CN100570918C

CN100570918C - Piezoelectric element, ink gun, angular-rate sensor, their manufacture method and inkjet recording device

Info

Publication number: CN100570918C
Application number: CN200580000228.XA
Authority: CN
Inventors: 友泽淳; 藤井映志; 乌井秀雄
Original assignee: Matsushita Electric Industrial Co Ltd
Current assignee: Panasonic Holdings Corp
Priority date: 2004-03-05
Filing date: 2005-02-21
Publication date: 2009-12-16
Anticipated expiration: 2025-02-21
Also published as: CN1771611A

Abstract

The invention discloses a kind of piezoelectric element, ink gun, angular-rate sensor, their manufacture method and inkjet recording device.Piezoelectric element comprises: two electrode films and the stacked film of piezoelectrics that is constituted by the two-layer piezoelectric film by (111) face preferred orientation that these electrode films clip.The two-layer piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other.The averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of the 1st piezoelectric film.The ratio of the thickness of the stacked film of piezoelectrics and the averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

Description

Piezoelectric element, ink gun, angular-rate sensor, their manufacture method and inkjet recording device

Technical field

The present invention relates to be the piezoelectric element of electromechanical mapping function, the ink gun that has used this piezoelectric element and angular-rate sensor, their manufacture method and the inkjet recording device that has used above-mentioned ink gun.

Background technology

Piezoelectric is that mechanical energy is transformed to electric energy, or transformation of electrical energy is the material of mechanical energy.As the typical example of piezoelectric, the lead zirconate titanate of the oxide of promising Ca-Ti ore type crystalline texture (Pb (Zr, Ti) O ₃, hereinafter referred to as PZT).The PZT of this Ca-Ti ore type crystalline texture is the boundary near the ratio Zr/Ti=53/47at% with Zr and Ti, and Zr is the rhombogen crystallographic system in the time of many, is tetragonal system when Zr is few.And, can be when being the rhombogen crystallographic system＜111〉and direction of principal axis obtains maximum displacement bimorph, can be＜001 when for tetragonal system direction of principal axis (c direction of principal axis) obtains the displacement bimorph of maximum.But a lot of piezoelectrics are many crystalline solid that the aggregate by crystalline particle constitutes, and the crystal axis of each crystalline particle points to different directions.Therefore, the arrangement of spontaneous polarization Ps is also different.

But, along with the miniaturization that in recent years electronics sets, the also miniaturization of strong request piezoelectric element.And, in order to satisfy this requirement, do not develop into just gradually and use piezoelectric element under the sintered body form that in the past was widely used, and use piezoelectric element under than the obviously little form of film of the volume of this sintered body, the research and development of piezoelectric element filming are in vogue.

Here,, generally more easily be oriented in (111) face though be the piezoelectric film that piezoelectric constitutes by PZT, should the orientation rate lower, with other oriented surface coexistence, so lower as the piezoelectric property of piezoelectric element, its difference is also bigger.

So, substrate and electrode etc. is worked hard, carried out the manufacturing of the piezoelectric film of following such (001) face or (100) planar orientation.

For example, the spontaneous polarization Ps of PZT points to＜111〉direction of principal axis when the rhombogen crystallographic system, point to＜001〉direction of principal axis when tetragonal system.So, even the piezoelectric property in order to realize that filming is also still high must make when the rhombogen crystallographic system＜111〉direction of principal axis be the direction vertical with substrate surface, when tetragonal system, must make＜001〉axle be the direction vertical with substrate surface.And, in order to make its degree of orientation be almost 100%, in the past, when tetragonal system Ca-Ti ore type crystalline texture, by having used the sputtering method of the target that tetragonal system PZT forms, under 600～700 ℃ temperature, crystal orientation (100) face protuberate, by the magnesium oxide of rock salt crystalline texture (below, MgO) on the single crystalline substrate of Gou Chenging, directly formed＜001 the axle be oriented in perpendicular to the good pzt thin film of the crystallinity of its surperficial direction (for example, with reference to patent documentation 1 and non-patent literature 1).At this moment, if on the Pt electrode that is oriented in (100) face, form by the PbTiO that does not contain Zr with sputtering method ₃(Pb, La) TiO ₃The thickness that constitutes is the bottom of the piezoelectric body layer of 0.1 μ m as pzt thin film, form the words that thickness is the pzt thin film of 2.5 μ m more thereon, then, be difficult to form the lower layer of crystallinity that constitutes by the Zr oxide, can obtain the higher pzt thin film of crystallinity at the formation initial stage of pzt thin film.That is to say, can obtain (001) planar orientation degree (α (001)) and be 100% pzt thin film roughly.Here, define degree of orientation α (001) with α (001)=I (001)/∑ I (hk1).∑ I (hk1), in X-ray diffraction method, 2 θ when having used Cu-K α line are the summation from the diffraction peak intensity of each crystal plane among 10～70 ° the PZT of Ca-Ti ore type crystalline texture.In addition, because (002) face and (200) face are equipotential surfaces with (001) face and (100) face, therefore be not contained among the ∑ I (hk1).

But at this moment, have such problem: owing to use the MgO single crystalline substrate as bottom substrate, therefore not only the price of piezoelectric element is very high, and has used the price of the ink gun of this piezoelectric element also to become very high.And, also have the shortcoming that backing material also only is restricted to the MgO monocrystalline.

So on low-cost substrates such as silicon, (001) face or (100) face crystalline orientation film of Ca-Ti ore type piezoelectrics such as formation PZT are being developed following the whole bag of tricks.

For example, in patent documentation 2, illustrated on the Pt electrode that is being oriented in (111) face, coating PZT or contain the PZT precursor solution of lanthanum, at first, by with 150～550 ℃ with this forerunner's liquid solution thermal decomposition, be heated processing with 550～800 ℃ then, make its crystallization (the collosol and gel state exchanges (solgel) method), can generate (100) face preferred orientation film of PZT.

And, in patent documentation 3, illustrated by on the iridium lower electrode, forming titanium layer as thin as a wafer, control the method for the crystalline orientation of the PZT film that forms thereon.The method, by forming with the zirconia on substrates such as silicon is the bottom of main component, on this bottom, form the lower electrode that contains iridium, on this lower electrode, form titanium layer as thin as a wafer, on this titanium layer, form the noncrystalline piezoelectrics precursor thin-film of containing metal element and oxygen element, with this amorphous film heat treatment, make its crystallization (the collosol and gel state exchanges (solgel) method) with high temperature, generate the Ca-Ti ore type piezoelectric film.Use the method, can control the crystalline orientation of piezoelectricity body thin film such as PZT,, then can obtain (111) planar orientation film if making the thickness of titanium layer is 10～20nm by the thickness of titanium layer.

And, in patent documentation 4, illustrated when (solgel) method of exchanging forms piezoelectric film with the collosol and gel state, by on the Pt electrode of (111) planar orientation, forming the titanium layer of 4～6nm, with the titanium oxide with the titanylization of this titanium layer is core, can obtain the method for the PZT film of (100) planar orientation.

And, in patent documentation 5, illustrated by being formed on SrTiO with sputtering method ₃RuO on the substrate ₂On the lower electrode, sol solutions with the concentration ratio Zr/Ti=75/25 of spin-applied Zr and Ti, make it cross heated drying and form precursor film, use the sol solutions of the concentration ratio Zr/Ti=52/48 of Zr and Ti more thereon, form the multilayer precursor film, then, with 900 ℃ of high temperature sinterings, coming under the situation that crackle does not take place the PZT with (001) crystalline orientation of column structure is the synthetic method of piezoelectric oxide film.

But, though above-mentioned each method, has superiority aspect the MgO single crystalline substrate of not using high price, but as for (solgel) method of exchanging forms piezoelectric film with the collosol and gel state, and the same when on the MgO single crystalline substrate, forming piezoelectric film, when forming film, be difficult to obtain the good film of crystallinity of crystalline orientation.So, form amorphous piezoelectric film earlier, be that unit heat-treats the stacked film that contains this piezoelectric film with each substrate then, make the crystal axis preferred orientation in suitable direction.

And, if exchange the words that (solgel) method is produced piezoelectric element in a large number with the collosol and gel state, then in removing organic degreasing process, be easy at the crackle of amorphous piezoelectrics precursor thin-film generation because of change in volume, and, even amorphous piezoelectrics precursor thin-film is being carried out heat, make in the operation of its crystallization, also be easy to crack and break away from the film of lower electrode because of crystallization changes.

And, exchange in (solgel) method at the collosol and gel state, there is such problem: owing to be about 100nm with the thickness of the PZT film of an operation (coating of precursor solution and subsequent heat treatment) formation, therefore in order to obtain necessary 1 μ m or the thickness more than the 1 μ m at piezoelectric element, above-mentioned operation must be carried out repeatedly reduced rate of finished products more than 10 times or 10 times.

So,, in

patent documentation

6 and 7, illustrated at lower electrode interpolation titanium and titanium oxide and compared effective method as solving the method that the collosol and gel state exchanges these problems in (solgel) method.Particularly, in patent documentation 7, illustrated and promptly used sputtering method, also can obtain the method for the PZT film of (100) planar orientation.

But, owing to be not on lower electrode, directly to obtain Ca-Ti ore type PZT film, but by the initial PZT film that under the low temperature below 200 ℃ or 200 ℃, forms noncrystalline or burnt green stone type crystalline texture, in the oxygen environment, under 500～700 ℃ the high temperature this PZT film is heat-treated then, make its crystallization, therefore the same with collosol and gel state exchange (solgel) method, have in heat to make in the operation of its crystallization, be easy to change the problem crack and to break away from the film of lower electrode because of crystallization.And, use the collosol and gel state to exchange (001) planar orientation degree or (100) planar orientation degree of the PZT film of (solgel) method and sputtering method formation, which kind of method that don't work all is below 85% or 85%.

And in patent documentation 3, though attempted forming for the time being amorphous film, the collosol and gel state that it is become the crystallinity film in reprocessings such as heat treatment exchanges (solgel) method (also comprising the MOD method) method in addition, just, there are not crystallization step such as heat treatment, directly form the one-tenth embrane method of crystallinity film, for example, use sputtering method, laser ablation (laser ablation) method or CVD method, the orientation of PZT film is controlled to be on the surface formed on iridium (Ir) basal electrode of titanium layer as thin as a wafer, fail to obtain alignment films but exchange (solgel) method method in addition with the collosol and gel state.Its reason is: exchange in (solgel) method at the collosol and gel state, the crystallization of PZT film upper electrode one side from lower electrode one side direction and is slowly carried out, and in CVD method and sputtering method etc., the crystallization of PZT film carries out at random, therefore no regularity is difficult to orientation control.

And, in patent documentation 8, as the method that does not need post annealed, show the electrode film of precious metal alloys such as platinum by forming titaniferous with sputtering method and iridium, as basal electrode, again thereon, crystalline orientation lanthanium titanate lead (PLT) etc., do not contain zirconium (Zr) in composition of oxide that forms Ca-Ti ore type crystalline texture with sputtering method is in the sull of (001) face, as initiation layer, with it is substrate, form pzt thin film thereon with sputtering method again, can obtain the method for crystalline orientation in the pzt thin film of (001) face.And, in patent documentation 9, show the electrode film that uses the precious metal alloys that contain cobalt, nickel, manganese, iron or copper, can directly obtain the method for the PZT film of (001) crystalline orientation thereon.As mentioned above, by forming crystalline orientation, form the higher piezoelectric film of piezoelectric property in the PZT film that is (001) face of the bigger crystal orientation of piezoelectric constant.Because this piezoelectric film is oriented in (001) face at the orientation preferentially vertical with substrate surface, therefore when for the tetragonal system perovskite structure, polarised direction is (001) face, and the preferred orientation of crystallization is identical with this polarised direction, higher piezoelectric constant occurs.So above-mentioned piezoelectric film produces big displacement by applying little voltage, as getting most of the attention at the actuator that every field is used.

[patent documentation 1] spy opens flat 10-209517 communique

No. 3021930 communique of [patent documentation 2] patent

[patent documentation 3] spy opens the 2001-88294 communique

[patent documentation 4] spy opens flat 11-191646 communique

[patent documentation 5] spy opens 2000-208828 communique (3-4 page or leaf)

[patent documentation 6] spy opens the 2000-252544 communique

[patent documentation 7] spy opens flat 10-81016 communique

No. 3481235 communique of [patent documentation 8] patent

[patent documentation 9] spy opens flat 2004-79991 communique

[non-patent literature 1] " applicating physical magazine (Journal of Applied Physics) ", the U.S., AIP, on February 15th, 1989, the 65th volume, No. 4, p.1666-1670

But, if the substrate during to film forming uses the substrate of the coefficient of expansion less than piezoelectric film, silicon monocrystalline substrate for example, then above-mentioned piezoelectric film is subjected to tension stress from substrate, (001) face that crystal axis is long, just polaxis is towards the direction parallel with substrate surface.If under this state, voltage is applied to film thickness direction, then the polaxis half-twist.Here, owing to applying voltage hour, polaxis is not easy rotation, therefore can not obtain desirable piezoelectric property, and if it is bigger to apply voltage, then the polaxis rotation is towards the direction vertical with substrate surface, and piezoelectric property uprises.Like this, above-mentioned piezoelectric film, piezoelectric property is higher to the interdependence of voltage.

And have such problem: because when the polaxis half-twist, crystallization produces big distortion, and is therefore and produce the film disengaging between the substrate, lower as the durability for the actuator that obtains big actuator displacement.

Summary of the invention

The present invention is the invention in view of the premises, purpose is: provide a kind of piezoelectric property lower to the voltage interdependence, do not produce that film is that break away from, piezoelectric element that have higher durability, that reliability is higher in order to obtain bigger actuator displacement and promptly to use high voltage drive yet, used ink gun and angular-rate sensor, their manufacture method and the inkjet recording device that has used this ink gun of this piezoelectric element.

In order to achieve the above object, in the present invention, on the electrode film that constitutes by noble metal, formed the stacked film of piezoelectrics of double-layer structure.At this moment,, form thereon again and form some the 2nd different piezoelectric film, form on the whole the higher stacked film of piezoelectrics of (111) planar orientation degree by at first forming the 1st piezoelectric film of preferred orientation in (111) face.

Specifically, the 1st invention is to be object with such piezoelectric element, comprising: the 1st electrode film, by being arranged on the 1st piezoelectric film on the 1st electrode film and being arranged on the stacked film of piezoelectrics that the 2nd piezoelectric film on the 1st piezoelectric film constitutes and being arranged on the 2nd electrode film on the stacked film of these piezoelectrics.That is to say that the 1st invention is that the piezoelectric element with the stacked film of piezoelectrics that is made of the 1st and the 2nd piezoelectric film that comprises the 1st and the 2nd electrode film and clipped by the 1st and the 2nd electrode film is an object.

And the present invention is that the stacked film of above-mentioned piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face.The the above-mentioned the 1st and the 2nd piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other.The averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of above-mentioned the 1st piezoelectric film.The ratio of the thickness of the stacked film of above-mentioned piezoelectrics and the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

So, can on the 1st electrode film, make the stacked film preferred orientation of the piezoelectrics that constitute by rhombogen crystallographic system or tetragonal perofskite type oxide in (111) face.So, the difference of piezoelectric property can be suppressed lower, reliability is improved.In other words, since with this piezoelectric element use for the direction of the film Surface Vertical of the stacked film of these piezoelectrics on apply electric field, therefore especially in the PZT film of the Ca-Ti ore type of rhombogen crystallographic system, because of (111) planar orientation, and make＜111〉polaxis directions are parallel with direction of an electric field, can obtain bigger piezoelectric property.And, owing to do not take place because of applying the polarization rotation that electric field causes,, can make the reliability raising simultaneously even therefore hour also the difference of piezoelectric property can be suppressed lower applying voltage.

And in the PZT of tetragonal Ca-Ti ore type film, because the polaxis direction is＜001〉direction, though therefore become about 54 ° angle with direction of an electric field because of (111) planar orientation makes the polaxis direction, but, can make polaxis remain fixed angle for direction of an electric field by making (111) planar orientation raising always.So, at this moment, do not take place because of applying the polarization rotation that electric field causes yet, therefore the difference of piezoelectric property can be suppressed lower, reliability is improved (for example, in the PZT film that does not have orientation, owing to be that the polaxis of specific crystal axis is towards all directions, therefore after applying electric field, polaxis is respectively towards the direction parallel with electric field.So piezoelectric property has the higher voltage interdependence, particularly ought apply voltage hour, it is big that its difference becomes.And, when applying voltage repeatedly, produce through the time change, aspect reliability, have problems.)

And, the the 1st and the 2nd piezoelectric film by making the stacked film of piezoelectrics is the aggregate of the columnar-shaped particle that joins continuously each other, the averga cross section diameter of columnar-shaped particle that makes the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of the 1st piezoelectric film, the thickness that makes the stacked film of piezoelectrics with the ratio of the averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60, can obtain the stacked film of the very large piezoelectrics of piezoelectric constant into the performance index of piezoelectric, even simultaneously, also can suppress the generation of film disengaging in order to obtain big actuator and use high voltage drive.

And, even owing to do not use the MgO single crystalline substrate of high price, also can obtain the stacked film of the good piezoelectrics of orientation at an easy rate, therefore, can reduce manufacturing cost by using low-cost glass substrate, metal substrate, ceramic substrate, silicon (Si) substrate etc.

And the method for exchanging repeats same operation several times even the thickness of the stacked film of piezoelectrics, also can resemble the collosol and gel state more than or equal to 1 μ m, with stacked films of formation piezoelectrics such as sputtering methods, can suppress the reduction of rate of finished products at an easy rate.

As mentioned above, can obtain to be oriented in the piezoelectric element of (111) face at an easy rate.And because (111) face was the face that is orientated easily originally, so the condition of film forming is very wide, and the difference of piezoelectric property suppresses lowlyer, also is easy to make rate of finished products to rise.And, because (111) planar orientation degree is higher, therefore can make piezoelectric property higher, make the voltage interdependence lower.

The 2nd the invention, the 1st the invention in, the columnar-shaped particle of above-mentioned the 1st piezoelectric film, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.

The 3rd the invention, the 1st the invention in, the columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, length more than or equal to 2500nm smaller or equal to 5000nm.

According to the 2nd and the 3rd invention, can form the stacked film of the higher piezoelectrics of piezoelectric property, even the while when using high voltage drive in order to obtain bigger actuator displacement, also can be suppressed the generation that film breaks away from.

The 4th invention, in the 1st invention, the above-mentioned the 1st and the 2nd piezoelectric film is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type.(111) crystalline orientation rate of above-mentioned the 1st piezoelectric film more than or equal to 50% smaller or equal to 80%.(111) crystalline orientation rate of above-mentioned the 2nd piezoelectric film more than or equal to 95% smaller or equal to 100%.

So, can form the stacked film of the higher piezoelectrics of piezoelectric property, the difference of piezoelectric property can be suppressed lower simultaneously, reliability is risen.

The 5th invention, in the 1st invention, the chemical composition of the stacked film of above-mentioned piezoelectrics compares by Pb: Zr: Ti=(1+a): b: (1-b) expression.The b value of the above-mentioned the 1st and the 2nd piezoelectric film is smaller or equal to 0.60 identical value more than or equal to 0.40.The Pb amount of above-mentioned the 1st piezoelectric film is more than the Pb amount of above-mentioned the 2nd piezoelectric film.The a value of above-mentioned the 1st piezoelectric film more than or equal to 0.05 smaller or equal to 0.15.The a value of above-mentioned the 2nd piezoelectric film more than or equal to 0 smaller or equal to 0.10.

So, by the stacked film of piezoelectrics is used lead zirconate titanate, the amount that makes zirconium smaller or equal to 60 moles of %, can form the stacked film of the higher piezoelectrics of piezoelectric property more than or equal to 40 moles of %.And, compare surplus by making plumbous amount with stoichiometric structure, above 0 and smaller or equal to 15 moles of %, the crystallinity of the stacked film of piezoelectrics is improved, piezoelectric constant is increased.And, by making superfluous plumbous amount, proof voltage is improved smaller or equal to 15 moles of %, can obtain high performance piezoelectric element.

The 6th invention, in the 1st invention, the stacked film of above-mentioned piezoelectrics is by at least a the making of having added to lead zirconate titanate in magnesium and the manganese, this addition surpasses 0 smaller or equal to 10 moles of %.

So, the crystallinity of the stacked film of piezoelectrics is improved, piezoelectric property is improved.

The 7th invention, in the 1st invention, above-mentioned the 1st electrode film, noble metal that is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

So, the 1st electrode film can be anti-be fully lived the temperature when forming each film of piezoelectric element with sputtering method etc., simultaneously, and by controlling the averga cross section diameter of the 1st electrode film, can improve the connecting airtight property with substrate, the film in the time of can positively suppressing piezoelectric element and make breaks away from.

The 8th invention, be to be object with such ink gun, comprise: the 1st electrode film, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level on the face of above-mentioned the 2nd electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 2nd electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink.Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue.

And above-mentioned piezoelectric element of the present invention is the piezoelectric element of the 1st invention.In other words, the stacked film of above-mentioned piezoelectrics, constitute by the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face, the the above-mentioned the 1st and the 2nd piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other, the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of above-mentioned the 1st piezoelectric film, the ratio of the thickness of the stacked film of above-mentioned piezoelectrics and the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

So, by on substrate, forming the 1st electrode film, the stacked film of piezoelectrics, the 2nd electrode film and vibration level successively with sputtering method etc., balancing gate pit's part bonding is being removed substrate after on this vibration level again, can obtain to have with the 1st invention the ink gun of piezoelectric element of same structure, (111) the planar orientation degree of the 2nd piezoelectric film that can make this piezoelectric element is more than or equal to 95%.Therefore, it is less to obtain the ink performance difference that spues, the ink gun that durability is more excellent.

The 9th invention, be to be object with such ink gun, comprise: the 1st electrode film, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level on the face of above-mentioned the 1st electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 1st electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink.Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue.

So, can be by being substrate with balancing gate pit's parts, form vibration level, the 1st electrode film, the stacked film of piezoelectrics and the 2nd electrode film successively with sputtering method etc. thereon, obtain the ink gun that has the same purpose effect with the 8th invention.

The 10th invention is such inkjet recording device, comprising: the ink gun of the 8th invention, and the relative moving mechanism that allows above-mentioned ink gun and recording medium relatively move.When allowing above-mentioned ink gun and above-mentioned recording medium relatively move by above-mentioned relative moving mechanism, carry out record from the ink of nozzle bore in above-mentioned recording medium spues above-mentioned balancing gate pit that is communicated with this balancing gate pit.

The 11st invention is such inkjet recording device, comprising: the ink gun of the 9th invention, and the relative moving mechanism that allows above-mentioned ink gun and recording medium relatively move.When allowing above-mentioned ink gun and above-mentioned recording medium relatively move by above-mentioned relative moving mechanism, carry out record from the ink of nozzle bore in above-mentioned recording medium spues above-mentioned balancing gate pit that is communicated with this balancing gate pit.

According to the 10th and the 11st invention, can more easily obtain lettering performance and the fabulous inkjet recording device of durability.

The 12nd invention is to be object with such angular-rate sensor, the substrate that comprises at least one pair of vibration section that has fixed part and extend from this fixed part towards prescribed direction, each vibration section at least of this substrate is provided with the 1st electrode film, the stacked film of piezoelectrics that constitutes by the 1st and the 2nd piezoelectric film, stack gradually the piezoelectric element that forms with the 2nd electrode film, the 2nd electrode film on above-mentioned each vibration section is patterned as and is used to make this vibration section at least one drive electrode in its Width vibration, at least one detecting electrode with the distortion of the thickness direction that is used to detect above-mentioned vibration section.

So, by between the drive electrode of the 2nd electrode film and the 1st electrode film, applying voltage, each vibration section that makes substrate is in its Width vibration, if when this vibrates because of Coriolis force, the vibration section is in the words of its thickness direction distortion, then between the detecting electrode of the 2nd electrode film and the 1st electrode film, produce voltage, can detect angular speed from the size (Coriolis force) of this voltage.And, because the piezoelectric element by the structure the same with the 1st invention constitutes the part (vibration section) that detects angular speed, therefore compare with the angular-rate sensor in the past that has used crystal and can make about 40 times of piezoelectric constant increases, can realize the miniaturization of certain degree.

And even produce in a large number in industry, reproducibility that also can acquired character is good, and difference is less, the angular-rate sensor that proof voltage and reliability are good.

And,, therefore be difficult to be subjected to the influence of the coefficient of expansion of substrate because the stacked film of piezoelectrics is oriented in (111) face into polaxis.

The 13rd the invention, the 12nd the invention in, the columnar-shaped particle of above-mentioned the 1st piezoelectric film, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.

The 14th the invention, the 12nd the invention in, the columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, its length more than or equal to 2500nm smaller or equal to 5000nm.

According to the 13rd and the 14th invention, can form the stacked film of the higher piezoelectrics of piezoelectric property, the sensitivity of transducer is improved, simultaneously, can realize miniaturization.

The 15th invention, in the 12nd invention, the above-mentioned the 1st and the 2nd piezoelectric film is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type.(111) crystalline orientation rate of above-mentioned the 1st piezoelectric film more than or equal to 50% smaller or equal to 80%.(111) crystalline orientation rate of above-mentioned the 2nd piezoelectric film more than or equal to 95% smaller or equal to 100%.

So, can form the stacked film of the higher piezoelectrics of piezoelectric property, simultaneously, the difference of piezoelectric property can be suppressed lower, and reliability is improved.

The 16th invention, in the 12nd invention, the chemical composition of the stacked film of above-mentioned piezoelectrics compares by [Pb]: [Zr]: [Ti]=(1+a): b: (1-b) expression.The b value of the above-mentioned the 1st and the 2nd piezoelectric film is smaller or equal to 0.60 identical value more than or equal to 0.40.The Pb amount of above-mentioned the 1st piezoelectric film is more than the Pb amount of above-mentioned the 2nd piezoelectric film.The a value of above-mentioned the 1st piezoelectric film more than or equal to 0.05 smaller or equal to 0.15.The a value of above-mentioned the 2nd piezoelectric film more than or equal to 0 smaller or equal to 0.10.

The 17th invention, in the 12nd invention, the stacked film of above-mentioned piezoelectrics is by at least a the making of having added to lead zirconate titanate in magnesium and the manganese, this addition surpasses 0 smaller or equal to 10 moles of %.

So, the crystallinity of the stacked film of piezoelectrics is improved, piezoelectric property is further improved.

The 18th invention, in the 12nd invention, above-mentioned the 1st electrode film, noble metal that is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

The 19th invention, in the 12nd invention, above-mentioned substrate is made of silicon (Si).

So, can reduce manufacturing cost.

The 20th invention is that the manufacture method with piezoelectric element is an object.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; And the operation that on the stacked film of above-mentioned piezoelectrics, forms the 2nd electrode film.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the piezoelectric element that has identical action effect with the 1st invention at an easy rate.

The 21st invention is that the manufacture method with ink gun is an object.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; On above-mentioned the 2nd electrode film, form the operation of vibration level; On above-mentioned vibration level and the face opposite side of above-mentioned the 2nd electrode film, engage the operation of the balancing gate pit's parts that are used to form the balancing gate pit; And after above-mentioned joint operation, the operation of removing above-mentioned substrate.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the ink gun that has the same purpose effect with the 8th invention at an easy rate.

The 22nd invention is that the manufacture method with ink gun is an object.

And, the present invention includes: the operation that on the balancing gate pit's substrate that forms the balancing gate pit, forms vibration level; On above-mentioned vibration level, form the operation of the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; And the operation that forms the balancing gate pit at above-mentioned balancing gate pit substrate.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the ink gun that has same action effect with the 9th invention at an easy rate.

The 23rd invention is that the manufacture method with angular-rate sensor is an object.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; Above-mentioned the 2nd electrode film patterning is formed the operation of drive electrode and detecting electrode; Operation with stacked film of above-mentioned piezoelectrics and above-mentioned the 1st electrode film patterning; And with the operation of above-mentioned underlay pattern formation fixed part and vibration section.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the angular-rate sensor that has same action effect with the 12nd invention at an easy rate.

And, in order to arrive above-mentioned purpose, in the invention beyond the present invention, on the electrode film that constitutes by noble metal, form the orientation controlling diaphragm, on this orientation controlling diaphragm, formed the stacked film of piezoelectrics of double-layer structure again.At this moment,, form the stacked film of piezoelectrics of double-layer structure more thereon, form on the whole the higher stacked film of piezoelectrics of (111) planar orientation degree by at first forming the orientation controlling diaphragm of preferred orientation in (111) face.

Specifically, the 24th invention in the 1st invention, also comprises: the orientation controlling diaphragm that is provided with between above-mentioned the 1st electrode film and above-mentioned the 1st piezoelectric film.Above-mentioned orientation controlling diaphragm is made of the perofskite type oxide of preferred orientation in cubic system or tetragonal (111) face.

In other words, be to be object with such piezoelectric element, it comprises: the 1st electrode film, be arranged on orientation controlling diaphragm on the 1st electrode film, by being arranged on the 1st piezoelectric film on this orientation controlling diaphragm and being arranged on the stacked film of piezoelectrics that the 2nd piezoelectric film on the 1st piezoelectric film constitutes and being arranged on the 2nd electrode film on the stacked film of these piezoelectrics.And, the present invention is, above-mentioned orientation controlling diaphragm is made of the perofskite type oxide of preferred orientation in cubic system or tetragonal (111) face, the stacked film of above-mentioned piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face, the the above-mentioned the 1st and the 2nd piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other, the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of above-mentioned the 1st piezoelectric film, the ratio of the thickness of the stacked film of above-mentioned piezoelectrics and the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

So, by the orientation controlling diaphragm of preferred orientation in the perofskite type oxide of cubic system or tetragonal (111) face is set on the 1st electrode film, can make the stacked film preferred orientation of the piezoelectrics that constitute by rhombogen crystallographic system or tetragonal system perofskite type oxide in same (111) face.So, the difference of piezoelectric property can be suppressed lower, reliability is improved.In other words, because this piezoelectric element is used to applying electric field in the direction of the film Surface Vertical of the stacked film of piezoelectrics therewith, therefore special in the Ca-Ti ore type PZT of rhombogen crystallographic system film, because of (111) planar orientation make＜111〉polaxis directions are parallel with direction of an electric field, can obtain bigger piezoelectric property.And, owing to do not take place because of applying the polarization rotation that electric field causes,, can make the reliability raising simultaneously even, also the difference of piezoelectric property can be suppressed lower therefore applying voltage hour.

And in tetragonal Ca-Ti ore type PZT film, because the polaxis direction is＜001〉direction, though therefore because of (111) planar orientation, the polaxis direction approximately becomes 54 ° angle with direction of an electric field, but by making (111) planar orientation raising, the angle that the angle of polaxis and direction of an electric field often is maintained fixed.Therefore, do not take place this moment because of applying the polarization rotation that electric field causes yet, so, the difference of piezoelectric property can be suppressed lower, reliability is improved (for example, in the PZT film that does not have orientation, owing to be that the polaxis of specific crystal axis is towards all directions, therefore after applying electric field, polaxis is respectively towards the direction parallel with electric field.So piezoelectric property has the higher voltage interdependence, applying voltage hour especially, it is big that its difference becomes.And, when applying voltage repeatedly, produce through the time change, aspect reliability, have problems).

And, the the 1st and the 2nd piezoelectric film by making the stacked film of piezoelectrics is the aggregate of the columnar-shaped particle that joins continuously each other, the averga cross section diameter of columnar-shaped particle that makes the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of the 1st piezoelectric film, the thickness that makes the stacked film of piezoelectrics with the ratio of the averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60, can obtain the stacked film of the very large piezoelectrics of piezoelectric constant, even simultaneously, also can suppress the generation of film disengaging in order to obtain big actuator displacement and use high voltage drive.

And the method for exchanging repeats same operation several times even the thickness of the stacked film of piezoelectrics, also needn't resemble the collosol and gel state more than or equal to 1 μ m, can suppress the reduction of rate of finished products at an easy rate with stacked films of formation piezoelectrics such as sputtering methods.

The 25th the invention, the 24th the invention in, the columnar-shaped particle of above-mentioned the 1st piezoelectric film, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.

The 26th the invention, the 24th the invention in, the columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, length more than or equal to 2500nm smaller or equal to 5000nm.

According to the 25th and the 26th invention, can form the stacked film of the higher piezoelectrics of piezoelectric property, even the while when using high voltage drive in order to obtain bigger actuator displacement, also can be suppressed the generation that film breaks away from.

The 27th invention, in the 24th invention, the above-mentioned the 1st and the 2nd piezoelectric film is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type.(111) crystalline orientation rate of above-mentioned the 1st piezoelectric film more than or equal to 50% smaller or equal to 80%.(111) crystalline orientation rate of above-mentioned the 2nd piezoelectric film more than or equal to 95% smaller or equal to 100%.

So, can form the stacked film of the higher piezoelectrics of piezoelectric property, the difference of piezoelectric property can be suppressed lower simultaneously, and reliability is risen.

The 28th invention, in the 24th invention, the chemical composition of the stacked film of above-mentioned piezoelectrics compares by [Pb]: [Zr]: [Ti]=(1+a): b: (1-b) expression.The b value of the above-mentioned the 1st and the 2nd piezoelectric film is smaller or equal to 0.60 identical value more than or equal to 0.40.The Pb amount of above-mentioned the 1st piezoelectric film is more than the Pb amount of above-mentioned the 2nd piezoelectric film.The a value of above-mentioned the 1st piezoelectric film more than or equal to 0.05 smaller or equal to 0.15.The a value of above-mentioned the 2nd piezoelectric film more than or equal to 0 smaller or equal to 0.10.

So, by the stacked film of piezoelectrics is used lead zirconate titanate, the amount that makes zirconium smaller or equal to 60 moles of %, can form the stacked film of the higher piezoelectrics of piezoelectric property more than or equal to 40 moles of %.And, compare surplus by making plumbous amount with stoichiometric structure, surpass 0 smaller or equal to 15 moles of %, the crystallinity of the stacked film of piezoelectrics is improved, piezoelectric constant is increased.And, by making superfluous plumbous amount, proof voltage is improved smaller or equal to 15 moles of %, can obtain high performance piezoelectric element.

The 29th invention, in the 24th invention, above-mentioned orientation controlling diaphragm is that the lead lanthanum zirconate titanate with Ca-Ti ore type is that the oxide of main component constitutes, (111) crystalline orientation rate of above-mentioned orientation controlling diaphragm is more than or equal to 50%.

The 30th invention, in the 24th invention, the chemical composition of above-mentioned orientation controlling diaphragm compares by [Pb]: [La]: [Zr]: [Ti]=x * (1-z): z: y: (1-y) expression.Above-mentioned x value more than or equal to 1.0 smaller or equal to 1.20.Above-mentioned y value is smaller or equal to 0.20 value more than or equal to 0.Above-mentioned z value surpasses 0 smaller or equal to 0.30.

So, (PLZT, the amount of zirconium are 0 by use lead lanthanum zirconate titanate in the orientation controlling diaphragm, in other words, contain lanthanium titanate lead (PLT)), can make the orientation controlling diaphragm more easily be oriented in (111) face, and, the orientation of the stacked film of piezoelectrics is improved.And the amount by making zirconium is difficult to form the lower layer of crystallinity that is made of zirconium (Zr) oxide at the crystalline growth initial stage smaller or equal to 20 moles of %.And, compare surplus by making plumbous amount with stoichiometric structure, surpass 0 smaller or equal to 20 moles of %, can positively suppress to be orientated the crystalline reduction of controlling diaphragm, therefore, the crystallinity of the stacked film of piezoelectrics that forms is improved thereon.Thereby, the crystallinity of the stacked film of piezoelectrics and orientation are improved, piezoelectric property is further improved.

The 31st invention, in the 24th invention, above-mentioned orientation controlling diaphragm is made by added at least a of magnesium and manganese in lead lanthanum zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

The 32nd invention is, in the 24th invention, the stacked film of above-mentioned piezoelectrics is made by added at least a of magnesium and manganese in lead zirconate titanate, and its addition surpasses 0 piezoelectric element smaller or equal to 10 moles of %.

According to the 31st and the 32nd invention, the crystallinity of orientation controlling diaphragm and the stacked film of piezoelectrics is improved, piezoelectric property is improved.

The 33rd invention, in the 24th invention, above-mentioned the 1st electrode film, noble metal that is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

The 34th invention is to be object with the ink gun, comprising: the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms; Be arranged on the vibration level on the face of above-mentioned the 2nd electrode film one side of this piezoelectric element; And be bonded on this vibration level and the face opposite side of above-mentioned the 2nd electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink.Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue.

And above-mentioned piezoelectric element of the present invention is the piezoelectric element of the 24th invention.In other words, above-mentioned orientation controlling diaphragm is made of the perofskite type oxide of preferred orientation in cubic system or tetragonal (111) face, the stacked film of above-mentioned piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face, the the above-mentioned the 1st and the 2nd piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other, the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of above-mentioned the 1st piezoelectric film, the ratio of the thickness of the stacked film of above-mentioned piezoelectrics and the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

So, by on substrate, form the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics, the 2nd electrode film and vibration level successively with sputtering method etc., balancing gate pit's part bonding is being removed substrate after on this vibration level again, can obtain the ink gun of piezoelectric element that has the same structure with the 24th invention, (111) the planar orientation degree of the 2nd piezoelectric film that can make this piezoelectric element is more than or equal to 95%.Therefore, it is less to obtain the ink performance difference that spues, the ink gun that durability is more excellent.

The 35th invention is to be object with such ink gun, comprise: the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level of face of above-mentioned the 1st electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 1st electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink.Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue.

So, by being substrate, form vibration level, the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics and the 2nd electrode film thereon successively, can obtain to have the ink gun of same action effect with the 34th invention with sputtering method etc. with balancing gate pit's parts.

The 36th invention is to be object with such inkjet recording device, comprising: ink gun and the relative moving mechanism that allows above-mentioned ink gun and recording medium relatively move.When allowing above-mentioned ink gun and above-mentioned recording medium relatively move by above-mentioned relative moving mechanism, carry out record from the ink of nozzle bore in above-mentioned recording medium spues above-mentioned balancing gate pit that is communicated with this balancing gate pit.

And above-mentioned ink gun of the present invention is the ink gun of the 34th invention.

The 37th invention is to be object with such inkjet recording device, comprising: ink gun and the relative moving mechanism that allows above-mentioned ink gun and recording medium relatively move.When allowing above-mentioned ink gun and above-mentioned recording medium relatively move by above-mentioned relative moving mechanism, carry out record from the ink of nozzle bore in above-mentioned recording medium spues above-mentioned balancing gate pit that is communicated with this balancing gate pit.

And above-mentioned ink gun of the present invention is the ink gun of the 35th invention.

According to the 36th and the 37th invention, can obtain lettering performance and the fabulous inkjet recording device of durability at an easy rate.

The 38th invention is an object with such angular-rate sensor, the substrate that comprises at least one pair of vibration section that has fixed part and extend from this fixed part towards prescribed direction, each vibration section at least of this substrate is provided with the 1st electrode film, the orientation controlling diaphragm, the stacked film of piezoelectrics that constitutes by the 1st and the 2nd piezoelectric film, stack gradually the piezoelectric element that forms with the 2nd electrode film, the 2nd electrode film on above-mentioned each vibration section is patterned as and is used to make this vibration section at least one drive electrode in its Width vibration, at least one detecting electrode with the distortion of the thickness direction that is used to detect above-mentioned vibration section.

So, by between the drive electrode of the 2nd electrode film and the 1st electrode film, applying voltage, each vibration section that makes substrate is in its Width vibration, if when this vibrates because of Coriolis force, the vibration section is in the words of its thickness direction distortion, then between the detecting electrode of the 2nd electrode film and the 1st electrode film, produce voltage, can detect angular speed from the size (Coriolis force) of this voltage.And, because the piezoelectric element by the structure the same with the 24th invention constitutes the part (vibration section) that detects angular speed, therefore compare with the angular-rate sensor in the past that has used crystal and can make about 40 times of piezoelectric constant increases, can realize the miniaturization of certain degree.

And even produce in a large number in industry, also can the acquired character reproducibility good, difference be less, the angular-rate sensor that proof voltage and reliability are good.

The 39th the invention, the 38th the invention in, the columnar-shaped particle of above-mentioned the 1st piezoelectric film, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.

The 40th the invention, the 38th the invention in, the columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, its length more than or equal to 2500nm smaller or equal to 5000nm.

According to the 39th and the 40th invention, can form the stacked film of the higher piezoelectrics of piezoelectric property, the sensitivity of transducer is improved, can seek miniaturization simultaneously.

The 41st invention, in the 38th invention, the above-mentioned the 1st and the 2nd piezoelectric film is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type.(111) crystalline orientation rate of above-mentioned the 1st piezoelectric film more than or equal to 50% smaller or equal to 80%.(111) crystalline orientation rate of above-mentioned the 2nd piezoelectric film more than or equal to 95% smaller or equal to 100%.

So, can form the stacked film of the higher piezoelectrics of piezoelectric property, the difference of piezoelectric property can be suppressed lower simultaneously, and reliability is improved.

The 42nd invention, in the 38th invention, the chemical composition of the stacked film of above-mentioned piezoelectrics compares by [Pb]: [Zr]: [Ti]=(1+a): b: (1-b) expression.The b value of the above-mentioned the 1st and the 2nd piezoelectric film is smaller or equal to 0.60 identical value more than or equal to 0.40.The Pb amount of above-mentioned the 1st piezoelectric film is more than the Pb amount of above-mentioned the 2nd piezoelectric film.The a value of above-mentioned the 1st piezoelectric film more than or equal to 0.05 smaller or equal to 0.15.The a value of above-mentioned the 2nd piezoelectric film more than or equal to 0 smaller or equal to 0.10.

So, by use lead zirconate titanate in the stacked film of piezoelectrics, the amount that makes zirconium smaller or equal to 60 moles of %, can form the stacked film of the higher piezoelectrics of piezoelectric property more than or equal to 40 moles of %.And, compare surplus by making plumbous amount with stoichiometric structure, surpass 0 smaller or equal to 15 moles of %, the crystallinity of the stacked film of piezoelectrics is improved, piezoelectric constant is increased.And, by making superfluous plumbous amount, proof voltage is improved smaller or equal to 15 moles of %, can obtain high performance piezoelectric element.

The 43rd invention, in the 38th invention, above-mentioned orientation controlling diaphragm is that the oxide of main component constitutes by the lead lanthanum zirconate titanate with Ca-Ti ore type.(111) crystalline orientation rate of above-mentioned orientation controlling diaphragm is more than or equal to 50%.

The 44th invention, in the 38th invention, the chemical composition of above-mentioned orientation controlling diaphragm is than by Pb: La: Zr: Ti=x * (1-z): z: y: (1-y) expression.Above-mentioned x value more than or equal to 1.0 smaller or equal to 1.20.Above-mentioned y value more than or equal to 0 smaller or equal to 0.20.Above-mentioned z value surpasses 0 smaller or equal to 0.30.

According to the 43rd and the 44th invention,, can obtain and the same action effect of the 29th and the 30th invention by in the orientation controlling diaphragm, using lead lanthanum zirconate titanate (PLZT, the amount of zirconium are 0, just, contain lanthanium titanate lead (PLT)).

The 45th invention, in the 38th invention, above-mentioned orientation controlling diaphragm is made by added at least a of magnesium and manganese in lead lanthanum zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

The 46th invention, in the 38th invention, the stacked film of above-mentioned piezoelectrics is made by added at least a of magnesium and manganese in lead zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

According to the 45th and the 46th invention, the crystallinity of orientation controlling diaphragm and the stacked film of piezoelectrics is improved, piezoelectric property is further improved.

The 47th invention, in the 38th invention, above-mentioned the 1st electrode film, noble metal that is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

The 48th invention, in the 38th invention, above-mentioned substrate is made by silicon (Si).

So, can reduce manufacturing cost.

The 49th invention is an object with the manufacture method of piezoelectric element.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the operation of the orientation controlling diaphragm that constitutes by cubic system or tetragonal perofskite type oxide with sputtering method; On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; And the operation that on the stacked film of above-mentioned piezoelectrics, forms the 2nd electrode film.Form the operation of above-mentioned orientation controlling diaphragm, comprise and allow this orientation controlling diaphragm preferred orientation in the operation of (111) face.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise by above-mentioned orientation controlling diaphragm and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the piezoelectric element that has the same action effect with the 24th invention at an easy rate.

The 50th invention is that the manufacture method with ink gun is an object.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the operation of the orientation controlling diaphragm that constitutes by cubic system or tetragonal perofskite type oxide with sputtering method; On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; On above-mentioned the 2nd electrode film, form the operation of vibration level; With balancing gate pit's part bonding of being used to form balancing gate pit operation on above-mentioned vibration level and the face opposite side of above-mentioned the 2nd electrode film; And after above-mentioned joint operation, the operation that above-mentioned substrate is removed.Form the operation of above-mentioned orientation controlling diaphragm, comprise and allow this orientation controlling diaphragm preferred orientation in the operation of (111) face.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise by above-mentioned orientation controlling diaphragm and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the ink gun that has the same action effect with the 34th invention at an easy rate.

The 51st invention is that the manufacture method with ink gun is an object.

And, the present invention includes: the operation that on the balancing gate pit's substrate that forms the balancing gate pit, forms vibration level; On above-mentioned vibration level, form the operation of the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the operation of the orientation controlling diaphragm that constitutes by cubic system or tetragonal perofskite type oxide with sputtering method; On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; And the operation that forms the balancing gate pit at above-mentioned balancing gate pit substrate.Form the operation of above-mentioned orientation controlling diaphragm, comprise and allow this orientation controlling diaphragm preferred orientation in the operation of (111) face.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise by above-mentioned orientation controlling diaphragm and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the ink gun that has the same action effect with the 35th invention at an easy rate.

The 52nd invention is that the manufacture method with angular-rate sensor is an object.

And, the present invention includes: the operation that on substrate, forms the 1st electrode film with sputtering method; On above-mentioned the 1st electrode film, form the operation of the orientation controlling diaphragm that constitutes by cubic system or tetragonal perofskite type oxide with sputtering method; On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide continuously with sputtering method, form the operation of the stacked film of piezoelectrics; On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film; Above-mentioned the 2nd electrode film patterning is formed the operation of drive electrode and detecting electrode; Operation with the stacked film of above-mentioned piezoelectrics, above-mentioned orientation controlling diaphragm and above-mentioned the 1st electrode film patterning; And with the operation of above-mentioned underlay pattern formation fixed part and vibration section.Form the operation of above-mentioned orientation controlling diaphragm, comprise and allow this orientation controlling diaphragm preferred orientation in the operation of (111) face.Form the operation of the stacked film of above-mentioned piezoelectrics, comprise by above-mentioned orientation controlling diaphragm and allow the stacked film preferred orientation of these piezoelectrics in the operation of (111) face.

So, can make the angular-rate sensor that has the same action effect with the 38th invention at an easy rate.

(effect of invention)

According to piezoelectric element of the present invention, can realize bigger displacement bimorph characteristic and higher durability.

According to the manufacture method of piezoelectric element of the present invention, can produce piezoelectric element at an easy rate in a large number with bigger displacement bimorph characteristic and higher durability.Therefore, even in industrial a large amount of productions, it is good also can to obtain the piezoelectric property reproducibility, and difference is less, the piezoelectric element that proof voltage and reliability are good.

According to ink gun of the present invention and inkjet recording device, can make the spue difference of performance of ink less, can realize higher durability.

According to angular-rate sensor of the present invention, can realize miniaturization and high dimension precision, and even in industrial a large amount of productions, it is good also can to obtain the piezoelectric property reproducibility, difference is less, the angular-rate sensor that proof voltage and reliability are good.

The simple declaration of accompanying drawing

Fig. 1 is the stereogram of the piezoelectric element of embodiments of the present invention 1.

Fig. 2 is the process chart of manufacture method that shows the piezoelectric element of execution mode 1.

Fig. 3 is the schematic diagram of membrane structure of the stacked film of piezoelectrics of execution mode 1.

Fig. 4 is with the electron micrograph shown in the section amplification of the stacked film of piezoelectrics of the 1st embodiment of execution mode 1.

Fig. 5 is the figure that shows the displacement that the piezoelectric element front end when to have applied frequency be the voltage of 2kHz of the 1st embodiment of execution mode 1 moves up and down in the Z direction.

Fig. 6 is the summary structure chart of the ink gun of execution mode 2.

Fig. 7 is the exploded perspective view of the part fracture of element that the ink of execution mode 2 is spued.

Fig. 8 is the VIII-VIII line profile of Fig. 7.

Fig. 9 is the process chart of a part of manufacture method of actuator portion that shows the 6th embodiment of execution mode 2.

Figure 10 is the process chart of a part of manufacture method of actuator portion that shows the 6th embodiment of execution mode 2.

Figure 11 is the figure of the VIII-VIII line profile that is equivalent to Fig. 7 of the actuator portion of the 7th embodiment of execution mode 2.

Figure 12 is the process chart of a part of manufacture method of actuator portion that shows the 7th embodiment of execution mode 2.

Figure 13 is the process chart of a part of manufacture method of actuator portion that shows the 7th embodiment of execution mode 2.

Figure 14 is the summary stereogram of the inkjet recording device of execution mode 3.

Figure 15 is the schematic diagram of the angular-rate sensor of execution mode 4.

Figure 16 is the profile of the angular-rate sensor of execution mode 4.

Figure 17 is the process chart of manufacture method that shows the angular-rate sensor of execution mode 4.

Figure 18 is the schematic diagram of manufacture method that shows the angular-rate sensor of execution mode 4.

Figure 19 is the schematic diagram of angular-rate sensor in the past.

Figure 20 is the stereogram of the piezoelectric element of execution mode 5.

Figure 21 is the process chart of manufacture method that shows the piezoelectric element of execution mode 5.

Figure 22 is the schematic diagram of membrane structure of the stacked film of piezoelectrics of execution mode 5.

Figure 23 is with the electron micrograph shown in the section amplification of the stacked film of piezoelectrics of the 8th embodiment of execution mode 5.

Figure 24 is the figure that shows the displacement that the piezoelectric element front end when to have applied frequency be the voltage of 2kHz of the 8th embodiment of execution mode 5 moves up and down in the Z direction.

Figure 25 is the figure of the VIII-VIII line profile that is equivalent to Fig. 7 of the actuator portion of the 13rd embodiment of execution mode 6.

Figure 26 is the process chart of a part of manufacture method of actuator portion that shows the 13rd embodiment of execution mode 6.

Figure 27 is the process chart of a part of manufacture method of actuator portion that shows the 13rd embodiment of execution mode 6.

Figure 28 is the figure of the VIII-VIII line profile that is equivalent to Fig. 7 of the actuator portion of the 14th embodiment of execution mode 6.

Figure 29 is the process chart of a part of manufacture method of actuator portion that shows the 14th embodiment of execution mode 6.

Figure 30 is the process chart of a part of manufacture method of actuator portion that shows the 14th embodiment of execution mode 6.

Figure 31 is the schematic diagram of the angular-rate sensor of execution mode 8.

Figure 32 is the profile of the angular-rate sensor of execution mode 8.

Figure 33 is the process chart of manufacture method that shows the angular-rate sensor of execution mode 8.

(explanation of symbol)

1,51-substrate; 2,52-the 1st electrode film; 3,41-orientation controlling diaphragm; 4,42-the 1st piezoelectric film; 5,43-the 2nd piezoelectric film; 6,44-the 2nd electrode film; The stacked film of 10-piezoelectrics; The 20-piezoelectric element; The 201-ink gun; The 202-ink element that spues; The 32-balancing gate pit; The 33-individual electrode; The 38-nozzle bore; 45-vibrating body layer; 58-balancing gate pit parts (balancing gate pit's parts); The 81-inkjet recording device; 82-recording medium; 83-transports (carriage) axle (relative moving mechanism); 84-transports portion's (relative moving mechanism); 85-roller (roller) (relative moving mechanism); The 400-angular-rate sensor; The 500-substrate; The 500a-fixed part; The 500b-vibration section; 502-the 1st electrode film; 503-is orientated controlling diaphragm; 504-the 1st piezoelectric film; 505-the 2nd piezoelectric film; 506-the 2nd electrode film; The 507-drive electrode; The 508-detecting electrode.

Embodiment

Below, with reference to accompanying drawing embodiments of the present invention are described in detail.

(execution mode 1)

Fig. 1 is the stereogram of the piezoelectric element 20 of embodiments of the present invention 1.As shown in Figure 1, piezoelectric element 20 comprises: length is that 15.0mm, thickness are that 0.40mm, width are the rectangular flat plate shape substrate 1 of 3.0mm; With the duplexer 11 that is configured on this substrate 1.This substrate 1 has the effect of oscillating plate, and described oscillating plate has obstruction and causes flexible effect because of the piezoelectric effect of duplexer 11.The width of piezoelectric element 20 is 3.0mm.With the width of piezoelectric element 20 is that 3.0mm, length are that the end (left part among Fig. 1) of 3.0mm is that binding agent 8 is fixed on the stainless steel support substrates 7 that thickness is 1.0mm (width is 3.0mm with epoxy, the degree of depth is 10.0mm) on, therefore, piezoelectric element 20 constitutes the beam with folk prescription.

Substrate 1 is provided with the 1st electrode film 2.On the remainder in addition of an end (left part among Fig. 1) of the 1st electrode film 2 (just, width in the 1st electrode film 2 is that 3.0mm, length are the part of 12.0mm), be provided with by the lead zirconate titanate of the Ca-Ti ore type crystalline texture of (111) preferential crystallization orientation (below, PZT) be the stacked film 10 of piezoelectrics that sull constitutes.The stacked film 10 of these piezoelectrics is made of the 1st piezoelectric film 4 and the 2nd piezoelectric film 5 that is arranged on the 1st piezoelectric film 4.The 2nd piezoelectric film 5 is by the 1st piezoelectric film 4 crystallization control orientations.The stacked film 10 of piezoelectrics is provided with the 2nd electrode film 6 that thickness is 100nm.Being connected with thickness on the 1st and the

2nd electrode film

2,6 respectively is metallic lead-in wire 9a, the 9b of 0.1mm.In addition, as shown in Figure 1, duplexer 11 is made of the 1st electrode film 2, the stacked film 10 of piezoelectrics and the 2nd electrode film 6.

Below, the feature of present embodiment is illustrated.

The stacked film 10 of piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face.The the 1st and the 2nd piezoelectric film 4,5 is the aggregate (with reference to Fig. 3) of the columnar-shaped particle that joins continuously each other.The averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film 5 is greater than the averga cross section diameter (mean particle diameter, average diameter) of the columnar-shaped particle of the 1st piezoelectric film 4.The ratio of the thickness of the stacked film 10 of piezoelectrics and the averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film 5 more than or equal to 20 smaller or equal to 60.

The columnar-shaped particle of best the 1st piezoelectric film 4, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.The columnar-shaped particle of best the 2nd piezoelectric film 5, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, length more than or equal to 2500nm smaller or equal to 5000nm.

The the best the 1st and the 2nd piezoelectric film 4,5 is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type, (111) crystalline orientation rate of the 1st piezoelectric film 4 more than or equal to 50% smaller or equal to (111) crystalline orientation rate of 80%, the 2 piezoelectric film 5 more than or equal to 95% smaller or equal to 100%.

The chemical composition of the stacked film 10 of piezoelectrics compares by Pb: Zr: Ti=(1+a): b: (1-b) expression, the b value of the best the 1st and the 2nd piezoelectric film 4,5 is smaller or equal to 0.60 identical value more than or equal to 0.40, the Pb amount of the 1st piezoelectric film 4 is more than the Pb amount of the 2nd piezoelectric film 5, the a value of the 1st piezoelectric film 4 more than or equal to 0.05 smaller or equal to a value of 0.15, the 2 piezoelectric film 5 more than or equal to 0 smaller or equal to 0.10.Perhaps, preferably the stacked film 10 of piezoelectrics is made of at least one side who has added magnesium and manganese in lead zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

Noble metal that best the 1st electrode film 2 is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

But if apply voltage by lead-in

wire

9a, 9b between the 1st and the

2nd electrode film

2,6, then the stacked film 10 of piezoelectrics extends on the directions X of Fig. 1.To apply voltage be E (V) when making, and the thickness that makes the stacked film 10 of piezoelectrics is t (m), and the length that makes the stacked film 10 of piezoelectrics is L (m), and the piezoelectric constant that makes the stacked film 10 of piezoelectrics is d ₃₁(pm/V) time, obtain the extension variation delta L (m) of the stacked film 10 of piezoelectrics with following formula.

ΔL＝d ₃₁×L×E/t

Here, the part that is arranged in the 2nd electrode film 6 one sides of the stacked film 10 of piezoelectrics is (at Fig. 1, the top of the stacked film 10 of piezoelectrics) extend at directions X, the part that is arranged in the 1st electrode film 2 one sides of the stacked film 10 of piezoelectrics (at Fig. 1, the bottom of the stacked film 10 of piezoelectrics) has suppressed its extension because of substrate 1.Its result, the front end of piezoelectric element 20 (right-hand member of Fig. 1) is displaced to the minus side (downside of Fig. 1) of Z direction.Therefore, if with certain frequency voltage application and non-applying repeatedly, then the front end of piezoelectric element 20 moves up and down with the displacement of stipulating on the Z direction.And, apply the relation of the displacement that voltage and piezoelectric element 20 front ends move up and down in the Z direction by inquiry, can estimate the placement property of piezoelectric element 20.

Below, with reference to Fig. 2 the manufacture method of piezoelectric element 20 is illustrated.

Fig. 2 is the process chart that shows the manufacture method of piezoelectric element.At first, shown in Fig. 2 (a), in length is that 20mm, the wide 20mm of being, thickness are on the substrate 101 of 0.30mm, use to have formed the stainless steel mask (mask) of wide thickness as 5.0mm, long oblong openings as 18.0mm, formed the 1st electrode film 102 by RF magnetron sputtering system described later as 0.2mm.

Secondly, uses formed wide as 5.0mm, grow as the thickness of the oblong openings of 12.0mm stainless steel mask as 0.2mm, on the 1st electrode film 102, correctly form the stacked film 110 of piezoelectrics with the RF magnetron sputtering system.The stacked film 110 of these piezoelectrics is to form like this: using PZT is the sintered body target of oxide, at first, on the 1st electrode film 102, form the 1st piezoelectric film 104 with the RF magnetron sputtering system, then, use same target, only membrance casting condition is changed, on the 1st piezoelectric film 104, form the 2nd piezoelectric film 105 continuously with same RF magnetron sputtering system.The stacked film 110 of piezoelectrics has identical structure with the schematic diagram of the membrane structure of the stacked film 110 of piezoelectrics shown in Figure 3.The operation that forms the stacked film 110 of these piezoelectrics comprises makes stacked film 110 preferred orientations of piezoelectrics in the operation of (111) face.

Secondly, use stainless steel mask same as described above,, on the stacked film 110 of piezoelectrics, correctly form the 2nd electrode film 106 with the RF sputtering method with above-mentioned the same.So, shown in Fig. 2 (b), can obtain to have the structure 121 of substrate 101 and duplexer 111.

Secondly, shown in Fig. 2 (c), correctly cutting off structure 121 with cast-cutting saw, is that 3.0mm, length are that expose the rectangle of 15.0mm and an end of the 1st electrode film 2 (left part of Fig. 2 (c)) so that it is a width.Its result can obtain the piezoelectric element structure body product 22 that are made of substrate shown in Figure 1 the 1, the 1st electrode film the 2, the 1st piezoelectric film the 4, the 2nd piezoelectric film 5 and the 2nd electrode film 6.Then, shown in Fig. 2 (d), being binding agent 8 with epoxy is bonded on stainless steel support substrates 7 with the end (left part of Fig. 2 (d)) of substrate 1.

Secondly, shown in Fig. 2 (e), be connected an end of the 1st electrode film 2, be connected an end of the 2nd electrode film 6 with the sealing wire 9b that will go between with the silver paste conductive adhesive 9a that will go between.Method can obtain piezoelectric element shown in Figure 1 20 by this.

Below, execution mode more specifically of the present invention is illustrated.

(the 1st embodiment)

Used silicon as substrate.Used thickness as iridium (Ir) film of 100nm as the 1st electrode film.This iridium film is by in 3 yuan of RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=15: 1) as sputter gas, total gas pressure is remained on 0.25Pa, the iridium target that uses 4 inch diameters applies the high frequency electricity of 200W as the 1st target, and sputter formed in 960 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 50nm constitutes by thickness, and described the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 3400nm by the thickness that is arranged on the 1st piezoelectric film.In other words, making all thickness of the stacked film of piezoelectrics is 3450nm.

Formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.53: 0.47) of 6 inch diameters of the PZT of the stoichiometric structure that the PbO that uses surplus to add about 20 moles of % allocates is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 580 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, under these conditions with forming the 1st piezoelectric film 104 50 seconds.Then, stop film forming, the mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with forming the 2nd piezoelectric film 2900 seconds.

Used platinum (Pt) film as the 2nd electrode film.This platinum film is with RF sputtering method film forming on the 2nd piezoelectric film.

In addition, for thickness, (111) orientation, composition and the cross-section structure of correctly obtaining the 1st piezoelectric film shown in Fig. 2 (b), after forming the 1st piezoelectric film, also formed the stacked film of ending film forming simultaneously.Relevant this sample, its surface has been carried out by scanning electron microscope observation, by X-ray diffraction parsing and by behind the composition analysis of X ray microanalyzer, this sample is destroyed, this section is observed with scanning electron microscope.

And,, after forming the 2nd piezoelectric film, also formed the stacked film of ending film forming simultaneously for thickness, (111) orientation, composition and the cross-section structure of correctly obtaining the 2nd piezoelectric film shown in Fig. 2 (b).Relevant this sample is also with above-mentioned the same, at the observation, parsing by X-ray diffraction and the composition analysis by the X ray microanalyzer that its surface have been carried out by scanning electron microscope.Then, this sample is destroyed, this section is observed with scanning electron microscope.

And, use the structure shown in Fig. 2 (b) as sample, by the Auger spectrum analysis, carried out from the surface of the stacked film of piezoelectrics to the composition analysis of depth direction.And, with scanning electron microscope the section of the stacked film of piezoelectrics is observed.Fig. 4 (a) shows the electron micrograph with the section amplification of the stacked film of piezoelectrics, and Fig. 4 (b) shows the part enlarged drawing of Fig. 4 (a).

The result of above-mentioned each analysis and above-mentioned observation, iridium electrode is that average profile diameter is the aggregate of the columnar-shaped particle of 30nm.The the 1st and the 2nd piezoelectric film exists as the particle assembly body of the column structure that joins continuously each other.The 1st piezoelectric film, thickness (length of columnar-shaped particle) is 50nm, the average profile diameter of columnar-shaped particle is 40nm.The 2nd piezoelectric film, thickness (length of columnar-shaped particle) is 3400nm, the average profile diameter of columnar-shaped particle is 100nm.The thickness of the stacked film of piezoelectrics (length of the columnar-shaped particle of the stacked film of piezoelectrics) is 34.5 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, the 1st and the 2nd piezoelectric film all is a Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 60%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 95%.Here, the PZT that will obtain according to the reflected intensity of each crystal plane of the diffraction pattern that utilizes X-ray diffraction method is that (111) crystalline orientation rate of piezoelectric film is defined as in spacing of lattice from 4.2

(Angstrom) to 1.5

The X-ray diffraction scope in, the percentage of total of (111) peak strength and the full peak strength that belongs to film.Just, the crystalline orientation rate for the peak strength that belongs to (111), with lead lanthanum zirconate titanate (below, PLZT) percentage of ratio of total of the peak strength of each crystal plane is waited in (001) of the X-ray diffraction pattern of film, pzt thin film, (100), (010), (110), (011), (101), (111).

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of the 1st and the 2nd piezoelectric film is respectively Pb: Zr: Ti=1.15: 0.53: 0.47 and Pb: Zr: Ti=1.10: 0.53: 0.47.Just, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.In other words, the 1st and the 2nd piezoelectric film is the crystalline growth direction from a side of the thickness direction of the stacked film of the piezoelectrics aggregate towards the opposing party's columnar-shaped particle.

And, by lead-in

wire

9a, 9b between the 1st and the

2nd electrode film

2,6 of piezoelectric element 20, apply 0V～-triangle wave voltage of 80V, use laser-Doppler vibration displacement determinator, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.Fig. 5 is the figure that shows the displacement that piezoelectric element 20 front ends when having applied frequency 2kHz voltage move up and down in the Z direction.As shown in Figure 5, when applied 0V～-during 80V voltage, the front end maximum displacement 34.0 μ m of piezoelectric element 20.And, carry out round driving by this triangle wave voltage, after driving 100,000,000 times (driving time 13.9 hours) and 1,000,000,000 times (driving time 138.9 hours), check the driving condition of piezoelectric element 20, simultaneously, with observation by light microscope its outward appearance.After driving 1,000,000,000 times, maximum displacement also is 34.0 μ m, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 2nd embodiment)

Use high temperature resistant pyrex (registered trade mark) glass at substrate, the 1st electrode film has been used platinum (Pt) film of thickness as 150nm.This platinum film is by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=15: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the platinum target as the 1st target, apply the high frequency electricity of 200W, sputter formed in 1080 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 100nm constitutes by thickness, and described the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 4000nm by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 4100nm.

The same with the 1st embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.10: 0.50: 0.50) of 6 inch diameters of the PZT of the stoichiometric structure that the PbO that uses surplus to add about 10 moles of % allocates is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 550 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=79: 1, making its flow is per minute 40ml, and making plasma generation power is 2kW, uses for 60 seconds with the 1st piezoelectric film film forming under these conditions.Then, stop film forming, making underlayer temperature is 590 ℃, and plasma generation power is 3kW, and other condition is constant, with 3800 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 1st embodiment analyzed and observed, platinum electrode is that average profile diameter is the aggregate of the columnar-shaped particle of 30nm.The the 1st and the 2nd piezoelectric film exists as the particle assembly body of the column structure that joins continuously each other.The 1st piezoelectric film, thickness are 100nm, and the average profile diameter of columnar-shaped particle is 50nm.The 2nd piezoelectric film, thickness are 4000nm, and the average profile diameter of columnar-shaped particle is 200nm.The thickness of the stacked film of piezoelectrics is 20.5 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, the 1st and the 2nd piezoelectric film all is a Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 70%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 98%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of the 1st and the 2nd piezoelectric film is respectively Pb: Zr: Ti=1.15: 0.51: 0.49 and Pb: Zr: Ti=1.00: 0.51: 0.49.Just, the same with the 1st embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 1st embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 37.0 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 3rd embodiment)

At the thermal endurance corrosion resistant plate of substrate use mirror finish, the 1st electrode film has been used the alloy firm of the thickness of titaniferous (Ti) as iridium (Ir) formation of 110nm.This alloy firm is by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the iridium target as the 1st target, use the titanium target as the 2nd target, apply the high frequency electricity of 200W and 60W respectively, sputter formed in 960 seconds.In addition, the purpose of adding titanium in iridium is in order to improve the connecting airtight property with substrate, even do not add titanium, also can not to have influence on the characteristic of piezoelectric element.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of 10 moles of % magnesium of interpolation of (111) preferred orientation of 10nm constitutes by thickness, and described the 2nd piezoelectric film is that (PZT+Mg) film of (111) orientation of 4990nm constitutes by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 5000nm.

The same with the 1st embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.Use the superfluous sintered body target (constitutive molar ratio Pb: Zr: Ti: Mg=1.10: 0.60: 0.40: 0.10) of 6 inch diameters that has added the PbO of about 10 moles of % and added 10 moles of % magnesium (Mg) lead zirconate titanates (PZT+Mg) allotment, stoichiometric structure as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 570 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, uses for 100 seconds with the 1st piezoelectric film film forming under these conditions.Then, stop film forming, the mixing ratio with sputter gas becomes argon immediately: oxygen=79: 1, other condition is constant, with 2500 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 1st embodiment analyzed and observed, the 1st electrode film is made of the iridium film of the titanium that contains 1 mole of %, and the averga cross section diameter is the aggregate of the columnar-shaped particle of 20nm.The the 1st and the 2nd piezoelectric film exists as the particle assembly body of the column structure that joins continuously each other.The 1st piezoelectric film, thickness are 10nm, and the average profile diameter of columnar-shaped particle is 40nm.The 2nd piezoelectric film, thickness are 4990nm, and the average profile diameter of columnar-shaped particle is 100nm.The thickness of the stacked film of piezoelectrics is 50.0 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, the 1st and the 2nd piezoelectric film all is a Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 50%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 95%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of the 1st and the 2nd piezoelectric film is respectively Pb: Zr: Ti: Mg=1.05: 0.60: 0.40: 0.09 and Pb: Zr: Ti: Mg=1.00: 0.60: 0.40: 0.10.Just, the same with the 1st embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 1st embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 36.0 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 4th embodiment)

At the ceramic material (alumina) of substrate use mirror ultrafinish, the 1st electrode film has been used the alloy firm of the thickness of nickeliferous (Ni) as ruthenium (Ru) formation of 120nm.This alloy firm is by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the ruthenium target as the 1st target, use the nickel target as the 2nd target, apply the high frequency electricity of 200W and 60W respectively, sputter formed in 960 seconds.In addition, the purpose of adding nickel in ruthenium is in order to improve the connecting airtight property with substrate, even do not add nickel, also can not to have influence on the characteristic of piezoelectric element.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of 5 moles of % manganese of interpolation of (111) preferred orientation of 50nm constitutes by thickness, and described the 2nd piezoelectric film is that (PZT+Mn) film of (111) orientation of 2500nm constitutes by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 2550nm.

The same with the 1st embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti: Mn=1.20: 0.40: 0.60: 0.05) of 6 inch diameters of PZT manganese (Mn) allotment, stoichiometric structure that has used the PbO of the about 20 moles of % of superfluous interpolation and added 5 moles of % is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned (PZT+Mn) target, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 550 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=79: 1, making its flow is per minute 40ml, and making plasma generation power is 2kW, uses for 5 seconds with the 1st piezoelectric film film forming under these conditions.Then, stop film forming, making underlayer temperature is 580 ℃, and making plasma generation power is 3kW, and other condition is constant, with 2000 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 1st embodiment analyzed and observed, the 1st electrode film is made of the ruthenium film of the nickel that contains 4 moles of %, and the averga cross section diameter is the aggregate of the columnar-shaped particle of 25nm.The the 1st and the 2nd piezoelectric film exists as the particle assembly body of the column structure that joins continuously each other.The 1st piezoelectric film, thickness are 50nm, and the average profile diameter of columnar-shaped particle is 30nm.The 2nd piezoelectric film, thickness are 2500nm, and the average profile diameter of columnar-shaped particle is 60nm.The thickness of the stacked film of piezoelectrics is 42.5 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, the 1st and the 2nd piezoelectric film all is a Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 70%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 97%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of the 1st and the 2nd piezoelectric film is respectively Pb: Zr: Ti: Mn=1.10: 0.40: 0.60: 0.05 and Pb: Zr: Ti: Mn=1.05: 0.40: 0.60: 0.05.Just, the same with the 1st embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 1st embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 38.7 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 5th embodiment)

Use silicon at substrate, the 1st electrode film has been used palladium (Pd) film of thickness as 120nm.This palladium membranes is by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 500 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the palladium target as the 1st target, apply the high frequency electricity of 200W, sputter formed in 960 seconds.

The stacked film 10 of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 100nm constitutes by thickness, and described the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 4900nm by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 5000nm.

The same with the 1st embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.58: 0.42) of 6 inch diameters of PZT of stoichiometric structure of PbO allotment that has used the about 20 moles of % of superfluous interpolation is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 580 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, uses for 75 seconds with the 1st piezoelectric film film forming under these conditions.Then, stop film forming, the mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 3700 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 1st embodiment analyzed and observed, palladium electrode is the aggregate of the columnar-shaped particle of 20nm for the averga cross section diameter.The the 1st and the 2nd piezoelectric film exists as the particle assembly body of the column structure that joins continuously each other.The 1st piezoelectric film, thickness are 100nm, and the average profile diameter of columnar-shaped particle is 50nm.The 2nd piezoelectric film, thickness are 4900nm, and the average profile diameter of columnar-shaped particle is 90nm.The thickness of the stacked film of piezoelectrics is 55.5 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, the 1st and the 2nd piezoelectric film all is a Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 75%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 100%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of the 1st and the 2nd piezoelectric film is respectively Pb: Zr: Ti=1.10: 0.58: 0.42 and Pb: Zr: Ti=1.05: 0.58: 0.42.Just, the same with the 1st embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 1st embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement of piezoelectric element 20 is 41.5 μ m, and after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

In addition, in the 1st embodiment～the 5th embodiment, used 3 dimensional-oxides of plumbous (Pb), zirconium (Zr) and titanium (Ti) and added the pzt thin film of magnesium (Mg) and manganese (Mn) to them, also can use the PZT film (plzt film just) that contains lanthanum (La) and contain niobium (Nb) and the PZT film of the ion of magnesium (Mg) etc., if use the sull of Ca-Ti ore type crystalline texture, then can obtain and the stacked film of piezoelectrics that the 1st embodiment～the 5th embodiment is the same.

(comparative example 1)

In order to compare, made following piezoelectric element with the 1st embodiment～the 5th embodiment.

Only form the 2nd piezoelectric film on the 1st electrode film that is made of iridium film, replace forming the stacked film of piezoelectrics in the 1st embodiment on the 1st electrode film that is made of iridium film, other and the 1st embodiment are just the same.

Sample about this comparative example, with above-mentioned the same, its surface carried out the scanning electron microscope observation, passing through the parsing of X-ray diffraction and,, observing its section with scanning electron microscope with this sample destruction by behind the composition analysis of X ray microanalyzer.

The result of above-mentioned each analysis and above-mentioned observation, the piezoelectric film of this comparative example exists as the particle assembly body of column structure.Piezoelectric film, thickness are 3500nm, and the averga cross section diameter of columnar-shaped particle is 200nm.The thickness of piezoelectric film (length of the columnar-shaped particle of piezoelectric film) is 17.5 with the ratio of the averga cross section diameter of the columnar-shaped particle of piezoelectric film.

With the result that X-ray diffraction method is resolved, the piezoelectric film of this comparative example is a Ca-Ti ore type crystalline texture.(111) crystalline orientation rate of the formation face of piezoelectric film is 55%.

The composition analysis result of the cation by the X ray microanalyzer, the composition Pb of the piezoelectric film of this comparative example: Zr: Ti=1.05: 0.53: 0.47.

By the Auger spectrum analysis from the surface of piezoelectric film the result towards the composition analysis of depth direction, the composition of Zr and Ti distribute from the interface of the 2nd electrode film to the interface of the 1st electrode film till all immobilize.

Just, this comparative example is with the something in common of the 1st embodiment: piezoelectric film is as the PZT film of the Ca-Ti ore type crystalline texture of the aggregate of columnar-shaped particle growth on the direction vertical with substrate surface.But the averga cross section diameter of the columnar-shaped particle of piezoelectric film is greater than the 1st embodiment, and (111) crystalline orientation rate of piezoelectric film is less than the 1st embodiment.

The same with the 1st embodiment, to the piezoelectric element of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that the piezoelectric element front end moves up and down in the Z direction.The front end maximum displacement of piezoelectric element 20.0 μ m, and, carry out round driving by this triangle wave voltage, after driving 100,000,000 times, carried out the inspection of the situation that drives and utilize light microscope the result of observation of outward appearance, maximum displacement drops to 3.5 μ m, the part film has taken place between the 1st electrode film and piezoelectric film peeled off.

(comparative example 2)

Only form the 2nd piezoelectric film on the 1st electrode film that is made of palladium membranes, replace forming the stacked film of piezoelectrics in the 5th embodiment on the 1st electrode film that is made of palladium membranes, other and the 5th embodiment are just the same.

The result of above-mentioned each analysis and above-mentioned observation, the piezoelectric film of this comparative example exists as the particle assembly body of column structure.Piezoelectric film, thickness are 4800nm, and the averga cross section diameter of columnar-shaped particle is 300nm.The length of the columnar-shaped particle of piezoelectric film is 16.0 with the ratio of the averga cross section diameter of the columnar-shaped particle of piezoelectric film.

With the result that X-ray diffraction method is resolved, the piezoelectric film of this comparative example is a Ca-Ti ore type crystalline texture.(111) crystalline orientation rate of piezoelectric film is 70%.

By the Auger spectrum analysis from the surface of piezoelectric film the result towards the composition analysis of depth direction, the composition of Zr and Ti distribute from the interface of the 2nd electrode film to the interface of the 1st electrode film till all immobilize.Pb forms, from the interface of the 1st electrode film scope till the extremely near 10nm in, (all Pb of piezoelectric film form about 1/20th) more or less tails off.This phenomenon can not observe out with the precision of Auger spectrum analysis, can think to be diffused in the 1st electrode film and the phenomenon that causes because only be made up of some Pb.

Just, this comparative example is with the something in common of the 5th embodiment: piezoelectric film is as the PZT film of the Ca-Ti ore type crystalline texture of the aggregate of columnar-shaped particle growth on the direction vertical with substrate surface.But, be with the difference of the 5th embodiment: the averga cross section diameter of the columnar-shaped particle of piezoelectric film is greater than the 5th embodiment, (111) crystalline orientation rate of piezoelectric film is less than the 5th embodiment, form equally with the Pb that Pb forms and piezoelectric film is all of the near interface of the 1st electrode film, and more or less tail off with the Pb composition at the interface of the 1st electrode film.

The same with the 5th embodiment, to the piezoelectric element of this comparative example apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that the piezoelectric element front end moves up and down in the Z direction.The front end maximum displacement of piezoelectric element 22.0 μ m.And, carry out round driving by this triangle wave voltage, after driving 1,000,000,000 times, to have carried out driving the inspection of situation and utilized the result of observation of the outward appearance of light microscope, driving stops, and between the 1st electrode film and piezoelectric film film has taken place and has peeled off.

(execution mode 2)

Present embodiment is the ink gun that possesses the piezoelectric element of embodiments of the present invention 1.Below, this ink gun is illustrated.

Fig. 6 is the summary structure chart that shows the ink gun 201 of embodiments of the present invention 2.As shown in Figure 6, ink gun 201 is by 10 identical inks of shape of the shape configuration of being arranged in rows spue element 202 and constituting in order to drive the spue driving power element 203 of element 202 of each ink of spuing with each ink that the aftermentioned individual electrode 33 of element 202 is connected.This driving power element 203 provides voltage by sealing wire to the spue individual electrode 33 of element 202 of each ink.

The exploded perspective view that Fig. 7 cuts off for the part of element 202 that ink is spued.As shown in Figure 7, A is balancing gate pit's parts (balancing gate pit's parts), and being formed with minor axis at the parts A of this balancing gate pit is that 200 μ m, major axis are the oval balancing gate pit peristome 31 of 400 μ m.B is arranged to the actuator portion of overburden pressure chamber with the upper end open face of peristome 31.C is configured to the ink stream road parts of overburden pressure chamber with the lower ending opening face of peristome 31.In other words, the balancing gate pit of the parts A of balancing gate pit is positioned at its B of actuator portion and ink stream road parts C zoning up and down with peristome 31, and thus, forming thickness is the balancing gate pit 32 of 0.2mm.The B of actuator portion comprises the individual electrode 33 that is positioned at 32 tops, balancing gate pit.Ink stream road parts C be formed with each ink spue shared common liquid chamber 35 between the balancing gate pit 32 of element 202, be communicated with the supply port 36 of this common liquid chamber 35 and balancing gate pit 32 and the ink flow path 37 that is communicated with balancing gate pit 32 in order to the ink liquid in the outflow pressure chamber 32.D is a nozzle plate, is equipped with the nozzle bore 38 that the diameter that is communicated with ink flow path 37 is 30 μ m at this nozzle plate D.Parts A～D bonds together with binding agent each other, thus, can obtain the ink element 202 that spues.

Below, the execution mode more specifically of the B of actuator portion is illustrated.

(the 6th embodiment)

With reference to Fig. 8 the B of actuator portion is illustrated.Fig. 8 is the VIII-VIII line profile of Fig. 7.As shown in Figure 8, the B of actuator portion has: be the individual electrode (the 1st electrode film) 33 of iridium (Ir) the film formation of 100nm by thickness; Be positioned at this individual electrode 33 under, by using Pb _1.15Zr _0.53Ti _0.48O ₃The thickness of expression is the 1st piezoelectric film 42 that the pzt thin film of 50nm constitutes; Be positioned at the 1st piezoelectric film 42 under, by using Pb _1.10Zr _0.53Ti _0.47O ₃The thickness of expression is the 2nd piezoelectric film 43 that the pzt thin film of 3500nm constitutes; Be positioned at the 2nd piezoelectric film 43 under, be the 2nd electrode film 44 that the platinum film of 100nm constitutes by thickness; And be positioned at the 2nd electrode film 44 under, be the vibrating body layer (oscillating plate) 45 that chromium (Cr) film of 3500nm constitutes by thickness.This vibrating body layer 45 is by the piezoelectric effect displacement vibration of the 1st and the 2nd piezoelectric film 42,43.The 2nd electrode film 44 and vibrating body layer 45, it is shared between the balancing gate pit 32 of element 202 to spue at each ink.The the 1st and the 2nd piezoelectric film 42,43 is processed to identical with the shape of individual electrode 33.Around the stacked film that constitutes by individual electrode the 33, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43 on the 2nd electrode film 44, be provided with thickness the electric insulation organic membrane 46 by poly-(acyl) imide resin formation identical with above-mentioned stacked film.On this electric insulation organic membrane 46, be provided be connected on the individual electrode 33, be the extraction electrode film 47 that the metallic film of 100nm constitutes by the thickness of lead format.Individual electrode 33, the stacked film of piezoelectrics and the 2nd electrode film 44 that are made of the 1st and the 2nd piezoelectric film 42,43 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 1, therefore, can obtain the B of actuator portion of high characteristic.

Below, the manufacture method of the B of actuator portion is illustrated.

Fig. 9 and Figure 10 are the process chart that shows the manufacture method of the B of actuator portion.At first,, the same long with the 1st embodiment of execution mode 1 for 20mm, wide for 20mm, thickness are on the silicon substrate 51 of 0.3mm, stack gradually the 1st electrode film the 52, the 1st piezoelectric film the 54, the 2nd piezoelectric film 55 and the 2nd electrode film 44.Therefore, can obtain the structure 56 shown in Fig. 9 (a).

Secondly, shown in Fig. 9 (b), at room temperature, having formed thickness with the RF sputtering method on structure 56 is the vibrating body layer 45 by chromium (Cr) film formation of 3500nm.

Secondly, shown in Fig. 9 (c), vibrating body layer 45 is attached on balancing gate pit's parts 58 of glass with acrylic resin binder 57.These balancing gate pit's parts 58 are configured to vibrating body layer 45 face-to-face, accompany binding agent 57 between balancing gate pit's parts 58 and vibrating body layer 45.

Secondly, shown in Fig. 9 (d), use the plasma reaction Etaching device, utilize SF ₆Silicon substrate 51 is removed in the dry ecthing of gas.

Secondly, shown in Fig. 9 (e), make and use up resin molding 59 against corrosion, it is that 180 μ m, major axis are the pattern of oval shapes of 380 μ m that the non-etching part of the stacked film that will be made of the 1st electrode film the 52, the 1st piezoelectric film 54 and the 2nd piezoelectric film 55 correctly is patterned as minor axis.Then, use the dry ecthing of argon (Ar) gas and the wet etching of weak fluoric acid, carried out etch processes.So, shown in Figure 10 (a), can obtain to have be processed to the light corrosion-resisting pattern, by the actuator structure body of the stacked film that is constituted by individual individual electrode the 33, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43.Then, shown in Figure 10 (b), light resin molding 59 against corrosion is handled, be removed with stripper against corrosion.

Secondly, shown in Figure 10 (c), on the 2nd electrode film 44, formed electric insulation organic membrane 46 with print process.Then, shown in Figure 10 (d), on electric insulation organic membrane 46, formed extraction electrode film 47 with the DC sputtering method.So, can obtain the B of actuator portion shown in Figure 8.

Made 30 inks element 202 that spues with the manufacture method shown in the present embodiment.Between these inks spue two

electrode films

33,44 of element 202, apply frequency and be 200Hz, 0V～-the sinusoidal waveform voltage of 60V, carried out the inspection of above-mentioned driving situation.After driving 1,000,000,000 times, all inks element 202 that spues does not break down yet.

Use 10 these inks element 202 that spues, made ink gun shown in Figure 6 201.In this ink gun 201, provide voltage by sealing wire to the spue individual electrode 33 of element 202 of each ink from driving power element 203, piezoelectric effect by the 1st and the 2nd

piezoelectric film

42,43, vibrating body layer 45 is in bed thickness direction displacement vibration, and the ink liquid in the common liquid chamber 35 spues from nozzle bore 38 by supply port 36, balancing gate pit 32 and ink flow path 37.

Here, in this ink gun 201, the 1st and the 2nd

piezoelectric film

42,43 of the B of actuator portion of element 202 because the formation ink spues, the crystalline orientation of face is (111) face entirely, the displacement bimorph characteristic is bigger value entirely, therefore can obtain bigger displacement bimorph.And, because the connecting airtight property of individual electrode 33 and the 1st piezoelectric film 54 is higher,, also be difficult to take place the fault that comes off and cause because of film even therefore apply high voltage with big displacement drive, can realize the driving of reliability higher stable.And because displacement bimorph is bigger, so the ability that spues of ink liquid is higher, can increase the limit of the adjustment width of supply voltage.So, each ink is spued control that the difference that spues of the ink liquid between the element 202 diminishes.

(the 7th embodiment)

With reference to Figure 11 the structure actuator portion B different with the 6th embodiment is illustrated.Figure 11 is the figure of actuator portion VIII-VIII line B, that the be equivalent to Fig. 7 profile of the 7th embodiment of execution mode 2.As shown in figure 11, the B of actuator portion has: be the individual electrode (the 2nd electrode film) 33 of platinum (Pt) the film formation of 100nm by thickness; Be positioned at this individual electrode 33 under, by using Pb _1.05Zr _0.58Ti _0.42O ₃The thickness of expression is the 2nd piezoelectric film 43 that the pzt thin film of 4500nm constitutes; Be positioned at the 2nd piezoelectric film 43 under, by using Pb _1.10Zr _0.58Ti _0.42O ₃The thickness of expression is the 1st piezoelectric film 42 that the pzt thin film of 80nm constitutes; Be positioned at the 1st piezoelectric film 42 under, be the 1st electrode film 52 that the palladium of 200nm constitutes by thickness; And be positioned at the 1st electrode film 52 under, be the silica (SiO of 5000nm by thickness ₂) the vibrating body layer 45 that constitutes of film.This vibrating body layer 45 is by the piezoelectric effect displacement vibration of the 1st and the 2nd piezoelectric film 42,43.The 1st electrode film 52 and vibrating body layer 45, it is shared between the balancing gate pit 32 of element 202 to spue at each ink.The the 1st and the 2nd piezoelectric film 42,43 is processed to identical with the shape of individual electrode 33.Around the stacked film that constitutes by individual electrode the 33, the 1st piezoelectric film 54 and the 2nd piezoelectric film 55 on the 1st electrode film 52, be provided with thickness the electric insulation organic membrane 46 by poly-(acyl) imide resin formation identical with above-mentioned stacked film.On this electric insulation organic membrane 46, be provided be connected on the individual electrode 33, be the extraction electrode film 47 that the metallic film of 100nm constitutes by the thickness of lead format.Individual electrode 33, the stacked film of piezoelectrics and the 1st electrode film 52 that are made of the 1st and the 2nd piezoelectric film 54,55 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 1, therefore, can obtain the B of actuator portion of high characteristic.

Below, the manufacture method of the B of actuator portion is illustrated.

Figure 12 and Figure 13 are the process chart that shows the manufacture method of the B of actuator portion.At first, long for 20mm, wide for 20mm, thickness be that the silicon substrate 51 (balancing gate pit's substrate) of 0.3mm is gone up and formed vibrating body layer 45, then, on vibrating body layer 45, the same with the 5th embodiment of execution mode 1, stack gradually the 1st electrode film the 52, the 1st piezoelectric film the 54, the 2nd piezoelectric film 55 and the 2nd electrode film 44.Therefore, can obtain the structure 56 shown in Figure 12 (a).

Secondly, shown in Figure 12 (b), make and use up resin molding 59 against corrosion, it is that 180 μ m, major axis are the pattern of oval shapes of 380 μ m that the non-etching part of the stacked film that will be made of the 2nd electrode film the 44, the 1st piezoelectric film 54 and the 2nd piezoelectric film 55 correctly is patterned as minor axis.

Then, use the dry ecthing of argon (Ar) gas and the wet etching of weak fluoric acid, carried out etch processes.So, shown in Figure 12 (c), can obtain to have be processed to the light corrosion-resisting pattern, by the actuator structure body of the stacked film that is constituted by individual individual electrode the 33, the 2nd piezoelectric film 43 and the 1st piezoelectric film 42., as Figure 12 (d) shown in, with against corrosion stripper light against corrosion resin molding 59 handled, be removed thereafter.Then, shown in Figure 13 (a), on the 1st electrode film 52, formed electric insulation organic membrane 46 with print process.

Secondly, shown in Figure 13 (b), use the plasma reaction Etaching device, use SF ₆The part of silicon substrate 51 is removed in the dry ecthing of gas, has formed balancing gate pit 32.

Secondly, shown in Figure 13 (c), on electric insulation organic membrane 46, formed extraction electrode film 47 with the DC sputtering method.Therefore, can obtain the B of actuator portion shown in Figure 11.

electrode films

33,52 of element 202, apply frequency and be 200Hz, 0V～-the sinusoidal waveform voltage of 60V, carried out the inspection of above-mentioned driving situation.After driving 1,000,000,000 times, all inks element 202 that spues does not break down yet.

Use 10 these inks element 202 that spues, made ink gun shown in Figure 6 201.Use this ink gun 201, can obtain the action effect the same with the 6th embodiment.

(execution mode 3)

Present embodiment is the inkjet recording device that possesses the ink gun of embodiments of the present invention 2.Below, this inkjet recording device is illustrated.

Figure 14 is the summary stereogram of the inkjet recording device of embodiments of the present invention 3.As shown in figure 14, inkjet recording device 81, the ink gun 201 that possesses the execution mode 2 that the piezoelectric effect of utilizing the 1st and the 2nd

piezoelectric film

42,43 writes down drops on the recording medium 82 such as paper by making the ink droplet that spues from ink gun 201, carries out record to recording medium 82.Ink gun 201 is contained in the portion of transporting 84 (relative moving mechanism), the described portion 84 that transports is slidably mounted in along transporting on axle 83 (relative moving mechanism) that main scanning direction (directions X of Figure 14) is provided with.And, transport portion 84 and move around along transporting axle 83, ink gun 201 is moved around on main scanning direction X.Inkjet recording device 81, possess recording medium of making 82 with the sub scanning direction Y of main scanning direction X approximate vertical on a plurality of rollers 85 (relative moving mechanism) of moving.And, in inkjet recording device 81,,, carry out record from the ink of nozzle bore 38 in recording medium 82 spues balancing gate pit 32 when by transport axle 83 grades when ink gun 201 is moved around on main scanning direction X.

As mentioned above, according to present embodiment, can easily control the spue ink gun 201 of execution mode 2 of the difference that spues of the ink liquid between the element 202 of each ink owing to use, make inkjet recording device 81, therefore the difference that writes down to recording medium 82 is diminished, thereby, can realize the higher inkjet recording device of reliability 81.

(execution mode 4)

Present embodiment is the angular-rate sensor that has possessed the piezoelectric element of embodiments of the present invention 1.Below, this angular-rate sensor is illustrated.

As 15 and Figure 16 be the schematic diagram and the profile of the angular-rate sensor 400 of embodiments of the present invention 4.This angular-rate sensor 400 is tuning-fork-type, is widely used in guider that is contained in the vehicle etc.

Angular-rate sensor 400, possessing by thickness is the substrate 500 that the silicon wafer of 0.3mm constitutes.This substrate 500, have fixed part 500a and from this fixed part 500a to the prescribed direction (direction that the rotary middle spindle of the angular speed of detection extends.Be the Y direction of Figure 15 in the present embodiment) a pair of vibration section 500b, the 500b that extend.These fixed parts 500a and a pair of

vibration section

500b, 500b are from the thickness direction (the Z direction of Figure 15) of substrate 500, become tuning fork-like, a pair of

vibration section

500b, 500b are equivalent to the arm of tuning fork, extend parallel to each other under the state of arranging on the Width of vibration section 500b.In addition, substrate 500 can be glass substrate, metal substrate, ceramic substrate etc.

On the part of vibration section 500b one side of each the vibration section 500b of substrate 500 and fixed part 500a, stacked gradually the 1st electrode film the 502, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506.The 1st electrode film 502, the stacked film of piezoelectrics and the 2nd electrode film 506 that are made of the 1st and the 2nd piezoelectric film 504,505 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 1.That is to say, the 1st electrode film the 502, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506, the 1st electrode film the 2, the 1st piezoelectric film the 4, the 2nd piezoelectric film 5 and the 2nd electrode film 6 with execution mode 1 is the same respectively.

The 2nd electrode film 506 is patterned on each vibration section 500b, be used to make two drive electrodes 507,507 of vibration section 500b in its Width (directions X of Figure 15) vibration, and a detecting electrode 508 of distortion (amount of deflection) that is used to detect the thickness direction (the Z direction of Figure 15) of vibration section 500b.

Two drive electrodes 507,507 are set on Width (directions X) both ends of vibration section 500b, cross over the appearance of the length direction (the Y direction of Figure 15) of whole vibration section 500b.The end of fixed part 500a one side of each drive electrode 507 is positioned at fixed part 500a and goes up formation splicing ear 507a.In addition, also can on Width one end of each vibration section 500b, a drive electrode 507 only be set.

On the other hand, detecting electrode 508 is set to cross over the length direction of whole vibration section 500b on the Width central portion of vibration section 500b.The end of fixed part 500a one side of detecting electrode 508, the same with drive electrode 507, be positioned at fixed part 500a and go up formation splicing ear 508a.In addition, also a plurality of detecting electrodes 508 can be set on each vibration section 500b.

The 1st electrode film 502 has on the middle position between a pair of vibration section 500b, the 500b on the fixed part 500a, towards opposite with vibration section 500b one side-prominent splicing ear 502a.

But, between the 1st electrode film 502 on each vibration section 500b and two drive electrodes 507,507, be applied with the voltage to frequency with the intrinsic vibration resonance of vibration section 500b, so that vibration section 500b is in its Width vibration.That is to say, the 1st electrode film 502 is applied earthed voltage, and two drive electrodes 507,507 are applied positive and negative reciprocal voltage, so, when Width one end side of each vibration section 500b was extended, other end side of vibration section 500b was shunk, vibration section 500b is in its other end side distortion, and when Width one end side of each vibration section 500b is shunk, other end side elongation of vibration section 500b, vibration section 500b is out of shape in the one end side.By alternately repeating this action, vibration section 500b is in its Width vibration.In addition, even only any one party of two drive electrodes 507,507 on each vibration section 500b is applied voltage, vibration section 500b is vibrated on its Width.And, a pair of

vibration section

500b, 500b, direction opposite towards each other on the Width of each vibration section 500b is out of shape, the central authorities between a pair of

vibration section

500b, 500b, and the L of Central Line that extends for the length direction at vibration section 500b vibrates symmetrically.

In angular-rate sensor 400, when making a pair of

vibration section

500b, 500b when its Width (directions X) vibrates symmetrically for the L of Central Line, if to applying the words of angular velocity omega around the L of its Central Line, two

vibration section

500b, 500b, because of Coriolis force in its thickness direction (Z direction) flexural deformation (a pair of

vibration section

500b, 500b are towards the crooked same amount of mutually opposite direction).So, also bend, between the 1st electrode film 502 and detecting electrode 508, produce big or small corresponding voltage with Coriolis force at the stacked film of piezoelectrics.Can detect angular velocity omega from the size (Coriolis force) of this voltage.That is to say that if making the speed of the Width of each vibration section 500b is v, the quality that makes each vibration section 500b is m, then because of Coriolis force Fc=2mv ω, so can know angular velocity omega according to Coriolis force Fc.

Below, with reference to Figure 17 and Figure 18 the manufacture method of angular-rate sensor 400 is illustrated.At first, shown in Figure 17 (a), being ready to by thickness is that 0.3mm, diameter are the substrate 500 of 4 inches silicon wafer (also with reference to Figure 18) formation, and shown in Figure 17 (b), having formed on substrate 500 by thickness with sputtering method is the 1st electrode film 502 of iridium (Ir) the film formation of 100nm.The 1st electrode film 502 is by using sputter equipment, substrate 500 is heated to 400 ℃, with iridium (Ir) target, in the argon gas body of 1Pa, carrying out 10 minutes film forming with 200W high frequency electricity and obtain.

Secondly, shown in Figure 17 (c), on the 1st electrode film 502, form the 1st piezoelectric film 504, then, shown in Figure 17 (d), on the 1st piezoelectric film 504, form the 2nd piezoelectric film 505 continuously, formed the stacked film of piezoelectrics with sputtering method with sputtering method.The 1st piezoelectric film 504 is that the pzt thin film of (111) preferred orientation of 100nm constitutes by thickness, and the 2nd piezoelectric film 505 is the pzt thin film formation of (111) orientation of 2900nm by thickness.The film forming of the stacked film of piezoelectrics is to form like this: at first, the sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.53: 0.47) of 6 inch diameters of PZT that surplus has been added the stoichiometric structure that the PbO allotment of about 20 moles of % forms is as target, silicon substrate 500 heating that will form the 1st electrode film 502 in advance on the surface remain to 580 ℃ temperature, the mist of argon and oxygen is used as sputter gas, making its gas pressure is 0.2Pa, making its mixing ratio is argon: oxygen=38: 2, making its flow is per minute 40ml, making plasma generation power is 3kW, used for 50 seconds with the 1st piezoelectric film 504 film forming under these conditions, then, stop film forming, mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 2500 seconds with the 2nd piezoelectric film 505 film forming.Form the operation of the stacked film of these piezoelectrics, comprise and make the stacked film preferred orientation of piezoelectrics in the operation of (111) face.

Secondly, shown in Figure 17 (e), having formed thickness with sputtering method on the 2nd piezoelectric film 505 is the 2nd electrode film 506 of 100nm.The 2nd electrode film 506 is by at room temperature, with platinum (Pt) target, in the argon gas body of 1Pa, carries out 10 minutes film forming with the high frequency electricity of 200W and obtains.

Secondly, as Figure 17 (f) and shown in Figure 180,, drive electrode 507,507 and detecting electrode 508 have been formed with the 2nd electrode film 506 patternings.That is to say, on the 2nd electrode film 506, apply photosensitive resin, to the pattern exposure of this photosensitive resin with drive electrode 507,507 and detecting electrode 508, then, to remove less than the photosensitive resin of the part of exposing, to remove the 2nd electrode film 506 of the part of this photosensitive resin with etching and remove, then, the photosensitive resin on drive electrode 507,507 and the detecting electrode 508 removed.

Secondly, with the 2nd piezoelectric film the 505, the 1st piezoelectric film 504 and the 1st electrode film 502 patternings, simultaneously,, fixed part 500a and

vibration section

500b, 500b have been formed with substrate 500 patternings.Then, substrate 500 is processed into tuning fork-like shown in Figure 15.Method can obtain angular-rate sensor 400 by this.

Below, for the angular-rate sensor 400 with present embodiment compares, in the past angular-rate sensor 401 is illustrated with reference to Figure 19.

Angular-rate sensor 401 in the past, comprise that by thickness be the piezoelectrics 600 that the crystal of 0.3mm constitutes, these piezoelectrics 600 are the same with the substrate 500 of the angular-rate sensor 400 of present embodiment, have fixed part 600a and (the Y direction of Figure 19) is parallel to each other and extends from this fixed part 600a towards prescribed direction a pair of vibration section 600b, 600b.And, be respectively arranged with on thickness direction (the Z direction of Figure 19) two sides of each vibration section 600b and be used to make the drive electrode 603 of vibration section 600b, be respectively arranged with a detecting electrode 607 of the distortion of the thickness direction that is used to detect vibration section 600b in the two sides of each vibration section 600b in its Width (directions X of Figure 19) vibration.

In angular-rate sensor 401 in the past, between two drive electrodes 603,603 of each vibration section 600b, apply the voltage to frequency that resonates with the intrinsic vibration of vibration section 600b, the same with the angular-rate sensor 400 of present embodiment, a pair of vibration section 600b, 600b are vibrated symmetrically at its Width (directions X) and with respect to the L of Central Line of the central authorities between a pair of vibration section 600b, 600b.At this moment, if to applying the words of angular velocity omega around the L of this Central Line, then a pair of vibration section 600b, 600b because of Coriolis force in its thickness direction (Z direction) flexural deformation, produce voltage between two detecting electrodes 607,607 in each vibration section 600b, can detect angular velocity omega according to the size (Coriolis force) of this voltage corresponding to the size of Coriolis force.

In angular-rate sensor 401 in the past, there is such problem: owing to use the piezoelectrics 600 that constitute by crystal, therefore its piezoelectric constant is-3pC/N, quite low, and, owing to form fixed part 600a and vibration section 600b, 600b with machining, therefore be difficult to miniaturization, dimensional accuracy is lower.

And in the angular-rate sensor 400 of present embodiment, owing to detect the part (vibration section 500b) of angular speed, constitute by the piezoelectric element the same with the piezoelectric element 20 of execution mode 1, therefore can make piezoelectric constant increase to about 40 times of in the past angular-rate sensor 401, extremely miniaturization.And, can use film formation technology to carry out microfabrication, dimensional accuracy is significantly improved.And even in industrial a large amount of productions, also can acquired character good, difference be less, the angular-rate sensor 400 of proof voltage and reliability.

In addition, in the present embodiment, only be provided with 1 group of a pair of

vibration section

500b, 500b, many group a pair of

vibration section

500b, 500b also can be set, so that detect the angular speed of a plurality of rotations of extending in all directions at substrate 500.

And, in the present embodiment, on the part of vibration section 500b one side of each the vibration section 500b of substrate 500 and fixed part 500a, stacked gradually the 1st electrode film the 502, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506, also can be only stacked on each vibration section 500b.

(execution mode 5)

Figure 20 is the stereogram of the piezoelectric element 20 of embodiments of the present invention 5.As shown in figure 20, piezoelectric element 20, possess length and be 15.0mm, thickness and be 0.40mm, width and be 3.0mm the rectangular flat plate shape substrate 1 and be configured in duplexer 11 on this substrate 1.This substrate 1 has the effect of the oscillating plate of the flexible obstruction that the piezoelectric effect because of duplexer 11 is caused.The width of piezoelectric element 20 is 3.0mm.Piezoelectric element 20, width is that 3.0mm, length are that the end (left part of Figure 20) of 3.0mm is that binding agent 8 is fixed on the stainless steel support substrates 7 that thickness is 1.0mm (width is 3.0mm by epoxy, the degree of depth is 10.0mm) on, therefore, piezoelectric element 20 constitutes the beam with folk prescription.

Substrate 1 is provided with the 1st electrode film 2.On the remainder in addition of an end (left part of Figure 20) of the 1st electrode film 2 (just, the width of the 1st electrode film 2 is 3.0mm, length is the part of 12.0mm) be provided with by the lead lanthanum zirconate titanate of the Ca-Ti ore type crystalline texture of (111) preferential crystallization orientation (below, PLZT) be the orientation controlling diaphragm 3 that sull constitutes.On this orientation controlling diaphragm 3, the PZT that is provided with size and this orientation controlling diaphragm 3 Ca-Ti ore type crystalline texture the same, that be orientated by (111) preferential crystallization is the stacked film 10 of piezoelectrics of sull formation.The stacked film 10 of these piezoelectrics is made of the 1st piezoelectric film 4 and the 2nd piezoelectric film 5 that is arranged on the 1st piezoelectric film 4.The stacked film 10 of piezoelectrics is by orientation controlling diaphragm 3 crystallization control orientations.The stacked film 10 of piezoelectrics is provided with the 2nd electrode film 6 that thickness is 250nm.Thickness is that metallic lead-in wire 9a, the 9b of 0.1mm is connected on the 1st and the 2nd electrode film 2,6.In addition, as shown in figure 20, duplexer 11 is made of the 1st electrode film 2, orientation controlling diaphragm 3, the stacked film 10 of piezoelectrics and the 2nd electrode film 6.

Below, the feature of present embodiment is illustrated.

Orientation controlling diaphragm 3 is made of the perofskite type oxide of preferred orientation in cubic system or tetragonal (111) face.The stacked film 10 of piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face.The the 1st and the 2nd piezoelectric film 4,5 is the aggregate (with reference to Figure 22) of the columnar-shaped particle that joins continuously each other.The averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film 5 is greater than the averga cross section diameter of the columnar-shaped particle of the 1st piezoelectric film 4.The ratio of the thickness of the stacked film 10 of piezoelectrics and the averga cross section diameter of the columnar-shaped particle of the 2nd piezoelectric film 5 more than or equal to 20 smaller or equal to 60.

Preferably being orientated controlling diaphragm 3 is that the oxide of main component constitutes by the lead lanthanum zirconate titanate with Ca-Ti ore type, and (111) crystalline orientation rate of orientation controlling diaphragm is more than or equal to 50%.

The chemical composition of orientation controlling diaphragm 3 is than using Pb: La: Zr: Ti=x * (1-z): z: y: (1-y) represent, preferably the x value is smaller or equal to 1.20 value more than or equal to 1.0, the y value is more than or equal to 0 smaller or equal to 0.20 value, and the z value is for surpassing 0 smaller or equal to 0.30.Perhaps, preferably be orientated controlling diaphragm 3 and be made of at least one side who has added magnesium and manganese in lead lanthanum zirconate titanate, its addition surpasses 0 smaller or equal to 10 moles of %.

Noble metal that best the 1st electrode film is formed by platinum (Pt), iridium (Ir), palladium (Pd) or ruthenium (Ru) or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

But, if apply voltage by lead-in

wire

9a, 9b between the 1st and the

2nd electrode film

2,6, then the same with execution mode 1, the stacked film 10 of piezoelectrics extends at the directions X of Figure 20, the front end of piezoelectric element 20 (right-hand member of Figure 20) is displaced to the minus side (downside of Figure 20) of Z direction.

Below, with reference to Figure 21 the manufacture method of piezoelectric element 20 is illustrated.

Figure 21 is the process chart that shows the manufacture method of piezoelectric element 20.At first, shown in Figure 21 (a), in length is that 20mm, width are that 20mm, thickness are to use on the substrate 101 of 0.3mm to have formed the stainless steel mask (mask) of wide thickness as 5.0mm, long oblong openings as 18.0mm as 0.2mm, has formed the 1st electrode film 102 by the RF magnetron sputtering system.

Secondly, uses formed wide as 5.0mm, grow as the thickness of the oblong openings of 12.0mm stainless steel mask as 0.2mm, on the 1st electrode film 102, correctly formed orientation controlling diaphragm 103 with the RF magnetron sputtering system.The operation that forms this orientation controlling diaphragm 103 comprises makes orientation controlling diaphragm 103 preferred orientations in the operation of (111) face.

Secondly, uses formed wide for 5.0mm, grow and be the thickness of the oblong openings of 12.0mm stainless steel mask as 0.2mm, correctly formed the stacked film 110 of piezoelectrics with the RF magnetron sputtering system being orientated on the controlling diaphragm 103.The stacked film 110 of these piezoelectrics is to form like this: using PZT is the sintered body target of oxide, at first, on orientation controlling diaphragm 103, form the 1st piezoelectric film 104 with the RF magnetron sputtering system, then, use same target, only change membrance casting condition, on the 1st piezoelectric film 104, form the 2nd piezoelectric film 105 continuously with same RF magnetron sputtering system.The stacked film 110 of piezoelectrics has identical structure with the schematic diagram of the membrane structure of the stacked film of piezoelectrics shown in Figure 22.The operation that forms the stacked film 110 of these piezoelectrics comprises by orientation controlling diaphragm 103 makes stacked film 110 preferred orientations of piezoelectrics in the operation of (111) face.

Secondly, use and above-mentioned the same stainless steel mask,, on the stacked film 110 of piezoelectrics, correctly formed the 2nd electrode film 106 with the RF magnetron sputtering system with above-mentioned the same.Therefore, shown in Figure 21 (b), can obtain to have possessed the structure 121 of substrate 101 and duplexer 111.

Secondly, shown in Figure 21 (c), correctly cutting off structure 121 with cast-cutting saw, is that 3.0mm, length are that expose the rectangle of 15.0mm and an end of the 1st electrode film (left part of Figure 21 (c)) so that it is a width.So, can obtain the piezoelectric element structure body product 22 that constitute by substrate shown in Figure 20 the 1, the 1st electrode film 2, orientation controlling diaphragm the 3, the 1st piezoelectric film the 4, the 2nd piezoelectric film 5 and the 2nd electrode film 6.Then, shown in Figure 21 (d), being binding agent 8 with epoxy is bonded on the end (left part of Figure 21 (d)) of substrate 1 on the stainless steel support substrates 7.

Secondly, shown in Figure 21 (e), be connected the end (left part of Figure 21 (e)) of the 1st electrode film 2, be connected the end (left part of Figure 21 (e)) of the 2nd electrode film 6 with the sealing wire 9b that will go between with the silver paste conductive adhesive 9a that will go between.Method can obtain piezoelectric element shown in Figure 20 20 by this.

(the 8th embodiment)

Silicon is used as substrate.With thickness is that iridium (Ir) film of 100nm is as the 1st electrode film.This iridium film is to form like this: by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, (gas volume is than Ar: O for the mist of use argon and oxygen ₂=15: 1) as sputter gas, total gas pressure is remained on 0.25Pa, the iridium target that uses 4 inch diameters applies the high frequency electricity of 200W as the 1st target, and sputter formed in 960 seconds.

Used thickness as the lanthanum lead titanates of (111) preferred orientation of 40nm (below, be called PLT) film as the orientation controlling diaphragm.This PLT film is to form like this: by in 3 identical dimension RF magnetic controlled tube sputtering apparatus, the substrate that will form the 1st electrode film on the surface heats the temperature that remains on 550 ℃ in advance, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=25: 1) as sputter gas, make this total gas pressure remain 0.5Pa, the sintered body target (constitutive molar ratio Pb: La: Ti=1.10: 0.10: 1.0) of 4 inch diameters of PLT that surplus has been added the stoichiometric structure that the PbO allotment of about 20mol% forms is as the 2nd target, apply the high frequency electricity of 250W, sputter formed in 3000 seconds.

The stacked film of piezoelectrics is made of the 1st piezoelectric film and the 2nd piezoelectric film.Above-mentioned the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 50nm constitutes by thickness, and above-mentioned the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 3500nm by thickness.That is to say that the thickness that makes the stacked film of whole piezoelectrics is 3550nm.

Use the RF magnetron sputtering system to form the 1st and the 2nd piezoelectric film.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.53: 0.47) of 6 inch diameters of PZT of stoichiometric structure of PbO allotment that has used the about 20 moles of % of superfluous interpolation is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film and orientation controlling diaphragm on the surface heats the temperature that remains on 580 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, uses 50 seconds under these conditions with the 1st piezoelectric film film forming.Then, stop film forming, the mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 2900 seconds with the 2nd piezoelectric film film forming.

Used platinum (Pt) film as the 2nd electrode film.This platinum film uses the RF sputtering film-forming on the 2nd piezoelectric film.

In addition, for thickness, (111) orientation, composition and the cross-section structure of correctly obtaining orientation controlling diaphragm shown in Figure 21 (b) and the 1st piezoelectric film, after having formed orientation controlling diaphragm and the 1st piezoelectric film, also formed the stacked film that stops film forming simultaneously.Relevant this sample, its surface has been carried out by scanning electron microscope observation, by X-ray diffraction parsing and by behind the composition analysis of X ray microanalyzer, this sample is destroyed, this section is observed with scanning electron microscope.

And,, after forming the 2nd piezoelectric film, also formed the stacked film of ending film forming simultaneously for thickness, (111) orientation, composition and the cross-section structure of correctly obtaining the 2nd piezoelectric film shown in Figure 21 (b).Relevant this sample, also with above-mentioned the same, its surface is carried out by scanning electron microscope observation, by X-ray diffraction parsing and by behind the composition analysis of X ray microanalyzer, this sample is destroyed, with scanning electron microscope this section is observed.

And, use the structure shown in Figure 21 (b) as sample, by the Auger spectrum analysis, carried out from the surface of the stacked film of piezoelectrics to the composition analysis of depth direction.And, with scanning electron microscope the section of the stacked film of piezoelectrics is observed.Figure 23 (a) shows the electron micrograph with the section amplification of the stacked film of piezoelectrics, and Figure 23 (b) shows the part enlarged drawing of Figure 23 (a).

The result of above-mentioned each analysis and above-mentioned observation, iridium electrode is that average profile diameter is the aggregate of the columnar-shaped particle of 20nm.Orientation controlling diaphragm and the 1st and the 2nd piezoelectric film exist as the particle assembly body of the column structure that joins continuously each other.The orientation controlling diaphragm, thickness is 40nm.The 1st piezoelectric film, thickness are 50nm, and the average profile diameter of columnar-shaped particle is 40nm.The 2nd piezoelectric film, thickness are 3500nm, and the average profile diameter of columnar-shaped particle is 160nm.The thickness of the stacked film of piezoelectrics is 22.2 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm and the 1st and the 2nd piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of orientation controlling diaphragm is 50%.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 70%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 98%.Here, the PLT system orientation controlling diaphragm that will obtain according to the reflected intensity of each crystal plane of the diffraction pattern that utilizes X-ray diffraction method and PZT (111) crystalline orientation rate of being piezoelectric film be defined as from spacing of lattice from

(Angstrom) arrive The X-ray diffraction scope in, the percentage of total of (111) peak strength and the full peak strength that belongs to film.Just, the crystalline orientation rate is for belonging to the peak strength of (111), waits the percentage of ratio of total of the peak strength of each crystal plane with (001), (100), (010), (110), (011), (101), (111) of the X-ray diffraction pattern of PLT film, PLZT film, pzt thin film.

The result of the composition analysis of the cation by the X ray microanalyzer, the orientation controlling diaphragm consist of Pb: La: Ti=1.05: 0.10: 0.98, the composition of the 1st and the 2nd piezoelectric film was respectively Pb: Zr: Ti=1.15: 0.53: 0.47 and Pb: Zr: Ti=1.10: 0.53: 0.47.Just, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.In other words, the 1st and the 2nd piezoelectric film is the crystalline growth direction is pointed to the opposing party's columnar-shaped particle from a side of the thickness direction of the stacked film of piezoelectrics a aggregate.

And, by lead-in

wire

9a, 9b between the 1st and the

2nd electrode film

2,6 of piezoelectric element 20, apply 0V～-triangle wave voltage of 80V, use laser-Doppler vibration displacement determinator, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.Figure 24 is the figure that shows the displacement that piezoelectric element 20 front ends when having applied that frequency is 2kHz voltage move up and down in the Z direction.As shown in figure 24, when applied 0V～-during 80V voltage, the front end maximum displacement 38.0 μ m of piezoelectric element 20.Carry out round driving, after driving 100,000,000 times (driving time 13.9 hours) and 1,000,000,000 times (driving time 138.9 hours), check the driving condition of piezoelectric element 20 by this triangle wave voltage, simultaneously, with observation by light microscope its outward appearance.After driving 1,000,000,000 times, maximum displacement is 38.0 μ m, does not take place also at piezoelectric element 20 that film is peeled off and crackle.

(the 9th embodiment)

Substrate is used high temperature resistant pyrex (registered trade mark) glass, the 1st electrode film has been used platinum (Pt) film of thickness as 150nm.This platinum film is to form like this: by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, (gas volume is than Ar: O for the mist of use argon and oxygen ₂=15: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the platinum target as the 1st target, apply the high frequency electricity of 200W, sputter formed in 1080 seconds.

Used thickness as the PLZT film of (111) preferred orientation of 50nm as the orientation controlling diaphragm.This PLZT film is such formation: by in 3 the same dimension RF magnetic controlled tube sputtering apparatus, the substrate heating that will form the 1st electrode film in advance on the surface remains on 550 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=25: 0.5) as sputter gas, total gas pressure is remained on 1.0Pa, the sintered body target (constitutive molar ratio Pb: La: Zr: Ti=1.15: 0.05: 0.10: 0.90) of 4 inch diameters of PLZT that has used the stoichiometric structure that the PbO allotment of the about 20 moles of % of superfluous interpolation forms is as the 2nd target, apply the high frequency electricity of 250W, sputter formed in 3600 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 100nm constitutes by thickness, and described the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 5000nm by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 5100nm.

The same with the 8th embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.10: 0.50: 0.50) of 6 inch diameters of PZT that has used the stoichiometric structure that the PbO allotment of the about 10 moles of % of superfluous interpolation forms is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film and orientation controlling diaphragm on the surface heats the temperature that remains on 550 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=79: 1, making its flow is per minute 40ml, and making plasma generation power is 2kW, uses 60 seconds under these conditions with the 1st piezoelectric film film forming.Then, stop film forming, making underlayer temperature is 590 ℃, and plasma generation power is 3kW, and other condition is constant, with 3800 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 8th embodiment analyzed and observed, platinum electrode is that average profile diameter is the aggregate of the columnar-shaped particle of 30nm.Orientation controlling diaphragm and the 1st and the 2nd piezoelectric film exist as the particle assembly body of the column structure that joins continuously each other.The orientation controlling diaphragm, thickness is 50nm.The 1st piezoelectric film, thickness are 100nm, and the average profile diameter of columnar-shaped particle is 40nm.The 2nd piezoelectric film, thickness are 5000nm, and the average profile diameter of columnar-shaped particle is 85nm.The thickness of the stacked film of piezoelectrics is 60.0 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm and the 1st and the 2nd piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of orientation controlling diaphragm is 60%.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 70%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 95%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of orientation controlling diaphragm, Pb: La: Zr: Ti=1.08: 0.05: 0.12: 0.88, the composition of the 1st and the 2nd piezoelectric film was respectively Pb: Zr: Ti=1.15: 0.51: 0.49 and Pb: Zr: Ti=1.00: 0.51: 0.49.Just, the same with the 8th embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 8th embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 35.2 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 10th embodiment)

Substrate is used the thermal endurance corrosion resistant plate of mirror finish, the 1st electrode film has been used the alloy firm that constitutes as the iridium (Ir) of 110nm by thickness of titaniferous (Ti).This alloy firm is to form like this: by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the iridium target as the 1st target, use the titanium target as the 2nd target, apply the high frequency electricity of 200W and 60W respectively, sputter formed in 960 seconds.In addition, titanium being added purpose in the iridium is in order to improve the connecting airtight property with substrate, even do not add titanium, also can not to have influence on the characteristic of piezoelectric element.

Used thickness as the PLT film of (111) preferred orientation of 20nm as the orientation controlling diaphragm.This PLT film is such formation: by in 3 the same dimension RF magnetic controlled tube sputtering apparatus, the substrate heating that will form the 1st electrode film in advance on the surface remains on 600 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=25: 0.2) as sputter gas, total gas pressure is remained on 1.0Pa, the sintered body target (constitutive molar ratio Pb: La: Ti=0.90: 0.20: 1.0) of 4 inch diameters of PLT that has used the stoichiometric structure that the PbO allotment of the about 10 moles of % of superfluous interpolation forms is as the 3rd target, apply the high frequency electricity of 250W, sputter formed in 1200 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of 10 moles of % magnesium of interpolation (Mg) of (111) preferred orientation of 100nm constitutes by thickness, and above-mentioned the 2nd piezoelectric film is that (PZT+Mg) film of (111) orientation of 3900nm constitutes by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 4000nm.

The same with the 8th embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti: Mg=1.10: 0.60: 0.40: 0.10) of 6 inch diameters of lead zirconate titanate (PZT+Mg) that has used the PbO of the about 10 moles of % of superfluous interpolation and added the stoichiometric structure that 10 moles of % magnesium (Mg) allotments forms is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film and orientation controlling diaphragm on the surface heats the temperature that remains on 570 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, uses 100 seconds under these conditions with the 1st piezoelectric film film forming.Then, stop film forming, the mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 2500 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 8th embodiment analyzed and observed, the 1st electrode film is made of the iridium film that contains 1 mole of % titanium, and average profile diameter is the aggregate of the columnar-shaped particle of 20nm.Orientation controlling diaphragm and the 1st and the 2nd piezoelectric film exist as the particle assembly body of the column structure that joins continuously each other.The orientation controlling diaphragm, thickness is 20nm.The 1st piezoelectric film, thickness are 100nm, and the average profile diameter of columnar-shaped particle is 70nm.The 2nd piezoelectric film, thickness are 3900nm, and the average profile diameter of columnar-shaped particle is 200nm.The thickness of the stacked film of piezoelectrics is 20.0 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm and the 1st and the 2nd piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of orientation controlling diaphragm is 70%.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 80%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 100%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of orientation controlling diaphragm, Pb: La: Ti=0.85: 0.22: 0.95, the composition of the 1st and the 2nd piezoelectric film was respectively Pb: Zr: Ti: Mg=1.05: 0.60: 0.40: 0.09 and Pb: Zr: Ti: Mg=1.00: 0.60: 0.40: 0.10.Just, the same with the 8th embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 8th embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 38.3 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 11st embodiment)

Substrate is used the ceramic material (alumina) of mirror ultrafinish, the 1st electrode film has been used the alloy firm that constitutes as the ruthenium (Ru) of 120nm by thickness of nickeliferous (Ni).This alloy firm is to form like this: by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 400 ℃ temperature, (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the ruthenium target as the 1st target, use the nickel target as the 2nd target, apply the high frequency electricity of 200W and 60W respectively, sputter formed in 960 seconds.In addition, nickel being added purpose in the ruthenium is in order to improve the connecting airtight property with substrate, even do not add nickel, also can not to have influence on the characteristic of piezoelectric element.

Used thickness as the PLZT film of (111) preferred orientation of 60nm as the orientation controlling diaphragm.This PLZT film is such formation: by in 3 the same dimension RF magnetic controlled tube sputtering apparatus, the substrate heating that will form the 1st electrode film in advance on the surface remains on 650 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=25: 1.0) as sputter gas, total gas pressure is remained on 0.5Pa, the sintered body target (constitutive molar ratio Pb: La: Zr: Ti=1.10: 0.10: 0.20: 0.80) of 4 inch diameters of PLZT that has used the stoichiometric structure that the PbO allotment of the about 20 moles of % of superfluous interpolation forms is as the 3rd target, apply the high frequency electricity of 250W, sputter formed in 3600 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of 5 moles of % manganese of interpolation (Mn) of (111) preferred orientation of 5nm constitutes by thickness, and described the 2nd piezoelectric film is that (PZT+Mn) film of (111) orientation of 2500nm constitutes by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 2505nm.

The same with the 8th embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti: Mn=1.20: 0.40: 0.60: 0.05) of 6 inch diameters of PZT that has used the PbO of the about 20 moles of % of superfluous interpolation and added the stoichiometric structure that 5 moles of % manganese (Mn) allotments forms is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned (PZT+Mn) target, the substrate that will form the 1st electrode film and orientation controlling diaphragm on the surface heats the temperature that remains on 550 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=79: 1, making its flow is per minute 40ml, and making plasma generation power is 2kW, uses 5 seconds under these conditions with the 1st piezoelectric film film forming.Then, stop film forming, making underlayer temperature is 580 ℃, and making plasma generation power is 3kW, and other condition is constant, with 2000 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 8th embodiment analyzed and observed, the 1st electrode film is made of the ruthenium film that contains 4 moles of % nickel, and average profile diameter is the aggregate of the columnar-shaped particle of 25nm.Orientation controlling diaphragm and the 1st and the 2nd piezoelectric film exist as the particle assembly body of the column structure that joins continuously each other.The orientation controlling diaphragm, thickness is 60nm.The 1st piezoelectric film, thickness are 5nm, and the average profile diameter of columnar-shaped particle is 40nm.The 2nd piezoelectric film, thickness are 2500nm, and the average profile diameter of columnar-shaped particle is 60nm.The thickness of the stacked film of piezoelectrics is 41.7 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm and the 1st and the 2nd piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of orientation controlling diaphragm is 75%.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 80%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 99%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of orientation controlling diaphragm, Pb: La: Zr: Ti=1.05: 0.10: 0.22: 0.78, the composition of the 1st and the 2nd piezoelectric film was respectively Pb: Zr: Ti: Mn=1.10: 0.40: 0.60: 0.05 and Pb: Zr: Ti: Mn=1.05: 0.40: 0.60: 0.05.Just, the same with the 8th embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 8th embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 32.7 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

(the 12nd embodiment)

Substrate is used silicon, the 1st electrode film has been used palladium (Pd) film of thickness as 120nm.This palladium membranes is to form like this: by in 3 dimension RF magnetic controlled tube sputtering apparatus, in advance the substrate heating is remained on 500 ℃ temperature, (gas volume is than Ar: O for the mist of use argon and oxygen ₂=16: 1) as sputter gas, total gas pressure is remained on 0.25Pa, use the palladium target as the 1st target, apply the high frequency electricity of 200W, sputter formed in 960 seconds.

Used thickness as the PLT film of (111) preferred orientation of 40nm as the orientation controlling diaphragm.This PLT film is such formation: by in 3 the same dimension RF magnetic controlled tube sputtering apparatus, the substrate heating that will form the 1st electrode film in advance on the surface remains on 600 ℃ temperature, and (gas volume is than Ar: O for the mist of use argon and oxygen ₂=25: 0.2) as sputter gas, total gas pressure is remained on 1.0Pa, the sintered body target (constitutive molar ratio Pb: La: Ti=0.90: 0.30: 1.0) of 4 inch diameters of PLT that has used the stoichiometric structure that the PbO allotment of the about 20 moles of % of superfluous interpolation forms is as the 2nd target, apply the high frequency electricity of 250W, sputter formed in 2400 seconds.

The stacked film of piezoelectrics is to be made of the 1st piezoelectric film and the 2nd piezoelectric film, wherein, described the 1st piezoelectric film is that the pzt thin film of (111) preferred orientation of 80nm constitutes by thickness, and above-mentioned the 2nd piezoelectric film is the pzt thin film formation of (111) orientation of 4500nm by thickness.In other words, making the thickness of the stacked film of piezoelectrics is 4580nm.

The same with the 8th embodiment, formed the 1st and the 2nd piezoelectric film with the RF magnetic controlled tube sputtering apparatus.The sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.58: 0.42) of 6 inch diameters of the PZT of the stoichiometric structure that the PbO allotment of using surplus to add about 20 moles of % forms is as target.Membrance casting condition is as follows.In other words, at first, in the film forming room that has adorned above-mentioned PZT target, the substrate that will form the 1st electrode film and orientation controlling diaphragm on the surface heats the temperature that remains on 580 ℃ in advance, and the mist that uses argon and oxygen is as sputter gas, and making this gas pressure is 0.2Pa, this mixing ratio is an argon: oxygen=38: 2, making its flow is per minute 40ml, and making plasma generation power is 3kW, uses 75 seconds under these conditions with the 1st piezoelectric film film forming.Then, stop film forming, the mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 3700 seconds with the 2nd piezoelectric film film forming.

The result that each the same with the 8th embodiment analyzed and observed, the 1st electrode film, average profile diameter is the aggregate of the columnar-shaped particle of 20nm.Orientation controlling diaphragm and the 1st and the 2nd piezoelectric film exist as the particle assembly body of the column structure that joins continuously each other.The orientation controlling diaphragm, thickness is 40nm.The 1st piezoelectric film, thickness are 80nm, and the average profile diameter of columnar-shaped particle is 50nm.The 2nd piezoelectric film, thickness are 4500nm, and the average profile diameter of columnar-shaped particle is 150nm.The thickness of the stacked film of piezoelectrics is 30.5 with the ratio of the average profile diameter of the columnar-shaped particle of the 2nd piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm and the 1st and the 2nd piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation of the formation face of orientation controlling diaphragm is 55%.(111) crystalline orientation of the formation face of the 1st piezoelectric film is 70%.(111) crystalline orientation rate of the formation face of the 2nd piezoelectric film is 98%.

The result of the composition analysis of the cation by the X ray microanalyzer, the composition of orientation controlling diaphragm, Pb: La: Ti=0.82: 0.28: 0.98, the composition of the 1st and the 2nd piezoelectric film was respectively Pb: Zr: Ti=1.10: 0.58: 0.42 and Pb: Zr: Ti=1.05: 0.58: 0.42.Just, the same with the 8th embodiment, the the 1st and the 2nd piezoelectric film, be the PZT film of (111) axle preferred orientation in the Ca-Ti ore type crystalline texture of the direction growth vertical with substrate surface, the composition of Zr and Ti is constant in the 1st and the 2nd piezoelectric film, and it is that the 1st piezoelectric film is more than the 2nd piezoelectric film that Pb forms.

The same with the 8th embodiment, to the piezoelectric element 20 of present embodiment apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement 31.5 μ m of piezoelectric element 20, after driving 1,000,000,000 times, maximum displacement is also constant, does not take place at piezoelectric element 20 that film is peeled off and crackle.

In addition, in the 8th embodiment～the 12nd embodiment, used the three-dimensional oxide of having added Pb, Zr and Ti and they have been added the pzt thin film of Mg and Mn as the stacked film of piezoelectrics, also can use PZT film (plzt film just) that contains La and the PZT film that contains the ion of Nb and Mg etc., if use the sull of Ca-Ti ore type crystalline texture, can obtain and the stacked film of piezoelectrics that the 8th embodiment～the 12nd embodiment is the same.

(comparative example 3)

In order to compare, formed following piezoelectric element with the 8th embodiment～the 12nd embodiment.

In the 8th embodiment, on the orientation controlling diaphragm, only form the 2nd piezoelectric film and replace the stacked film of piezoelectrics, other forms the same with the 8th embodiment.

The result of above-mentioned each analysis and above-mentioned observation, orientation controlling diaphragm of this comparative example and piezoelectric film exist as the particle assembly body of column structure.Piezoelectric film, thickness are 3500nm, and the averga cross section diameter of columnar-shaped particle is 230nm.The length of the columnar-shaped particle of piezoelectric film is 15.2 with the ratio of the averga cross section diameter of the columnar-shaped particle of piezoelectric film.

With the result that X-ray diffraction method is resolved, orientation controlling diaphragm of this comparative example and piezoelectric film all are Ca-Ti ore type crystalline texture.(111) crystalline orientation rate of the formation face of orientation controlling diaphragm is 50%.(111) crystalline orientation rate of the formation face of piezoelectric film is 65%.

The composition analysis result of the cation by the X ray microanalyzer, the composition Pb of the orientation controlling diaphragm of this comparative example: La: Ti=1.05: 0.10: 0.98, the composition Pb of piezoelectric film: Zr: Ti=1.05: 0.53: 0.47.

By the Auger spectrum analysis from the surface of piezoelectric film the result towards the composition analysis of depth direction, the composition of Zr and Ti distribute from the interface of the 2nd electrode film to the interface of orientation controlling diaphragm till all immobilize.

Just, this comparative example is with the something in common of the 8th embodiment: piezoelectric film is as the PZT film of the Ca-Ti ore type crystalline texture of the aggregate of columnar-shaped particle growth on the direction vertical with substrate surface.But the averga cross section diameter of the columnar-shaped particle of piezoelectric film is greater than the 8th embodiment, and (111) crystalline orientation rate of piezoelectric film is less than the 8th embodiment.

The same with the 8th embodiment, to the piezoelectric element of this comparative example apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that piezoelectric element 20 front ends move up and down in the Z direction.The front end maximum displacement of piezoelectric element 20.0 μ m.And, carry out round driving, after driving 100,000,000 times, carried out driving the inspection of situation and utilized the result of observation of the outward appearance of light microscope by this triangle wave voltage, maximum displacement drops to 5.5 μ m, between the 1st electrode film and orientation controlling diaphragm the part film has taken place and has peeled off.

(comparative example 4)

In order to compare, made following piezoelectric element with the 8th embodiment～the 12nd embodiment.

In the 12nd embodiment, on the 1st electrode film that constitutes by palladium membranes, only directly form the 2nd piezoelectric film and replace being orientated controlling diaphragm and the stacked film of piezoelectrics, other and the 12nd embodiment are just the same.

The result of above-mentioned each analysis and above-mentioned observation, the piezoelectric film of this comparative example exists as the aggregate of the particle of column structure.Piezoelectric film, thickness are 4500nm, and the averga cross section diameter of columnar-shaped particle is 300nm.The length of the columnar-shaped particle of piezoelectric film is 15.0 with the ratio of the averga cross section diameter of the columnar-shaped particle of piezoelectric film.

With the result that X-ray diffraction method is resolved, the piezoelectric film of this comparative example is a Ca-Ti ore type crystalline texture.(111) crystalline orientation rate of piezoelectric film is 30%.

Just, this comparative example is with the something in common of the 12nd embodiment: piezoelectric film is as the PZT film of the Ca-Ti ore type crystalline texture of the aggregate of columnar-shaped particle growth on the direction vertical with substrate surface.But, be with the difference of the 12nd embodiment: the averga cross section diameter of the columnar-shaped particle of piezoelectric film is greater than the 12nd embodiment, (111) crystalline orientation rate of piezoelectric film is less than the 12nd embodiment, form equally with the Pb that Pb forms and piezoelectric film is all of the near interface of the 1st electrode film, and more or less tail off with the Pb composition at the interface of the 1st electrode film.

The same with the 12nd embodiment, to the piezoelectric element of this comparative example apply frequency be 2kHz, 0V～-triangle wave voltage of 80V, measured the displacement that the piezoelectric element front end moves up and down in the Z direction.The front end maximum displacement of piezoelectric element 12.0 μ m.And, carry out round driving by this triangle wave voltage, after driving 1,000,000,000 times, to have carried out driving the inspection of situation and utilized the result of observation of the outward appearance of light microscope, driving stops, and between the 1st electrode film and piezoelectric film film has taken place and has peeled off.

(execution mode 6)

Present embodiment is the ink gun that possesses the piezoelectric element of embodiments of the present invention 5.Below, this ink gun is illustrated.

The ink gun 201 of embodiments of the present invention 6 is by 10 inks spue element 202 and constituting in order to drive the spue driving power element 203 of element 202 of each ink of spuing with each ink that the individual electrode 33 of element 202 is connected.This ink element 202 that spues comprises that the piezoelectric element 20 with execution mode 5 has the B of actuator portion of same piezoelectric element.Other part almost with execution mode 2 the same (with reference to Fig. 6).

(the 13rd embodiment)

With reference to Figure 25 the B of actuator portion is illustrated.

Figure 25 is the figure of actuator portion VIII-VIII line B, that the be equivalent to Fig. 7 profile of the 13rd embodiment of execution mode 6.As shown in figure 25, the B of actuator portion has: be the individual electrode (the 1st electrode film) 33 of iridium (Ir) the film formation of 100nm by thickness; Be positioned at this individual electrode 33 under, by using Pb _1.10La _0.10Ti _1.00O ₃The thickness of expression is the orientation controlling diaphragm 41 that the PLT film of 40nm constitutes; Be positioned at this orientation controlling diaphragm 41 under, by using Pb _1.15Zr _0.53Ti _0.48O ₃The thickness of expression is the 1st piezoelectric film 42 that the pzt thin film of 50nm constitutes; Be positioned at the 1st piezoelectric film 42 under, by using Pb _1.10Zr _0.53Ti _0.47O ₃The thickness of expression is the 2nd piezoelectric film 43 that the pzt thin film of 3500nm constitutes; Be positioned at the 2nd piezoelectric film 43 under, be the 2nd electrode film 44 that the platinum film of 100nm constitutes by thickness; And be positioned at the 2nd electrode film 44 under, be the vibrating body layer 45 that chromium (Cr) film of 3500nm constitutes by thickness.This vibrating body layer 45 is by the piezoelectric effect displacement vibration of the 1st and the 2nd piezoelectric film 42,43.The 2nd electrode film 44 and vibrating body layer 45, it is shared between the balancing gate pit 32 of element 202 to spue at each ink.Orientation controlling diaphragm 41 and the 1st piezoelectric film 42 and the 2nd piezoelectric film 43 are processed to identical with the shape of individual electrode 33.Around the stacked film that constitutes by individual electrode 33, orientation controlling diaphragm the 41, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43 on the 2nd electrode film 44, be provided with thickness the electric insulation organic membrane 46 by poly-(acyl) imide resin formation identical with above-mentioned stacked film.On this electric insulation organic membrane 46, be provided be connected on the individual electrode 33, be the extraction electrode film 47 that the metallic film of 100nm constitutes by the thickness of lead format.Individual electrode 33, orientation controlling diaphragm 41, the stacked film of piezoelectrics and the 2nd electrode film 44 that are made of the 1st and the 2nd piezoelectric film 42,43 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 5, therefore, can obtain the B of actuator portion of high characteristic.

Below, the manufacture method of the B of actuator portion is illustrated.

Figure 26 and Figure 27 are the process chart that shows the manufacture method of the B of actuator portion.At first, in length is that 20mm, the wide 20mm of being, thickness are on the silicon substrate 51 of 0.3mm, the same with the 8th embodiment of execution mode 5, stack gradually the 1st electrode film 52, orientation controlling diaphragm the 53, the 1st piezoelectric film the 54, the 2nd piezoelectric film 55 and the 2nd electrode film 44.Therefore, can obtain the structure 56 shown in Figure 26 (a).

Secondly, shown in Figure 26 (b), at room temperature, having formed thickness with the RF sputtering method on structure 56 is the vibrating body layer 45 by chromium (Cr) film formation of 3500nm.

Secondly, shown in Figure 26 (c), vibrating body layer 45 is attached on balancing gate pit's parts 58 of glass with acrylic resin binder 57.These balancing gate pit's parts 58 are configured to vibrating body layer 45 face-to-face, accompany binding agent 57 between balancing gate pit's parts 58 and vibrating body layer 45.

Secondly, shown in Figure 26 (d), use the plasma reaction Etaching device, utilize SF ₆Silicon substrate 51 has been removed in the dry ecthing of gas.

Secondly, shown in Figure 26 (e), make and use up resin molding 59 against corrosion, it is that 180 μ m, major axis are the pattern of oval shapes of 380 μ m that the non-etching part of the stacked film that will be made of the 1st electrode film 52, orientation controlling diaphragm the 53, the 1st piezoelectric film 54 and the 2nd piezoelectric film 55 correctly is patterned as minor axis.Then, use the dry ecthing of argon (Ar) gas and the wet etching of weak fluoric acid, carried out etch processes.So, can obtain being processed to the light corrosion-resisting pattern, having actuator structure body shown in Figure 27 (a) by the stacked film that is constituted by individual individual electrode 33, orientation controlling diaphragm the 41, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43.Then, shown in Figure 27 (b), light resin molding 59 against corrosion is handled, be removed with stripper against corrosion.

Secondly, shown in Figure 27 (c), on the 2nd electrode film 44, formed electric insulation organic membrane 46 with print process.Then, shown in Figure 27 (d), on electric insulation organic membrane 46, formed extraction electrode film 47 with the DC sputtering method.So, can obtain the B of actuator portion shown in Figure 25.

electrode films

33,44 of element 202, apply frequency and be 200Hz, 0V～-the sinusoidal waveform voltage of 60V, carried out the inspection of above-mentioned driving situation.After driving 1,000,000,000 times, in spuing element 202, all inks do not break down yet.

(the 14th embodiment)

With reference to Figure 28 the structure actuator portion B different with the 13rd embodiment is illustrated.

Figure 28 is the figure of actuator portion VIII-VIII line B, that the be equivalent to Fig. 7 profile of the 14th embodiment of execution mode 6.As shown in figure 28, the B of actuator portion has: be the individual electrode (the 2nd electrode film) 33 of platinum (Pt) the film formation of 100nm by thickness; Be positioned at this individual electrode 33 under, by using Pb _1.05La _0.58Ti _0.42O ₃The thickness of expression is the 2nd piezoelectric film 43 that the pzt thin film of 4500nm constitutes; Be positioned at the 2nd piezoelectric film 43 under, by using Pb _1.10Zr _0.58Ti _0.42O ₃The thickness of expression is the 1st piezoelectric film 42 that the pzt thin film of 80nm constitutes; Be positioned at the 1st piezoelectric film 42 under, by using Pb _0.09Zr _0.30Ti _1.00O ₃The thickness of expression is the orientation controlling diaphragm 41 that the PLT film of 40nm constitutes; Be positioned at this orientation controlling diaphragm 41 under, be the 1st electrode film 52 that the palladium of 200nm constitutes by thickness; And be positioned at the 1st electrode film 52 under, be the silica (SiO of 5000nm by thickness ₂) the vibrating body layer 45 that constitutes of film.This vibrating body layer 45 is by the piezoelectric effect displacement vibration of the 1st and the 2nd piezoelectric film 42,43.The 1st electrode film 52 and vibrating body layer 45, it is shared between the balancing gate pit 32 of element 202 to spue at each ink.Orientation controlling diaphragm 41 and the 1st piezoelectric film 42 and the 2nd piezoelectric film 43 are processed to identical with the shape of individual electrode 33.Around the stacked film that constitutes by individual electrode 33, orientation controlling diaphragm the 41, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43 on the 1st electrode film 52, be provided with thickness the electric insulation organic membrane 46 by poly-(acyl) imide resin formation identical with above-mentioned stacked film.On this electric insulation organic membrane 46, be provided be connected on the individual electrode 33, be the extraction electrode film 47 that the metallic film of 100nm constitutes by the thickness of lead format.Individual electrode 33, orientation controlling diaphragm 41, the stacked film of piezoelectrics and the 1st electrode film 52 that are made of the 1st and the 2nd piezoelectric film 42,43 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 5, so, can obtain the B of actuator portion of high characteristic.

Below, the manufacture method of the B of actuator portion is illustrated.

Figure 29 and Figure 30 are the process chart that shows the manufacture method of the B of actuator portion.At first, long for 20mm, wide for 20mm, thickness be that the silicon substrate 51 (balancing gate pit's substrate) of 0.3mm is gone up and formed vibrating body layer 45, then, on vibrating body layer 45, the same with the 12nd embodiment of execution mode 5, stack gradually the 1st electrode film 52, orientation controlling diaphragm the 53, the 1st piezoelectric film the 54, the 2nd piezoelectric film 55 and the 2nd electrode film 44.So, can obtain the structure 56 shown in Figure 29 (a).

Secondly, shown in Figure 29 (b), make and use up resin molding 59 against corrosion, it is that 180 μ m, major axis are the pattern of oval shapes of 380 μ m that the non-etching part of the stacked film that will be made of the 2nd electrode film 44, orientation controlling diaphragm the 53, the 1st piezoelectric film 54 and the 2nd piezoelectric film 55 correctly is patterned as minor axis.

Secondly, use the dry ecthing of argon (Ar) gas and the wet etching of weak fluoric acid, carried out etch processes.So, can obtain being processed to the light corrosion-resisting pattern, having actuator structure body shown in Figure 29 (c) by the stacked film that is constituted by individual individual electrode 33, orientation controlling diaphragm the 41, the 1st piezoelectric film 42 and the 2nd piezoelectric film 43.Then, shown in Figure 29 (d), light resin molding 59 against corrosion is handled, be removed with stripper against corrosion.Then, shown in Figure 30 (a), on the 1st electrode film 52, formed electric insulation organic membrane 46 with print process.

Secondly, shown in Figure 30 (b), use the plasma reaction Etaching device, utilize SF ₆The part of silicon substrate 51 is removed in the dry ecthing of gas, has formed balancing gate pit 32.

Secondly, shown in Figure 30 (c), utilize the DC sputtering method on electric insulation organic membrane 46, to form extraction electrode film 47.So, can obtain the B of actuator portion shown in Figure 28.

electrode films

33,52 of element 202, apply frequency and be 200Hz, 0V～-the sinusoidal waveform voltage of 60V, carried out the inspection of above-mentioned driving situation.After driving 1,000,000,000 times, in spuing element 202, all inks do not break down yet.

(execution mode 7)

Present embodiment is the inkjet recording device of the ink gun that possessed embodiments of the present invention 6.Below, this inkjet recording device is illustrated.

The inkjet recording device 81 of embodiments of the present invention 7 possesses the ink gun 201 of execution mode 6.Other part and execution mode 3 be (with reference to Figure 14) much at one.

Use present embodiment, can obtain the action effect the same with execution mode 3.

(execution mode 8)

Present embodiment is the angular-rate sensor that has possessed the piezoelectric element of embodiments of the present invention 5.Below, this angular-rate sensor is illustrated.

Figure 31 and Figure 32 are the schematic diagram and the profile of the angular-rate sensor 400 of embodiments of the present invention 8.

Angular-rate sensor 400, possessing by thickness is the substrate 500 that the silicon wafer of 0.3mm constitutes.This substrate 500, have fixed part 500a and from this fixed part 500a to the prescribed direction (direction that the rotary middle spindle of the angular speed of detection extends.Be the Y direction of Figure 31 in the present embodiment) a pair of vibration section 500b, the 500b that extend.These fixed parts 500a and a pair of

vibration section

500b, 500b are from the thickness direction (the Z direction of Figure 31) of substrate 500, become tuning fork-like, a pair of

vibration section

500b, 500b are equivalent to the arm of tuning fork, extend parallel to each other under the state of arranging on the Width of vibration section 500b.In addition, substrate 500 also can be glass substrate, metal substrate, ceramic substrate etc.

On the part of vibration section 500b one side of each the vibration section 500b of substrate 500 and fixed part 500a, the 1st electrode film 502, orientation controlling diaphragm the 503, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506 have been stacked gradually.The 1st electrode film 502, orientation controlling diaphragm 503, the stacked film of piezoelectrics and the 2nd electrode film 506 that are made of the 1st and the 2nd piezoelectric film 504,505 constitute piezoelectric element.This piezoelectric element is the same with the piezoelectric element 20 of execution mode 5.That is to say, the 1st electrode film 502, orientation controlling diaphragm the 503, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506, the 1st electrode film 2, orientation controlling diaphragm the 3, the 1st piezoelectric film the 4, the 2nd piezoelectric film 5 and the 2nd electrode film 6 with execution mode 5 is the same respectively.

Other part is almost the same with execution mode 4.

Below, with reference to Figure 33 the manufacture method of angular-rate sensor 400 is illustrated.At first, shown in Figure 33 (a), being ready to by thickness is that 0.3mm, diameter are the substrate 500 of 4 inches silicon wafer (also with reference to Figure 18) formation, and shown in Figure 33 (b), having formed on substrate 500 by thickness with sputtering method is the 1st electrode film 502 of iridium (Ir) the film formation of 220nm.The 1st electrode film 502 is by using sputter equipment, substrate 500 is heated to 400 ℃, with iridium (Ir) target, in the argon gas body of 1Pa, carrying out 12 minutes film forming with 200W high frequency electricity and obtain.

Secondly, shown in Figure 33 (c), having formed thickness with sputtering method on the 1st electrode film 502 is the orientation controlling diaphragm 503 of 40nm.This orientation controlling diaphragm 503 is such formation: allocate the sintering target that forms by the lead oxide (PbO) that uses superfluous 12 moles of % of adding in the PLT that contains 14 moles of % lanthanums, substrate 500 is heated to 600 ℃ temperature, and (gas volume is than Ar: 0 in the hybird environment of argon and oxygen ₂=19: 1), making vacuum degree is 0.8Pa, with the high frequency electricity film forming acquisition in 12 minutes of 300W.The operation that forms this orientation controlling diaphragm 503 comprises makes orientation controlling diaphragm 503 preferred orientations in the operation of (111) face.

Secondly, shown in Figure 33 (d), on orientation controlling diaphragm 503, form the 1st piezoelectric film 504, then, on the 1st piezoelectric film 504, form the 2nd piezoelectric film 505 continuously, formed the stacked film of piezoelectrics with sputtering method with sputtering method.The stacked film 504 of the 1st piezoelectrics is that the pzt thin film of (111) preferred orientation of 50nm constitutes by thickness, and the 2nd piezoelectric film 505 is the pzt thin film formation of (111) orientation of 3500nm by thickness.The film forming of the stacked film of piezoelectrics is to form like this: at first, the sintered body target (constitutive molar ratio Pb: Zr: Ti=1.20: 0.53: 0.47) of 6 inch diameters of PZT that surplus has been added the stoichiometric structure that the PbO allotment of about 20 moles of % forms is as target, the silicon substrate 500 that will form the 1st electrode film 502 and orientation controlling diaphragm 503 on the surface heats the temperature that remains to 580 ℃ in advance, the mist that uses argon and oxygen is as sputter gas, making its gas pressure is 0.2Pa, make its mixing ratio argon: oxygen=38: 2, making its flow is per minute 40ml, making plasma generation power is 3kW, under these conditions with 50 seconds of the 1st piezoelectric film 504 film forming, then, stop film forming, mixing ratio with sputter gas becomes argon at once: oxygen=79: 1, other condition is constant, with 2900 seconds of the 2nd piezoelectric film 505 film forming.The operation that forms the stacked film of these piezoelectrics comprises by orientation controlling diaphragm 503 makes the stacked film preferred orientation of piezoelectrics in the operation of (111) face.

Secondly, shown in Figure 33 (e), having formed thickness with sputtering method on the 2nd piezoelectric film 505 is the 2nd electrode film 506 of 200nm.The 2nd electrode film 506 is by at room temperature, uses platinum (Pt) target, in the argon gas body of 1Pa, obtains in 10 minutes with the electric film forming of the high frequency of 200W.

Secondly, shown in Figure 33 (f),, drive electrode 507,507 and detecting electrode 508 (also with reference to Figure 18) have been formed with the 2nd electrode film 506 patternings.That is to say, on the 2nd electrode film 506, apply photosensitive resin, to the pattern exposure of this photosensitive resin with drive electrode 507,507 and detecting electrode 508, then, to remove less than the photosensitive resin of the part of exposing, to remove the 2nd electrode film 506 of the part of this photosensitive resin with etching and remove, then, the photosensitive resin on drive electrode 507,507 and the detecting electrode 508 removed.

Secondly, with the 1st piezoelectric film the 504, the 2nd piezoelectric film 505, orientation controlling diaphragm 503 and the 1st electrode film 502 patternings, simultaneously,, fixed part 500a and

vibration section

500b, 500b have been formed with substrate 500 patternings.Then, substrate 500 is processed into tuning fork-like shown in Figure 31.Method can obtain angular-rate sensor 400 by this.

As mentioned above, use present embodiment, can obtain the action effect the same with execution mode 4.

vibration section

500b, 500b, many group a pair of

vibration section

And, in the present embodiment, on the part of vibration section 500b one side of each the vibration section 500b of substrate 500 and fixed part 500a, stacked gradually the 1st electrode film 502, orientation controlling diaphragm the 503, the 1st piezoelectric film the 504, the 2nd piezoelectric film 505 and the 2nd electrode film 506, also can be only stacked on each vibration section 500b.

(other execution mode)

In the respective embodiments described above, piezoelectric element of the present invention has been used in ink gun (inkjet recording device) and the angular-rate sensor, outside this, also can be applicable to the electric charge accumulation capacitance of film capacitor, permanent storage element, various actuator, infrared ray sensor, ultrasonic sensor, pressure sensor, acceleration sensor, flow sensor, vibrating sensor, piezoelectric transformer, piezo-electric ignition element, piezoelectric microphone, piezoelectric micromotor telephone set, piezoelectric filter, piezoelectricity adapter, fork generator, delay line etc.Be specially adapted on substrate, to be provided with the disk that is driven in rotation in the device for disc (as the uses such as storage device of computer) is carried out in the head support mechanism of head of recording of information or regeneration, make substrate distortion by the film piezoelectric element that is arranged on the substrate, make the device for disc film piezoelectric actuator (for example, opening the 2001-332041 communique) of a displacement with reference to the spy.Just, this film piezoelectric element, the same with the respective embodiments described above, be to stack gradually the 1st electrode film, the 1st piezoelectric film, the 2nd piezoelectric film and the 2nd electrode film, the 2nd electrode film is bonded on the substrate to form, perhaps, be to stack gradually the 1st electrode film, orientation controlling diaphragm, the 1st piezoelectric film, the 2nd piezoelectric film and the 2nd electrode film, make the 2nd electrode film be bonded on above-mentioned substrate and form.

(utilizing on the industry possibility)

Piezoelectric element of the present invention, not only useful as ink gun, also as being used in the gyroscope element Deng in angular-rate sensor useful. And, also can be applied to take the photoswitch parts to representative Micro mechanical device etc.

Claims

1, a kind of piezoelectric element, comprise: the 1st electrode film, by being arranged on the 1st piezoelectric film on the 1st electrode film and being arranged on the stacked film of piezoelectrics that the 2nd piezoelectric film on the 1st piezoelectric film constitutes and being arranged on the 2nd electrode film on the stacked film of these piezoelectrics is characterized in that:

The stacked film of above-mentioned piezoelectrics is made of the perofskite type oxide of preferred orientation in rhombogen crystallographic system or tetragonal (111) face;

The the above-mentioned the 1st and the 2nd piezoelectric film is the aggregate of the columnar-shaped particle that joins continuously each other;

The averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film is greater than the averga cross section diameter of the columnar-shaped particle of above-mentioned the 1st piezoelectric film;

The ratio of the thickness of the stacked film of above-mentioned piezoelectrics and the averga cross section diameter of the columnar-shaped particle of above-mentioned the 2nd piezoelectric film more than or equal to 20 smaller or equal to 60.

2, piezoelectric element according to claim 1 is characterized in that:

The columnar-shaped particle of above-mentioned the 1st piezoelectric film, averga cross section diameter more than or equal to 40nm smaller or equal to 70nm, length more than or equal to 5nm smaller or equal to 100nm.

3, piezoelectric element according to claim 1 is characterized in that:

The columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, length more than or equal to 2500nm smaller or equal to 5000nm.

4, piezoelectric element according to claim 1 is characterized in that:

The the above-mentioned the 1st and the 2nd piezoelectric film is that the oxide of main component constitutes by the lead zirconate titanate with Ca-Ti ore type;

(111) crystalline orientation rate of above-mentioned the 1st piezoelectric film more than or equal to 50% smaller or equal to 80%;

(111) crystalline orientation rate of above-mentioned the 2nd piezoelectric film more than or equal to 95% smaller or equal to 100%.

5, piezoelectric element according to claim 1 is characterized in that:

The chemical composition of the stacked film of above-mentioned piezoelectrics compares by Pb: Zr: Ti=(1+a): b: (1-b) expression;

The b value of the above-mentioned the 1st and the 2nd piezoelectric film is smaller or equal to 0.60 identical value more than or equal to 0.40;

The Pb amount of above-mentioned the 1st piezoelectric film is more than the Pb amount of above-mentioned the 2nd piezoelectric film;

The a value of above-mentioned the 1st piezoelectric film more than or equal to 0.05 smaller or equal to 0.15;

The a value of above-mentioned the 2nd piezoelectric film more than or equal to 0 smaller or equal to 0.10.

6, piezoelectric element according to claim 1 is characterized in that:

The stacked film of above-mentioned piezoelectrics is by at least a the making of having added in lead zirconate titanate in magnesium and the manganese, and this addition surpasses 0 smaller or equal to 10 moles of %.

7, piezoelectric element according to claim 1 is characterized in that:

Above-mentioned the 1st electrode film, noble metal that is formed by platinum, iridium, palladium or ruthenium or the alloy that contains this noble metal constitute, and are that the averga cross section diameter is more than or equal to the aggregate of 20nm smaller or equal to the columnar-shaped particle of 30nm.

8, piezoelectric element according to claim 1 is characterized in that:

Also comprise: the orientation controlling diaphragm that between above-mentioned the 1st electrode film and above-mentioned the 1st piezoelectric film, is provided with;

Above-mentioned orientation controlling diaphragm is made of the perofskite type oxide of preferred orientation in cubic system or tetragonal (111) face.

9, piezoelectric element according to claim 8 is characterized in that:

10, piezoelectric element according to claim 8 is characterized in that:

11, piezoelectric element according to claim 8 is characterized in that:

12, piezoelectric element according to claim 8 is characterized in that:

13, piezoelectric element according to claim 8 is characterized in that:

Above-mentioned orientation controlling diaphragm is that the oxide of main component constitutes by the lead lanthanum zirconate titanate with Ca-Ti ore type;

(111) crystalline orientation rate of above-mentioned orientation controlling diaphragm is more than or equal to 50%.

14, piezoelectric element according to claim 8 is characterized in that:

The chemical composition of above-mentioned orientation controlling diaphragm is than by Pb: La: Zr: Ti=x * (1-z): z: y: (1-y) expression;

Above-mentioned x value more than or equal to 1.0 smaller or equal to 1.20;

Above-mentioned y value is smaller or equal to 0.20 value more than or equal to 0;

Above-mentioned z value surpasses 0 smaller or equal to 0.30.

15, piezoelectric element according to claim 8 is characterized in that:

Above-mentioned orientation controlling diaphragm is made by added at least a of magnesium and manganese in lead lanthanum zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

16, piezoelectric element according to claim 8 is characterized in that:

The stacked film of above-mentioned piezoelectrics is made by added at least a of magnesium and manganese in lead zirconate titanate, and its addition surpasses 0 smaller or equal to 10 moles of %.

17, piezoelectric element according to claim 8 is characterized in that:

18, a kind of ink gun, comprise: the 1st electrode film, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level of face of above-mentioned the 2nd electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 2nd electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink; Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue, and it is characterized in that:

Above-mentioned piezoelectric element is the described piezoelectric element of claim 1.

19, a kind of ink gun, comprise: the 1st electrode film, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level of face of above-mentioned the 1st electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 1st electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink; Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue, and it is characterized in that:

20, a kind of inkjet recording device is characterized in that:

Comprise: the described ink gun of claim 18, and

The relative moving mechanism that allows above-mentioned ink gun and recording medium relatively move;

When allowing above-mentioned ink gun and above-mentioned recording medium relatively move by above-mentioned relative moving mechanism, carry out record from the ink of nozzle bore in above-mentioned recording medium spues above-mentioned balancing gate pit that is communicated with this balancing gate pit.

21, a kind of inkjet recording device is characterized in that:

Comprise: the described ink gun of claim 19, and

22, a kind of angular-rate sensor, comprise and have fixed part and the substrate of at least one pair of vibration section of the direction extension that the rotary middle spindle towards the angular speed that detects extends from this fixed part, each vibration section at least of this substrate is provided with the 1st electrode film, the stacked film of piezoelectrics that constitutes by the 1st and the 2nd piezoelectric film, stack gradually the piezoelectric element that forms with the 2nd electrode film, the 2nd electrode film on above-mentioned each vibration section is patterned as and is used to make this vibration section at least one drive electrode in its Width vibration, at least one detecting electrode with the distortion of the thickness direction that is used to detect above-mentioned vibration section is characterized in that:

23, angular-rate sensor according to claim 22 is characterized in that:

24, angular-rate sensor according to claim 22 is characterized in that:

The columnar-shaped particle of above-mentioned the 2nd piezoelectric film, averga cross section diameter more than or equal to 60nm smaller or equal to 200nm, its length more than or equal to 2500nm smaller or equal to 5000nm.

25, angular-rate sensor according to claim 22 is characterized in that:

26, angular-rate sensor according to claim 22 is characterized in that:

27, angular-rate sensor according to claim 22 is characterized in that:

28, angular-rate sensor according to claim 22 is characterized in that:

29, angular-rate sensor according to claim 22 is characterized in that:

Above-mentioned substrate is made of silicon.

30, a kind of manufacture method of piezoelectric element is characterized in that:

Comprise: the usefulness sputtering method forms the operation of the 1st electrode film on substrate,

On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide with sputtering method, form the operation of the stacked film of piezoelectrics, and

On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film;

In the operation that forms the stacked film of above-mentioned piezoelectrics, the stacked film of these piezoelectrics is formed preferred orientation in (111) face.

31, a kind of manufacture method of ink gun is characterized in that:

On above-mentioned the 1st electrode film, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide with sputtering method, form the operation of the stacked film of piezoelectrics,

On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film,

On above-mentioned the 2nd electrode film, form the operation of vibration level,

On above-mentioned vibration level and the face opposite side of above-mentioned the 2nd electrode film, engage the operation of the balancing gate pit's parts that are used to form the balancing gate pit, and

After above-mentioned joint operation, the operation of removing above-mentioned substrate;

32, a kind of manufacture method of ink gun is characterized in that:

Comprise: on the balancing gate pit's substrate that forms the balancing gate pit, form the operation of vibration level,

On above-mentioned vibration level, form the operation of the 1st electrode film with sputtering method,

On the stacked film of above-mentioned piezoelectrics, form the operation of the 2nd electrode film, and

Form the operation of balancing gate pit at above-mentioned balancing gate pit substrate;

33, a kind of manufacture method of angular-rate sensor is characterized in that:

With the operation of above-mentioned the 2nd electrode film patterning formation drive electrode and detecting electrode,

With the operation of stacked film of above-mentioned piezoelectrics and above-mentioned the 1st electrode film patterning, and

Operation with above-mentioned underlay pattern formation fixed part and vibration section;

34, a kind of ink gun, comprise: the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level on the face of above-mentioned the 2nd electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 2nd electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink; Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue, and it is characterized in that:

Above-mentioned piezoelectric element is the described piezoelectric element of claim 8.

35, a kind of ink gun, comprise: the 1st electrode film, orientation controlling diaphragm, the stacked film of piezoelectrics and the 2nd electrode film that are made of the 1st and the 2nd piezoelectric film are stacked gradually the piezoelectric element that forms, be arranged on the vibration level on the face of above-mentioned the 1st electrode film one side of this piezoelectric element, and be bonded on this vibration level and the face opposite side of above-mentioned the 1st electrode film and formed balancing gate pit's parts of the balancing gate pit that holds ink; Piezoelectric effect by the stacked film of above-mentioned piezoelectrics makes above-mentioned vibration level in the displacement of bed thickness direction, allows the ink in the above-mentioned balancing gate pit spue, and it is characterized in that:

36, a kind of inkjet recording device is characterized in that:

Comprise: the described ink gun of claim 34, and

37, a kind of inkjet recording device is characterized in that:

Comprise: the described ink gun of claim 35, and

38, a kind of angular-rate sensor, comprise and have fixed part and the substrate of at least one pair of vibration section of the direction extension that the rotary middle spindle towards the angular speed that detects extends from this fixed part, each vibration section at least of this substrate is provided with the 1st electrode film, the orientation controlling diaphragm, the stacked film of piezoelectrics that constitutes by the 1st and the 2nd piezoelectric film, stack gradually the piezoelectric element that forms with the 2nd electrode film, the 2nd electrode film on above-mentioned each vibration section is patterned as is used to make this vibration section at least one drive electrode in its Width vibration, at least one detecting electrode with the distortion of the thickness direction that is used to detect above-mentioned vibration section is characterized in that:

39, according to the described angular-rate sensor of claim 38, it is characterized in that:

40, according to the described angular-rate sensor of claim 38, it is characterized in that:

41, according to the described angular-rate sensor of claim 38, it is characterized in that:

42, according to the described angular-rate sensor of claim 38, it is characterized in that:

43, according to the described angular-rate sensor of claim 38, it is characterized in that:

44, according to the described angular-rate sensor of claim 38, it is characterized in that:

Above-mentioned x value more than or equal to 1.0 smaller or equal to 1.20;

Above-mentioned y value more than or equal to 0 smaller or equal to 0.20;

Above-mentioned z value surpasses 0 smaller or equal to 0.30.

45, according to the described angular-rate sensor of claim 38, it is characterized in that:

46, according to the described angular-rate sensor of claim 38, it is characterized in that:

47, according to the described angular-rate sensor of claim 38, it is characterized in that:

48, according to the described angular-rate sensor of claim 38, it is characterized in that:

Above-mentioned substrate is made by silicon.

49, a kind of manufacture method of piezoelectric element is characterized in that:

On above-mentioned the 1st electrode film, form the operation of the orientation controlling diaphragm that constitutes by cubic system or tetragonal perofskite type oxide with sputtering method,

On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide with sputtering method, form the operation of the stacked film of piezoelectrics, and

In the operation that forms above-mentioned orientation controlling diaphragm, this orientation controlling diaphragm is formed preferred orientation in (111) face;

In the operation that forms the stacked film of above-mentioned piezoelectrics, be formed preferred orientation in (111) face by the stacked film of above-mentioned these piezoelectrics of orientation controlling diaphragm.

50, a kind of manufacture method of ink gun is characterized in that:

On above-mentioned orientation controlling diaphragm, form the 1st and the 2nd piezoelectric film that constitutes by rhombogen crystallographic system or tetragonal perofskite type oxide with sputtering method, form the operation of the stacked film of piezoelectrics,

With balancing gate pit's part bonding of being used to form balancing gate pit operation on above-mentioned vibration level and the face opposite side of above-mentioned the 2nd electrode film, and

After above-mentioned joint operation, the operation that above-mentioned substrate is removed;

51, a kind of manufacture method of ink gun is characterized in that:

52, a kind of manufacture method of angular-rate sensor is characterized in that:

With the operation of the stacked film of above-mentioned piezoelectrics, above-mentioned orientation controlling diaphragm and above-mentioned the 1st electrode film patterning, and