CN1127430A - Piezoelectric/electrostrictive film element and method of producing the same - Google Patents
Piezoelectric/electrostrictive film element and method of producing the same Download PDFInfo
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- CN1127430A CN1127430A CN 95115342 CN95115342A CN1127430A CN 1127430 A CN1127430 A CN 1127430A CN 95115342 CN95115342 CN 95115342 CN 95115342 A CN95115342 A CN 95115342A CN 1127430 A CN1127430 A CN 1127430A
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Images
Classifications
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
- H04R17/00—Piezoelectric transducers; Electrostrictive transducers
- H04R17/04—Gramophone pick-ups using a stylus; Recorders using a stylus
- H04R17/08—Gramophone pick-ups using a stylus; Recorders using a stylus signals being recorded or played back by vibration of a stylus in two orthogonal directions simultaneously
Abstract
A piezoelectric/electrostrictive film element which includes a ceramic substrate (2, 22) having at least one window (6, 36) and an integrally formed diaphragm portion (10) for closing each window, and a piezoelectric/electrostrictive unit (18, 24) including a lower electrode (12, 40), a piezoelectric/electrostrictive layer (14, 42) and an upper electrode (16, 44), which are formed in this order on the diaphragm portion. The piezoelectric/electrostrictive layer consists of a dense body having a crystal grain size of not smaller than 0.7 u m, and a porosity (x) of not greater than 15%, and the diaphragm portion has a deflection percentage (y) of 0-8%, The porosity (x) and the deflection percentage (y) satisfies the following formula: y </= 0.1167x<2> - 3.317x + 25.5.
Description
The present invention relates to the piezoelectricity or the electrostrictive film element of a kind of monocrystalline, twin crystal or other types, this element produces or surveys the displacement or the power of bending, skew or deflection form, and this element can be used for actuator, filter, display device, converter, pick-up, sounding body (as loud speaker), various resonator or oscillator, transducer and miscellaneous part or device." element " used herein speech is a kind ofly can or convert mechanical energy to transformation of electrical energy, i.e. mechanical force, displacement, strain or vibration perhaps is transformed into a kind of like this mechanical energy the element of electric energy.
In recent years, for example, optical field and precision positioning or process operation field, be extensive use of and need day by day a kind of for the member of adjusting or control an optical path length or a device or position component and on micron (μ m) order of magnitude element of its displacement of control, and a kind ofly be suitable for surveying the detecting element of an object along with the micro-displacement of electric variation.In order to address this need, the piezoelectricity or the electrostrictive film element that are used for actuator or transducer have been developed, this element comprises the piezoelectric such as ferroelectric material, and utilize reciprocal piezoelectric effect or inverse piezoelectric effect when this piezoelectric is applied an electric field, to produce a mechanical displacement, perhaps utilize piezoelectric effect so that when applying pressure or mechanical stress, produce an electric field.In these elements, a kind of monocrystalline type piezo-electric/electrostrictive membrane type element of routine has been used for such as a kind of loud speaker well.
Proposed to be used for the piezoelectric ceramics/electrostrictive film element of various purposes, in No. the 5-49270, No. the 3-128681, Japanese patent application that proposes as assignee of the present invention and the Japanese patent application disclosed.An embodiment of disclosed element has a ceramic substrate, and this substrate has a window at least, and forms integral body with a diaphragm, and this diaphragm seals this window or those windows so that at least one thin-walled diaphragm portion is provided.On an outer surface of each diaphragm portion of this ceramic substrate, form a piezoelectric unit (P/E unit hereinafter referred to as), this unit is a kind of by a bottom electrode, a piezoelectric layer (P/E layer hereinafter referred to as) and the whole laminated construction that top electrode is formed.This P/E unit is formed on the relevant diaphragm portion of ceramic substrate by a kind of suitable film formation method.The piezo-electric/electrostrictive membrane type element size of Xing Chenging is less and more cheap like this, and can be used as an electrical converter with high reliability.In addition, this element has very fast work response, and by applying a low-voltage, provides bigger displacement with bigger generative power amplitude.So said elements is advantageously used for a member that is used for actuator, filter, display device, transducer or a miscellaneous part or device.
In order to make aforesaid piezo-electric/electrostrictive membrane type element, be stacked on the bottom electrode of each P/E unit, P/E layer and top electrode on the diaphragm portion of ceramic substrate by this order with suitable film formation method, and heat-treat (firing) on demand so that this P/E whole unit be formed on this diaphragm portion.The present inventor's further research discloses, and the piezoelectric characteristic of this piezo-electric/electrostrictive membrane type element is because in this P/E unit, more particularly, and the heat treatment of being implemented during the formation of this P/E layer (firing) and by deterioration.
In other words, during the heat treatment of this P/E layer, this P/E layer stands owing to shrink the stress that causes with firing of contacted P/E layer of the diaphragm portion of ceramic substrate or P/E unit.As a result, this P/E layer may be because this stress and sintering fully not, and still stands to remain in stress wherein after firing.In this occasion, this piezo-electric/electrostrictive membrane type element can not show it intrinsic piezoelectric characteristic.
For the agglutinating property that improves the P/E layer and density so that improve the piezoelectric characteristic of this membrane component, can improve the firing temperature of this P/E layer, or reduce to support the thickness of this diaphragm portion of this P/E layer thereon.Yet these solutions are not enough to improve the density of this P/E layer, and residual stress can deterioration piezoelectric characteristic after this P/E layer is fired.Displacement when especially, this residual stress can reduce this P/E unit drives.In addition, this diaphragm portion thickness reduces to make and makes this ceramic substrate more as difficulty.
The solution of above-mentioned routine also can cause very big diaphragm portion side-play amount, and this causes the displacement of diaphragm portion when this P/E unit drives to reduce.Particularly, when P/E unit adjacent more than two is driven simultaneously, compares obviously when the displacement of these unit is driven with single P/E unit and reduce.Because the side-play amount of diaphragm portion is very big, this piezoelectricity/electricity system Flexible film element may or damage between the operating period in the making of this element, causes functional reliability to reduce.
Thereby first purpose of the present invention is to provide a kind of piezo-electric/electrostrictive membrane type element, wherein each P/E unit is formed on by a kind of film formation method on the outer surface of a thin-walled diaphragm portion of a ceramic substrate, and be formed on wherein that this P/E layer on this diaphragm portion shows very high agglutinating property and density and the influence that is not subjected to this diaphragm portion, guarantee reliability that this membrane component is very high and very high electromechanical conversion efficiency.
Second purpose of the present invention is to provide a kind of making a kind of like this method with piezoelectric/electrostrictive film element of aforesaid excellent characteristic.
A kind of piezo-electric/electrostrictive membrane type element is provided according to a first aspect of the invention, this element comprises: the ceramic substrate that the diaphragm portion of each window of at least one window and one sealing is arranged, and this diaphragm portion forms as an integral part of this ceramic substrate; Reach one and comprise a bottom electrode, the P/E unit of a P/E layer and a top electrode, these bottom electrodes, P/E layer and top electrode are formed on the outer surface of this diaphragm portion by a kind of film formation method by narrating order, so that a kind of laminated construction to be provided, this P/E layer is made up of a DB with the crystallite dimension that is not less than 0.7 μ m and the porosity (X) that is not more than 15%, this diaphragm portion has 0～8% deviation ratio (Y), this deviation ratio equals the side-play amount of core of this diaphragm portion to extend and pass the percentage of length of the short lines of this window center across the window of correspondence, and this porosity (X) and this deviation ratio (Y) satisfy following formula: Y≤0.1167X
2-3.317x+25.5.
In the piezo-electric/electrostrictive membrane type element that constitutes as mentioned above, the displacement that the diaphragm portion of this ceramic substrate experience reduces, and also this P/E layer shows high agglutinating property, the functional reliability of this element of assurance raising.The skew of diaphragm portion reduces to cause the displacement of diaphragm portion when producing less power by this P/E unit to strengthen.In addition, have high agglutinating property P/E layer and produce bigger power, this causes the displacement that strengthens.So this piezo-electric/electrostrictive membrane type element shows outstanding piezoelectric characteristic.
Driven occasion simultaneously in a plurality of P/E unit of this membrane component, displacement are compared with driven occasion in P/E unit only and are not reduced.So displacement does not change because of the difference of driving condition that should (respectively) P/E unit, guarantees the placement property and the qualitative height homogeneity of this membrane component.In addition, this piezoelectric/electrostrictive film element is in its making or be not easy damage between the operating period, guarantees to improve reliability effectively.
Aforesaid piezo-electric/electrostrictive membrane type element can be made by one of following three kinds of methods (A)～(C), guarantees the high electromechanical conversion efficiency and the high agglutinating property of resulting element.
A kind of method (A) of making a kind of piezo-electric/electrostrictive membrane type element is provided according to a second aspect of the invention, this element comprises: the ceramic substrate that the diaphragm portion of each window of at least one window and one sealing is arranged, and this diaphragm portion forms as an integral part of this ceramic substrate; And P/E unit that comprises a bottom electrode, a P/E layer and a top electrode, these bottom electrodes, P/E layer and top electrode are formed on the outer surface of this diaphragm portion by narrating order, so that a kind of laminated construction to be provided, the method comprising the steps of: (a) prepare this ceramic substrate, wherein this diaphragm portion is outwards outstanding so that a convex diaphragm portion to be provided; (b) on the outer surface of this convex diaphragm portion, form this bottom electrode and this P/E layer by a kind of film formation method; (c) fire this P/E layer like this, so that recessed this window of this convex diaphragm portion; And (d) on this P/E layer, form this top electrode by a kind of film formation method.
A kind of method (B) of making a kind of piezo-electric/electrostrictive membrane type element is provided according to a third aspect of the invention we, this element comprises: the ceramic substrate that the diaphragm portion of each window of at least one window and one sealing is arranged, and this diaphragm portion forms as an integral part of this ceramic substrate; And P/E unit that comprises a bottom electrode, a P/E layer and a top electrode, these bottom electrodes, P/E layer and top electrode are formed on the outer surface of this diaphragm portion by narrating order, so that a kind of laminated construction to be provided, the method comprising the steps of: (a) prepare this ceramic substrate; (b) form this bottom electrode and this P/E layer by a kind of film formation method on the outer surface of this diaphragm portion, this P/E layer comprises a kind of ceramic powders of 60% of filling this P/E layer before it is fired at least; (c) fire this P/E layer; And (d) on this P/E layer, form this top electrode by a kind of film formation method.
A kind of method (C) of making a kind of piezo-electric/electrostrictive membrane type element is provided according to a forth aspect of the invention, this element comprises: the ceramic substrate that the diaphragm portion of each window of at least one window and one sealing is arranged, and this diaphragm portion forms as an integral part of this ceramic substrate; And P/E unit that comprises a bottom electrode, a P/E layer and a top electrode, these bottom electrodes, P/E layer and top electrode are formed on the outer surface of this diaphragm portion by narrating order, so that a kind of laminated construction to be provided, the method comprising the steps of: (a) prepare this ceramic substrate, wherein this diaphragm portion is outwards outstanding so that a convex diaphragm portion to be provided; (b) form this bottom electrode and this P/E layer by a kind of film formation method on the outer surface of this convex diaphragm portion, this P/E layer comprises a kind of ceramic powders of 60% of filling this P/E layer before it is fired at least; (c) fire this P/E layer like this, so that recessed this window of this convex diaphragm portion; And (d) on this P/E layer, form this top electrode by a kind of film formation method.
By reading the following detailed description to some most preferred embodiments of this invention when considering in conjunction with the accompanying drawings, above and optional purpose of the present invention, feature and advantage will be better understood, in these accompanying drawings:
Fig. 1 is a decomposition diagram, an example of the basic structure of a kind of piezo-electric/electrostrictive membrane type element that expression constitutes according to the present invention;
Fig. 2 is the cutaway view of this piezo-electric/electrostrictive membrane type element of Fig. 1;
Fig. 3 is an enlarged drawing, and the section of this membrane component of presentation graphs 1, this section are along short distance footpath (minor face of this window) intercepting of passing a window center;
Fig. 4 (a) is that the partial sectional view that amplifies is represented an a kind of processing step making the method for piezoelectric/electrostrictive film element of the present invention;
Fig. 4 (b) is and the corresponding figure of Fig. 4 (a) that another processing step of this method of this membrane component is made in expression;
Fig. 4 (c) is and the corresponding figure of Fig. 4 (a) that another processing step of this method of this membrane component is made in expression;
Fig. 5 is a cutaway view, represents another embodiment of piezo-electric/electrostrictive membrane type element of the present invention; And
Fig. 6 is a decomposition diagram, the piezo-electric/electrostrictive membrane type element shown in the presentation graphs 5.
Referring to expression Fig. 1 and Fig. 2 as an example of the basic structure of a kind of piezo-electric/electrostrictive membrane type element of one embodiment of the present of invention, a ceramic substrate 2 has a kind of overall structure, the composition of this structure comprises the substrate 4 and the relatively thinner diaphragm plate 8 that is used for sealing this window 6 that have the rectangular window 6 of an appropriate size.This diaphragm plate 8 is superimposed on as one of opposed first type surface of this substrate 4 of supporting member.This diaphragm plate 8 has the window 6 corresponding diaphragm portions 10 with this substrate 4.On the outer surface of this diaphragm portion 10 of this plane ceramic substrate 2, lower electrode film 12, a P/E layer 14 and a upper electrode film 16 are by this order lamination, so that form a membranaceous P/E unit 18.Such as is known in the art, the leading part (not shown) by separately applies a suitable voltage to this bottom electrode 12 and top electrode 16.
In the occasion of this piezo-electric/electrostrictive membrane type element that constitutes as mentioned above as an actuator, a voltage puts between two electrodes 12,16 of this P/E unit 18 in the known manner, so that this P/E layer 14 is exposed to an electric field, and stands the mechanical deformation that caused by this electric field.Therefore, because the transversal effect of the distortion of this P/E layer 14, this P/E unit 18 causes bending or offset displacement or power, thus this displacement or power along the directive effect vertical with the plane surface of this substrate 2 on this ceramic substrate 2 (diaphragm portion 10).
In this piezo-electric/electrostrictive membrane type element, this P/E layer 14 by one have 0.7 μ m or above crystallite dimension and 15% or the DB of following porosity (x) form.Meanwhile, as shown in Figure 3, this diaphragm portion 10 of this ceramic substrate 2 is offset like this, so that the maximum offset (d) at the middle part of this diaphragm portion 10 extends and passes the ratio of length (m) of short lines at the center of this window 6 to this window 6 across this substrate 2, in other words, by the deviation ratio that [y=(d/m) * 100] expresses, remain in 0～8% the scope.In addition, this porosity (x) and this deviation ratio (y) are determined to be and satisfy following formula (1):
Y≤0.1167X
2－3.317X＋25.5????????????????????(1)
The piezo-electric/electrostrictive membrane type element that obtains like this has effective piezoelectric characteristic that has improved, and stands bigger displacement with the electromechanical conversion efficiency that has improved.In addition, this piezo-electric/electrostrictive membrane type element has been eliminated damage and other defect, the functional reliability that has guaranteed to improve.
The DB of this P/E layer 14 forms by firing suitable piezoelectric/electrostrictive material, and has and be controlled in 0.7 μ m or above crystallite dimension, best 1.5 μ m or more than, 2.0 μ m or above then better.If this crystallite dimension is too little, the piezoelectric deterioration in characteristics of this piezo-electric/electrostrictive membrane type element then.If the porosity of the DB of this P/E layer 14 (x) surpasses 15%, for this piezo-electric/electrostrictive membrane type element, also be difficult to show enough piezoelectric characteristics.
In addition, this deviation ratio (y), promptly the middle part side-play amount (d) of this diaphragm portion 10 as the expressed person in (d/m) * 100 (%), must remain on 0% (not having skew) to the percentage of the length (m) of the short lines at the center of crossing this window 6 to 8% scope.If the side-play amount of this diaphragm portion 10 (d) is too big, then when this P/E unit 18 is applied a voltage and drives to it, become difficult to achieve enough big displacement or high electromechanical conversion efficiency.
In addition, aforesaid porosity (x) and deviation ratio (y) must satisfy above-mentioned formula (1).If do not satisfy formula (1), then this piezo-electric/electrostrictive membrane type element can not provide outstanding piezoelectric characteristic.Best, this porosity (x) and deviation ratio (y) are determined to be and satisfy following formula (2):
Y≤0.2X
2－3.9X＋20.5??????????????????????????(2)
(X in the formula≤10,0≤Y≤6)
It is then better that this porosity (x) and deviation ratio (y) are determined to be satisfied following formula (3):
Y≤-X＋7???????????????????????????????(3)
(X in the formula≤6,0≤Y≤3)
Support this ceramic substrate 2 of this P/E unit 18 thereon and make, and preferably from stabilizing zirconia, PSZ, aluminium oxide and their mixture, select by known ceramic material.What particularly advantageously use is the inventor at disclosed a kind of material in No. the 5-270912, Japanese patent application, this material comprises the partially stabilized zirconia by the compound that adds yittrium oxide and so on as a kind of main component, and this material has mainly by cubic crystalline phase or be the two kinds of cubical combinations of cubic crystalline phase and monocline crystalline phase or the crystalline phase of mixing to form at least.The crystallite dimension of this ceramic substrate 2 preferably is controlled to and is not more than 1 μ m.Even these ceramic substrate 2 very little thickness of being made by above-mentioned material also show high mechanical properties and high tenacity, and be difficult for and the piezoelectric/electrostrictive material chemically reactive.This ceramic substrate 2 should be made in order to the below method: 1) one of preparation provides substrate 4 and forms the raw cook that has a perforate (window 6) by the use metal die or with ultrasonic Machining or machining, 2) superimposed a thin green sheet that provides this diaphragm plate 8 (diaphragm portion 10) in this raw cook that is used for substrate 4, and these raw cooks are bonded together, and 3) these raw cooks are fired into a kind of overall structure by hot pressing.This ceramic substrate 2 that obtains like this shows high reliability.The thickness of the diaphragm portion 10 of this ceramic substrate 2 is generally 50 μ m or following, is preferably in 1 μ m～30 mu m ranges, and is then better in 3 μ m～15 mu m ranges.
Each raw cook that is used for substrate 4 and diaphragm plate 8 can be made up of mutual superimposed a plurality of thin slices.Though window 6 or this diaphragm portion 10 of this ceramic substrate 2 have rectangular shape in the present embodiment, but the shape of window 6 can suitably be selected from other shapes, as circle, polygon or elliptical shape, the perhaps combination of these shapes is decided on the application scenario or the purposes of this piezo-electric/electrostrictive membrane type element.Have the occasion of for example round-shaped, rectangular shape or elliptical shape at this window 6, the length (m) of the short lines at the above-mentioned center of passing this window 6 corresponds respectively to bond length or this oval-shaped minor axis length of this circular diameter, this rectangle.
Above-mentioned electrode 12,16 and P/E layer 14 are formed on the diaphragm portion 10 of this ceramic substrate 2 by a kind of suitable film formation method as mentioned above, and this P/E unit 18 is provided whereby.This P/E layer 14 suitably forms by a kind of thick-film formation method such as silk screen printing, spraying, being coated with or immersing.This thick-film formation method uses a kind of thickener or pug, so that on the diaphragm portion 10 of this ceramic substrate 2, form membranaceous P/E layer 14, this thickener or pug contain average particle size particle size as main component and are about 0.01 μ m to 7 μ m, preferably are about the piezoelectric/electrostrictive porcelain particle of 0.05 μ m to 5 μ m.In this occasion, resulting membrane component shows outstanding piezoelectric characteristic.In above-mentioned thick-film formation method, silk screen printing is particularly advantageously adopted, because it can be with lower cost delicate execution wiring pattern.In order to obtain the big displacement of P/E layer 14 with lower voltage, wish that the thickness of this P/E layer 14 is not more than 50 μ m, then better in the scope of 3 μ m to 40 μ m.
The upper and lower electrode 16,12 of this P/E unit 18 is formed by a kind of electric conducting material that can tolerate the oxidizing atmosphere with quite high temperature.For example, electrode 12,16 can be by the mixture of single metal, a kind of metal alloy, a kind of metal or alloy and conductivity ceramics, and perhaps a kind of conductivity ceramics forms.Yet this electrode material preferably has a kind of main component, and this composition has dystectic noble metal, perhaps a kind of alloy composition such as silver palladium alloy, silver-platinum alloy or platinum-nickel alloys by a kind of such as platinum, palladium or rhodium.Electrode 12,16 also can be formed by the cermet of platinum and the piezoelectric/electrostrictive material that is used for the ceramic material of substrate 2 or is used for P/E layer 14.Preferable is that electrode 12,16 is only made by platinum or comprised a kind of platinum alloy that contains as main component.State ceramic-metallic occasion in the use, the content of substrate material preferably remains in the scope of 6～30% volumes, and this piezoelectric/electrostrictive material preferably is maintained at about in the scope of 5～20% volumes.
One of known membrane formation method by a kind of suitable selection, form electrode 12,16 with above-mentioned electric conducting material, these methods comprise aforesaid thick-film formation method, and the film formation method such as sputtering deposit, ion beam method, vacuum vapor deposition, ion plating, chemical vapor deposition and plating.In these methods, the thick-film formation method such as silk screen printing, spraying, immerse and being coated with advantageously is used for forming electrode 12,16.Above-mentioned film formation method can advantageously be used for forming top electrode 16 as thick-film formation method.The thickness of the electrode 12,16 of Xing Chenging generally is not more than 20 μ m like this, preferably is not more than 5 μ m.Gross thickness as the P/E unit 18 of the thickness sum of these electrodes 12,16 and P/E layer 14 is generally 100 μ m or following, is preferably 50 μ m or following.
The piezoelectric/electrostrictive material that is used for forming the P/E layer 14 of this P/E unit 18 preferably comprises lead zirconate titanate (PZT), lead magnesium niobate (PMN), lead niobate nickel (PNN), lead niobate manganese, lead stannate antimony, lead niobate zinc, lead titanates, lead tantanate magnesium, lead tantanate nickel or their a kind of mixture as main component.In addition, a kind ofly contain the oxide of lanthanum, barium, niobium, zinc, cerium, cadmium, chromium, cobalt, antimony, iron, yttrium, tantalum, tungsten, nickel, manganese, lithium, strontium or bismuth or the material of other compounds (as PLZT) can make an addition to above-mentioned piezoelectric/electrostrictive material as required.
In aforesaid piezoelectric/electrostrictive material, recommend to adopt a kind of material that comprises one of following mixture as main component: a kind of mixture of lead magnesium niobate, lead zirconates and lead titanates; A kind of mixture of lead niobate nickel, lead magnesium niobate, lead zirconates and lead titanates; A kind of mixture of lead magnesium niobate, lead tantanate nickel, lead zirconates and lead titanates; And a kind of mixture of lead tantanate magnesium, lead magnesium niobate, lead zirconates and lead titanates.When by a kind of thick-film formation method,, when forming this P/E layer 14, recommend these piezoelectric/electrostrictive material as silk screen printing.When employing contained the piezoelectric/electrostrictive material of composition more than three kinds, its piezoelectric characteristic changed according to the difference of the component prescription of this material.Yet, the three composition materials of forming by lead magnesium niobate, lead zirconates and lead titanates, the perhaps four-component material of being made up of lead magnesium niobate, lead tantanate nickel, lead zirconates and lead titanates, perhaps the four-component material of being made up of lead tantanate magnesium, lead magnesium niobate, lead zirconates and lead titanates has a prescription near being preferably in practising physiognomy of pseudo-cube crystalline phase, cubic crystalline phase and triangle crystalline phase.In order to guarantee sufficiently high piezoelectric constant and electromechanical coupling coefficient, one of following prescription is adopted in special hope, promptly, 1) prescription that contains 15～50mol% lead magnesium niobate, 10～45mol% lead zirconates and 30～45mol% lead titanates, 2) prescription that contains 15～50mol% lead magnesium niobate, 10～40mol% lead tantanate nickel, 10～45mol% lead zirconates and 30～45mol% lead titanates, perhaps 3) prescription that contains 15～50mol% lead magnesium niobate, 10～40mol% lead tantanate magnesium, 10～45mol% lead zirconates and 30～45mol% lead titanates.
As mentioned above this electrode film that on the outer surface of the diaphragm portion 10 of this ceramic substrate 2, forms and P/E layer (12,14,16) can or in these films and layer each in different steps, heat-treat (firing) with whole after forming with 2 one-tenths of substrates, perhaps all these films with layer all be formed on this diaphragm portion 10 after in a step, heat-treat simultaneously (firing) with 2 one-tenth integral body of substrate.In addition, may not need the above heat treatment (firing) of electrode film (12,16) to decide on the method that forms these films.Make electrode film and P/E layer become whole heat treatment (firing) temperature generally to be controlled in 500 ℃ to 1400 ℃ scope with this diaphragm portion, be preferably in 1000 ℃ to 1400 ℃ the scope.Change for fear of the composition of the piezoelectric/electrostrictive material of this P/E layer 14 at high temperature, wish in heat treatment or when firing this P/E layer 14 the control firing atmosphere to comprise the evaporation source of this piezoelectric/electrostrictive material.With suitable covering it is covered so that the surface of this P/E layer 14 directly is not exposed to firing atmosphere when also recommending to fire this P/E layer 14.This covering can be formed by the material with the materials similar of ceramic substrate 2.
The piezo-electric/electrostrictive membrane type element of Gou Chenging is by advantageously making according to one of following three kinds of methods of the present invention (A)～(C) as mentioned above.
In method (A), this ceramic substrate 2 is prepared into its diaphragm portion 2 has a kind of convex shape, it is outwards outstanding promptly to leave this window 6 with amount h, as shown in Fig. 4 (a).After this ceramic substrate 2 is fired, with suitable film formation method lamination bottom electrode 12 and P/E layer 14 successively on the outer surface of this convex diaphragm portion 10, as shown in Fig. 4 (b).When after having formed top electrode 16 on demand, firing this P/E layer 14, this P/E layer 14 have than through this diaphragm portion of firing 10 bigger fire contraction, thereby these diaphragm portion 10 recessed these windows 6 are as shown in Fig. 4 (C).Thereby in this P/E unit 18, shrinking the stress cause by firing of this P/E layer 14 can be reduced effectively, guarantee simultaneously this P/E layer 14 raising density, thereby resulting membrane component shows the piezoelectric characteristic that has improved effectively.
In other words, in order to realize satisfactorily via this bottom electrode 12 at the sintering that passes through this P/E layer 14 that forms on this diaphragm portion 10 of firing, invention it is found that, to make these convex diaphragm portion 10 recessed these windows 6 be effectively because the firing of this P/E layer 14 shunk, so that reduce the contact area of this P/E layer 14 and this diaphragm portion 10 or bottom electrode 12 significantly.This cause fully improving of this P/E layer 14 density and the residual stress that has reduced, guarantee the excellent characteristic of the piezo-electric/electrostrictive membrane type element of gained.
When applying a voltage, the influence of the coercive field that is produced by the piezoelectric/electrostrictive material of this P/E layer 14 should take in conjunction with the displacement of this P/E layer 14.In order to realize the enough big displacement of this P/E layer 14, must apply a voltage along shrinkage direction parallel plane, this P/E layer 14, so that this P/E layer 14 is exposed to an electric field along polarised direction with this diaphragm portion 10.As a result, this P/E layer 14 to bottom offset or bending, promptly enters in the window 6 of ceramic substrate 2 when it drives.If it is outwards outstanding that piezo-electric/electrostrictive membrane type element appearance becomes this diaphragm portion 10 to leave this window 6, this P/E layer 14 has bigger rigidity during then along the orientation measurement opposite with its bending direction, causes a displacement that has not desirably reduced.Therefore, wish to make this diaphragm portion 10 recessed these windows 6, so that deviation ratio remains in 0～8% the scope.
The ceramic substrate 2 that has outwards outstanding convex diaphragm portion 10 that is used for said method (A) can be by the rate of firing or the speed or the shrinkage of control basal plate 4 and diaphragm plate 8 (Fig. 1 and Fig. 2), before it is fired, suitably adjust the shape of this diaphragm plate 8, or utilize the difference that thermal expansion is compared between these two plates 4,8 and obtain at an easy rate.More particularly, when the sintering of the raw cook that provides this diaphragm plate 8 during prior to the sintering of the raw cook that provides this substrate 4, perhaps when the caused shrinkage of the sintering of the raw cook that is used for this substrate 4 during greater than the shrinkage of the raw cook that is used for this diaphragm plate 8, this diaphragm portion 10 is outwards outstanding.
The overhang h of the diaphragm portion 10 of this ceramic substrate 2 be generally the above-mentioned center of passing this window 6 short lines length (m) 1～20%, be preferably 2～10% of this length (m).If h is too little for this overhang, then when firing this P/E layer 14, it is excessive that the side-play amount of this diaphragm portion 10 may become.If h is too little for this overhang, then when firing this P/E layer 14, may be difficult to make in these diaphragm portion 10 recessed these windows 6.
In the method that is used for making piezo-electric/electrostrictive membrane type element (B), prepare ceramic substrate 2 at the beginning, and with outer surface superimposed layer bottom electrode 12 and the P/E layer 14 of suitable film formation method at the diaphragm portion 10 of this ceramic substrate 2.This P/E layer 14 of Xing Chenging comprises a kind of ceramic powders (a kind of powder of piezoelectric/electrostrictive material) like this, and this powder is filled 60% of the ceramic green body that is used for this P/E layer 14.Then, after having formed top electrode 16 on demand, fire this P/E layer 14.So, before firing, improve to fill the percentage of the ceramic powders of the living body that is used for this P/E layer 14, so that reduce when it is fired the stress that the contraction by this P/E layer 14 causes effectively.Therefore, this diaphragm portion 10 has the skew that has reduced, and resulting membrane component shows the piezoelectric characteristic that has improved, and especially, uses the less power that is produced by this P/E layer 14 that bigger displacement is provided.
The ceramic substrate that is used for the method (B) does not need as being used for top method (A) individual convex diaphragm portion is arranged, but can adopt common planar patch portion.Some raw cooks by being formed for substrate and diaphragm plate with identical materials and these raw cook hot pressing be fired into the whole ceramic body of stopping are easy to obtain to have this ceramic substrate of planar patch portion.
In said method (B), the powder of this ceramic powders or this piezoelectric/electrostrictive material fill be used for this P/E layer 14 living body before it is fired 60% or more than, best 65% or more than, 70% or above then better, so that reduce when it is fired the stress that the contraction owing to this P/E layer 14 occurs.If should fill percentage, then can not fully reduce the stress that when firing this P/E layer 14, occurred, thereby this membrane component can not realized improvement enough or former plan aspect its piezoelectric characteristic less than 60%.
In order to make piezoelectric/electrostrictive film element with method of the present invention (C), it is outwards outstanding to form a kind of convex shape at the beginning this ceramic substrate 2 to be prepared into its diaphragm portion 10, in method (A), form bottom electrode 12 and P/E layer 14 with suitable film formation method on the outer surface superimposed layer ground of the convex diaphragm portion 10 of this substrate 2 then.Like this this P/E layer 14 of Xing Chenging with method (B) in identical mode comprise a kind of ceramic powders, this powder fill the living body that is used for this P/E layer 14 60% or more than.Then, after having formed top electrode 16 on demand, fire this P/E layer 14, so that make in the window 6 of diaphragm portion 10 recessed these ceramic substrates 2.
The method (C) is method (A) and (B) comprehensive, and overhang of diaphragm portion 10 (h) and the ceramic powders filling percentage in P/E layer 14 be controlled to above with regard to the method (A) and (B) scope separately of defined.
At said method (A), (B) with (C), on the outer surface of the diaphragm portion 10 of ceramic substrate 2, form lower electrode film, P/E layer and upper electrode film 12,14,16 with above-mentioned film formation method, under above-mentioned firing temperature, fire then, film separately and layer with one-tenth-value thickness 1/10 of wanting are provided thus.So, on diaphragm portion 10, integrally form P/E unit 18.Though wish after P/E layer 14 just forms, promptly before top electrode 16 forms, to fire this P/E layer 14 on bottom electrode 12, can after top electrode 16 forms, carry out firing of this P/E layer 14 on layer 14.
The piezo-electric/electrostrictive membrane type element of other advantages that have outstanding piezoelectric characteristic and produce by the present invention can by adopt said method (A), (B) and (C) in any making.
In the piezo-electric/electrostrictive membrane type element that obtains like this according to the present invention, the diaphragm portion 10 of ceramic substrate 2 has skew or the deflection that has advantageously reduced, and the P/E layer 14 of P/E unit 18 has the density that has improved.Therefore, this membrane component shows the piezoelectric characteristic with high reliability, and when P/E unit adjacent more than two is driven simultaneously the displacement displacement when only a P/E unit is driven no better than of each P/E unit.
Though aforesaid piezo-electric/electrostrictive membrane type element can be used for the various uses such as transducer and actuator, but this membrane component is advantageously used for a piezoelectric actuator, because this element stands displacement effectively when driving is formed on this P/E unit on the outer surface of diaphragm portion.For example, P/E membrane component of the present invention is advantageously used for the piezoelectric actuator of monocrystalline, twin crystal or other types, these actuators are used for such as servo displacement component, pulsed drive motor and ultrasonic motor are controlled described in (Kenji Uchino) work " application foundation of piezoelectric actuator " as the infield constitution of Japanese industry technique center.This P/E unit also is used for the filter of power device and communication device, various transducers, converter, pick-up, sounding body (as loud speaker), and various resonators and oscillator such as acceleration transducer or shock transducer.
Below with reference to the Fig. 5 that schematically represents according to an example of piezo-electric/electrostrictive membrane type element of the present invention, and reference is as Fig. 6 of the decomposition diagram of this membrane component, piezo-electric/electrostrictive membrane type element 20 has a kind of overall structure, and this structure comprises the piezoelectric unit (P/E unit hereinafter referred to as) 24 that forms on the outer surface of a ceramic substrate 22 and a plurality of some thin-walled diaphragm portions at this substrate 22.At work, when applying voltage in the P/E unit 24 to correspondence, each diaphragm portion of this ceramic substrate 22 is offset or is out of shape.
More particularly, this ceramic substrate 22 has a kind of laminated construction of integral body, and its composition comprises that 28 and one thin of 26, connecting plates of shut (diaphragm plate) (substrate) are clipped in the dividing plate (substrate) 30 between this shut 26 and this connecting plate 28.These 26,28,30 are formed by zirconia material.Connecting plate 28 has three to pass the ditch through hole 32 that its thickness forms.The quantity of ditch through hole 32, shape, size and position can suitably be determined according to this piezo-electric/electrostrictive membrane type element application scenario or purposes.Dividing plate 30 has a plurality of square window of passing it and forming 36 (being three in the present embodiment) and superimposed like this on connecting plate 28, so that each ditch through hole 32 of connecting plate 28 communicates with corresponding window 36.Shut 26 is superimposed on a first type surface away from connecting plate 28 of dividing plate 30, so that seal the opening of all windows 36 of this dividing plate 30.By means of mutual so superimposed shut 26, dividing plate 30 and connecting plate 28, in this ceramic substrate 22, form three pressure chambers 38, so that these chambeies 38 are linked up with extraneous space by ditch through hole 32 separately.Ceramic substrate 22 is whole fired body that formed by ceramic material suitable such as zirconia material as mentioned above.Though this ceramic substrate 22 has a kind of three-decker that comprises shut (diaphragm plate), dividing plate (substrate) and connecting plate (substrate), this substrate 22 can have a kind of four layers or other sandwich constructions.
Membranaceous P/E unit 24 is formed on the outer surface of shut 26, so that these unit 24 align with separately pressure chamber 38 when watching in the plane parallel with shut 26.Each P/E unit 24 comprises a bottom electrode 40,42 and top electrodes 44 of piezoelectric layer (P/E layer hereinafter referred to as), they are formed on successively with a kind of suitable film formation method or several different methods on the part that is in one of window 36 with this dividing plate 30 aligned position of this shut 26, promptly on the outer surface of a diaphragm portion of this ceramic substrate 22.At work, when driving in the P/E unit 24 of correspondence, the pressure in the pressure chamber 38 raises, so that the fluid that is contained in this pressure chamber 38 can be discharged effectively through the ditch through hole 32 of correspondence.The piezo-electric/electrostrictive membrane type element of Gou Chenging not only as an actuator, also can be used as a transducer like this, and this transducer is surveyed a voltage signal of representing the offset displacement amount of this diaphragm portion.
In the piezo-electric/electrostrictive membrane type element that constitutes as mentioned above, the crystallite dimension of P/E layer 42 and porosity, and the deviation ratio of diaphragm portion (26) is controlled to respectively within the scope that is in top defined, and porosity and deviation ratio also are specified to and satisfy above-mentioned formula (1).
Though piezo-electric/electrostrictive membrane type element of the present invention can be advantageously used for actuator or the transducer that is used for loud speaker, display device, servo displacement component, pulsed drive motor, ultrasonic motor, acceleration transducer or shock transducer, this membrane component can also be advantageously used in other known applications occasions.
[example]
In order further to illustrate the present invention, some example of various details piezoelectric/electrostrictive film element.Yet should be noted that, the present invention is not limited to the details of following example, but can implement with various changes, modification and improvement, the professional and technical personnel can carry out these changes, revises and improve and not break away from principle and scope as this invention of defined in the appended claims.[example 1] has the test specimen of 20 piezo-electric/electrostrictive membrane type elements of ceramic substrate 2 preparations of the rectangular window of ten sizes that 0.5mm * 0.7mm respectively arranged by use.Thereby size m is 0.5mm.These rectangular windows make the minor face (0.5mm) of these windows and the parallel longitudinal of this substrate 2, and make these windows leave the spacing distance of 0.2mm mutually along vertical arrangement of this substrate 2.Each ceramic substrate 2 has some diaphragm portions 10, and the one-tenth-value thickness 1/10 of these diaphragm portions and overhang (h) are shown in table 1.Has living body that a kind of filling is used for each layer 14 P/E layer 14 by preparation to the ceramic powders of as shown in fig. 1 certain percentage, on the diaphragm portion separately 10 of this ceramic substrate 2, form these P/E layers 14, under firing temperature, fire these P/E layers 14 then and make each test specimen as defined in the table 1.Like this, obtain the test specimen of these 20 piezo-electric/electrostrictive membrane type elements.
In the piezo-electric/electrostrictive membrane type element of each test specimen, the substrate 4 of this ceramic body 2 has thickness 200 μ m, and the diaphragm plate 8 that provides this diaphragm portion 10 has thickness as shown in table 1.This substrate 4 and this diaphragm plate 8 are by being formed by the partially stabilized zirconia of 3mol% yittrium oxide.For the ceramic substrate 2 of the inner laminate structure that obtains having substrate 4 and diaphragm plate 8, preparation is used for the raw cook of these plates 4,8 in a manner described below, folded be incorporated under the pressure bonding it, and fire them.
The raw cook that is used for substrate 4
With the partially stabilized Zirconium oxide powder of 3mol% yittrium oxide
(average particle size particle size 0.8 μ m) 100 parts of weight
10 parts of weight of polyvinyl butyral resin (adhesive)
5 parts of weight of dibutyl phthalate (plasticizer)
The 2 parts of weight of dispersant that contain anhydro sorbitol
Contain 50/50 toluene and 73 parts of weight of solvent of isopropyl alcohol
Mentioned component mixes in a pot mill that has a zirconia ball, so that provide the pug of the initial viscosity of a kind of 1000CPS of having (centipoise).The pug that obtains like this outgases under vacuum, and its viscosity is controlled so as to 10000CPS.Then, make this pug form a raw cook, provide the substrate 4 of 200 μ m thickness after this raw cook is fired with a kind of scraper plate method.This raw cook is following dry three hours at 80 ℃.
The raw cook that is used for diaphragm plate 8
With the partially stabilized Zirconium oxide powder of 3mol% yittrium oxide
(average particle size particle size: (100-Z) parts of weight 0.8 μ m)
Alumina powder (average particle size particle size: Z part weight 0.2 μ m)
9 parts of weight of polyvinyl butyral resin (adhesive)
4 parts of weight of dibutyl phthalate (plasticizer)
The 2 parts of weight of dispersant that contain anhydro sorbitol
The 70 parts of weight of solvent that contain 50/50 toluene and isopropyl alcohol
Mentioned component mixes in a pot mill that has a zirconia ball, so that provide the pug of the initial viscosity of a kind of 1000CPS of having (centipoise).The pug that obtains like this outgases under vacuum, and its viscosity is controlled so as to 3000CPS.Then, make this pug form a raw cook, provide the diaphragm portion 10 of thickness as shown in table 1 after this raw cook is fired with a kind of contrary roll-coater.This raw cook is following dry 20 minutes at 80 ℃.The content of the alumina powder relevant with the content of lead oxide powder (Z part weight) variation as follows is so that change the initial burst output (h) of the diaphragm portion 10 of this diaphragm plate 8.
Overhang (μ m) alumina content
(Z part weight)
0????????????????????????????????????????0
5????????????????????????????????????????0.05
10???????????????????????????????????????0.10
20???????????????????????????????????????0.30
50???????????????????????????????????????1.00
The raw cook that is used for substrate 4 that obtains like this by means of a kind of proper metal mould by the pattern punching to form window 6.Then, this raw cook is superimposed at the raw cook of making as mentioned above that is used for diaphragm plate 8, and passes through at 100kg/cm
2Pressure under thereon bonding with 80 ℃ of hot pressing 1min.The whole laminated construction that obtains was like this fired under 1500 ℃ two hours, so that the ceramic substrate 2 of band with the outside diaphragm portion of giving prominence to 10 of the amount shown in the table 1 (h) is provided.
On the outer surface of each diaphragm portion 10 of the ceramic substrate 2 of each test specimen, stamp the platinum thickener with silk screen printing, at 120 ℃ of dry 10min down, and under 1350 ℃, fired two hours, so that the bottom electrode 12 with 5 μ m thickness to be provided.Then, on bottom electrode 12, form the piezoelectric layer 14 of each test specimen as shown in table 1 in the following manner.This P/E layer 14 is formed by a kind of powders A of piezoelectric/electrostrictive material, and this material is made up of 38mol% lead magnesium niobate, 24mol% lead zirconates and 38mol% lead titanates, and wherein a part of Pb is replaced by Sr and La.This powders A is formed thickener, with silk screen printing this thickener is imprinted on the bottom electrode 12, and dry 20min under 120 ℃ fired under temperature as shown in table 1 two hours, then so that the P/E layer 14 with 30 μ m thickness to be provided.
In order to be formed for the thickener of P/E layer 14, prepared compound as follows:
100 parts of weight of powders A with 0.9 μ m average particle size particle size
3 parts of weight of acrylic adhesives
20 parts of weight of terpineol (solvent)
Mediate this compound with three-roller and have 100, the thickener of the viscosity of 000CPS to provide.Then, this thickener is imprinted on the bottom electrode 12 with silk screen printing, and 120 ℃ down dry 20min so that solvent evaporates, thereby P/E layer (not firing) 14 is provided.After drying and before firing, 55% P/E layer 14 is filled by the powder of this piezoelectric/electrostrictive material (ceramic powders).
Improve with the following methods at it and fire the filling percentage of pre-ceramic powder in this P/E layer 14.In other words, the another kind of P/E powder of a part (10～30%) piezoelectric (P/E) powders A with average particle size particle size of composition identical with powders A and 0.3 μ m replaces.Then, two kinds of one of P/E powder inputs are had in the polyethylene jar of 10mm diameter zirconia ball, and in a dry ball mill, pulverized three hours.This crushing operation is used as disintegrator to carry out the ethanol that the P/E powder of 100 parts of weight adds 0.5 part of weight.Then, the P/E powder of 100 parts of weight is added the acetone of 50 parts of weight, and the wet fusion of this compound five hours.After this, add the acrylic adhesives of 3 parts of weight and the terpineol (solvent) of 20 parts of weight, and wet fusion one hour, then the pug that obtains is like this kept 15 hours down so that make acetone evaporated at 40 ℃, mediate with three-roller then and have 100 with formation, the thickener of the viscosity of 000CPS.Measure the thickener obtain like this with the percentage of this ceramic powder filled and be expressed as follows, this percentage changes because of the P/E powder of average particle size particle size with the 0.9 μ m ratio to the P/E powder of average particle size particle size with 0.3 μ m.So, form the P/E layer 14 of test specimen as shown in table 1 by thickener separately with different ceramic powder filled percentage.Percentage 0.9 μ m/0.3 μ m 90,/10 65%0.9 μ m/0.3 μ m 80,/20 70%0.9 μ m/0.3 μ m 70,/30 75% is filled in the combination of P/E powder ratio (% weight) ceramic powders
The filling percentage expression of ceramic powders (powder of piezoelectric (P/E) material) becomes (density of dry thickener) * [(weight portion of P/E material)/(weight portion of the weight portion+adhesive of P/E material)] * (solid density of 1/P/E material) * 100 (%).
When firing of P/E layer 14 finished, on P/E layer 14, form a Cr film by sputtering deposit, and on this Cr film, form a Cu film, to form top electrode 16.So, obtain the piezo-electric/electrostrictive membrane type element of those test specimens as shown in table 1.By between the upper/ lower electrode 16,12 of each P/E unit 18, applying 100V, make all membrane components that obtain like this stand polarization and handle.
Each test specimen at all piezo-electric/electrostrictive membrane type elements that obtain like this, the side-play amount of diaphragm portion 10 and the crystallite dimension and the porosity of P/E layer 14 have been measured, evaluated the operating characteristic of this membrane component simultaneously, as the displacement of each P/E layer 14 when relevant P/E unit is applied voltage.These measurement results are shown in Table 1.
More particularly, with electron microscope in the side-play amount of measuring this diaphragm portion 10 along the middle part of the cross section of the diaphragm portion 10 of short lines (m) intercepting at the center of passing window 6.Obtain crystallite dimension in the following manner.At the beginning, a cross section of this P/E layer 14 of grinding and mirror finish carries out heat etching so that demonstrate crystal boundary with commonsense method then.With number of die (n) and the chip area (s) of electron microscope measurement in the visual field, and calculate crystallite dimension D= (4S/ π n).In order to measure porosity, a cross section of mirror finish P/E layer 14, avoid crystal grain to come off simultaneously, and measure in the area in the visual field micropore of this cross section or the area of space part, so that calculate by the expressed porosity of (micropore area/visual field area) * 100 (%) with electron microscope.
In order to evaluate the piezoelectric characteristic, apply the voltage of a 30V between the upper/ lower electrode 16,12 of each in ten P/E unit 18 of the membrane component of each sample, and with the displacement of the driven P/E of laser-Doppler measurement device unit 18.Like this, drive all ten P/E unit 18 one by one, and calculate first mean value of the displacement of these P/E unit 18.Equally, apply a 30V voltage to all ten P/E unit 18 of the membrane component of each sample, and measure the displacement of each P/E unit 18.Also calculate second mean value of the displacement of driven ten P/E unit simultaneously.According to the result who obtains like this, calculate the ratio (%) of the displacement that the displacement that records records when driving single P/E unit by expression formula (second mean value/first mean value) * 100 (%) when driving all P/E unit.
As can be seen from Table 1, No. 1 the piezo-electric/electrostrictive membrane type element that constitutes according to the present invention to No. 13 test specimens, because the displacement when driving all P/E unit 18 of this element that has reduced is poor with the displacement when driving single P/E unit 18, provide bigger displacement with the height homogeneity of amount and matter.Should be noted that, at No. 1 to the membrane component of No. 13 test specimens, be in as the DB of crystallite dimension within the scope given to this invention and porosity and form P/E layer 14 as having, and the side-play amount (d) at the middle part of diaphragm portion 10 (window 6) is in as within the scope given to this invention.
On the other hand, No. 14 diaphragm portions 10 to No. 20 test specimens of example have bigger side-play amount and higher porosity in contrast.It can also be seen that from table 1 these 14～No. 20 membrane components provide less displacement, and the ratio of the less displacement that records when driving all P/E unit to the displacement that records when driving single P/E unit is arranged.So the element of these reference examples has the bigger variation of relatively poor piezoelectric characteristic He its quality.When the element of No. 16 test specimens of preparation, improved firing temperature so that improve the density of P/E layer 14.Yet the diaphragm portion 10 with little thickness does not obtain the element of former plan owing to high-temperature firing damages.Though the element of No. 19 test specimens prepares to avoid it to destroy when firing at its high temperature (1325 ℃) by the thickness that strengthens diaphragm portion 10, diaphragm portion 10 stands bigger side-play amount, causes the piezoelectric characteristic of this element deficiency.
Table 1
| Sequence number | Diaphragm portion (10) | Piezoelectric layer (14) (P/E layer) | Piezoelectric (P/E) characteristic | ||||||
| Thickness (μ m) | Overhang h (μ m) | Side-play amount: d (μ m) | Firing temperature (℃) | The filling percentage (%) of ceramic powders | Crystallite dimension (μ m) | Porosity (%) | Displacement (μ m) | Whole driving/single driving (%) | |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 | ????10 ????10 ????10 ????12 ????15 ????6 ????6 ????10 ????10 ????10 ????10 ????10 ????10 | ????5 ????10 ????20 ????20 ????20 ????20 ????50 ????0 ????0 ????0 ????0 ????10 ????20 | ????10 ????7 ????3 ????8 ????20 ????7 ????7 ????20 ????14 ????8 ????12 ????4 ????2 | ?1250 ?1250 ?1250 ?1275 ?1300 ?1250 ?1250 ?1275 ?1250 ?1250 ?1275 ?1250 ?1250 | ????55 ????55 ????55 ????55 ????55 ????55 ????55 ????65 ????70 ????75 ????75 ????65 ????65 | ????2.1 ????2.3 ????2.4 ????2.9 ????3.4 ????2.5 ????2.4 ????2.6 ????1.9 ????2.2 ????2.5 ????2.3 ????2.4 | ????9 ????6 ????7 ????4 ????3 ????7 ????5 ????9 ????10 ????9 ????8 ????4 ????3 | ????0.24 ????0.28 ????0.29 ????0.31 ????0.28 ????0.29 ????0.33 ????0.20 ????0.23 ????0.25 ????0.26 ????0.32 ????0.32 | ????90 ????93 ????100 ????95 ????90 ????95 ????97 ????86 ????90 ????95 ????92 ????100 ????100 |
| ???*14 ???*15 ???*16 ???*17 ???*18 ???*19 ???*20 | ????10 ????10 ????10 ????6 ????15 ????15 ????10 | ????0 ????0 ????0 ????0 ????0 ????0 ????0 | 26 39 destroy 42 44 63 10 | ?1250 ?1275 ?1300 ?1275 ?1300 ?1325 ?1225 | ????55 ????55 ????55 ????55 ????55 ????55 ????55 | ????1.6 ????2.3 ????— ????????2.4 ????2.9 ????3.5 ????4.2 | ????25 ????16 ????— ????????14 ????14 ????7 ????30 | ????0.15 ????0.18 ????— ????????0.19 ????0.17 ????0.20 ????0.11 | ????75 ????70 ????— ????????65 ????65 ????45 ????75 |
* reference examples is when being reduced to firing temperature 1225 ℃ so that when reducing the skew of diaphragm portion 10, and porosity improves, and the result has not desirably reduced the density of P/E unit 14.The element that obtains like this is unsafty on its piezoelectric characteristic.[example 2]
By using a kind of powder B of piezoelectric/electrostrictive material, 15 test specimens that prepared piezo-electric/electrostrictive membrane type element with structure identical with the structure of example 1, this material has the average particle size particle size of 0.4 μ m, and form by 22mol% lead magnesium niobate, 15mol% lead tantanate nickel, 25mol% lead zirconates and 38mol% lead titanates, and wherein a part of Pb is replaced by Sr.In this occasion, the thickener that is used for forming P/E layer 14 has following composition:
100 parts of weight of powder B with average particle size particle size of 0.4 μ m
3 parts of weight of polyvinyl butyral resin (adhesive)
20 parts of weight of 2-ethyl hexanol (solvent)
Mediate this composition with three-roller and have 100, the thickener of the viscosity of 000CPS to provide.With silk screen printing this thickener is imprinted on the bottom electrode 12 of P/E unit 18, and 120 ℃ down dry 20min so that solvent evaporates, thereby P/E layer 14 (not firing) is provided.Before firing, the P/E layer 14 of 50% drying is filled by the powder of this piezoelectric/electrostrictive material (ceramic powders).
By with example 1 in identical mode, the powder of the above-mentioned powder B of average particle size particle size and a kind of piezoelectric/electrostrictive material of the average particle size particle size with the composition identical and 0.1 μ m with powder B with 0.4 μ m in ratio fusion shown below, so that a kind of thickener with the ceramic powder filled percentage that has improved is provided.So, made the membrane component of each test specimen.Percentage 0.4 μ m/0.1 μ m 80,/20 65%0.4 μ m/0.1 μ m 70,/30 70% is filled in the combination of P/E powder ratio (% weight) ceramic powders
At the piezoelectric/electrostrictive film element of each test specimen, measured the side-play amount of diaphragm portion 10 and the crystallite dimension and the porosity of P/E layer 14, and evaluated the piezoelectric characteristic.These are measured and evaluation result is shown in the following table 2.
Table 2
* reference examples
As can be seen from Table 2, No. 21 piezo-electric/electrostrictive membrane type elements that constitute according to the present invention to No. 30 test specimens, owing to reduced displacement and displacement when the single P/E of the driving unit 18 poor when driving all P/E unit 1 of this element, to measure and the height homogeneity of matter provides bigger displacement.Should be noted that, at No. 21 to the membrane component of No. 30 test specimens, be in as the DB of crystallite dimension within the scope given to this invention and porosity and form P/E layer 14 as having, and the side-play amount (d) at the middle part of diaphragm portion 10 (window 6) is in as within the scope given to this invention.
In the device of being introduced, this diaphragm is drawn as covers this window fully.Yet this invention goes for this diaphragm and only covers the occasion that this window ground extends fully along a direction.
Claims (17)
1. piezo-electric/electrostrictive membrane type element, this element comprises: one has at least one window (6,36) and a ceramic substrate (2,22) that is used for sealing the diaphragm portion (10) of each described at least one window, described diaphragm portion is as an integral part of described ceramic substrate and form; Reach one and comprise a bottom electrode (12,40), piezoelectric layer (14,42) and a top electrode (16,44) piezoelectric unit (18,24), these bottom electrodes, piezoelectric layer and top electrode are formed on the outer surface of described diaphragm portion by a kind of film formation method by narrating order, so that a kind of laminated construction to be provided, it is characterized in that:
Described piezoelectric layer is made up of a DB with the crystallite dimension that is not less than 0.7 μ m and the porosity (X) that is not more than 15%, described diaphragm portion has 0～8% deviation ratio (Y), the percentage of length of short lines at the center of this window is extended and passed to the side-play amount that this show off rate of moving equals the middle part of described diaphragm portion across the window of a correspondence in described at least one window to one, described porosity (X) and described deviation ratio (Y) satisfy following formula:
Y≤0.1167X
2—3.317X＋25.5
2. piezo-electric/electrostrictive membrane type element according to claim 1, the described crystallite dimension that wherein is used for the described DB of described piezoelectric layer is not less than 1.5 μ m.
3. piezo-electric/electrostrictive membrane type element according to claim 2, wherein said crystallite dimension are not less than 2.0 μ m.
4. according to any one described piezo-electric/electrostrictive membrane type element in the claim 1～3, wherein said porosity (X) and described deviation ratio (Y) satisfy following formula:
Y≤0.2X
2－3.9X＋20.5
X in the formula≤10,0≤Y≤6
5. piezo-electric/electrostrictive membrane type element according to claim 4, wherein said porosity (X) and described deviation ratio (Y) satisfy following formula:
Y≤-X＋7
X in the formula≤6,0≤Y≤3
6. according to any one described piezo-electric/electrostrictive membrane type element in the claim 1～5, the described diaphragm portion of wherein said ceramic substrate has the thickness of 1 μ m～30 μ m.
7. piezo-electric/electrostrictive membrane type element according to claim 6, the described diaphragm portion of wherein said ceramic substrate has the thickness of 3 μ m～15 μ m.
8. method of making a kind of piezo-electric/electrostrictive membrane type element, this element comprises: one has at least one window (6,36) and a ceramic substrate (2 that is used for sealing the diaphragm portion (10) of each described at least one window, 22), described diaphragm portion is as an integral part of described ceramic substrate and form; Reach one and comprise a bottom electrode (12,40), piezoelectric layer (14,42) and a top electrode (16,44) piezoelectric unit (18,24), these bottom electrodes, piezoelectric layer and top electrode are formed on by narrating order on the outer surface of described diaphragm portion, and so that a kind of laminated construction to be provided, the method comprising the steps of:
Prepare described ceramic substrate, wherein said diaphragm portion is outwards outstanding to carry a convex diaphragm portion (10);
On the outer surface of described convex diaphragm portion, form described bottom electrode and described piezoelectric layer by a kind of film formation method;
Fire described piezoelectric layer like this, consequently the window of a correspondence in recessed described at least one window of described convex diaphragm portion; And
On described piezoelectric layer, form described top electrode by a kind of film formation method.
9. method according to claim 8 wherein formed described top electrode on described piezoelectric layer before firing this piezoelectric layer.
10. according to Claim 8 or 9 described methods, the outwards outstanding amount of the described diaphragm portion of wherein said ceramic substrate, this amount are in a window across a correspondence in described at least one window and extend and pass in 1～20% the scope of length of short lines at center of this window.
11. method of making a kind of piezo-electric/electrostrictive membrane type element, this element comprises: one has at least one window (6,36) and a ceramic substrate (2 that is used for sealing the diaphragm portion (10) of each described at least one window, 22), described diaphragm portion is as an integral part of described ceramic substrate and form; Reach one and comprise a bottom electrode (12,40), piezoelectric layer (14,42) and a top electrode (16,44) piezoelectric unit (18,24), these bottom electrodes, piezoelectric layer and top electrode are formed on by narrating order on the outer surface of described diaphragm portion, and so that a kind of laminated construction to be provided, the method comprising the steps of:
Prepare described ceramic substrate;
On the described outer surface of described diaphragm portion, form described bottom electrode and described piezoelectric layer by a kind of film formation method, described piezoelectric layer comprises a kind of ceramic powders, and this powder was filled 60% of this piezoelectric layer at least before this layer fired;
Fire described piezoelectric layer; And
On described piezoelectric layer, form described top electrode by a kind of film formation method.
12. method according to claim 11 wherein formed described top electrode on described piezoelectric layer before firing this piezoelectric layer.
13. according to claim 11 or 12 described methods, wherein said ceramic powders was filled 65% of described piezoelectric layer at least before this piezoelectric layer is fired.
14. method according to claim 13, wherein said ceramic powders was filled 70% of described piezoelectric layer at least before this piezoelectric layer is fired.
15. an a kind of piezoelectricity/electricity of making causes to contract and stretches the method for membrane component, this element comprises: one has at least one window (6,30), with a ceramic substrate (2 that is used for sealing the diaphragm portion (10) of each described at least one window, 22), described diaphragm portion is as an integral part of described ceramic substrate and form; Reach one and comprise a bottom electrode (12,40), piezoelectric layer (14,42) and a top electrode (16,44) piezoelectricity/electricity causes to contract stretches unit (18,24), these bottom electrodes, piezoelectric layer and top electrode are formed on by narrating order on the outer surface of described diaphragm portion, and so that a kind of laminated construction to be provided, the method comprising the steps of:
Prepare described ceramic substrate, wherein said diaphragm portion is outwards outstanding so that a convex diaphragm portion to be provided;
On the outer surface of described convex diaphragm portion, form described bottom electrode and described piezoelectric layer by a kind of film formation method, described piezoelectric layer comprises a kind of ceramic powders, and this powder was filled 60% of this piezoelectric layer at least before this layer fired;
Fire described piezoelectric layer like this, consequently the window of a correspondence in recessed described at least one window of described convex diaphragm portion; And
On described piezoelectric layer, form described top electrode by a kind of film formation method.
16. method according to claim 15 wherein formed described top electrode on described piezoelectric layer before firing this piezoelectric layer.
17. according to claim 15 or 16 described methods, the outwards outstanding amount of the described diaphragm portion of wherein said ceramic substrate, this amount are in a window across a correspondence in described at least one window and extend and pass in 1～20% the scope of length of short lines at center of this window.
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| JP18920394 | 1994-08-11 | ||
| JP189203/94 | 1994-08-11 | ||
| JP24117294A JP3162584B2 (en) | 1994-02-14 | 1994-10-05 | Piezoelectric / electrostrictive film element and method of manufacturing the same |
| JP241172/94 | 1994-10-05 |
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| CN1127430A true CN1127430A (en) | 1996-07-24 |
| CN1050008C CN1050008C (en) | 2000-03-01 |
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Cited By (7)
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| CN100444422C (en) * | 2004-03-31 | 2008-12-17 | 株式会社东芝 | Electronic component, electronic component module and mfg. method for said electronic component |
| CN1780009B (en) * | 2004-11-19 | 2010-05-05 | 日本碍子株式会社 | Piezoelectric/electrostrictive device |
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| JP2693291B2 (en) * | 1990-07-26 | 1997-12-24 | 日本碍子株式会社 | Piezoelectric / electrostrictive actuator |
| US5210455A (en) * | 1990-07-26 | 1993-05-11 | Ngk Insulators, Ltd. | Piezoelectric/electrostrictive actuator having ceramic substrate having recess defining thin-walled portion |
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- 1995-08-11 CN CN95115342A patent/CN1050008C/en not_active Expired - Fee Related
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| CN100444422C (en) * | 2004-03-31 | 2008-12-17 | 株式会社东芝 | Electronic component, electronic component module and mfg. method for said electronic component |
| CN1780009B (en) * | 2004-11-19 | 2010-05-05 | 日本碍子株式会社 | Piezoelectric/electrostrictive device |
| CN1780010B (en) * | 2004-11-19 | 2010-09-01 | 日本碍子株式会社 | Piezoelectric/electrostrictive device |
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| CN102484201A (en) * | 2009-09-07 | 2012-05-30 | 日本碍子株式会社 | Method for manufacturing piezoelectric/electrostrictive film type element |
| CN102484201B (en) * | 2009-09-07 | 2014-11-26 | 日本碍子株式会社 | Method for manufacturing piezoelectric/electrostrictive film type element |
| CN108075033A (en) * | 2017-12-26 | 2018-05-25 | 广东奥迪威传感科技股份有限公司 | Piezoelectric vibrator and preparation method thereof |
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| CN110702743B (en) * | 2019-10-16 | 2021-09-28 | 南京大学 | Nano electromechanical hydrogen sensor and preparation method thereof |
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