JP2013079194A - 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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- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 33
- 239000011575 calcium Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 20
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 5
- -1 calcium cations Chemical class 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 3
- 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 81
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 81
- 239000010936 titanium Substances 0.000 description 45
- 239000002019 doping agent Substances 0.000 description 36
- 239000010955 niobium Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000013078 crystal Substances 0.000 description 28
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 23
- 150000001768 cations Chemical class 0.000 description 21
- 239000000919 ceramic Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- 239000006104 solid solution Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000654 additive Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000001419 dependent effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229940006465 strontium cation Drugs 0.000 description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- VIUKNDFMFRTONS-UHFFFAOYSA-N distrontium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Sr+2].[Sr+2].[Nb+5].[Nb+5] VIUKNDFMFRTONS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
【解決手段】分子式P1−c−dDcZd(ただし、0<c≦0.15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はストロンチウムあるいはカルシウムを表す)を表し、材料Dがクリオライト型の構造を含む。これにより、PZTホスト格子のBサイトのドーピングを達成することができる。
【選択図】なし
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 (7)
- 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む、圧電材料。 - 組成P1−c−dDcZd[PbO]mを有し、
このときDは化学式[(BaO)1−p(CaO)p]a(Nb2O5)1−a](a=34/41かつp=5/17)で表されるクリオライト化合物を表し、これは等価なクリオライト表記ではBa4(Ca5/3Nb7/3)O11.5V0;0.5(ただし、0<c≦0.15、0≦m≦0.05かつd=0)と表される、
請求項1に記載の圧電材料。 - 化学式
[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、
請求項1又は2に記載の圧電材料。 - カルシウム陽イオンの34%がPZTホスト格子の正規Bサイトを占める、請求項3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4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4のいずれか1項に記載の圧電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4のいずれか1項に記載の圧電材料の使用法。
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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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