JP4281726B2 - Piezoelectric ceramic composition, piezoelectric ceramic and piezoelectric ceramic element - Google Patents

Piezoelectric ceramic composition, piezoelectric ceramic and piezoelectric ceramic element Download PDF

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JP4281726B2
JP4281726B2 JP2005295877A JP2005295877A JP4281726B2 JP 4281726 B2 JP4281726 B2 JP 4281726B2 JP 2005295877 A JP2005295877 A JP 2005295877A JP 2005295877 A JP2005295877 A JP 2005295877A JP 4281726 B2 JP4281726 B2 JP 4281726B2
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敏和 竹田
行雄 坂部
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Murata Manufacturing Co Ltd
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本発明は、圧電磁器組成物、圧電磁器および圧電セラミック素子に関し、特にたとえば、圧電セラミックフィルタ、圧電セラミック発振子等の圧電セラミック素子材料として有用な圧電磁器組成物、圧電磁器および圧電セラミック素子に関する。 The present invention is a piezoelectric ceramic composition relates piezoelectric ceramic and pressure electric ceramic element, in particular for example, piezoelectric ceramic filter, useful piezoelectric ceramic composition as a piezoelectric ceramic element material such as a piezoelectric ceramic oscillator, piezoelectric ceramic and about pressure electric ceramic elements.

従来より、圧電セラミックフィルタ等の圧電素子には、チタン酸ジルコン酸鉛(Pb(TiXZr1-X)O3)、または、チタン酸鉛(PbTiO3)を主成分とする圧電磁器組成物が広く用いられている。また、最近ではCaBi4Ti415などのビスマス層状化合物を主成分とする圧電磁器組成物が開発され始めている。 Conventionally, a piezoelectric ceramic composition such as a piezoelectric ceramic filter has a piezoelectric ceramic composition mainly composed of lead zirconate titanate (Pb (Ti x Zr 1-x ) O 3 ) or lead titanate (PbTiO 3 ). Is widely used. Recently, a piezoelectric ceramic composition mainly composed of a bismuth layered compound such as CaBi 4 Ti 4 O 15 has been developed.

しかしながら、チタン酸ジルコン酸鉛、または、チタン酸鉛を主成分とする圧電磁器組成物は、有害なPb等が含まれているため、製造あるいは廃棄時に環境や人体に関する影響が問題になる。さらに、その製造過程において一般的に鉛酸化物が用いられているが、この鉛化合物の蒸発のため製品の均一性が低下する。また、ビスマス層状化合物を主成分とする圧電磁器組成物は、電気機械結合係数k33が20%未満と小さいため、広く実用に供されるに至っていない。 However, the piezoelectric ceramic composition mainly composed of lead zirconate titanate or lead titanate contains harmful Pb and the like, and therefore the influence on the environment and human body becomes a problem at the time of manufacture or disposal. Furthermore, lead oxide is generally used in the manufacturing process, but the uniformity of the product is reduced due to evaporation of the lead compound. The piezoelectric ceramic composition mainly composed of a bismuth layer compound, for the electromechanical coupling coefficient k 33 is as small as less than 20%, not come to be subjected to practical use widely.

それゆえに、本発明の主たる目的は、有害物であるPbを含まず、ビスマス層状化合物に比べ電気機械結合係数が大きな圧電磁器組成物、圧電磁器および圧電セラミック素子を提供することである。 Another object of the present invention does not contain a hazardous substance Pb, electromechanical coupling coefficient is large piezoelectric ceramic composition than in the bismuth layer compound is to provide a piezoelectric ceramic and pressure electric ceramic element .

本発明にかかる圧電磁器組成物は、
一般式:(Ag1-xLix(Nb 1-y Ta y 3で表される組成を主成分とし、
0.075≦x<0.40
0≦y<0.20
であることを特徴とし、
Mn酸化物、Si酸化物のうち少なくとも1つを副成分として含有し、
上述したMn酸化物が主成分100重量部に対し、MnCO 3 に換算して5重量部以下の範囲で含有し、
上述したSi酸化物が主成分100重量部に対し、SiO 2 に換算して5重量部以下の範囲で含有する、圧電磁器組成物である
た、本発明にかかる圧電磁器は、上述した圧電磁器組成物からなるものである。
また、本発明にかかる圧電セラミック素子は、上述の圧電磁器に電極を形成したことを特徴とする、圧電セラミック素子である。
The piezoelectric ceramic composition according to the present invention is:
The main component is a composition represented by the general formula: (Ag 1-x Li x ) (Nb 1-y Ta y ) O 3 ,
0.075 ≦ x <0.40
0 ≦ y <0.20
It is characterized by
Containing at least one of Mn oxide and Si oxide as a subcomponent ,
The above-mentioned Mn oxide is contained in a range of 5 parts by weight or less in terms of MnCO 3 with respect to 100 parts by weight of the main component ,
The piezoelectric ceramic composition contains the Si oxide described above in an amount of 5 parts by weight or less in terms of SiO 2 with respect to 100 parts by weight of the main component .
Also, the piezoelectric ceramic according to the present invention is made of a pressure electromagnetic unit composition described above.
A piezoelectric ceramic element according to the present invention is a piezoelectric ceramic element characterized in that an electrode is formed on the above-described piezoelectric ceramic.

本発明にかかる圧電磁器組成物の一般式において、x<0.075の範囲では、圧電体として機能する強誘電相から圧電体として機能しない常誘電相もしくは反強誘電相への転移温度が小さくなり、当該圧電磁器組成物をもって構成された素子の温度安定性の点で問題が生じるため好ましくない。また、0.40≦xの範囲では、共振周波数定数が2000Hz/mより小さくなるうえ、分極がしづらくなる。また、yが0.20以上の場合も転移温度が小さくなる。そこで本発明では、xの範囲を0.075≦x<0.40とし、yの範囲を0y<0.20とした。
また、本発明において、Mn酸化物やSi酸化物を主成分に対して添加することにより焼成温度を低下させることができる。Mn酸化物は、前記主成分100重量部に対し、MnCO3に換算して5重量部以下の範囲で含有すること、および、Si酸化物は、前記主成分100重量部に対し、SiO2に換算して5重量部以下の範囲で含有することが、無添加時の特性を劣化させない。
また、本発明にかかる誘電体磁器組成物は、固溶体であってもよいし、固溶体およびその混合物であってもよい。さらに、本発明にかかる誘電体磁器組成物は、多結晶体であってもよいし、単結晶体であってもよい。
In the general formula of the piezoelectric ceramic composition according to the present invention, in the range of x <0.075, the transition temperature from a ferroelectric phase that functions as a piezoelectric body to a paraelectric or antiferroelectric phase that does not function as a piezoelectric body is small. This is not preferable because a problem arises in terms of temperature stability of an element configured with the piezoelectric ceramic composition. In the range of 0.40 ≦ x, the resonance frequency constant is smaller than 2000 Hz / m, and polarization is difficult. Also, the transition temperature becomes small when y is 0.20 or more. Therefore, in the present invention, the range of x is 0.075 ≦ x <0.40, and the range of y is 0 y <0.20.
In the present invention, the firing temperature can be lowered by adding Mn oxide or Si oxide to the main component . The Mn oxide is contained in an amount of 5 parts by weight or less in terms of MnCO 3 with respect to 100 parts by weight of the main component, and the Si oxide is SiO 2 with respect to 100 parts by weight of the main component. be contained in an amount of 5 parts by weight or less in terms of the, it has such degrade the characteristics at no addition.
The dielectric ceramic composition according to the present invention may be a solid solution, a solid solution, or a mixture thereof. Furthermore, the dielectric ceramic composition according to the present invention may be a polycrystal or a single crystal.

本発明の誘電体磁器組成物を用いれば、有害物であるPbを含むことなく、ビスマス層状化合物に比べ電気機械結合係数k33が大きく(20%以上)実用に供し得る圧電磁器組成物を得ることができる。また、本発明にかかる圧電磁器組成物の主成分に対し、Mn酸化物、Si酸化物のうち少なくとも1つを副成分として含有することで、比誘電率、厚み振動における電気機械結合係数k33、厚み振動における圧電定数d33、厚み振動における共振周波数定数N、および転移温度などの特性を損なわずに、より低温で焼成することが可能となる。 By using the dielectric ceramic composition of the present invention to obtain a rather large electromechanical coupling coefficient k 33 is compared with the bismuth layered compound (20% higher) piezoelectric ceramic composition that can be put to practical use include a hazardous substance Pb be able to. Further, by containing at least one of Mn oxide and Si oxide as a subcomponent with respect to the main component of the piezoelectric ceramic composition according to the present invention, the dielectric constant and the electromechanical coupling coefficient k 33 in thickness vibration are included. It is possible to perform firing at a lower temperature without impairing characteristics such as the piezoelectric constant d 33 in the thickness vibration, the resonance frequency constant N in the thickness vibration, and the transition temperature.

この発明の上述の目的,その他の目的,特徴および利点は、図面を参照して行う以下の発明を実施するための最良の形態の説明から一層明らかとなろう。   The above object, other objects, features, and advantages of the present invention will become more apparent from the following description of the best mode for carrying out the invention with reference to the drawings.

電体磁器組成物は、通常の強誘電体や、誘電体材料と同様に作製できる。たとえば、まず、Ag2O、Nb25、Ta25、Li2CO3を所定量調合し、水、エタノールなどの溶媒中で、ジルコニアボールなどのメディアとともに4〜24h混合する。その際、より均一混合とするためにソルビタンエステルなどの分散剤を添加してもよい。その後、混合されたスラリーを乾燥させ、通常の電気炉により、酸化性雰囲気中、800℃〜1100℃、1〜24h仮焼成する。この仮焼物を水、エタノールなどの溶媒中にポリビニルアルコールなどのバインダーとともにメディアにより粉砕、混合し、これを乾燥させる。この乾燥粉末を一軸プレスにより、縦横12mm、厚さ3mmの角柱試料を作製する。さらに試料を酸化性雰囲気中、950℃〜1200℃、3〜10h焼成する。これらの作業により圧電磁気組成物からなる圧電磁器を得ることができる。以下に、本発明を実施例に基づいて説明する。 Dielectrics ceramic composition, conventional ferroelectric and can be manufactured similarly to the dielectric material. For example, first, Ag 2 O, Nb 2 O 5 , Ta 2 O 5 , and Li 2 CO 3 are mixed in a predetermined amount and mixed with a medium such as zirconia balls in a solvent such as water or ethanol for 4 to 24 hours. At that time, a dispersing agent such as a sorbitan ester may be added for more uniform mixing. Thereafter, the mixed slurry is dried and pre-baked in an oxidizing atmosphere at 800 ° C. to 1100 ° C. for 1 to 24 hours using a normal electric furnace. The calcined product is pulverized and mixed with a medium such as polyvinyl alcohol in a solvent such as water or ethanol, and dried. A prismatic sample having a length and width of 12 mm and a thickness of 3 mm is produced from the dry powder by uniaxial pressing. Further, the sample is baked at 950 ° C. to 1200 ° C. for 3 to 10 hours in an oxidizing atmosphere. It is possible to obtain a piezoelectric ceramic composed of I Ri圧 electromagnetic compositions in these tasks. Hereinafter, the present invention will be described based on examples.

(参考例)
まず、Ag2O、Nb25、Ta25、Li2CO3の各粉末をxに従って表1に示すように所定量調合した後、電気炉により、酸化性雰囲気中、850℃〜1100℃、10h仮焼成を行った。これにより得られた粉末を粉砕し、粉末100重量部に対しポリビニルアルコールが5重量部となるように混合し、これを乾燥して得た粉末を一軸プレス(10ton/cm2)で縦横12mm、厚み約2.5mmに成形し、角柱試料を得た。これらの試料を表1に示す温度で、酸化性雰囲気中焼成した。
(Reference example)
First, a predetermined amount of each powder of Ag 2 O, Nb 2 O 5 , Ta 2 O 5 , and Li 2 CO 3 was prepared as shown in Table 1 according to x, and then in an oxidizing atmosphere in an oxidizing atmosphere at 850 ° C. to Pre-baking was performed at 1100 ° C. for 10 hours. The powder thus obtained was pulverized, mixed so that polyvinyl alcohol was 5 parts by weight with respect to 100 parts by weight of the powder, and dried to obtain a powder obtained by uniaxial pressing (10 ton / cm 2 ) of 12 mm in length and width. Molded to a thickness of about 2.5 mm to obtain a prism sample. These samples were fired in an oxidizing atmosphere at the temperatures shown in Table 1.

その後、Agペーストを試料板端面に塗付し、800℃にて焼き付けた。その後、絶縁オイルバス中100℃〜150℃で、50kV/cm〜200kV/cmの直流電圧を3〜10分間印加して分極処理を行った。次にダイシングマシーンにて2mm×2mm×3mmの角柱に切り出した。このようにして得た試料について比誘電率、厚み振動における電気機械結合係数k33、厚み振動における圧電定数d33、厚み振動における共振周波数定数N、および転移温度を測定した。その結果を表2に示す。表2のうち、*印は本発明外の組成を示している。表2から参考例の組成範囲において20%以上の良好な電気機械結合係数k33をもち、転移温度も200℃以上であるものもあるのがわかる。 Thereafter, Ag paste was applied to the end face of the sample plate and baked at 800 ° C. Thereafter, a polarization treatment was performed by applying a DC voltage of 50 kV / cm to 200 kV / cm for 3 to 10 minutes at 100 to 150 ° C. in an insulating oil bath. Next, it cut out into the prism of 2 mm x 2 mm x 3 mm with the dicing machine. The sample thus obtained was measured for relative permittivity, electromechanical coupling coefficient k 33 in thickness vibration, piezoelectric constant d 33 in thickness vibration, resonance frequency constant N in thickness vibration, and transition temperature. The results are shown in Table 2. Of Table 2, asterisks are shown the composition of the extracellular present invention. From Table 2, it can be seen that there are some having a good electromechanical coupling coefficient k 33 of 20% or more in the composition range of the reference example and a transition temperature of 200 ° C. or more.

(実施例)
参考例と同様に、まず、Ag2O、Nb25、Ta25、Li2CO3の各粉末をxが表3に示すように所定量調合した後、電気炉により、酸化性雰囲気中、900℃〜1200℃、10hで仮焼成を行った。これにより得られた粉末にMnCO3および/またはSiO2の各粉末を表3のように添加し、その後、該粉末100重量部に対しポリビニルアルコールが5重量部となるように混合し、これを乾燥して得た粉末を一軸プレス(10ton/cm2)で縦横12mm、厚み約2.5mmに成形し、角柱試料を得た。これら試料を表3に示す温度で、酸化性雰囲気中焼成した。その後、Agペーストを試料板端面に塗付し、800℃にて焼き付けた。
(Example)
As in the reference example , first, a predetermined amount of each powder of Ag 2 O, Nb 2 O 5 , Ta 2 O 5 , and Li 2 CO 3 was prepared as shown in Table 3, and then oxidized by an electric furnace. Temporary baking was performed in an atmosphere at 900 ° C. to 1200 ° C. for 10 hours. Each powder of MnCO 3 and / or SiO 2 was added to the resulting powder as shown in Table 3, and then mixed so that polyvinyl alcohol was 5 parts by weight with respect to 100 parts by weight of the powder. The powder obtained by drying was molded into a length and width of 12 mm and a thickness of about 2.5 mm with a uniaxial press (10 ton / cm 2 ) to obtain a prism sample. These samples were fired in an oxidizing atmosphere at the temperatures shown in Table 3. Thereafter, Ag paste was applied to the end face of the sample plate and baked at 800 ° C.

その後、絶縁オイルバル中100℃〜150℃で、50kV/cm〜200kV/cmの直流電圧を3〜10分間印加して分極処理を行った。次にダイシングマシーンにて2mm×2mm×3mmの角柱に切り出した。このようにして得た試料について比誘電率、厚み振動における電気機械結合係数k33、厚み振動における圧電定数d33、厚み振動における共振周波数定数N、および転移温度を測定した。その結果を表4に示す。表4のうち、*印は本発明外の組成を示している。表4に示すように、MnCO3および/またはSiO2を添加することで、無添加の試料と同等の20%以上の良好な電気機械結合係数k33をもち、転移温度も200℃以上であり、焼成温度の低い圧電磁器組成物を得ることができる。 Thereafter, a polarization treatment was performed by applying a DC voltage of 50 kV / cm to 200 kV / cm for 3 to 10 minutes at 100 to 150 ° C. in an insulating oil valve. Next, it cut out into the prism of 2 mm x 2 mm x 3 mm with the dicing machine. The sample thus obtained was measured for relative permittivity, electromechanical coupling coefficient k 33 in thickness vibration, piezoelectric constant d 33 in thickness vibration, resonance frequency constant N in thickness vibration, and transition temperature. The results are shown in Table 4. Of Table 4, * mark is shows the composition of the extracellular present invention. As shown in Table 4, by adding MnCO 3 and / or SiO 2 , it has a good electromechanical coupling coefficient k 33 of 20% or more equivalent to that of the additive-free sample, and the transition temperature is 200 ° C. or more. A piezoelectric ceramic composition having a low firing temperature can be obtained.

図1は本発明にかかる圧電セラミック素子の一例を示す斜視図であり、図2はその断面図である。図1および図2に示す圧電セラミック素子は圧電セラミック振動子10である。圧電セラミック振動子10はたとえば直方体状の圧電磁器12を含む。圧電磁器12は2枚の圧電磁器層12aおよび12bを含む。これらの圧電磁器層12aおよび12bは、上述の本発明にかかる圧電磁器組成物からなり、積層されかつ一体的に形成される。また、これらの圧電磁器組成物12aおよび12bは、図2の矢印で示すように、同じ厚み方向に分極されている。   FIG. 1 is a perspective view showing an example of a piezoelectric ceramic element according to the present invention, and FIG. 2 is a sectional view thereof. The piezoelectric ceramic element shown in FIGS. 1 and 2 is a piezoelectric ceramic vibrator 10. The piezoelectric ceramic vibrator 10 includes, for example, a rectangular parallelepiped piezoelectric ceramic 12. The piezoelectric ceramic 12 includes two piezoelectric ceramic layers 12a and 12b. These piezoelectric ceramic layers 12a and 12b are made of the above-described piezoelectric ceramic composition according to the present invention, and are laminated and integrally formed. Further, these piezoelectric ceramic compositions 12a and 12b are polarized in the same thickness direction as indicated by arrows in FIG.

圧電磁器層12aおよび12bの間には、その中央にたとえば円形の振動電極14aが形成され、その振動電極14aから圧電磁器12の一端面にわたってたとえばT字形の引出電極16aが形成される。また、圧電磁器層12aの表面には、その中央にたとえば円形の振動電極14bが形成され、その振動電極14bから圧電磁器12の他端面にわたってたとえばT字形の引出電極16bが形成される。さらに、圧電磁器層12bの表面には、その中央にたとえば円形の振動電極14cが形成され、その振動電極14cから圧電磁器12の他端面にわたってたとえばT字形の引出電極16cが形成される。   Between the piezoelectric ceramic layers 12a and 12b, for example, a circular vibrating electrode 14a is formed at the center, and for example, a T-shaped lead electrode 16a is formed from the vibrating electrode 14a to one end face of the piezoelectric ceramic 12. Further, on the surface of the piezoelectric ceramic layer 12a, for example, a circular vibrating electrode 14b is formed at the center, and for example, a T-shaped lead electrode 16b is formed from the vibrating electrode 14b to the other end face of the piezoelectric ceramic 12. Further, on the surface of the piezoelectric ceramic layer 12b, for example, a circular vibrating electrode 14c is formed at the center thereof, and for example, a T-shaped extraction electrode 16c is formed from the vibrating electrode 14c to the other end surface of the piezoelectric ceramic 12.

そして、引出電極16aにはリード線18aを介して一方の外部電極20aが接続され、引出電極16bおよび16cには別のリード線18bを介して他方の外部電極20bが接続される。   One external electrode 20a is connected to the lead electrode 16a via a lead wire 18a, and the other external electrode 20b is connected to the lead electrodes 16b and 16c via another lead wire 18b.

なお、本発明は、上述の圧電セラミック振動子10以外の圧電セラミック振動子、圧電セラミックフィルタおよび圧電セラミック発振子などの他の圧電セラミック素子にも適用される。   The present invention is also applicable to other piezoelectric ceramic elements such as piezoelectric ceramic vibrators, piezoelectric ceramic filters, and piezoelectric ceramic oscillators other than the piezoelectric ceramic vibrator 10 described above.

この発明にかかる圧電セラミック振動子の一例を示す斜視図である。1 is a perspective view showing an example of a piezoelectric ceramic vibrator according to the present invention. 図1に示す圧電セラミック振動子の断面図解図である。FIG. 2 is a cross-sectional schematic view of the piezoelectric ceramic vibrator shown in FIG. 1.

符号の説明Explanation of symbols

10 圧電セラミック振動子
12 圧電磁器
12a、12b 圧電磁器層
14a、14b、14c 振動電極
16a、16b、16c 引出電極
18a、18b リード線
20a、20b 外部端子
DESCRIPTION OF SYMBOLS 10 Piezoelectric ceramic vibrator | oscillator 12 Piezoelectric ceramic 12a, 12b Piezoelectric ceramic layer 14a, 14b, 14c Vibrating electrode 16a, 16b, 16c Lead electrode 18a, 18b Lead wire 20a, 20b External terminal

Claims (3)

一般式:(Ag1-xLix(Nb 1-y Ta y 3で表される組成を主成分とし、
0.075≦x<0.40
0≦y<0.20
であることを特徴とし、
Mn酸化物、Si酸化物のうち少なくとも1つを副成分として含有し、
前記Mn酸化物は前記主成分100重量部に対し、MnCO 3 に換算して5重量部以下の重量部範囲で含有し、
前記Si酸化物は前記主成分100重量部に対し、SiO 2 に換算して5重量部以下の重量部範囲で含有する、圧電磁器組成物。
The main component is a composition represented by the general formula: (Ag 1-x Li x ) (Nb 1-y Ta y ) O 3 ,
0.075 ≦ x <0.40
0 ≦ y <0.20
It is characterized by
Containing at least one of Mn oxide and Si oxide as a subcomponent ,
The Mn oxide is contained in a range of 5 parts by weight or less in terms of MnCO 3 with respect to 100 parts by weight of the main component ,
The piezoelectric ceramic composition, wherein the Si oxide is contained in a range of 5 parts by weight or less in terms of SiO 2 with respect to 100 parts by weight of the main component .
請求項1に記載の圧電磁器組成物からなる圧電磁器 A piezoelectric ceramic comprising the piezoelectric ceramic composition according to claim 1 . 請求項2に記載の圧電磁器に電極を形成したことを特徴とする、圧電セラミック素子 A piezoelectric ceramic element, wherein an electrode is formed on the piezoelectric ceramic according to claim 2 .
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