WO2011065197A1 - Matériau piézoélectrique et élément piézoélectrique - Google Patents

Matériau piézoélectrique et élément piézoélectrique Download PDF

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Publication number
WO2011065197A1
WO2011065197A1 PCT/JP2010/069628 JP2010069628W WO2011065197A1 WO 2011065197 A1 WO2011065197 A1 WO 2011065197A1 JP 2010069628 W JP2010069628 W JP 2010069628W WO 2011065197 A1 WO2011065197 A1 WO 2011065197A1
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WO
WIPO (PCT)
Prior art keywords
piezoelectric body
group
piezoelectric
lead
less
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Application number
PCT/JP2010/069628
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English (en)
Japanese (ja)
Inventor
健 木島
本多　祐二
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株式会社ユーテック
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Publication of WO2011065197A1 publication Critical patent/WO2011065197A1/fr

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    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/02535—Details of surface acoustic wave devices
    • H03H9/02543—Characteristics of substrate, e.g. cutting angles
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H3/00—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators
    • H03H3/007—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks
    • H03H3/08—Apparatus or processes specially adapted for the manufacture of impedance networks, resonating circuits, resonators for the manufacture of electromechanical resonators or networks for the manufacture of resonators or networks using surface acoustic waves
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
    • H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead-based oxides
    • H10N30/8554—Lead-zirconium titanate [PZT] based

Definitions

  • the present invention relates to a piezoelectric body and a piezoelectric element using the piezoelectric body.
  • Patent Document 1 An example of a conventional lead-based ferroelectric film is Pb (Zr, Ti, Nb) O 3 (see, for example, Patent Document 1).
  • the conventional lead-based ferroelectric film can be used for a piezoelectric element.
  • having a good hysteresis characteristic with squareness causes a decrease in reliability.
  • the reason is that a time for the polarization inversion of the ferroelectric film is required during the operation of the piezoelectric element, and the operation is delayed by that time.
  • An object of one embodiment of the present invention is to provide a piezoelectric body whose reliability is improved by not having a good hysteresis characteristic of squareness and a piezoelectric element using the piezoelectric body.
  • One embodiment of the present invention is a piezoelectric body characterized in that the coercive electric field Ec is 25 kV / cm or less, the remanent polarization value Pr is 10 ⁇ C / cm 2 or less, and the relative dielectric constant is 400 or more (preferably 1000 or more). .
  • the piezoelectric body has a PE hysteresis curve and has little time loss when a hysteresis curve is drawn when an electric field is applied.
  • the piezoelectric body is formed by heating and crystallizing an amorphous thin film containing a ferroelectric material
  • the ferroelectric material is: ABO 3 or (Bi 2 O 2 ) 2+ (A m ⁇ 1 B m O 3m + 1 ) 2 ⁇ (where A is Li, Na, K, Rb, Pb, Ca, Sr, Ba, Bi, La, and Hf) At least one selected from the group consisting of B, B is at least one selected from the group consisting of Ru, Fe, Ti, Zr, Nb, Ta, V, W and Mo, and m is a natural number of 5 or less.) Perovskite and bismuth layered structure oxide represented by LanBa 2 Cu 3 O 7, Trm 2 Ba 2 Ca n-1 Cu n O 2n + 4 or TrmBa 2 Ca n-1 Cu n O 2n + 3 ( wherein, Lan is Y, La, Ce, Pr, Nd, Pm, Sm
  • the piezoelectric element according to one embodiment of the present invention includes any one of the above piezoelectric bodies.
  • a piezoelectric body whose reliability is improved by not having a hysteresis characteristic with good squareness and a piezoelectric element using the piezoelectric body.
  • FIG. 1 It is a figure which shows the flowchart for forming the PZTN film
  • (A) to (C) are diagrams showing a P [ ⁇ C / cm 2 ] -E [kV / cm] hysteresis curve of PZN.
  • 6 is a perspective view for explaining a SAW filter according to Embodiment 3.
  • FIG. 1 shows the flowchart for forming the PZTN film
  • a base film oriented in a predetermined crystal plane is formed on a substrate.
  • a (111) -oriented Pt film is used as the base film.
  • an amorphous thin film containing a ferroelectric material is formed on the base film.
  • One of the following (1) to (6) is used for this ferroelectric material.
  • perovskite and bismuth layered structure oxide represented by) (2) LanBa 2 Cu 3 O 7, Trm 2 Ba 2 Ca n-1 Cu n O 2n + 4 or TrmBa 2 Ca n-1 Cu n O 2n + 3
  • Lan is at least one selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • Trm is Bi, Tl.
  • Hg At least one selected from the group consisting, n represents 5 or less is a natural number.
  • Superconducting oxide represented by) (3) A 0.5 BO 3 ( tetragonal bronze structure) or A 0.3 BO 3 ( (Hexagonal bronze structure) (wherein A is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Pb, Ca, Sr, Ba, Bi and La, B is Ru, Fe, Ti, It is at least one selected from the group consisting of Zr, Nb, Ta, V, W and Mo.) (4) CaO, BaO, PbO, ZnO, MgO, B 2 O 3 , Al 2 O 3 , Y 2 O 3 , La 2 O 3 , Cr 2 O 3 , Bi 2 O 3 , Ga 2 O 3 , ZrO 2 , TiO 2 , HfO 2 , NbO 2 , MoO 3 , WO 3 and It is selected from the group consisting of V 2 O 5 At least one kind of material, (5) The material containing SiO 2 in the at least one material (6) The material containing SiO 2
  • the amorphous thin film is heated and crystallized to form a piezoelectric body on the base film. Since this piezoelectric body has almost no P-E hysteresis curve, there is almost no time loss when drawing a hysteresis curve when an electric field is applied.
  • the reliability can be improved by forming a piezoelectric body that does not have a good hysteresis characteristic of squareness.
  • Lead-based ferroelectric film (lead-based piezoelectric material) according to the present embodiment will be described.
  • a mixed solution composed of first to third raw material solutions containing at least one of Pb, Zr, Ti, and Nb is prepared, and oxides contained in these mixed solutions are subjected to heat treatment, etc. Can be obtained by crystallization.
  • the first raw material solution is a solution in which a polycondensation polymer is dissolved in a solvent such as n-butanol in an anhydrous state in order to form a PbZrO 3 perovskite crystal of Pb and Zr among the constituent metal elements of the lead-based ferroelectric film. Can be illustrated.
  • the second raw material solution a solution obtained by dissolving a polycondensation polymer in an anhydrous state in a solvent such as n-butanol in order to form a PbTiO 3 perovskite crystal of Pb and Ti among the constituent metal elements of the lead-based ferroelectric film Can be illustrated.
  • the third raw material solution is a solution obtained by dissolving a polycondensate in an anhydrous state in a solvent such as n-butanol in order to form a PbNbO 3 perovskite crystal of Pb and Nb among the constituent metal elements of the lead-based ferroelectric film. Can be illustrated.
  • the above problem is solved by, for example, using a solution obtained by dissolving a condensation polymer in a solvent such as n-butanol in an anhydrous state to form PbSiO 3 crystals as a fourth raw material solution, for example, 1 mol% or more. It can be solved by further adding 5 mol% or less into the mixed solution.
  • a lead-based ferroelectric film is formed according to the flowchart shown in FIG. A series of steps including a mixed solution coating step (step ST11), an alcohol removal step, a drying heat treatment step, a degreasing heat treatment step (steps ST12 and ST13) are performed a desired number of times, and then baked by crystallization annealing (step ST14). A lead-based ferroelectric film is formed.
  • a lower electrode is formed by coating a noble metal for electrodes such as Pt on a Si substrate (step ST10).
  • the mixed solution is applied by a coating method such as spin coating (step ST11). Specifically, the mixed solution is dropped on the Pt-coated substrate. For the purpose of spreading the dropped solution over the entire surface of the substrate, spinning is performed at about 500 rpm, and then the number of rotations is reduced to 50 rpm or less and the rotation is performed for about 10 seconds.
  • the drying heat treatment step is performed at 150 ° C. to 180 ° C. (step ST13). The drying heat treatment is performed using a hot plate or the like in an air atmosphere.
  • the degreasing heat treatment step is performed in an air atmosphere on a hot plate maintained at 300 ° C. to 350 ° C. (step ST13).
  • Firing for crystallization is performed using rapid thermal annealing (RTA) or the like in an oxygen atmosphere (step ST14).
  • the film thickness after firing can be about 100 to 200 nm.
  • post-annealing is performed for the purpose of forming the interface between the upper electrode and the lead-based ferroelectric film and improving the crystallinity of the lead-based ferroelectric film.
  • RTA rapid thermal annealing
  • the lower electrode and the upper electrode may be formed of a simple substance of a platinum group element such as Pt, Ir, Ru, or a composite material mainly composed of the platinum group element.
  • sample A a metal film (electrode) made of Pt is formed on a Si substrate by sputtering, and the composition of Pb (Zr 0.7 Ti 0.1 Nb 0.2 ) O 3 is formed on the electrode.
  • a lead-based ferroelectric film was prepared.
  • sample B a metal film (electrode) made of Pt is formed on a Si substrate by sputtering, and the composition of Pb (Zr 0.75 Ti 0.05 Nb 0.2 ) O 3 is formed on the electrode.
  • a lead-based ferroelectric film was prepared.
  • a metal film (electrode) made of Pt is formed on a Si substrate by sputtering, and lead-based ferroelectric having a composition of Pb (Zr 0.8 Nb 0.2 ) O 3 is formed on the electrode.
  • a body membrane was prepared.
  • 5 mol% of PbSiO 3 silicate is added.
  • dimethyl succinate was added to a sol-gel solution for forming a ferroelectric film as a raw material for film formation to adjust the pH to 6.
  • FIG. 1 is used for all film forming flows.
  • the coercive electric field Ec is 25 kV / cm or less
  • the remanent polarization value Pr is 10 ⁇ C / cm 2 or less
  • the relative dielectric constant is 400 or more (preferably 1000 or more).
  • FIG. 3 is a perspective view for explaining a surface acoustic wave (SAW) filter according to the third embodiment.
  • SAW surface acoustic wave
  • a piezoelectric substrate 1 using a piezoelectric body according to Embodiment 1 or 2 is prepared.
  • regular comb-shaped electrodes 2a and 2b are formed on the piezoelectric substrate 1.
  • the comb-shaped electrodes 2a and 2b are electrodes having the same wavelength as the radio wave that is a necessary signal to be extracted.
  • the radio wave entered from the radio wave entrance passes through the comb electrodes 2a and 2b on the piezoelectric substrate 1
  • only a wavelength having the same length as that of the comb electrode can reach the radio wave exit. That is, since the radio wave that becomes noise is different from the wave on the surface of the piezoelectric body, it is canceled out and only a necessary signal can be taken out from the outlet.
  • the piezoelectric substrate 1 of the SAW filter is formed using the piezoelectric body that does not have the hysteresis characteristics according to the first or second embodiment, the piezoelectric body is polarized during the operation of the SAW filter. There is no inversion. Therefore, a highly reliable SAW filter can be obtained.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Surface Acoustic Wave Elements And Circuit Networks Thereof (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne un matériau piézoélectrique ne présentant pas de caractéristiques hystérétiques sensiblement rectangulaires, et offrant de ce fait une fiabilité améliorée, ainsi qu'un élément piézoélectrique comprenant le matériau piézoélectrique. Le matériau piézoélectrique est caractérisé en ce qu'il est représenté par Pb(ZrXTiYNbZ)O3, avec : X + Y + Z = 1 0 ≤ Y ≤ 0,25 0,05 ≤ Z ≤ 0,25.
PCT/JP2010/069628 2009-11-26 2010-11-04 Matériau piézoélectrique et élément piézoélectrique WO2011065197A1 (fr)

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JP2009268854A JP5504533B2 (ja) 2009-11-26 2009-11-26 圧電体及び圧電素子
JP2009-268854 2009-11-26

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JP6347084B2 (ja) * 2014-02-18 2018-06-27 アドバンストマテリアルテクノロジーズ株式会社 強誘電体セラミックス及びその製造方法
DE102018132904B4 (de) * 2018-12-19 2020-10-29 RF360 Europe GmbH Piezoelektrisches Material und piezoelektrische Vorrichtung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005101491A (ja) * 2003-03-28 2005-04-14 Seiko Epson Corp 強誘電体薄膜及びその製造方法、強誘電体メモリ、圧電素子
JP2006094472A (ja) * 2004-08-27 2006-04-06 Kyocera Corp 弾性表面波素子およびその製造方法ならびに通信装置
JP2008290937A (ja) * 2004-05-31 2008-12-04 Seiko Epson Corp 前駆体組成物の製造方法

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JP4217906B2 (ja) * 2004-09-17 2009-02-04 セイコーエプソン株式会社 前駆体溶液の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005101491A (ja) * 2003-03-28 2005-04-14 Seiko Epson Corp 強誘電体薄膜及びその製造方法、強誘電体メモリ、圧電素子
JP2008290937A (ja) * 2004-05-31 2008-12-04 Seiko Epson Corp 前駆体組成物の製造方法
JP2006094472A (ja) * 2004-08-27 2006-04-06 Kyocera Corp 弾性表面波素子およびその製造方法ならびに通信装置

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