CN100539228C - Piezoelectricity layered product, surface acoustic wave element, piezo-electric resonator and piezoelectric actuator - Google Patents
Piezoelectricity layered product, surface acoustic wave element, piezo-electric resonator and piezoelectric actuator Download PDFInfo
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- CN100539228C CN100539228C CNB2006101606936A CN200610160693A CN100539228C CN 100539228 C CN100539228 C CN 100539228C CN B2006101606936 A CNB2006101606936 A CN B2006101606936A CN 200610160693 A CN200610160693 A CN 200610160693A CN 100539228 C CN100539228 C CN 100539228C
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Abstract
The invention provides a kind of piezoelectricity layered product that on matrix, is formed with the piezoelectric body layer that comprises potassium-sodium niobate.Piezoelectricity layered product (100) comprises matrix (1) and is formed at first piezoelectric body layer top, that comprise potassium-sodium niobate (3) of described matrix (1).Described first piezoelectric body layer (3) is with composition formula (K
aNa
1-a)
xNbO
3Expression, in this composition formula, 0.1＜a＜1,1≤x≤1.2.
Description
Technical field
The present invention relates to have the piezoelectricity layered product of potassium-sodium niobate layer, the surface acoustic wave element that comprises this piezoelectricity layered product, film bulk acoustic-wave resonator and piezoelectric actuator.
Background technology
Along with the developing rapidly of the communications field that with mobile communicatings such as for example portable phones is the center, the demand of surface acoustic wave element is also enlarged rapidly.Miniaturization, high efficiency, high frequencyization are the R﹠D directions of surface acoustic wave.Therefore, need bigger electromechanical coupling factor (k
2), more stable temperature characterisitic, surface acoustic wave propagate speed faster.
Existing surface acoustic wave element mainly is to adopt the structure that forms the interdigitation electrode on the monocrystalline of piezoelectrics.Representative species as piezoelectric monocrystal has crystal, lithium niobic acid (LiNbO
3), lithium tantalic acid (LiTaO
3) etc.When being when for example requiring the RF filter of low-lossization of broad in band or passband, adopts the big LiNbO of electromechanical coupling factor
3On the other hand, even narrow-band, when being when needing the IF filter of stable temperature characterisitic, adopts the little crystal of centre frequency temperature coefficient.And, work as LiTaO
3Electromechanical coupling factor and centre frequency temperature coefficient lay respectively at LiNbO
3And crystal between the time, LiTaO
3The effect of being brought into play also between it between the two.And, recently, at potassium niobic acid (KNbO
3) find the angle of cut of the value of the electromechanical coupling factor that performance is bigger in the monocrystalline.KNbO
3The monocrystalline plate is recorded in the spy and opens in the flat 10-65488 communique.
In the surface acoustic wave element that adopts single crystal piezoelectric substrate, characteristics such as electromechanical coupling factor, temperature coefficient, velocity of sound are the intrinsic values of material, are determined by the angle of cut and the direction of propagation.0 ° of Y-XKNbO for example
3The monocrystalline matrix shows excellent on electromechanical coupling factor, but does not show the rotation Y-XKNbO from 45 ° to 75 ° near room temperature
3The zero degree characteristic that the monocrystalline matrix is such.
Summary of the invention
The objective of the invention is to, be provided at the piezoelectricity layered product that is formed with the potassium-sodium niobate layer on the matrix.
Another object of the present invention is to, surface acoustic wave element and film bulk acoustic-wave resonator with piezoelectricity layered product of the present invention are provided.
Another object of the present invention is to, the piezoelectric actuator with piezoelectricity layered product of the present invention is provided.
The piezoelectricity layered product that the present invention relates to comprises: matrix; And first piezoelectric body layer top, that comprise potassium-sodium niobate that is formed at described matrix.
In the present invention, when specific A parts (below, be called " A parts ") top when specific B parts (below, be called " B parts ") are set, it is included in situation that the B parts directly are set above the A parts, and the situation of B parts is set across miscellaneous part on the A parts.
According to piezoelectricity layered product of the present invention, described first piezoelectric body layer is with composition formula (K
aNa
1-a)
xNbO
3Expression, in this composition formula, 0.1＜a＜1,1≤x≤1.2.
According to piezoelectricity layered product of the present invention, in the described composition formula of described first piezoelectric body layer, 1＜x≤1.1.
In piezoelectricity layered product of the present invention, can below described first piezoelectric body layer, be formed with the orientation key-course.
In piezoelectricity layered product of the present invention, described orientation key-course can comprise the acid of lanthanum nickel.The acid of described lanthanum nickel is the acid of polycrystalline lanthanum nickel.
Piezoelectricity layered product of the present invention comprises and described first piezoelectric body layer second piezoelectric body layer that be connected, that comprise potassium-sodium niobate, described second piezoelectric body layer comprise constitute connect with described second piezoelectric body layer and be positioned at the opposite side of described first piezoelectric body layer layer element.
According to piezoelectricity layered product of the present invention, described first piezoelectric body layer comprises: the first phase part, it comprises with composition formula (K
aNa
1-a) NbO
3The piezoelectrics of expression; And the second phase part, it comprises with composition formula (K
aNa
1-a)
xNbO
3The piezoelectrics of expression, wherein, 1＜x.
Piezoelectricity layered product of the present invention comprises the electrode that is formed at described first piezoelectric body layer top.
Piezoelectricity layered product of the present invention comprises: first electrode is formed between described matrix and described first piezoelectric body layer; And second electrode, be formed at the top of described first piezoelectric body layer.
The surface acoustic wave member that the present invention relates to comprises piezoelectricity layered product of the present invention.
The film bulk acoustic-wave resonator that the present invention relates to comprises piezoelectricity layered product of the present invention.
The piezoelectric actuator that the present invention relates to comprises piezoelectricity layered product of the present invention.
Description of drawings
Fig. 1 is the profile of the first piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 2 is the profile of the piezoelectric body layer of the piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 3 is the profile of the piezoelectric body layer of the piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 4 is the profile of the variation of the first piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 5 is the profile of the second piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 6 is the profile of the variation of the second piezoelectricity layered product that relates to of the schematically illustrated embodiment of the invention.
Fig. 7 is the schematic diagram of the hysteresis characteristic of piezoelectric body layer in the embodiment of the invention.
Fig. 8 (A), (B) are by piezoelectric body layer table in the embodiment of the invention of SEM detection
The figure of face (C) is the figure on piezoelectric body layer surface in the comparative example that is detected by SEM.
Fig. 9 is the XRD figure of the embodiment of the invention and comparative example.
Figure 10 is the figure of the relation of the electric field of piezoelectric body layer in the embodiment of the invention and strain.
Figure 11 is the schematic diagram of the SAW waveform of piezoelectric body layer in the embodiment of the invention.
Figure 12 is the Raman luminesceence analysis result's of the embodiment of the invention a schematic diagram.
Figure 13 is the surplus of Na in the embodiment of the invention and the schematic diagram of spaced relationship.
Figure 14 (A) is the schematic diagram by the surface of the embodiment of the invention of SEM detection, (B) is the figure by surface in the reference example of SEM detection.
Figure 15 (A) illustrates the XRD figure of the embodiment of the invention, (B) is the figure of the XRD of reference example.
Figure 16 is the figure of the surface acoustic wave element that relates to of the schematically illustrated embodiment of the invention.
Figure 17 is the schematically illustrated figure that has used the frequency filter of the surface acoustic wave element that the embodiment of the invention relates to.
Figure 18 is the schematically illustrated figure that has used the oscillator of the surface acoustic wave element that the embodiment of the invention relates to.
Figure 19 is the figure of the first film piezo-electric resonator that relates to of the schematically illustrated embodiment of the invention.
Figure 20 is the figure of second film bulk acoustic-wave resonator that relates to of the schematically illustrated embodiment of the invention.
Figure 21 is the figure of the piezoelectric actuator of the schematically illustrated application embodiment of the invention.
Figure 22 is the stereogram of the ink jet type head of the piezoelectric actuator that relates to of the schematically illustrated application embodiment of the invention.
Embodiment
Below, with reference to accompanying drawing the embodiment that the present invention relates to is described.
1. piezoelectricity layered product
1.1. the first piezoelectricity layered product
Fig. 1 is the profile that schematically shows an example of the first piezoelectricity layered product 100 that present embodiment relates to.
Piezoelectricity layered product 100 comprises: matrix 1; Be formed at piezoelectric body layer 3 on the matrix 1, that comprise potassium-sodium niobate; And be formed at electrode 4 on the piezoelectric body layer 3.
As shown in Figure 4, can comprise orientation key-course 6 on the matrix 1 as required.Orientation key-course 6 is called resilient coating or crystal seed layer, has the function of the crystalline orientation of may command piezoelectric body layer 3.That is it is similar with the crystalline texture that is orientated key-course 6, to be formed at the crystalline texture of the piezoelectric body layer 3 of orientation on the key-course 6.Orientation key-course 6 as relevant can use the composite oxides that have with piezoelectric body layer 3 identical crystalline textures.Can use for example lanthanum nickel acid (LaNiO as orientation key-course 6
3) perofskite type oxide that waits.The acid of lanthanum nickel can be polycrystalline structure.As long as orientation key-course 6 is the orientation of may command piezoelectric body layer 3, for example has 50 to 100nm thickness and gets final product.
In the present embodiment, piezoelectric body layer 3 is the layer of homogeneous, or have as Fig. 2, structure shown in Figure 3 layer.Fig. 2 and Fig. 3 are figure conceptization or medelling.
That is, as shown in Figure 2, piezoelectric body layer 3 comprises: first piezoelectric body layer 32, it comprises composition formula (K
aNa
1-a) NbO
3Represented potassium-sodium niobate; Second piezoelectric body layer 34, it is formed between first piezoelectric body layer 32 and the matrix 1, comprises piezoelectrics, and these piezoelectrics comprise the element that constitutes the layer (illustrated situation is a matrix 1) that is connected with piezoelectric body layer 3 at least.Second piezoelectric body layer 34 is compared with first piezoelectric body layer 32, excessively contains potassium and sodium as A bit element.And second piezoelectric body layer 34 comprises the element that constitutes matrix 1 in the potassium-sodium niobate of first piezoelectric body layer 32.For example, when using STO (SrTiO
3) substrate is during as matrix 1, second piezoelectric body layer 34 comprises strontium and titanium in potassium-sodium niobate.Use Nb:STO (Nb doping SrTiO
3) during as matrix 1, second piezoelectric body layer 34 can comprise strontium, titanium and niobium in potassium-sodium niobate.And as shown in Figure 4, when having orientation key-course 6 on the matrix 1, second piezoelectric body layer 34 can comprise the element that constitutes orientation key-course 6.For example, when using the lanthanum niobic acid as orientation key-course 6, second piezoelectric body layer 34 contains lanthanum and nickel in potassium-sodium niobate.
And as shown in Figure 3, piezoelectric body layer 3 comprises: the first phase part 36 comprises with composition formula (K
aNa
1-a) NbO
3The piezoelectrics of expression; And the second phase part 38, comprise with composition formula (K
aNa
1-a)
xNbO
3The piezoelectrics of expression, wherein, 1＜x.
The piezoelectric body layer 3 preferred preferred orientations of this enforcement are for intending cube crystalline substance (100).
The representational bed thickness of piezoelectric body layer 3 is selected according to the purposes of piezoelectricity layered product 100.The representational bed thickness of piezoelectric body layer 3 is 300nm to 3.0 μ m.But, in the scope of keeping as the densification of thin layer and crystalline orientation, can thicken this thickness, higher limit allows about 10 μ m.
Electrode 4 can comprise metal level or conductive complex oxide thing layer.Electrode 4 also can be the layered product of metal level and conductive complex oxide thing layer.As the material of electrode 4, can use conductive complex oxide thing layers such as metal levels such as platinum, iridium, aluminium or yttrium oxide.
The first piezoelectricity layered product 100 of present embodiment can followingly form.
(1) at first, prepare matrix 1.Matrix 1 is selected according to the purposes of aforesaid piezoelectricity layered product 100.Matrix 1 can use for example STO (SrTiO
3) substrate, Nb:STO (Nb doping SrTiO
3) substrate and sapphire substrate.
(2) as shown in Figure 1, on matrix 1, form piezoelectrics 3, comprise the piezoelectrics that above-mentioned composition formula is represented.
When utilizing gel sol method or MOD method to form piezoelectric body layer 3, can use precursor solution formation coating layer, form piezoelectric body layer 3 by making this coating layer crystallization as the composition of above-mentioned composition formula.
Precursor solution as the formation material of piezoelectric body layer 3 can followingly be made: by the mixed in molar ratio organo-metallic compound of desirable each metal, and further use organic solvent such as alcohol with the above-mentioned substance dissolving or disperse and make, wherein, above-mentioned organo-metallic compound contains the formation metal of the piezoelectric that forms piezoelectric body layer 3 respectively.Can use metal alkoxide or acylate, beta diketone complex compound organo-metallic compound as the formation metal that contains piezoelectric respectively.Particularly, can exemplify following material as piezoelectric.
As the organo-metallic compound that comprises sodium (Na), can enumerate for example sodium ethoxide.As the organo-metallic compound that comprises potassium (K), can enumerate for example ethyoxyl potassium.As the organo-metallic compound that comprises niobium (Nb), can enumerate for example ethyoxyl niobium.The organo-metallic compound that comprises the formation metal of piezoelectric can not be subjected to above-mentioned restriction and uses known material.
In precursor solution, can add the various additives of stabilizer etc. as required.And, when in precursor solution, producing hydrolysis, polycondensation, in precursor solution, add in an amount of water, can add acid or alkali as catalyst.
Preparation raw material solution is so that piezoelectric body layer 3 is desirable ratio of components.After coating this material solution on the matrix 1, implement heat treatment and make the coating crystallization, can form piezoelectric body layer 3 thus.Particularly, for example carry out a series of steps such as the dry heat treatment step of removal step, coating of the application step of the material solution of desired number of times, pure equal solvent and degreasing heat treatment step, burn till by crystallization annealing afterwards and form piezoelectric body layer 3.And, by carrying out desirable number of times, also can form piezoelectric body layer 3 by the removal step of above-mentioned application step, solvent, a series of step that dry heat treatment step, degreasing heat treatment step and the crystallization annealing steps of coating constitute.
(3) as shown in Figure 1, on piezoelectric body layer 3, form electrode 4.The metal level or the conductive complex oxide thing layer that constitute electrode 4 can be by formation such as for example known sputtering methods.
(4) then, as required, can under the oxygen environment, adopt RTA (hot short annealing) etc. to carry out post-weld annealed.Thus, the good interface of electrode 4 and piezoelectric body layer 3 can be formed, and the crystallinity of piezoelectric body layer 3 can be improved.
As shown in Figure 4, when being when having the piezoelectricity layered product 100 of orientation key-course 6 on the matrix 1, after above-mentioned (1) step, on matrix 1, form orientation key-course 6.When using the acid of lanthanum nickel, can use sputtering method as orientation key-course 6.By forming orientation key-course 6, piezoelectric body layer 3 can reflect the crystal structure that is orientated key-course 6 and have higher crystallinity and orientation.
By above-mentioned steps, can make the first relevant piezoelectricity layered product 100 of present embodiment.
As mentioned above, by forming piezoelectric body layer 3, piezoelectric body layer 3 comprises with composition formula (K
aNa
1-a)
xNbO
3The piezoelectrics of expression.These piezoelectrics are the perofskite type oxides that have the orthorhombic system structure in room temperature.
1.2. the second piezoelectricity layered product
Fig. 5 schematically shows the profile of an example of the second piezoelectricity layered product 200 that present embodiment relates to.
Piezoelectricity layered product 200 comprises: matrix 1; Be formed at first electrode (lower electrode) 2 on the matrix 1; Be formed at the piezoelectric body layer 3 on the lower electrode 2; And be formed at second electrode (upper electrode) 4 on the piezoelectric body layer 3.
As shown in Figure 6, on lower electrode 2, can have orientation key-course 6 as required.Orientation key-course 6 is identical with the description in the first piezoelectricity layered product 100, is called resilient coating or thin layer, has the function of the crystalline orientation of control piezoelectric body layer 3.
When piezoelectric body layer had the formation corresponding with Fig. 2, piezoelectric body layer 3 comprised: first piezoelectric body layer 32, it comprises with composition formula (K
aNa
1-a) NbO
3The piezoelectrics of expression; And second piezoelectric body layer 34, be formed between first piezoelectric body layer 32 and the matrix 1, comprise the piezoelectrics (containing the excessive potassium and/or the potassium-sodium niobate of sodium) of the element that constitutes layer (being equivalent to the lower electrode 2 in the accompanying drawing) that be connected with piezoelectric body layer 3 at least.
And when piezoelectric body layer had the formation corresponding with Fig. 3, piezoelectric body layer 3 comprised: the first phase part 36 comprises with composition formula (K
aNa
1-a) NbO
3The piezoelectrics of expression; And the second phase part 38, comprise with composition formula (K
aNa
1-a)
xNbO
3The piezoelectrics of expression, wherein, 1＜x.
The second piezoelectricity layered product 200 of this enforcement can followingly form.
(1) at first, prepare matrix 1.As matrix 1 can use with at the identical material of the matrix described in the first piezoelectricity layered product 100 1.Can use for example silicon substrate as matrix 1.
(2) as shown in Figure 5, on matrix 1, form lower electrode 2.The metal level or the conductive complex oxide thing layer that constitute lower electrode 2 can be by formation such as for example known sputtering methods.
(3) as shown in Figure 5, on lower electrode 2, form the piezoelectric body layer 3 that above-mentioned composition formula is represented.The formation method of piezoelectric body layer 3 is identical with the situation of the first piezoelectricity layered product 100, so omit detailed explanation.
(4) as shown in Figure 5, on piezoelectric body layer 3, form upper electrode 4.The metal level of formation upper electrode 4 or formation, the formation method of conductive complex oxide thing layer are identical with the electrode 4 of the first piezoelectricity layered product 100, so can omit detailed explanation.
(5) then, as required, can under the oxygen environment, adopt RTA etc. to carry out post-weld annealed.Thus, the good interface between lower electrode 2, upper electrode 4 and the piezoelectric body layer 3 can be formed, and the crystallinity of piezoelectric body layer 3 can be improved.
As shown in Figure 6, when being when on lower electrode 2, having the piezoelectricity layered product 200 of orientation key-course 6, after the step of above-mentioned (2), on lower electrode 2, form orientation key-course 6.When using the acid of lanthanum nickel, can use sputtering method for orientation key-course 6.By forming orientation key-course 6, piezoelectric body layer 3 can reflect the crystal structure that is orientated key-course 6 and have higher crystallinity and orientation.
By above-mentioned steps, can prepare the second piezoelectricity layered product 200 that present embodiment relates to.
In addition, piezoelectric body layer 3 not only can use the liquid phase method of gel sol method or MOD (MetalOrganic Decomposition) method, also can use vapor phase methods such as laser ablation method or sputtering method and forms.
First, second piezoelectricity layered product 100,200 has the good piezoelectric body layer of piezoelectric property 3, applicable to various uses described later.
2. embodiment
Below, embodiments of the invention are described, but the present invention is not limited in these.
2.1. embodiment 1
Ethyoxyl potassium, sodium ethoxide and ethyoxyl niobium are with K: Na: Nb=1.0: 0.2: 1.0 mixed in molar ratio, this mixed liquor is refluxed in butyl cellosolve, and adjust three alkoxide solutions.Further add diethanol amine as the stabilizer of this solution.Adjust precursor solution thus.In addition, can replace diethanol amine to use acetic acid.This precursor solution being formed with the matrix of platinum layer (platinum layer/silicon oxide layer/silicon substrate) upward by the coating of spin rubbing method, after drying, pre-burning on the hot plate, is implemented hot short annealings under 700 ℃.Obtain polycrystalline potassium-sodium niobate (KNN) layer of the about 1.5 μ m of thickness through repeating for several times this step acquisition.On this KNN layer, form the platinum electrode of thickness 100nm, diameter 200 μ m by sputtering method.Obtain capacitor sample thus.
Use above-mentioned capacitor sample, when carrying out the hysteresis characteristic evaluation, can obtain B-H loop as shown in Figure 7.Can confirm that from Fig. 7 the capacitor sample of present embodiment has good hysteresis characteristic, the KNN layer has ferroelectricity.
2.2. embodiment 2, comparative example 1
The potassium in change embodiment 1 as shown in table 1 and the mol ratio of sodium (mole %), with the precursor solution of embodiment 1 identical preparation formation KNN layer usefulness.That is, potassium in the precursor solution is mixed with 10 moles of %, 20 moles of %, 40 moles of % and 50 moles of % than the amount (excessive Na) of sodium.At Nb: STO (Nb doping SrTiO
3) on the monocrystal substrate by the above-mentioned precursor solution of spin rubbing method coating, after dry on the hot plate, pre-burning, implement hot short annealings down at 700 ℃.Repeat above-mentioned steps for several times, obtain the polycrystalline KNN layer of four kinds of about 1 μ m of thickness.
Table 1:
| Na surplus [mol%] in the solution | Form (K aNa 1-a) xNbO 3 |
| 10 | X＝1.04 a＝0.85 |
| 20 | X＝1.09 a＝0.79 |
| 40 | X＝1.08 a＝0.63 |
| 50 | X＝1.08 a＝0.56 |
And, as a comparative example 1, in precursor solution, do not contain and receive, but except ethyoxyl potassium and ethyoxyl niobium with K: Nb=1.0: form potassium niobic acid layer (KN layer) 1.0 the mixed in molar ratio similarly to Example 2.
For KNN layer that obtains and KN layer, carry out following evaluation.
(1) composition analysis of KNN layer
By ICP (inductively coupled plasma) luminescence analysis, carry out the composition analysis of the KNN layer that embodiment 2 relates to.It the results are shown in table 1.Can confirm by table 1, in the KNN of embodiment layer, formula (K
aNa
1-a)
xNbO
3In x greater than 1, with respect to Nb, K and Na compare excessively with stoichiometric composition and contain.And Na content increases in the precursor solution even make, and " x " maximum is about 1.1.
(2) laminar surface of observing by SEM
The surface of the KN layer that two kinds of KNN layers (x=1.04,1.09) that related to by SEM observation embodiment 2 and comparative example 1 relate to.Fig. 8 illustrates its result.Fig. 8 (A), (B) are the results of embodiment 2, and Fig. 8 (C) is the result of comparative example 1.Can confirm that from Fig. 8 (A), (B) the KNN layer that embodiment 2 relates to can obtain homogeneous and good form.Corresponding therewith, can confirm from Fig. 8 (C), in the KN of comparative example 1 layer, be formed with out-phase.
(3) crystallinity that detects by XRD
Detect and above-mentioned (2) the middle identical sample that uses by XRD.Its result as shown in Figure 9.In Fig. 9, mark " a " reaches the result that the chart shown in " b " is the KNN layer that relates to of embodiment 2, and the chart shown in the mark " c " is the result of the related KN layer of comparative example 1.
Can confirm that from Fig. 9 the KNN layer that embodiment 2 relates to demonstrates good crystallinity, carry out (100) orientation.Corresponding therewith, the KN layer of comparative example 1 shows out-phase (K
4Nb
6O
17) the peak, can not obtain good crystallinity.
(4) Raman spectroscopy
To the KNN layer that obtains among the embodiment 2 promptly, use content (excess sodium) with respect to the sodium of potassium to be mixed with the precursor solution of 10 moles of %, 20 moles of %, 40 moles of % and 50 moles of % and the KNN layer that obtains, and use and excessive Na to be mixed with the precursor solution of 30 moles of % and to handle equally with embodiment 2 and the KNN layer that obtains, carry out Raman spectrum analysis.Its result as shown in figure 12.In Figure 12, the spectrum when described excessive Na is shown from mark a to mark e from 10 moles of % to 50 mole of %.
Can confirm from the spectrogram of Figure 12, because excessive N a, and make first peak that the A position by KNN produces (from 500cm
-1To 550cm
-1Between the peak) be subjected to displacement and 600cm
-1Near broadening of peak.Thus, potassium and sodium are present on the A position.
(5) from interval that X-ray analysis is tried to achieve
Ask for each sample among the embodiment 2 from the peak of X-ray analysis (θ-2 θ) to the interval of (100) face.Its result represents in Figure 13.
Can confirm from Figure 13, with the increase of excessive N a at interval the value of (d (100)) diminish.This is because the atomic radius of sodium less than the radius of potassium, increases and diminishes at interval with the addition of sodium.Can confirm also that from this some potassium and sodium are present in the A position.
2.3. embodiment 3
Adopt and the identical method described in the embodiment 1, preparation forms the precursor solution of KNN layer usefulness.At Nb: STO (Nb doping SrTiO
3) be coated with this precursor solution by the spin rubbing method on the monocrystal substrate, after carrying out drying, pre-burning on the hot plate, implement hot short annealings down at 700 ℃.This step for several times repeatedly obtains the polycrystalline KNN layer of the about 1 μ m of thickness.On this KNN layer,, form the platinum electrode of the about 100nm of thickness, the about 30 μ m of diameter by peeling off (lift-off) method.In the cambial process of platinum, use sputtering method.On the silicon substrate that covers platinum, pass through bonding this substrate of silver paste.
By AFM (atomic force microscope) to carrying out the electric field strain measurement by the above-mentioned sample of making.Its result as shown in figure 10.The electric field strain curve of Figure 10 illustrates the piezoelectric vibration that the KNN layer of present embodiment produces owing to voltage.And, can confirm among the embodiment 1 that by this result the B-H loop of observation is that piezoelectric property by the KNN layer causes.
2.4. embodiment 4
Use and identical method described in the embodiment 1, preparation forms the precursor solution of KNN layer usefulness.This gel solution is passed through the spin rubbing method at STO (SrTiO
3) be coated with on the monocrystal substrate, after dry on the hot plate, pre-burning, implement hot short annealings at 700 ℃.This step is repeated tens of times, obtain the polycrystalline KNN layer of the about 10 μ m of thickness.After using CMP with this KNN layer planarization, the aluminium lamination of evaporation thickness 100nm on the KNN layer forms both-end shape of the mouth as one speaks comb electrode (L/S=5 μ m) by photoetching process, uses network analyser to represent the mensuration of the S21 parameter of SAW propagation characteristic.
Shown in Figure 11 is the measurement result of S21 parameter, near the waveform of the substrate of the KNN/STO of observation fixed percentage bandwidth about 15% 240MHz (with mark " a " expression).Can confirm that from Figure 11 the KNN/STO substrate of present embodiment is by stress drive surface sound wave.
2.5. embodiment 5, reference example 1
With ethyoxyl potassium, sodium ethoxide and ethyoxyl niobium with K: Na: Nb=1.0: 0.2: 1.0 mixed in molar ratio, this mixed liquor is refluxed in butyl cellosolve, adjust three alkoxide solutions.Further add diethanol amine as the stabilizer of this solution.Adjust precursor solution thus.In addition, can replace diethanol amine to use acetic acid.This precursor solution is gone up by the coating of spin rubbing method at the matrix (lanthanum niobic acid layer/platinum layer/silicon oxide layer/silicon substrate) that is formed with polycrystalline lanthanum niobic acid (LNO) layer, after dry on the hot plate, pre-burning, implemented hot short annealings down at 700 ℃.Repeat polycrystalline potassium-sodium niobate (KNN) layer that this step obtains the about 1 μ m of thickness through eight times.
Use this sample, estimate this surface by SEM.It the results are shown among Figure 14 (A).Can confirm the crystallinity of the KNN layer reflection of present embodiment from this result, and have densification and good crystallinity as the LNO layer of orientation key-course.And, this sample is detected crystallinity by XRD, obtain the result that Figure 15 (A) illustrates.Can confirm in the present embodiment from this result, even the KNN layer is the thickness of 1 μ m, also be that (100) are single-orientated.
And, can confirm that during to the S parameter of the KNN layer of present embodiment 5 observation expression SAW propagation characteristic, propagation loss is smaller or equal to-1db, be smaller value applicable to SAW equipment etc.
As a reference example 1, the orientation key-course in not forming embodiment 5, with the embodiment 5 identical KNN layers that are formed with.Estimate the surface of this KNN layer by SEM.It the results are shown among Figure 14 (B).Can confirm that from this result the KNN layer of present embodiment is not because have LNO layer as the orientation key-course, so to compare surface relatively poor with embodiment 5.And, detect this KNN layer by XRD.It the results are shown in Figure 15 (B).Can confirm that from this result when forming the KNN layer on platinum layer, the KNN layer is an arbitrary orientation.
3. application examples
3.1. surface acoustic wave element
Below, press an example of the surface acoustic wave element of layered product 100 to describe with reference to accompanying drawing to using of the present invention first.
Figure 16 is the profile of the surface acoustic wave element 300 that relates to of schematically illustrated present embodiment.
Surface acoustic wave element 300 application drawings 1 and the first piezoelectricity layered product 100 shown in Figure 4 and form.That is, surface acoustic wave element 300 comprises: the matrix 1 in the piezoelectricity layered product 100; Be formed at the piezoelectric body layer 3 on the matrix 1; And to be formed at electrode on the piezoelectric body layer 3 be interdigitation electrode (below, be called " IDT electrode ") 18,19. IDT electrode 18,19 graphical electrodes 4 shown in Figure 2 and forming.
3.2. frequency filter
Below, describe with reference to the example of accompanying drawing the frequency filter of using surface acoustic wave element of the present invention.Figure 17 is the figure of schematically illustrated frequency filter.
As shown in figure 17, frequency filter has layered product 140.Can use the layered product (with reference to Figure 16) identical as this layered product 140 with above-mentioned surface acoustic wave element 300.That is, layered product 140 can have as Fig. 1 and matrix 1 and piezoelectric body layer 3 shown in Figure 4.
The upper surface of layered product 140 comprises as Fig. 1 and electrode 4 is the graphical and IDT electrode 141,142 that forms shown in Figure 4.And, form sound-absorbing part 143,144 at the upper surface of layered product 140 in mode across IDT electrode 141,142.Sound-absorbing part 143,144 is absorbed in the surface acoustic wave of the surface propagation of layered product 140.On an IDT electrode 141, connect high-frequency signal source 145, on another IDT electrode 142, connect holding wire.
3.3. oscillator
Below, describe with reference to the example of accompanying drawing the oscillator of using surface acoustic wave element of the present invention.Figure 18 is the figure of schematically illustrated oscillator.
As shown in figure 18, oscillator has layered product 150.Can use the layered product (with reference to Figure 16) identical as this layered product 150 with above-mentioned surface acoustic wave element 300.That is, layered product 150 can have Fig. 1 and matrix 1 and piezoelectric body layer 3 shown in Figure 4.
Upper surface at layered product 150 is formed with IDT electrode 151, and, be formed with IDT electrode 152,153 in mode across IDT electrode 151.On a comb electrode 151a who constitutes IDT electrode 151, be connected with high-frequency signal source 154, on another comb electrode 151b, be connected with holding wire.In addition, IDT electrode 151 is equivalent to the signal of telecommunication and applies and use electrode, and IDT electrode 152,153 is equivalent to make the specific frequency content of surface acoustic wave or specific zone frequency content to produce the vibration electrode of vibration, and this surface acoustic wave is by 151 generations of IDT electrode.
And, with above-mentioned oscillator application in VCSO (Voltage Controlled SAWOscillator: voltage control SAW oscillator).
As mentioned above, frequency filter and oscillator can comprise the surface acoustic wave element that the present invention relates to.
3.4. film bulk acoustic-wave resonator
Below, with reference to accompanying drawing, an example of the film bulk acoustic-wave resonator of using piezoelectricity layered product of the present invention is described.
3.4.1. the first film piezo-electric resonator
Figure 19 is the figure of the first film piezo-electric resonator 700 of an example of schematically illustrated present embodiment.The first film piezo-electric resonator 700 is film bulk acoustic-wave resonators of film-type.
The first film piezo-electric resonator 700 comprises substrate 701, elastic layer 703, lower electrode 704, piezoelectric body layer 705 and upper electrode 706.Substrate 701 in the film bulk acoustic-wave resonator 700, lower electrode 704, piezoelectric body layer 705, and upper electrode 706 be equivalent to matrix 1, lower electrode 2, piezoelectric body layer 3, and upper electrode 4 in Fig. 5 and the piezoelectricity layered product 200 shown in Figure 6 respectively.And, as elastic layer 703, can use the layer of resilient coating not shown among Fig. 5 (the orientation key-course among Fig. 6) etc.That is, the first film piezo-electric resonator 700 has Fig. 5 and piezoelectricity layered product 200 shown in Figure 6.
On substrate 701, be formed with the through hole 702 that connects substrate 701.Upper electrode 706 is provided with distribution 708.Distribution 708 is electrically connected by pad 710 with electrode 709 on being formed at elastic layer 703.
3.4.2. second film bulk acoustic-wave resonator
Figure 20 is the figure of second film bulk acoustic-wave resonator 800 of an example of schematically illustrated present embodiment.Second film bulk acoustic-wave resonator 800 and the first film piezo-electric resonator shown in Figure 19 700 main differences are, do not form through hole and form space 802 between substrate 801 and elastic layer 803.
Second film bulk acoustic-wave resonator 800 comprises substrate 801, elastic layer 803, lower electrode 804, piezoelectric body layer 805 and upper electrode 806.In film bulk acoustic-wave resonator 800, substrate 801, lower electrode 804, piezoelectric body layer 805, and upper electrode 806 be equivalent to matrix 1, lower electrode 2, piezoelectric body layer 3, and upper electrode 4 in Fig. 5 and the piezoelectricity layered product 200 shown in Figure 6 respectively.And, as elastic layer 803, can use the layer of resilient coating not shown among Fig. 5 (the orientation key-course 6 among Fig. 6) etc.That is, second film bulk acoustic-wave resonator 800 has Fig. 5 and piezoelectricity layered product 200 shown in Figure 6.Space 802 is the spaces that are formed between substrate 801 and the elastic layer 803.
The related piezoelectricity thin layer resonator (for example, the first film piezo-electric resonator 700 and and second film bulk acoustic-wave resonator 800) of present embodiment can have the function of resonator, frequency filter or oscillator.
3.5. piezoelectric actuator
Example as the second piezoelectricity layered product 200 of the present invention being applied to piezoelectric actuator describes ink jet recording head.Figure 21 is the end view that the summary of the ink jet recording head of the application piezoelectric actuator relevant with present embodiment constitutes, and Figure 22 is the exploded perspective view of this ink jet recording head, illustrates on the contrary up and down with normally used state.
As Figure 21 and shown in Figure 22, ink jet recording head 50 comprises a body 57, is formed at the piezoelectric part 54 on the body 57.Application drawing 5 and piezoelectricity layered product 200 shown in Figure 6 on piezoelectric part 54, lower electrode 2, piezoelectric body layer 3 and upper electrode 4 be lamination and constituting in order.In the ink jet recording head, piezoelectric part 54 plays a role as piezoelectric actuator.
Each piezoelectric part constitutes: be electrically connected with piezoelectric element driving circuit (not shown), based on the signalizing activity (vibration, distortion) of piezoelectric element driving circuit.That is, each piezoelectric part 54 plays a role as vibration source (brake) respectively.Elastic layer 55 vibrates by the vibration (bending) of piezoelectric part 54, makes internal pressure moment of cartridge 521 raise and play a role.It is 20V～40V that the maximum that puts on piezoelectrics applies voltage, drives under 20kHz～50kHz.Representational ink spray volume is that 2 slight litres are between 5 picoliters.
In addition, in above-mentioned, the ink jet recording head of ejection ink is illustrated as an example, present embodiment is as object with jet head liquid that the piezoelectricity layered product is used as piezoelectric actuator.Can enumerate the organism organic substance that electrode material injector head that the color material injector head, OLED display, the FED electrodes such as (electroluminescent displays) that use in the manufacturing of chromatic filter of the recording head that uses in the image recording structure of printer for example etc., LCD etc. use in forming and biochip use in making as jet head liquid spray first-class.
In addition, the present invention is not limited in the above embodiments, can carry out various distortion.For example, present invention resides in the formation that illustrates among the embodiment and be essentially identical formation (for example function, method and the formation that comes to the same thing, or purpose and effect are identical formation).And what the present invention includes formation that displacement illustrates among the embodiment is not the part of essence.And, the present invention can comprise with embodiment in the formation that the illustrates formation that plays same function maybe can realize the formation of identical purpose.And, present invention resides in the formation of adding known technology in the formation of explanation of embodiment.
Description of reference numerals
1 matrix, 2 lower electrodes
3 piezoelectric body layers, 4 electrodes (upper electrode)
6 orientation key-courses, 32 first piezoelectric body layers
34 second piezoelectric body layers, 36 first-phase parts
38 second-phase parts 100,200 piezoelectric layer laminates
300 surface acoustic wave elements 700,800 film bulk acoustic-wave resonators
Claims (11)
1. piezoelectricity layered product comprises:
Matrix; And
First piezoelectric body layer is formed at the top of described matrix, with composition formula (K
aNa
1-a)
xNbO
3Expression, wherein, in the described composition formula of described first piezoelectric body layer, 1＜x≤1.1,0.1＜a＜1.
2. piezoelectricity layered product according to claim 1 wherein, has the orientation key-course that contacts with described first piezoelectric body layer below described first piezoelectric body layer.
3. piezoelectricity layered product according to claim 2, wherein, described orientation key-course comprises the acid of lanthanum nickel.
4. piezoelectricity layered product according to claim 3, wherein, the acid of described lanthanum nickel is the acid of polycrystalline lanthanum nickel.
5. according to each described piezoelectricity layered product in the claim 1 to 4, comprise being formed at second piezoelectric body layer between the described matrix and first piezoelectric body layer, that comprise potassium-sodium niobate,
Described second piezoelectric body layer comprises the element that constitutes the layer that is formed at the below of described second piezoelectric body layer and contacts with this second piezoelectric body layer.
6. according to each described piezoelectricity layered product in the claim 1 to 4, wherein, described first piezoelectric body layer comprises by with composition formula (K
aNa
1-a) NbO
3The part that the piezoelectrics of expression constitute.
7. according to each described piezoelectricity layered product in the claim 1 to 4, also comprise the electrode that is formed at described first piezoelectric body layer top.
8. according to each described piezoelectricity layered product in the claim 1 to 4, also comprise:
First electrode is formed between described matrix and described first piezoelectric body layer; And
Second electrode is formed at the top of described first piezoelectric body layer.
9. a surface acoustic wave element comprises the described piezoelectricity layered product of claim 7.
10. a film bulk acoustic-wave resonator comprises the described piezoelectricity layered product of claim 8.
11. a piezoelectric actuator comprises the described piezoelectricity layered product of claim 8.
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| JP5391395B2 (en) * | 2007-10-15 | 2014-01-15 | 日立金属株式会社 | Substrate with piezoelectric thin film and piezoelectric element |
| JP5515675B2 (en) * | 2009-11-20 | 2014-06-11 | 日立金属株式会社 | Piezoelectric thin film element and piezoelectric thin film device |
| JP5071503B2 (en) * | 2010-03-25 | 2012-11-14 | 日立電線株式会社 | Piezoelectric thin film element and piezoelectric thin film device |
| JP5056914B2 (en) * | 2010-07-07 | 2012-10-24 | 日立電線株式会社 | Piezoelectric thin film element and piezoelectric thin film device |
| CN103889603B (en) * | 2011-10-20 | 2016-06-29 | 佳能株式会社 | Dust arrester and imaging device |
| JP2015070203A (en) * | 2013-09-30 | 2015-04-13 | ダイハツ工業株式会社 | Power-generating material, power-generating element, and power-generating system |
| WO2015080256A1 (en) * | 2013-11-28 | 2015-06-04 | 京セラ株式会社 | Piezoelectric element, and piezoelectric member, liquid discharge head, and recording device using piezoelectric element |
| WO2016121204A1 (en) * | 2015-01-26 | 2016-08-04 | 株式会社ユーテック | Pressurizing-type lamp annealing device, ferroelectric film and method for producing same |
| JP6610856B2 (en) * | 2015-03-20 | 2019-11-27 | セイコーエプソン株式会社 | Piezoelectric element, piezoelectric element applied device, and method of manufacturing piezoelectric element |
| US10355196B2 (en) | 2016-02-10 | 2019-07-16 | Seiko Epson Corporation | Piezoelectric element, piezoelectric element application device, and method of manufacturing piezoelectric element |
| JP7240083B2 (en) | 2017-03-21 | 2023-03-15 | Ｋｙｂ株式会社 | Servo valve controller |
| JP6922326B2 (en) | 2017-03-28 | 2021-08-18 | セイコーエプソン株式会社 | Piezoelectric element and piezoelectric element application device |
| US20210234527A1 (en) * | 2017-09-22 | 2021-07-29 | Anhui Anuki Technologies Co., Ltd. | Manufacturing Method for Piezoelectric Resonator and Piezoelectric Resonator |
| US11851747B2 (en) | 2018-03-01 | 2023-12-26 | Jx Metals Corporation | Potassium sodium niobate sputtering target and production method thereof |
| JP7196503B2 (en) | 2018-09-27 | 2022-12-27 | セイコーエプソン株式会社 | Piezoelectric element and its manufacturing method, liquid ejection head, and printer |
| JP7331424B2 (en) | 2019-04-10 | 2023-08-23 | セイコーエプソン株式会社 | Piezoelectric elements, liquid ejection heads, and printers |
| JP6756886B1 (en) | 2019-04-26 | 2020-09-16 | Ｊｘ金属株式会社 | Potassium niobate sodium sputtering target |
| JP7423978B2 (en) | 2019-10-28 | 2024-01-30 | セイコーエプソン株式会社 | Piezoelectric elements, liquid ejection heads, and printers |
| FR3135868A1 (en) * | 2022-05-18 | 2023-11-24 | Soitec | SURFACE ACOUSTIC WAVE DEVICE INTEGRATING A THIN LAYER OF METALLIC MATERIAL |
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| US3768032A (en) * | 1971-05-24 | 1973-10-23 | Philips Corp | Acoustic surface wave devices |
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| JP4212289B2 (en) * | 2002-04-04 | 2009-01-21 | Ｔｄｋ株式会社 | Method of manufacturing a piezoelectric ceramic |
| JP2004066600A (en) * | 2002-08-05 | 2004-03-04 | Seiko Epson Corp | Liquid ejection head and liquid ejector |
| JP4480967B2 (en) * | 2003-01-23 | 2010-06-16 | 株式会社デンソー | Piezoelectric ceramic composition, piezoelectric element, and dielectric element |
| US7009328B2 (en) * | 2003-06-20 | 2006-03-07 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive device made of piezoelectric/electrostrictive film and manufacturing method |
| JP4450636B2 (en) * | 2004-02-12 | 2010-04-14 | 株式会社豊田中央研究所 | Method for manufacturing piezoelectric ceramics |
| JP4795748B2 (en) * | 2004-09-13 | 2011-10-19 | 株式会社デンソー | Piezoelectric actuator |
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| US3768032A (en) * | 1971-05-24 | 1973-10-23 | Philips Corp | Acoustic surface wave devices |
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| CN1979908A (en) | 2007-06-13 |
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| JP2014033210A (en) | 2014-02-20 |
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