JPH06263534A - Piezoelectric ceramic - Google Patents
Piezoelectric ceramicInfo
- Publication number
- JPH06263534A JPH06263534A JP5071062A JP7106293A JPH06263534A JP H06263534 A JPH06263534 A JP H06263534A JP 5071062 A JP5071062 A JP 5071062A JP 7106293 A JP7106293 A JP 7106293A JP H06263534 A JPH06263534 A JP H06263534A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric ceramic
- piezoelectric
- present
- mol
- atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、セラミック発振子、
セラミックフィルタ、セラミックディスクリミネータな
どの圧電素子、特に、耐熱性が要求される表面実装型の
圧電部品に使用される圧電磁器に関する。BACKGROUND OF THE INVENTION The present invention relates to a ceramic oscillator,
The present invention relates to a piezoelectric element such as a ceramic filter or a ceramic discriminator, and particularly to a piezoelectric ceramic used for a surface-mounted piezoelectric component that is required to have heat resistance.
【０００２】[0002]
【従来の技術】セラミックフィルタなどに用いられる圧
電磁器（圧電磁器組成物）として、従来より、チタン酸
ジルコン酸鉛（Ｐｂ（ＴｉXＺｒ1-X）Ｏ3）を主成分と
する圧電磁器が広く用いられており、その圧電特性を改
善するために種々の微量添加物を添加した圧電磁器が用
いられている。2. Description of the Related Art As a piezoelectric ceramic (piezoelectric composition) used for a ceramic filter or the like, a piezoelectric ceramic mainly containing lead zirconate titanate (Pb (Ti x Zr 1-x ) O 3 ) has been conventionally used. It is widely used, and in order to improve its piezoelectric characteristics, piezoelectric ceramics to which various trace additives are added are used.
【０００３】そして、これらの圧電磁器の中でも、特
に、群遅延時間（ＧＤＴ）特性が平坦で、位相歪が小さ
いセラミックフィルタ（圧電フィルタ）用の圧電磁器に
は、機械的品質係数Ｑｍ値の小さいことが要求される。Among these piezoelectric ceramics, a piezoelectric ceramic for a ceramic filter (piezoelectric filter) having a flat group delay time (GDT) characteristic and a small phase distortion has a small mechanical quality factor Qm. Is required.
【０００４】ところで、この機械的品質係数Ｑｍ値の小
さい圧電磁器としては、チタン酸ジルコン酸鉛（Ｐｂ
（ＴｉXＺｒ1-X）Ｏ3）に添加物として、酸化ニオブ、
酸化アンチモン、酸化タンタルなどを添加した圧電磁器
や、チタン酸ジルコン酸鉛（Ｐｂ（ＴｉXＺｒ1-X）
Ｏ3）のＰｂ原子の一部をＬａなどの希土類元素で置換
した圧電磁器などが知られている。By the way, as a piezoelectric ceramic having a small mechanical quality factor Qm value, lead zirconate titanate (Pb) is used.
(Ti x Zr 1-x ) O 3 ) as an additive, niobium oxide,
Piezoelectric ceramics containing antimony oxide, tantalum oxide, etc., and lead zirconate titanate (Pb (Ti X Zr 1-X )
There is known a piezoelectric ceramic in which a part of Pb atoms of O 3 ) is replaced with a rare earth element such as La.
【０００５】また、上記の圧電磁器の他にも、圧電磁器
に微量成分を拡散させた材料として、Ｐｂ（Ｚｒ0.52Ｔ
ｉ0.48）Ｏ3にＳｎを拡散させた材料が報告されている
（特公昭５１−２８３５７）。In addition to the above-mentioned piezoelectric ceramic, Pb (Zr 0.52 T
A material in which Sn is diffused in i 0.48 ) O 3 has been reported (Japanese Patent Publication No. 51-28357).
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記従来の機
械的品質係数Ｑｍ値の小さい圧電磁器は、アクチュエー
タ用として圧電ｄ定数を増大させたものや、広帯域フィ
ルタ用として電気機械結合係数Ｋを増大させることを主
たる目的とするものが多く、キュリー温度が低く、耐熱
性が不十分なものが多い。However, the above-mentioned conventional piezoelectric ceramics having a small mechanical quality factor Qm have an increased piezoelectric d constant for actuators and an electromechanical coupling factor K for broadband filters. In many cases, the main purpose is to do so, the Curie temperature is low, and the heat resistance is insufficient.
【０００７】また、上記従来の機械的品質係数Ｑｍ値が
小さい圧電磁器は、キュリー温度が高いものであって
も、半田付け工程などで温度上昇を伴う場合において
は、圧電磁器の両端に形成した電極間を短絡させたとき
はよいが、開放したときには、電気機械結合係数Ｋが低
下し、共振・反共振周波数が大きくずれてしまうという
問題点がある。Further, the conventional piezoelectric ceramic having a small mechanical quality factor Qm value is formed at both ends of the piezoelectric ceramic even if the Curie temperature is high, even if the temperature rises in the soldering process or the like. Although it is good when the electrodes are short-circuited, there is a problem that when they are opened, the electromechanical coupling coefficient K is lowered, and the resonance / anti-resonance frequencies are greatly deviated.
【０００８】このため、上記従来のＱｍ値が小さい圧電
磁器は、表面実装型のフィルタ素子として使用した場
合、リフロー半田付けの工程で高温（約２５０℃）にさ
らされると、フィルタ特性が大きく劣化するという問題
点がある。Therefore, when the conventional piezoelectric ceramic having a small Qm value is used as a surface-mounting type filter element, when it is exposed to a high temperature (about 250 ° C.) in the reflow soldering process, the filter characteristic is largely deteriorated. There is a problem of doing.
【０００９】また、Ｐｂ（Ｚｒ0.52Ｔｉ0.48）Ｏ3にＳ
ｎを拡散させた材料（特公昭５１−２８３５７）では、
共振・反共振周波数の温度特性が悪いという問題点があ
り、フィルタ素子用の材料として用いるには不適当であ
る。Further, Pb (Zr 0.52 Ti 0.48 ) O 3 contains S
In the material in which n is diffused (Japanese Patent Publication No. 51-28357),
There is a problem that the temperature characteristics of resonance / anti-resonance frequency are poor, and it is unsuitable for use as a material for a filter element.
【００１０】この発明は、上記の問題点を解決するもの
であり、機械的品質係数Ｑｍ値が小さく、かつ、耐熱性
に優れた圧電磁器であって、特に、群遅延時間特性が平
坦で位相歪が小さく、かつ、表面実装に対応することが
可能なフィルタ素子用の圧電磁器を提供することを目的
とする。The present invention solves the above problems, and is a piezoelectric ceramic having a small mechanical quality factor Qm value and excellent heat resistance, and in particular, has a flat group delay time characteristic and a phase. An object of the present invention is to provide a piezoelectric ceramic for a filter element, which has a small distortion and is compatible with surface mounting.
【００１１】[0011]
【課題を解決するための手段】上記問題点を解決するた
めに、この発明の圧電磁器は、一般式：ＰｂＺｒ1-XＴ
ｉXＯ3（但し、Ｘ＝０．４６〜０．５４）で表されるチ
タン酸ジルコン酸鉛のＰｂ原子の０．１〜５．０モル％
を、Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，及びＧｄか
らなる群より選ばれる少なくとも１種で置換し、さら
に、Ｐｂ原子の８モル％までを、Ｃａ，Ｓｒ，及びＢａ
からなる群より選ばれる少なくとも１種で置換した組成
を有する圧電磁器に対して、ＳｎをＳｎＯ2に換算して
０．００５〜２．０重量％含有させたことを特徴とす
る。In order to solve the above problems, the piezoelectric ceramic of the present invention has a general formula: PbZr 1-X T
0.1 to 5.0 mol% of Pb atom of lead zirconate titanate represented by i X O 3 (where X = 0.46 to 0.54)
Is replaced with at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, and Gd, and up to 8 mol% of Pb atoms are replaced with Ca, Sr, and Ba.
It is characterized in that 0.005 to 2.0% by weight of Sn is converted to SnO 2 and contained in a piezoelectric ceramic having a composition substituted with at least one selected from the group consisting of
【００１２】また、この発明の圧電磁器は、前記Ｓｎを
拡散により含有せしめたことを特徴とする。Further, the piezoelectric ceramic of the present invention is characterized in that the Sn is contained by diffusion.
【００１３】また、この発明の圧電磁器は、前記Ｓｎ
が、圧電磁器の粒内部より、粒界層に高濃度で存在して
いることを特徴とする。Further, the piezoelectric ceramic of the present invention is the Sn
Is present in the grain boundary layer at a higher concentration than inside the grains of the piezoelectric ceramic.
【００１４】上記のように、この発明の圧電磁器は、機
械的品質係数Ｑｍ値が小さく、キュリー温度が高い圧電
磁器に対して、Ｓｎを含有させることにより、抵抗率を
低下させることを特徴とするものであり、特にＳｎを
（例えば９００〜１２００℃の温度で）圧電磁器中に熱
拡散させ、Ｓｎを粒内部よりも粒界層で高濃度になるよ
うに偏在させることにより、その抵抗率を低下させるよ
うにしたものである。As described above, the piezoelectric ceramic of the present invention is characterized in that the piezoelectric ceramic having a small mechanical quality factor Qm value and a high Curie temperature contains Sn to reduce the resistivity. In particular, Sn is thermally diffused in a piezoelectric ceramic (for example, at a temperature of 900 to 1200 ° C.), and Sn is unevenly distributed so that the Sn concentration is higher in the grain boundary layer than in the inside of the grain. It is intended to lower the.
【００１５】[0015]
【作用】例えば、分極処理済みの圧電磁器を加熱し、こ
れを室温に戻したときには焦電電荷が発生する。この焦
電電荷による電場は、圧電磁器の分極方向と反対方向に
発生し、圧電磁器の分極の大きさを減少させる。For example, when the polarized piezoelectric ceramic is heated and returned to room temperature, pyroelectric charge is generated. An electric field due to this pyroelectric charge is generated in a direction opposite to the polarization direction of the piezoelectric ceramic, and reduces the magnitude of polarization of the piezoelectric ceramic.
【００１６】この発明は、焦電電荷を速やかに消滅さ
せ、圧電磁器の分極の大きさが低下することを防止する
ために、圧電磁器にＳｎを含有させるものであり、特
に、Ｓｎを、例えば９００〜１２００℃の温度で熱拡散
させて含有させることにより、圧電磁器の抵抗率を低下
させ、焦電電荷を速やかに放電させ、分極方向と反対方
向の電場が長時間印加されることを防止するものであ
る。そして、これにより、残留分極の大きさが減少する
ことを抑制し、共振・反共振周波数の変化量を減少させ
ることができる。In the present invention, in order to quickly extinguish the pyroelectric charge and prevent the polarization of the piezoelectric ceramic from decreasing, Sn is contained in the piezoelectric ceramic. By thermal diffusion at a temperature of 900 to 1200 ° C and containing it, the resistivity of the piezoelectric ceramic is reduced, pyroelectric charge is quickly discharged, and an electric field in the opposite direction to the polarization direction is prevented from being applied for a long time. To do. Thus, it is possible to suppress the reduction of the magnitude of the remanent polarization and reduce the variation amount of the resonance / anti-resonance frequency.
【００１７】[0017]
【実施例】以下に、この発明の実施例を示して、その特
徴をさらに具体的に説明する。まず、圧電磁器の構成材
料であるＰｂＯ，ＳｒＣＯ3，ＢａＣＯ3，ＣａＣＯ3，
Ｌａ2Ｏ3，ＣｅＯ2，Ｐｒ2Ｏ3，Ｎｄ2Ｏ3，Ｓｍ2Ｏ3，
Ｅｕ2Ｏ3，Ｇｄ2Ｏ3，ＴｉＯ2，ＺｒＯ2，の各原料を表
１に示すような組成となるように秤取し、これに水を加
え、ボールミルを用いて湿式混合する。そして、湿式混
合により得られた混合物を乾燥した後、８００〜９００
℃で２時間仮焼し、この仮焼材料をボールミルを用いて
湿式粉砕することにより調整粉末を得た。EXAMPLES The features of the present invention will be described in more detail below by showing examples of the present invention. First, PbO, SrCO 3 , BaCO 3 , CaCO 3 , which are the constituent materials of the piezoelectric ceramic,
La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Sm 2 O 3 ,
Raw materials of Eu 2 O 3 , Gd 2 O 3 , TiO 2 , and ZrO 2 are weighed so as to have the composition shown in Table 1, water is added thereto, and they are wet-mixed using a ball mill. Then, after the mixture obtained by the wet mixing is dried, 800 to 900
The powder was calcined at 0 ° C. for 2 hours, and the calcined material was wet pulverized using a ball mill to obtain an adjusted powder.
【００１８】そして、この調整粉末に水またはポリビニ
ルアルコールなどの粘結材を添加し、プレス成形を行な
った後、１１５０〜１２５０℃の温度で２時間焼成を行
ない、直径１０mm、厚さ１mmの円板状の磁器を得た。こ
の磁器の表面に、ＳｎＯ2をワニスで練って作製したペ
ーストを塗布し、乾燥させた後、これを９００〜１２０
０℃の温度で２時間加熱して熱拡散処理を施した。その
後、この磁器を厚さ０．５mmに研磨し、両端面（両主
面）に銀電極を焼き付けした後、８０℃の絶縁オイル中
で３０分間、２〜３ｋＶ／mmの電界で分極処理を行ない
圧電磁器（振動子試料）を得た。なお、比較のため、上
記実施例と同様の方法でこの発明の範囲外の圧電磁器
（振動子試料）を作製した。Then, after adding a binder such as water or polyvinyl alcohol to the adjusted powder and press-molding the mixture, it is fired at a temperature of 1150 to 1250 ° C. for 2 hours to give a circle having a diameter of 10 mm and a thickness of 1 mm. A plate-shaped porcelain was obtained. The surface of this porcelain was coated with a paste prepared by kneading SnO 2 with a varnish and dried, and then 900 to 120
Heat diffusion treatment was performed by heating at a temperature of 0 ° C. for 2 hours. After that, this porcelain was polished to a thickness of 0.5 mm, silver electrodes were baked on both end surfaces (both main surfaces), and then polarized in an insulating oil at 80 ° C. for 30 minutes in an electric field of 2 to 3 kV / mm. A piezoelectric ceramic (vibrator sample) was obtained. For comparison, a piezoelectric ceramic (vibrator sample) outside the scope of the present invention was manufactured by the same method as in the above-mentioned embodiment.
【００１９】そして、これらの試料について、比抵抗
ρ，径方向の振動における電気機械結合係数Ｋｐ，機械
的品質係数Ｑｍｐ，及び共振周波数Ｆｒの温度変化率
（Ｆｒ−ＴＣ（温度係数）と表記）を測定した。その結
果を表１に示す。With respect to these samples, the specific resistance ρ, the electromechanical coupling coefficient Kp in the radial vibration, the mechanical quality coefficient Qmp, and the temperature change rate of the resonance frequency Fr (expressed as Fr-TC (temperature coefficient)). Was measured. The results are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
【００２１】また、振動子試料を２５０℃の恒温槽に３
分間入れて加熱処理を施し、両端電極間を開放させたま
ま取り出した後、約１時間放置し、共振周波数Ｆｒ及び
反共振周波数Ｆａの変化量ΔＦｒ，ΔＦａを測定した。
その結果も併せて表１に示す。The oscillator sample was placed in a constant temperature bath at 250 ° C.
After being placed for a minute and subjected to heat treatment, the electrode was taken out with both electrodes open and then left for about 1 hour, and the changes ΔFr and ΔFa of the resonance frequency Fr and the anti-resonance frequency Fa were measured.
The results are also shown in Table 1.
【００２２】なお、表１において、Ａ，Ｗ，Ｂ，Ｙ，
Ｘ，αはそれぞれ、下記の式(1)： Ｐｂ1-W-YＡWＢYＺｒ1-XＴｉXＯ3 ＋ α(wt%)ＳｎＯ2 ……(1) における各成分とその添加割合を示している。すなわ
ち、ＡはＰｂと置換した元素（Ｃａ，Ｓｒ，及びＢａの
少なくとも１種）の種類，Ｗはその割合（モル比）を示
しており、ＢはＰｂと置換した元素（Ｌａ，Ｃｅ，Ｐ
ｒ，Ｎｄ，Ｓｍ，Ｅｕ，及びＧｄの少なくとも１種）の
種類，Ｙはその割合（モル比）を示している。また、Ｘ
はＴｉの割合（モル比）を示しており、αはＳｎＯ2の
含有割合（重量％）を示している。In Table 1, A, W, B, Y,
X and α are the respective components in the following formula (1): Pb 1-WY A W B Y Zr 1-X Ti X O 3 + α (wt%) SnO 2 ...... (1) and their addition ratios, respectively. Shows. That is, A represents the type of element (at least one of Ca, Sr, and Ba) substituted with Pb, W represents the ratio (molar ratio), and B represents the element substituted with Pb (La, Ce, P).
At least one kind of r, Nd, Sm, Eu, and Gd), and Y represents the ratio (molar ratio). Also, X
Indicates the proportion of Ti (molar ratio), and α indicates the proportion of SnO 2 contained (% by weight).
【００２３】表１において、試料No.に*印を付したもの
はこの発明の範囲外の圧電磁器（比較例）を示してい
る。In Table 1, the sample numbers marked with * indicate piezoelectric ceramics (comparative examples) outside the scope of the present invention.
【００２４】なお、表１に示した試料以外の他の試料を
も含めて検討した結果、Ａ（Ｃａ，Ｓｒ，Ｂａ）の置換
量Ｗが合計０．０８（すなわち、８モル％）を越えると
キュリー温度が低下するとともに、加熱後の共振・反共
振周波数の変化量ΔＦｒ，ΔＦａが大きくなり、耐熱性
が悪化することがわかった。したがって、Ａ（Ｃａ，Ｓ
ｒ，Ｂａ）の置換量Ｗは０．０８（８モル％）以内であ
ることが好ましい。As a result of examination including samples other than the samples shown in Table 1, the substitution amount W of A (Ca, Sr, Ba) exceeds 0.08 (that is, 8 mol%) in total. It was found that the Curie temperature was lowered and the changes ΔFr and ΔFa of the resonance / anti-resonance frequency after heating were increased and the heat resistance was deteriorated. Therefore, A (Ca, S
The substitution amount W of r, Ba) is preferably within 0.08 (8 mol%).
【００２５】また、Ｂ（Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅ
ｕ，Ｇｄ）の置換量Ｙが０．００１（すなわち、０．１
モル％）未満の場合、Ｆｒの温度変化率Ｆｒ−ＴＣが大
きくなるなどの問題があり、また、置換量Ｙが０．０５
（５．０モル％）を越えるとキュリー温度が低下し、耐
熱性が悪化するため、Ｂ（Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅ
ｕ，Ｇｄ）の置換量Ｙは、０．００１〜０．０５（０．
１〜５．０モル％）の範囲にあることが好ましい。In addition, B (Ce, Pr, Nd, Sm, E
The substitution amount Y of u, Gd) is 0.001 (that is, 0.1).
If it is less than 100 mol%, there is a problem that the temperature change rate Fr-TC of Fr becomes large, and the substitution amount Y is 0.05.
If it exceeds (5.0 mol%), the Curie temperature is lowered and the heat resistance is deteriorated. Therefore, B (Ce, Pr, Nd, Sm, E
The substitution amount Y of (u, Gd) is 0.001 to 0.05 (0.
It is preferably in the range of 1 to 5.0 mol%).
【００２６】さらに、Ｔｉの割合Ｘが０．５４を越える
と電気機械結合係数Ｋｐが低下し、また、Ｘが０．４６
未満になるとキュリー温度が低下し、耐熱性が悪化する
ため、Ｔｉの割合Ｘは、０．４６〜０．５４（すなわ
ち、４６〜５４モル％）の範囲にあることが好ましい。Further, when the Ti content X exceeds 0.54, the electromechanical coupling coefficient Kp decreases, and X is 0.46.
If it is less than the lower limit, the Curie temperature is lowered and the heat resistance is deteriorated. Therefore, the Ti content X is preferably in the range of 0.46 to 0.54 (that is, 46 to 54 mol%).
【００２７】また、表１より、この発明の範囲外の試料
（試料No.１）とこの発明の実施例の試料（例えば、試
料No.２）を比較すると、実施例の圧電磁器（試料No.
２）は、Ｓｎを含有していない試料（試料No.１）に比
べて、比抵抗（抵抗率）ρが１桁以上小さくなっている
ことがわかる。Further, from Table 1, comparing the sample (Sample No. 1) outside the scope of the present invention with the sample of the embodiment of the present invention (for example, Sample No. 2), the piezoelectric ceramic (Sample No. .
In 2), it can be seen that the specific resistance (resistivity) ρ is smaller by one digit or more as compared with the sample containing no Sn (Sample No. 1).
【００２８】これは、拡散により磁器中に含有させたＳ
ｎＯ2が粒界層に偏在しているためである。This is the S contained in the porcelain by diffusion.
This is because nO 2 is unevenly distributed in the grain boundary layer.
【００２９】そして、比抵抗ρが低下した結果、表１に
示すように、加熱後の共振周波数及び反共振周波数の周
波数変化量ΔＦｒ，ΔＦａが大幅に小さくなっている。
しかもこの場合、機械的品質係数ＱｍｐはＳｎを含有し
ない試料No.１とほとんど変らず、電気機械結合係数Ｋ
ｐの値は、試料No.１よりもかなり大きくなっており、
この点においても、実施例の圧電磁器はその特性が向上
していることがわかる。As a result of the decrease in the specific resistance ρ, as shown in Table 1, the frequency changes ΔFr and ΔFa of the resonant frequency and the antiresonant frequency after heating are significantly reduced.
Moreover, in this case, the mechanical quality factor Qmp is almost the same as the sample No. 1 containing no Sn, and the electromechanical coupling factor K
The value of p is considerably larger than that of sample No. 1,
Also in this respect, it can be seen that the characteristics of the piezoelectric ceramic of the embodiment are improved.
【００３０】なお、Ｓｎの含有量がＳｎＯ2に換算して
０．００５重量％未満の場合、比抵抗（抵抗率）ρや周
波数変化量ΔＦｒ，ΔＦａなどの特性改善の効果が不十
分であり、また、２．０重量％を越えると機械的品質係
数Ｑｍｐが大きくなったり、周波数変化量ΔＦｒ，ΔＦ
ａが大きくなったりするという問題が生じるため、Ｓｎ
の含有量は、ＳｎＯ2に換算して０．００５〜２．０重
量％の範囲にあることが好ましい。When the Sn content is less than 0.005 wt% in terms of SnO 2 , the effect of improving the characteristics such as the specific resistance (resistivity) ρ and the frequency changes ΔFr and ΔFa is insufficient. Further, if it exceeds 2.0% by weight, the mechanical quality factor Qmp becomes large, and the frequency change amounts ΔFr, ΔF.
Since there is a problem that a becomes large, Sn
The content of is preferably 0.005 to 2.0% by weight in terms of SnO 2 .
【００３１】[0031]
【発明の効果】上述のように、この発明の圧電磁器は、
ＰｂＺｒ1-XＴｉXＯ3（但し、Ｘ＝０．４６〜０．５
４）で表されるチタン酸ジルコン酸鉛のＰｂ原子の０．
１〜５．０モル％を、Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，
Ｅｕ，及びＧｄからなる群より選ばれる少なくとも１種
で置換し、さらに、Ｐｂ原子の８モル％までを、Ｃａ，
Ｓｒ，及びＢａからなる群より選ばれる少なくとも１種
で置換した組成を有する圧電磁器に対して、ＳｎをＳｎ
Ｏ2に換算して０．００５〜２．０重量％含有させるよ
うにしているので、電気機械結合係数Ｋが大きく、か
つ、共振周波数及び反共振周波数の温度変化率、及び機
械的品質係数Ｑｍの値が小さい圧電磁器を得ることがで
きる。As described above, the piezoelectric ceramic of the present invention is
PbZr 1-X Ti X O 3 (however, X = 0.46 to 0.5
0) of the Pb atom of lead zirconate titanate represented by 4).
1 to 5.0 mol% of La, Ce, Pr, Nd, Sm,
Substituting at least one selected from the group consisting of Eu and Gd, and further, up to 8 mol% of Pb atoms, Ca,
For a piezoelectric ceramic having a composition in which at least one selected from the group consisting of Sr and Ba is substituted, Sn is replaced by Sn
Since it is contained in an amount of 0.005 to 2.0% by weight in terms of O 2 , the electromechanical coupling coefficient K is large, and the temperature change rate of the resonance frequency and the antiresonance frequency and the mechanical quality coefficient Qm. A piezoelectric ceramic having a small value of can be obtained.
【００３２】そして、この発明の圧電磁器をセラミック
フィルタ（圧電フィルタ）素子に用いた場合、広い周波
数帯域において、群遅延時間（ＧＤＴ）特性が平坦で、
しかも位相歪が小さいという優れた特性を発揮させるこ
とが可能になり、デジタル信号に対してビット誤りを生
じにくくすることが可能になる。したがって、この発明
の圧電磁器は、デジタル対応の圧電フィルタ素子用の材
料として特に有意義である。When the piezoelectric ceramic of the present invention is used for a ceramic filter (piezoelectric filter) element, the group delay time (GDT) characteristic is flat in a wide frequency band,
Moreover, it is possible to exhibit the excellent characteristic that the phase distortion is small, and it is possible to make it difficult for bit errors to occur in the digital signal. Therefore, the piezoelectric ceramic of the present invention is particularly significant as a material for a digital-compatible piezoelectric filter element.
【００３３】また、この発明の圧電磁器は、加熱及び加
熱後の冷却に対する共振周波数及び反共振周波数の変化
量が小さいという特徴を有している。Further, the piezoelectric ceramic of the present invention is characterized in that the amount of change in the resonance frequency and the anti-resonance frequency with respect to heating and cooling after heating is small.
【００３４】したがって、この発明にかかる圧電磁器
は、リフロー半田などにより表面実装されるフィルタ素
子材料として用いられた場合にも、高温（〜２５０℃）
による特性劣化、特にフィルタの通過帯域のずれ、及び
通過帯域幅の減少割合が小さく、表面実装に十分に対応
することができる。Therefore, the piezoelectric ceramic according to the present invention has a high temperature (up to 250 ° C.) even when it is used as a filter element material surface-mounted by reflow soldering or the like.
The deterioration of characteristics due to, especially the deviation of the pass band of the filter and the reduction rate of the pass band width are small, and it is possible to sufficiently cope with surface mounting.
Claims (3)
Ｘ＝０．４６〜０．５４）で表されるチタン酸ジルコン
酸鉛のＰｂ原子の０．１〜５．０モル％を、Ｌａ，Ｃ
ｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，及びＧｄからなる群より
選ばれる少なくとも１種で置換し、さらに、Ｐｂ原子の
８モル％までを、Ｃａ，Ｓｒ，及びＢａからなる群より
選ばれる少なくとも１種で置換した組成を有する圧電磁
器に対して、ＳｎをＳｎＯ2に換算して０．００５〜
２．０重量％含有させたことを特徴とする圧電磁器。1. A general formula: PbZr 1-X Ti X O 3 (however,
X = 0.46 to 0.54), 0.1 to 5.0 mol% of the Pb atom of lead zirconate titanate represented by La, C
e, Pr, Nd, Sm, Eu, and at least one selected from the group consisting of Gd, and up to 8 mol% of Pb atoms, at least 1 selected from the group consisting of Ca, Sr, and Ba. For a piezoelectric ceramic having a composition substituted with seeds, Sn is converted to SnO 2 and 0.005
A piezoelectric ceramic containing 2.0% by weight.
のであることを特徴とする請求項１記載の圧電磁器。2. The piezoelectric ceramic according to claim 1, wherein the Sn is contained by diffusion.
界層に高濃度で存在していることを特徴とする請求項１
記載の圧電磁器。3. The Sn is present in the grain boundary layer in a higher concentration than in the grains of the piezoelectric ceramic.
The described piezoelectric ceramic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07106293A JP3257129B2 (en) | 1993-03-04 | 1993-03-04 | Piezoelectric ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07106293A JP3257129B2 (en) | 1993-03-04 | 1993-03-04 | Piezoelectric ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06263534A true JPH06263534A (en) | 1994-09-20 |
| JP3257129B2 JP3257129B2 (en) | 2002-02-18 |
Family
ID=13449668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07106293A Expired - Fee Related JP3257129B2 (en) | 1993-03-04 | 1993-03-04 | Piezoelectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3257129B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747740A (en) * | 2020-06-28 | 2020-10-09 | 安徽容知日新科技股份有限公司 | Samarium ion doped lead zirconate titanate based high-performance piezoelectric ceramic and preparation method thereof |
-
1993
- 1993-03-04 JP JP07106293A patent/JP3257129B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747740A (en) * | 2020-06-28 | 2020-10-09 | 安徽容知日新科技股份有限公司 | Samarium ion doped lead zirconate titanate based high-performance piezoelectric ceramic and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3257129B2 (en) | 2002-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100282598B1 (en) | Piezoelectric Ceramic Composition | |
| JP2737532B2 (en) | Piezoelectric ceramic composition | |
| JPH09100159A (en) | Piezoelectric ceramic and its production | |
| JP3221147B2 (en) | Piezoelectric ceramic | |
| EP0575966B1 (en) | Piezoelectric ceramics | |
| JP3198906B2 (en) | Piezoelectric porcelain composition | |
| JP3384043B2 (en) | Piezoelectric ceramic | |
| KR100200181B1 (en) | Piezoelectric ceramic and manufacturing method thereof | |
| JP3204056B2 (en) | Piezoelectric ceramic | |
| JP3384044B2 (en) | Piezoelectric ceramic | |
| JP3125624B2 (en) | Piezoelectric ceramic | |
| JP3221145B2 (en) | Piezoelectric ceramic | |
| JP3257129B2 (en) | Piezoelectric ceramic | |
| JP3257046B2 (en) | Piezoelectric ceramic | |
| JP3232667B2 (en) | Piezoelectric ceramic | |
| JP3257047B2 (en) | Piezoelectric ceramic | |
| JP3309479B2 (en) | Piezoelectric ceramic | |
| JP3221049B2 (en) | Piezoelectric ceramic composition | |
| JP2001130961A (en) | Piezoelectric ceramic composition and piezoelectric ceramic element by using the same | |
| JP2910340B2 (en) | Piezoelectric porcelain composition | |
| JP2737451B2 (en) | Piezoelectric material | |
| JP3097217B2 (en) | Piezoelectric ceramic composition | |
| JP2910338B2 (en) | Piezoelectric porcelain composition | |
| JP3106507B2 (en) | Piezoelectric porcelain composition | |
| JP2910339B2 (en) | Piezoelectric ceramic composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20011106 |
|
| LAPS | Cancellation because of no payment of annual fees |