CN116234412A - High-electro-strain bismuth sodium titanate-based lead-free piezoelectric film and preparation method thereof - Google Patents
High-electro-strain bismuth sodium titanate-based lead-free piezoelectric film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high electro-strain bismuth sodium titanate-based lead-free piezoelectric film, which has the chemical general formula: 0.9212 (Bi) 0.5 Na 0.5 )TiO 3 ‑0.0588BaTiO 3 ‑0.02La 0.7 Sr 0.3 MnO 3 . The invention also provides a preparation method of the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film, which comprises the following steps: step S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the sodium bismuth titanate-based leadless piezoelectric film, and dissolving the bismuth nitrate, the sodium acetate, the barium acetate, the lanthanum acetate and the strontium acetate in acetic acid to prepare a first solution; s2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical general formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving the manganese acetate tetrahydrate in ethylene glycol monomethyl ether to prepare a second solution; step S3, mixing the first solution and the second solution to obtain a mixed solution, and adjusting the concentration and the pH value of the mixed solution to obtain a precursorA solution; s4, cleaning the substrate and drying the substrate; and S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Description
Technical Field
The invention belongs to the field of electronic functional materials and devices, and particularly relates to a sodium bismuth titanate-based lead-free piezoelectric film with high electro-strain and a preparation method thereof.
Background
Various functional devices are required in the future information society, such as micro-actuators, micro-ultrasonic transducers and the like to realize the functions of energy conversion, driving, sensing and the like, and piezoelectric thin film materials are paid attention to by researchers due to the excellent comprehensive properties of ferroelectricity, piezoelectricity, electro-optics and the like. At present, the piezoelectric films are widely used and lead-containing piezoelectric films with excessively high lead content are prepared and recycled, so that serious damage is brought to the environment and human beings, and although lead ban in commercial electronic products is gradually implemented, lead-based piezoelectric materials are still in an irreplaceable position in some high-precision technology and aerospace fields. Thus, achieving greater electrical strain in piezoelectric materials, particularly in lead-free materials, is a critical requirement for driving lead-free material applications.
In the lead-free piezoelectric material, bismuth sodium titanate (Bi 0.5 Na 0.5 )TiO 3 (BNT) -based materials have attracted extensive research interest due to their large strain response and high inverse piezoelectric coefficients. For example, by introducing a second or third phase to form a binary or ternary system, has excellent electro-strain at its quasi-homotypic phase boundaries (adv. Mate. 2016, 28, 574-578.). Also, most microelectronic devices are integrated on silicon substrates, and it is highly necessary to grow piezoelectric films directionally on Si substrates in order to bond them with other functional materials and develop new multifunctional devices. For this strategy, some buffer layer must be used, lanthanum nickelate LaNiO 3 (LNO) is a very attractive buffer layer candidate with a pseudo-cubic lattice parameter (0.384 nm) matching most ferroelectric perovskite materials. Based on theoretical calculation, in the presence of LaNiO 3 0.94 (Bi) of the (001) texture on the platinized silicon wafer of the buffer layer 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 In (BNTBT 6) films, not only the piezoelectric properties are improved, but also the depolarization temperature Td is increased. From this, both the (001) texture structure and the in-plane stretching strain induced by the bottom LNO layer can stabilize the low symmetry ferroelectric order and improve the piezoelectricity and thermal stability of the BNTBT6 film (adv. Electron. Mater.,2018,4,1800351.). However, as the thickness of the membrane increases, the stretching of the bottom LNO layer will decrease and the piezoelectric properties of the membrane will decrease. However, the prior artThere is no report in the art of at what thickness scale the piezoelectric film can exhibit excellent electrostrictive properties. In addition, although the bismuth sodium titanate-barium titanate component piezoelectric film has stronger ferroelectricity, the larger leakage current and the lower Curie temperature greatly limit the application of the bismuth sodium titanate-barium titanate component piezoelectric film in the aspect of devices.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a sodium bismuth titanate-based lead-free piezoelectric film with high electro-strain and a method for producing the same.
The invention provides a high electro-strain bismuth sodium titanate-based lead-free piezoelectric film, which has the following characteristics: the chemical general formula of the bismuth sodium titanate based leadless piezoelectric film is as follows: 0.9212 (Bi) 0.5 Na 0.5 )TiO 3 -0.0588BaTiO 3 -0.02La 0.7 Sr 0.3 MnO 3 。
The high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: wherein, the thickness range of the bismuth sodium titanate-based leadless piezoelectric film is 50 nm-500 nm.
The invention also provides a preparation method of the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film, which has the characteristics that the preparation method comprises the following steps: step S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the sodium bismuth titanate-based leadless piezoelectric film, and dissolving the bismuth nitrate, the sodium acetate, the barium acetate, the lanthanum acetate and the strontium acetate in acetic acid to prepare a first solution;
s2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical general formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving the manganese acetate tetrahydrate in ethylene glycol monomethyl ether to prepare a second solution;
step S3, mixing the first solution and the second solution to obtain a mixed solution, and adjusting the concentration and the pH value of the mixed solution to obtain a precursor solution;
s4, cleaning the substrate and drying the substrate;
and S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: in the step S1, bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate are dissolved in acetic acid, stirred and heated to boil, and kept for 20-30 minutes to prepare a first solution.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: in the step S2, after acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate are dissolved in ethylene glycol monomethyl ether, stirring and heating to 40-60 ℃, and keeping stirring for 20-30 minutes to prepare a second solution.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: in the step S3, the concentration of the mixed solution is regulated by using acetic acid, the pH value of the mixed solution is regulated by using ammonia water, and the mixed solution is stirred for 200-400 minutes at 40-60 ℃ after the regulation is completed, so as to prepare the precursor solution.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: in the step S3, the concentration of the mixed solution is adjusted to be 0.1 mol/L to 0.4 mol/L, and the pH value of the mixed solution is adjusted to be 4 to 6.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: the substrate is LaNiO 3 /Pt/Ti/SiO 2 Si substrate.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: in the step S4, the substrate is respectively ultrasonically cleaned for 20 minutes by using acetone, deionized water and ethanol in sequence, and then the substrate is dried by using high-purity nitrogen.
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film provided by the invention can also have the following characteristics: step S5 further comprises the sub-steps of:
step S5-1, spin coating a layer of precursor solution on a substrate, wherein the rotation speed is 4000 rpm, and the time is 30 seconds, so as to obtain a film;
s5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes;
and step S5-3, repeating the step S5-1 and the step S5-2 until a film with the required thickness is obtained, and finally, annealing at 600-750 ℃ for 30-60 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Effects and effects of the invention
According to the bismuth sodium titanate-based lead-free piezoelectric film with high electro-strain, the lanthanum strontium manganate is doped into the bismuth sodium titanate-barium titanate film, so that the leakage current of the bismuth sodium titanate-barium titanate film is reduced, domain pinning is weakened, the polarization intensity of the film is improved, and the electro-strain characteristic is enhanced. The preparation method disclosed by the invention is simple in process, the thickness of the prepared bismuth sodium titanate-based leadless piezoelectric film can be controlled by repeatedly carrying out spin coating and heat treatment, the control of the lanthanum nickelate substrate on the film structure is realized, and the electro-strain performance of the bismuth sodium titanate-based leadless piezoelectric film can be further improved.
Drawings
FIG. 1 is a flow chart of a method of preparing a high electro-strain bismuth sodium titanate based lead-free piezoelectric film in an embodiment of the present invention;
FIG. 2 is a sectional scanning electron microscope image of the sodium bismuth titanate-based leadless piezoelectric film prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern of the sodium bismuth titanate based leadless piezoelectric film prepared in examples 1 to 4 and comparative example of the present invention;
FIG. 4 is the displacement generated by electrostriction of the sodium bismuth titanate based leadless piezoelectric films prepared in examples 1 to 4 and the comparative example of the present invention;
fig. 5 is an electric field-strain curve of the sodium bismuth titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative examples of the present invention.
Detailed Description
In order to make the technical means, creation characteristics, achievement purposes and effects of the invention easy to understand, the following examples specifically describe the high electro-strain bismuth sodium titanate-based leadless piezoelectric film and the preparation method thereof according to the present invention with reference to the accompanying drawings.
Example 1 ]
Fig. 1 is a flow chart of a method for preparing a high electro-strain bismuth sodium titanate based lead-free piezoelectric film according to example 1 of the present invention.
As shown in fig. 1, the preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film of the embodiment comprises the following steps:
step S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving the bismuth nitrate, the sodium acetate, the barium acetate, the lanthanum acetate and the strontium acetate in acetic acid to prepare a first solution, wherein the specific operation is as follows:
bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate are weighed according to the stoichiometric ratio of the chemical general formula of the bismuth sodium titanate-based leadless piezoelectric film, and as bismuth element and sodium element volatilize more severely at high temperature, bismuth nitrate and sodium acetate are excessively weighed to 5%, and the weighed medicines are dissolved in acetic acid, stirred and heated to boil for 20 minutes, so as to prepare a first solution.
Step S2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical general formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving in ethylene glycol methyl ether to prepare a second solution, wherein the specific operation comprises the following steps:
and weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, dissolving in ethylene glycol methyl ether, stirring, heating to 50 ℃, and stirring for 20 minutes to obtain a second solution.
Step S3, mixing the first solution and the second solution to obtain a mixed solution, and adjusting the concentration and the pH value of the mixed solution to obtain a precursor solution, wherein the specific operation is as follows:
mixing the first solution and the second solution to obtain a mixed solution, adding ammonia water to regulate the pH value until the solute is completely dissolved, adding acetic acid to regulate the concentration to 0.15 mol/L, and stirring at 50 ℃ for 300 minutes to obtain a precursor solution.
Step S4, cleaning the substrate, and drying the substrate by blow, wherein the specific operation is as follows:
LaNiO is processed by 3 /Pt/Ti/SiO 2 The Si substrate was cut into a square with a side length of 10 mm, and sequentially washed with acetone, deionized water and ethanol for 20 minutes, respectively, and then dried with high-purity nitrogen gas.
And S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Step S5 further comprises the sub-steps of:
and step S5-1, spin-coating a layer of precursor solution on the substrate at 4000 rpm for 30 seconds to obtain the film.
And S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes.
And step S5-3, repeating the step S5-1 and the step S5-2 for 13 times to obtain a film with the thickness of 250 nanometers, and finally annealing at 700 ℃ for 45 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
In the embodiment, spin coating is repeated for 13 times, and the bismuth sodium titanate-based lead-free piezoelectric film with the thickness of 250 nanometers is prepared. And after the preparation was completed, an electrode having a diameter of 1 mm was plated on the surface of the sodium bismuth titanate-based leadless piezoelectric film using a sputtering apparatus.
FIG. 2 is a sectional scanning electron microscope image of a sodium bismuth titanate-based leadless piezoelectric film prepared in example 1 of the present invention.
As shown in FIG. 2, the bismuth sodium titanate based leadless piezoelectric film prepared in the embodiment has a flat and smooth surface, no obvious air holes, and a thickness of about 250 nanometers, which indicates that the preparation method of the invention has good operability, has simple process and can control the thickness of the bismuth sodium titanate based leadless piezoelectric film by repeatedly carrying out spin coating and heat treatment.
Example 2 ]
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film comprises the following steps:
and S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, weighing 5% of bismuth nitrate and sodium acetate excessively because bismuth element and sodium element volatilize more severely at high temperature, dissolving the weighed medicine in acetic acid, stirring and heating to boil for 20 minutes, and preparing a first solution.
And S2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, dissolving in ethylene glycol methyl ether, stirring, heating to 50 ℃, and stirring for 20 minutes to obtain a second solution.
And S3, mixing the first solution and the second solution to obtain a mixed solution, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to 0.15 mol/liter, and stirring at 50 ℃ for 300 minutes to obtain a precursor solution.
Step S4, laNiO is processed 3 /Pt/Ti/SiO 2 The Si substrate was cut into a square with a side length of 10 mm, and sequentially washed with acetone, deionized water and ethanol for 20 minutes, respectively, and then dried with high-purity nitrogen gas.
And S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Step S5 further comprises the sub-steps of:
and step S5-1, spin-coating a layer of precursor solution on the substrate at 4000 rpm for 30 seconds to obtain the film.
And S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes.
And step S5-3, repeating the step S5-1 and the step S5-2 for 3 times to obtain a film with the thickness of 60 nanometers, and finally annealing at 700 ℃ for 45 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
In the embodiment, spin coating is repeated for 3 times, and the bismuth sodium titanate-based lead-free piezoelectric film with the thickness of 60 nanometers is prepared. And after the preparation was completed, an electrode having a diameter of 1 mm was plated on the surface of the sodium bismuth titanate-based leadless piezoelectric film using a sputtering apparatus.
Example 3 ]
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film comprises the following steps:
and S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, weighing 5% of bismuth nitrate and sodium acetate excessively because bismuth element and sodium element volatilize more severely at high temperature, dissolving the weighed medicine in acetic acid, stirring and heating to boil for 20 minutes, and preparing a first solution.
And S2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, dissolving in ethylene glycol methyl ether, stirring, heating to 50 ℃, and stirring for 20 minutes to obtain a second solution.
And S3, mixing the first solution and the second solution to obtain a mixed solution, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to 0.15 mol/liter, and stirring at 50 ℃ for 300 minutes to obtain a precursor solution.
Step S4, laNiO is processed 3 /Pt/Ti/SiO 2 The Si substrate was cut into a square with a side length of 10 mm, and sequentially washed with acetone, deionized water and ethanol for 20 minutes, respectively, and then dried with high-purity nitrogen gas.
And S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Step S5 further comprises the sub-steps of:
and step S5-1, spin-coating a layer of precursor solution on the substrate at 4000 rpm for 30 seconds to obtain the film.
And S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes.
And step S5-3, repeating the step S5-1 and the step S5-2 for 7 times to obtain a film with the thickness of 134 nanometers, and finally annealing at 700 ℃ for 45 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
In the embodiment, spin coating is repeated for 7 times, and the sodium bismuth titanate-based lead-free piezoelectric film with the thickness of 134 nanometers is prepared. And after the preparation was completed, an electrode having a diameter of 1 mm was plated on the surface of the sodium bismuth titanate-based leadless piezoelectric film using a sputtering apparatus.
Example 4 ]
The preparation method of the high electro-strain bismuth sodium titanate-based lead-free piezoelectric film comprises the following steps:
and S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, weighing 5% of bismuth nitrate and sodium acetate excessively because bismuth element and sodium element volatilize more severely at high temperature, dissolving the weighed medicine in acetic acid, stirring and heating to boil for 20 minutes, and preparing a first solution.
And S2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, dissolving in ethylene glycol methyl ether, stirring, heating to 50 ℃, and stirring for 20 minutes to obtain a second solution.
And S3, mixing the first solution and the second solution to obtain a mixed solution, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to 0.15 mol/liter, and stirring at 50 ℃ for 300 minutes to obtain a precursor solution.
Step S4, laNiO is processed 3 /Pt/Ti/SiO 2 The Si substrate was cut into a square with a side length of 10 mm, and sequentially washed with acetone, deionized water and ethanol for 20 minutes, respectively, and then dried with high-purity nitrogen gas.
And S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Step S5 further comprises the sub-steps of:
and step S5-1, spin-coating a layer of precursor solution on the substrate at 4000 rpm for 30 seconds to obtain the film.
And S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes.
And step S5-3, repeating the step S5-1 and the step S5-2 for 26 times to obtain a film with the thickness of 500 nanometers, and finally annealing at 700 ℃ for 45 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
In the embodiment, spin coating is repeated 26 times to prepare the bismuth sodium titanate-based lead-free piezoelectric film with the thickness of 500 nanometers. And after the preparation was completed, an electrode having a diameter of 1 mm was plated on the surface of the sodium bismuth titanate-based leadless piezoelectric film using a sputtering apparatus.
Comparative example
In this comparative example, undoped lanthanum strontium manganate La 0.7 Sr 0.3 MnO 3 The chemical general formula of the prepared bismuth sodium titanate-based lead-free piezoelectric film is 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 The preparation process comprises the following steps:
step S1, according to the chemical formula 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 Bismuth nitrate, sodium acetate and barium acetate are weighed according to the stoichiometric ratio, and bismuth element and sodium element volatilize more severely at high temperature, bismuth nitrate and sodium acetate are weighed 5% excessively, and the weighed medicines are dissolved in acetic acid, stirred and heated to boil for 20 minutes, so that a first solution is prepared.
Step S2, according to the chemical formula 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 The stoichiometric ratio of the chemical formula of (2) is that acetylacetone and tetrabutyl titanate are dissolved in ethylene glycol methyl ether, and the mixture is stirred and heated to 50 ℃ and stirred for 20 minutes to prepare a second solution.
And S3, mixing the first solution and the second solution to obtain a mixed solution, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to 0.15 mol/liter, and stirring at 50 ℃ for 300 minutes to obtain a precursor solution.
Step S4, laNiO is processed 3 /Pt/Ti/SiO 2 The Si substrate was cut into a square with a side length of 10 mm, and sequentially washed with acetone, deionized water and ethanol for 20 minutes, respectively, and then dried with high-purity nitrogen gas.
And S5, coating the precursor solution on a substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
Step S5 further comprises the sub-steps of:
and step S5-1, spin-coating a layer of precursor solution on the substrate at 4000 rpm for 30 seconds to obtain the film.
And S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes.
And step S5-3, repeating the step S5-1 and the step S5-2 for 13 times to obtain a film with the thickness of 250 nanometers, and finally annealing at 700 ℃ for 45 minutes to obtain the bismuth sodium titanate-based leadless piezoelectric film.
In the comparative example, spin coating was repeated 13 times to prepare a bismuth sodium titanate-based lead-free piezoelectric film of undoped lanthanum strontium manganate having a thickness of 250 nm. And after the preparation was completed, an electrode having a diameter of 1 mm was plated on the surface of the sodium bismuth titanate-based leadless piezoelectric film using a sputtering apparatus.
FIG. 3 is an X-ray diffraction pattern of the sodium bismuth titanate based leadless piezoelectric film prepared in example 1 to example 4 of the present invention and comparative example.
As shown in fig. 3, the sodium bismuth titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative example all have typical perovskite structures, no significant impurity phase occurs, and the film has a preferred orientation of (001).
The sodium bismuth titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative example were subjected to an alternating electric field of 500kV/cm, and the change in displacement due to electrostriction was measured. Fig. 4 is a displacement generated by electrostriction of the sodium bismuth titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative examples of the present invention.
As shown in FIG. 4, the displacement generated by electrostriction of the bismuth sodium titanate-based leadless piezoelectric film with the film thickness of 60 nanometers prepared in example 2 is slightly lower than that generated by electrostriction of the bismuth sodium titanate-based leadless piezoelectric film prepared in comparative example, and the doped La of 2% prepared in examples 1, 3 and 4 0.7 Sr 0.3 MnO 3 0.9212 (Bi) 0.5 Na 0.5 )TiO 3 -0.0588BaTiO 3 -0.02La 0.7 Sr 0.3 MnO 3 The displacement generated by the electrostriction of the film is obviously higher than 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 The displacement generated by the electrostriction of the film is obviously increased along with the increase of the thickness of the sodium bismuth titanate-based lead-free piezoelectric film.
The bismuth sodium titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative examples were subjected to an electric field of 0kV/cm to 500kV/cm, and strain changes generated with the increase of the electric field strength were measured. Fig. 5 is an electric field-strain curve of the sodium bismuth titanate-based leadless piezoelectric films prepared in examples 1 to 4 and comparative examples of the present invention.
As shown in FIG. 5, the bismuth sodium titanate-based leadless piezoelectric film prepared in example 2 has a film thickness of 60 nm and an electro-strain property slightly lower than that of the bismuth sodium titanate-based leadless piezoelectric film prepared in comparative example, and has a film thickness of 250 nm 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 The electro-strain characteristics of the films were all better than those of the sodium bismuth titanate-based leadless piezoelectric films prepared in comparative examples 1, 3 and 4, and were all 0.94 (Bi 0.5 Na 0.5 )TiO 3 -0.06BaTiO 3 The electro-strain properties of the film.
And when the thickness of the prepared bismuth sodium titanate based leadless piezoelectric film is 250 nanometers, the bismuth sodium titanate based leadless piezoelectric film can generate a high strain value of 0.64 percent under the application of an electric field of 500 kV/cm. The substrate binding effect is strong to prevent the film from vibrating when the film thickness is low, the electro-strain performance of the film is affected, and in addition, when the film thickness is too high, the (001) preferential orientation structure of the film is weakenedSince the enhancement of domain pinning also leads to the reduction of the electro-strain performance of the film, when preparing a bismuth sodium titanate-based lead-free piezoelectric film, the film thickness needs to be controlled within a proper range, and LaNiO is used as a substrate 3 /Pt/Ti/SiO 2 The Si substrate can effectively enhance the piezoelectric performance of the sodium bismuth titanate-based lead-free piezoelectric film.
Effects and effects of the examples
As can be seen from comparison of examples 1-4 and comparative examples, the bismuth sodium titanate-based leadless piezoelectric film with high electro-strain according to the invention can reduce leakage current of bismuth sodium titanate-barium titanate film, reduce domain pinning, further improve polarization intensity of the film and enhance electro-strain characteristics by doping strontium lanthanum manganate into bismuth sodium titanate-barium titanate film.
As can be seen from comparison of examples 1-4, the thickness of the bismuth sodium titanate-based leadless piezoelectric film is related to the electro-strain performance, the thickness of the bismuth sodium titanate-based leadless piezoelectric film can be controlled by the preparation method of the invention, the control of the lanthanum nickelate substrate on the film structure is realized, the better electro-strain performance can be obtained at the film thickness of 50-500 nanometers, and particularly, the most excellent electro-strain performance can be obtained at the film thickness of 250 nanometers.
Claims (10)
1. The high electro-strain bismuth sodium titanate based lead-free piezoelectric film is characterized by having a chemical general formula:
0.9212(Bi 0.5 Na 0.5 )TiO 3 -0.0588BaTiO 3 -0.02La 0.7 Sr 0.3 MnO 3 。
2. the high electro-strain bismuth sodium titanate based lead-free piezoelectric film according to claim 1, wherein:
wherein the thickness range of the bismuth sodium titanate-based lead-free piezoelectric film is 50 nm-500 nm.
3. A method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film as claimed in any one of claims 1 to 2, comprising the steps of:
step S1, weighing bismuth nitrate, sodium acetate, barium acetate, lanthanum acetate and strontium acetate according to the stoichiometric ratio of the chemical formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving the bismuth nitrate, the sodium acetate, the barium acetate, the lanthanum acetate and the strontium acetate in acetic acid to prepare a first solution;
s2, weighing acetylacetone, tetrabutyl titanate and manganese acetate tetrahydrate according to the stoichiometric ratio of the chemical general formula of the bismuth sodium titanate-based leadless piezoelectric film, and dissolving the acetylacetone, the tetrabutyl titanate and the manganese acetate tetrahydrate in ethylene glycol monomethyl ether to prepare a second solution;
step S3, mixing the first solution and the second solution to obtain a mixed solution, and adjusting the concentration and the pH value of the mixed solution to obtain a precursor solution;
s4, cleaning the substrate and drying the substrate;
and S5, coating the precursor solution on the substrate to prepare the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
4. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
in step S1, after the bismuth nitrate, the sodium acetate, the barium acetate, the lanthanum acetate, and the strontium acetate are dissolved in the acetic acid, stirring and heating to boil, and maintaining for 20 minutes to 30 minutes, to obtain the first solution.
5. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
in the step S2, after the acetylacetone, the tetrabutyl titanate and the manganese acetate tetrahydrate are dissolved in the ethylene glycol monomethyl ether, stirring and heating to 40-60 ℃, and keeping stirring for 20-30 minutes to prepare the second solution.
6. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
in the step S3, the concentration of the mixed solution is regulated by using acetic acid, the pH value of the mixed solution is regulated by using ammonia water, and the mixed solution is stirred for 200-400 minutes at 40-60 ℃ after the regulation is completed to prepare the precursor solution.
7. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
in the step S3, the concentration of the mixed solution is adjusted to be 0.1 mol/L to 0.4 mol/L, and the pH value of the mixed solution is adjusted to be 4 to 6.
8. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
wherein the substrate is LaNiO 3 /Pt/Ti/SiO 2 Si substrate.
9. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
in step S4, acetone, deionized water and ethanol are sequentially used to ultrasonically clean the substrate for 20 minutes, and then high-purity nitrogen is used to blow-dry the substrate.
10. The method for preparing the high electro-strain bismuth sodium titanate based leadless piezoelectric film according to claim 3, wherein the method comprises the following steps:
wherein step S5 further comprises the sub-steps of:
step S5-1, spin-coating a layer of the precursor solution on the substrate, wherein the rotating speed is 4000 rpm, and the time is 30 seconds, so as to obtain a film;
step S5-2, placing the film in a tube furnace, and sequentially treating at 200 ℃ for 5 minutes, 450 ℃ for 5 minutes and 700 ℃ for 5 minutes;
and step S5-3, repeating the step S5-1 and the step S5-2 until the film with the required thickness is obtained, and finally, annealing at 600-750 ℃ for 30-60 minutes to obtain the high-electro-strain bismuth sodium titanate-based lead-free piezoelectric film.
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