JP5166449B2 - 圧電材料、多層アクチュエータ、および、圧電素子の製造方法 - Google Patents
圧電材料、多層アクチュエータ、および、圧電素子の製造方法 Download PDFInfo
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Description
(M1)4[(M2)2−2x/3Nb2+2x/3]O11+xVO;1−x(ただし、0≦x≦1)
このとき、aとパラメータxの関係は以下の通り:
a=6/7−2x/35
に従った、系に場合によっては既存のあるいはこの系に追加しての焼結助剤PbOの結合の結果、等量のニオブ酸鉛の生成を誘導する。ニオブ酸鉛は、混晶を形成しながら、PZT格子中に同様に溶解し得、このとき鉛空孔VPbが、PZTホスト格子のPbサイトで生じる。a=4/5に対応するM1あるいはM2の量と同量のNb2O5は、パラメータp=1/4が満たされる場合、PZTホスト格子中でクリオライト系の位相範囲の他方に従う限界組成(M1)4[(M2)4/3Nb8/3]O12を有するクリオライト化合物の固溶体の形成を生じ、このとき、M2陽イオンはペロブスカイト混晶のBサイトになおも残り続けるが、酸素空孔は取り除かれる。
0<c≦0.15かつ0≦d≦0.5
である。
M1=M2=Sr
Sr4(Sr5/3Nb7/3)O11.5V0;0.5と表現され得、以上のとき、
0<c≦0.15かつ0≦m≦0.05、d=0である。
[Pb(Zr0.53Ti0.47)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.00213
[Pb(Zr0.53Ti0.47)O3]0.017[PbVPb(Nb2O6)]0.003(PbO)0.029
で表される組成を有する材料が提供される。
0<c≦0.15かつ0≦m≦0.05、d=0である。
[Pb(Zr0.53Ti0.47)O3]0.973[Ba4(Ca4/3Nb8/3)O12]0.00213
[Ba(Zr0.53Ti0.47)O3]0.0115[Ca(Zr0.53Ti0.47)O3]0.0055
[PbVPb(Nb2O6)]0.003(PbO)0.029
で表される組成を有する材料が提供される。
[Pb(FeIII 2/3WVI 1/3)O3]
[Pb(MII 1/3MV 2/3)O3](ただし、MIIはMg,Zn,Co,Ni,MnあるいはCuを、MVはNb,TaあるいはSbを表す)
[Pb(MIII 1/2MV 1/2)O3](ただし、MIIIはFe,Mn,CrあるいはGaを、MVはNb,TaあるいはSbを表す)
[Pb(MIII 2/3MVI 1/3)O3](ただし、MIIIはMn,Cr,Gaを、MVIはWをを表す)
[Pb(LiI 1/4MV 3/4)O3](ただし、MVはNb,TaあるいはSbを表す)
[Pb(Zr0.53Ti0.47)O3]0.995[Sr4(Sr5/3Nb7/3)O11.5VO;0.5]0.005
[PbO]0.01
熱処理過程で、以下の化学式で表される圧電セラミックとなり、
[Pb(Zr0.53Ti0.47)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.00213
[Sr(Zr0.53Ti0.47)O3]0.017[PbVPb(Nb2O6)]0.003(PbO)0.029
このとき、角括弧の成分は、ペロブスカイト混晶相を形成しながら、互いに溶解し、かつ、酸素空孔は無視できるほど少ない濃度でのみ存在する。Nb2O5の放出を伴うPbOのSrOによる漸次的置換の結果として、このセラミックにおいて正規Aサイト(Pbサイト)での鉛空孔(VPb)の形成が生じ、全ストロンチウム量の約10%が配位数6のNb陽イオンの近傍の正規Bサイト(Zr/Tiサイト)に残る。
[Pb(Zr0.52Ti0.48)O3]0.995[Ba4(Ca5/3Nb7/3)O11.5V0.5]0.005
[PbO]0.01
熱処理過程で、以下の化学式で表される圧電セラミックとなり、
[Pb(Zr0.52Ti0.48)O3]0.973[Ba4(Ca4/3Nb8/3)O12]0.00213
[Ba(Zr0.52Ti0.48)O3]0.0115[Ca(Zr0.52Ti0.48)O3]0.0055
[PbVPb(Nb2O6)]0.003(PbO)0.029
このとき、全カルシウム量の約34%はペロブスカイト混晶の正規Bサイトに導入される。
Sr4(Sr2−2x/3Nb2+2x/3)O11+xVO;1−x、
Ba4(Sr2−2x/3Nb2+2x/3)O11+xVO;1−x、
Ba4(Ca2−2x/3Nb2+2x/3)O11+xVO;1−x、あるいは
Sr4(Ca2−2x/3Nb2+2x/3)O11+xVO;1−x(ただし、0≦x≦1)
で表される上記のクリオライト化合物から作製済みの化合物を各割合で加えた混合物を使用してもよい。
[Pb(Zr1−yTiy)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.00213
[Sr(Zr1−yTiy)O3]0.017[PbVPb(Nb2O6)]0.003(PbO)0.029
[Pb(Zr1−yTiy)O3]0.974[Sr4(Sr4/3Nb8/3)O12]0.00183
[Sr(Zr1−yTiy)O3]0.0146[PbVPb(NbO3)]0.0097(PbO)0.01
[Pb(Zr1−yTiy)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.0020
[Sr(Zr1−yTiy)O3]0.0161[PbVPb(NbO3)]0.0117(PbO)0.0078
[Pb(Zr1−yTiy)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.0020
[Sr(Zr1−yTiy)O3]0.0161[PbVPb(NbO3)]0.0093(PbO)0.010
[Pb(Zr1−yTiy)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.0020
[Sr(Zr1−yTiy)O3]0.0161[PbVPb(NbO3)]0.0093(PbO)0.010
[Pb(Zr1−yTiy)O3]0.973[Ba4(Ca4/3Nb8/3)O12]0.00213
[Ba(Zr1−yTiy)O3]0.0115[Ca(Zr1−yTiy)O3]0.0055[Pb0.5VPb;0.5(NbO3)]0.006(PbO)0.02
Claims (35)
- 分子式P1−c−dDcZd(ただし、0.0255<c<0.0443かつ0≦d≦0.5)を有する材料を含む圧電材料であって、
Pが化合物Pb(Zr1−yTiy)O3(ただし、0.50≦1−y≦0.60)を表し、
Zがペロブスカイト型構造の付加的成分を表し、
Dが一般式[(M1O)1−p(M2O)p]a[Nb2O5]1−a(ただし2/3<a<1かつ0<p<1)(このとき、M1はBa1−tSrt、ただし0≦t≦1、を表し、M2はストロンチウムとカルシウムとの両方あるいは一方を表す)を表し、
前記材料Dがクリオライト型の構造を含み、かつ、
前記成分Pと前記成分Dとの反応生成物としてSr(Zr1−yTiy)O3を含む、圧電材料。 - ペロブスカイト型の構造のABO3をホスト格子として有する前記成分Pと前記成分Dとを含む混晶を含有し、前記M2陽イオンの少なくとも一部がPZTペロブスカイトホスト格子の正規のBサイトを占める、請求項1に記載の圧電材料。
- 6/7<a<1である、請求項1または2に記載の圧電材料。
- 2/3<a<4/5である、請求項1または2に記載の圧電材料。
- 4/5≦a≦6/7かつ1/4≦p≦1/3であり、一般式(M1)4[(M2)2−2x/3Nb2+2x/3]O11+xVO;1−x(ただし、0≦x≦1であり、このときVOは酸素空孔を表す)で表されるクリオライト型構造の前記成分Dが前記PZTホスト格子と固溶体を形成し、a=22/35+24p/35かつa=6/7−2x/35である、請求項1または2に記載の圧電材料。
- さらに5mol%までのPbOを含む、請求項1から5のいずれか1項に記載の圧電材料。
- 化学式(M1)4[(M2)2Nb2]O11VO;1で表されるクリオライト化合物が前記PZTホスト格子によって固溶体を形成する、請求項1から6のいずれか1項に記載の圧電材料。
- 前記クリオライト化合物が前記成分Dの構成成分であり、MがM1あるいはM2を表すとき、前記成分DのMOの超過分が少なくとも部分的に前記成分Pと反応してM(Zr1−yTiy)O3とPbOを生成する、請求項1から3のいずれか1項に記載の圧電材料。
- 化学式(M1)4[(M2)4/3Nb8/3]O12で表されるクリオライト化合物が前記PZTホスト格子によって固溶体を形成する、請求項1または2に記載の圧電材料。
- 前記クリオライト化合物が前記成分Dの構成成分であり、前記成分DのNb2O5の超過分が少なくとも部分的には追加で存在するPbOと反応してニオブ酸鉛を生成する、請求項1、2、または4に記載の圧電材料。
- 前記成分Dと前記PZTホスト格子との反応生成物として、MがM1あるいはM2を表すとき、M(Zr1−yTiy)O3を含む、請求項1から10のいずれか1項に記載の圧電材料。
- 化学式(M1)4[(M2)4/3Nb8/3]O12が前記PZTホスト格子によって少なくとも部分的にはニオブ酸鉛に変換される、請求項1から11のいずれか1項に記載の圧電材料。
- (M1)4[(M2)5/3Nb7/3]O11.5VO;0.5が前記PZTホスト格子によって少なくとも部分的には(M1)4[(M2)4/3Nb8/3]O12に変換される、請求項1から11のいずれか1項に記載の圧電材料。
- (M1)4[(M2)2Nb2]O11VO;1が前記PZTホスト格子によって少なくとも部分的には(M1)4[(M2)5/3Nb7/3]O11.5VO;0.5に変換される、請求項1から11のいずれか1項に記載の圧電材料。
- 前記成分Dに関してM1=M2=Srであり、
以下の化学式、
Sr4(Sr2−2x/3Nb2+2x/3)O11+xVO;1−x(ただし、0≦x≦1)で表されるクリオライト化合物が生じ、
Sr陽イオンの一部が前記成分Pのペロブスカイトホスト格子の正規Bサイトを占める、請求項1から14のいずれか1項に記載の圧電材料。 - 組成P1−c−dDcZd[PbO]mを有し、
このときDは化学式[(SrO)a(Nb2O5)1−a](ただし、a=29/35)を表し、これは等価なクリオライト表記ではSr4(Sr5/3Nb7/3)O11.5V0;0.5(ただし、0≦m≦0.05かつd=0)と表現することができる、
請求項1または2に記載の圧電材料。 - 化学式
[Pb(Zr0.53Ti0.47)O3]0.973[Sr4(Sr4/3Nb8/3)O12]0.00213
[Sr(Zr0.53Ti0.47)O3]0.017[PbVPb(Nb2O6)]0.003(PbO)0.029
で表される組成を有する、請求項16に記載の圧電材料。 - ストロンチウム陽イオンの10%が前記PZTホスト格子の正規Bサイトを占める、
請求項17に記載の圧電材料。 - 前記付加的成分Zを含む混晶相を形成する、請求項1から18のいずれか1項に記載の圧電材料。
- 前記付加的成分は、化学式[Pb(FeIII 2/3WVI 1/3)O3]で表される化合物を含む、請求項19に記載の圧電材料。
- 前記付加的成分は、化学式[Pb(MII 1/3MV 2/3)O3](ただし、MIIはMg,Zn,Co,Ni,MnあるいはCuを、MVはNb,TaあるいはSbを表す)で表される化合物を含む、請求項19に記載の圧電材料。
- 前記付加的成分は、化学式[Pb(MIII 1/2MV 1/2)O3](ただし、MIIIはFe,Mn,CrあるいはGaを、MVはMb,TaあるいはSbを表す)で表される化合物を含む、請求項19に記載の圧電材料。
- 前記付加的成分は、化学式[Pb(MIII 2/3MVI 1/3)O3](ただし、MIIIはMn,Cr,Gaを、MVIはWを表す)で表される化合物を含む、請求項19に記載の圧電材料。
- 前記付加的成分は、化学式[Pb(LiI 1/4MV 3/4)O3](ただし、MVはNb,TaあるいはSbを表す)で表される化合物を含む、請求項19に記載の圧電材料。
- [Pb(FeIII 2/3WVI 1/3)O3]のない、請求項1から19のいずれか1項に記載の圧電材料。
- [Pb(FeIII 1/2Nb1/2)O3]のない、請求項1から23のいずれか1項に記載の圧電材料。
- KNbO3のない、請求項1から23のいずれか1項に記載の圧電材料。
- Sr(K1/4Nb3/4)O3のない、請求項1から24のいずれか1項に記載の圧電材料。
- MがM1あるいはM2を表す場合、M陽イオンの10%がPZTホスト格子の正規Bサイトを占める、請求項1から28のいずれか1項に記載の圧電材料。
- 6/7<a<1のとき、MがM1あるいはM2を表す場合、成分DのMOの超過分が少なくとも部分的に成分Pと反応してM(Zr1−yTiy)O3とPbOを生成する、請求項1から3のいずれか1項に記載の圧電材料。
- 2/3<a<4/5のとき、前記成分DのNb2O5の超過分が少なくとも部分的には余剰に存在するPbOと反応してニオブ酸鉛を生成する、請求項1、2、または4に記載の圧電材料。
- d=0である、請求項1から31のいずれか1項に記載の圧電材料。
- 少なくとも1つの誘電体層と少なくとも2つの電極とを含み、
少なくとも1つの前記誘電体層は請求項1から32のいずれか1項に記載の圧電材料を含む、
圧電多層アクチュエータ。 - 酸素空孔の濃度はセラミック材料の焼結中に増加し、冷却中に再び減少する、
請求項1から32のいずれか1項に記載の材料を含む圧電素子を製造するための方法。 - 圧電多層アクチュエータを製造するための請求項1から32のいずれか1項に記載の圧電材料の使用法。
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DE102009000236A1 (de) * | 2009-01-15 | 2010-07-22 | Robert Bosch Gmbh | Dotierungszusammensetzung für PZT-Keramiken |
DE102009058795A1 (de) | 2009-12-18 | 2011-06-22 | Epcos Ag, 81669 | Piezoelektrisches Keramikmaterial, Verfahren zur Herstellung des piezoelektrischen Keramikmaterials, piezoelektrisches Vielschichtbauelement und Verfahren zur Herstellung des piezoelektrischen Vielschichtbauelements |
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JP5575609B2 (ja) * | 2010-11-02 | 2014-08-20 | 日本碍子株式会社 | 鉛系圧電材料及びその製造方法 |
DE102011109008A1 (de) * | 2011-07-29 | 2013-01-31 | Epcos Ag | Verfahren zur Herstellung eines piezoelektrischen Vielschichtbauelements |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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