WO2015146877A1 - CeドープのPZT系圧電体膜 - Google Patents
CeドープのPZT系圧電体膜 Download PDFInfo
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- WO2015146877A1 WO2015146877A1 PCT/JP2015/058666 JP2015058666W WO2015146877A1 WO 2015146877 A1 WO2015146877 A1 WO 2015146877A1 JP 2015058666 W JP2015058666 W JP 2015058666W WO 2015146877 A1 WO2015146877 A1 WO 2015146877A1
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- WIPO (PCT)
- Prior art keywords
- piezoelectric film
- pzt
- film
- source
- doped pzt
- Prior art date
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- 230000010287 polarization Effects 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 58
- 239000000203 mixture Substances 0.000 description 49
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- 230000000052 comparative effect Effects 0.000 description 30
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 29
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- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- SQNZLBOJCWQLGQ-UHFFFAOYSA-N 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F SQNZLBOJCWQLGQ-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a PZT-based piezoelectric film doped with Ce and used for piezoelectric elements, IPDs, pyroelectric elements, gyro sensors, vibration power generation elements, actuators, and the like.
- Patent Document 1 as a composition for forming a ferroelectric thin film for forming one kind of ferroelectric thin film selected from the group consisting of PLZT, PZT, and PT, the general formula is (Pb x La y ) (Zr the z Ti (1-z)) O 3 composite metal oxide a represented, the liquid composition for forming a thin film in the form of a mixed composite metal oxide mixed composite metal oxide B containing Ce is It is disclosed.
- the liquid composition is dissolved in an organic solvent in such a ratio that the raw material for constituting the composite metal oxide A and the raw material for constituting the composite metal oxide B give the metal atomic ratio represented by the above general formula.
- a composition for forming a ferroelectric thin film comprising an organometallic compound solution.
- x, y and z in the above general formula satisfy 0.9 ⁇ x ⁇ 1.3, 0 ⁇ y ⁇ 0.1 and 0 ⁇ z ⁇ 0.9, respectively. .
- a ferroelectric thin film When a ferroelectric thin film is formed using the composition for forming a ferroelectric thin film thus configured, it has a relative dielectric constant comparable to that of a general ferroelectric thin film and a low leakage current density.
- a ferroelectric thin film suitable for high capacity density thin film capacitor applications can be obtained by a simple technique. Therefore, when the leakage current density is about the same as that of a general ferroelectric thin film, it is possible to further reduce the film thickness and obtain a higher relative dielectric constant.
- Non-Patent Document 1 the effect exerted when Nb is doped to a ⁇ 100 ⁇ oriented PZT thin film grown on a PbTiO 3 seed layer prepared by a chemical solution deposition (CSD) method is studied. It was done. Specifically, the effect of doping Nb in the range of 0 to 4 atomic% in a 1 ⁇ m thick Pb 1.1 Zr 0.52 Ti 0.48 O 3 thin film oriented in ⁇ 100 ⁇ was studied.
- JP 2010-206151 A (Claim 1, paragraph [0022])
- the ferroelectric thin film forming composition disclosed in Patent Document 1 cannot be used as a piezoelectric body immediately after forming a ferroelectric thin film using this composition.
- a high voltage was applied, so that polarization treatment was necessary.
- the polarization treatment is performed, there is a risk that the polarization may be depolarized during a subsequent heat treatment such as a reflow process, and there is a problem that polarization stability is low.
- a first object of the present invention is to provide a Ce-doped PZT piezoelectric film capable of improving the piezoelectric constant of the piezoelectric film and reducing the dielectric constant by doping with Ce. It is in.
- the second object of the present invention is to control the film orientation together with Ce doping, so that the polarization direction is aligned immediately after film formation, thereby improving the stability of polarization after device formation. It is an object of the present invention to provide a Ce-doped PZT-based piezoelectric film in which the polarization direction is further aligned immediately after film formation by controlling the orientation, thereby further improving the polarization stability.
- the first aspect of the present invention have the general formula: Pb z Ce x Zr y Ti 1-y O 3 made of a composite metal oxide of Ce-doped represented by, in the general formula x, y and z are 0. It is a Ce-doped PZT-based piezoelectric film that satisfies 005 ⁇ x ⁇ 0.05, 0.40 ⁇ y ⁇ 0.55, and 0.95 ⁇ z ⁇ 1.15.
- the second aspect of the present invention is an invention relating to a PZT-based piezoelectric film based on the first aspect, and it is preferable that the hysteresis of the polarization amount further shifts from the center to the negative side by 4 kV / cm or more.
- the third aspect of the present invention is an invention relating to a PZT-based piezoelectric film based on the first or second aspect, and it is preferable that the (100) orientation degree by X-ray diffraction is 80% or more.
- a fourth aspect of the present invention is an invention relating to a PZT-based piezoelectric film based on any one of the first to third aspects.
- the film thickness is preferably 1000 nm or more and 5000 nm or less.
- the piezoelectric constant can be improved by doping with Ce, so that a larger displacement can be obtained and the dielectric constant can be lowered.
- the gain increases. This is because the domain is pinned by doping Ce into the (100) / (001) oriented film with respect to the normal direction of the lower electrode, and the polarization direction is aligned downward immediately after film formation. It is thought that.
- the Ce-doped PZT piezoelectric film of the present invention can be operated as a device without polarization by applying a voltage to the positive side.
- the Ce-doped PZT-based piezoelectric film of the present invention is used as a gyro sensor or the like, the polarization process is not required, so that the number of manufacturing steps can be reduced.
- the PZT-based piezoelectric film according to the third aspect of the present invention by setting the (100) orientation degree by X-ray diffraction to 80% or more, a piezoelectric film with a more uniform polarization direction can be formed immediately after film formation, The stability of polarization can be further improved.
- a Ce-doped PZT-based piezoelectric film is formed on the LNO film whose crystal orientation is preferentially controlled on the (100) plane by the CSD method, whereby the orientation of the piezoelectric film is (100 ), And a piezoelectric film having a more uniform polarization direction can be formed immediately after film formation, and the stability of polarization can be further improved.
- PZT piezoelectric film of Ce dope of the present invention have the general formula: comprising a composite metal oxide of Pb z Ce x Zr y Ti 1 -y O 3 with Ce doped shown. And x, y, and z in the above general formula satisfy 0.005 ⁇ x ⁇ 0.05, 0.40 ⁇ y ⁇ 0.55, and 0.95 ⁇ z ⁇ 1.15, respectively.
- This Ce-doped PZT-based piezoelectric film is a piezoelectric film obtained by adding a Ce element to a composite metal oxide having a Pb-containing perovskite structure such as lead zirconate titanate (PZT).
- the Ce-doped PZT precursor contained in the composition for forming the Ce-doped PZT-based piezoelectric film is a raw material for constituting the composite metal oxide and the like in the formed piezoelectric film. These are included in proportions that provide the desired metal atomic ratio.
- the metal atomic ratio (Pb: Ce: Zr: Ti) in the composition is (1.00 to 1.20) :( 0.005 to 0.05) :( 0.40 to 0). .55): the PZT-based precursor is included at a ratio satisfying (0.60 to 0.45) and a total ratio of the metal atomic ratio of Zr to Ti of 1.
- x in the general formula is limited to the range of 0.005 ⁇ x ⁇ 0.05 is that the polarization direction of the piezoelectric film immediately after film formation cannot be sufficiently aligned if it is less than 0.005. If it exceeds 0.05, cracks are likely to occur in the piezoelectric film.
- y in the general formula is limited to the range of 0.40 ⁇ y ⁇ 0.55 when the piezoelectric constant of the piezoelectric body is not sufficiently increased when the value is less than 0.40, and when 0.55 is exceeded. This is because the polarization direction of the piezoelectric film immediately after the film is not uniform.
- z in the general formula is limited to the range of 0.95 ⁇ z ⁇ 1.15 is that when it is less than 0.95, a large amount of pyrochlore phase is contained in the film, and electrical characteristics such as piezoelectric characteristics are obtained. If it exceeds 1.15, a large amount of PbO remains in the fired film, and the leakage current increases and the electrical reliability of the film decreases. This is because lead tends to remain and deteriorates leakage characteristics and insulation characteristics.
- x, y, and z in the general formula preferably satisfy 0.01 ⁇ x ⁇ 0.03, 0.50 ⁇ y ⁇ 0.52, and 0.99 ⁇ z ⁇ 1.05, respectively.
- the hysteresis of the polarization amount of the Ce-doped PZT-based piezoelectric film is preferably shifted from the center to the negative side by 4 kV / cm or more, more preferably 9 to 15 V / cm.
- the center refers to zero bias.
- the center of hysteresis is the following when the absolute value of the coercive electric field on the positive side and negative side is Ec + and Ec ⁇ in the graph where the X axis is the electric field (kV / cm) and the Y axis is the polarization ( ⁇ C / cm 2 ). It is expressed by the following formula.
- the Ce-doped PZT-based piezoelectric film has a (100) degree of orientation by X-ray diffraction of preferably 80% or more, and more preferably 95% or more.
- the upper limit of the (100) orientation degree is 100%.
- the thickness of the Ce-doped PZT-based piezoelectric film is preferably 1000 nm or more and 5000 nm or less, and more preferably 2000 nm or more and 3000 nm or less.
- the shift amount of the hysteresis of the polarization amount of the Ce-doped PZT-based piezoelectric film is limited to 4 kV / cm or more from the center to the negative side because the polarization direction is not sufficiently aligned at less than 4 kV / cm. is there.
- the reason why the degree of (100) orientation by X-ray diffraction of the Ce-doped PZT-based piezoelectric film is limited to 80% or more is that if it is less than 80%, a sufficient hysteresis shift is not observed.
- the thickness of the Ce-doped PZT-based piezoelectric film is limited to the range of 1000 nm or more and 5000 nm or less because sufficient piezoelectric characteristics cannot be obtained if the film thickness is less than 1000 nm, and productivity decreases if the film thickness exceeds 5000 nm. It is.
- Ce-doped PZT-based precursor a compound in which an organic group is bonded to each metal element of Pb, Ce, Zr, and Ti via an oxygen or nitrogen atom is used as each metal source (Pb source, (Ce source, Zr source, and Ti source).
- Pb source, (Ce source, Zr source, and Ti source a compound in which an organic group is bonded to each metal element of Pb, Ce, Zr, and Ti via an oxygen or nitrogen atom is used as each metal source (Pb source, (Ce source, Zr source, and Ti source).
- Pb source Ce source, Zr source, and Ti source
- metal alkoxide metal diol complex
- metal triol complex metal carboxylate
- metal ⁇ -diketonate complex metal ⁇ -diketoester complex
- metal ⁇ -iminoketo complex metal amino complex Or 2 or more types
- Particularly suitable compounds are metal alkoxides, partial hydrolysates thereof, and organic acid salts.
- examples of the Pb compound include acetates such as lead acetate: Pb (OAc) 2 and alkoxides such as lead diisopropoxide: Pb (OiPr) 2 .
- examples of Ce compounds include organic acid salts such as cerium 2-ethylhexanoate and cerium 2-ethylbutyrate, alkoxides such as cerium tri-n-butoxide and cerium triethoxide, and metal ⁇ such as tris (acetylacetonate) cerium. -Diketonate complexes.
- Ti compounds include titanium tetraethoxide: Ti (OEt) 4 , titanium tetraisopropoxide: Ti (OiPr) 4 , titanium tetra n-butoxide: Ti (OnBu) 4 , titanium tetraisobutoxide: Ti (OiBu). 4 , alkoxides such as titanium tetra-t-butoxide: Ti (OtBu) 4 and titanium dimethoxydiisopropoxide: Ti (OMe) 2 (OiPr) 2 .
- the same alkoxides as the Ti compound namely, zirconium tetraethoxide: Zr (OEt) 4 , zirconium tetraisopropoxide: Zr (OiPr) 4 , zirconium tetra n-butoxide: Zr (OnBu) 4 Zirconium tetraisobutoxide: Zr (OiBu) 4 , zirconium tetra-t-butoxide: Zr (OtBu) 4 , zirconium dimethoxydiisopropoxide: Zr (OMe) 2 (OiPr) 2 and the like are preferable.
- the metal alkoxide may be used as it is, a partially hydrolyzed product thereof may be used in order to promote decomposition.
- the composition for forming the Ce-doped PZT-based piezoelectric film preferably contains a diol and polyvinyl pyrrolidone or polyethylene glycol in addition to the Ce-doped PZT-based precursor.
- the diol contained in the composition is a component that serves as a solvent for the composition. Specific examples include propylene glycol, ethylene glycol, or 1,3-propanediol. Of these, propylene glycol or ethylene glycol is preferred.
- diol as an essential solvent component, the storage stability of the composition can be enhanced.
- Polyvinyl pyrrolidone (PVP) or polyethylene glycol may be added as a crack suppressing material.
- the composition for forming the Ce-doped PZT-based piezoelectric film may contain a linear monoalcohol.
- a linear monoalcohol having 6 to 12 carbon atoms is particularly preferable because of its low affinity with the PZT precursor and low vapor pressure.
- solvents include carboxylic acids, alcohols (eg, polyhydric alcohols other than ethanol, 1-butanol and diol), esters, ketones (eg, acetone, methyl ethyl ketone), ethers (eg, dimethyl ether, diethyl ether). ), Cycloalkanes (for example, cyclohexane, cyclohexanol), aromatic (for example, benzene, toluene, xylene), other tetrahydrofuran, etc., and a mixture obtained by further adding one or more of these to a diol It can also be a solvent.
- alcohols eg, polyhydric alcohols other than ethanol, 1-butanol and diol
- esters eg, ketones (eg, acetone, methyl ethyl ketone), ethers (eg, dimethyl ether, diethyl ether).
- ketones eg, acetone,
- carboxylic acid examples include n-butyric acid, ⁇ -methylbutyric acid, i-valeric acid, 2-ethylbutyric acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,3-dimethylbutyric acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2,2-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2- Ethylhexanoic acid and 3-ethylhexanoic acid are preferably used.
- ester ethyl acetate, propyl acetate, n-butyl acetate, sec-butyl acetate, tert-butyl acetate, isobutyl acetate, n-amyl acetate, sec-amyl acetate, tert-amyl acetate, isoamyl acetate are used.
- alcohol 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butyl alcohol, 1-pentanol, 2-pentanol, 2-methyl-2-pentanol, 2-methoxy It is preferred to use ethanol.
- ⁇ -diketones for example, acetylacetone, heptafluorobutanoylpivaloylmethane, dipivaloylmethane, trifluoroacetylacetone, benzoylacetone, etc.
- Ketone acids for example, acetoacetic acid, propionyl acetic acid, benzoylacetic acid, etc.
- ⁇ -ketoesters for example, lower alkyl esters of the above ketone acids such as methyl, propyl, butyl, etc.
- oxyacids for example, lactic acid, glycolic acid) , ⁇ -oxybutyric acid, salicylic acid, etc.
- lower alkyl esters of the above oxyacids, oxyketones eg, diacetone alcohol, acetoin, etc.
- diols, triols higher carboxylic acids, alkanolamines (eg, diethanolamine, triethanol) Am
- PZT-based precursors such as the Pb compound described above are prepared, and these are weighed so as to have a ratio that gives the desired metal atomic ratio.
- the above-mentioned weighed PZT precursor and diol are put into a reaction vessel and mixed, and a synthetic solution is preferably prepared by refluxing and reacting at a temperature of 130 to 175 ° C. for 0.5 to 3 hours in a nitrogen atmosphere. To do. After the reflux, it is preferable to remove the solvent by a method of atmospheric distillation or vacuum distillation.
- a stabilizer such as acetylacetone
- ⁇ ⁇ A linear monoalcohol is added to the cooled synthesis solution to prepare a sol-gel solution.
- the concentration of the PZT precursor in 100% by mass of the composition is adjusted to be 17 to 35% by mass in terms of oxide concentration, and the proportion of diol is adjusted to be 16 to 56% by mass.
- a solvent other than diol is added to the sol-gel solution.
- the sol-gel solution is refluxed again in a predetermined atmosphere, for example, in a nitrogen atmosphere at a temperature of 100 to 175 ° C. for 0.5 to 10 hours.
- the Ce-doped PZT-based piezoelectric film forming composition of the present invention is obtained.
- the PZT-based precursor 1 mol of Ce-doped, indicating that Pb z Ce x Zr y Ti 1 -y O 3 contained in the precursor is 1 mol.
- the monomer conversion is a value obtained by converting the molecular weight of the polymer using the molecular weight of the monomer constituting the polymer as a reference (1 mol).
- the number of particles having a particle size of 0.5 ⁇ m or more is 50 or less per milliliter of the composition It is preferable to do this. If the number of particles having a particle size of 0.5 ⁇ m or more in the composition exceeds 50 particles per milliliter of the composition, the long-term storage stability becomes poor.
- the number of particles having a particle size of 0.5 ⁇ m or more in the composition is preferably as small as possible, and particularly preferably 30 or less per milliliter of the composition. In addition, it is preferable that particles having a size of 0.2 ⁇ m or more in the composition are removed by removing the particles by filtration or the like.
- a light scattering particle counter is used for measuring the number of particles in the composition.
- the method of treating the composition after adjusting the number of particles to be in the above range is not particularly limited, and examples thereof include the following methods.
- the first method is a filtration method in which a commercially available membrane filter having a pore size of 0.2 ⁇ m is used and pressure-fed with a syringe.
- the second method is a pressure filtration method combining a commercially available membrane filter having a pore diameter of 0.05 ⁇ m and a pressure tank.
- the third method is a circulation filtration method in which the filter used in the second method and the solution circulation tank are combined.
- the particle capture rate by the filter varies depending on the pressure of the composition. It is generally known that the lower the pressure, the higher the capture rate.
- the number of particles having a particle size of 0.5 ⁇ m or more is 50 per milliliter of the composition. In order to achieve the following conditions, it is preferable to pass the composition through the filter very slowly at low pressure.
- This forming method is a method for forming a piezoelectric film by a sol-gel method, and the above-described composition for forming a Ce-doped PZT-based piezoelectric film of the present invention is used as a raw material solution.
- the Ce-doped PZT piezoelectric film forming composition is applied onto a substrate to form a coating film (gel film) having a desired thickness.
- the coating method is not particularly limited, and examples thereof include spin coating, dip coating, LSMCD (Liquid Source Misted Chemical Deposition) method, and electrostatic spraying method.
- a heat resistant substrate such as a silicon substrate or a sapphire substrate on which an orientation control film and a lower electrode are formed is used.
- the orientation control film formed on the substrate is formed of an LNO film (LaNiO 3 film) whose crystal orientation is preferentially controlled on the (100) plane.
- the lower electrode formed on the substrate is made of a material having conductivity such as Pt, TiO x , Ir, and Ru and that does not react with the piezoelectric film.
- the lower electrode can have a two-layer structure of a TiO x film and a Pt film in order from the substrate side.
- a specific example of the TiO x film is a TiO 2 film.
- an SiO 2 film can be formed on the substrate surface.
- this coating film is calcined and further baked for crystallization.
- the calcination is performed under a predetermined condition using a hot plate or a rapid heating process (RTA).
- RTA rapid heating process
- the calcination is performed in order to remove the solvent and to convert the metal compound into a composite oxide by thermal decomposition or hydrolysis, and is therefore preferably performed in air, in an oxidizing atmosphere, or in a steam-containing atmosphere. Even in heating in the air, the moisture required for hydrolysis is sufficiently secured by the humidity in the air.
- low temperature heating may be performed at a temperature of 70 to 90 ° C. for 0.5 to 5 minutes using a hot plate or the like.
- Firing is a process for firing and crystallizing the coating film after calcination at a temperature equal to or higher than the crystallization temperature, whereby a piezoelectric film is obtained.
- the firing atmosphere in this crystallization step is preferably O 2 , N 2 , Ar, N 2 O, H 2, or a mixed gas thereof.
- Firing is performed at 600 to 700 ° C. for about 1 to 5 minutes.
- Firing may be performed by rapid heat treatment (RTA). In the case of firing by rapid heating treatment (RTA), the rate of temperature rise is preferably 2.5 to 100 ° C./second.
- the PZT-based piezoelectric film-forming composition contains a linear monoalcohol such as 1 octal
- FIGS. 1 (e) the liquid inside the gel film is raised to the vicinity of the surface by capillary force, and the gel is dried and baked to form a dense crystal film having no voids inside.
- a linear monoalcohol such as 1 octal is evaporated by capillary force, so that the first temporary as shown in FIG. 1 (c). Appropriate gaps are formed in the fired film.
- the first calcined film is further heated, as shown in FIG.
- FIGS. 2 (a) to 2 (d) when there is no solvent that evaporates by capillary force such as 1-octanol and evaporates, it is shown in FIGS. 2 (a) to (c). As shown, no gap is formed inside the calcined film, and diamond-like carbon is generated in the calcined film (FIG. 2D). This diamond-like carbon causes voids (FIG. 2 (e)) to be generated in the crystal film after firing.
- the Ce-doped PZT-based piezoelectric film of the present invention is preferably used as a constituent material (electrode) in composite electronic parts such as piezoelectric elements, IPDs, pyroelectric elements, gyro sensors, vibration power generation elements, and actuators. Can do.
- the Ce-doped PZT piezoelectric film of the present invention can be operated as a device without polarization by applying a voltage to the positive side. Further, when the Ce-doped PZT-based piezoelectric film of the present invention is used as a gyro sensor or the like, the polarization process is not required, so that the number of manufacturing steps can be reduced.
- the Ce-doped PZT-based piezoelectric film of the present invention is manufactured through a high-temperature firing of 600 to 700 ° C., a device using the piezoelectric film is exposed to a high temperature for reflow soldering. However, the piezoelectric characteristics are not lost.
- each molecule 11 a in the piezoelectric film 11 is polarized before the DC voltage 14 is applied between the electrodes 12 and 13 disposed on both surfaces of the piezoelectric film 11.
- the state is maintained (FIG. 3A).
- the orientation of the piezoelectric film becomes the (100) plane.
- a piezoelectric film having a uniform polarization direction can be formed immediately after film formation.
- the piezoelectric film formed on the LNO film can be applied to a gyro sensor or the like.
- FIG. 3B when a voltage is applied between the electrodes 12 and 13 respectively disposed on both surfaces of the piezoelectric film 11, the piezoelectric film 11 extends in the direction in which the voltage is applied, and this voltage is increased.
- the piezoelectric film 11 extending in the direction in which the voltage is applied contracts and returns to its original state (FIG. 3A), and can be applied to a piezoelectric element or the like.
- the piezoelectric film having the characteristic of extending in the direction in which the voltage is applied is described.
- a piezoelectric film having the characteristic of extending in the direction orthogonal to the direction in which the voltage is applied may be used.
- Example 1 First, lead acetate trihydrate (Pb source) and propylene glycol (diol) are placed in a reaction vessel and refluxed at a temperature of 150 ° C. for 1 hour in a nitrogen atmosphere. Then, cerium 2-ethylhexanoate is placed in the reaction vessel. (Ce source), zirconium tetrabutoxide (Zr source), titanium tetraisopropoxide (Ti source) and acetylacetone (stabilizer) are further added and refluxed at a temperature of 150 ° C. for 1 hour in a nitrogen atmosphere. Thus, a synthesis solution was prepared.
- Pb source lead acetate trihydrate
- diol propylene glycol
- Ce source zirconium tetrabutoxide
- Ti source titanium tetraisopropoxide
- stabilizer acetylacetone
- the lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source), and titanium tetraisopropoxide (Ti source) are Ce-doped PZT.
- the system precursor was weighed so that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.005: 0.40: 0.60.
- Propylene glycol (diol) is added to 35% by mass with respect to 100% by mass of the Ce-doped PZT precursor, and acetylacetone (stabilizer) is 2% with respect to 1 mol of Ce-doped PZT precursor. It added so that it might become a mole.
- the concentration of the Ce-doped PZT precursor in 100% by mass of the synthesis solution was 35% in terms of oxide concentration.
- the oxide concentration in the concentration of the Ce-doped PZT precursor in the synthesis solution was calculated on the assumption that all the metal elements contained in the synthesis solution became the target oxide. This refers to the concentration of metal oxide in mass%.
- the synthesis solution was allowed to cool to room temperature by cooling at room temperature.
- 1-octanol linear monoalcohol having 8 carbon atoms
- ethanol solvent
- the concentration of the Ce-doped PZT precursor in 100% by mass of the sol-gel solution is oxidized.
- a sol-gel solution having an object concentration of 25% by mass was obtained.
- 1-octanol (linear monoalcohol having 8 carbon atoms) and ethanol (solvent) were added to the synthesis solution until the target concentration was reached.
- the oxide concentration in the concentration of the Ce-doped PZT-based precursor in the sol-gel solution was calculated on the assumption that all metal elements contained in the sol-gel solution became the target oxide. This refers to the concentration of metal oxide in mass%.
- PVP polyvinyl pyrrolidone
- This composition used a commercially available membrane filter having a pore size of 0.05 ⁇ m, and was pressure-fed with a syringe and filtered, whereby the number of particles having a particle size of 0.5 ⁇ m or more was 1 per 1 ml of the solution.
- the concentration of the Ce-doped PZT precursor in 100% by mass of the composition was 25% by mass in terms of oxide concentration.
- 1-octanol linear monoalcohol having 8 carbon atoms
- the k value is a viscosity characteristic value that correlates with the molecular weight, and is a value calculated by applying a relative viscosity value (25 ° C.) measured by a capillary viscometer to the following Fikentscher equation.
- k value (1.5 log ⁇ rel ⁇ 1) / (0.15 + 0.003c) + (300 clog ⁇ rel + (c + 1.5 clog ⁇ rel) 2 ) 1/2 /(0.15c+0.003c 2 )
- ⁇ rel indicates the relative viscosity of the aqueous polyvinylpyrrolidone solution with respect to water
- c indicates the polyvinylpyrrolidone concentration (mass%) in the aqueous polyvinylpyrrolidone solution.
- the composition obtained is composed of SiO 2 film, TiO 2 film, Pt film and LNO film (orientation control film: LaNiO 3 whose crystal orientation is controlled preferentially on the (100) plane) from the bottom to the top.
- a coating film (gel film) is formed on the LNO film by dropping onto the LNO film on the top layer of the silicon substrate that is sequentially laminated and set on the spin coater, and performing spin coating at a rotational speed of 2100 rpm for 60 seconds. did.
- the silicon substrate on which this coating film (gel film) is formed is heated and held (dried) at 65 ° C. for 2 minutes using a hot plate to remove the low boiling point solvent and water, and then the 300 ° C.
- the gel film is thermally decomposed by heating and holding for 5 minutes (first stage calcination), and further heated and held for 5 minutes (second stage calcination) on a hot plate at 450 ° C. Residual organic matter and adsorbed water were removed. In this way, a calcined film (Ce-doped PZT amorphous film) having a thickness of 200 nm was obtained. By repeating the same operation twice as above, a calcined film having a thickness of 400 nm was obtained. Next, the silicon substrate on which the 400 nm-thick calcined film was formed was fired by being held at 700 ° C. for 1 minute in an oxygen atmosphere by rapid heating treatment (RTA).
- RTA rapid heating treatment
- the temperature rising rate at this time was 10 ° C./second.
- a Ce-doped PZT film having a thickness of 400 nm was formed on the LNO film (orientation control film).
- the above operation was repeated 5 times to produce a Ce-doped PZT piezoelectric film having a final film thickness of 2000 nm.
- the film thickness of the piezoelectric film was measured by SEM (manufactured by Hitachi, Ltd .: S4300) as a cross-sectional thickness (total thickness) of the piezoelectric film.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.40: 0.60
- a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.40: 0.60, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.40 Ti 0.60 O 3 .
- Example 2 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.005: 0.50: 0.50. A piezoelectric film was formed. Although the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0.005: 0.50: 0.50, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.50: 0.50, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.50 Ti 0.50 O 3 .
- Example 3 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.005: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.52: 0.48, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.52 Ti 0.48 O 3 .
- Example 4 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors. Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.005: 0.55: 0.45. A piezoelectric film was formed. In addition, although the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.55: 0.45, a part of Pb was evaporated by firing.
- Pb source cerium 2-ethylhexanoate
- Zr source zirconium tetrabutoxide
- Ti source titanium tetraisopropoxide
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.55: 0.45, and the general formula: Pb 1.01 Ce 0.005 Zr 0.55 Ti 0.45 O 3
- Example 5 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1 except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.01: 0.40: 0.60. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.40: 0.60, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.40: 0.60, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.40 Ti 0.60 O 3 .
- Example 6 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.01: 0.50: 0.50. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0.005: 0.50: 0.50, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.50: 0.50, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.50 Ti 0.50 O 3 .
- Example 7 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1 except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.03: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.52: 0.48, and the general formula: It is represented by Pb 1.01 Ce 0.005 Zr 0.52 Ti 0.48 O 3 .
- Example 8 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.05: 0.55: 0.45. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.55: 0.45, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.01: 0.005: 0.55: 0.45, and the general formula: Pb 1.01 Ce 0.005 Zr 0.55 Ti 0.45 O 3
- Example 9 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.03: 0.40: 0.60. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.40: 0.60, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.03: 0.005: 0.40: 0.60, and the general formula: It is represented by Pb 1.03 Ce 0.005 Zr 0.40 Ti 0.60 O 3 .
- Example 10 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.03: 0.50: 0.50. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0.005: 0.50: 0.50, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.03: 0.005: 0.50: 0.50, and the general formula: It is represented by Pb 1.03 Ce 0.005 Zr 0.50 Ti 0.50 O 3 .
- Example 11 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1 except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.03: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.03: 0.005: 0.52: 0.48, and the general formula: Pb 1.03 Ce 0.005 Zr 0.52 Ti 0.48 O 3
- Example 12 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.03: 0.55: 0.45. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.55: 0.45, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.03: 0.005: 0.55: 0.45, and the general formula: Pb 1.03 Ce 0.005 Zr 0.55 Ti 0.45 O 3
- Example 13 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.05: 0.40: 0.60. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.40: 0.60, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.04: 0.005: 0.40: 0.60, and the general formula: It is represented by Pb 1.04 Ce 0.005 Zr 0.40 Ti 0.60 O 3 .
- Example 14 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.05: 0.50: 0.50. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0.005: 0.50: 0.50, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.04: 0.005: 0.50: 0.50, and the general formula: Pb 1.04 Ce 0.005 Zr 0.50 Ti 0.50 O 3
- Example 15 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.05: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.04: 0.005: 0.52: 0.48, and the general formula: It is represented by Pb 1.04 Ce 0.005 Zr 0.52 Ti 0.48 O 3 .
- Example 16 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 1, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.15: 0.05: 0.55: 0.45. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.15: 0.005: 0.55: 0.45, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.04: 0.005: 0.55: 0.45, and the general formula: It is represented by Pb 1.04 Ce 0.005 Zr 0.55 Ti 0.45 O 3 .
- Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- the metal atomic ratio (Pb: Ce: Zr: Ti) is weighed so as to be 1.08: 0.03: 0.52: 0.48, and the mixing ratio of polyvinylpyrrolidone (PVP) is Ce-doped PZT precursor.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 0.95: 0.03: 0.52: 0.48, and the general formula: Pb 0.95 Ce 0.03 Zr 0.52 Ti 0.48 O 3
- Example 18 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 17, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.12: 0.03: 0.52: 0.48. A piezoelectric film was formed. Although the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.12: 0.03: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 0.99: 0.03: 0.52: 0.48, and the general formula: Pb 0.99 Ce 0.03 Zr 0.52 Ti 0.48 O 3
- Example 19 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 17, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.18: 0.03: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.18: 0.03: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.05: 0.03: 0.52: 0.48, and the general formula: Pb 1.05 Ce 0.03 Zr 0.52 Ti 0.48 O 3
- Example 20 Lead acetate trihydrate (Pb source), cerium 2-ethylhexanoate (Ce source), zirconium tetrabutoxide (Zr source) and titanium tetraisopropoxide (Ti source) are Ce-doped PZT precursors.
- Ce-doped PZT system in the same manner as in Example 17, except that the metal atomic ratio (Pb: Ce: Zr: Ti) was 1.18: 0.03: 0.52: 0.48. A piezoelectric film was formed.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT-based precursor was 1.18: 0.03: 0.52: 0.48, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.15: 0.03: 0.52: 0.48, and the general formula: It is represented by Pb 1.15 Ce 0.03 Zr 0.52 Ti 0.48 O 3 .
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.00: 0.004: 0.52: 0.48, and the general formula: It is represented by PbCe 0.004 Zr 0.52 Ti 0.48 O 3 .
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.00: 0.06: 0.40: 0.60, and the general formula: It is represented by PbCe 0.06 Zr 0.40 Ti 0.60 O 3 .
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0: 0.52: 0.48
- a part of Pb was evaporated and flew by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.02: 0: 0.52: 0.48
- Pb source cerium 2-ethylhexanoate
- Ce source zirconium tetrabutoxide
- Ti source titanium tetraisopropoxide
- a PZT piezoelectric film was formed in the same manner as in Example 1 except that the weight was adjusted so that Pb: Ce: Zr: Ti was 1.15: 0.03: 0.38: 0.62.
- the metal atomic ratio (Pb: Ce: Zr: Ti) of the PZT precursor was 1.15: 0.03: 0.38: 0.62, a part of Pb was evaporated by firing.
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.02: 0.03: 0.38: 0.62, and the general formula: It is represented by Pb 1.02 Ce 0.03 Zr 0.38 Ti 0.62 O 3 .
- the Ce-doped PZT-based piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.02: 0.03: 0.57: 0.43, and the general formula: It is represented by Pb 1.02 Ce 0.03 Zr 0.57 Ti 0.43 O 3 .
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 0.94: 0.03: 0.52: 0.48, and the general formula: Pb 0.94 Ce 0.03 Zr 0.52 Ti 0.48 O 3
- the Ce-doped PZT piezoelectric film after firing has a metal atomic ratio (Pb: Ce: Zr: Ti) of 1.16: 0.03: 0.52: 0.48, and the general formula: It is represented by Pb 1.16 Ce 0.03 Zr 0.52 Ti 0.48 O 3 .
- the deviation in hysteresis of the polarization amount of the piezoelectric film was measured using TF-analyzer2000 (manufactured by aix ACCT). Specifically, first, a pair of electrodes having a diameter of 200 ⁇ m are formed on both surfaces of a Ce-doped PZT-based piezoelectric film by a sputtering method, followed by rapid heating treatment (RTA), which is performed at 700 ° C. in an oxygen atmosphere. An MIM (Metal-Insulator-Metal) capacitor structure was fabricated by holding for a minute and annealing to recover the damage.
- RTA rapid heating treatment
- the degree of orientation in the (100) plane of the crystal of the Ce-doped PZT-based piezoelectric film was determined from the diffraction results obtained by the concentration method using an X-ray diffraction (XRD) apparatus (manufactured by Panalytic, model name: Empyrean). , (100) plane strength / ⁇ (100) plane strength + (110) plane strength + (111) plane strength ⁇ ).
- XRD X-ray diffraction
- the piezoelectric constant e 31.f was measured using a piezoelectric evaluation apparatus (aix ACCT, 4-Point Bending System). The above measurement was performed at a frequency of 1 kHz.
- the presence or absence of cracks was observed by observing an image obtained by photographing the structure of the film surface and the film cross section with a scanning electron microscope (SEM) with the scanning electron microscope used for the film thickness measurement, and observing the presence or absence of cracks from this SEM image.
- the crack is a crack having a minor axis of 30 nm or more and a major axis of 200 nm or more in an SEM image of 26 ⁇ m ⁇ 19 ⁇ m (magnification: ⁇ 5000). Measurement was performed in three regions selected at random from the piezoelectric films obtained in each of the examples and comparative examples. When no crack was observed, “no crack” was determined, and when no crack was observed, “cracked”. These results are shown in Tables 1 and 2.
- Example 1 850, Example 2: 1280, Example 3: 1300, Example 4: 1280, Example 5: 800, Example 6: 1190, Example 7: 1210, Example 8: 1190, Example 9: 720, Example 10: 1090, Example 11: 1120, Example 12: 1100, Example 13: 670, Example 14: 1010, Example 15: 1030, Example 16: 1020, Example 17: 1010, Example 18: 1100, Example 19: 1130, Example 20: 1140, Comparative Example 1: 1390, Comparative Example 2: 620, Comparative Example 3: 1420, Comparative Example 4: 680, Comparative Example 5: 1320, Comparative Example 6: 1050, Comparative Example 7: 1140.
- Example 1 850, Example 2: 1280, Example 3: 1300, Example 4: 1280, Example 5: 800, Example 6: 1190, Example 7: 1210, Example 8: 1190, Example 9: 720, Example 10: 1090, Example 11: 1120, Example 12: 1100, Example 13: 670, Example 14
- the Ce-doped PZT-based piezoelectric film of the present invention can be used for manufacturing a constituent material (electrode) in a composite electronic component of a piezoelectric element, an IPD, a pyroelectric element, a gyro sensor, a vibration power generation element, and an actuator.
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Abstract
Description
本願は、2014年3月27日に、日本に出願された特願2014-065632号に基づき優先権を主張し、その内容をここに援用する。
ここで中心とはバイアス0をさす。ヒステリシスの中心はX軸を電界(kV/cm)、Y軸を分極量(μC/cm2)としたグラフにおける正側、負側の抗電界の絶対値をEc+、Ec-としたとき以下の式で表される。以下のヒステリシスの中心のバイアス0からのずれをヒステリシスのシフトとした。
ヒステリシスの中心 = Ec+-{ (Ec+ + Ec-) / 2}
また上記CeドープのPZT系圧電体膜のX線回折による(100)配向度は80%以上であることが好ましく、95%以上であることが更に好ましい。なお、(100)配向度の上限値は100%である。
更に上記CeドープのPZT系圧電体膜の膜厚は1000nm以上かつ5000nm以下であることが好ましく、2000nm以上かつ3000nm以下であることが更に好ましい。
ここで、CeドープのPZT系圧電体膜の分極量のヒステリシスのシフト量をその中心から負側に4kV/cm以上に限定したのは、4kV/cm未満では十分に分極方向が揃わないからである。また、CeドープのPZT系圧電体膜のX線回折による(100)配向度を80%以上に限定したのは、80%未満では十分なヒステリシスのシフトが見られないからである。更に、CeドープのPZT系圧電体膜の膜厚を1000nm以上かつ5000nm以下の範囲内に限定したのは、1000nm未満では十分な圧電特性が得られず、5000nmを超えると生産性が低下するからである。
組成物中に含まれるジオールは、組成物の溶媒となる成分である。具体的には、プロピレングリコール、エチレングリコール又は1,3―プロパンジオール等が挙げられる。このうち、プロピレングリコール又はエチレングリコールが好ましい。ジオールを必須の溶媒成分とすることにより、組成物の保存安定性を高めることができる。また、ポリビニルピロリドン(PVP)又はポリエチレングリコールはクラック抑制材として加えてもよい。
また、上記CeドープのPZT系圧電体膜を形成するための組成物は、直鎖状モノアルコールを含有してもよい。直鎖状モノアルコールとしては、特に炭素数を6以上12以下の直鎖状モノアルコールが、PZT前駆物質との親和性が低く、かつ蒸気圧が低いため好ましい。
ここで、CeドープのPZT系前駆体1モルとは、前駆物質に含まれるPbzCexZryTi1-yO3が1モルであることを示す。
また、モノマー換算とは、ポリマーを構成するモノマーの分子量を基準(1モル)として、ポリマーの分子量を換算して得る値である。
なお、濾過処理等によるパーティクルの除去によって組成物内の0.2μm以上のパーティクルは除去されている状態であることが好ましい。なお、組成物中のパーティクルの個数の測定には、光散乱式パーティクルカウンターを用いる。
一方、図2(a)~(d)に示すように、1-オクタノールのような毛管力によりゲル膜表面まで上昇して蒸発する溶媒が存在しない場合、図2(a)~(c)で示すように仮焼膜の内部に隙間が形成されず、仮焼膜内にダイヤモンドライクカーボンが生成されてしまう(図2(d))。このダイヤモンドライクカーボンは、焼成後、結晶膜内にボイド(図2(e))が発生する原因となる。
先ず、反応容器に酢酸鉛三水和物(Pb源)とプロピレングリコール(ジオール)とを入れ、窒素雰囲気中、150℃の温度で1時間還流した後、この反応容器に2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)、チタンテトライソプロポキシド(Ti源)及びアセチルアセトン(安定化剤)を更に加え、窒素雰囲気中、150℃の温度で1時間還流して反応させることにより、合成液を調製した。ここで、上記酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.005:0.40:0.60となるように秤量した。またプロピレングリコール(ジオール)はCeドープのPZT系前駆体100質量%に対して35質量%となるように添加し、アセチルアセトン(安定化剤)はCeドープのPZT系前駆体1モルに対して2モルとなるように添加した。次いで上記合成液100質量%中に占めるCeドープのPZT系前駆体の濃度が、酸化物濃度で35%となるように減圧蒸留を行って不要な溶媒を除去した。ここで、合成液中に占めるCeドープのPZT系前駆体の濃度における酸化物濃度とは、合成液に含まれる全ての金属元素が目的の酸化物になったと仮定して算出した、合成液100質量%に占める金属酸化物の濃度をいう。
上記k値とは、分子量と相関する粘性特性値であり、毛細管粘度計により測定される相対粘度値(25℃)を下記のFikentscherの式に適用して算出される値である。
k値=(1.5 logηrel -1)/(0.15+0.003c)+(300clogηrel +(c+1.5clogηrel)2)1/2/(0.15c+0.003c2)
上記式中、「ηrel」は、ポリビニルピロリドン水溶液の水に対する相対粘度を示し、「c」は、ポリビニルピロリドン水溶液中のポリビニルピロリドン濃度(質量%)を示す。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.005:0.50:0.50となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.50:0.50であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.50:0.50となり、一般式:Pb1.01Ce0.005Zr0.50Ti0.50O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.005:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.52:0.48となり、一般式:Pb1.01Ce0.005Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.005:0.55:0.45となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.55:0.45であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.55:0.45となり、一般式:Pb1.01Ce0.005Zr0.55Ti0.45O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.01:0.40:0.60となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.40:0.60であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.40:0.60となり、一般式:Pb1.01Ce0.005Zr0.40Ti0.60O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.01:0.50:0.50となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.50:0.50であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.50:0.50となり、一般式:Pb1.01Ce0.005Zr0.50Ti0.50O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.52:0.48となり、一般式:Pb1.01Ce0.005Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.05:0.55:0.45となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.55:0.45であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.01:0.005:0.55:0.45となり、一般式:Pb1.01Ce0.005Zr0.55Ti0.45O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.40:0.60となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.40:0.60であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.03:0.005:0.40:0.60となり、一般式:Pb1.03Ce0.005Zr0.40Ti0.60O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.50:0.50となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.50:0.50であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.03:0.005:0.50:0.50となり、一般式:Pb1.03Ce0.005Zr0.50Ti0.50O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.03:0.005:0.52:0.48となり、一般式:Pb1.03Ce0.005Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.55:0.45となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.55:0.45であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.03:0.005:0.55:0.45となり、一般式:Pb1.03Ce0.005Zr0.55Ti0.45O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.05:0.40:0.60となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.40:0.60であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.04:0.005:0.40:0.60となり、一般式:Pb1.04Ce0.005Zr0.40Ti0.60O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.05:0.50:0.50となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.50:0.50であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.04:0.005:0.50:0.50となり、一般式:Pb1.04Ce0.005Zr0.50Ti0.50O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.05:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.04:0.005:0.52:0.48となり、一般式:Pb1.04Ce0.005Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.05:0.55:0.45となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.005:0.55:0.45であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.04:0.005:0.55:0.45となり、一般式:Pb1.04Ce0.005Zr0.55Ti0.45O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.08:0.03:0.52:0.48となるように秤量し、ポリビニルピロリドン(PVP)の混合割合をCeドープのPZT系前駆体1モルに対して0.05モルとし、更にプロピレングリコール(ジオール)の混合割合を組成物100質量%に対して30質量%としたこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.08:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が0.95:0.03:0.52:0.48となり、一般式:Pb0.95Ce0.03Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.12:0.03:0.52:0.48となるように秤量したこと以外は、実施例17と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.12:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が0.99:0.03:0.52:0.48となり、一般式:Pb0.99Ce0.03Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.18:0.03:0.52:0.48となるように秤量したこと以外は、実施例17と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.18:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.05:0.03:0.52:0.48となり、一般式:Pb1.05Ce0.03Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.18:0.03:0.52:0.48となるように秤量したこと以外は、実施例17と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.18:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.52:0.48となり、一般式:Pb1.15Ce0.03Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.004:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.004:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.00:0.004:0.52:0.48となり、一般式:PbCe0.004Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.06:0.40:0.60となるように秤量したこと以外は、実施例1と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.06:0.40:0.60であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.00:0.06:0.40:0.60となり、一般式:PbCe0.06Zr0.40Ti0.60O3で表される。
2-エチルヘキサン酸セリウム(Ce源)を添加しなかった、即ち酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0:0.52:0.48となるように秤量したこと以外は、実施例1と同様にしてPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.02:0:0.52:0.48となり、一般式:Pb1.02Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.38:0.62となるように秤量したこと以外は、実施例1と同様にしてPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.03:0.38:0.62であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.02:0.03:0.38:0.62となり、一般式:Pb1.02Ce0.03Zr0.38Ti0.62O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.15:0.03:0.57:0.43となるように秤量したこと以外は、実施例1と同様にしてPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.15:0.03:0.57:0.43であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.02:0.03:0.57:0.43となり、一般式:Pb1.02Ce0.03Zr0.57Ti0.43O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.07:0.03:0.52:0.48となるように秤量したこと以外は、実施例17と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.07:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が0.94:0.03:0.52:0.48となり、一般式:Pb0.94Ce0.03Zr0.52Ti0.48O3で表される。
酢酸鉛三水和物(Pb源)、2-エチルヘキサン酸セリウム(Ce源)、ジルコニウムテトラブトキシド(Zr源)及びチタンテトライソプロポキシド(Ti源)は、CeをドープしたPZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)が1.29:0.03:0.52:0.48となるように秤量したこと以外は、実施例17と同様にしてCeドープのPZT系圧電体膜を形成した。なお、PZT系前駆体の金属原子比(Pb:Ce:Zr:Ti)は1.29:0.03:0.52:0.48であったけれども、Pbの一部が焼成により蒸発して飛んでしまい、焼成後のCeドープのPZT系圧電体膜は、金属原子比(Pb:Ce:Zr:Ti)が1.16:0.03:0.52:0.48となり、一般式:Pb1.16Ce0.03Zr0.52Ti0.48O3で表される。
実施例1~20及び比較例1~7で形成したCeドープのPZT系圧電体膜について、膜組成、分極量のヒステリシスのずれ、配向度、圧電定数e31.f及びクラックの有無をそれぞれ測定した。
各実施例で示す、焼成後のCeドープPZT系圧電体膜の膜組成(原子金属比)は、蛍光X線分析装置(リガク社製 型式名:Primus III+)を用いた蛍光X線分析により測定した。
圧電体膜の分極量のヒステリシスのずれは、TF-analyzer2000(aix ACCT社製)を用いて測定した。具体的には、先ずCeドープのPZT系圧電体膜の両面に、スパッタ法により直径200μmの一対の電極をそれぞれ形成した後、急速加熱処理(RTA)を行い、酸素雰囲気中で700℃に1分間保持して、ダメージを回復するためのアニーリングを行い、MIM(Metal-Insulator-Metal)キャパシタ構造をそれぞれ作製した。次にこれらを試験用サンプルとし、1kHzの周波数で25Vの電圧を印加して圧電体膜の分極量のヒステリシスを測定し、更に得られた分極量のヒステリシスのずれを求めた。
Claims (4)
- 一般式:PbzCexZryTi1-yO3で示されるCeドープの複合金属酸化物からなり、
前記一般式中のx、y及びzが、0.005≦x≦0.05、0.40≦y≦0.55、及び0.95≦z≦1.15をそれぞれ満たす、CeドープのPZT系圧電体膜。 - 分極量のヒステリシスがその中心から負側に4kV/cm以上シフトした請求項1記載のCeドープのPZT系圧電体膜。
- X線回折による(100)配向度が80%以上である請求項1又は2記載のCeドープのPZT系圧電体膜。
- 膜厚が1000nm以上かつ5000nm以下である請求項1ないし3いずれか1項に記載のCeドープのPZT系圧電体膜。
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KR1020167026248A KR102385773B1 (ko) | 2014-03-27 | 2015-03-23 | Ce 도프의 PZT 계 압전체막 |
CN201580015884.0A CN106133933A (zh) | 2014-03-27 | 2015-03-23 | 掺杂Ce的PZT系压电膜 |
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Title |
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S.B.MAJUMDER ET AL.: "Effect of cerium doping on the micro-structure and electrical properties of sol-gel derived Pb1.05(Zr0.53-deltaCe6Ti0.47)O3 (delta?10 at.%) thin films", MATERIALS SCIENCE AND ENGINEERING B, vol. 98, no. Issue 1, 25 February 2003 (2003-02-25), pages 25 - 32, XP004412841 * |
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JP2015191899A (ja) | 2015-11-02 |
KR20160138416A (ko) | 2016-12-05 |
CN106133933A (zh) | 2016-11-16 |
TWI648887B (zh) | 2019-01-21 |
EP3125315A4 (en) | 2017-10-25 |
TW201603338A (zh) | 2016-01-16 |
US20170107156A1 (en) | 2017-04-20 |
KR102385773B1 (ko) | 2022-04-11 |
JP6237399B2 (ja) | 2017-11-29 |
EP3125315A1 (en) | 2017-02-01 |
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