CN109912304B - Bismuth ferrite based ternary solid solution dielectric thin film material and preparation method thereof - Google Patents
Bismuth ferrite based ternary solid solution dielectric thin film material and preparation method thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 127
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Abstract
A bismuth ferrite based ternary solid solution dielectric film material and a preparation method thereof belong to the technical field of dielectric materials. The general formula of the chemical composition of the dielectric film material is (1-x-y) BiFeO3‑xBaTiO3‑ySrTiO3Wherein x and y are mole fractions and 0<x<1,0<y<1,0<x+y<1. The preparation method is that Bi is added2O3、Fe2O3、BaCO3、SrCO3And TiO2Mixing the raw materials according to a selected stoichiometric ratio to obtain raw material powder, pre-sintering the raw material powder to obtain a ceramic blank, then burying and sintering the blank to obtain a ceramic target material, and finally performing pulse laser deposition and annealing treatment on the ceramic target material to obtain the bismuth ferrite-based ternary solid solution dielectric thin film material. Experiments prove that the breakdown field strength of the material can reach 3.0-5.3 MV/cm, and the energy storage density can reach 112J/cm3The energy storage efficiency is about 80%; the lead-free dielectric material is a novel lead-free dielectric material which has excellent properties such as large dielectric constant, small dielectric loss, strong polarization, high breakdown, high energy storage density and the like and is environment-friendly.
Description
Technical Field
The invention relates to a bismuth ferrite-based ternary solid solution dielectric film material and a preparation method thereof, belonging to the technical field of dielectric materials.
Background
The capacitor based on the dielectric material is used as an important energy storage device, has the characteristics of extremely high discharge speed, ultrahigh power density, high voltage resistance, long service life and the like, and is widely applied to the fields of electronic circuits, electrical systems, pulse power technologies and the like. However, the energy storage density of the general dielectric material is lower, and the energy storage density of the current commercial dielectric material (biaxial oriented polypropylene) is only about 1J/cm3Compared with lithium batteries or fuel cells, the number of the lithium batteries or fuel cells is one to two orders of magnitude lower, and the requirements of advanced electronic power systems on integration and miniaturization cannot be met. Therefore, the development of dielectric materials for capacitors having high energy storage density has been a hotspot and difficulty in the related art.
The inorganic ceramic dielectric film material has the advantages of large dielectric constant, strong polarization and high breakdown field strength, and is a dielectric material with potential for realizing high energy storage density. Lead zirconate titanate (Pb (Ti, Zr) O, which has been widely studied and used at present3) Realizes 85J/cm in the base dielectric film material3High energy storage density (see Journal of Materials Science: Materials in Electronics, Vol.26, No. 12, p.9279-9287). However, lead-containing materials are seriously harmful to the ecological environment and human health and are difficult to recycle. Therefore, it is an urgent task to find a lead-free dielectric material having a high energy storage density. However, conventional barium titanate (BaTiO)3) The polarization of the base dielectric material is much lower than that of the lead-containing dielectric material, and the energy storage density is relatively low. Such as zirconium doped barium titanate dielectric films (BaZr)0.2Ti0.8O3) The polarization is only 31 mu C/cm under the electric field of 3.0MV/cm2The energy storage density is 30J/cm3(see ACS Applied Materials&Journal of Interfaces, volume 9, stage 20, page 17096-. Therefore, the development of new lead-free dielectric materials with strong polarization, high breakdown, and high energy storage density is a key issue facing the related fields and industries at present.
Disclosure of Invention
The invention aims to provide a bismuth ferrite-based ternary solid solution dielectric thin film material and a preparation method thereof, and aims to obtain a novel lead-free dielectric material which has excellent properties such as strong polarization, high breakdown and high energy storage density and is environment-friendly.
The technical scheme of the invention is as follows:
the bismuth ferrite-based ternary solid solution dielectric thin film material is characterized in that the chemical component general formula of the solid solution dielectric thin film material is (1-x-y) BiFeO3-xBaTiO3-ySrTiO3Wherein x and y are mole fractions and 0<x<1,0<y<1,0<x+y<1。
The thickness of the film material of the invention is preferably 50nm-10 μm.
The invention provides a preparation method of a bismuth ferrite-based ternary solid solution dielectric film material, which is characterized by comprising the following steps of:
1) adding Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2Mixing the raw materials according to a selected stoichiometric ratio, mixing the raw materials with an organic solvent, and performing ball milling, drying and screening treatment in sequence to obtain uniformly mixed raw material powder;
2) pre-sintering the raw material powder at the temperature of 700-900 ℃ for 2-4 hours; then mixing the powder with an organic solvent, carrying out secondary ball milling and drying, mixing the obtained raw material powder with an adhesive, and carrying out granulation, tabletting and cold isostatic pressing to obtain a bismuth ferrite-based ternary solid solution ceramic blank;
3) embedding the ceramic blank at 1000-1300 ℃ for 0.5-3.0 h; obtaining the bismuth ferrite-based ternary solid solution ceramic target material;
4) and carrying out pulsed laser deposition and annealing treatment on the bismuth ferrite-based ternary solid solution ceramic target material to obtain the bismuth ferrite-based ternary solid solution dielectric thin film material.
In the method of the present invention, it is characterized in that, in step 1), Bi2O3The raw materials are 5 to 20 percent in excess based on the stoichiometric ratio to make up the volatilization loss of the Bi element in the preparation process.
Preferably, in step 1) and step 2), the organic solvent is at least one selected from the group consisting of absolute ethanol, propanol, isopropanol, and ethylene glycol. The ball milling treatment time is 6-12 hours; the particle size of the raw material powder is 100-500 nm.
In step 2) of the present invention, preferably, the granulated particle size is 20 to 80 mesh; the pressure of the tabletting treatment is 5-15 MPa; the pressure of the cold isostatic pressing treatment is 20-50MPa, and the pressure maintaining time is 5-20 minutes.
In the step 4), the parameters of the pulse laser deposition treatment are that the background vacuum degree in the pulse laser deposition cavity is lower than 5 × 10-6mbar, substrate temperature is 600-The light energy is 0.5-2.5J/cm2. The temperature of the annealing treatment is preferably 400-600 ℃, the oxygen partial pressure is 200-800mbar, and the time of the annealing treatment is 15-60 minutes.
In another aspect of the invention, the invention provides an application of the bismuth ferrite-based ternary solid solution dielectric thin film material in a dielectric energy storage device.
The invention has the following advantages and prominent technical effects: by regulating and controlling the values of x and y, the breakdown field strength of the bismuth ferrite-based ternary solid solution dielectric thin film material can reach 3.0-5.3 MV/cm, and the energy storage density can reach 112J/cm3And has high energy storage efficiency of 80%. Experiments prove that the bismuth ferrite-based ternary solid solution dielectric film material has the advantages of higher dielectric constant, lower dielectric loss, higher breakdown field strength and excellent energy storage performance, is a material which is hopefully applied to the dielectric energy storage fields of embedded capacitors, electrostatic energy storage components, pulse power technology and the like and is environment-friendly.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a bismuth ferrite-based ternary solid solution dielectric thin film material according to one embodiment of the invention.
FIG. 2 is a schematic view showing the structure and the test of the bismuth ferrite-based ternary solid solution thin films of examples 1 to 7;
in the figure: 1-a gold electrode; 2-bismuth ferrite based ternary solid solution thin film material; 3-conductive substrate.
FIG. 3 is a transmission electron microscope cross-sectional view of the bismuth ferrite-based ternary solid solution thin film obtained in example 1.
FIG. 4 is a tangent angle spectrum of dielectric constant and dielectric loss of the bismuth ferrite-based ternary solid solution thin films prepared in examples 1 to 4.
FIGS. 5a, 5b, 5c and 5d are ferroelectric hysteresis loops of the bismuth ferrite-based ternary solid solution thin films prepared in examples 1-4 at different electric field strengths, respectively.
Detailed Description
The following detailed description of the invention is provided in conjunction with the accompanying drawings and the specific embodiments for the purpose of illustrating the invention so that one skilled in the art can understand and implement the invention.
Examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout.
The inventors found that bismuth ferrite (BiFeO)3) The ferroelectric material is a rhombohedral phase perovskite structure ferroelectric material, and the ferroelectricity of the ferroelectric material is 6s of Bi ions2The theoretical ferroelectric polarization of the ferroelectric polarization is up to 100 mu C/cm caused by the combination of lone pair electrons and the displacement of Bi and Fe ions2. However, it is very difficult to prepare high-quality bismuth ferrite experimentally, and there are a lot of defects and impurities, so it is difficult to measure the real ferroelectric polarization value. The ferroelectric polarization usually measured in bismuth ferrite ceramics is only a few μ C/cm2. Barium titanate (BaTiO)3) The ferroelectric material with the perovskite structure which is tetragonal phase at room temperature has the spontaneous polarization of about 26 mu C/cm2. Strontium titanate (SrTiO)3) The material is of a cubic phase perovskite structure, and has the advantages of low dielectric loss, good thermal stability, high breakdown strength and the like. Although the three crystal phases are different, the crystallographic parameters are not greatly different, and a complete solid solution can be formed.
The invention provides a bismuth ferrite-based ternary solid solution dielectric film material, and the general formula of the chemical components of the dielectric film is (1-x-y) BiFeO3-xBaTiO3-ySrTiO3Wherein x and y are mole fractions and 0<x<1,0<y<1,0<x+y<1。
Thus, (1-x-y) BiFeO was designed3-xBaTiO3-ySrTiO3(x, y are mole fractions and 0<x<1,0<y<1,0<x+y<1). By regulating and controlling the values of x and y, the breakdown field strength can reach 3.0-5.3 MV/cm, and the energy storage density can reach 112J/cm3And has high energy storage efficiency of 80%. Experiments prove that the bismuth ferrite-based ternary solid solution dielectric film material has the advantages of higher dielectric constant, lower dielectric loss, higher breakdown field strength and excellent energy storage performance, is a material which is hopefully applied to the dielectric energy storage fields of embedded capacitors, electrostatic energy storage components, pulse power technology and the like and is environment-friendly.
The thickness of the bismuth ferrite-based ternary solid solution dielectric thin film material according to an embodiment of the present invention is not particularly limited and may be selected by those skilled in the art according to practical needs, and according to an embodiment of the present invention, the thickness of the bismuth ferrite-based dielectric thin film for high density energy storage is preferably 50nm to 10 μm. The inventor finds that if the thickness of the bismuth ferrite-based ternary solid solution dielectric thin film material is too low, the capacitance value of the dielectric thin film is higher, but the insulativity is poor, so that the breakdown and the energy storage performance are not facilitated to be improved; if the thickness of the bismuth ferrite-based ternary solid solution dielectric thin film material is too high, a very high voltage needs to be applied in practical application, which is not beneficial to the miniaturization of an energy storage device. Therefore, the thickness of the bismuth ferrite-based dielectric film can improve the insulativity of the bismuth ferrite-based dielectric film, and is beneficial to the miniaturization application of an energy storage device.
The invention provides a preparation method of the bismuth ferrite-based ternary solid solution dielectric thin film material, which comprises the following steps:
step 1): mixing the raw materials, performing ball milling, drying and screening to obtain raw material powder;
in this step, Bi is added2O3、Fe2O3、BaCO3、SrCO3And TiO2Mixing the raw materials according to a selected stoichiometric ratio, mixing the raw materials with an organic solvent, and performing ball milling, drying and screening treatment in sequence to obtain uniformly mixed raw material powder; the chemical composition of the raw material is not particularly limited according to the embodiment of the present invention, and can be selected by those skilled in the art according to the actual requirement, and according to a specific embodiment of the present invention, the composition of the raw material can be (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x, y are mole fractions and 0<x<1,0<y<1,0<x+y<1) The inventors found that with SrTiO3The ratio of the bismuth ferrite-based ternary solid solution dielectric film is increased, the dielectric constant and the ferroelectric polarization strength of the bismuth ferrite-based ternary solid solution dielectric film are weakened, but the dielectric loss is obviously reduced, and the insulativity and the breakdown field strength are obviously improved. Random BaTiO3The ratio of the bismuth ferrite-based ternary solid solution dielectric film is increased, the dielectric constant and the ferroelectric polarization strength of the bismuth ferrite-based ternary solid solution dielectric film are slightly weakened, but the hysteresis loss under a high electric field is obviously reduced, and the ferroelectric phase returnsThe wire becomes significantly thinner. In SrTiO3In a proportion of 45%, BaTiO3When the proportion of the bismuth ferrite-based ternary solid solution dielectric film is 30 percent, the bismuth ferrite-based ternary solid solution dielectric film has the most excellent comprehensive performance, the breakdown field strength can reach 4.9MV/cm, and the ferroelectric polarization can reach 69 mu C/cm2The energy storage density can reach 112J/cm3And the energy storage efficiency reaches 80 percent.
According to another embodiment of the present invention, the excess of the Bi element in the raw material is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the excess of the Bi element may be 5 to 20%. Therefore, the volatilization loss of the Bi element in the preparation process can be effectively compensated, and the dielectric and energy storage performance of the bismuth ferrite-based ternary solid solution dielectric film is improved.
According to still another embodiment of the present invention, the type of the organic solvent is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the organic solvent may be at least one selected from the group consisting of absolute ethanol, propanol, isopropanol and ethylene glycol.
According to another embodiment of the present invention, the time of the ball milling process is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the time of the ball milling process may be 6 to 12 hours.
According to another embodiment of the present invention, the particle size of the raw material powder of the bismuth ferrite-based ternary solid solution dielectric thin film is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the particle size of the bismuth ferrite-based ternary powder may be 100-500 nm.
Step 2): pre-sintering the raw material powder, ball-milling for the second time, granulating, tabletting, and cold isostatic pressing to obtain ceramic blank
In the step, the raw material powder of the bismuth ferrite-based ternary solid solution dielectric film is sequentially subjected to pre-sintering treatment, secondary ball milling, granulation, tabletting and cold isostatic pressing treatment so as to obtain a bismuth ferrite-based ternary ceramic blank.
According to an embodiment of the present invention, the conditions of the pre-burning treatment are not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to an embodiment of the present invention, the temperature of the pre-burning treatment may be 700-. The inventors found that when the calcination time is too short and the temperature is too low, volatile organic compounds, crystal water, decomposition products, and the like cannot be sufficiently removed, and the densification of the raw material is insufficient; if the pre-sintering time is too long and the temperature is too high, the processing cost is high and side reactions may occur. Therefore, the adoption of the presintering treatment conditions provided by the application is beneficial to fully removing impurities in the raw material powder, densifying the raw material powder and reducing the processing cost.
According to another embodiment of the present invention, the time of the secondary ball milling process is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the time of the ball milling process may be 6 to 12 hours.
According to another embodiment of the present invention, the particle size of the granules is not particularly limited, and those skilled in the art can select the granules according to actual needs, and according to a specific embodiment of the present invention, the particle size can be 20-80 mesh.
According to another embodiment of the present invention, the pressure of the tableting process is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the pressure of the tableting process may be 5 to 15 MPa.
According to another embodiment of the present invention, the pressure and dwell time of the cold isostatic pressing process are not particularly limited and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the pressure of the cold isostatic pressing process may be 20 to 50MPa, and the dwell time may be 5 to 20 minutes. The inventor finds that if the pressure of the cold isostatic pressing treatment is too low and the pressure maintaining time is too short, the density of the pressed bismuth ferrite-based ternary ceramic blank is poor and the strength is low; if the pressure of the tabletting process is too high and the pressure maintaining time is too long, the cost is high and danger is easy to occur. Therefore, the pressure of the tabletting treatment provided by the application is favorable for obtaining the high-quality bismuth ferrite-based ternary ceramic blank.
According to still another embodiment of the present invention, the diameter and thickness of the bismuth ferrite-based ternary ceramic green body are not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the bismuth ferrite-based ternary ceramic green body may have a diameter of 0.5 to 2 inches and a thickness of 2 to 7 mm.
Step 3): the ceramic blank is subjected to buried burning treatment to obtain the ceramic target material
In the step, the bismuth ferrite-based ternary ceramic blank is subjected to buried burning treatment so as to obtain the bismuth ferrite-based ceramic target. The inventor finds that the bismuth ferrite-based ternary ceramic blank is subjected to buried burning treatment, so that the volatilization of Bi element in the sintering process can be reduced, and the quality and the energy storage performance of the bismuth ferrite-based ternary solid solution film can be improved.
According to an embodiment of the present invention, the conditions of the burying treatment are not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to an embodiment of the present invention, the temperature of the burying treatment may be 1000-. The inventor finds that if the burying sintering temperature is too low and the time is too short, the bismuth ferrite-based ternary solid solution ceramic target material has insufficient sintering density, incomplete reaction and poor target material quality; if the burying sintering temperature is too high and the burying sintering time is too long, the preparation cost is increased, excessive grain growth and secondary recrystallization are easily generated, and the quality of the target material is deteriorated. Therefore, the quality of the bismuth ferrite-based ternary solid solution ceramic target can be obviously improved by adopting the burying and sintering treatment conditions provided by the application.
Step 4): carrying out pulsed laser deposition treatment and annealing treatment on the ceramic target material to obtain the dielectric film
In the step, pulse laser deposition treatment and annealing treatment are carried out on the bismuth ferrite-based ternary solid solution ceramic target material, so that the bismuth ferrite-based dielectric film for high-density energy storage is obtained. Specifically, the bismuth ferrite-based ternary solid solution ceramic target material is bombarded by laser to enable the components to be diffused to a conductive single crystal base according to the stoichiometric ratioAnd preparing the epitaxial dielectric film under the conditions of proper substrate temperature, oxygen partial pressure and annealing. The conductive single crystal substrate is selected from pure strontium titanate (SrTiO)3) Magnesium aluminate (MgAl)2O4) Lanthanum strontium aluminum tantalum ((La, Sr) (Al, Ta) O3) Lanthanum aluminate (LaAlO)3) And at least one of magnesium oxide, and epitaxial perovskite ABO on single crystal3Structural conductive films, e.g. lanthanum nickelate (LaNiO)3) Lanthanum strontium manganate, lanthanum strontium cobaltate, or niobium doped strontium titanate single crystal substrates.
The parameters of the pulsed laser deposition process according to an embodiment of the present invention are not particularly limited and may be selected by one skilled in the art according to actual needs, and according to an embodiment of the present invention, the parameters of the pulsed laser deposition process may be such that the background vacuum of the reaction chamber is not higher than 5 × 10-6mbar, substrate temperature of 600-2. The inventor finds that under the parameters, the bismuth ferrite-based ternary solid solution film grows epitaxially at a proper speed, and the obtained bismuth ferrite-based ternary solid solution film has high quality and is beneficial to improving the dielectric and energy storage performance of the film.
According to another embodiment of the present invention, the conditions of the annealing treatment are not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the temperature of the annealing treatment may be 400-. The inventor finds that under the parameters, the oxygen vacancy in the bismuth ferrite-based ternary solid solution film is fully compensated, and the insulation capability, the breakdown property and the energy storage performance of the film are favorably improved.
According to the method for preparing the bismuth ferrite-based ternary solid solution film for high-density dielectric energy storage, which is disclosed by the embodiment of the invention, Bi is added2O3、Fe2O3、BaCO3、SrCO3And TiO2The raw materials are mixed, ball-milled, dried and screened according to the selected stoichiometric ratio to obtain the bismuth ferrite-based ternary solid solutionRaw material powder of dielectric film, Bi2O3The excessive raw materials can make up the volatilization loss of the Bi element in the subsequent preparation process. The uniform and compact bismuth ferrite-based ternary solid solution ceramic blank can be obtained by pre-sintering, secondary ball milling, granulation, tabletting and cold isostatic pressing treatment of the raw material powder. The bismuth ferrite-based ternary solid solution ceramic target material with high density, low porosity and low Bi volatilization can be obtained by burying and burning the blank. The high-quality bismuth ferrite-based ternary solid solution dielectric film can be obtained by performing pulsed laser deposition and annealing treatment on the ceramic target, and the component of the film is (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x, y are mole fractions and 0<x<1,0<y<1,0<x+y<1). SrTiO 23The ratio of the bismuth ferrite-based ternary solid solution film is increased, the dielectric constant and the ferroelectric polarization strength of the bismuth ferrite-based ternary solid solution film are weakened, but the dielectric loss is obviously reduced, and the insulativity and the breakdown field strength are obviously improved. Random BaTiO3The ratio of the bismuth ferrite-based ternary solid solution film is increased, the dielectric constant and the ferroelectric polarization strength of the bismuth ferrite-based ternary solid solution film are slightly weakened, but the hysteresis loss under a high electric field is obviously reduced, and the ferroelectric loop is obviously thinned. By regulating and controlling the values of x and y, the breakdown field strength of the bismuth ferrite-based ternary solid solution film can reach 3.0-5.3 MV/cm, and the energy storage density can reach 112J/cm3And has high energy storage efficiency of 80%. Experiments prove that the bismuth ferrite-based ternary solid solution dielectric film material has the advantages of higher dielectric constant, lower dielectric loss, higher breakdown field strength and excellent energy storage performance, is a material which is hopefully applied to the dielectric energy storage fields of embedded capacitors, electrostatic energy storage components, pulse power technology and the like and is environment-friendly. It should be noted that the features and advantages described above for the bismuth ferrite based ternary solid solution dielectric thin film material are also applicable to the method for preparing the bismuth ferrite based ternary solid solution thin film for high-density dielectric energy storage, and are not described herein again.
In yet another aspect of the invention, the invention provides an energy storage device, which according to an embodiment of the invention comprises the bismuth ferrite-based ternary solid solution dielectric thin film material or the bismuth ferrite-based ternary solid solution dielectric thin film material obtained by the method for preparing the bismuth ferrite-based ternary solid solution dielectric thin film material. It should be noted that the features and advantages described above for the bismuth ferrite based ternary solid solution dielectric thin film material and the method for preparing the bismuth ferrite based ternary solid solution dielectric thin film material are also applicable to the energy storage device, and are not described herein again. Specifically, the energy storage device can be a dielectric capacitor, an electrostatic energy storage component, a pulse power element, an embedded capacitor or a device further developed and assembled based on the above-mentioned device.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
The following examples were tested for various properties as follows: and preparing a metal round electrode (the diameter is 100-400 mu m, and the thickness is about 100nm) on the upper surface of the bismuth ferrite-based ternary solid solution film by a direct current sputtering method. The dielectric property test was performed using an E4294A impedance analyzer manufactured by Agilent, USA, and the ferroelectric hysteresis loop test was performed using a Precision Premier II ferroelectric test platform manufactured by Radiationtechnology, USA, and the energy storage density and efficiency were calculated from the hysteresis loop.
Example 1
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.3 and y is 0.45), wherein Bi is added2O3The raw material is excessive by 10 percent. The raw materials are ball-milled for 8 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 2 hours at 800 ℃. And performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 mass percent of polyvinyl alcohol solution for granulation, pressing into tablets under a 12MPa tablet press, and keeping the pressure for 10 minutes by using 25MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 1 inch and the thickness of about 5 millimeters. After heat preservation and polyvinyl alcohol removal, the wafer blank is buried and burned for 2 hours at 1100 ℃, and the high-quality bismuth ferrite-based ternary solid solution ceramic target is obtained.
Bombarding bismuth ferrite-based ternary solid solution by using pulsed laserThe ceramic target material is prepared through ablation and vaporization of target material components in stoichiometric ratio to form high temperature and high pressure plasma plume in vacuum cavity, and the plasma plume is diffused to the conductive single crystal substrate of Nb doped strontium titanate to deposit high quality dielectric film, and the pulsed laser deposition technology has parameters including reaction cavity background vacuum degree of 4.5 × 10-6mbar; during deposition, the substrate temperature is 700 ℃, the oxygen partial pressure of the cavity is 2.6Pa, the oxygen flow is 1.5sccm, and the laser energy is 1.7J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 500 ℃ for 20 minutes at an oxygen partial pressure of 800mbar and then cooled to room temperature at a rate of 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 500nm, and a sectional transmission electron microscope image of the bismuth ferrite-based ternary solid solution film is shown in FIG. 3, so that the film has good epitaxial quality, small surface roughness and is uniform, compact and free of defects. Fig. 4 shows the dielectric constant and the dielectric loss tangent angle of a bismuth ferrite-based ternary solid solution thin film (x 0.3 and y 0.45). Fig. 5a shows the dielectric polarization response of bismuth ferrite-based ternary solid solution thin film (x 0.3, y 0.45) at different electric field strengths. The performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: the dielectric constant and the loss tangent angle are 266 and 0.015 respectively at 1kHz, the breakdown field strength is 4.9MV/cm, and the polarization is 69 mu C/cm2The energy storage density reaches 112J/cm3The energy storage efficiency is 80%.
Example 2
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.2 and y is 0.45), wherein Bi is added2O3The raw material is excessive by 15 percent. The raw materials are ball-milled for 8 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 2 hours at 780 ℃. And performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 mass percent of polyvinyl alcohol solution for granulation, pressing into tablets under a 12MPa tablet press, and keeping the pressure for 10 minutes by using 25MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 1 inch and the thickness of about 5 millimeters. Heat preservation rowAfter polyvinyl alcohol is removed, the wafer blank is buried and burned for 1.5 hours at 1080 ℃ to obtain the high-quality bismuth ferrite-based ternary solid solution ceramic target material.
Bombarding a bismuth ferrite-based ternary solid solution ceramic target by using pulsed laser to ablate and vaporize target components according to a stoichiometric ratio, forming a high-temperature and high-pressure plasma plume in a vacuum cavity, diffusing the plasma plume onto a niobium-doped strontium titanate conductive single crystal substrate, and depositing and growing a high-quality dielectric film, wherein the parameters of the pulsed laser deposition technology comprise that the background vacuum degree of the reaction cavity is 4.5 × 10-6mbar; during deposition, the substrate temperature is 700 ℃, the oxygen partial pressure of the cavity is 2.6Pa, the oxygen flow is 1.75sccm, and the laser energy is 1.7J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 500 ℃ for 20 minutes at an oxygen partial pressure of 800mbar and then cooled to room temperature at a rate of 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 500nm, and fig. 4 shows the dielectric constant and the dielectric loss tangent angle of the bismuth ferrite-based ternary solid solution film (x is 0.2, and y is 0.45). Fig. 5b shows the dielectric polarization response of bismuth ferrite-based ternary solid solution thin film (x 0.2, y 0.45) at different electric field strengths. The performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: dielectric constant and loss tangent angle of 281 and 0.031 respectively at 1kHz, breakdown field strength of 4.4MV/cm, and polarization of 69 μ C/cm2The energy storage density reaches 96J/cm3The energy storage efficiency is 79%.
Example 3
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.1 and y is 0.45), wherein Bi is added2O3The raw material is excessive by 15 percent. The raw materials are ball-milled for 8 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 2 hours at 750 ℃. Performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 percent (mass percentage) polyvinyl alcohol solution for granulation, pressing into tablets under a 12MPa tablet press, and then performing cold isostatic pressing for 10 minutes under 25MPa to obtain the powder with the diameter of aboutA 1 inch wafer blank having a thickness of about 5 mm. After heat preservation and polyvinyl alcohol removal, the wafer blank is buried and burned for 1.5 hours at 1050 ℃ to obtain the high-quality bismuth ferrite-based ternary solid solution ceramic target material.
Bombarding a bismuth ferrite-based ternary solid solution ceramic target by using pulsed laser to ablate and vaporize target components according to a stoichiometric ratio, forming a high-temperature and high-pressure plasma plume in a vacuum cavity, diffusing the plasma plume onto a niobium-doped strontium titanate conductive single crystal substrate, and depositing and growing a high-quality dielectric film, wherein the parameters of the pulsed laser deposition technology comprise that the background vacuum degree of the reaction cavity is 4.5 × 10-6mbar; during deposition, the substrate temperature is 700 ℃, the oxygen partial pressure of the cavity is 2.6Pa, the oxygen flow is 1.5sccm, and the laser energy is 1.7J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 500 ℃ for 20 minutes at an oxygen partial pressure of 800mbar and then cooled to room temperature at a rate of 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 500nm, and fig. 4 shows the dielectric constant and the dielectric loss tangent angle of the bismuth ferrite-based ternary solid solution film (x is 0.1, and y is 0.45). Fig. 5c shows the dielectric polarization response of bismuth ferrite-based ternary solid solution thin film (x 0.1, y 0.45) at different electric field strengths. The performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: the dielectric constant and the loss tangent angle are respectively 312 and 0.039 at 1kHz, the breakdown field strength is 3.6MV/cm, and the polarization is 66 mu C/cm2The energy storage density reaches 74J/cm3The energy storage efficiency is 76%.
Example 4
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.4, y is 0.45) and Bi is added2O3The raw material is excessive by 10 percent. The raw materials are ball-milled for 8 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 2 hours at 820 ℃. Performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 percent (mass percentage) of polyvinyl alcohol solution for granulation, pressing into tablets under the pressure of 12MPa, and then performing secondary ball milling on the tabletsAnd keeping the pressure for 10 minutes by using 25MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 1 inch and the thickness of about 5 millimeters. After heat preservation and polyvinyl alcohol removal, the wafer blank is buried and burned for 2.5 hours at 1200 ℃, and the high-quality bismuth ferrite-based ternary solid solution ceramic target is obtained.
Bombarding a bismuth ferrite-based ternary solid solution ceramic target by using pulsed laser to ablate and vaporize target components according to a stoichiometric ratio, forming a high-temperature and high-pressure plasma plume in a vacuum cavity, diffusing the plasma plume onto a niobium-doped strontium titanate conductive single crystal substrate, and depositing and growing a high-quality dielectric film, wherein the parameters of the pulsed laser deposition technology comprise that the background vacuum degree of the reaction cavity is 4.5 × 10-6mbar; during deposition, the substrate temperature is 700 ℃, the oxygen partial pressure of the cavity is 2.6Pa, the oxygen flow is 1.5sccm, and the laser energy is 1.7J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 500 ℃ for 20 minutes at an oxygen partial pressure of 800mbar and then cooled to room temperature at a rate of 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 500nm, and fig. 4 shows the dielectric constant and the dielectric loss tangent angle of the bismuth ferrite-based ternary solid solution film (x is 0.4, and y is 0.45). Fig. 5d shows the dielectric polarization response of the bismuth ferrite-based ternary solid solution thin film (x 0.4 and y 0.45) at different electric field strengths. The performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: the dielectric constant and the loss tangent angle at 1kHz were 240 and 0.013, respectively, the breakdown field strength was 5.3MV/cm, and the polarization was 62 μ C/cm2The energy storage density reaches 110J/cm3The energy storage efficiency was 81%.
Example 5
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.3 and y is 0.3) and preparing the material, wherein Bi is2O3The raw material is excessive by 15 percent. The raw materials are ball-milled for 10 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 3 hours at 750 ℃. Ball-milling the obtained powder for 10 hours for the second time, drying, adding 5% (mass percent) polyvinyl alcoholGranulating with the solution, pressing into tablets under a 10MPa tablet press, and keeping the pressure for 15 minutes by using 30MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 1 inch and the thickness of about 7 millimeters. After heat preservation and polyvinyl alcohol removal, the wafer blank is buried and burned for 1.5 hours at 1100 ℃, and the high-quality bismuth ferrite-based ternary solid solution ceramic target is obtained.
Bombarding a bismuth ferrite-based ternary solid solution ceramic target by using pulsed laser to ablate and vaporize target components according to a stoichiometric ratio, forming a high-temperature and high-pressure plasma plume in a vacuum cavity, diffusing the plasma plume onto a niobium-doped strontium titanate conductive single crystal substrate, and depositing and growing a high-quality dielectric film, wherein the parameters of the pulsed laser deposition technology comprise that the background vacuum degree of the reaction cavity is 4.0 × 10-6mbar; during deposition, the substrate temperature is 700 ℃, the oxygen partial pressure of the cavity is 4.0Pa, the oxygen flow is 2sccm, and the laser energy is 2.5J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 550 ℃ for 30 minutes at 500mbar oxygen partial pressure and then cooled to room temperature at 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 400nm, and the performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: the dielectric constant and the loss tangent angle are 310 and 0.042 respectively at 1kHz, the breakdown field strength is 3.3MV/cm, and the polarization is 56 mu C/cm2The energy storage density reaches 52J/cm3The energy storage efficiency is 70%.
Example 6
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.25 and y is 0.4) and Bi is added2O3The raw material is excessive by 10 percent. The raw materials are ball-milled for 8 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 2 hours at 900 ℃. And performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 mass percent polyvinyl alcohol solution for granulation, pressing into tablets under a 5MPa tablet press, and keeping the pressure for 20 minutes by using 25MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 1.5 inches and the thickness of about 5 millimeters. Heat preservation elimination polyvinyl alcoholAnd then, burying and burning the wafer blank at 1300 ℃ for 2.5 hours to obtain the high-quality bismuth ferrite-based ternary solid solution ceramic target material.
Bombarding a bismuth ferrite-based ternary solid solution ceramic target by using pulsed laser to ablate and vaporize target components according to a stoichiometric ratio, forming a high-temperature and high-pressure plasma plume in a vacuum cavity, diffusing the plasma plume onto a niobium-doped strontium titanate conductive single crystal substrate, and depositing and growing a high-quality dielectric film, wherein the parameters of the pulsed laser deposition technology comprise that the background vacuum degree of the reaction cavity is 4.7 × 10-6mbar; the substrate temperature during deposition is 750 ℃, the oxygen partial pressure of the cavity is 1.3Pa, the flow of the introduced oxygen is 2sccm, and the laser energy is 1.5J/cm2The frequency was 10 Hz. After deposition, the film was annealed at 450 ℃ for 40 minutes at 400mbar oxygen partial pressure and then cooled to room temperature at 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 1.5 mu m, and the performance of the bismuth ferrite-based ternary solid solution film can reach the following indexes: the dielectric constant and the loss tangent angle are respectively 280 and 0.021 at 1kHz, the breakdown field strength is 3.5MV/cm, and the polarization is 61 mu C/cm2The energy storage density reaches 67J/cm3The energy storage efficiency was 83%.
Example 7
The raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2According to (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x is 0.2 and y is 0.6) and Bi is added2O3The raw material is excessive by 10 percent. The raw materials are ball-milled for 10 hours by using absolute ethyl alcohol as a medium, dried and sieved, and the prepared powder is presintered for 4 hours at 780 ℃. And performing secondary ball milling on the obtained powder for 8 hours, drying, adding 5 mass percent polyvinyl alcohol solution for granulation, pressing into tablets under an 8MPa tablet press, and keeping the pressure for 5 minutes by using 40MPa cold isostatic pressing to obtain a wafer blank with the diameter of about 0.5 inch and the thickness of about 4 millimeters. After heat preservation and polyvinyl alcohol removal, the wafer blank is buried and burned for 3 hours at 1150 ℃ to obtain the high-quality bismuth ferrite-based ternary solid solution ceramic target.
Bombardment with pulsed laserA bismuth ferrite-based ternary solid solution ceramic target material is prepared through ablating and vaporizing target material components according to stoichiometric ratio to form high-temperature and high-pressure plasma plume in vacuum cavity, diffusing the plasma plume onto the niobium-doped strontium titanate conductive single crystal substrate, and depositing to grow high-quality dielectric film, wherein the parameters of pulse laser deposition technique include that the background vacuum degree of reaction cavity is 4.0 × 10-6mbar; the substrate temperature during deposition is 670 ℃, the oxygen partial pressure of the cavity is 2.0Pa, the flow of the introduced oxygen is 5sccm, and the laser energy is 2.0J/cm2The frequency was 5 Hz. After deposition, the film was annealed at 475 ℃ for 20 minutes at 600mbar oxygen partial pressure and then cooled to room temperature at 10 ℃ per minute.
The thickness of the prepared bismuth ferrite-based ternary solid solution film is about 800nm, and the performance of the bismuth ferrite-based ternary solid solution film reaches the following indexes: the dielectric constant and the loss tangent angle are 240 and 0.017 respectively at 1kHz, the breakdown field strength is 4.5MV/cm, and the polarization is 74 mu C/cm2The energy storage density reaches 92J/cm3The energy storage efficiency is 84%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., 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 are not necessarily intended to 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. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (6)
1. The bismuth ferrite-based ternary solid solution dielectric film material for dielectric energy storage is characterized in that the chemical component general formula of the solid solution dielectric film material is (1-x-y) BiFeO3-xBaTiO3-ySrTiO3Wherein x and y are mole fractions, x is more than or equal to 0.2 and less than or equal to 0.4, y is more than or equal to 0.45 and less than or equal to 0.6, and 0<x+y<1；
The dielectric film material is prepared by the following method:
1) adding Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2Mixing the raw materials according to a selected stoichiometric ratio to prepare Bi2O35-20% of the raw material is excessive on the basis of the stoichiometric ratio to make up for the volatilization loss of the Bi element in the preparation process; mixing the raw materials with an organic solvent, and performing ball milling, drying and screening treatment in sequence to obtain uniformly mixed raw material powder;
2) pre-sintering the raw material powder at the temperature of 700-900 ℃ for 2-4 hours; then mixing the powder with an organic solvent, carrying out secondary ball milling and drying, wherein the ball milling treatment time is 6-12 hours, and the particle size of the raw material powder is 100-500 nm; mixing the obtained raw material powder with an adhesive, and performing granulation, tabletting and cold isostatic pressing to obtain a bismuth ferrite-based ternary solid solution ceramic blank;
3) embedding the ceramic blank at 1000-1300 ℃ for 0.5-3.0 h; obtaining the bismuth ferrite-based ternary solid solution ceramic target material;
4) and carrying out pulsed laser deposition and annealing treatment on the bismuth ferrite-based ternary solid solution ceramic target material to obtain the bismuth ferrite-based ternary solid solution dielectric thin film material.
2. The bismuth ferrite based ternary solid solution dielectric thin film material for dielectric energy storage of claim 1, wherein: the thickness of the film material is 50nm-10 μm.
3. The bismuth ferrite based ternary solid solution dielectric thin film material for dielectric energy storage according to claim 1 or 2, wherein in step 1) and step 2), the organic solvent is at least one selected from the group consisting of absolute ethyl alcohol, propyl alcohol, isopropyl alcohol and ethylene glycol.
4. The bismuth ferrite based ternary solid solution dielectric thin film material for dielectric energy storage according to claim 1 or 2, wherein the grain size of the granulation of step 2) is 20-80 mesh; the pressure of the tabletting treatment is 5-15 MPa; the pressure of the cold isostatic pressing treatment is 20-50MPa, and the pressure maintaining time is 5-20 minutes.
5. The bismuth ferrite based ternary solid solution dielectric thin film material for dielectric energy storage as claimed in claim 1 or 2, wherein in the step 4), the parameter of the pulse laser deposition treatment is that the background vacuum degree in the pulse laser deposition cavity is lower than 5 × 10-6mbar, substrate temperature of 600-2。
6. The bismuth ferrite based ternary solid solution dielectric thin film material for dielectric energy storage as claimed in claim 1 or 2, wherein in the step 4), the temperature of the annealing treatment is 400-600 ℃, the oxygen partial pressure is 200-800mbar, and the time of the annealing treatment is 15-60 minutes.
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| CN100341817C (en) * | 2004-11-18 | 2007-10-10 | 中国电子科技集团公司第五十五研究所 | Preparation method of barium strontium titanate film material |
| US9423295B2 (en) * | 2013-04-24 | 2016-08-23 | Agency For Science, Technology And Research | Photo-sensor with a transparent substrate and an in-plane electrode pair |
| CN107056276A (en) * | 2017-03-28 | 2017-08-18 | 清华大学 | Bismuth ferrite based dielectric film for high density energy storage and its preparation method and application |
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