CN113213920A - Sodium bismuth titanate-based lead-free piezoelectric film and preparation method thereof - Google Patents

Sodium bismuth titanate-based lead-free piezoelectric film and preparation method thereof Download PDF

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CN113213920A
CN113213920A CN202110631050.XA CN202110631050A CN113213920A CN 113213920 A CN113213920 A CN 113213920A CN 202110631050 A CN202110631050 A CN 202110631050A CN 113213920 A CN113213920 A CN 113213920A
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based lead
bismuth titanate
sodium
piezoelectric film
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沈波
朱坤
翟继卫
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Tongji University
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Abstract

The invention relates to a sodium bismuth titanate-based lead-free piezoelectric film and a preparation method thereof, belonging to the field of electronic functional materials and devices. The preparation method provided by the invention comprises the following steps: step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A; step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B; step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and step 4, coating the mixed solution C on the treated substrate by using a spin coating method, and obtaining (0.72-x) (Bi) after high-temperature treatment0.5Na0.5)TiO3‑0.28SrTiO3‑xBi(Fe0.95Mn0.03Ti0.02)O3The ternary system sodium bismuth titanate lead-free piezoelectric film. Therefore, the piezoelectric film prepared by the invention has the advantages of flat and smooth surface, typical perovskite structure and high yieldHigh polarization strength and excellent piezoelectric performance, and the highest inverse piezoelectric coefficient can reach 179.7 picometers per volt, thereby having very important significance for developing high-performance lead-free piezoelectric films.

Description

Sodium bismuth titanate-based lead-free piezoelectric film and preparation method thereof
Technical Field
The invention relates to the field of electronic functional materials and devices, in particular to a sodium bismuth titanate-based lead-free piezoelectric film and a preparation method thereof.
Background
The piezoelectric thin film material has been rapidly developed as a hot spot in the scientific community, mainly because it has excellent comprehensive properties of ferroelectric, piezoelectric and electro-optical, and can be widely applied to micro-electro-mechanical systems (MEMS) to realize functions of energy conversion, driving, sensing, etc. Compared with piezoelectric ceramics, the piezoelectric film material has the advantages of lower driving voltage (generally, a voltage of 3-5V is enough to enable the piezoelectric film material to work), large inductive force, good driving range and wider working frequency range. However, most of the piezoelectric thin film devices on the market today are mainly made of lead-based piezoelectric materials, and in view of human health and environmental protection, researchers have been working on the basic research of lead-free piezoelectric materials to put them into practical use in recent years.
Among all lead-free candidate materials, the bismuth ferrite material has a multiferroic perovskite structure, is an electronic functional ceramic material with wide application, has the advantages of high dielectric constant, high Curie temperature, strong ferroelectricity and the like, and is widely applied to the electronic, mechanical and ceramic industries. The piezoelectric film with the bismuth sodium titanate-strontium titanate component has stronger ferroelectricity, but the application of the piezoelectric film in the aspect of devices is greatly limited by larger leakage current and lower Curie temperature.
The sodium bismuth titanate material has Curie temperature (T)c320 deg.C), strong ferroelectric property (P)r＝38μC/cm2) And good electromechanical properties (k)p50%) and the like (Ferroelectrics,1982,40(1): 75-77), and the characteristics are very favorable for preparing piezoelectric thin film integrated devices. However, at room temperature, the coercive field of sodium bismuth titanate is large (E)c73kV/cm), high conductivity and difficult polarization, and manganese and titanium doping can reduce the coercive field and improve the polarization condition, so as to improve the performance, researchers in various countries find that a binary or ternary system is formed by introducing a second phase or a third phase, and the ferroelectric and piezoelectric performance at the quasi-homomorphic phase boundary is excellent. (1-x) (Bi)0.5Na0.5)TiO3-xSrTiO3(BNT-xST) piezoelectric material, which is of great interest due to increased strain at the phase boundary under low electric field (j.eur.center.soc.2010, 30: 1827-.
Bismuth ferrite (BiFeO)3) Is a multiferroic perovskite with ferroelectric ordered antiferromagnetism and has better polarization characteristics (Science 2009,326: 977-. However, BiFeO3The large leakage current of the film at room temperature limits its wide application. (Mn, Ti) Co-doped Bi (Fe)0.95Mn0.03Ti0.02)O3The film not only has good ferroelectricity, but also has low leakage current (appl. phys. Lett.2009,94(11):112904), and can be used as a candidate material for modifying BNT-ST-based film, but no relevant report is made.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a sodium bismuth titanate-based lead-free piezoelectric film and a method for producing the same.
The invention provides a sodium bismuth titanate-based lead-free piezoelectric film, which is characterized by having the following chemical formula: (0.72-x) (Bi)0.5Na0.5)TiO3-0.28SrTiO3-xBi(Fe0.95Mn0.03Ti0.02)O3Wherein, 0<x<0.025, x is preferably 0.015.
The invention provides a preparation method of a sodium bismuth titanate-based lead-free piezoelectric film, which is used for preparing the sodium bismuth titanate-based lead-free piezoelectric film and has the characteristics that the preparation method comprises the following steps: step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A; step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B; step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and step 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: the mass excess of the bismuth nitrate and the sodium acetate is 10 percent, wherein the molar ratio of the bismuth nitrate to the sodium acetate to the strontium acetate is (0.3-0.5): (0.35-0.4): (0.2-0.3), preferably 0.40425: 0.38775: 0.28.
the preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein the mol ratio of acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate is (1.5-2.0): (0.5-1.0): (0.01-0.02): (0.0007-0.0008), preferably 1.9706: 0.9853: 0.01395: 0.00075.
the preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein the concentration of the mixed liquid C is 0.15-0.40 mol/L.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein, the processing procedure of the substrate is as follows: step 1, adding a solvent into a substrate, and ultrasonically cleaning the substrate for a certain time to obtain a cleaned substrate; and step 2, drying the cleaned substrate by using nitrogen to obtain the processed substrate.
The preparation method of the bismuth titanate sodium-based lead-free piezoelectric film provided by the invention is also characterized in that the substrate is Pt/Ti/SiO2a/Si substrate.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein, the high-temperature treatment comprises the following steps: and rotationally coating the mixed solution C on the treated substrate to obtain a first film, treating the first film in a tubular furnace at the temperature of 200-750 ℃ for 3-10 min, and annealing for 30-60 min to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein the reverse piezoelectric coefficient of the bismuth titanate sodium-based lead-free piezoelectric film is 170.0-180.0 picometers/volt, and is preferably 179.7 picometers/volt.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein the certain time is 10min-30min, preferably 20 min.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film provided by the invention is also characterized in that: wherein the thickness of the sodium bismuth titanate-based lead-free piezoelectric film is 300-400 nanometers.
Action and Effect of the invention
According to the preparation method of the sodium bismuth titanate-based lead-free piezoelectric film, the preparation method comprises the following steps: step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A; step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B; step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and step 4, coating the mixed solution C on the treated substrate by using a spin coating method, and obtaining (0.72-x) (Bi) after high-temperature treatment0.5Na0.5)TiO3-0.28SrTiO3-xBi(Fe0.95Mn0.03Ti0.02)O3The ternary system sodium bismuth titanate lead-free piezoelectric film. Therefore, the piezoelectric film prepared by the method has the advantages of flat and smooth surface, typical perovskite structure, higher polarization strength and excellent piezoelectric performance, and the inverse piezoelectric coefficient can reach 179.7 picometers per volt at most, thereby having very important significance for developing high-performance lead-free piezoelectric films.
Drawings
Fig. 1 is a sectional scanning electron microscope image of a sodium bismuth titanate-based lead-free piezoelectric film obtained in example 2 of the present invention;
FIG. 2 is grazing incidence X-ray diffraction patterns of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4 of the present invention;
FIG. 3 is a hysteresis loop diagram of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4 of the present invention; and
fig. 4 is a piezoelectric response phase-voltage curve and a displacement-voltage curve of the sodium bismuth titanate-based lead-free piezoelectric thin film obtained in comparative example 1 and examples 1 to 4 of the present invention.
Detailed Description
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A;
step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B;
step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and step 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In order to make the technical means, the creation features, the achievement objects and the effects of the present invention easy to understand, the following will specifically describe a sodium bismuth titanate based lead-free piezoelectric film and a preparation method thereof with reference to the embodiments and the accompanying drawings.
< example 1>
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, 3.9746 g of bismuth nitrate, 1.0735 g of sodium acetate, 1.2270 g of strontium acetate were dissolved in 40 ml of acetic acid and stirred at 50 ℃ for 20 minutes to prepare solution A.
Step 2, 4.0452 g of acetylacetone, 6.8086 g of tetrabutyltitanate, 0.0767 g of iron (III) nitrate nonahydrate, 0.0025 g of manganese (II) acetate tetrahydrate are dissolved in 10 ml of ethylene glycol monomethyl ether, heated to 50 ℃ and stirred for 20 minutes to obtain solution B.
And 3, mixing the solution A and the solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to be 0.25 mol/L, and stirring for 300 minutes at 50 ℃ to obtain a mixed solution C.
And 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In this example 1, the substrate was processed as follows: mixing Pt/Ti/SiO2Cutting the Si substrate into squares with the side length of 12 mm, sequentially washing the squares for 20 minutes by using acetone, deionized water and ethanol, and blow-drying the substrate by using high-purity nitrogen to obtain the processed substrate.
In this embodiment 1, the high temperature treatment process includes the following steps:
step 1, spin coating on Pt/Ti/SiO2Spin coating a layer of mixture on a/Si substrateAnd (3) mixing the solution C at the rotating speed of 3000 r/s for 30 s to obtain a first film.
And 2, treating the first film in a tube furnace at 200 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 750 ℃ for 5 minutes in sequence.
Step 3, repeating the step 2 until a film with the thickness of 390 nm is obtained, and annealing the film with the thickness of 390 nm at 750 ℃ for 45 minutes to obtain 0.71 (Bi)0.5Na0.5)TiO3-0.28SrTiO3-0.01Bi(Fe0.95Mn0.03Ti0.02)O3Sodium bismuth titanate based lead-free piezoelectric film.
And 4, plating an electrode with the diameter of 0.5 mm on the surface of the sodium bismuth titanate-based lead-free piezoelectric film by using a sputtering instrument.
< example 2>
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, 4.0018 g of bismuth nitrate, 1.0660 g of sodium acetate, 1.2270 g of strontium acetate were dissolved in 40 ml of acetic acid and stirred at 50 ℃ for 20 minutes to prepare solution A.
Step 2, 4.0452 g of acetylacetone, 6.7749 g of tetrabutyltitanate, 0.1150 g of iron (III) nitrate nonahydrate, 0.0037 g of manganese (II) acetate tetrahydrate were dissolved in 10 ml of ethylene glycol monomethyl ether, heated to 50 ℃ and stirred for 20 minutes to prepare a solution B.
And 3, mixing the solution A and the solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to be 0.25 mol/L, and stirring for 300 minutes at 50 ℃ to obtain a mixed solution C.
And 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In this embodiment, the substrate is processed as follows: mixing Pt/Ti/SiO2Cutting the Si substrate into squares with the side length of 12 mm, sequentially washing the squares for 20 minutes by using acetone, deionized water and ethanol, and blow-drying the substrate by using high-purity nitrogen to obtain the processed substrate.
In this embodiment 2, the high temperature treatment process includes the following steps:
step 1, spin coating on Pt/Ti/SiO2And coating a layer of mixed solution C on the Si substrate in a rotating way, wherein the rotating speed is 3000 rpm for 30 seconds, and obtaining a first film.
And 2, treating the first film in a tube furnace at 200 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 750 ℃ for 5 minutes in sequence.
Step 3, repeating the step 2 until a film with the thickness of 0.71 (Bi) is obtained, and annealing the film with the thickness of 0 ℃ for 45 minutes at 750 DEG C0.5Na0.5)TiO3-0.28SrTiO3-0.01Bi(Fe0.95Mn0.03Ti0.02)O3Sodium bismuth titanate based lead-free piezoelectric film.
And 4, plating an electrode with the diameter of 0.5 mm on the surface of the sodium bismuth titanate-based lead-free piezoelectric film by using a sputtering instrument.
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of a sodium bismuth titanate-based lead-free piezoelectric thin film obtained in example 2. As can be seen from fig. 1, the piezoelectric film prepared in example 2 has a flat and smooth surface, no obvious pores, and a thickness of 390 nm, and can be prepared by simple repeated preparation, which indicates that the piezoelectric film has good operability.
< example 3>
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, 4.0290 g of bismuth nitrate, 1.0584 g of sodium acetate, 1.2270 g of strontium acetate were dissolved in 40 ml of acetic acid and stirred at 50 ℃ for 20 minutes to prepare solution A.
Step 2, 4.0452 g of acetylacetone, 6.7412 g of tetrabutyltitanate, 0.1534 g of iron (III) nitrate nonahydrate, 0.0050 g of manganese (II) acetate tetrahydrate were dissolved in 10 ml of ethylene glycol monomethyl ether, heated to 50 ℃ and stirred for 20 minutes to prepare a solution B.
And 3, mixing the solution A and the solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to be 0.25 mol/L, and stirring for 300 minutes at 50 ℃ to obtain a mixed solution C.
And 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In this example 3, the substrate was processed as follows: mixing Pt/Ti/SiO2Cutting the Si substrate into squares with the side length of 12 mm, sequentially washing the squares for 20 minutes by using acetone, deionized water and ethanol, and blow-drying the substrate by using high-purity nitrogen to obtain the processed substrate.
In this embodiment 3, the high temperature treatment process includes the following steps:
step 1, spin coating on Pt/Ti/SiO2And coating a layer of mixed solution C on the Si substrate in a rotating way, wherein the rotating speed is 3000 rpm for 30 seconds, and obtaining a first film.
And 2, treating the first film in a tube furnace at 200 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 750 ℃ for 5 minutes in sequence.
Step 3, repeating the step 2 until a film with the thickness of 0.7 is obtained, and annealing the film with the thickness of 0 ℃ for 45 minutes at 750 ℃ to obtain the film (Bi)0.5Na0.5)TiO3-0.28SrTiO3-0.02Bi(Fe0.95Mn0.03Ti0.02)O3Sodium bismuth titanate based lead-free piezoelectric film.
And 4, plating an electrode with the diameter of 0.5 mm on the surface of the sodium bismuth titanate-based lead-free piezoelectric film by using a sputtering instrument.
< example 4>
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, 4.0563 g of bismuth nitrate, 1.0508 g of sodium acetate, 1.2270 g of strontium acetate were dissolved in 40 ml of acetic acid and stirred at 50 ℃ for 20 minutes to prepare solution A.
Step 2, 4.0452 g of acetylacetone, 6.7075 g of tetrabutyltitanate, 0.1917 g of iron (III) nitrate nonahydrate, 0.0062 g of manganese (II) acetate tetrahydrate were dissolved in 10 ml of ethylene glycol monomethyl ether, heated to 50 ℃ and stirred for 20 minutes to prepare a solution B.
And 3, mixing the solution A and the solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to be 0.25 mol/L, and stirring for 300 minutes at 50 ℃ to obtain a mixed solution C.
And 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In this example 4, the substrate was processed as follows: mixing Pt/Ti/SiO2Cutting the Si substrate into squares with the side length of 12 mm, sequentially washing the squares for 20 minutes by using acetone, deionized water and ethanol, and blow-drying the substrate by using high-purity nitrogen to obtain the processed substrate.
In this embodiment 4, the high temperature treatment process includes the following steps:
step 1, spin coating on Pt/Ti/SiO2And coating a layer of mixed solution C on the Si substrate in a rotating way, wherein the rotating speed is 3000 rpm for 30 seconds, and obtaining a first film.
And 2, treating the first film in a tube furnace at 200 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 750 ℃ for 5 minutes in sequence.
Step 3, repeating the step 2 until a film with the thickness of 750 ℃ is obtained, and annealing the film with the thickness of 750 ℃ for 45 minutes to obtain 0.695 (Bi)0.5Na0.5)TiO3-0.28SrTiO3-0.025Bi(Fe0.95Mn0.03Ti0.02)O3Sodium bismuth titanate based lead-free piezoelectric film.
And 4, plating an electrode with the diameter of 0.5 mm on the surface of the sodium bismuth titanate-based lead-free piezoelectric film by using a sputtering instrument.
< comparative example 1>
A preparation method of a sodium bismuth titanate-based lead-free piezoelectric film comprises the following steps:
step 1, 3.9206 g of bismuth nitrate, 1.0886 g of sodium acetate, 1.2270 g of strontium acetate were dissolved in 40 ml of acetic acid and stirred at 50 ℃ for 20 minutes to prepare solution A.
Step 2, 4.0452 g of acetylacetone and 6.8760 g of tetrabutyl titanate are dissolved in 10 ml of ethylene glycol monomethyl ether, heated to 50 ℃ and stirred for 20 minutes to obtain solution B.
And 3, mixing the solution A and the solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration to be 0.25 mol/L, and stirring for 300 minutes at 50 ℃ to obtain a mixed solution C.
And 4, coating the mixed solution C on the treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
In comparative example 1, the substrate was treated as follows: mixing Pt/Ti/SiO2Cutting the Si substrate into squares with the side length of 12 mm, sequentially washing the squares for 20 minutes by using acetone, deionized water and ethanol, and blow-drying the substrate by using high-purity nitrogen to obtain the processed substrate.
In comparative example 1, the process of high temperature treatment comprises the following steps:
step 1, spin coating on Pt/Ti/SiO2And coating a layer of mixed solution C on the Si substrate in a rotating way, wherein the rotating speed is 3000 rpm for 30 seconds, and obtaining a first film.
And 2, treating the first film in a tube furnace at 200 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 750 ℃ for 5 minutes in sequence.
Step 3, repeating the step 2 until a film with the thickness of 0.72 is obtained, and annealing the film with the thickness of 0 ℃ for 45 minutes at 750 ℃ to obtain the film (Bi)0.5Na0.5)TiO3-0.28SrTiO3Sodium bismuth titanate based lead-free piezoelectric film.
And 4, plating an electrode with the diameter of 0.5 mm on the surface of the sodium bismuth titanate-based lead-free piezoelectric film by using a sputtering instrument.
< test example 1>
Grazing incidence X-ray diffraction test
The test method comprises the following steps: the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4 were subjected to grazing incidence X-ray diffraction continuous scanning mode, with an incident angle of 1 ° and a scanning rate of 2 °/min, during which the voltage and current of the scanning tube were maintained at 40kV and 40mA, respectively.
The test results are shown in fig. 2.
FIG. 2 is grazing incidence X-ray diffraction patterns of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4. As can be seen from FIG. 2, all thin films have a typical perovskite structure, the first oneThree-component Bi (Fe)0.95Mn0.03Ti0.02)O3The introduction of (a) does not result in significant hetero-phase in the film.
< test example 2>
Hysteresis loop test
The test method comprises the following steps: the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4 were subjected to an electric hysteresis loop test.
The test results are shown in fig. 3.
Fig. 3 shows hysteresis loops of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 4. As can be seen from FIG. 3, with BiMnO3The increase in the content, the increase in the maximum polarization strength of comparative example 1 first and then decrease, indicates that Bi (Fe) was properly added0.95Mn0.03Ti0.02)O3Can increase (Bi)0.5Na0.5)TiO3–SrTiO3The film had a tapered polarization strength and a tapered hysteresis loop, and the composition in example 2 was 0.705 (Bi)0.5Na0.5)TiO3-0.28SrTiO3-0.015Bi(Fe0.95Mn0.03Ti0.02)O3Has the highest maximum polarization.
< test example 3>
Piezoelectric response phase-voltage and displacement-voltage testing
The test method comprises the following steps: the sodium bismuth titanate-based lead-free piezoelectric films obtained in comparative example 1 and examples 1 to 3 were subjected to piezoelectric response phase-voltage and displacement-voltage tests, respectively.
The test results are shown in fig. 4.
Fig. 4a and 4b are a phase-voltage curve and a displacement-voltage curve of the piezoelectric response of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 3, respectively.
As can be seen from FIGS. 4a and 4b, Bi (Fe)0.95Mn0.03Ti0.02)O3The increase of the content and the decrease of the inverse piezoelectric coefficient of each piezoelectric film after the increase indicate that Bi (Fe) is properly added0.95Mn0.03Ti0.02)O3Can increase (Bi)0.5Na0.5)TiO3–SrTiO3The inverse piezoelectric effect of the thin film, the electric field required for phase reversal gradually decreased, the piezoelectric hysteresis decreased, and the composition in example 2 was 0.705 (Bi)0.5Na0.5)TiO3-0.28SrTiO3-0.015Bi(Fe0.95Mn0.03Ti0.02)O3The film of (2) had the highest reverse piezoelectric coefficient (a reverse piezoelectric coefficient of 179.7 pm/v when 10 v was applied).
Effects and effects of the embodiments
According to the method for preparing the sodium bismuth titanate-based lead-free piezoelectric film, the method comprises the following steps: step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A; step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B; step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and step 4, coating the mixed solution C on the treated substrate by using a spin coating method, and obtaining (0.72-x) (Bi) after high-temperature treatment0.5Na0.5)TiO3-0.28SrTiO3-xBi(Fe0.95Mn0.03Ti0.02)O3The ternary system sodium bismuth titanate lead-free piezoelectric film. Therefore, the piezoelectric film prepared by the embodiment has a flat and smooth surface, a typical perovskite structure, higher polarization strength and excellent piezoelectric performance, and the inverse piezoelectric coefficient can reach 179.7 picometers per volt at most, so that the method has a very important significance for developing a high-performance lead-free piezoelectric film.
Further, in the embodiment, by doping the manganese-titanium co-doped bismuth ferrite, the leakage current of the sodium bismuth titanate-strontium titanate film is reduced, the curie temperature is increased, the polarization strength of the film is further improved, the leakage current of the film is reduced, the P-E curve of the film gradually becomes thin and long, the electric field required by phase inversion is reduced, the piezoelectric property of the film is further improved, and the hysteresis is reduced. When the content of bismuth ferrite (co-doped manganese and titanium) is high, the saturation polarization of the film is significantly reduced, so that the piezoelectric performance of the film is reduced, and therefore, the content of bismuth ferrite (co-doped manganese and titanium) is controlled to be less than 0.02 in the embodiment.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.

Claims (10)

1. A sodium bismuth titanate-based lead-free piezoelectric film is characterized by having the following chemical formula:
(0.72-x)(Bi0.5Na0.5)TiO3-0.28SrTiO3-xBi(Fe0.95Mn0.03Ti0.02)O3，
wherein 0< x < 0.025.
2. A method for preparing a sodium bismuth titanate-based lead-free piezoelectric film, which is used for preparing the sodium bismuth titanate-based lead-free piezoelectric film of claim 1, and is characterized by comprising the following steps:
step 1, adding bismuth nitrate, sodium acetate and strontium acetate into a solvent, and stirring to obtain a solution A;
step 2, dissolving acetylacetone, tetrabutyl titanate, ferric nitrate nonahydrate and manganese acetate tetrahydrate in a solvent, stirring and heating to obtain a solution B;
step 3, mixing the solution A and the solution B, and pretreating to obtain a mixed solution C; and
and 4, coating the mixed solution C on a treated substrate by using a spin coating method, and performing high-temperature treatment to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
3. The method for producing a sodium bismuth titanate-based lead-free piezoelectric thin film according to claim 2, characterized in that:
wherein the molar ratio of the bismuth nitrate to the sodium acetate to the strontium acetate is (0.3-0.5): (0.35-0.4): (0.2-0.3).
4. The method for producing a sodium bismuth titanate-based lead-free piezoelectric thin film according to claim 2, characterized in that:
wherein the molar ratio of the acetylacetone, the tetrabutyltitanate, the ferric nitrate nonahydrate and the manganese acetate tetrahydrate is (1.5-2.0): (0.5-1.0): (0.01-0.02): (0.0007-0.0008).
5. The method for producing a sodium bismuth titanate-based lead-free piezoelectric thin film according to claim 2, characterized in that:
wherein the concentration of the mixed solution C is 0.15-0.40 mol/L.
6. The method for producing a sodium bismuth titanate-based lead-free piezoelectric thin film according to claim 2, characterized in that:
wherein the substrate is treated as follows:
step 1, adding a solvent into the substrate, and ultrasonically cleaning the substrate for a certain time to obtain a cleaned substrate; and
and 2, drying the cleaned substrate by using nitrogen to obtain the processed substrate.
7. The method for producing a sodium bismuth titanate-based lead-free piezoelectric film according to claim 6,
wherein the substrate is Pt/Ti/SiO2a/Si substrate.
8. The method for producing a sodium bismuth titanate-based lead-free piezoelectric thin film according to claim 2, characterized in that:
wherein the high-temperature treatment comprises the following steps:
and rotationally coating the mixed solution C on the treated substrate to obtain a first film, treating the first film in a tube furnace at the temperature of 200-750 ℃ for 3-10 min, and annealing for 30-60 min to obtain the sodium bismuth titanate-based lead-free piezoelectric film.
9. The method for preparing a sodium bismuth titanate-based lead-free piezoelectric film according to claim 8, characterized in that:
wherein the reverse piezoelectric coefficient of the bismuth titanate sodium-based lead-free piezoelectric film is 170.0-180.0 picometers per volt.
10. The method for preparing a sodium bismuth titanate-based lead-free piezoelectric film according to claim 6, characterized in that:
wherein the certain time is 10min-30 min.
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