CN115974548A - Lead-free high-entropy ferroelectric film and preparation method and application thereof - Google Patents
Lead-free high-entropy ferroelectric film and preparation method and application thereof Download PDFInfo
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- 239000010408 film Substances 0.000 claims abstract description 99
- 238000004146 energy storage Methods 0.000 claims abstract description 59
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 8
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
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- 159000000000 sodium salts Chemical class 0.000 claims description 6
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 4
- 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 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 2
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- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention belongs to the technical field of thin film materials, and discloses a lead-free high-entropy ferroelectric thin film, and a preparation method and application thereof. The method utilizes the sol-gel method to prepare the lead-free high-entropy ferroelectric film with controllable thickness, and the sol-gel method has the advantages of simple process, low equipment requirement, low production cost and good film forming efficiency and uniformity, and is suitable for large-area film forming; and the material prepared by the sol-gel method has easily controlled proportion of chemical components, can be designed by molecular structure engineering, and is particularly suitable for preparing the lead-free high-entropy ferroelectric film multi-component material. The lead-free high-entropy ferroelectric film prepared by the invention has ultrahigh breakdown field strength and good temperature stability, the breakdown field strength which can be borne by the lead-free high-entropy ferroelectric film can be more than 8MV/cm, and the energy storage density can reach 5.88J/cm 3 The energy storage efficiency can reach 93 percent and can be between 55 ℃ below zero and 200 DEG CThe material can work normally under the condition, and has larger dielectric constant and smaller dielectric loss.
Description
Technical Field
The invention belongs to the technical field of film materials, and particularly relates to a lead-free high-entropy ferroelectric film as well as a preparation method and application thereof.
Background
The general ferroelectric thin film has been reported to have a breakdown field strength of 1-2MV/cm (see 1 Xie, yanjiang, et al, "Ultra-high Energy storage density and enhanced dielectric properties in BNT-BT based depth filter," Ceramics International 47.16 (2021): 23259-23266; see 2. Penta, et al, "Low-temperature-poled high Energy density and deposition improvement of discharge Energy density of (Pb, la) (Zr, sn, ti) O3 playback viscosity" Nacapillary No. (No. 77, see 3. J.S. Pat. No. 4. The polymer of ceramic, no. 12. J.S. Pat. No. 15. The polymer of ceramic, no. 12. J.S. Pat. No. 4. The polymer of ceramic, no. 10. 12. The polymer of ceramic, no. 12. The polymer of viscosity of No. 15. 12. The polymer of ceramic, no. 15. 12. The polymer of viscosity, no. 7. 12. The polymer of ceramic, no. 7. III, no. 7. C, no. 7. 12. The polymer of ceramic Nano-compositions. "Journal of Materials Chemistry A5.9 (2017): 4710-4718). The breakdown electric field intensity of the thin film materials is low, and the market demand for higher breakdown electric field intensity (more than 5 MV/cm) cannot be met.
The high-entropy ferroelectric material is a solid solution compound formed by more than 4 metal elements at a certain site in the crystal structure of the material according to an equimolar ratio or an approximately equimolar ratio, and is characterized in that the configuration entropy is maximized by enhancing the chemical disorder, so that a more stable system is realized. Compared with the traditional ferroelectric material, the high-entropy ferroelectric material has the inherent characteristics of stable thermodynamic phase, obvious lattice distortion, composition complexity and the like. The properties enable the high-entropy ferroelectric material to have good thermal stability, strong mechanical property, outstanding piezoelectric property and dielectric property.
The traditional preparation of the high-entropy ferroelectric material generally adopts a physical solid-phase reaction method, but the method is suitable for preparing corresponding block materials and is not suitable for preparing the high-entropy ferroelectric film. The ferroelectric thin film material is generally prepared by Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). Among them, PVD is a method of vaporizing a metal in a vacuum high temperature environment and depositing the metal on a substrate by interatomic collision to form a thin film, but this method has a high requirement on the degree of vacuum. For a multicomponent compound, the melting point and vapor pressure of the gas phase among elements are strictly required, and the control degree of the component ratio is small, so that the film is formed unevenly and has poor quality. CVD is the chemical reaction of a variety of vapor phase species at high temperatures to deposit thin films on a substrate. However, this method has great limitations, for example, toxic reaction gases generated during the production process, some reaction products (impurities) may remain in the coating film, the substrate has good high temperature resistance (> 1000 ℃) and the production cost is high.
Therefore, how to overcome the problems of high equipment requirement and high cost of the preparation method of the high-entropy ferroelectric film and how to develop the high-entropy ferroelectric film with higher breakdown field strength is an urgent need of the electronic industry at present.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of the lead-free high-entropy ferroelectric film, the sol-gel method is utilized to prepare the lead-free high-entropy ferroelectric film with controllable thickness, the equipment requirement is low, the cost is low, the prepared lead-free high-entropy ferroelectric film has ultrahigh breakdown electric field intensity, and the breakdown electric field intensity of the lead-free high-entropy ferroelectric film is more than 8MV/cm.
The first aspect of the invention provides a preparation method of a lead-free high-entropy ferroelectric film, which comprises the following steps:
1) Preparing a BNKLST precursor solution, the chemical formula of the BNKLST being (Bi) x Na x K y La y Sr y )TiO 3 Wherein x > 0, y > 0,2x +3y =1;
2) Spin-coating the BNKLST precursor solution obtained in the step 1) on a conductive substrate to obtain a wet film;
3) Drying the wet film obtained in the step 2) at 200-250 ℃ for 3-5min, and then pyrolyzing the wet film at 400-450 ℃ for 3-5min to obtain an amorphous film;
4) Carrying out rapid heating treatment on the amorphous film obtained in the step 3); the rapid heating treatment comprises the following steps: heating to 650-700 ℃ at a heating rate of 50-100 ℃/s, and keeping the temperature for 3-5min;
5) And (3) annealing the amorphous film subjected to the rapid heating treatment in the step 4) to obtain the lead-free high-entropy ferroelectric film.
Preferably, the preparation of the BNKLST precursor solution in step 1) is carried out in the following steps:
weighing bismuth salt, sodium salt, potassium salt, strontium salt, lanthanum salt and titanium salt according to the stoichiometric ratio of the chemical general formula;
dissolving the bismuth salt in a solvent, adding the sodium salt, the potassium salt, the strontium salt and the lanthanum salt, and dissolving to obtain a solution A;
mixing the titanium salt with a solvent and a chelating agent to obtain a solution B;
and adding the solution B into the solution A, adding formamide with the volume ratio of 0.5-1%, stirring for 24-36h, standing for 72-84h, and reacting to obtain the BNKLST precursor solution.
Preferably, the bismuth salt includes at least one of bismuth acetate, bismuth nitrate, and bismuth sulfate; the sodium salt comprises at least one of sodium acetate trihydrate, sodium nitrate and sodium sulfate; the potassium salt comprises at least one of potassium acetate, potassium nitrate and potassium sulfate; the strontium salt comprises at least one of strontium acetate, strontium nitrate and strontium sulfate; the lanthanum salt comprises at least one of lanthanum nitrate hexahydrate, lanthanum nitrate and lanthanum sulfate; the titanium salt is tetrabutyl titanate.
Preferably, the solvent comprises at least one of glacial acetic acid, ethylene glycol methyl ether, ethanol and isopropanol; the chelating agent comprises at least one of acetylacetone, EDTA, potassium sodium tartrate and ammonium citrate.
Preferably, the ratio of x and y is 0.5 to 2.
Preferably, the conditions of the annealing treatment include: the annealing temperature is 650-700 deg.C, and the annealing time is 10-15min.
Preferably, step 2), step 3) and step 4) are repeated a plurality of times before said step 5) is carried out, resulting in a multilayer amorphous film.
Preferably, the number of the layers of the lead-free high-entropy ferroelectric thin film is 4-10, and the thickness of each layer of the lead-free high-entropy ferroelectric thin film is 40-50nm.
The second aspect of the invention provides a lead-free high-entropy ferroelectric film which is prepared by the preparation method, and the breakdown electric field intensity of the lead-free high-entropy ferroelectric film is more than 8MV/cm.
Preferably, the lead-free high-entropy ferroelectric thin film has a single-phase crystal structure.
A third aspect of the invention provides a dielectric energy storage device comprising the lead-free high-entropy ferroelectric thin film of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the lead-free high-entropy ferroelectric film utilizes the sol-gel method to prepare the lead-free high-entropy ferroelectric film with controllable thickness, and the sol-gel method has the advantages of simple process, low equipment requirement, low production cost and good film forming efficiency and uniformity, and is suitable for large-area film forming; and the material prepared by the sol-gel method has easily controlled proportion of chemical components, can be designed by molecular structure engineering, and is particularly suitable for preparing the lead-free high-entropy ferroelectric film multi-component material.
(2) The lead-free high-entropy ferroelectric film prepared by the invention has ultrahigh breakdown field strength and good temperature stability, the breakdown field strength which can be borne by the lead-free high-entropy ferroelectric film is more than 8MV/cm, and the energy storage density can reach 5.88J/cm 3 The energy storage efficiency can reach 93%, the normal work can be carried out under the condition of-55-200 ℃, and the high-dielectric-constant energy storage device has a high dielectric constant and low dielectric loss.
(3) The lead-free high-entropy ferroelectric film prepared by the method does not contain toxic elements such as lead and the like, and is more environment-friendly compared with a lead-containing ferroelectric film; the dielectric energy storage device prepared by the lead-free high-entropy ferroelectric film has excellent energy storage density and energy storage efficiency.
Drawings
FIG. 1 is an XRD pattern of a lead-free high entropy ferroelectric thin film obtained in example 1;
FIG. 2 is an SEM photograph of a cross-section of a lead-free high-entropy ferroelectric thin film obtained in example 1;
FIG. 3 is a graph of the dielectric constant and dielectric loss versus frequency for the dielectric energy storage device assembled in example 1;
FIG. 4 is a graph of conductivity versus temperature for a dielectric energy storage device assembled in accordance with example 1;
FIG. 5 is a Weber distribution plot of the breakdown field of the dielectric energy storage device assembled in example 1;
FIG. 6 is a ferroelectric hysteresis loop of the dielectric energy storage device assembled in example 1;
fig. 7 is an SEM image of a cross section of the lead-free high-entropy ferroelectric thin film obtained in comparative example 1;
fig. 8 is a hysteresis loop diagram of the dielectric energy storage device assembled in comparative example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The raw materials, reagents and apparatuses used in the following examples are all available from conventional commercial sources or can be obtained by existing known methods, unless otherwise specified.
The room temperature in the invention is 25 +/-5 ℃; the slow dropping is that the dropping speed is 5-10 seconds per drop; the slow stirring means that the stirring speed is 10-20rpm; the amorphous film refers to a film which is amorphous and has not yet been crystallized.
Example 1
A preparation method of a lead-free high-entropy ferroelectric film comprises the following steps:
1)preparation of (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution:
according to (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water, stirring for 30min, then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and lanthanum nitrate hexahydrate, stirring for 2.5h, and dissolving to obtain a solution A;
mixing tetrabutyl titanate, ethylene glycol monomethyl ether and acetylacetone at room temperature according to a volume ratio of 1;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid into the solution B after the solution B is completely added so as to avoid hydrolysis reaction of tetrabutyl titanate, stirring the mixture for 3 hours, adding formamide with the volume ratio of 0.5 percent, slowly stirring the mixture for 24 hours at room temperature, standing the mixture for 72 hours, and reacting the mixture to obtain (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution;
2) Pt (111)/Ti/SiO at 1cm × 1cm 2 5 drops of (Bi) are dripped on a/Si (100) conductive substrate 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Spin-coating the precursor solution for 9s at a rotation speed of 600r/min by using a spin coater, and then spin-coating for 30s at a rotation speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Rapidly heating the amorphous film; the rapid heating treatment comprises the following steps: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at the heating rate of 80 ℃/s, and preserving heat for 5min;
5) And (3) repeating the step 2), the step 3) and the step 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 4 layers of lead-free high-entropy ferroelectric films.
Product characterization:
1. the lead-free high-entropy ferroelectric thin film obtained in example 1 was subjected to X-ray diffraction, and the XRD spectrum thereof is shown in fig. 1. It can be seen from fig. 1 that the lead-free high-entropy ferroelectric thin film of the present invention exhibits a perovskite crystal structure, and is free from a hetero phase and impurities.
2. The cross section of the lead-free high-entropy ferroelectric thin film obtained in example 1 was subjected to SEM electron scanning, and the SEM image thereof is shown in fig. 2. In FIG. 2, from top to bottom, "1" indicates the background of the stage of the SEM, and "2" indicates (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 "3" represents the Pt/Ti electrode layer of the conductive substrate, and "4" represents the SiO of the conductive substrate 2 A layer of/Si. It can be seen from fig. 2 that the lead-free high-entropy ferroelectric thin film of the present invention has high crystallinity and a dense structure.
And (3) product performance testing:
the lead-free high-entropy ferroelectric film obtained in example 1 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of the dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter and the thickness of the gold electrode are 0.4mm and 0.25 mu m respectively. Carrying out related electrical performance test on the assembled dielectric energy storage device;
as shown in FIG. 3, the test frequency range is 1-10 5 kHz. At a test frequency of 10kHz, the dielectric constant of the dielectric energy storage device is higher than 100, while the dielectric loss is lower than 0.05.
As shown in FIG. 4, the test voltage was 150V, and the conductivity of the dielectric energy storage device at room temperature was 5.13X 10 -4 S/m, leakage current of about 10 -7 A. Meanwhile, the conductivity can be stably maintained at 3.3 multiplied by 10 within the range of 60-140 DEG C -3 S/m。
As shown in fig. 5, the breakdown electric field strength Eb of the dielectric energy storage device is measured in terms of a weber distribution, and Eb =10.99MV/cm. The dielectric energy storage device obtains a higher energy storage effect with ultrahigh breakdown electric field intensity.
As shown in FIG. 6, under the condition of a periodic triangular wave signal with a frequency of 1000Hz and a maximum voltage of 95V, the dielectric energy storage device is subjected to an electric hysteresis loop test to obtain 5.88J/cm 3 And an excellent energy storage efficiency of 93%.
Comparative example 1 (different from example 1 in that the amorphous film is treated by conventional heating)
A preparation method of a lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation of (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution:
according to (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water, stirring for 30min, then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and lanthanum nitrate hexahydrate, stirring for 2.5h, and dissolving to obtain a solution A;
mixing tetrabutyl titanate, ethylene glycol monomethyl ether and acetylacetone at room temperature according to a volume ratio of 1;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid into the solution B after the solution B is completely added so as to avoid hydrolysis reaction of tetrabutyl titanate, stirring the mixture for 3 hours, adding formamide with the volume ratio of 0.5 percent, slowly stirring the mixture for 24 hours at room temperature, standing the mixture for 72 hours, and reacting the mixture to obtain (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Precursor solution;
2) Pt (111)/Ti/SiO at 1cm × 1cm 2 5 drops of (Bi) are dripped on a/Si (100) conductive substrate 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 Spin coating the precursor solution for 9s at a rotation speed of 600r/min by using a spin coater, and then rotatingSpin-coating at 3000r/min for 30s to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Carrying out conventional heating treatment on the amorphous film; the conventional heating treatment is as follows: heating the amorphous film to 650 ℃ by adopting a muffle furnace at the heating rate of 30 ℃/min, and preserving heat for 5min;
5) And (3) repeating the step 2), the step 3) and the step 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain 4 layers of lead-free high-entropy ferroelectric films.
The cross section of the lead-free high-entropy ferroelectric thin film obtained in comparative example 1 was subjected to electron microscope scanning, and the SEM image thereof is shown in fig. 7. In FIG. 7, from top to bottom, "1" indicates the stage background of the SEM sample, and "2" indicates (Bi) 0.2 Na 0.2 K 0.2 La 0.2 Sr 0.2 )TiO 3 "3" represents the Pt/Ti electrode layer of the conductive substrate, and "4" represents the SiO of the conductive substrate 2 A layer of/Si. It can be seen from fig. 7 that the lead-free high-entropy ferroelectric thin film of comparative example 1 has poor crystallinity and a loose structure.
And (3) assembling the lead-free high-entropy ferroelectric film obtained in the comparative example 1 into a dielectric energy storage device by using the lead-free high-entropy ferroelectric film as a dielectric material. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of the dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter and the thickness of the gold electrode are 0.4mm and 0.25 mu m respectively. The assembled dielectric energy storage device was subjected to relevant electrical performance tests (test conditions were the same as those in example 1). As shown in FIG. 8, the energy storage density of the dielectric energy storage device was measured to be at most 0.61J/cm under the same test conditions 3 Significantly lower than the energy storage density of the dielectric energy storage device assembled in example 1.
Example 2
A preparation method of a lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation of (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Precursor solution:
according to (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Weighing bismuth acetate, sodium acetate trihydrate, potassium acetate, strontium acetate, lanthanum nitrate hexahydrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth acetate into a proper amount of glacial acetic acid, heating and stirring for 30min at 70 ℃, adding a small amount of deionized water, stirring for 30min, then sequentially adding sodium acetate trihydrate, potassium acetate, strontium acetate and lanthanum nitrate hexahydrate, stirring for 3h, and dissolving to obtain a solution A;
mixing tetrabutyl titanate, ethylene glycol monomethyl ether and acetylacetone at room temperature according to a volume ratio of 1;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid into the solution B after the solution B is completely added so as to avoid hydrolysis reaction of tetrabutyl titanate, stirring the mixture for 3 hours, adding formamide with the volume ratio of 0.5 percent, slowly stirring the mixture for 24 hours at room temperature, standing the mixture for 72 hours, and reacting the mixture to obtain (Bi) 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Precursor solution;
2) Pt (111)/Ti/SiO at 1cm × 1cm 2 Dripping 5 drops of (Bi) on a Si (100) conductive substrate 0.26 Na 0.26 K 0.16 La 0.16 Sr 0.16 )TiO 3 Spin-coating the precursor solution for 9s at a rotation speed of 600r/min by using a spin coater, and then spin-coating for 30s at a rotation speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Rapidly heating the amorphous film; the rapid heating treatment comprises the following steps: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at the heating rate of 80 ℃/s, and preserving heat for 5min;
5) And (3) repeating the step 2), the step 3) and the step 4) for 3 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain the 4-layer lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric thin film obtained in example 2 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of the dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter and the thickness of the gold electrode are 0.4mm and 0.25 mu m respectively. The assembled dielectric energy storage device is subjected to a dielectric energy storage performance test (the test conditions are the same as those in the example 1), and the energy storage density of the dielectric energy storage device is measured to be 5.6J/cm 3 And an energy storage efficiency of 90%.
Example 3
A preparation method of a lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation of (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 Precursor solution:
according to (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 Weighing bismuth nitrate, sodium nitrate, potassium nitrate, strontium nitrate, lanthanum nitrate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth nitrate into a proper amount of glacial acetic acid, heating and stirring for 30min at the temperature of 60 ℃, adding a small amount of deionized water, stirring for 30min, then sequentially adding sodium nitrate, potassium nitrate, strontium nitrate and lanthanum nitrate, stirring for 2h, and dissolving to obtain a solution A;
mixing tetrabutyl titanate, ethylene glycol monomethyl ether and acetylacetone at room temperature according to a volume ratio of 1;
heating the solution A to 80 ℃, slowly dripping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid into the solution B after the solution B is completely added so as to avoid hydrolysis reaction of tetrabutyl titanate, stirring the mixture for 3 hours, adding formamide with the volume ratio of 0.5 percent, slowly stirring the mixture for 24 hours at room temperature, standing the mixture for 72 hours, and reacting the mixture to obtain (Bi) 1/4 Na 1/4 K 1/6 La 1/6 Sr 1/6 )TiO 3 Precursor solution;
2) Pt (111)/Ti/SiO at 1cm × 1cm 2 5 drops of (Bi) are dripped on a/Si (100) conductive substrate 1/4 Na 1/4 K 1/ 6 La 1/6 Sr 1/6 )TiO 3 Spin-coating the precursor solution for 9s at a rotation speed of 600r/min by using a spin coater, and then spin-coating for 30s at a rotation speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 5min at 200 ℃, and then pyrolyzing for 5min at 400 ℃ to obtain an amorphous film;
4) Rapidly heating the amorphous film; the rapid heating treatment comprises the following steps: heating the amorphous film to 650 ℃ by adopting a rapid annealing furnace at the heating rate of 50 ℃/s, and preserving heat for 3min;
5) And (3) repeating the step 2), the step 3) and the step 4) for 5 times, and then carrying out annealing treatment for 15min at 650 ℃ to obtain the 6-layer lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric thin film obtained in example 3 was used as a dielectric material to assemble a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of the dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter and the thickness of the gold electrode are 0.4mm and 0.25 mu m respectively. The assembled dielectric energy storage device is subjected to a dielectric energy storage performance test (the test conditions are the same as those in example 1), and the energy storage density of the dielectric energy storage device is measured to be 5.63J/cm 3 And an energy storage efficiency of 91%.
Example 4
A preparation method of a lead-free high-entropy ferroelectric film comprises the following steps:
1) Preparation (Bi) 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 Precursor solution:
according to (Bi) 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 Weighing bismuth sulfate, sodium sulfate, potassium sulfate, strontium sulfate, lanthanum sulfate and tetrabutyl titanate as raw materials according to the stoichiometric ratio, adding bismuth sulfate into a proper amount of glacial acetic acid, heating and stirring for 30min at the temperature of 80 ℃, and then adding a small amount of deionized waterStirring for 30min, then sequentially adding sodium sulfate, potassium sulfate, strontium sulfate and lanthanum sulfate, stirring for 3h, and dissolving to obtain a solution A;
mixing tetrabutyl titanate, ethylene glycol monomethyl ether and acetylacetone at room temperature according to a volume ratio of 1;
heating the solution A to 80 ℃, slowly dropping the solution B into the solution A, adding a proper amount of 0.2M glacial acetic acid after the solution B is completely added to avoid hydrolysis reaction of tetrabutyl titanate, stirring for 3h, adding formamide with the volume ratio of 1%, slowly stirring for 24h at room temperature, standing for 72h, and reacting to obtain (Bi) 2/7 Na 2/7 K 1/7 La 1/7 Sr 1/7 )TiO 3 Precursor solution;
2) Pt (111)/Ti/SiO at 1cm × 1cm 2 Dripping 4 drops of (Bi) on a Si (100) conductive substrate 2/7 Na 2/7 K 1/ 7 La 1/7 Sr 1/7 )TiO 3 Spin-coating the precursor solution for 9s at a rotation speed of 600r/min by using a spin coater, and then spin-coating for 30s at a rotation speed of 3000r/min to obtain a wet film;
3) Placing the wet film on an electric heating flat plate, drying for 3min at the temperature of 250 ℃, and then pyrolyzing for 3min at the temperature of 450 ℃ to obtain an amorphous film;
4) Rapidly heating the amorphous film; the rapid heating treatment comprises the following steps: heating the amorphous film to 700 ℃ by adopting a rapid annealing furnace at the heating rate of 100 ℃/s, and preserving heat for 4min;
5) And (3) repeating the step 2), the step 3) and the step 4) for 9 times, and then carrying out annealing treatment for 10min at 700 ℃ to obtain 10 layers of the lead-free high-entropy ferroelectric film.
The lead-free high-entropy ferroelectric thin film obtained in example 4 is used as a dielectric material to be assembled into a dielectric energy storage device. The conductive substrate of the lead-free high-entropy ferroelectric film is used as one electrode of the dielectric energy storage device, the other electrode of the dielectric energy storage device is prepared by depositing gold on the other surface of the lead-free high-entropy ferroelectric film through magnetron sputtering, and the diameter and the thickness of the gold electrode are 0.4mm and 0.25 mu m respectively. The assembled dielectric energy storage device is subjected to dielectric energy storage performance measurementIn a test (the test conditions were the same as those in example 1), the energy storage density of the dielectric energy storage device was measured to be 5.87J/cm 3 And an energy storage efficiency of 90%.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.
Claims (10)
1. A preparation method of a lead-free high-entropy ferroelectric film is characterized by comprising the following steps:
1) Preparing a BNKLST precursor solution, the chemical formula of the BNKLST being (Bi) x Na x K y La y Sr y )TiO 3 Wherein x > 0, y > 0,2x +3y =1;
2) Spin-coating the BNKLST precursor solution obtained in the step 1) on a conductive substrate to obtain a wet film;
3) Drying the wet film obtained in the step 2) at the temperature of 200-250 ℃ for 3-5min, and then pyrolyzing the wet film at the temperature of 400-450 ℃ for 3-5min to obtain an amorphous film;
4) Carrying out rapid heating treatment on the amorphous film obtained in the step 3); the rapid heating treatment comprises the following steps: heating to 650-700 ℃ at a heating rate of 50-100 ℃/s, and keeping the temperature for 3-5min;
5) And (3) annealing the amorphous film subjected to the rapid heating treatment in the step 4) to obtain the lead-free high-entropy ferroelectric film.
2. The preparation process according to claim 1, characterized in that the preparation of the BNKLST precursor solution in step 1) is carried out in particular by the following steps:
weighing bismuth salt, sodium salt, potassium salt, strontium salt, lanthanum salt and titanium salt according to the stoichiometric ratio of the chemical general formula;
dissolving the bismuth salt in a solvent, adding the sodium salt, the potassium salt, the strontium salt and the lanthanum salt, and dissolving to obtain a solution A;
mixing the titanium salt with a solvent and a chelating agent to obtain a solution B;
and adding the solution B into the solution A, adding formamide with the volume ratio of 0.5-1%, stirring for 24-36h, standing for 72-84h, and reacting to obtain the BNKLST precursor solution.
3. The production method according to claim 2, wherein the bismuth salt includes at least one of bismuth acetate, bismuth nitrate, and bismuth sulfate; the sodium salt comprises at least one of sodium acetate trihydrate, sodium nitrate and sodium sulfate; the potassium salt comprises at least one of potassium acetate, potassium nitrate and potassium sulfate; the strontium salt comprises at least one of strontium acetate, strontium nitrate and strontium sulfate; the lanthanum salt comprises at least one of lanthanum nitrate hexahydrate, lanthanum nitrate and lanthanum sulfate; the titanium salt is tetrabutyl titanate.
4. The method according to claim 2, wherein the solvent comprises at least one of glacial acetic acid, ethylene glycol monomethyl ether, ethanol, isopropanol; the chelating agent comprises at least one of acetylacetone, EDTA, potassium sodium tartrate and ammonium citrate.
5. The method according to claim 1, wherein the ratio of x to y is 0.5 to 2.
6. The production method according to claim 1, wherein the conditions of the annealing treatment include: the annealing temperature is 650-700 ℃, and the annealing time is 10-15min.
7. The method of claim 1, wherein step 2), step 3) and step 4) are repeated a plurality of times before performing step 5) to obtain a multilayer amorphous film.
8. The preparation method according to claim 7, wherein the number of the layers of the lead-free high-entropy ferroelectric thin film is 4-10, and the thickness of each layer of the lead-free high-entropy ferroelectric thin film is 40-50nm.
9. A lead-free high-entropy ferroelectric thin film, which is obtained by the production method according to any one of claims 1 to 8, and which has a breakdown field strength of more than 8MV/cm.
10. A dielectric energy storage device comprising the lead-free high-entropy ferroelectric thin film according to claim 9.
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