mn and B sites are at least replaced with Si.
【００１４】従来から、ＮａＮｂＯ3に対し、Ｂａ0.5Ｎ
ｂＯ3やＳｒ0.5ＮｂＯ3などの副成分を含有させると、
比較的高い電気機械結合係数を示すようになるが、共振
周波数の温度依存性が劣っており、高い精度が要求され
るフィルタ・発振子用材料などの用途には不向きである
ことが知られている。Conventionally, Ba 0.5 N against NaNbO 3
When an auxiliary component such as bO 3 or Sr 0.5 NbO 3 is contained,
It has a relatively high electromechanical coupling coefficient, but its temperature dependence of the resonance frequency is poor, and it is known to be unsuitable for applications such as filters and resonator materials that require high accuracy. There is.
【００１５】本発明では、ＮａＮｂＯ3の結晶粒子にお
いて、Ａサイトを占めるＮａの一部を（Ｂｉ
1/2Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）
のうちの少なくとも１種とＭｎで置換し、Ｂサイトを占
めるＮｂの一部を少なくともＳｉで置換することによっ
て、特に、厚み滑りモードを用いた場合の電気機械結合
係数を向上し、かつ、共振周波数の温度依存性が小さい
圧電磁器を得ることができる。また、Ｎｂの一部をＬｉ
で置換することにより、電気機械結合係数を向上させ、
磁器の焼結性を高めることができる。In the present invention, in the crystal particles of NaNbO 3 , a part of Na occupying the A site is (Bi
1/2 K 1/2 ), (Bi 1/2 Na 1/2 ), (Bi 1/2 Li 1/2 ).
By substituting at least one of the above with Mn and substituting at least Si with at least part of Nb occupying the B site, the electromechanical coupling coefficient is improved particularly when the thickness sliding mode is used, and resonance It is possible to obtain a piezoelectric ceramic whose frequency dependence of temperature is small. In addition, a part of Nb is Li
To improve the electromechanical coupling coefficient,
The sinterability of porcelain can be improved.
【００１６】また、磁器の結晶粒子は通常は球形状であ
るが、略立方体状の結晶粒子から構成されている。結晶
粒子としては１〜１５μｍの粒子径のものが分散した磁
器の構造を有している。Further, the crystal grains of the porcelain are usually spherical, but are composed of substantially cubic crystal grains. The crystal particles have a porcelain structure in which particles having a particle diameter of 1 to 15 μm are dispersed.
【００１７】また、本発明の圧電磁器では、金属元素と
して少なくとも、Ｎａ、ＳｉおよびＮｂを含有し、これ
らの金属元素のモル比による組成を（１−ｘ）Ｎａ
y（Ｎｂ1-aＳｉa）Ｏ3＋ｘＭy（Ｎｂ1-bＬｉb）Ｏf（た
だし、Ｍは（Ｂｉ1/2Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、
（Ｂｉ1/2Ｌｉ1/2）のうちの少なくとも１種とＭｎ、ｆ
は任意）とした時、前記ａ、ｂ、ｘ，ｙが、
０．００２≦ａ≦０．０５
０≦ｂ≦１
０．００５≦ｘ≦０．０５
０．９５≦ｙ≦１
を満足するものである。In the piezoelectric ceramic of the present invention, at least Na, Si and Nb are contained as metal elements, and the composition based on the molar ratio of these metal elements is (1-x) Na.
y (Nb 1-a Si a ) O 3 + xM y (Nb 1-b Li b) O f ( although, M is (Bi 1/2 K 1/2), ( Bi 1/2 Na 1/2),
At least one of (Bi 1/2 Li 1/2 ) and Mn, f
Is arbitrary), the above a, b, x, y satisfy 0.002 ≦ a ≦ 0.05 0 ≦ b ≦ 1 0.005 ≦ x ≦ 0.05 0.95 ≦ y ≦ 1 It is a thing.
【００１８】前記構成において、ＮｂのＳｉによる置換
量ａを０．００２〜０．０５の範囲としたのは、電気機
械結合係数を向上できるからであり、ａが０．００２よ
りも小さい場合には電気機械結合係数を高くする効果が
ほとんどなく、また、０．０５よりも大きいと磁器の粒
界部において第２相が顕著に発生し、電気機械結合係数
を低下させるからである。電気機械結合係数を高くする
という観点から、ａは０．００５〜０．０３の範囲とす
ることが望ましく、特に、第２相の発生が少なく、電気
機械結合係数が高いという理由から、ａは０．０１〜
０．０２の範囲とすることがより望ましい。In the above structure, the reason why the substitution amount a of Nb by Si is set in the range of 0.002 to 0.05 is that the electromechanical coupling coefficient can be improved, and when a is smaller than 0.002. This is because there is almost no effect of increasing the electromechanical coupling coefficient, and when it is larger than 0.05, the second phase remarkably occurs in the grain boundary portion of the porcelain, which lowers the electromechanical coupling coefficient. From the viewpoint of increasing the electromechanical coupling coefficient, it is desirable that a is in the range of 0.005 to 0.03. In particular, since a second phase is rarely generated and the electromechanical coupling coefficient is high, a is 0.01 ~
The range of 0.02 is more desirable.
【００１９】そして、ＳｉはＢサイトを占めるＮｂの一
部を置換しているが、Ｓｉの含有量が１．５原子％を越
えると、磁器の粒界部に第２相が多く発生し始めるが、
５原子％までの範囲であれば圧電特性に優れた圧電磁器
を得ることができる。Si replaces a part of Nb occupying the B site, but when the Si content exceeds 1.5 atomic%, a large amount of second phase begins to occur at the grain boundary portion of the porcelain. But,
A piezoelectric ceramic excellent in piezoelectric characteristics can be obtained in the range of up to 5 atomic%.
【００２０】また、前記構成のＭy（Ｎｂ1-bＬｉb）Ｏf
（ただし、Ｍは、（Ｂｉ1/2Ｋ1/2）、（Ｂｉ1/2Ｎ
ａ1/2）、（Ｂｉ1/2Ｌｉ1/2）のうち少なくとも１種に
おいて、ＬｉとＮｂの比率を表わすｂの範囲は０〜１の
範囲にあれば良く、構成中の（Ｎｂ 1-bＬｉb）は、例え
ば、（Ｌｉ1/4Ｎｂ3/4）、（Ｌｉ1/2Ｎｂ1/2）などで表
わすことが出来る。電気機械結合係数の向上効果が高
く、磁器の焼結性に優れるという観点から、ｂは０〜
０．５の範囲であることが望ましい。Further, the above-mentioned My(Nb1-bLib) Of
(However, M is (Bi1/2K1/2), (Bi1/2N
a1/2), (Bi1/2Li1/2) To at least one
In the above, the range of b representing the ratio of Li and Nb is 0 to 1
If it is within the range, (Nb 1-bLib) Is an analogy
For example, (Li1/4Nb3/4), (Li1/2Nb1/2), Etc.
I can forget. Highly effective in improving the electromechanical coupling coefficient
From the viewpoint of excellent porcelain sinterability, b is 0 to
A range of 0.5 is desirable.
【００２１】さらに、前記構成について、Ｍy（Ｎｂ1-b
Ｌｉb）Ｏf（ただし、Ｍは、（Ｂｉ 1/2Ｋ1/2）、（Ｂｉ
1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）のうち少なくとも１
種とＭｎ）の含有量ｘを、０．００５〜０．０５の範囲
としたのは、電気機械結合係数を向上できるからであ
り、ｘが０．００５よりも小さいと電気機械結合係数の
向上効果がほとんど認められず、また、ｘが０．０５よ
りも大きくなると、電気機械結合係数が顕著に低下し実
用に供さなくなるからである。Further, regarding the above-mentioned configuration, My(Nb1-b
Lib) Of(However, M is (Bi 1/2K1/2), (Bi
1/2Na1/2), (Bi1/2Li1/2) At least 1
Seed and Mn) content x in the range of 0.005-0.05
The reason is that the electromechanical coupling coefficient can be improved.
If x is smaller than 0.005, the electromechanical coupling coefficient
Almost no improvement effect is recognized, and x is 0.05
The electromechanical coupling coefficient decreases significantly when the
This is because it will no longer be available for use.
【００２２】また、前記構成のＭy（Ｎｂ1-bＬｉb）Ｏf
において、Ｍとして、Ｂａ、Ｓｒ、Ｃａのうち少なくと
も１種含有してもよい。これらのＢａ、Ｓｒ、ＣａはＡ
サイトに固溶する。In addition, M y (Nb 1-b Li b ) O f of the above structure
In M, at least one of Ba, Sr, and Ca may be contained as M. These Ba, Sr and Ca are A
Solid solution on the site.
【００２３】さらにまた、前記構成において、Ａサイト
とＢサイトの原子比（Ａ／Ｂ比）を表わすｙの範囲を
０．９５≦ｙ≦１の範囲としたのは、ｙを１以下とする
ことにより、電気機械結合係数をさらに向上し、共振周
波数の温度依存性を小さく抑えることが可能となるから
である。ｙが０．９５よりも小さい場合は、磁器の焼結
性が悪化し、磁器を安定に供給することが困難となり、
また、ｙが１よりも大きい場合にも、焼結性が悪化し、
電気機械結合係数が低下するので望ましくない。電気機
械結合係数が高く、かつ、共振周波数の温度依存性が小
さいという点から、ｙは０．９８〜０．９９の範囲にあ
ることが望ましい。Further, in the above structure, the range of y representing the atomic ratio (A / B ratio) between the A site and the B site is set to 0.95 ≦ y ≦ 1 because y is 1 or less. This makes it possible to further improve the electromechanical coupling coefficient and suppress the temperature dependence of the resonance frequency to a small level. When y is smaller than 0.95, the sinterability of the porcelain deteriorates, making it difficult to stably supply the porcelain.
Also, when y is larger than 1, the sinterability deteriorates,
The electromechanical coupling coefficient decreases, which is not desirable. It is desirable that y is in the range of 0.98 to 0.99 because the electromechanical coupling coefficient is high and the temperature dependence of the resonance frequency is small.
【００２４】また、Ｍy（Ｎｂ1-bＬｉb）Ｏfとして含有
するＬｉは、ＡサイトのＮａの一部と置換されるが、Ｂ
サイトのＮｂにも一部置換される。Li contained as M y (Nb 1-b Li b ) O f is replaced with a part of Na at the A site, but B
The site Nb is also partially replaced.
【００２５】本発明の圧電磁器は、例えば、次のように
して製造することができる。まず、Ｎｂ2Ｏ5、Ｋ2Ｃ
Ｏ3、Ｎａ2ＣＯ3、Ｌｉ2ＣＯ3、ＳｉＯ2、Ｂｉ2Ｏ3、Ｍ
ｎＣＯ3の原料を用いて、予め所望の組成になるよう秤
量し、これを湿式方式でボールミル混合する。この混合
粉体を９５０〜１１００℃の温度で仮焼成し、所望の組
成の合成粉体を得る。The piezoelectric ceramic of the present invention can be manufactured, for example, as follows. First, Nb 2 O 5 and K 2 C
O 3 , Na 2 CO 3 , Li 2 CO 3 , SiO 2 , Bi 2 O 3 , M
A raw material of nCO 3 is used and weighed so as to have a desired composition in advance, and this is ball-mill mixed by a wet system. This mixed powder is calcined at a temperature of 950 to 1100 ° C. to obtain a synthetic powder having a desired composition.
【００２６】これを上記ボールミルを用いて湿式粉砕
し、乾燥させ、この混合粉末に有機バインダーを加え、
金型プレス、静水圧プレス等により所望の形状に成形し
た後、これを大気中、１２００〜１３５０℃の温度で２
〜３時間焼成して磁器を得ることができる。This was wet-milled using the above ball mill and dried, and an organic binder was added to this mixed powder,
After molding into a desired shape by a die press, a hydrostatic press, etc., this is subjected to 2 at a temperature of 1200 to 1350 ° C. in the atmosphere.
~ Porcelain can be obtained by firing for 3 hours.
【００２７】仮焼粉体の粉砕後における粉末の平均粒径
は、磁器の焼結性を向上させ、緻密な磁器を得るという
観点から、０．３〜０．７μｍの範囲であることが望ま
しい。さらに、使用する各原料粉末は酸化物だけでな
く、炭酸塩、酢酸塩または有機金属などの化合物のいず
れであっても、焼成などの熱処理プロセスによって酸化
物になるものであれば何ら差し支えない。The average particle size of the powder after pulverization of the calcined powder is preferably in the range of 0.3 to 0.7 μm from the viewpoint of improving the sinterability of the porcelain and obtaining a dense porcelain. . Further, each raw material powder to be used may be not only an oxide but also a compound such as a carbonate, an acetate or an organic metal as long as it becomes an oxide by a heat treatment process such as firing.
【００２８】尚、本発明の圧電磁器では、プレス金型の
成分などが混入する場合がある。また、不純物として、
Ｚｒ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｂ等が混入する場合があ
る。In the piezoelectric ceramic of the present invention, components of the press die may be mixed in. Also, as impurities,
Zr, Fe, Co, Ni, Rb, etc. may be mixed in.
【００２９】さらに、本発明の圧電磁器に対し、第１遷
移金属、Ｔａ、希土類元素等を含有させても良い。特
に、機械的品質係数を向上する目的で、第１遷移金属と
して、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉなどを酸化物として添加
しても優れた磁器とすることができる。さらに、耐熱性
を付与し、電気機械結合係数を向上する目的で、副成分
として、ＫＮｂＯ3やＬｉＮｂＯ3を適量含有させても、
優れた圧電磁器とすることができる。Further, the piezoelectric ceramic of the present invention may contain a first transition metal, Ta, a rare earth element or the like. In particular, even if Cr, Fe, Co, Ni, or the like is added as an oxide as the first transition metal for the purpose of improving the mechanical quality factor, an excellent porcelain can be obtained. Furthermore, for the purpose of imparting heat resistance and improving the electromechanical coupling coefficient, even if KNbO 3 or LiNbO 3 is contained in an appropriate amount as an auxiliary component,
It can be an excellent piezoelectric ceramic.
【００３０】本発明の圧電素子は、上記した圧電磁器の
対向する両面またはその内部に電極を形成してなるもの
である。The piezoelectric element of the present invention comprises electrodes formed on opposite surfaces of the above-mentioned piezoelectric ceramic or inside thereof.
【００３１】[0031]
【実施例】出発原料として、Ｎｂ2Ｏ5、Ｋ2ＣＯ3、Ｎａ
2ＣＯ3、Ｌｉ2ＣＯ3、ＳｉＯ2、ＭｎＣＯ3、Ｂｉ2Ｏ3の
原料粉末を混合した後、この混合粉体を９５０〜１１０
０℃で３時間仮焼し、金属元素のモル比による組成を、
（１−ｘ）Ｎａy（Ｎｂ1 -aＳｉa）Ｏ3＋ｘＭy（Ｎｂ1-b
Ｌｉb）Ｏf（ただし、Ｍは（Ｂｉ1/2Ｋ1/2）、（Ｂｉ
1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）のうち少なくとも１
種とＭｎ、ｆは任意）とした時、前記ａ、ｂ、ｘ、ｙが
表１に示す値となる仮焼粉体を作製した。Example As starting materials, Nb 2 O 5 , K 2 CO 3 , Na
After mixing the raw material powders of 2 CO 3 , Li 2 CO 3 , SiO 2 , MnCO 3 , and Bi 2 O 3 , the mixed powder is mixed with 950 to 110.
It is calcined at 0 ° C for 3 hours, and the composition according to the molar ratio of metal elements is
(1-x) Na y ( Nb 1 -a Si a) O 3 + xM y (Nb 1-b
Li b ) O f (where M is (Bi 1/2 K 1/2 ), (Bi
At least 1 of 1/2 Na 1/2 ) and (Bi 1/2 Li 1/2 )
When the seed, Mn, and f are arbitrary), a calcined powder having the values of a, b, x, and y shown in Table 1 was prepared.
【００３２】これらの混合仮焼粉体をボールミルによる
湿式粉砕で平均粒径が０．５μｍとなるまで粉砕した。These mixed calcined powders were pulverized by a wet mill using a ball mill until the average particle size became 0.5 μm.
【００３３】次いで、この仮焼粉体の粉砕物に有機バイ
ンダーを混合して造粒し、得られた粉末を１５０ＭＰａ
の圧力で長さ３５ｍｍ×幅２２ｍｍ×厚さ１．５ｍｍの
寸法からなる角板状にプレス成形した。Next, an organic binder is mixed with the pulverized product of the calcined powder and granulated, and the obtained powder is subjected to 150 MPa.
It was press-molded into a rectangular plate having dimensions of length 35 mm × width 22 mm × thickness 1.5 mm.
【００３４】次に、この成形体を大気中１２００〜１３
５０℃の温度下で３時間焼成して角板状の磁器を作製
し、得られた磁器を０．５ｍｍの厚さまで研磨した。こ
の角板状の磁器の粉末Ｘ線回折パターンを測定した結
果、本発明に係る試料は、いずれもペロブスカイト型の
結晶構造を有していることがわかった。また、Ｘ線マイ
クロアナリシス（ＥＰＭＡ）を用いて結晶粒子の元素分
析を行った。結果、結晶粒子から、金属元素：Ｂｉ、
Ｋ、Ｎａ、Ｌｉ、Ｎｂ、ＭｎおよびＳｉが検出され、こ
れらの元素が固溶していることがわかった。Next, this molded body was placed in the atmosphere at 1200-13.
The plate-like porcelain was produced by firing at a temperature of 50 ° C. for 3 hours, and the obtained porcelain was polished to a thickness of 0.5 mm. As a result of measuring the powder X-ray diffraction pattern of this rectangular plate-shaped porcelain, it was found that all the samples according to the present invention had a perovskite type crystal structure. In addition, the elemental analysis of the crystal particles was performed using X-ray micro analysis (EPMA). As a result, from the crystal particles, the metal element: Bi,
K, Na, Li, Nb, Mn and Si were detected, and it was found that these elements were in solid solution.
【００３５】研磨した磁器を長さ３０ｍｍ×幅５ｍｍ×
厚さ０．５ｍｍの短冊形状に加工し、これらの端面に銀
電極を形成した後、２００℃のシリコンオイル中で３〜
４ｋＶ／ｍｍの直流電界を印加して分極処理を行った。
この後、これらの短冊状の磁器を０．２５ｍｍの厚さに
なるまで研磨し、それらの上下面に銀電極を蒸着し、幅
１．５ｍｍ×長さ４ｍｍの厚み滑りモードの圧電素子を
作製した。Polished porcelain is 30 mm long × 5 mm wide ×
After processing into a strip shape with a thickness of 0.5 mm, and forming silver electrodes on these end faces, 3 to 3 in silicon oil at 200 ° C.
Polarization was performed by applying a DC electric field of 4 kV / mm.
After that, these strip-shaped porcelains were polished to a thickness of 0.25 mm, silver electrodes were vapor-deposited on the upper and lower surfaces thereof, and a thickness-sliding mode piezoelectric element with a width of 1.5 mm and a length of 4 mm was prepared. did.
【００３６】そして、これらの圧電素子の共振・***振
周波数をインピーダンス・アナライザーで測定し、電気
機械結合係数を求めた。さらに、共振周波数をｆｒとし
て、−２０〜８０℃の温度範囲で測定し、−２０〜８０
℃におけるｆｒの変化量（Δｆｒ）、２０℃での共振周
波数ｆｒ（２０）を用いて、式：ｆｒＴＣ＝Δｆｒ／
｛ｆｒ（２０）×１００｝×１０6（ｐｐｍ／℃）か
ら、共振周波数の温度係数ｆｒＴＣを求め、これらの結
果を表１に記載した。Then, the resonance / anti-resonance frequencies of these piezoelectric elements were measured by an impedance analyzer to obtain the electromechanical coupling coefficient. Furthermore, the resonance frequency is set to fr, it measures in the temperature range of -20 to 80 degreeC, and it is -20 to 80
Using the amount of change in fr at ΔC (Δfr) and the resonance frequency fr (20) at 20 ° C., the expression: frTC = Δfr /
The temperature coefficient frTC of the resonance frequency was determined from {fr (20) × 100} × 10 6 (ppm / ° C.), and these results are shown in Table 1.
【００３７】[0037]
【表１】 [Table 1]
【００３８】表１の結果から明らかなように、ＮａＮｂ
Ｏ3を主成分とするペロブスカイト型の結晶粒子を主成
分とし、Ａサイトを占めるＮａの一部を、（Ｂｉ1/2Ｋ
1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）のう
ち少なくとも１種とＭｎで置換し、また、Ｂサイトを占
めるＮｂの一部をＳｉで置換した本発明の試料Ｎｏ．２
〜２３では、電気機械結合係数は４０％以上と高く、特
に、５０％以上のものも得られ、共振周波数の温度係数
が１５０ｐｐｍ／℃以下となり圧電特性を改善できた。
また、Ｎｂの一部をＬｉで置換した試料では、電気機械
結合係数を向上する効果があった。As is clear from the results shown in Table 1, NaNb
The main component is perovskite type crystal particles containing O 3 as a main component, and a part of Na occupying the A site is converted into (Bi 1/2 K
1/2 ), (Bi 1/2 Na 1/2 ), and (Bi 1/2 Li 1/2 ) at least one of which is replaced with Mn, and a part of Nb occupying the B site is replaced with Si. The replaced sample No. of the present invention. Two
In Nos. 23 to 23, the electromechanical coupling coefficient was as high as 40% or more, and particularly, 50% or more was obtained, and the temperature coefficient of the resonance frequency was 150 ppm / ° C. or less, and the piezoelectric characteristics could be improved.
Further, the sample in which a part of Nb was replaced with Li had an effect of improving the electromechanical coupling coefficient.
【００３９】また、Ａ／Ｂ比（表１ではｙ）を１より小
さくした試料では、共振周波数ｆｒの温度係数ｆｒＴＣ
が１０５ｐｐｍ／℃以下となり大きく改善できた。Further, in the sample in which the A / B ratio (y in Table 1) is smaller than 1, the temperature coefficient frTC of the resonance frequency fr is
Was 105 ppm / ° C or less, which was a great improvement.
【００４０】特に、Ａ／Ｂ比を１より小さくするととも
に、副成分であるＭy（Ｎｂ1-bＬｉ b）Ｏf化合物におけ
るＭを等モル比の（Ｂｉ1/2Ｋ1/2）と（Ｂｉ1/2Ｌ
ｉ1/2）と、Ｍｎを加え、この副成分を主成分に対して
２モル％添加した試料Ｎｏ．１５では、電気機械結合係
数が５８％、温度係数が４５ｐｐｍ／℃以下と最も良好
な特性となった。Especially, when the A / B ratio is made smaller than 1,
And M which is a sub ingredienty(Nb1-bLi b) OfIn the compound
Of M in an equimolar ratio (Bi1/2K1/2) And (Bi1/2L
i1/2) And Mn are added, and this subcomponent is added to the main component.
Sample No. with 2 mol% added 15, the electromechanical coupling
The best number is 58% and the temperature coefficient is 45ppm / ° C or less.
It became a characteristic.
【００４１】一方、ＮａＮｂＯ3を主成分とするペロブ
スカイト型の結晶粒子のＢサイトを占めるＮｂをＳｉで
置換しなかった試料Ｎｏ．１は、電気機械結合係数が小
さく、共振周波数の温度係数が２１０ｐｐｍ／℃と高か
った。On the other hand, sample No. 1 in which Nb occupying the B site of the perovskite type crystal particles containing NaNbO 3 as a main component was not replaced with Si was used. In No. 1, the electromechanical coupling coefficient was small, and the temperature coefficient of the resonance frequency was as high as 210 ppm / ° C.
【００４２】[0042]
【発明の効果】本発明の圧電磁器では、ＮａＮｂＯ3を
主成分とするペロブスカイト型の結晶粒子を主成分と
し、Ａサイトを占めるＮａの一部を、（Ｂｉ
1/2Ｋ1/2）、（Ｂｉ 1/2Ｎａ1/2）、（Ｂｉ1/2Ｌｉ1/2）
のうち少なくとも１種とＭｎで置換するとともに、Ｂサ
イトを占めるＮｂの一部をＳｉで置換することにより、
厚み滑りモードを利用した場合の電気機械結合係数が高
く、共振周波数の温度係数が小さいという優れた特徴を
有する圧電磁器および圧電素子を提供することが出来
る。According to the piezoelectric ceramic of the present invention, NaNbO is used.3To
Perovskite type crystal particles as the main component
A part of Na occupying the A site is converted into (Bi
1/2K1/2), (Bi 1/2Na1/2), (Bi1/2Li1/2)
At least one of the
By substituting Si for a part of Nb occupying
High electromechanical coupling coefficient when using the thickness sliding mode
And the excellent characteristic that the temperature coefficient of the resonance frequency is small.
It is possible to provide a piezoelectric ceramic and a piezoelectric element having
It
Claims (4)
ト型の結晶粒子からなり、Ａサイトを占めるＮａの一部
が、（Ｂｉ1/2Ｋ1/2）、（Ｂｉ1/2Ｎａ1/2）、（Ｂｉ
1/2Ｌｉ1/2）のうち少なくとも１種とＭｎで置換され、
Ｂサイトを占めるＮｂの一部が少なくともＳｉで置換さ
れていることを特徴とする圧電磁器。1. A perovskite-type crystal particle containing NaNbO 3 as a main component, wherein a part of Na occupying the A site is (Bi 1/2 K 1/2 ), (Bi 1/2 Na 1/2 ). ), (Bi
1/2 Li 1/2 ), at least one of which is replaced by Mn,
A piezoelectric ceramic characterized in that at least part of Nb occupying the B site is replaced with Si.
特徴とする請求項１記載の圧電磁器。2. A piezoelectric ceramic according to claim 1, wherein a part of Nb is replaced with Li.
Ｌｉb）Ｏf （ただし、Ｍは（Ｂｉ1/2Ｋ1/2）、（Ｂｉ1/2Ｎ
ａ1/2）、（Ｂｉ1/2Ｌｉ1/2）のうち少なくとも１種と
Ｍｎ、ｆは任意）と表した時、前記ａ、ｂ、ｘ、ｙが、 ０．００２≦ａ≦０．０５ ０≦ｂ≦１ ０．００５≦ｘ≦０．０５ ０．９５≦ｙ≦１ を満足することを特徴とする請求項１または２記載の圧
電磁器。3. The composition based on the molar ratio of metal elements is (1-x) Na y (Nb 1-a Si a ) O 3 + xM y (Nb 1-b
Li b ) O f (where M is (Bi 1/2 K 1/2 ), (Bi 1/2 N
a 1/2 ), (Bi 1/2 Li 1/2 ) and at least one of Mn and f are optional), a, b, x, y are 0.002 ≦ a ≦ 0 0.05 0 ≤ b ≤ 1 0.005 ≤ x ≤ 0.05 0.95 ≤ y ≤ 1 is satisfied, and the piezoelectric ceramic according to claim 1 or 2.
磁器の両面に電極を形成してなることを特徴とする圧電
素子。4. A piezoelectric element comprising electrodes formed on both surfaces of the piezoelectric ceramic according to any one of claims 1 to 3.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049764A1 (en) * | 2005-10-27 | 2007-05-03 | Kyocera Corporation | Piezoelectric ceramic composition and piezoelectric ceramic |
| US7267783B2 (en) | 2002-03-20 | 2007-09-11 | Denso Corporation | Piezoelectric ceramic composition, its production method, and piezoelectric device and dielectric device |
| JP2010052977A (en) * | 2008-08-28 | 2010-03-11 | Kyocera Corp | Piezoelectric ceramic and piezoelectric element using the same |
| JP2011093791A (en) * | 2009-09-30 | 2011-05-12 | Canon Inc | Piezoelectric material, piezoelectric element, liquid discharge head and ultrasonic motor |
-
2001
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267783B2 (en) | 2002-03-20 | 2007-09-11 | Denso Corporation | Piezoelectric ceramic composition, its production method, and piezoelectric device and dielectric device |
| WO2007049764A1 (en) * | 2005-10-27 | 2007-05-03 | Kyocera Corporation | Piezoelectric ceramic composition and piezoelectric ceramic |
| US7959823B2 (en) | 2005-10-27 | 2011-06-14 | Kyocera Corporation | Piezoelectric ceramic composition and piezoelectric ceramic |
| JP2010052977A (en) * | 2008-08-28 | 2010-03-11 | Kyocera Corp | Piezoelectric ceramic and piezoelectric element using the same |
| JP2011093791A (en) * | 2009-09-30 | 2011-05-12 | Canon Inc | Piezoelectric material, piezoelectric element, liquid discharge head and ultrasonic motor |
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