CN110473959B - Sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient and preparation method thereof - Google Patents
Sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient and preparation method thereof Download PDFInfo
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- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 57
- 239000011734 sodium Substances 0.000 claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 26
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004528 spin coating Methods 0.000 claims abstract description 13
- 229910003087 TiOx Inorganic materials 0.000 claims abstract description 10
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract 3
- 239000010408 film Substances 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 29
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000010409 thin film Substances 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 235000017281 sodium acetate Nutrition 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 13
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 12
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004544 sputter deposition Methods 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- BOATWIZKDIMFGZ-UHFFFAOYSA-N sodium nitrate pentahydrate Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[Na+] BOATWIZKDIMFGZ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8561—Bismuth-based oxides
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Abstract
The invention relates to a sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient and a preparation method thereof, wherein the chemical composition of the lead-free piezoelectric film is (0.94-x) Bi0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Wherein x is a mole fraction, x is 0-0.015 and is not 0, and the preparation method is a metallorganic thermal decomposition method, namely, firstly preparing a precursor solution, and then dripping the solution to clean Pt/TiOx/SiO2Spin coating is carried out on the Si substrate, heat treatment is carried out at different temperatures in sequence, and the processes of spin coating and heat treatment are repeated until the film thickness reaches 300-500 nm. Compared with the prior art, the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient prepared by the invention has excellent piezoelectric performance, and the inverse piezoelectric coefficient reaches 76.6 picometers per volt.
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 a high inverse piezoelectric coefficient and a preparation method thereof.
Background
The piezoelectric thin film refers to a thin film material having piezoelectricity and a thickness of several nanometers to several tens of nanometers. Compared with the bulk material, the piezoelectric film has similar mechanical, thermal, acoustic, optical and electrical properties, and has the advantages of small volume, low working voltage, integration with semiconductor process, etc., so that the piezoelectric film has wide application prospect in many high-tech fields of microelectronics, optoelectronics, micro-electro-mechanics, etc.
However, piezoelectric thin films which are currently in commercial use are, without exception, lead-containing piezoelectric thin films such as lead titanate-based and lead magnesium niobate-based piezoelectric thin films and the like. It is known that lead is a highly toxic neurotoxin, and the preparation and recovery of these piezoelectric films containing too much lead can cause serious damage to the environment and humans. A series of laws and regulations have been successively issued in European Union and China to limit the application of lead-containing piezoelectric films. In this regard, researchers in various countries around the world have developed a series of lead-free piezoelectric materials, of which bismuth sodium titanate is undoubtedly one of the most spotlighted by researchers. The material has a perovskite structure, belongs to a tripartite phase at room temperature, has good piezoelectricity and ferroelectricity, has Curie temperature of about 320 ℃ (Ferroelectrics,1982,40(1): 75-77), but has high coercive field and large hysteresis, and limits the application of the material in the aspect of piezoelectric materials to a certain extent.
A series of related researches show that after the second or third component is added, the sodium bismuth titanate-based piezoelectric film has excellent ferroelectric and piezoelectric properties at the morphotropic phase boundary. Wherein the binary system film with excellent performance is Bi0.5Na0.5TiO3–BaTiO3Binary system film, which is proved to be Bi0.5Na0.5TiO3And BaTiO3The piezoelectric performance is best when the molar ratio of (A) is 47:3 (J.alloy.Compd.,2010,504(1): 129-133). In addition, it has been shown that BiInO also has a typical perovskite structure3The electrical properties of the material can be well regulated by adding the second or third component into a lead-containing and lead-free matrix material (chem.mater.,2006,18(7): 1964-. However, these studies are mainly focused on ceramic materials, and the reports related to thin film materials are still extremely poor, as to Bi0.5Na0.5TiO3–BaTiO3Adding BiInO into binary system film3What effect on the material properties is had never been studied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient and a preparation method thereof3What effect on the material properties is had never been studied. Based on this background, we prepared (0.94-x) Bi0.5Na0.5TiO3–0.06BaTiO3–xBiInO3And when x is an optimal value of 0.005, the prepared piezoelectric film has excellent piezoelectric performance, and the inverse piezoelectric coefficient reaches 76.6 picometers per volt.
The purpose of the invention can be realized by the following technical scheme:
a sodium bismuth titanate-based lead-free piezoelectric film with a high inverse piezoelectric coefficient, the lead-free piezoelectric filmThe chemical composition of the piezoelectric film is (0.94-x) Bi0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Wherein x is a mole fraction, 0-0.015, and is not 0.
The value of x is preferably 0.005.
The thickness of the sodium bismuth titanate-based lead-free piezoelectric film is 300-500 nanometers.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient comprises the following steps:
(1) bi according to the chemical composition formula (0.94-x)0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) bi according to the chemical composition formula (0.94-x)0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Weighing bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof, barium acetate and indium nitrate or hydrate thereof according to the stoichiometric ratio, wherein bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof can be weighed slightly excessively due to violent volatilization of bismuth and sodium elements at high temperature, then the weighed medicines are dissolved in acetic acid, and stirring is carried out at 20-70 ℃ for 60-80 minutes to obtain precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.1-0.4 mol/L, and stirring at room temperature for 4-5 hours to prepare a precursor solution;
(4) mixing Pt with TiOx/SiO2the/Si substrate is cut into a square or rectangle, and the side length is 0.8-1.5 cm. And then ultrasonically cleaning the silicon wafer in acetone for 10-20 minutes, ultrasonically cleaning the silicon wafer in distilled water for 10-20 minutes, and ultrasonically cleaning the silicon wafer in ethanol for 15-30 minutes. After cleaning, drying by using high-purity nitrogen or spin-drying at high speed by using a spin coater;
(5) preparing a film: chamberPt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Performing one-time rotary coating on the Si substrate, wherein the rotating speed is 2000-4000 revolutions per minute, and the glue homogenizing time is 20-60 seconds;
(b) sequentially carrying out heat treatment on the film obtained in the step (a) in a tubular furnace at 100-250 ℃ for 3-5 minutes, at 350-450 ℃ for 3-5 minutes, and at 700-750 ℃ for 5-10 minutes;
(c) repeating the step (b) for a plurality of times until the film thickness reaches the expected thickness. And finally, annealing at 700-750 ℃ for 30-60 minutes to obtain the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient.
(6) And sputtering a circular metal top electrode with the diameter of 0.3-1.0 mm on the surface of the piezoelectric film by using a sputtering instrument.
The existing method for adding BiMeO into binary ferroelectric thin film with perovskite structure3The research on the improvement of various physical properties of the film by the third component of the type (Me represents certain trivalent metal ions) is mainly focused on BiFeO3、 BiMnO3And BiAlO3And on the third component, because Fe and Mn have various valences and Al organic salt is decomposed and volatilized violently at high temperature, small changes of raw materials and process parameters can have great influence on the final performance of the film. And BiInO3Has a typical perovskite structure, has been used as a secondary or tertiary component to control the electrical properties of materials In both lead-containing and lead-free dielectric ceramics, and In3+The ions do not have the possibility of valence change and the organic salts thereof are not volatilized violently at high temperature, so compared with the prior film preparation technology, the production process of the invention is stable and has good repeatability. This patent is through regulation and control BiInO3May be in the range of 0.94Bi0.5Na0.5TiO3–0.06BaTiO3A quasi-homomorphic phase boundary is formed in the binary material, so that the dielectric constant and the polarization strength of the piezoelectric film are increased, and the inverse piezoelectric coefficient of the piezoelectric film is improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sodium bismuth titanate-based lead-free piezoelectric thin film obtained in comparative example 1 and examples 1 and 2;
FIG. 2 is a dielectric spectrum of a sodium bismuth titanate-based lead-free piezoelectric film obtained in comparative example 1 and examples 1 to 3;
FIG. 3 is a dielectric temperature spectrum of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 3;
FIG. 4 is a hysteresis loop of the sodium bismuth titanate-based lead-free piezoelectric thin film obtained in comparative example 1 and examples 1 and 2;
FIGS. 5-1 to 5-6 are a piezoelectric response phase-voltage curve, a displacement-voltage curve, and an inverse piezoelectric coefficient-voltage curve of the sodium bismuth titanate-based lead-free piezoelectric thin film obtained in comparative example 1 and examples 1 and 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The chemical composition of the lead-free piezoelectric film is (0.94-x) Bi0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Wherein x is a mole fraction, 0-0.015, and is not 0. The best technical effect can be obtained when the value of x is 0.005. The thickness of the prepared sodium bismuth titanate-based lead-free piezoelectric film is 300-500 nanometers.
The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient comprises the following steps:
(1) bi according to the chemical composition formula (0.94-x)0.5Na0.5TiO3–0.06BaTiO3–xBiInO3The stoichiometric ratio of the above-mentioned raw materials is measured, titanium n-butoxide and acetylacetone are dissolved in ethylene glycol monomethyl ether, in which the acetylacetone can be used for complexing titanium n-butoxide, then the above-mentioned solution is addedStirring for 20 minutes at room temperature on a magnetic stirrer to obtain a precursor solution A;
(2) bi according to the chemical composition formula (0.94-x)0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Weighing bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof, barium acetate and indium nitrate or hydrate thereof according to the stoichiometric ratio, wherein bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof can be weighed slightly excessively due to violent volatilization of bismuth and sodium elements at high temperature, then the weighed medicines are dissolved in acetic acid, and stirring is carried out at 20-70 ℃ for 60-80 minutes to obtain precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.1-0.4 mol/L, and stirring at room temperature for 4-5 hours to prepare a precursor solution;
(4) mixing Pt with TiOx/SiO2the/Si substrate is cut into a square or rectangle, and the side length is 0.8-1.5 cm. And then ultrasonically cleaning the silicon wafer in acetone for 10-20 minutes, ultrasonically cleaning the silicon wafer in distilled water for 10-20 minutes, and ultrasonically cleaning the silicon wafer in ethanol for 15-30 minutes. After cleaning, drying by using high-purity nitrogen or spin-drying at high speed by using a spin coater;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Performing one-time rotary coating on the Si substrate, wherein the rotating speed is 2000-4000 revolutions per minute, and the glue homogenizing time is 20-60 seconds;
(b) sequentially carrying out heat treatment on the film obtained in the step (a) in a tubular furnace at 100-250 ℃ for 3-5 minutes, at 350-450 ℃ for 3-5 minutes, and at 700-750 ℃ for 5-10 minutes;
(c) repeating the step (b) for a plurality of times until the film thickness reaches the expected thickness. And finally, annealing at 700-750 ℃ for 30-60 minutes to obtain the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient.
(6) And sputtering a circular metal top electrode with the diameter of 0.3-1.0 mm on the surface of the piezoelectric film by using a sputtering instrument.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Comparative example 1
(1) According to the chemical composition formula of 0.94Bi0.5Na0.5TiO3–0.06BaTiO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) according to the chemical composition formula of 0.94Bi0.5Na0.5TiO3–0.06BaTiO3Weighing bismuth nitrate pentahydrate, sodium acetate trihydrate, barium acetate and indium nitrate hydrate according to the stoichiometric ratio, wherein the bismuth element and the sodium element are volatilized violently at high temperature, the bismuth nitrate pentahydrate and the sodium acetate trihydrate are weighed to be 10% in excess, then the weighed medicines are dissolved in acetic acid, and stirring is carried out for 1 hour at 45 ℃ to obtain a precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.25 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with a side length of 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time rotary coating on the Si substrate, wherein the rotating speed is 3000 r/min, and the glue homogenizing time is 30 seconds;
(b) sequentially heat-treating the film obtained after step (a) in a tube furnace at 150 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 720 ℃ for 10 minutes;
(c) repeating the step (b)6 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 45 minutes at 720 ℃, and the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient is prepared.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
Example 1
(1) According to the chemical composition general formula of 0.935Bi0.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) according to the chemical composition general formula of 0.935Bi0.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3Weighing bismuth nitrate pentahydrate, sodium acetate trihydrate, barium acetate and indium nitrate hydrate according to the stoichiometric ratio, wherein the bismuth element and the sodium element are volatilized violently at high temperature, the bismuth nitrate pentahydrate and the sodium acetate trihydrate are weighed to be 10% in excess, then the weighed medicines are dissolved in acetic acid, and stirring is carried out for 1 hour at 45 ℃ to obtain a precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.25 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with a side length of 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: pt ^ obtained in step (3) at room temperatureTiOx/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time rotary coating on the Si substrate, wherein the rotating speed is 3000 r/min, and the glue homogenizing time is 30 seconds;
(b) sequentially heat-treating the film obtained after step (a) in a tube furnace at 150 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 720 ℃ for 10 minutes;
(c) repeating the step (b)6 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 45 minutes at 720 ℃, and the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient is prepared.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
Example 2
(1) According to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) according to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3Weighing bismuth nitrate pentahydrate, sodium acetate trihydrate, barium acetate and indium nitrate hydrate according to the stoichiometric ratio, wherein the bismuth element and the sodium element are volatilized violently at high temperature, the bismuth nitrate pentahydrate and the sodium acetate trihydrate are weighed to be 10% in excess, then the weighed medicines are dissolved in acetic acid, and stirring is carried out for 1 hour at 45 ℃ to obtain a precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.25 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with side lengthsIs 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time rotary coating on the Si substrate, wherein the rotating speed is 3000 r/min, and the glue homogenizing time is 30 seconds;
(b) sequentially heat-treating the film obtained after step (a) in a tube furnace at 150 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 720 ℃ for 10 minutes;
(c) repeating the step (b)6 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 45 minutes at 720 ℃, and the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient is prepared.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
Example 3
(1) Bi according to the chemical composition general formula of 0.9250.5Na0.5TiO3–0.06BaTiO3–0.015BiInO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) bi according to the chemical composition general formula of 0.9250.5Na0.5TiO3–0.06BaTiO3–0.015BiInO3Weighing bismuth nitrate pentahydrate, sodium acetate trihydrate, barium acetate and indium nitrate hydrate according to the stoichiometric ratio, wherein the bismuth element and the sodium element are volatilized violently at high temperature, the bismuth nitrate pentahydrate and the sodium acetate trihydrate are weighed to be 10% in excess, then the weighed medicines are dissolved in acetic acid, and stirring is carried out for 1 hour at 45 ℃ to obtain a precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.25 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with a side length of 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time rotary coating on the Si substrate, wherein the rotating speed is 3000 r/min, and the glue homogenizing time is 30 seconds;
(b) sequentially heat-treating the film obtained after step (a) in a tube furnace at 150 ℃ for 5 minutes, at 450 ℃ for 5 minutes and at 720 ℃ for 10 minutes;
(c) repeating the step (b)6 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 45 minutes at 720 ℃, and the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient is prepared.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
Example 4
(1) According to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3Weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A;
(2) according to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3The stoichiometric ratio of the sodium nitrate pentahydrate, the sodium acetate trihydrate, the barium acetate and the indium nitrate hydrate is weighed, and the bismuth is usedElements and sodium elements are volatilized violently at high temperature, 10% of bismuth nitrate pentahydrate and sodium acetate trihydrate are weighed excessively, the weighed medicines are dissolved in acetic acid, and the precursor solution B is obtained after stirring for 1 hour at the temperature of 20 ℃;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.1 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with a side length of 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time rotary coating on the Si substrate, wherein the rotating speed is 2000 r/min, and the glue homogenizing time is 60 seconds;
(b) heat treating the film obtained after step (a) in sequence in a tube furnace at 100 ℃ for 3 minutes, at 350 ℃ for 4 minutes, and at 700 ℃ for 5 minutes;
(c) repeating the step (b)8 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 60 minutes at 700 ℃, and the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient is prepared.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
Example 5
(1) According to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3The method comprises the steps of weighing titanium n-butoxide and acetylacetone according to the stoichiometric ratio, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, wherein the acetylacetone has the function of complexing the titanium n-butoxide, and stirring the solution on a magnetic stirrer at room temperature for 20 minutes to obtain a precursor solution A；
(2) According to the chemical composition formula of 0.93Bi0.5Na0.5TiO3–0.06BaTiO3–0.01BiInO3Weighing bismuth nitrate pentahydrate, sodium acetate trihydrate, barium acetate and indium nitrate hydrate according to the stoichiometric ratio, wherein the bismuth element and the sodium element are volatilized violently at high temperature, the bismuth nitrate pentahydrate and the sodium acetate trihydrate are weighed 10% in excess, then the weighed medicines are dissolved in acetic acid, and stirring is carried out for 1 hour at 70 ℃ to obtain a precursor solution B;
(3) mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.4 mol/L, and stirring at room temperature for 5 hours to prepare a precursor solution;
(4) mixing Pt (111)/TiOx/SiO2the/Si (100) substrate is cut into squares with a side length of 1 cm. The silicon wafer was then ultrasonically cleaned first in acetone for 15 minutes, then in distilled water for 15 minutes, and finally in ethanol for 20 minutes. After cleaning, drying by using high-purity nitrogen;
(5) preparing a film: Pt/TiO obtained in step (3) at room temperaturex/SiO2Spin coating on a/Si substrate, specifically as follows:
(a) Pt/TiO obtained in step (3) at room temperaturex/SiO2Carrying out one-time spin coating on the Si substrate, wherein the rotation speed is 4000 revolutions per minute, and the glue homogenizing time is 20 seconds;
(b) sequentially heat-treating the film obtained after step (a) in a tube furnace at 250 ℃ for 3 minutes, at 400 ℃ for 4 minutes, and at 750 ℃ for 5 minutes;
(c) repeating the step (b)8 times until the film thickness reaches the expected thickness. Finally, annealing treatment is carried out for 30 minutes at 750 ℃ to prepare the sodium bismuth titanate-based lead-free piezoelectric film with high inverse piezoelectric coefficient.
(6) A circular gold top electrode having a diameter of 0.5 mm was sputtered on the surface of the piezoelectric film using a sputtering apparatus.
FIG. 1 is an X-ray diffraction pattern of a sodium bismuth titanate-based lead-free piezoelectric thin film obtained in comparative example 1 and examples 1 and 2. As can be seen from the figures, it is,all thin films have a typical perovskite structure, the third component BiMnO3The introduction of (a) does not result in significant hetero-phase in the film.
FIG. 2 shows dielectric spectra of sodium bismuth titanate-based lead-free piezoelectric films obtained in comparative example 1 and examples 1 to 3. As can be seen from the figure, with BiMnO3The increase in the content, increase in the dielectric constant first and then decrease, indicates that BiMnO was properly added3Can increase Bi0.5Na0.5TiO3–BaTiO3Dielectric constant of the film, and the composition of example 1 is 0.935Bi0.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3The film of (2) has the highest dielectric constant (room temperature relative dielectric constant of 1111.2 at a frequency of 10 kHz).
FIG. 3 is a dielectric temperature spectrum of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 3. As can be seen from the figure, with BiMnO3The increase in the content, increase in the dielectric constant first and then decrease, indicates that BiMnO was properly added3Can increase Bi0.5Na0.5TiO3–BaTiO3Dielectric constant of the film, and the composition of example 1 is 0.935Bi0.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3The film has the highest dielectric constant (the relative dielectric constant reaches 1774.1 at a Curie temperature of 261.7 ℃ at which the dielectric constant reaches a maximum at a frequency of 10 kHz) in the whole temperature range of 30-360 ℃.
FIG. 4 shows hysteresis loops of the sodium bismuth titanate-based lead-free piezoelectric thin films obtained in comparative example 1 and examples 1 to 3. As can be seen from the figure, with BiMnO3The increase in the content, the increase in maximum polarization first and then the decrease, indicates that BiMnO was properly added3Can increase Bi0.5Na0.5TiO3–BaTiO3Dielectric constant of the film, and the composition of example 1 is 0.935Bi0.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3Has the highest maximum polarization.
FIGS. 5-1 to 5-6 show the sodium bismuth titanate-based lead-free compacts obtained in comparative example 1 and examples 1 and 2The piezoelectric response phase-voltage curves (solid lines in fig. 5-1 to 5-3), the displacement-voltage curves (solid points in fig. 5-4 to 5-6), and the inverse piezoelectric coefficient-voltage curves ((open points in fig. 5-4 to 5-6) of the electric thin film are seen along with the BiMnO3The content is increased, the inverse piezoelectric coefficient is increased firstly and then reduced, which indicates that BiMnO is properly added3Can increase Bi0.5Na0.5TiO3–BaTiO3The reverse piezoelectric coefficient of the film and the composition of 0.935Bi in example 10.5Na0.5TiO3–0.06BaTiO3–0.005BiInO3The film of (2) had the highest reverse piezoelectric coefficient (a reverse piezoelectric coefficient of 76.6 pm/v when 10 v was applied).
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The sodium bismuth titanate-based lead-free piezoelectric thin film with high inverse piezoelectric coefficient is characterized in that the chemical composition of the lead-free piezoelectric thin film is (0.94-x) Bi0.5Na0.5TiO3–0.06BaTiO3–xBiInO3Wherein x is a mole fraction, x ═0 to 0.015 and not 0;
the thickness of the sodium bismuth titanate-based lead-free piezoelectric film is 300-500 nanometers;
preparing a precursor by adopting a metallorganic thermal decomposition method and coating the precursor on a substrate, wherein the method comprises the following steps:
weighing titanium n-butoxide and acetylacetone, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, and stirring at room temperature to obtain a precursor solution A;
weighing bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof, barium acetate and indium nitrate or hydrate thereof, dissolving the bismuth nitrate or hydrate thereof, and stirring at 20-70 ℃ to obtain precursor solution B;
mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.1-0.4 mol/L, and stirring at room temperature to obtain a precursor solution;
cleaning and drying the substrate;
and coating the prepared precursor solution on a substrate to prepare the sodium bismuth titanate-based lead-free piezoelectric film with the high inverse piezoelectric coefficient.
2. The sodium bismuth titanate-based lead-free piezoelectric thin film having a high inverse piezoelectric coefficient according to claim 1, wherein x is preferably 0.005.
3. The method for preparing the sodium bismuth titanate-based lead-free piezoelectric thin film with high inverse piezoelectric coefficient according to claim 1 or 2, wherein the precursor is prepared by a metallorganic thermal decomposition method and coated on the substrate, and the method comprises the following steps:
weighing titanium n-butoxide and acetylacetone, dissolving the titanium n-butoxide and the acetylacetone in ethylene glycol monomethyl ether, and stirring at room temperature to obtain a precursor solution A;
weighing bismuth nitrate or hydrate thereof, sodium acetate or hydrate thereof, barium acetate and indium nitrate or hydrate thereof, dissolving the bismuth nitrate or hydrate thereof, and stirring at 20-70 ℃ to obtain precursor solution B;
mixing the precursor solution A and the precursor solution B, adding ammonia water to adjust the pH value until the solute is completely dissolved, adding acetic acid to adjust the concentration of the mixed solution to 0.1-0.4 mol/L, and stirring at room temperature to obtain a precursor solution;
cleaning and drying the substrate;
and coating the prepared precursor solution on a substrate to prepare the sodium bismuth titanate-based lead-free piezoelectric film with the high inverse piezoelectric coefficient.
4. The method for preparing a sodium bismuth titanate-based lead-free piezoelectric thin film with a high inverse piezoelectric coefficient according to claim 3, wherein the substrate is Pt/TiOx/SiO2a/Si substrate.
5. The method for preparing a sodium bismuth titanate-based lead-free piezoelectric thin film with a high inverse piezoelectric coefficient according to claim 4, wherein the substrate is cleaned by ultrasonic cleaning in acetone, ultrasonic cleaning in distilled water, and ultrasonic cleaning in ethanol.
6. The method for preparing the sodium bismuth titanate-based lead-free piezoelectric film with the high inverse piezoelectric coefficient according to claim 4, wherein the cleaned substrate is dried by high-purity nitrogen or dried by spin drying at high speed by a spin coater.
7. The preparation method of the sodium bismuth titanate-based lead-free piezoelectric film with the high inverse piezoelectric coefficient according to claim 3 is characterized in that the precursor solution is coated on the substrate by spin coating, and the substrate cleaned and dried is subjected to spin coating once at room temperature, wherein the rotation speed is 2000-4000 revolutions per minute, and the glue homogenizing time is 20-60 seconds; and after coating, performing heat treatment at 100-250 ℃ for 3-5 minutes, at 350-450 ℃ for 3-5 minutes, and at 700-750 ℃ for 5-10 minutes, wherein the heat treatment operation is repeated for several times until the thickness of the film reaches the expected value, and finally performing annealing treatment at 700-750 ℃ for 30-60 minutes to complete coating.
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