CN113264766A - Lead-free piezoelectric film material and preparation method thereof - Google Patents
Lead-free piezoelectric film material and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种无铅压电薄膜材料及其制备方法，无铅压电薄膜材料的化学通式为：(1‑x％)(Bi0.5Na0.5)TiO3‑x％BaZrO3；包括，将BNT‑xBZ前驱体溶液陈化，得到溶胶；将溶胶均匀旋涂在基片上，得到湿膜；对湿膜进行热解，烧结处理，得到中间薄膜；在中间薄膜上，重复旋涂溶胶，热解及烧结处理，得到预设厚度的薄膜；对预设厚度的薄膜进行退火热处理，得到所述的无铅压电薄膜材料；本发明通过在(Bi0.5Na0.5)TiO3基体中引入BaZrO3，构建了独特的准同型相界，即弛豫‑铁电相界；位于弛豫‑铁电相界的薄膜组分压电活性增强，在电场作用下产生可逆的场致相变效应，从而获得显著提高的应变性能，其应变及压电性能远超现有的铅基材料。
The invention discloses a lead-free piezoelectric thin film material and a preparation method thereof. The general chemical formula of the lead-free piezoelectric thin film material is: (1-x%)(Bi 0.5 Na 0.5 )TiO 3 -x% BaZrO 3 ; , ageing the BNT-xBZ precursor solution to obtain a sol; evenly spin-coating the sol on the substrate to obtain a wet film; pyrolyzing and sintering the wet film to obtain an intermediate film; on the intermediate film, spin-coating the sol repeatedly , pyrolysis and sintering treatment to obtain a film with a preset thickness; annealing and heat treatment for the film with a preset thickness to obtain the lead-free piezoelectric thin film material; the present invention is introduced into the (Bi 0.5 Na 0.5 )TiO 3 matrix by introducing BaZrO 3 , constructs a unique quasi-homotype phase boundary, namely the relaxor-ferroelectric phase boundary; the piezoelectric activity of the thin film components located at the relaxor-ferroelectric phase boundary is enhanced, resulting in a reversible field-induced phase transition effect under the action of an electric field , resulting in a significantly improved strain performance, whose strain and piezoelectric properties far exceed those of existing lead-based materials.
Description
Technical Field
The invention belongs to the technical field of lead-free functional thin film materials, and particularly relates to a lead-free piezoelectric thin film material and a preparation method thereof.
Background
The micro-displacement technology is a very important high-precision technology applied to a micro-electromechanical system (MEMS) and a nano-electromechanical system (NEMS), and mainly comprises a micro driver, a high-precision displacer and the like; the high-precision electric signal control displacement driving can be realized by utilizing the inverse piezoelectric property of the piezoelectric material; the development trend of device miniaturization and miniaturization requires that the piezoelectric material is developed from a block to a film; at present, piezoelectric materials with high strain performance applied to micro-actuators and high precision displacers are based on lead-based materials, such as: lead zirconate titanate (PZT); the use of lead-based piezoelectric materials violates the requirements of environmental protection and sustainable development, and therefore, a lead-free piezoelectric material with high strain performance needs to be found out for replacement.
The sodium bismuth titanate (BNT) system can form a unique morphotropic phase boundary with other ferroelectric materials in a solid solution mode, BNT component ceramics in the morphotropic phase boundary not only have a structure that ferroelectric phases and relaxation phases coexist, but also have a phase transition process of converting the relaxation phases to the ferroelectric phases under the action of an electric field, and generate enough strain in the process. As early as 2007, Zhang et al reported that KNN-doped BNT-BT component ceramics obtain strain as high as 0.45% and an inverse piezoelectric coefficient of 560pm/V, and therefore research on BNT-based high-strain materials and devices by scientific researchers is pulled back; later Jamil Ur Rahman et al prepared BNT-xBaZrO with a simpler composition3(BNT-xBZ) component ceramics, also achieving strains of up to 0.4%, and not containing the very volatile potassium element that deteriorates performance; in a material system with a plurality of lead-free perovskite structures, sodium bismuth titanateThe (BNT) system has the characteristics of large strain and good sintering characteristics, and is currently the most promising lead-free material for replacing lead-based materials for micro actuators and high precision displacers.
Therefore, to meet the requirements of device miniaturization and large-scale integrated circuits, sodium bismuth titanate-based thin film materials with large strain are receiving more and more attention. Compared with the ceramic material with the same component, the film material has great difficulty in both the preparation technology and the characterization technology, such as poor strain performance and piezoelectric performance; in addition, for the bismuth sodium titanate-based piezoelectric film, the leakage conduction and the loss are large, and the performance of the piezoelectric film is greatly hindered in practical use.
Therefore, a lead-free piezoelectric film material which is simple and stable in component, has large strain and small hysteresis is urgently sought, the requirements of miniaturization, high precision and industrialized large-scale production can be met, the loss and the leakage conductance of the film material can be reduced by improving and optimizing a preparation process, and the performance exertion of the film material in practical application is improved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a lead-free piezoelectric film material and a preparation method thereof, aiming at solving the technical problems of lower strain and piezoelectric property of the existing lead-free piezoelectric film material.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a lead-free piezoelectric film material, which has a chemical general formula as follows: (1-x%) (Bi)0.5Na0.5)TiO3-x％BaZrO3(ii) a Wherein x% is BaZrO3The value range of x is more than or equal to 0 and less than or equal to 7.
Further, the strain value of the lead-free piezoelectric film material is 0.4% -0.7%.
Further, the thickness of the lead-free piezoelectric thin film material is 900-1000 nm.
The invention also provides a preparation method of the lead-free piezoelectric film material; the method specifically comprises the following steps:
step 1, preparing a BNT-xBZ precursor solution;
step 3, uniformly spin-coating the sol on a substrate to obtain a wet film;
step 5, repeating the step 3-4 on the intermediate film in the step 4 to obtain a film with a preset thickness;
and 6, carrying out annealing heat treatment on the film with the preset thickness in the step 5 to obtain the lead-free piezoelectric film material.
Further, in the step 1, bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate and tetrabutyl zirconate are used as raw materials to prepare a BNT-xBZ precursor solution; wherein said bismuth acetate is provided in a 2% to 5% excess and said sodium acetate is provided in a 5% to 15% excess.
Further, in the step 4, the wet film is pyrolyzed and sintered, the pyrolysis temperature is 410-; the sintering treatment temperature is 650-700 ℃, and the heat preservation time is 3-10 min.
Further, in step 6, annealing heat treatment is performed on the film with a preset thickness in an oxygen atmosphere.
Further, the annealing heat treatment temperature is 700-750 ℃, and the annealing heat treatment time is 30-60 min.
Further, in the step 2, standing the BNT-xBZ precursor solution for 24-36h at room temperature during the aging process.
Further, in step 3, the substrate adopts Pt substrate and TiO substrate2Substrate, SiO2A substrate or a Si substrate.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a lead-free piezoelectric film material and a preparation method thereof, wherein (Bi) is used for preparing the lead-free piezoelectric film material0.5Na0.5)TiO3Introduction of BaZrO into matrix3By constructing a unique morphotropic phase boundary, i.e. relaxation-a ferroelectric phase boundary; the piezoelectric activity of the film component positioned at the relaxation-ferroelectric phase boundary is enhanced, and a reversible field-induced phase transition effect is generated under the action of an electric field, so that the strain performance is obviously improved, and the strain performance and the piezoelectric performance of the film component are far superior to those of the conventional lead-based material.
Furthermore, on the basis of preparing the thin film material by a sol-gel method, a two-step annealing heat treatment mode is adopted, so that the defects of the thin film material are effectively reduced, and the loss and the leakage current of the thin film are reduced; the dielectric loss at room temperature and 1kHz frequency is obviously reduced.
Furthermore, annealing heat treatment is carried out in an oxygen atmosphere, so that oxygen vacancies of the film material are effectively reduced, and the loss and leakage current of the film are reduced.
The lead-free piezoelectric film material disclosed by the invention can generate a reversible field-induced phase change effect under the action of an electric field, so that the strain performance is remarkably improved, and is 0.4% -0.7%, even can reach 1%; through a two-step annealing heat treatment mode, the defects of the film material are effectively reduced, the film loss is reduced, and the dielectric loss at the room temperature of 1kHz can be reduced by 2-3%; the lead-free piezoelectric film material can be used in micro-mechanical electronic systems such as micro-drivers and high-precision displacers, and the use efficiency of the film material in practical application is improved.
Drawings
FIG. 1 is a schematic XRD view of lead-free piezoelectric thin film materials prepared in examples 1 to 4;
FIG. 2 is a graph showing the dielectric loss spectra of lead-free piezoelectric thin film materials prepared in examples 1 to 4;
fig. 3 is a strain graph of the lead-free piezoelectric thin film materials prepared in examples 1 to 4.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention more apparent, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a lead-free piezoelectric film material, which is prepared from a lead-free piezoelectric film materialThe chemical formula of the lead-free piezoelectric film material is represented as follows: (1-x%) (Bi)0.5Na0.5)TiO3-x％BaZrO3(ii) a Wherein x% is BaZrO3The value range of x is more than or equal to 0 and less than or equal to 7.
The lead-free piezoelectric film material provided by the invention has the advantages that BZ is introduced into the BNT matrix to construct a relaxation-ferroelectric phase boundary, the piezoelectric activity of film components positioned at the phase boundary is enhanced, and a field-induced phase transition effect is generated under the action of an electric field, so that the strain performance is obviously improved.
The invention also provides a preparation method of the lead-free piezoelectric film material, which is prepared by adopting a sol-gel method and specifically comprises the following steps:
step 1, selecting bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate and tetrabutyl zirconate with purity higher than analytical purity as raw materials to prepare BNT-xBZ precursor solution; wherein, the concentration of the BNT-xBZ precursor solution is 0.3-0.4mol/L, and the volume of the prepared solution is 30-40 mL; as the alkali elements Bi and Na are easy to volatilize during the annealing treatment, when the raw materials are weighed, the bismuth acetate is provided according to the excess of 2-5 percent, and the sodium acetate is provided according to the excess of 5-15 percent.
The preparation process of the BNT-xBZ precursor solution is specifically as follows:
firstly, measuring 10-15mL of ethylene glycol monomethyl ether; then, respectively weighing bismuth acetate, sodium acetate and barium acetate; finally, 10-15mL of acetic acid is measured, heated and stirred until the acetic acid is completely dissolved, and the stirring time is 60-80min, so that a solution I is obtained;
then, weighing 2-3mL of ethylene glycol monomethyl ether, weighing tetrabutyl titanate and acetylacetone, and stirring for 40-60min until the tetrabutyl titanate and the acetylacetone are completely dissolved to obtain a solution II;
stopping heating after the solution I is completely dissolved, cooling to room temperature, adding the weighed tetrabutyl zirconate, and stirring until the tetrabutyl zirconate is completely dissolved; then dropwise adding the solution II into the solution I while stirring; then heating and stirring for 60-80min to obtain a completely uniform and clear solution A; then, adding PVP into the solution A, and then stirring for 60-80min to obtain a completely uniform and clear solution B;
and finally, carrying out constant volume on the completely uniform clear solution B, filtering, bottling, and standing at room temperature for 24-36h to obtain a BNT-xBZ precursor solution.
Specifically, firstly, a substrate needs to be cleaned before use, dried by a nitrogen gun and then annealed in a rapid annealing furnace for use; the substrate is blown clean by a nitrogen gun before spin coating, then BNT-xBZ precursor solution is dripped on the substrate blown clean by a dropper, a uniform wet film is obtained after spin coating, and the spin coating rotating speed is as follows: the low speed is 1000 and 1500rpm, and the temperature is kept for 10 to 15 seconds; keeping the speed at 3000 and 4000rpm for 40-60 s; then, carrying out pyrolysis and sintering treatment on the obtained wet film in a rapid annealing furnace to obtain an intermediate film; wherein the pyrolysis temperature is 410-420 ℃, and the temperature is kept for 10-15 min; the sintering temperature is 650-700 ℃, and the temperature is kept for 3-5 min.
Step 3, repeating the step 2 for times until a film with a preset thickness is obtained; then carrying out annealing heat treatment on the obtained film material with the preset thickness in an oxygen atmosphere so as to better eliminate the influence of oxygen vacancy, defect and the like on the film performance; wherein the annealing heat treatment temperature is 700-750 ℃, and the temperature is kept for 30-60 min; the thickness of the prepared lead-free piezoelectric film is 900-1000 nm.
The lead-free piezoelectric film material and the preparation method thereof generate reversible field-induced phase change effect under the action of an electric field, and obtain remarkably improved strain performance, wherein the strain performance is 0.4-0.7 percent and even can reach 1 percent; through a two-step annealing heat treatment mode, the defects of the film material are effectively reduced, the film loss is reduced, and the dielectric loss at the room temperature of 1kHz can be reduced by 2-3%; the lead-free piezoelectric film material can be used in micro-mechanical electronic systems such as micro-drivers and high-precision displacers, and the use efficiency of the film material in practical application is improved.
Example 1
This example1, providing a lead-free piezoelectric film material, wherein the component chemical general formula of the lead-free piezoelectric film material is as follows: (1-x) (Bi)0.5Na0.5)TiO3-x％BaZrO3Wherein x is 0.
The method for preparing the lead-free piezoelectric thin film material in embodiment 1 specifically includes the following steps:
step 1, selecting raw materials of bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate, tetrabutyl zirconate and the like with purity higher than analytical purity to prepare a BNT-0BZ precursor solution, wherein the concentration of the precursor solution is 0.3mol/L, and the volume of the prepared solution is 30 mL; since the alkali metal elements Bi and Na are easily volatilized at the time of annealing, when weighing bismuth acetate and sodium acetate, bismuth acetate was supplied in an excess of 2%, and sodium acetate was supplied in an excess of 5%.
The preparation process comprises the following steps:
firstly, weighing 10mL of ethylene glycol monomethyl ether in a bottle 1, then weighing bismuth acetate, sodium acetate and barium acetate respectively, finally weighing 10mL of acetic acid, heating and stirring until the acetic acid is completely dissolved, wherein the stirring time is 60min, and thus obtaining a solution I;
then, weighing 2mL of ethylene glycol methyl ether in 2 bottles, weighing tetrabutyl titanate and acetylacetone, and stirring for 40min till complete dissolution to obtain a solution II;
stopping heating after the solution I is completely dissolved, cooling to room temperature, adding the weighed tetrabutyl zirconate, and stirring until the tetrabutyl zirconate is completely dissolved; then dropwise adding the solution II into the solution I while stirring; heating and stirring for 60min after the dropwise addition is finished to obtain a completely uniform and clear solution A;
then, adding PVP into the solution A, and stirring for 60min to obtain a completely uniform and clear solution B;
and finally, carrying out constant volume on the obtained uniform and clear solution B, filtering, bottling, and standing at room temperature for 24h to obtain a BNT-0BZ precursor solution.
firstly, a substrate needs to be cleaned before use, is dried by a nitrogen gun, and is annealed in a rapid annealing furnace for use; blowing the substrate clean by a nitrogen gun before spin coating;
then, dripping the BNT-0BZ precursor solution on a clean substrate by a dropper, and obtaining a uniform wet film after spin coating, wherein the spin coating rotating speed is as follows: low speed 1000rpm, keeping 10 s; high speed 3000rpm, keeping for 40 s;
then, carrying out pyrolysis and sintering treatment on the obtained wet film in a rapid annealing furnace to obtain an intermediate film; wherein the pyrolysis temperature is 410 ℃, and the temperature is kept for 10 min; the sintering temperature was 650 deg.C and held for 3 min.
Step 3, repeating the step 2 six times to obtain a BNT-0BZ piezoelectric film material, and then carrying out post-annealing heat treatment on the obtained film material in an oxygen atmosphere to better eliminate the influence of oxygen vacancy, defects and the like on the film performance, wherein the annealing temperature is 700 ℃, and keeping for 30 min; the thickness of the film was measured to be 900 nm.
Example 2
The embodiment 2 provides a lead-free piezoelectric thin film material, and the component chemical general formula of the lead-free piezoelectric thin film material is as follows: (1-x) (Bi)0.5Na0.5)TiO3-x％BaZrO3Wherein x is 4.
The method for preparing the lead-free piezoelectric thin film material in embodiment 2 specifically includes the following steps:
step 1, selecting raw materials of bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate, tetrabutyl zirconate and the like with purity higher than analytical purity to prepare a BNT-4BZ precursor solution, wherein the concentration of the precursor solution is 0.35mol/L, and the volume of the prepared solution is 35 mL; since the alkali metal elements Bi and Na are easily volatilized at the time of annealing, when weighing bismuth acetate and sodium acetate, bismuth acetate was supplied at an excess of 3%, and sodium acetate was supplied at an excess of 10%.
The preparation process comprises the following steps:
firstly, weighing 10mL of ethylene glycol monomethyl ether in a bottle 1, then weighing bismuth acetate, sodium acetate and barium acetate respectively, finally weighing 10mL of acetic acid, heating and stirring until the acetic acid is completely dissolved, wherein the stirring time is 70min, and thus obtaining a solution I;
then, 2.5mL of ethylene glycol methyl ether is weighed in 2 bottles, tetrabutyl titanate and acetylacetone are weighed and stirred until being completely dissolved, and the stirring time is 50min, so that a solution II is obtained;
stopping heating after the solution I is completely dissolved, cooling to room temperature, adding the weighed tetrabutyl zirconate, and stirring until the tetrabutyl zirconate is completely dissolved; then dropwise adding the solution II into the solution I while stirring; heating and stirring for 70min after the dripping is finished to obtain a completely uniform and clear solution A;
then, adding PVP into the solution A, and stirring for 70min to obtain a completely uniform and clear solution B;
and finally, carrying out constant volume on the obtained uniform and clear solution B, filtering, bottling, and standing at room temperature for 24h to obtain a BNT-4BZ precursor solution.
firstly, a substrate needs to be cleaned before use, is dried by a nitrogen gun, and is annealed in a rapid annealing furnace for use; blowing the substrate clean by a nitrogen gun before spin coating;
then, dripping the BNT-4BZ precursor solution on a clean substrate by a dropper, and obtaining a uniform wet film after spin coating, wherein the spin coating rotating speed is as follows: low speed 1200rpm, hold for 12 s; high speed 3500rpm, keeping 50 s;
then, carrying out pyrolysis and sintering treatment on the obtained wet film in a rapid annealing furnace to obtain an intermediate film; wherein the pyrolysis temperature is 410 ℃, and the temperature is kept for 10 min; the sintering temperature is 675 deg.C, and the temperature is maintained for 5 min.
Step 3, repeating the step 2 six times to obtain a BNT-4BZ piezoelectric film material, and then carrying out post-annealing heat treatment on the obtained film material in an oxygen atmosphere to better eliminate the influence of oxygen vacancies, defects and the like on the film performance, wherein the annealing temperature is 725 ℃, and the annealing temperature is kept for 40 min; the thickness of the film was measured to be 930 nm.
Example 3
This example 3 provides a lead-free piezoelectric thin film materialThe chemical formula of the components of the material is as follows: (1-x) (Bi)0.5Na0.5)TiO3-x％BaZrO3Wherein x is 5.5.
The method for preparing the lead-free piezoelectric thin film material in embodiment 3 specifically includes the following steps:
step 1, selecting raw materials of bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate, tetrabutyl zirconate and the like with purity higher than analytical purity to prepare BNT-5.5BZ precursor solution, wherein the concentration of the precursor solution is 0.4mol/L, and the volume of the prepared solution is 40 mL; since the alkali metal elements Bi and Na are easily volatilized at the time of annealing, when weighing bismuth acetate and sodium acetate, bismuth acetate was supplied at an excess of 3%, and sodium acetate was supplied at an excess of 12%.
The preparation process comprises the following steps:
firstly, weighing 12mL of ethylene glycol monomethyl ether in a bottle 1, then weighing bismuth acetate, sodium acetate and barium acetate respectively, finally weighing 12mL of acetic acid, heating and stirring until the acetic acid is completely dissolved, wherein the stirring time is 70min, and thus obtaining a solution I;
then, 3mL of ethylene glycol methyl ether is weighed in 2 bottles, tetrabutyl titanate and acetylacetone are weighed and stirred until being completely dissolved, and the stirring time is 50min, so that a solution II is obtained;
stopping heating after the solution I is completely dissolved, cooling to room temperature, adding the weighed tetrabutyl zirconate, and stirring until the tetrabutyl zirconate is completely dissolved; then dropwise adding the solution II into the solution I while stirring; heating and stirring for 70min after the dripping is finished to obtain a completely uniform and clear solution A;
then, adding PVP into the solution A, and stirring for 80min to obtain a completely uniform and clear solution B;
and finally, carrying out constant volume on the obtained uniform and clear solution B, filtering, bottling, and standing at room temperature for 30h to obtain a BNT-5.5BZ precursor solution.
firstly, a substrate needs to be cleaned before use and dried by a nitrogen gun, then annealing is carried out in a rapid annealing furnace for use, and the substrate is blown clean by the nitrogen gun before spin coating;
then, dripping the BNT-5.5BZ precursor solution on a clean substrate by a dropper, and obtaining a uniform wet film after spin coating, wherein the spin coating rotating speed is as follows: low speed 1500rpm, keeping 10 s; high speed 3000rpm, keeping for 40 s;
then, carrying out pyrolysis and sintering treatment on the obtained wet film in a rapid annealing furnace to obtain an intermediate film; wherein the pyrolysis temperature is 415 ℃, and the temperature is kept for 12 min; the sintering temperature is 700 deg.C, and the temperature is maintained for 7 min.
Step 3, repeating the step 2 six times to obtain a BNT-5.5BZ piezoelectric film material, and then carrying out post-annealing heat treatment on the obtained film material in an oxygen atmosphere to better eliminate the influence of oxygen vacancies, defects and the like on the film performance, wherein the annealing temperature is 750 ℃, and keeping the annealing temperature for 50 min; the thickness of the film was measured to be 960 nm.
Example 4
This embodiment 4 provides a lead-free piezoelectric thin film material, where the component chemical formula of the lead-free piezoelectric thin film material is: (1-x) (Bi)0.5Na0.5)TiO3-x％BaZrO3Wherein x is 7.
The method for preparing the lead-free piezoelectric thin film material in embodiment 4 specifically includes the following steps:
step 1, selecting raw materials of bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate, tetrabutyl zirconate and the like with purity higher than analytical purity to prepare a BNT-7BZ precursor solution, wherein the concentration of the precursor solution is 0.4mol/L, and the volume of the prepared solution is 40 mL; since the alkali metal elements Bi and Na are easily volatilized at the time of annealing, when weighing bismuth acetate and sodium acetate, bismuth acetate was provided at an excess of 5%, and sodium acetate was provided at an excess of 15%.
The preparation process comprises the following steps:
firstly, weighing 15mL of ethylene glycol monomethyl ether in a bottle 1, then weighing bismuth acetate, sodium acetate and barium acetate respectively, finally weighing 15mL of acetic acid, heating and stirring until the acetic acid is completely dissolved, wherein the stirring time is 80min, and thus obtaining a solution I;
then, 3mL of ethylene glycol methyl ether is weighed in 2 bottles, tetrabutyl titanate and acetylacetone are weighed and stirred until being completely dissolved, and the stirring time is 60min, so that a solution II is obtained;
stopping heating after the solution I is completely dissolved, cooling to room temperature, adding the weighed tetrabutyl zirconate, and stirring until the tetrabutyl zirconate is completely dissolved; then dropwise adding the solution II into the solution I while stirring; heating and stirring for 80min after the dropwise addition is finished to obtain a completely uniform and clear solution A;
then, adding PVP into the solution A, and stirring for 80min to obtain a completely uniform and clear solution B;
and finally, carrying out constant volume on the obtained uniform and clear solution B, filtering, bottling, and standing at room temperature for 36h to obtain a BNT-7BZ precursor solution.
firstly, a substrate needs to be cleaned before use and dried by a nitrogen gun, then annealing is carried out in a rapid annealing furnace for use, and the substrate is blown clean by the nitrogen gun before spin coating;
then, dripping the BNT-7BZ precursor solution on a clean substrate by a dropper, and obtaining a uniform wet film after spin coating, wherein the spin coating rotating speed is as follows: low speed 1500rpm, keeping for 15 s; high speed 4000rpm, keeping for 60 s;
then, carrying out pyrolysis and sintering treatment on the obtained wet film in a rapid annealing furnace to obtain an intermediate film; wherein the pyrolysis temperature is 420 ℃, and the temperature is kept for 15 min; the sintering temperature is 700 deg.C, and the temperature is maintained for 10 min.
Step 3, repeating the step 2 six times to obtain a BNT-7BZ piezoelectric film material, and then carrying out post-annealing heat treatment on the obtained film material in an oxygen atmosphere to better eliminate the influence of oxygen vacancy, defects and the like on the film performance, wherein the annealing temperature is 700 ℃, and the annealing temperature is kept for 60 min; the thickness of the film was measured to be 1000 nm.
In examples 1 to 4, the substrate used was a Pt substrate or TiO substrate2Substrate, SiO2A substrate or a Si substrate.
And (3) test results:
the lead-free piezoelectric thin film materials prepared in the above examples 1 to 4 were tested for their structure, dielectric loss and strain properties, taking examples 1 to 4 as the subjects of study. The test results were as follows:
as shown in FIG. 1, FIG. 1 shows XRD schematic diagrams of piezoelectric thin film materials BNT-0BZ, BNT-4BZ, BNT-5.5BZ and BNT-7BZ prepared in examples 1-4; as can be seen from fig. 1, the lead-free piezoelectric thin film materials prepared in examples 1 to 4 were of a single pure perovskite structure, and no impurity phase was generated, indicating that BZ had been completely dissolved in the BNT matrix, and no second phase other than the perovskite structure was introduced.
As shown in FIG. 2, FIG. 2 shows the dielectric loss at room temperature of the piezoelectric thin film materials BNT-0BZ, BNT-4BZ, BNT-5.5BZ and BNT-7BZ prepared in examples 1-4; as can be seen from the attached figure 2, the dielectric loss of the lead-free piezoelectric thin film materials prepared in the examples 1-4 at room temperature and 1k Hz frequency is only 3-4%, which is obviously lower than the reported value in the prior literature; along with the increase of the test frequency, the dielectric loss is not obviously increased, which shows that the annealing of the film material prepared by the method in the oxygen atmosphere reduces the internal defects of the film, such as oxygen vacancy and the like, obviously reduces the loss and leakage current of the component film, and improves the use efficiency of the film.
As shown in FIG. 3, FIG. 3 shows the bilateral strain plots of the piezoelectric thin film materials BNT-0BZ, BNT-4BZ, BNT-5.5BZ and BNT-7BZ prepared in examples 1-4; as can be seen from fig. 3, the lead-free piezoelectric thin film materials prepared in examples 1-4 can obtain a strain value of 0.4% -0.7% at room temperature under 900kV/cm electric field, which is much higher than that of BNT-based other systems and lead-based bulk materials, and can meet the application requirements of the lead-free piezoelectric thin film materials in micro-drivers and high precision shifters.
The above-described embodiment is only one of the embodiments that can implement the technical solution of the present invention, and the scope of the present invention is not limited by the embodiment, but includes any variations, substitutions and other embodiments that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed.
Claims (10)
1. A lead-free piezoelectric film material is characterized in that the chemical general formula of the lead-free piezoelectric film material is as follows: (1-x%) (Bi)0.5Na0.5)TiO3-x％BaZrO3(ii) a Wherein x% is BaZrO3The value range of x is more than or equal to 0 and less than or equal to 7.
2. The lead-free piezoelectric film material according to claim 1, wherein the strain value of the lead-free piezoelectric film material is 0.4% to 0.7%.
3. The lead-free piezoelectric thin film material as claimed in claim 1, wherein the thickness of the lead-free piezoelectric thin film material is 900-1000 nm.
4. A method for preparing a lead-free piezoelectric thin film material, wherein the lead-free piezoelectric thin film material is the lead-free piezoelectric thin film material according to any one of claims 1 to 3; the method specifically comprises the following steps:
step 1, preparing a BNT-xBZ precursor solution;
step 2, aging the BNT-xBZ precursor solution to obtain sol;
step 3, uniformly spin-coating the sol on a substrate to obtain a wet film;
step 4, pyrolyzing and sintering the wet film to obtain an intermediate film;
step 5, repeating the step 3-4 on the intermediate film in the step 4 to obtain a film with a preset thickness;
and 6, carrying out annealing heat treatment on the film with the preset thickness in the step 5 to obtain the lead-free piezoelectric film material.
5. The method for preparing a lead-free piezoelectric film material according to claim 1, wherein in step 1, bismuth acetate, sodium acetate, tetrabutyl titanate, barium acetate and tetrabutyl zirconate are used as raw materials to prepare a BNT-xBZ precursor solution; wherein said bismuth acetate is provided in a 2% to 5% excess and said sodium acetate is provided in a 5% to 15% excess.
6. The method as claimed in claim 4, wherein in step 4, the wet film is pyrolyzed and sintered at a temperature of 410-420 ℃ for 10-15 min; the sintering treatment temperature is 650-700 ℃, and the heat preservation time is 3-10 min.
7. The method for preparing a lead-free piezoelectric thin film material according to claim 4, wherein in step 6, the annealing heat treatment process is performed on the thin film with a preset thickness in an oxygen atmosphere.
8. The method as claimed in claim 7, wherein the annealing temperature is 700-750 ℃ and the annealing time is 30-60 min.
9. The method for preparing a lead-free piezoelectric film material as claimed in claim 4, wherein in step 2, the BNT-xBZ precursor solution is aged for 24-36h at room temperature.
10. The method for preparing a lead-free piezoelectric film material according to claim 4, wherein in the step 3, the substrate is Pt substrate or TiO substrate2Substrate, SiO2A substrate or a Si substrate.
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