CN107068848A - Piezoelectric element and piezoelectric element application apparatus - Google Patents
Piezoelectric element and piezoelectric element application apparatus Download PDFInfo
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- CN107068848A CN107068848A CN201610855455.0A CN201610855455A CN107068848A CN 107068848 A CN107068848 A CN 107068848A CN 201610855455 A CN201610855455 A CN 201610855455A CN 107068848 A CN107068848 A CN 107068848A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14201—Structure of print heads with piezoelectric elements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
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- Particle Formation And Scattering Control In Inkjet Printers (AREA)
Abstract
The present invention provides a kind of piezoelectric element and piezoelectric element application apparatus, wherein, piezoelectric element possesses first electrode, second electrode and the piezoelectric body layer being arranged between above-mentioned first electrode and above-mentioned second electrode, piezoelectric body layer is by Pb (Ni, Nb, Zr, Ti) O3Represented perovskite composite oxide is constituted, the content of Ni and Nb in perovskite composite oxide it is total relative to the total content of the element contained by B for more than 1 [mol%] 5 [mol%] below.
Description
Technical field
The present invention relates to the excellent piezoelectric element of placement property and piezoelectric element application apparatus.
Background technology
Generally, piezoelectric element has：Two electricity of piezoelectric body layer and clamping piezoelectric body layer with data-collection characteristic
Pole.In recent years, actively entering to be about to the equipment that such piezoelectric element uses as driving source, (piezoelectric element application is set
It is standby) exploitation.As the piezoelectric element application apparatus in exploitation, the liquid spray using ink jet recording head as representative can be included
Penetrate head, using piezoelectric mems element as the MEMS component of representative, with ultrasonic measurement device that ultrasonic sensor etc. is representative, with
And piezoelectric actuator device etc..
Piezoelectric requirement has higher piezoelectric property used in piezoelectric body layer, is used as such piezoelectric, many institutes
It there are known to composite oxides (perovskite composite oxide), i.e. lead zirconate titanate (Pb (Zr, Ti) O3, hereinafter referred to as " PZT "),
Above-mentioned composite oxides, which have, includes lead titanates (PbTiO3, hereinafter referred to as " PT ") and zirconium oxide lead (PbZrO3, hereinafter referred to as
" PZ ") binary system perovskite construction.
In addition, in recent years, also make the perovskite composite oxide that PZT contains ternary multicomponent system in exploitation,
It is used as the PZT of such multicomponent system, it is known that contain niobic acid nickel lead plumbate (Pb (Ni, Nb) O3, hereinafter referred to as " PNN ") and it is used as the 3rd
The PZT (PNN-PZT) of composition (for example, referring to patent document 1, patent document 2).
Patent document 1：Japanese Unexamined Patent Publication 11-129478 publications
Patent document 2：Japanese Unexamined Patent Publication 11-207957 publications
However, PNN-PZT can not obtain being equipped with needed for high performance of various devices of piezoelectric element application apparatus etc.
The placement property wanted, at least needs with the placement property being equal to PZT phases.In order to obtain excellent placement property, it is necessary to pin
Selection, replacement amount of permutated bits, substitutional element to perovskite composite oxide etc. are further studied, come realize into
The optimization of one step.In addition, so the problem of be not only limited to be equipped on the piezoelectric element of ink jet recording head, in piezoelectric mems member
Similarly exist in part, ultrasound sensor element, piezoelectric actuator component etc..
The content of the invention
The present invention be in view of above-mentioned actual conditions and propose, its object is to provide a kind of raising for realizing displacement,
Excellent placement property can be obtained, and can realize that the piezoelectric element of the reduction of leakage current and piezoelectric element application are set
It is standby.
The mode involved in the present invention for solving above-mentioned problem is a kind of piezoelectric element, it is characterised in that possess the first electricity
Pole, second electrode and the piezoelectric body layer being arranged between first electrode and second electrode, above-mentioned piezoelectric body layer is by following formula (1)
Represented perovskite composite oxide is constituted, total phase of the content of Ni and Nb in above-mentioned perovskite composite oxide
For the total content of the element contained by B be more than 1 [mol%] 5 [mol%] below,
Pb (Ni, Nb, Zr, Ti) O3……(1)。
In aforesaid way, perovskite composite oxide of the above-mentioned piezoelectric body layer represented by above-mentioned formula (1) is constituted, should
The content of Ni and Nb in composite oxides it is total relative to being more than 1 [mol%] in the total content of the element contained by B
5 [mol%] below, therefore, it is possible to form the piezoelectric element with excellent placement property.
Here, above-mentioned piezoelectric body layer can also be made up of the perovskite composite oxide represented by following formula (2),
XPb (Ni, Nb) O3- (1-x) Pb (Zr, Ti) O3... (2),
In formula, 0.01≤x≤0.05 is met.
Root is hereby it is possible to realize the raising of the displacement of above-mentioned piezoelectric element.
Here, for above-mentioned piezoelectric body layer, the Ca-Ti ore type composite oxygen represented by preferably above-mentioned formula (1) or formula (2)
The Ni and Nb mol ratio that the Chemistry and Physics Institute is contained are 1：2.
According to this, in addition to it can realize the raising of displacement of above-mentioned piezoelectric element, additionally it is possible to realize leakage current
Reduce.
In addition, the other modes involved in the present invention for solving above-mentioned problem are a kind of piezoelectric element application apparatus, its
It is characterised by possessing the piezoelectric element of any one above-mentioned mode.
In aforesaid way, the piezoelectric element application apparatus with excellent placement property can be formed.
Brief description of the drawings
Fig. 1 is the figure for the brief configuration for showing inkjet recording device.
Fig. 2 is the exploded perspective view for the brief configuration for showing ink jet recording head.
Fig. 3 is the top view for the brief configuration for showing ink jet recording head.
Fig. 4 is the sectional view for the brief configuration for showing ink jet recording head.
Fig. 5 is the figure illustrated to the Production Example of ink jet recording head.
Fig. 6 is the figure illustrated to the Production Example of ink jet recording head.
Fig. 7 is the figure illustrated to the Production Example of ink jet recording head.
Fig. 8 is the figure illustrated to the Production Example of ink jet recording head.
Fig. 9 is the figure illustrated to the Production Example of ink jet recording head.
Figure 10 is the figure illustrated to the Production Example of ink jet recording head.
Figure 11 is the figure illustrated to the Production Example of ink jet recording head.
Embodiment
Hereinafter, embodiments of the present invention are illustrated referring to the drawings.The following description shows the side of the present invention
Formula, can arbitrarily be changed in the range of idea of the invention is not departed from.In addition, marking identical accompanying drawing mark in the drawings
The part of note represents identical part, and the description thereof is omitted as appropriate.In addition, in Fig. 2~Figure 11, X, Y and Z represent mutual
Three orthogonal spatial axes.In this manual, using the direction along these axles as first direction X (X-direction), second
Direction Y (Y-direction) and third direction Z (Z-direction) is illustrated.The face of X-direction and Y-direction display plate, layer and film
Interior direction, the thickness direction or stacked direction of Z-direction display plate, layer and film.
Embodiment 1
First, 1 pair of inkjet recording device as an example of liquid injection apparatus of reference picture is illustrated.
Fig. 1 shows the brief configuration of inkjet recording device.As illustrated, at inkjet recording device (tape deck I)
In, ink jet recording head unit (head unit II) is arranged at print cartridge 2A, print cartridge 2B in the way of it can load and unload.Print cartridge 2A, print cartridge
2B constitutes ink feed mechanism.Head unit II has multiple ink jet recording heads described later (record first 1, reference picture 2 etc.), and takes
It is loaded in balladeur train 3.Balladeur train 3 is arranged in the way of it can move freely vertically on the balladeur train axle 5 of apparatus main body 4.This
A little head unit II, balladeur train 3 are for example configured to be able to injection black ink composition and color ink compositions.
Moreover, the driving force of motor 6 is transferred to balladeur train 3 via multiple gears and timing belt 7 (not shown), so that
The balladeur train 3 for being equipped with head unit II is moved along balladeur train axle 5.On the other hand, it is provided with apparatus main body 4 as conveying mechanism
Conveying roller 8, is conveyed as the recording sheet S of the recording mediums such as paper by conveying roller 8.In addition, conveying recording sheet S conveyer
Structure be not limited to conveying roller or with, drum etc..
In record first 1, as piezoelectric actuator device, the piezoelectric element involved by embodiments of the present invention is used
300, the narration detailed to this progress later.By using piezoelectric element 300, the various spies in tape deck I can be avoided
The reduction of property (durability, ink spray characteristic etc.).
Next, 2~Fig. 4 of reference picture, to an example as the jet head liquid for being equipped on liquid injection apparatus
Ink jet recording head is illustrated.
Fig. 2 is the exploded perspective view of ink jet recording head.Fig. 3 is the top view of the piezoelectric element side of stream formation substrate
(top view from piezoelectric element side during stream formation substrate), Fig. 4 is the sectional view on the basis of Fig. 3 A-A ' lines.
Stream formation substrate 10 (hereinafter referred to as " substrate 10 ") for example it is made up of silicon single crystal substrate, and it is formed with pressure production
Raw room 12.Moreover, the ink that the pressure generating chamber 12 divided by multiple next doors 11 sprays same color along being set up in parallel is more
The direction (X-direction) of individual nozzle opening 21 is set up in parallel.The material of substrate 10 is not limited to silicon or SOI, glass
Deng.
The one end side of the Y-direction of pressure generating chamber 12 in substrate 10, is formed with ink supply road 13 and access
14.Interconnecting part 15 is formed with the outside (+Y direction side) of access 14.Interconnecting part 15 constitutes a part for manifold 100.Manifold
100 turn into the shared ink chamber of each pressure generating chamber 12.Like this, it is formed with the substrate 10 by pressure generating chamber 12, oil
The liquid flow path that ink supply road 13, access 14 and interconnecting part 15 are constituted.
Such as SUS nozzle plate 20 is bonded on a face (face of -Z direction side) for substrate 10.In nozzle plate 20
On be set side by side with nozzle opening 21 in X direction.Nozzle opening 21 is connected with each pressure generating chamber 12.Nozzle plate 20 can pass through
Bonding agent, thermal welding film etc. are engaged with substrate 10.
Oscillating plate 50 is formed with another face (face of +Z direction side) of substrate 10.Oscillating plate 50 is for example formed from
Elastic membrane 51 on substrate 10 and the insulator film 52 being formed in elastic membrane 51 are constituted.Elastic membrane 51 is for example by silica
(SiO2) constitute, insulator film 52 is for example by zirconium oxide (ZrO2) constitute.
Being formed with insulator film 52 includes the piezoelectric element of first electrode 60, piezoelectric body layer 70 and second electrode 80
300.And, although diagram is eliminated in Fig. 2~Fig. 4, but in order to viscous between reinforced insulation body film 52 and first electrode 60
The property, is provided with adhesion coating 56 (5~Figure 11 of reference picture) between insulator film 52 and first electrode 60.Adhesion can also be omitted
Layer 56.
First electrode 60 is set for each pressure generating chamber 12.That is, first electrode 60 is configured to be directed to each pressure
Generating chamber 12 and independent discrete electrodes.Also, piezoelectric body layer 70 is set also for each pressure generating chamber 12.
Second electrode 80 is continuously set throughout X-direction on first electrode 60, piezoelectric body layer 70 and oscillating plate 50.That is,
Second electrode 80 is configured to common electrode.Can not also using second electrode 80 as common electrode, and using first electrode 60 as
Common electrode.
Expose the end of end (end of -Y direction side) from the -Y direction side of piezoelectric body layer 70 of first electrode 60.First
The end of the -Y direction side of electrode 60 is connected with lead electrode 90a.
In addition, connecting leaded electrode 90b in second electrode 80.It can be formed by the substrate 10 throughout entire surface
After the layer for the material for constituting lead electrode 90a and lead electrode 90b, by the pattern layers into defined shape, come simultaneously
Form lead electrode 90a and lead electrode 90b.
It is being formed with the substrate 10 of piezoelectric element 300, protective substrate 30 is bonded to by bonding agent 35.Protective substrate 30
With manifold portion 32.At least a portion of manifold 100 is constituted by manifold portion 32.Manifold portion 32 involved by present embodiment exists
Insertion protective substrate 30 on thickness direction (Z-direction), and throughout width (X-direction) formation of pressure generating chamber 12.And
And, manifold portion 32 is connected with the interconnecting part 15 of substrate 10 as described above.Using these structures, composition forms each pressure generating chamber
The manifold 100 of 12 shared ink chamber.
The flexible base board 40 being made up of diaphragm seal 41 and fixed plate 42 is bonded on protective substrate 30.Fixed plate 42
The region opposed with manifold 100 turns into the opening portion 43 being completely removed on thickness direction (Z-direction).One of manifold 100
Face (face of +Z direction side) with flexible diaphragm seal 41 only by sealing.
Such ink jet recording head discharges ink droplet by following action.First, supplied from outside ink (not shown)
Ink is obtained to the ink introducing port that mechanism is connected, is made from manifold 100 to nozzle opening 21 internal full of ink.Then, according to
Tracer signal from drive circuit (not shown), to each first electrode 60 corresponding with pressure generating chamber 12 and second electrode
Apply voltage between 80, and make the deflection deformation of piezoelectric element 300.Accordingly, the pressure increase in each pressure generating chamber 12, so that from
Nozzle opening 21 discharges ink droplet.
Next, piezoelectric element 300 is further described in detail.Piezoelectric element 300 includes first electrode 60, the
Two electrodes 80 and the piezoelectric body layer 70 being arranged between first electrode 60 and second electrode 80.The thickness of first electrode 60 is about
For 50nm.Piezoelectric body layer 70 is piezoelectrics of the thickness in more than 50nm below 2000nm so-called film.Second electrode 80
Thickness is about 50nm.The thickness of each component included herein is an example, can not change idea of the invention
In the range of changed.
As long as the material of first electrode 60 and second electrode 80 is able to maintain that the material of electric conductivity, special limit is not just done
It is fixed.As such material, the noble metal such as can include platinum (Pt), iridium (Ir) or with lanthanum nickel oxide (LNO)
Deng the electroconductive oxide for representative.
Piezoelectric body layer 70 is used by least containing lead (Pb), nickel (Ni), niobium (Nb), zirconium (Zr) and each metal member of titanium (Ti)
The piezoelectric that element and the composite oxides (perovskite composite oxide) constructed with perovskite are constituted is constituted.
Here, perovskite composite oxide is to use formula ABO3One kind of the composite oxides of expression.For perovskite
For type composite oxides, 12 oxygen are coordinated at A, 6 oxygen are coordinated at B, are constituted octahedra (Octahedron).Constitute pressure
The composite oxides of electrics layer 70 contain Pb at A, contain Ni, Nb, Zr and Ti at B.
The composite oxides of piezoelectric body layer 70 are constituted it can be said that being niobic acid nickel lead plumbate (Pb (Ni, Nb) O3, hereinafter referred to as
For " PNN ") and lead zirconate titanate (Pb (Zr, Ti) O3, hereinafter referred to as " PZT ") mixed crystal or PNN and PZT equably solid solution and
Into solid solution, but in X-ray diffraction pattern, PNN, PZT can not be individually detected.Therefore, piezoelectric body layer 70 is constituted
The composition of composite oxides can be represented as following formula (3).
Pb (Ni, Nb, Zr, Ti) O3……(3)
It is excellent in the composite oxides of formula (3) from the viewpoint of the sufficient displacement ensured in piezoelectric element 300
Total total content relative in the element contained by B of the content of Ni and Nb in the composite oxides is selected to be less than 6
[mol%], more than more preferably 1 [mol%] 5 [mol%] is below.
In addition, from the viewpoint of taking into account and ensuring sufficient displacement in piezoelectric element 300 and reduce leakage current, it is excellent
The total of content for choosing the Ni and Nb that state in composite oxides is less than 3 [mol%], more preferably meets more than 1 [mol%]
2.5 [mol%] are below.
In addition, the composition statement of the perovskite composite oxide represented by formula (3) is based on stoichiometry statement,
Perovskite construction can be obtained by constituting the composite oxides of piezoelectric body layer 70, then is allowed certainly by lattice mismatch, oxygen defect etc.
Caused inevitable composition deviation, and also allow such as potassium (K), sodium (Na), lanthanum (La), samarium (Sm), cerium (Ce), aluminium
(Al), aliquot replacement of element such as cobalt (Co) etc..If for example, stoichiometric proportion is set into 1, allowing less than more than 0.85 1.20
In the range of composition.Also, different in the case of being represented with formula, there is also by the element of the element of A and B
The situation for being considered as identical composite oxides than identical composite oxides.
On the other hand, the composite oxides for constituting piezoelectric body layer 70 can also use the calcium titanium represented by following formula (4)
The piezoelectric that ore deposit type composite oxides are constituted is constituted.
XPb (Ni, Nb) O3- (1-x) Pb (Zr, Ti) O3……(4)
In formula, 0.01≤x≤0.05 is met.
In formula (4), from the viewpoint of the sufficient displacement ensured in piezoelectric element 300, x ＜ are preferably met
0.06, more preferably meet 0.01≤x≤0.05.
In addition, in formula (4), ensure sufficient displacement in piezoelectric element 300 from taking into account and reduce leakage current
Viewpoint considers, more preferably meets x ＜ 0.03, more preferably meets 0.01≤x≤0.025.
In addition, PNN, PZT are respectively the known piezoelectric constructed with perovskite, and there are various compositions.As
PNN, PZT of such composition, can for example include each metallic element (Pb, Ni, Nb, Zr, Ti) contained by PNN, PZT with
And a part of defect or superfluous composition, a part for each element of oxygen are replaced into composition of other elements etc..Therefore, exist
In the case of being expressed as PNN, PZT, as long as not changing basic characteristic, then cause the group with stoichiometry because of defect, surplus
Into producing the composition of deviation, a part for element is replaced into the compositions of other elements and is also contained in PNN, PZT scope.
For constituting the composite oxides of piezoelectric body layer 70, from taking into account the sufficient position that ensures in piezoelectric element 300
From the viewpoint of shifting amount and reduction leakage current, preferably Ni contained in its composition and Nb mol ratio is 1: 2.
The piezoresistive material that piezoelectric body layer 70 is constituted by using the perovskite composite oxide represented by formula (3) or formula (4)
Material is constituted, so as to make the crystallization of the composite oxides in (100) face preferred orientation.Also, the piezoelectric can not make
With tropism control layer, and in (100) face natural orientation.In addition, in the present embodiment, " in (100) face preferred orientation " refers to
It is more than the ratio in (110) face, the crystallization of (111) planar orientation in the ratio of the crystallization of (100) planar orientation.The ratio is, for example,
More than 60%, preferably more than 75%, more preferably more than 80%.
Next, 5~Figure 11 of reference picture, with reference to ink jet recording head manufacture method come to being equipped on ink jet recording head
The example of manufacture method of piezoelectric element illustrate.
First, as shown in figure 5, preparing silicon substrate 110 (stream formation substrate 10).Next, by the way that silicon substrate 110 is warm
Oxidation, so as to be formed on its surface by silica (SiO2) constitute elastic membrane 51.In addition, passing through sputtering in elastic membrane 51
Method formation zirconium film, and by its thermal oxide, so as to obtain by zirconium oxide (ZrO2) constitute insulator film 52.So, formed by bullet
Property film 51 and insulator film 52 constitute oscillating plate 50.
Next, being formed on insulator film 52 by titanium oxide (TiOx) constitute adhesion coating 56.Adhesion coating 56 can lead to
Cross the formation such as sputtering method, thermal oxide.But it is also possible to omit adhesion coating 56.Next, forming first electrode on adhesion coating 56
60.First electrode 60 such as can by sputtering method, vacuum vapour deposition (PVD method), laser ablation method gas phase film forming, spin-coating method
Formed etc. liquid phase film forming etc..
Next, as shown in fig. 6, adhesion coating 56 and first electrode 60 are patterned simultaneously.Adhesion coating 56 and first
The patterning of electrode 60 can for example pass through reactive ion etching (RIE：Reactive Ion Etching), ion milling etc.
Dry-etching, use the Wet-type etching of etching solution to carry out.In addition, the shape of adhesion coating 56 and the patterning of first electrode 60
Shape is not specially limited.
Next, forming piezoelectric body layer 70 as shown in Figure 7.The forming method of piezoelectric body layer 70 is not limited.For example,
It can use and dry the solution (precursor solution) containing metal complex by applying, then be sintered to obtain gold with high temperature
Belong to MOD (the Metal-Organic Decomposition of oxide：Metal-organic decomposition) chemistry such as method, sol-gel process
Solwution method (damp process).Furthermore it is also possible to use laser ablation method, sputtering method, pulsed laser deposition (PLD methods), CVD
(Chemical Vapor Deposition：Chemical vapour deposition) method, aerosol deposition method etc. or liquid phase method or solid phase method come
Manufacture piezoelectric body layer 70.
For example, the piezoelectric body layer 70 formed by damp process has multiple piezoelectric body films 74, the piezoelectric body film 74 is by applying
Apply the precursor solution formation process (working procedure of coating) of precursor film, the process (drying process) of dried precursor film, to before dried
Body film is heated, the process of degreasing (degreasing process) and sintering degreasing after precursor film process (sintering circuit) one
The process of series and formed, later to this detailed narration of progress.That is, piezoelectric body layer 70 passes through repeatedly from working procedure of coating
Formed to a series of process of sintering circuit.In addition, in a series of process from working procedure of coating to sintering circuit,
Sintering circuit can be implemented after repeatedly from working procedure of coating to degreasing process.
Layer, the film formed by damp process has interface.Coating is remained on the layer, film formed by damp process or is burnt
The vestige of knot, this vestige turns into by observing in its section or analytic sheaf the concentration distribution of the element in (or in film) and energy
" interface " enough confirmed." interface " is strictly speaking the meaning on interlayer or intermembranous border, but also has the side of layer or film here
The meaning near boundary.The layer that is formed in observation by damp process, in the case of the section of film, this interface with adjacent layer,
Near the border of film, it is identified as the color part deeper than other parts or the color part lighter than other parts.In addition,
In the case where being parsed to the concentration distribution of element, this interface with adjacent layer, the border of film near, be used as element
The high part of concentration ratio other parts or element the low part of concentration ratio other parts and be identified.Piezoelectric body layer 70 passes through
A series of process repeatedly from working procedure of coating to sintering circuit or repeatedly from working procedure of coating to degreasing process it
Implement sintering circuit afterwards to be formed and (be made up of multiple piezoelectric body films 74), therefore accordingly there are multiple boundaries with each piezoelectric body film 74
Face.
The example that particular order in the case of piezoelectric body layer 70 is formed by damp process is as follows.First, be made by containing
There are the MOD solution of metal complex, colloidal sol to constitute and be used for the precursor solution (modulating process) for forming piezoelectric body layer 70.Then,
The precursor solution is coated in first electrode 60 using spin-coating method etc. to form precursor film (working procedure of coating).Next, should
Precursor film is heated to set point of temperature, such as 130 DEG C~250 DEG C or so and drying certain time (drying process), then by after drying
Precursor film be heated to set point of temperature, such as 300 DEG C~450 DEG C or so and kept for certain time so as to carrying out degreasing (degreasers
Sequence).Further, by the precursor film after degreasing be heated to higher temperature, such as 650 DEG C~800 DEG C or so, and at such a temperature
Kept for certain time, so that it is crystallized, form piezoelectric body film 74 (sintering circuit).Then, by repeatedly above-mentioned
Working procedure of coating, drying process, degreasing process and sintering circuit, so as to form being made up of multi-layer piezoelectric body film 74 shown in Fig. 7
Piezoelectric body layer 70.
In addition, above-mentioned precursor solution is to be possible to form the Ca-Ti ore type containing above-mentioned PNN and PZT by sintering
The metal complex of composite oxides dissolves or is dispersed to the solution of organic solvent respectively.That is, precursor solution be containing
Pb, Ni, Nb, Zr and Ti each element as the central metal of metal complex solution.At this time it is also possible to will contain above-mentioned
The metal complex of element beyond element, the metal complex of the additive such as containing K, Na, La, Sm, Ce, Al, Co enter
One step is mixed into precursor solution.
As the metal complex containing above-mentioned each element, for example, it can use alkoxide, acylate, beta-diketon complex compound
Deng.In precursor solution, if the mixed proportion of these metal complexs so that Pb contained by perovskite composite oxide,
The mode that Ni, Nb, Zr and Ti turn into desired mol ratio is mixed.
As the metal complex containing Pb for making precursor solution, such as can include lead acetate.As
Metal complex containing Ni, such as can include nickel acetate, nickel nitrate, 2 ethyl hexanoic acid nickel.It is used as the gold containing Nb
Belong to complex compound, such as can include five ethyoxyl niobiums, 2 ethyl hexanoic acid niobium.As the metal complex containing Zr, for example
Acetylacetone,2,4-pentanedione zirconium, four acetylacetone,2,4-pentanedione zirconiums, single acetyl acetone zirconium, bis-acetylacetonate zirconium etc. can be included.It is used as the gold containing Ti
Belong to complex compound, such as can include isopropyl titanate, 2 ethyl hexanoic acid titanium, (diisopropoxy) double (acetylacetone,2,4-pentanedione) titaniums.This
When, can also and with two or more metal complexs.
As the organic solvent of the making for precursor solution, for example, it can include propyl alcohol, butanol, amylalcohol, hexanol, pungent
Alcohol, ethylene glycol, propane diols, octane, decane, thiacyclohexane, dimethylbenzene, toluene, tetrahydrofuran, acetic acid, octanoic acid, 2- n-butoxy second
Alcohol, normal octane etc. or their mixed solvent etc..Precursor solution, which can contain, makes the metal network containing Pb, Ni, Nb, Zr and Ti
The additive of the dispersion stability of compound.As such additive, 2 ethyl hexanoic acid etc. can be included.
In addition, as the heater used in drying process, degreasing process and sintering circuit, such as can enumerate
Go out RTA (the Rapid Thermal Annealing heated by the irradiation of infrared lamp：Rapid thermal annealing) device, plus
Hot plate etc..
Next, as shown in figure 8, being patterned to the piezoelectric body layer 70 being made up of multiple piezoelectric body films 74.Patterning
Can by dry-etchings such as so-called reactive ion etching or ion millings, used the Wet-type etching of etching solution to enter
OK.In addition, the shape to the patterning of piezoelectric body layer 70 is not specially limited.Then, on piezoelectric body layer 70 after patterning
Form second electrode 80.Second electrode 80 can be by forming with the identical method of first electrode 60.Process more than, it is complete
Into the piezoelectric element 300 for possessing first electrode 60, piezoelectric body layer 70 and second electrode 80.In other words, first electrode 60, piezoelectricity
Body layer 70 and the equitant part of second electrode 80 turn into piezoelectric element 300.
Next, as shown in figure 9, face in the side of piezoelectric element 300 of silicon substrate 110, connects via bonding agent (not shown)
Protective substrate is closed with chip 130 (protective substrate 30).Then, carrying out cutting with the surface of chip 130 to protective substrate becomes it
It is thin.In addition, in protective substrate formation manifold portion 32, through hole (not shown) 33 (2~Fig. 4 of reference picture) on chip 130.Connect down
Come, as shown in Figure 10, in silicon substrate 110 with forming mask film 53 on the face of the opposite side of piezoelectric element 300, and patterned
Established practice setting shape.Then, as shown in figure 11, via mask film 53, silicon substrate 110 is implemented to have used each of the aqueous slkalis such as KOH
Anisotropy etches (Wet-type etching).Thus, in addition to pressure generating chamber 12 corresponding with each piezoelectric element 300, also formed
Ink supply road 13 (not shown), access 14 and interconnecting part 15 (2~Fig. 4 of reference picture).
Next, by cutting etc. that silicon substrate 110 and protective substrate is unwanted with the periphery edge of chip 130
Partial cut, removing.Also, engage nozzle plate 20 (not shown) with the face of the opposite side of piezoelectric element 300 in silicon substrate 110
(reference picture 2, Fig. 4).In addition, engaging flexible base board 40 (not shown) (2~Fig. 4 of reference picture) in protective substrate chip 130.It is logical
The process carried out so far is crossed, so as to complete the aggregate of the chip of record first 1.By the way that the aggregate is divided into each chip,
So as to obtain first 1 (2~Fig. 4 of reference picture) of record.
Embodiment
Hereinafter, the present invention is carried out in the way of embodiment is shown more specifically bright.In addition, the present invention is not limited
In following embodiment.
The making of sample 1
First, thermal oxide is carried out by monocrystalline silicon (Si) substrate (silicon substrate 110) to (100) face, so that in the Si bases
Thickness 1200nm silica (SiO is formed on the surface of plate2) film (elastic membrane 51).Next, by using RF magnetron sputterings
Method, in SiO2Thickness 40nm titanium film is made on film, and thermal oxide is carried out to the titanium film, so that titanium oxide (TiO is madex) film is (viscous
Layer 56).Next, by RF magnetron sputtering methods, in TiOxIt is orientated on film in (111) face, so as to form thickness 100nm
Platinum (Pt) film (first electrode 60).
Next, mixing lead acetate (II) trihydrate, nickel acetate (II) tetrahydrate, five n-butoxy niobiums, four (2,4-
Pentane diketone) zirconium (IV) and tetraisopropoxy titanium, and as main solvent add butyl cellosolve, be used as stabilizer to add diethyl
Hydramine, as thickener add polyethylene glycol, so that precursor solution (modulating process) is made.Next, the precursor solution is dripped
Add in first electrode 60, after substrate is rotated 6 seconds with 500rpm, rotated 20 seconds with 3000rpm, so that by spin-coating method the
Precursor film (working procedure of coating) is made on one electrode 60.Next, mounted board on hot plate, enters at 180 DEG C to precursor film
The row drying of 2 minutes (drying process).Next, the degreasing carried out 2 minutes to precursor film at 380 DEG C using heating plate (is taken off
Fat process).Next, be repeated twice it is above-mentioned from working procedure of coating to degreasing process after, filled in oxygen atmosphere by RTA
The sintering carried out at 700 DEG C to precursor film 5 minutes is put, so as to obtain perovskite composite oxide film (piezoelectric body film 74)
(sintering circuit).
In this way, be repeated twice it is above-mentioned from working procedure of coating to degreasing process after be sintered, and by these process weights
It is multiple six times, so that total film forming for carrying out 12 precursor films, is consequently formed perovskite composite oxide layer (piezoelectric body layer
70).In addition, the ratio of components of each metal adjusted in precursor solution and the ratio of components of piezoelectric body layer 70 are almost without deviation.
Next, thickness 100nm platinum (Pt) film (the second electricity is formed by RF magnetron sputtering methods on piezoelectric body layer 70
Pole 80), so that sample 1 (piezoelectric element 300) is made.
By the cantilever displacement amount of the composition of the piezoelectric body layer 70 in sample 1 and measure sample 1 described later (hereinafter referred to as
" displacement ") and the result of leakage current be shown in table 1 below.Also, thickness, the relative dielectric for determining sample 1 described later is normal
The result of several and Young's modulus and the piezoelectric voltage coefficient g31 calculated using them are shown in table 2 below.In addition, being directed to
The measurement result of the constituting of piezoelectric body layer 70 in 2~sample of sample 11 described later, the displacement of each sample and leakage current,
Table 1 is shown in identically with sample 1.Also, for determining 2~sample of sample 8 described later and thickness in sample 11, it is relative
The result of dielectric constant and Young's modulus and the piezoelectric voltage coefficient g31 calculated using them are also identical with sample 1
Ground is shown in table 2.
The making of 2~sample of sample 11
Except the mol ratio of Pb, Ni, Nb, Zr and Ti contained by piezoelectric body layer 70 are adjusted to table 1 below to be remembered
The stoichiometric proportion of load is unanimously made beyond precursor solution, and remaining is identical with sample 1,2~sample of sample 11 is respectively prepared.
Table 1
For the displacement and leakage current of the 1~sample of sample 11 determined, result of determination is shown in table 1.In table 1
In, on the basis of the displacement and leakage current by sample 11 in the case of, by displacement increase and leakage current reduction sample
Labeled as " ◎ ", displacement is increased and leakage current is that the sample labeling of same degree is "○", displacement is reduced and leaked electricity
Stream is that the sample labeling of same degree or increase is "×".
Table 2
For the piezoelectric voltage coefficient g31 of the 1~sample of sample 8 determined, result of determination is shown in table 2.In table 2,
In the case of on the basis of the piezoelectric voltage coefficient g31 by sample 11, it is by the larger sample labelings of piezoelectric voltage coefficient g31
"○", is "×" by the less sample labelings of piezoelectric voltage coefficient g31.Related judgement is the sample of "○" applied to various
In the case of sensor, compared with the sensor for applying PZT, expect to see the superiority of its performance.
Test example 1
For 1~sample of sample 11, using laser displacement instrument under room temperature (25 DEG C), electrode area 0.3cm is used2Electricity
Pole figure case, applies frequency 100Hz, voltage 20V triangular wave, to obtain displacement, and the results are shown in table 1.In addition, cantilever
Size be total length 1.5cm, width 0.4cm, 625 μm of substrate thickness.
It can be seen from the result of table 1, PNN content for the 1~samples of sample 6 of more than 1 [mol%] 5 [mol%] below with
Sample 11 is compared, and displacement is larger.
On the other hand, it can be seen from the result of table 1, PNN content is 6 [mol%] sample 7 and 0.5 [mol%]
Sample 8 is compared with sample 11, and displacement is smaller.Also, understand to be free of the sample 9 of any one and sample in Ni and Nb
10 compared with sample 11, and displacement is smaller.In addition, the mol ratio for understanding sample 9 and sample 10 and Ni and Nb is 1：2 sample
1~sample 6 is compared, and displacement is smaller.
Test example 2
Apply ± 80V voltage for 1~sample of sample 11, obtain relation (the I-V songs between current density and voltage
Line)." 4140B " that the measure of I-V curve is produced using Hewlett-Packard and retention time when making measure for 2 seconds in atmosphere
Carry out.Also, determine using the probe after shading and exclude the influence of photoelectromotive force etc. and carry out.Then, according to resulting
I-V curve obtain the leakage current applied in voltage 20V, and the results are shown in table 1.
It can be seen from the result of table 1, PNN content is the 1~samples of sample 3 of more than 1 [mol%] 2.5 [mol%] below
Compared with sample 11, leakage current is smaller.In addition, understand PNN content for the following samples 4 of more than 3 [mol%] 5 [mol%]~
Sample 6 and the leakage current that sample 11 is same degree.
On the other hand, it can be seen from the result of table 1, PNN content for 6 [mol%] sample 7 compared with sample 11, leakage
Electric current is larger.In addition, understanding 0.5 [mol%] sample 8 and the leakage current that sample 11 is same degree.In addition, understanding to be free of Ni
And the sample 9 and sample 10 of any one in Nb, compared with sample 11, leakage current is larger.In addition, understand sample 9 and
Sample 10 and Ni and Nb mol ratio is 1：2 1~sample of sample 8 is compared, and leakage current is larger.
Test example 3
For 1~sample of sample 8 and sample 11, five performance indications (piezoelectric strain coefficient d, the pressure of piezoelectric are calculated
Piezoelectric voltage coefficient g, electromechanical coupling factor k, mechanical quality coefficient Qm, acoustic impedance Z) one of piezoelectric voltage coefficient g, to evaluate pressure
Electrical property.In addition, in this test example, calculating piezoelectric voltage coefficient g31.Piezoelectric voltage coefficient g31 is asked by following formula (5)
.
G31=d31/ (ε0×K)……(5)
In formula, d31 represents piezoelectric strain coefficient, ε0The dielectric constant of vacuum is represented, K represents relative dielectric constant.
In addition, the piezoelectric strain coefficient d31 of formula (5) is tried to achieve by following formula (6).
In formula, hisRepresent Si substrate thickness, S11PiezoRepresent compliance (the Young mould of=piezoelectric body layer 70 of piezoelectric body layer 70
The inverse of amount), δ represent that displacement, L represent jib-length, S11SiThe compliance of expression Si substrates be (Young's modulus of=Si substrates
It is reciprocal), V represents to apply voltage.
In test example 3, the Young mould of the piezoelectric body layer 70 of 1~sample of sample 8 and sample 11 is determined by resonance method
Amount.Here, resonance method refers to apply test specimen mechanical or electric forced vibration to measure resonant frequency (intrinsic vibration frequency
Rate), and calculate according to the resonant frequency determination method of Young's modulus (longitudinal elastic coefficient).In this test example, using altogether
Most common free oscillation is measured in method of shaking.Specifically, cutting processing is become band using two messenger wires (3mm ×
Sample 40mm) is kept, and electric capacity is formed between driving stage and test specimen, thus intrinsic vibration is produced, passes through vibrating sensing
Device detects the intrinsic vibration, so as to obtain Young's modulus and be shown in table 2.According to resulting Young's modulus and in experiment
The displacement determined in example 1, piezoelectric strain coefficient d31 is calculated based on formula (6), and piezoelectric voltage coefficient is calculated based on formula (5)
G31 is simultaneously shown in table 2.In addition, the thickness and relative dielectric constant of the piezoelectric body layer 70 of 1~sample of sample 8 and sample 11
As shown in table 2.
It can be seen from the result of table 2, PNN content for the 1~samples of sample 6 of more than 1 [mol%] 5 [mol%] below with
Sample 11 is compared, and piezoelectric voltage coefficient g31 is larger.On the other hand, it is known that PNN content is 6 [mol%] sample 7 and 0.5
The sample 8 of [mol%] is compared with sample 11, and piezoelectric voltage coefficient g31 is smaller.
Other embodiment
In above-mentioned embodiment 1, enumerate ink jet recording head to carry out as an example of jet head liquid
Illustrate, but the present invention can also apply to spray the jet head liquid of the liquid beyond ink certainly.Beyond injection ink
Liquid jet head liquid, color material used in the manufacture of the chromatic filter such as can include liquid crystal display
Material injector head, organic el display, FED (field-emitter display) etc. electrode formed used in electrode material injector head,
The injection of organism organic matter is first-class used in the manufacture of biochip.
In addition, in above-mentioned embodiment 1, as an example of piezoelectric element application apparatus, enumerating and being equipped on liquid
The jet head liquid of injection apparatus is illustrated, but the application of the present invention is not limited to this.
For example, also ultrasonic measurement device can be constituted by possessing the piezoelectric element of the present invention and controlling organization, its
In, above-mentioned controlling organization utilizes the ultrasonic wave sent based on the piezoelectric element by the present invention and the piezoelectricity member for passing through the present invention
The signal of at least one party in the ultrasonic wave that part is received, to determine detection object.
Such ultrasonic measurement device based on from send ultrasonic wave at the time of to receive its transmission ultrasonic wave be measured
Time untill at the time of the echo-signal that object is reflected, obtain the position with measuring object, shape and speed
Deng related information, sometimes as be used to producing the element of ultrasonic wave, the element for detecting echo-signal and use piezoelectricity first
Part.It is used as such ultrasonic wave generating element, detection of the backscatter signal element, using the teaching of the invention it is possible to provide the ultrasound with excellent placement property
Ripple determines device.
In addition, the piezoelectric element application apparatus of the present invention can also be supersonic motor, temperature-electric transducer, pressure-electricity
The cut-off filter of harmful light such as converter, piezoelectric transformer, infrared ray, the photon that produces because of quantum dot formation is used
Filters such as the optical light filter of crystal effect, the optical light filter of the interference of light that make use of film etc..Alternatively, it is also possible to being super
Sensor beyond Sound wave measurement device (ultrasonic sensor), e.g. infrared ray sensor, heat-sensitive sensor, pressure sensing
Device, gyro sensor (angular-rate sensor).
In addition, the present invention can also be preferably used as ferroelectric element., can be with as the ferroelectric element that can be preferably used
Include ferroelectric storage, ferroelectricity body transistor (FeFET), ferroelectric computing circuit (FeLogic), ferroelectric capacitor
Deng.In addition, the piezoelectric element of the present invention shows good pyroelecthc properties, so thermoelectric element can be preferably used as.Also, this hair
Bright robot that can also apply to utilize by driving source of above-mentioned motor etc..
Description of reference numerals：I ... tape decks；II ... head units；S ... recording sheets；1 ... record head；2A, 2B ... ink
Box；3 ... balladeur trains；4 ... apparatus main bodies；5 ... balladeur train axles；6 ... motors；7 ... timing belts；8 ... conveying rollers；10 ... streams are formed
Substrate (substrate)；11 ... next doors；12 ... pressure generating chamber；13 ... ink supply road；14 ... access；15 ... interconnecting parts；20…
Nozzle plate；21 ... nozzle openings；30 ... protective substrates；32 ... manifold portions；33 ... through holes；35 ... bonding agents；40 ... flexible bases
Plate；41 ... diaphragm seals；42 ... fixed plates；43 ... opening portions；50 ... oscillating plates；51 ... elastic membranes；52 ... insulator films；53 ... cover
Mould film；56 ... adhesion coatings；60 ... first electrodes；70 ... piezoelectric body layers；74 ... piezoelectric body films；80 ... second electrodes；90a、90b…
Lead electrode；100 ... manifolds；110 ... silicon substrates；130 ... protective substrate chips；300 ... piezoelectric elements.
Claims (4)
1. a kind of piezoelectric element, it is characterised in that
Possess first electrode, second electrode and the piezoelectric body layer being arranged between the first electrode and the second electrode,
Perovskite composite oxide of the piezoelectric body layer represented by following formula (1) is constituted, the Ca-Ti ore type composite oxygen
The content of Ni and Nb in compound it is total relative to being more than 1 [mol%] 5 in the total content of the element contained by B
[mol%] below,
Pb (Ni, Nb, Zr, Ti) O3……(1)。
2. piezoelectric element according to claim 1, it is characterised in that
Perovskite composite oxide of the piezoelectric body layer represented by following formula (2) is constituted,
XPb (Ni, Nb) O3- (1-x) Pb (Zr, Ti) O3... (2),
In formula, 0.01≤x≤0.05 is met.
3. piezoelectric element according to claim 1 or 2, it is characterised in that
For the piezoelectric body layer, the Ni contained by perovskite composite oxide represented by the formula (1) or formula (2)
Mol ratio with Nb is 1：2.
4. a kind of piezoelectric element application apparatus, it is characterised in that
Possesses the piezoelectric element described in any one in claims 1 to 3.
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| JP2015191995 | 2015-09-29 | ||
| JP2015-191995 | 2015-09-29 | ||
| JP2016-145733 | 2016-07-25 | ||
| JP2016145733A JP2017069545A (en) | 2015-09-29 | 2016-07-25 | Piezoelectric element and piezoelectric element-applied device |
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| CN107068848A true CN107068848A (en) | 2017-08-18 |
| CN107068848B CN107068848B (en) | 2019-06-18 |
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|---|---|---|---|---|
| CN111830295A (en) * | 2019-04-18 | 2020-10-27 | 云谷（固安）科技有限公司 | Device for testing electric performance of micro-element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4765919A (en) * | 1984-12-17 | 1988-08-23 | Nippon Soken, Inc. | Piezoelectric ceramic materials |
| US20070197370A1 (en) * | 2006-02-23 | 2007-08-23 | Fujifilm Corporation | Lead zirconate titanate type composition, process for producing the same, piezoelectric body, and piezoelectric device |
-
2016
- 2016-07-25 JP JP2016145733A patent/JP2017069545A/en active Pending
- 2016-09-27 CN CN201610855455.0A patent/CN107068848B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4765919A (en) * | 1984-12-17 | 1988-08-23 | Nippon Soken, Inc. | Piezoelectric ceramic materials |
| US20070197370A1 (en) * | 2006-02-23 | 2007-08-23 | Fujifilm Corporation | Lead zirconate titanate type composition, process for producing the same, piezoelectric body, and piezoelectric device |
Non-Patent Citations (2)
| Title |
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| FANG B. J., ET AL: "Development of perovskite structure and electrical properties of Pb(Zr1/2Ti1/2)O3-Pb(Ni1/3Nb2/3)O3 system", 《THE EUROPEAN PHYSICAL JOURNAL-APPLIED PHYSICS》 * |
| REN XUE-TING, ET AL: "Crystal Structures and Properties of Pb(Ni1/3,Nb2/3)O3–Pb(Zr1/2,Ti1/2)O3 Thin Films on Silicon Substrates", 《ENERGY HARVESTING AND SYSTEMS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111830295A (en) * | 2019-04-18 | 2020-10-27 | 云谷（固安）科技有限公司 | Device for testing electric performance of micro-element |
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| JP2017069545A (en) | 2017-04-06 |
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