JP5504533B2 - Piezoelectric body and piezoelectric element - Google Patents
Piezoelectric body and piezoelectric element Download PDFInfo
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- JP5504533B2 JP5504533B2 JP2009268854A JP2009268854A JP5504533B2 JP 5504533 B2 JP5504533 B2 JP 5504533B2 JP 2009268854 A JP2009268854 A JP 2009268854A JP 2009268854 A JP2009268854 A JP 2009268854A JP 5504533 B2 JP5504533 B2 JP 5504533B2
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- 239000000463 material Substances 0.000 claims description 17
- 230000005684 electric field Effects 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 6
- 239000010408 film Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 229910052758 niobium Inorganic materials 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229910052745 lead Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010897 surface acoustic wave method Methods 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 229910000906 Bronze Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical group [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004151 rapid thermal annealing Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000911772 Homo sapiens Hsc70-interacting protein Proteins 0.000 description 1
- 101001139126 Homo sapiens Krueppel-like factor 6 Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- -1 Pm Inorganic materials 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
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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)
Description
本発明は、圧電体及びそれを用いた圧電素子に関する。 The present invention relates to a piezoelectric body and a piezoelectric element using the piezoelectric body.
従来の鉛系強誘電体膜としてはＰｂ（Ｚｒ、Ｔｉ、Ｎｂ）Ｏ３が挙げられる（例えば特許文献１参照）。この特許文献１には、Ｐｂ：Ｚｒ：Ｔｉ：Ｎｂ＝１：０．２：０．６：０．２としたＰｂ（Ｚｒ、Ｔｉ、Ｎｂ）Ｏ３が角型性の良好なヒステリシス特性を有することが開示されている。 An example of a conventional lead-based ferroelectric film is Pb (Zr, Ti, Nb) O 3 (see, for example, Patent Document 1). In this Patent Document 1, Pb (Zr, Ti, Nb) O 3 with Pb: Zr: Ti: Nb = 1: 0.2: 0.6: 0.2 has a good hysteresis characteristic with squareness. It is disclosed to have.
上記従来の鉛系強誘電体膜は圧電素子に用いることができる。しかし、圧電素子に用いる場合、角型性の良好なヒステリシス特性を有することが信頼性を低下させる原因となる。その理由は、圧電素子の動作時に強誘電体膜が分極反転する時間が必要となり、その時間だけ動作に遅れが生じるからである。 The conventional lead-based ferroelectric film can be used for a piezoelectric element. However, when used in 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.
本発明の一態様は、角型性の良好なヒステリシス特性を有しないことで信頼性を向上させた圧電体及びそれを用いた圧電素子を提供することを課題とする。 An object of one embodiment of the present invention is to provide a piezoelectric body in which reliability is improved by not having hysteresis characteristics with favorable squareness and a piezoelectric element using the piezoelectric body.
本発明の一態様は、抗電界Ecは25kV/cm以下、残留分極値Prは10μC/cm2以下、かつ比誘電率400以上（好ましくは1000以上）であることを特徴とする圧電体である。 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 μC / cm 2 or less, and the relative dielectric constant is 400 or more (preferably 1000 or more). .
また、本発明の一態様に係る圧電体において、
前記圧電体は、P-Eヒステリシス曲線を殆ど有しておらず、電界印加時のヒステリシスカーブ描写時の時間的ロスが殆どないことを特徴とする圧電体である。
In the piezoelectric body according to one aspect of the present invention,
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.
また、本発明の一態様に係る圧電体において、
前記圧電体は、強誘電体材料を含むアモルファス薄膜を加熱して結晶化することにより形成されるものであり、
前記強誘電体材料は、
ＡＢＯ３あるいは（Ｂｉ２Ｏ２）２＋（Ａｍ−１ＢｍＯ３ｍ＋１）２−（式中、ＡはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｐｂ、Ｃａ、Ｓｒ、Ｂａ、Ｂｉ、Ｌａ及びＨｆからなる群から選択される少なくとも１種、ＢはＲｕ、Ｆｅ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｖ、Ｗ及びＭｏからなる群から選択される少なくとも１種、ｍは５以下の自然数である。）で表されるペロブスカイト及びビスマス層状構造酸化物、
ＬａｎＢａ２Ｃｕ３Ｏ７、Ｔｒｍ２Ｂａ２Ｃａｎ−１ＣｕｎＯ２ｎ＋４又はＴｒｍＢａ２Ｃａｎ−１ＣｕｎＯ２ｎ＋３（式中、ＬａｎはＹ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕからなる群から選択される少なくとも１種、ＴｒｍはＢｉ、Ｔｌ及びＨｇからなる群から選択される少なくとも１種、ｎは５以下の自然数である。）で表される超伝導酸化物、
Ａ０．５ＢＯ３（正方ブロンズ構造）又はＡ０．３ＢＯ３（六方ブロンズ構造）（式中、ＡはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｐｂ、Ｃａ、Ｓｒ、Ｂａ、Ｂｉ及びＬａからなる群から選択される少なくとも１種、ＢはＲｕ、Ｆｅ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｖ、Ｗ及びＭｏからなる群から選択される少なくとも１種である。）で表されるタングステンブロンズ構造酸化物、
ＣａＯ、ＢａＯ、ＰｂＯ、ＺｎＯ、ＭｇＯ、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｃｒ２Ｏ３、Ｂｉ２Ｏ３、Ｇａ２Ｏ３、ＺｒＯ２、ＴｉＯ２、ＨｆＯ２、ＮｂＯ２、ＭｏＯ３、ＷＯ３及びＶ２Ｏ５からなる群から選択される少なくとも１種の材料、
前記少なくとも１種の材料にＳｉＯ２を含む材料、及び、
前記少なくとも１種の材料にＳｉＯ２及びＧｅＯ２を含む材料の少なくとも１つからなることも可能である。
In the piezoelectric body according to one aspect of the present invention,
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, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and at least one selected from the group consisting of Lu, Trm is at least one selected from the group consisting of Bi, Tl and Hg, and n is 5 or less A superconducting oxide represented by
A 0.5 BO 3 (tetragonal bronze structure) or A 0.3 BO 3 (hexagonal bronze structure) (wherein A is Li, Na, K, Rb, Cs, Pb, Ca, Sr, Ba, Bi, and La) At least one selected from the group consisting of, and B is at least one selected from the group consisting of Ru, Fe, Ti, Zr, Nb, Ta, V, W, and Mo.) Structural oxides,
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 At least one material selected from the group consisting of HfO 2 , NbO 2 , MoO 3 , WO 3 and V 2 O 5 ;
A material comprising SiO 2 in the at least one material; and
The at least one material may be made of at least one material including SiO 2 and GeO 2 .
本発明の一態様は、Ｐｂ（ＺｒＸＴｉＹＮｂＺ）Ｏ３で示され、以下の関係、
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．２５
０．０５≦Ｚ≦０．２５
が成立することを特徴とする圧電体である。
One aspect of the present invention is shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.25
0.05 ≦ Z ≦ 0.25
This is a piezoelectric body characterized in that
また、本発明の一態様に係る圧電素子は、上記のいずれかの圧電体を有することを特徴とする。 A piezoelectric element according to one embodiment of the present invention includes any one of the above piezoelectric bodies.
本発明の一態様は、下電極と、
前記下電極上に形成された鉛系圧電体と、
前記鉛系圧電体上に形成された上電極と、
を具備し、
前記鉛系圧電体は、Ｐｂ（ＺｒＸＴｉＹＮｂＺ）Ｏ３で示され、以下の関係、
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．２５
０．０５≦Ｚ≦０．２５
が成立することを特徴とする圧電素子である。
One embodiment of the present invention includes a lower electrode,
A lead-based piezoelectric body formed on the lower electrode;
An upper electrode formed on the lead-based piezoelectric body;
Comprising
The lead-based piezoelectric material is shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.25
0.05 ≦ Z ≦ 0.25
Is a piezoelectric element characterized in that
本発明の一態様によれば、角型性の良好なヒステリシス特性を有しないことで信頼性を向上させた圧電体及びそれを用いた圧電素子を提供することができる。 According to one embodiment of the present invention, it is possible to provide a piezoelectric body in which reliability is improved by not having a hysteresis characteristic with good squareness and a piezoelectric element using the piezoelectric body.
以下では、本発明の実施形態について図面を用いて詳細に説明する。ただし、本発明は以下の説明に限定されず、本発明の趣旨及びその範囲から逸脱することなくその形態及び詳細を様々に変更し得ることは、当業者であれば容易に理解される。従って、本発明は以下に示す実施の形態の記載内容に限定して解釈されるものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below.
（実施形態１）
本実施形態による圧電体は、P-Eヒステリシス曲線を殆ど有していない為、電界印加時のヒステリシスカーブ描写時の時間的ロスが殆どないものである。この圧電体の製造方法について以下に説明する。
(Embodiment 1)
Since the piezoelectric body according to the present embodiment has almost no PE hysteresis curve, there is almost no time loss when drawing the hysteresis curve when an electric field is applied. A method for manufacturing this piezoelectric body will be described below.
基板上に所定の結晶面に配向した下地膜を形成する。この下地膜には、例えば（１１１）配向させたPt膜が用いられる。 A base film oriented in a predetermined crystal plane is formed on the substrate. For example, a (111) -oriented Pt film is used as the base film.
次いで、この下地膜上に強誘電体材料を含むアモルファス薄膜を形成する。この強誘電体材料には下記の(1)〜(6)のいずれかが用いられる。
(1)ＡＢＯ３あるいは（Ｂｉ２Ｏ２）２＋（Ａｍ−１ＢｍＯ３ｍ＋１）２−（式中、ＡはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｐｂ、Ｃａ、Ｓｒ、Ｂａ、Ｂｉ、Ｌａ及びＨｆからなる群から選択される少なくとも１種、ＢはＲｕ、Ｆｅ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｖ、Ｗ及びＭｏからなる群から選択される少なくとも１種、ｍは５以下の自然数である。）で表されるペロブスカイト及びビスマス層状構造酸化物
(2)ＬａｎＢａ２Ｃｕ３Ｏ７、Ｔｒｍ２Ｂａ２Ｃａｎ−１ＣｕｎＯ２ｎ＋４又はＴｒｍＢａ２Ｃａｎ−１ＣｕｎＯ２ｎ＋３（式中、ＬａｎはＹ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕからなる群から選択される少なくとも１種、ＴｒｍはＢｉ、Ｔｌ及びＨｇからなる群から選択される少なくとも１種、ｎは５以下の自然数である。）で表される超伝導酸化物
(3)Ａ０．５ＢＯ３（正方ブロンズ構造）又はＡ０．３ＢＯ３（六方ブロンズ構造）（式中、ＡはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｐｂ、Ｃａ、Ｓｒ、Ｂａ、Ｂｉ及びＬａからなる群から選択される少なくとも１種、ＢはＲｕ、Ｆｅ、Ｔｉ、Ｚｒ、Ｎｂ、Ｔａ、Ｖ、Ｗ及びＭｏからなる群から選択される少なくとも１種である。）で表されるタングステンブロンズ構造酸化物
(4)ＣａＯ、ＢａＯ、ＰｂＯ、ＺｎＯ、ＭｇＯ、Ｂ２Ｏ３、Ａｌ２Ｏ３、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｃｒ２Ｏ３、Ｂｉ２Ｏ３、Ｇａ２Ｏ３、ＺｒＯ２、ＴｉＯ２、ＨｆＯ２、ＮｂＯ２、ＭｏＯ３、ＷＯ３及びＶ２Ｏ５からなる群から選択される少なくとも１種の材料、
(5)前記少なくとも１種の材料にＳｉＯ２を含む材料
(6)前記少なくとも１種の材料にＳｉＯ２及びＧｅＯ２を含む材料
Next, 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.
(1) 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 at least one selected from the group consisting of Hf, 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. And perovskite and bismuth layered structure oxides
(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 ( wherein, Lan is Y, La, Ce, Pr, Nd, Pm , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, at least one selected from the group consisting of Bi, Tl and Hg, n Is a natural number of 5 or less.)
(3) A 0.5 BO 3 (tetragonal bronze structure) or A 0.3 BO 3 (hexagonal bronze structure) (wherein A is Li, Na, K, Rb, Cs, Pb, Ca, Sr, Ba, At least one selected from the group consisting of Bi and La, and B is at least one selected from the group consisting of Ru, Fe, Ti, Zr, Nb, Ta, V, W, and Mo. Tungsten bronze structure oxide
(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 At least one material selected from the group consisting of TiO 2 , HfO 2 , NbO 2 , MoO 3 , WO 3 and V 2 O 5 ,
(5) Material containing SiO 2 in the at least one material
(6) A material containing SiO 2 and GeO 2 in the at least one material.
次に、前記アモルファス薄膜を加熱して結晶化することにより、下地膜上には圧電体が形成される。この圧電体は、P-Eヒステリシス曲線を殆ど有していない為、電界印加時のヒステリシスカーブ描写時の時間的ロスが殆どないものである。 Next, 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.
上記実施形態１によれば、角型性の良好なヒステリシス特性を有しない圧電体を形成することで信頼性を向上させることができる。 According to Embodiment 1 described above, the reliability can be improved by forming a piezoelectric body that does not have a good hysteresis characteristic of squareness.
（実施形態２）
まず、本実施形態による鉛系強誘電体膜（鉛系圧電体）について説明する。
鉛系強誘電体膜は、Ｐｂ（ＺｒＸＴｉＹＮｂＺ）Ｏ３で示され、以下の関係、
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．２５
０．０５≦Ｚ≦０．２５
が成立する鉛系セラミックスからなるものである。
なお、この組成範囲は、特許文献１に記載されているＰｂ（Ｚｒ、Ｔｉ、Ｎｂ）Ｏ３の強誘電体膜の組成範囲と重複しない。
(Embodiment 2)
First, the lead-based ferroelectric film (lead-based piezoelectric material) according to the present embodiment will be described.
Lead-based ferroelectric film is shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.25
0.05 ≦ Z ≦ 0.25
It is made of lead-based ceramics that holds
This composition range does not overlap with the composition range of the Pb (Zr, Ti, Nb) O 3 ferroelectric film described in Patent Document 1.
次に、本実施形態による圧電素子に適用される鉛系強誘電体膜の成膜方法の一例について説明する。 Next, an example of a method for forming a lead-based ferroelectric film applied to the piezoelectric element according to the present embodiment will be described.
鉛系強誘電体膜は、Ｐｂ、Ｚｒ、Ｔｉ、およびＮｂの少なくともいずれかを含む第１〜第３の原料溶液からなる混合溶液を用意し、これらの混合溶液に含まれる酸化物を熱処理等により結晶化させて得ることができる。 For the lead-based ferroelectric film, a mixed solution composed of first to third raw material solutions containing at least one of Pb, Zr, Ti, and Nb is prepared, and the oxide contained in these mixed solutions is subjected to a heat treatment or the like. Can be obtained by crystallization.
第１の原料溶液としては、鉛系強誘電体膜の構成金属元素のうち、ＰｂおよびＺｒによるＰｂＺｒＯ３ペロブスカイト結晶を形成するため縮重合体をｎ−ブタノール等の溶媒に無水状態で溶解した溶液が例示できる。 As the first raw material solution, a solution in which a polycondensation polymer is dissolved in a solvent such as n-butanol in an anhydrous state 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.
第２の原料溶液としては、鉛系強誘電体膜の構成金属元素のうち、ＰｂおよびＴｉによるＰｂＴｉＯ３ペロブスカイト結晶を形成するため縮重合体をｎ−ブタノール等の溶媒に無水状態で溶解した溶液が例示できる。 The second 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 PbTiO 3 perovskite crystal of Pb and Ti among the constituent metal elements of the lead-based ferroelectric film. Can be illustrated.
第３の原料溶液としては、鉛系強誘電体膜の構成金属元素のうち、ＰｂおよびＮｂによるＰｂＮｂＯ３ペロブスカイト結晶を形成するため縮重合体をｎ−ブタノール等の溶媒に無水状態で溶解した溶液が例示できる。 As the third raw material solution, among the constituent metal elements of the lead-based ferroelectric film, a solution obtained by dissolving a condensation polymer in an anhydrous state in a solvent such as n-butanol in order to form a PbNbO 3 perovskite crystal with Pb and Nb Can be illustrated.
上記第１、第２および第３の原料溶液を用いて、例えば、ＰｂＺｒ０．７５Ｔｉ０．０５Ｎｂ０．２Ｏ３（ＰＺＴＮ）からなる鉛系強誘電体膜を形成する場合、（第１の原料溶液）：(第２の原料溶液)：(第３の原料溶液)＝７．５：０．５：２の比で混合することになるが、この混合溶液をそのまま結晶化させようとしても、鉛系強誘電体膜を作製するには、高い結晶化温度を必要とする。すなわち、Ｎｂを混合すると、結晶化温度が急激に上昇してしまい、７００℃以下の素子化可能な温度範囲では結晶化が不可能なため、従来では５モル％以上のＮｂはＴｉの置換元素としては用いられていなかった。 When forming a lead-based ferroelectric film made of, for example, PbZr 0.75 Ti 0.05 Nb 0.2 O 3 (PZTN) using the first, second, and third raw material solutions, 1 raw material solution) :( second raw material solution) :( third raw material solution) = 7.5: 0.5: 2 is mixed, but this mixed solution will be crystallized as it is. Even so, a high crystallization temperature is required to produce a lead-based ferroelectric film. That is, when Nb is mixed, the crystallization temperature rises rapidly, and crystallization is impossible in the temperature range where the element can be formed at 700 ° C. or less. It was not used as.
そこで、本実施形態では、上記課題を、第４の原料溶液としての、ＰｂＳｉＯ３結晶を形成するため縮重合体をｎ−ブタノール等の溶媒に無水状態で溶解した溶液を例えば、１モル％以上５モル％以下で上記混合溶液中に更に添加することで解決することができる。 Therefore, in the present embodiment, 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.
すなわち、上記第１、第２、第３および第４の原料溶液の混合溶液を用いることで、ＰＺＴＮの結晶化温度を７００℃以下の素子化可能な温度範囲で結晶化させることが可能となる。 That is, by using the mixed solution of the first, second, third, and fourth raw material solutions, it becomes possible to crystallize the crystallization temperature of PZTN within a temperature range in which an element can be formed at 700 ° C. or less. .
具体的には、図１に示したフローチャートに従い鉛系強誘電体膜を成膜する。混合溶液塗布工程（ステップＳＴ１１）、アルコール除去工程〜乾燥熱処理工程〜脱脂熱処理工程（ステップＳＴ１２，ステップＳＴ１３）の一連の工程を所望の回数行い、その後に結晶化アニール（ステップＳＴ１４）により焼成して鉛系強誘電体膜を形成する。 Specifically, a lead-based ferroelectric film is formed according to the flowchart shown in FIG. A series of steps of 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.
各工程における条件の例を下記に示す。 Examples of conditions in each step are shown below.
初めにＳｉ基板上にＰｔ等の電極用貴金属を被覆して下電極を成膜する（ステップＳＴ１０）。次に、混合溶液の塗布をスピンコートなどの塗布法で行う（ステップＳＴ１１）。具体的には、Ｐｔ被覆基板上に混合溶液を滴下する。滴下された溶液を基板全面に行き渡らせる目的で５００ｒｐｍ程度でスピンを行った後、５０ｒｐｍ以下に回転数を低下させて１０秒ほど回転させる。乾燥熱処理工程は１５０℃〜１８０℃で行う（ステップＳＴ１３）。乾燥熱処理は大気雰囲気下でホットプレート等を用いて行う。同様に脱脂熱処理工程では３００℃〜３５０℃に保持されたホットプレート上で、大気雰囲気下で行う（ステップＳＴ１３）。結晶化のための焼成は、酸素雰囲気中でラピッドサーマルアニール（ＲＴＡ）等を用いて行う（ステップＳＴ１４）。 First, a lower electrode is formed by coating a noble metal for electrodes such as Pt on a Si substrate (step ST10). Next, 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. Similarly, 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).
また焼成後の膜厚は１００〜２００ｎｍ程度とすることができる。次に、上電極をスパッタ法等により形成した後に（ステップＳＴ１５）、上電極と鉛系強誘電体膜との界面形成、および鉛系強誘電体膜の結晶性改善を目的としてポストアニールを、焼成時と同様に、酸素雰囲気中でＲＴＡ（rapid thermal anneal）等を用いて行い（ステップＳＴ１６）、鉛系強誘電体膜を得る。なお、下電極及び上電極は、Ｐｔ、Ｉｒ、Ｒｕ等の白金族元素の単体または白金族元素を主体とした複合材料によって形成されていても良い。 Moreover, the film thickness after baking can be about 100-200 nm. Next, after forming the upper electrode by sputtering or the like (step ST15), 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. Similarly to the firing, RTA (rapid thermal anneal) or the like is performed in an oxygen atmosphere (step ST16) to obtain a lead-based ferroelectric film. Note that 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.
次に、上記成膜方法を用いて成膜された鉛系強誘電体膜のサンプルＡ〜Ｃを作製し、それらのサンプルＡ〜Ｃのヒステリシス曲線及び圧電効果を評価した結果を図２（Ａ）〜（Ｃ）に示す。 Next, samples A to C of the lead-based ferroelectric film formed by using the film forming method described above were prepared, and the hysteresis curves and the piezoelectric effect of these samples A to C were evaluated. ) To (C).
サンプルＡは、Ｓｉ基板上にスパッタ法を用いてＰｔからなる金属膜（電極）を形成し、その電極上にＰｂ（Ｚｒ０．７Ｔｉ０．１Ｎｂ０．２）Ｏ３の組成となる鉛系強誘電体膜を作製した。サンプルＢは、Ｓｉ基板上にスパッタ法を用いてＰｔからなる金属膜（電極）を形成し、その電極上にＰｂ（Ｚｒ０．７5Ｔｉ０．０５Ｎｂ０．２）Ｏ３の組成となる鉛系強誘電体膜を作製した。サンプルＣは、Ｓｉ基板上にスパッタ法を用いてＰｔからなる金属膜（電極）を形成し、その電極上にＰｂ（Ｚｒ０．８Ｎｂ０．２）Ｏ３の組成となる鉛系強誘電体膜を作製した。全てのサンプルにおいてＰｂＳｉＯ３シリケートを５モル％添加している。また、膜形成のための原料となる強誘電体膜形成用ゾルゲル溶液には、コハク酸ジメチルを添加してｐＨを６とした。成膜フローは全て前述の図１を用いている。 In 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. In 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. In sample C, 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. In all samples, 5 mol% of PbSiO 3 silicate is added. Further, 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. The above-described FIG. 1 is used for all film forming flows.
図２（Ａ）〜（Ｃ）によれば、サンプルＡ〜Ｃはすべてヒステリシス特性を有しないが圧電効果のあることが確認された。また、Ｔｉの量は少ないほうがヒステリシスが発生しにくくて良いことも確認された。従って、鉛系強誘電体膜のより好ましい組成範囲は、Ｐｂ（ＺｒＸＴｉＹＮｂＺ）Ｏ３で示され、以下の関係、
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．１
０．０５≦Ｚ≦０．２５
が成立することである。
2A to 2C, it was confirmed that the samples A to C did not have hysteresis characteristics but had a piezoelectric effect. It was also confirmed that hysteresis is less likely to occur when the amount of Ti is smaller. Therefore, a more preferred composition range of the lead-based ferroelectric film is shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.1
0.05 ≦ Z ≦ 0.25
Is established.
サンプルＣでは、図２（Ｃ）に示すように、抗電界Ecは25kV/cm以下、残留分極値Prは10μC/cm2以下、かつ比誘電率400以上（好ましくは1000以上）であることが分かる。このようにサンプルＣでは、P-Eヒステリシス曲線を殆ど有していない為、電界印加時のヒステリシスカーブ描写時の時間的ロスが殆どない。従って、このような鉛系強誘電体膜を用いた圧電素子では、圧電素子の動作時に強誘電体膜が分極反転する時間が必要ないため、その時間だけ動作に遅れることがない。よって、圧電素子の信頼性を向上させることができる。 In the sample C, as shown in FIG. 2C, the coercive electric field Ec is 25 kV / cm or less, the remanent polarization value Pr is 10 μC / cm 2 or less, and the relative dielectric constant is 400 or more (preferably 1000 or more). I understand. Thus, since sample C has almost no PE hysteresis curve, there is almost no time loss when drawing the hysteresis curve when an electric field is applied. Accordingly, in such a piezoelectric element using a lead-based ferroelectric film, there is no need for time for the ferroelectric film to undergo polarization reversal during the operation of the piezoelectric element, so that the operation is not delayed by that time. Therefore, the reliability of the piezoelectric element can be improved.
（実施形態３）
図３は、実施形態３によるＳＡＷ（surface acoustic wave）フィルタを説明するための斜視図である。このＳＡＷフィルタは、必要な信号以外の他の周波数を雑音としてカットし、必要な信号だけを取り出すものである。
(Embodiment 3)
FIG. 3 is a perspective view for explaining a surface acoustic wave (SAW) filter according to the third embodiment. This SAW filter cuts out frequencies other than necessary signals as noise and extracts only necessary signals.
実施形態１又は２による圧電体を用いた圧電体基板１を用意する。この圧電体基板１の上に、規則性のあるくし型電極２ａ，２ｂを形成する。くし型電極２ａ，２ｂは、取り出したい必要な信号である電波と同じ波長の長さに電極を作ったものである。電波の入口から入った電波は、圧電体基板１上のくし型電極２ａ，２ｂを通る際に、くし型電極と同じ長さの波長しか電波の出口に到達することができない。つまり、雑音になる電波は圧電体の表面の波と異なっているため打ち消され、必要な信号のみを出口から取り出すことができる。 A piezoelectric substrate 1 using the piezoelectric body according to Embodiment 1 or 2 is prepared. On the piezoelectric substrate 1, regular comb-shaped electrodes 2a and 2b are formed. 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. When 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.
上記実施形態３によれば、ＳＡＷフィルタの圧電体基板１を、実施形態１又は２によるヒステリシス特性を有していない圧電体を用いて形成しているため、ＳＡＷフィルタの動作時に圧電体が分極反転することがない。従って、信頼性の高いＳＡＷフィルタを得ることができる。 According to the third embodiment, since 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.
１…圧電体基板
２ａ，２ｂ…くし型電極
DESCRIPTION OF SYMBOLS 1 ... Piezoelectric substrate 2a, 2b ... Comb-type electrode
Claims (3)
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．２５
０．０５≦Ｚ≦０．２５
が成立する圧電体であり、
前記圧電体は、抗電界Ecは25kV/cm以下、残留分極値Prは10μC/cm2以下、かつ比誘電率400以上であることを特徴とする圧電体。 Shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.25
0.05 ≦ Z ≦ 0.25
Is a piezoelectric body, and
The piezoelectric body is characterized in that the coercive electric field Ec is 25 kV / cm or less, the remanent polarization value Pr is 10 μC / cm 2 or less, and the relative dielectric constant is 400 or more.
前記下電極上に形成された鉛系圧電体と、
前記鉛系圧電体上に形成された上電極と、
を具備し、
前記鉛系圧電体は、Ｐｂ（Ｚｒ Ｘ Ｔｉ Ｙ Ｎｂ Ｚ ）Ｏ ３ で示され、以下の関係、
Ｘ＋Ｙ＋Ｚ＝１
０≦Ｙ≦０．２５
０．０５≦Ｚ≦０．２５
が成立し、
前記鉛系圧電体は、抗電界Ecは25kV/cm以下、残留分極値Prは10μC/cm2以下、かつ比誘電率400以上であることを特徴とする圧電素子。 A lower electrode;
A lead-based piezoelectric body formed on the lower electrode;
An upper electrode formed on the lead-based piezoelectric body;
Comprising
The lead-based piezoelectric material is shown by Pb (Zr X Ti Y Nb Z ) O 3, the following relationship,
X + Y + Z = 1
0 ≦ Y ≦ 0.25
0.05 ≦ Z ≦ 0.25
Is established,
The lead-based piezoelectric element has a coercive electric field Ec of 25 kV / cm or less, a remanent polarization value Pr of 10 μC / cm 2 or less, and a relative dielectric constant of 400 or more.
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