CN109912304A - A kind of bismuth ferrite-based ternary solid solution dielectric film material and preparation method thereof - Google Patents
A kind of bismuth ferrite-based ternary solid solution dielectric film material and preparation method thereof Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 21
- 238000004146 energy storage Methods 0.000 claims abstract description 62
- 239000000919 ceramic Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 17
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- -1 bismuthino Chemical group 0.000 description 105
- 239000002253 acid Substances 0.000 description 104
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 101
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
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- 229910052742 iron Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 229910052712 strontium Inorganic materials 0.000 description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 9
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- 230000005684 electric field Effects 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 8
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
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- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
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- IGPAMRAHTMKVDN-UHFFFAOYSA-N strontium dioxido(dioxo)manganese lanthanum(3+) Chemical compound [Sr+2].[La+3].[O-][Mn]([O-])(=O)=O IGPAMRAHTMKVDN-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
一种铁酸铋基三元固溶体介电薄膜材料及其制备方法，属于介电材料技术领域。该介电薄膜材料的化学成分通式为(1‑x‑y)BiFeO3‑xBaTiO3‑ySrTiO3，其中，x、y为摩尔分数，且0<x<1,0<y<1,0<x+y<1。其制备方法是将Bi2O3、Fe2O3、BaCO3、SrCO3和TiO2原料按选定的化学计量比混合得到原料粉体，对原料粉体进行预烧处理，得到陶瓷胚体，然后对胚体进行埋烧，得到陶瓷靶材，最后对陶瓷靶材进行脉冲激光沉积和退火处理，即可得到所述的铁酸铋基三元固溶体介电薄膜材料。实验证明，该材料其击穿场强可达3.0～5.3MV/cm，储能密度可达112J/cm3，储能效率约80％；是一种具有较大介电常数、较小的介电损耗、强极化、高击穿和高储能密度等优异性质且环境友好的新型无铅介电材料。
A bismuth ferrite-based ternary solid solution dielectric thin film material and a preparation method thereof belong to the technical field of dielectric materials. The general chemical composition formula of the dielectric thin film material is (1‑x‑y)BiFeO 3 ‑xBaTiO 3 ‑ySrTiO 3 , wherein x and y are mole fractions, and 0<x<1,0<y<1,0 <x+y<1. The preparation method is as follows: mixing Bi 2 O 3 , Fe 2 O 3 , BaCO 3 , SrCO 3 and TiO 2 raw materials according to a selected stoichiometric ratio to obtain raw material powder, and pre-sintering the raw material powder to obtain a ceramic embryo body Then, the embryo body is buried and fired to obtain a ceramic target, and finally the ceramic target is subjected to pulsed laser deposition and annealing treatment to obtain the bismuth ferrite-based ternary solid solution dielectric thin film material. Experiments show that the material has a breakdown field strength of 3.0-5.3MV/cm, an energy storage density of 112J/cm 3 , and an energy storage efficiency of about 80%. Environmentally friendly new lead-free dielectric materials with excellent properties such as electrical loss, strong polarization, high breakdown and high energy storage density.
Description
Technical field
The present invention relates to a kind of ferrous acid bismuthino ternary solid solution dielectric film materials and preparation method thereof, belong to dielectric material
Technical field.
Background technique
Based on the capacitor of dielectric material as a kind of important energy storage device, there is the velocity of discharge, superelevation being exceedingly fast
The features such as power density, high pressure resistant, long working life, thus it is widely used in electronic circuit, electrical system, pulse power skill
The fields such as art.However general dielectric material energy storage density is lower, current commercialized dielectric material (Biaxially oriented polypropylene)
Energy storage density only about 1J/cm3, one or two low order of magnitude, is unable to satisfy advanced compared with lithium battery or fuel cell etc.
Demand of the electric power systems to integrated miniaturization.Therefore, exploitation has the capacitor dielectric material one of high energy storage density
It is directly the hot and difficult issue of related fields.
Inorganic ceramic dielectric film material has both big dielectric constant, strong polarization and high breakdown field strength, is a kind of potential reality
The dielectric material of existing high energy storage density.At present in extensive lead zirconate titanate (Pb (Ti, Zr) O studied and apply3) base dielectric
85J/cm is realized in thin-film material3High energy storage density (referring to Journal of Materials Science:
Materials in Electronics magazine, volume 26, the 12nd phase, 9279-9287 pages).But lead-containing materials are to ecological ring
Border and human health have serious harm, it is difficult to be recycled.Therefore, finding, there is the unleaded dielectric material of high energy storage density to become
Urgent task.But traditional barium titanate (BaTiO3) polarization of base dielectric material is far below leaded dielectric material, energy storage is close
It spends relatively low.Barium titanate dielectric film (the BaZr adulterated such as zirconium0.2Ti0.8O3) polarization only 31 μ under 3.0MV/cm electric field
C/cm2, energy storage density 30J/cm3(referring to ACS Applied Materials&Interfaces magazine, volume 9, the 20th phase,
17096-17101 pages).Therefore, novel lead-free dielectric material of the exploitation with strong polarization, high breakdown, high energy storage density is current
The critical issue that related fields and industry face.
Summary of the invention
The purpose of the present invention is directed to a kind of ferrous acid bismuthino ternary solid solution dielectric film material and preparation method thereof, purport
It is a kind of with excellent properties and environmental-friendly novel lead-free dielectric materials such as strong polarization, high breakdown and high energy storage densities obtaining
Material.
Technical scheme is as follows:
A kind of ferrous acid bismuthino ternary solid solution dielectric film material, which is characterized in that the solid solution dielectric film material
Chemical component general formula be (1-x-y) BiFeO3-xBaTiO3-ySrTiO3, wherein x, y are molar fraction, and 0 < x < 1,0 < y <
1,0<x+y<1。
The thickness of thin-film material of the present invention is preferably 50nm-10 μm.
The preparation method of a kind of ferrous acid bismuthino ternary solid solution dielectric film material provided by the invention, it is characterised in that should
Method includes the following steps:
1) by Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2Raw material carries out mix by selected stoichiometric ratio, will
The raw material and organic solvent mixing, successively carry out ball milling, drying and screening process, the material powder being uniformly mixed；
2) material powder is subjected to preheating, the temperature of preheating is 700-900 degrees Celsius, time 2-4
Hour；Then mixed with organic solvent carry out secondary ball milling, drying, gained material powder is mixed with adhesive be granulated,
Tabletting and cold isostatic compaction processing, obtain ferrous acid bismuthino ternary solid solution ceramic idiosome；
3) ceramic idiosome is carried out burying burning processing, the temperature burnt and handled of burying is 1000-1300 degrees Celsius, the time
It is 0.5-3.0 hours；Obtain ferrous acid bismuthino ternary solid solution ceramic target；
4) the ferrous acid bismuthino ternary solid solution ceramic target is subjected to pulse laser deposition and annealing to get iron is arrived
Sour bismuthino ternary solid solution dielectric film material.
In the method described in the present invention, which is characterized in that in step 1), Bi2O3Raw material is on the basis of stoichiometric ratio
Excessive 5-20% is to make up the volatilization loss of Bi element in preparation process.
Preferably, in step 1) and step 2), the organic solvent is selected from dehydrated alcohol, propyl alcohol, isopropanol and second
At least one of glycol.The time of the ball-milling treatment is 6-12 hours；The partial size of the raw material powder is 100-
500nm。
In step 2) of the invention, it is preferable that the partial size of the granulation is 20-80 mesh；The pressure of the compressing tablet process
For 5-15MPa；The pressure of the isostatic cool pressing processing is 20-50MPa, and the dwell time is 5-20 minutes.
In step 4) of the invention, the parameter of the pulse laser deposition processes are as follows: in pulse laser deposition chamber originally
Bottom vacuum degree is lower than 5 × 10-6Mbar, base reservoir temperature is 600-800 degrees Celsius when deposition, and cavity partial pressure of oxygen is 0.5-20Pa, is led to
Oxygen flow is 1-20sccm, laser energy 0.5-2.5J/cm2.The temperature of the annealing is preferably 400-600 Celsius
Degree, partial pressure of oxygen 200-800mbar, the time of annealing are 15-60 minutes.
An additional aspect of the present invention proposes a kind of ferrous acid bismuthino ternary solid solution dielectric film material and is being situated between
Application in electric energy accumulator part.
The present invention has the following advantages that and the technical effect of high-lighting: the value by regulating and controlling x and y, above-mentioned ferrous acid bismuthino three
The disruptive field intensity of first solid solution dielectric film material is up to 3.0~5.3MV/cm, and energy storage density is up to 112J/cm3, and have
80% high energy storage efficiency.Experiments have shown that have both biggish dielectric normal for this ferrous acid bismuthino ternary solid solution dielectric film material
Several, lesser dielectric loss, higher disruptive field intensity and excellent energy-storage property are that one kind is hopeful to be applied to embedded capacitance
Dielectrics energy storage field and the environment friendly materials such as device, electrostatic energy storage component, Pulse Power Techniques.
Detailed description of the invention
Fig. 1 is the method stream according to an embodiment of the invention for preparing ferrous acid bismuthino ternary solid solution dielectric film material
Journey schematic diagram.
Fig. 2 is the structure and test schematic diagram of embodiment 1-7 ferrous acid bismuthino ternary solid solution film；
In figure: 1- gold electrode；2- ferrous acid bismuthino ternary solid solution thin-film material；3- conductive substrates.
Fig. 3 is the section transmission electron microscope picture of 1 gained ferrous acid bismuthino ternary solid solution film of embodiment.
Fig. 4 is the dielectric constant and dielectric loss tangent of the ferrous acid bismuthino ternary solid solution film prepared in embodiment 1-4
Angular spectrum figure.
Fig. 5 a, 5b, 5c and 5d are respectively the ferrous acid bismuthino ternary solid solution film for preparing in embodiment 1-4 in not same electric field
Ferroelectric hysteresis loop under intensity.
Specific embodiment
The present invention is described in detail in the following with reference to the drawings and specific embodiments, it is intended to be used to explain the present invention, so that this field
Those of ordinary skill it will be appreciated that and realize the present invention.
Examples of the embodiments are shown in the accompanying drawings, and in which the same or similar labels are throughly indicated identical or classes
As element or element with the same or similar functions.
Inventors have found that bismuth ferrite (BiFeO3) be rhombohedral phase perovskite structure ferroelectric material, ferroelectricity be by Bi from
The 6s of son2Caused by the displacement of lone pair electrons and Bi, Fe ion jointly, theoretical iron electric polarization is up to 100 μ C/cm2.But it tests
Upper preparation high quality bismuth ferrite is extremely difficult, wherein there are a large amount of defect and miscellaneous phases, it is difficult to measure its true iron electric polarization
Value.The iron electric polarization usually measured in bismuth ferrite ceramics only has several μ C/cm2.Barium titanate (BaTiO3) it is at room temperature four directions
The perovskite structure ferroelectric material of phase, about 26 μ C/cm of spontaneous polarization2.Strontium titanates (SrTiO3) it is cubic phase perovskite structure,
Have many advantages, such as that dielectric loss is low, thermal stability is good, breakdown strength is high.Although three's crystal phase is different, crystallographic parameter difference
Less, it is capable of forming complete solid solution.
A kind of ferrous acid bismuthino ternary solid solution dielectric film material proposed by the present invention, the dielectric film chemical component
General formula is (1-x-y) BiFeO3-xBaTiO3-ySrTiO3, wherein x, y are molar fraction, and 0 < x < 1,0 < y < 1,0 < x+y < 1.
(1-x-y) BiFeO is designed as a result,3-xBaTiO3-ySrTiO3(x, y are molar fraction, and 0 < x < 1,0 < y < 1,0 < x
+y<1).By regulating and controlling the value of x and y, disruptive field intensity is up to 3.0~5.3MV/cm, and energy storage density is up to 112J/cm3, and have
There is 80% high energy storage efficiency.Experiments have shown that have both biggish dielectric normal for this ferrous acid bismuthino ternary solid solution dielectric film material
Several, lesser dielectric loss, higher disruptive field intensity and excellent energy-storage property are that one kind is hopeful to be applied to embedded capacitance
Dielectrics energy storage field and the environment friendly materials such as device, electrostatic energy storage component, Pulse Power Techniques.
According to one embodiment of present invention, the thickness of ferrous acid bismuthino ternary solid solution dielectric film material is not by special
Limitation, those skilled in the art can select according to actual needs, a specific embodiment according to the present invention, for height
The thickness of the ferrous acid bismuthino dielectric film of density energy storage is preferably 50nm-10 μm.Inventors have found that if ferrous acid bismuthino ternary is dissolved
The thickness of body dielectric film material is too low, then the capacitance of dielectric film is higher, but insulating properties is deteriorated, and is unfavorable for breakdown and energy storage
The promotion of performance；And if the thickness of ferrous acid bismuthino ternary solid solution dielectric film material is excessively high, when practical application, needs to apply
Very high voltage is unfavorable for the micromation of energy storage device.The thickness of the ferrous acid bismuthino dielectric film proposed as a result, using the application can
To improve the insulating properties of ferrous acid bismuthino dielectric film, while being conducive to the micromation application of energy storage device.
Above-mentioned a kind of preparation method of ferrous acid bismuthino ternary solid solution dielectric film material proposed by the present invention, the method
It is as follows:
Step 1): raw material is subjected to mix, ball milling, drying and screening process, obtains material powder；
In the step, by Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2Raw material is mixed by selected stoichiometric ratio
Ingredient mixes the raw material and organic solvent, successively carries out ball milling, drying and screening process, the raw material being uniformly mixed
Powder；According to an embodiment of the invention, the chemical composition of raw material is not particularly restricted, those skilled in the art can be according to reality
Border is selected, a specific embodiment according to the present invention, and the composition of raw material can be (1-x-y) BiFeO3-
xBaTiO3-ySrTiO3(x, y are molar fraction, and 0 < x < 1,0 < y < 1,0 < x+y < 1) is inventors have found that with SrTiO3Ratio
Increase, dielectric constant, the iron electric polarization remitted its fury of ferrous acid bismuthino ternary solid solution dielectric film, but dielectric loss obviously drops
Low, insulating properties and disruptive field intensity are obviously improved.With BaTiO3Ratio increase, Jie of ferrous acid bismuthino ternary solid solution dielectric film
Electric constant, iron electric polarization intensity slightly weaken, but significant decrease is lost in the electric hysteresis under high electric field, and ferroelectricity loop line obviously attenuates.?
SrTiO3Ratio be 45%, BaTiO3Ratio be 30% when, the comprehensive performance of ferrous acid bismuthino ternary solid solution dielectric film is most
To be excellent, disruptive field intensity is up to 4.9MV/cm, and iron electric polarization is up to 69 μ C/cm2, energy storage density is up to 112J/cm3, energy storage efficiency
Up to 80%.
Still another embodiment in accordance with the present invention, the excessive value of Bi element is not particularly restricted in raw material, this field skill
Art personnel can select according to actual needs, a specific embodiment according to the present invention, and the excessive value of Bi element can be with
For 5-20%.Thus, it is possible to effectively make up the volatilization loss of Bi element in preparation process, promotes ferrous acid bismuthino ternary solid solution and be situated between
The dielectric and energy-storage property of conductive film.
According to still another embodiment of the invention, the type of organic solvent is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, a specific embodiment according to the present invention, and organic solvent can be for selected from anhydrous
At least one of ethyl alcohol, propyl alcohol, isopropanol and ethylene glycol.
The time of still another embodiment in accordance with the present invention, ball-milling treatment is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, and a specific embodiment according to the present invention, the time of ball-milling treatment can be 6-
12 hours.
According to still another embodiment of the invention, the partial size of the material powder of ferrous acid bismuthino ternary solid solution dielectric film is simultaneously
It is not particularly limited, those skilled in the art can select according to actual needs, and one according to the present invention specific real
Example is applied, the partial size of ferrous acid bismuthino ternary powder can be 100-500nm.
Step 2): material powder is subjected to preheating, secondary ball milling, granulation, tabletting, cold isostatic compaction processing, is obtained
To ceramic idiosome
In the step, the material powder of ferrous acid bismuthino ternary solid solution dielectric film is successively subjected to preheating, secondary
Ball milling, granulation, tabletting, cold isostatic compaction processing, to obtain ferrous acid bismuthino ternary ceramics idiosome.
According to one embodiment of present invention, the condition of preheating is not particularly restricted, those skilled in the art
It can be selected according to actual needs, a specific embodiment according to the present invention, the temperature of preheating can be 700-
900 degrees Celsius, the time can be 2-4 hours.Inventors have found that being unable to fully exclude if burn-in time is too short, temperature is too low
Volatile organic matter, the crystallization water, decomposition product etc., and raw material densification is inadequate；And if burn-in time is too long, temperature is excessively high, plus
Work is at high cost, thereby increases and it is possible to generate side reaction.Be conducive to sufficiently exclude raw material using the preheating condition that the application proposes as a result,
Impurity in powder densifies material powder and reduces processing cost.
The time of still another embodiment in accordance with the present invention, secondary ball milling processing is not particularly restricted, the skill of this field
Art personnel can select according to actual needs, a specific embodiment according to the present invention, and time of ball-milling treatment can be with
It is 6-12 hours.
According to still another embodiment of the invention, the partial size of granulation is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, a specific embodiment according to the present invention, particle size can be 20-80 mesh.
According to still another embodiment of the invention, the pressure of compressing tablet process is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, and a specific embodiment according to the present invention, the pressure of compressing tablet process can be 5-
15MPa。
According to still another embodiment of the invention, the pressure of isostatic cool pressing processing and dwell time are not particularly restricted,
Those skilled in the art can select according to actual needs, a specific embodiment according to the present invention, isostatic cool pressing
The pressure of processing can be 20-50MPa, and the dwell time can be 5-20 minutes.Inventors have found that if the pressure of isostatic cool pressing processing
Power is too low, the dwell time is too short, then the low density for the ferrous acid bismuthino ternary ceramics idiosome suppressed, and intensity is low；And if at tabletting
The hypertonia of reason, dwell time are too long, then higher cost, easily cause danger.The compressing tablet process proposed as a result, using the application
Pressure be conducive to obtain the ferrous acid bismuthino ternary ceramics idiosome of high-quality.
According to still another embodiment of the invention, the diameter and thickness of ferrous acid bismuthino ternary ceramics idiosome is not limited especially
System, those skilled in the art can select according to actual needs, a specific embodiment according to the present invention, bismuth ferrite
The diameter of base ternary ceramics idiosome can be 0.5-2 inches, and thickness can be 2-7mm.
Step 3): ceramic idiosome is carried out to bury burning processing, obtains ceramic target
In the step, ferrous acid bismuthino ternary ceramics idiosome is carried out to bury burning processing, to obtain ferrous acid bismuthino ceramic target.
Inventors have found that ferrous acid bismuthino ternary ceramics idiosome is carried out to bury burning processing, the volatilization of Bi element in sintering process can be reduced,
Be conducive to be promoted the quality and energy-storage property of ferrous acid bismuthino ternary solid solution film.
According to one embodiment of present invention, it buries the condition burnt and handled to be not particularly restricted, those skilled in the art
It can be selected according to actual needs, a specific embodiment according to the present invention, burying the temperature burnt and handled can be 1000-
1300 degrees Celsius, the time can be 0.5-3.0 hours.Inventors have found that if burying, burning temperature is too low, the time is too short, will lead to iron
Sour bismuthino ternary solid solution ceramic target sintered density is inadequate, and not exclusively, target is of poor quality for reaction；And if burying and burning temperature mistake
High, overlong time, then preparation cost increases, and is also easy to produce excessive grain and grows up and secondary recrystallization, and target quality is caused to be deteriorated.
The quality burnt treatment conditions and be remarkably improved ferrous acid bismuthino ternary solid solution ceramic target is buried using what the application proposed as a result,.
Step 4): ceramic target is subjected to pulse laser deposition processes and annealing, obtains dielectric film
In the step, ferrous acid bismuthino ternary solid solution ceramic target is subjected to pulse laser deposition processes and annealing,
To obtain the ferrous acid bismuthino dielectric film for high density energy storage.Specifically, being dissolved using laser bombardment ferrous acid bismuthino ternary
Body ceramic target makes its ingredient be diffused into conductive single crystal substrate with stoichiometric ratio, in suitable base reservoir temperature, partial pressure of oxygen and moves back
Extension dielectric film is made under the conditions of fire.Conductive single crystal substrate is selected from pure strontium titanates (SrTiO3), magnesium aluminate (MgAl2O4), lanthanum
Strontium aluminium tantalum ((La, Sr) (Al, Ta) O3) lanthanum aluminate (LaAlO3) and the monocrystalline of at least one of magnesia on extension perovskite
ABO3Structural conductive film, such as nickel acid lanthanum (LaNiO3), lanthanum strontium manganate, cobalt acid lanthanum-strontium or niobium doping strontium titanate monocrystal base
Bottom.
According to one embodiment of present invention, the parameter of pulse laser deposition processes is not particularly restricted, this field
Technical staff can select according to actual needs, a specific embodiment according to the present invention, pulse laser deposition processes
Parameter can be with are as follows: reaction cavity background vacuum is not higher than 5 × 10-6Mbar, base reservoir temperature is that 600-800 is Celsius when deposition
Degree, cavity partial pressure of oxygen are 0.5-20Pa, and leading to oxygen flow is 1-20sccm, laser energy 0.5-2.5J/cm2.Invention human hair
Existing, under the above parameters, ferrous acid bismuthino ternary solid solution film is with suitable speed epitaxial growth, resulting ferrous acid bismuthino ternary
Solid solution membrane quality is high, is conducive to the dielectric and energy-storage property that improve film.
The condition of still another embodiment in accordance with the present invention, annealing is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, a specific embodiment according to the present invention, and the temperature of annealing can be
400-600 degrees Celsius, partial pressure of oxygen can be 200-800mbar, and the time of annealing can be 15-60 minutes.Invention human hair
Existing, under the above parameters, the Lacking oxygen in ferrous acid bismuthino ternary solid solution film is sufficiently made up, and is conducive to improve film
Insulating capacity, breakdown property and energy-storage property.
The side of ferrous acid bismuthino ternary solid solution film of the preparation according to an embodiment of the present invention for the energy storage of high density dielectric
Method, by Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2Raw materials are waited to be mixed according to selected stoichiometric ratio, ball milling, drying
The material powder of ferrous acid bismuthino ternary solid solution dielectric film, Bi are obtained with screening2O3The excess of raw material can make up subsequent preparation
The volatilization loss of Bi element in the process.By will material powder carry out pre-burning, secondary ball milling, granulation, tabletting, at isostatic cool pressing
Reason, the ferrous acid bismuthino ternary solid solution ceramic idiosome of available even compact.By carrying out idiosome to bury burning processing, can obtain
To the ferrous acid bismuthino ternary solid solution ceramic target of the low Bi volatilization of high density low porosity.By that ceramic target will be carried out pulse
Laser deposition and annealing, the ferrous acid bismuthino ternary solid solution dielectric film of available high quality, the ingredient of film are (1-
x-y)BiFeO3-xBaTiO3-ySrTiO3(x, y are molar fraction, and 0 < x < 1,0 < y < 1,0 < x+y < 1).With SrTiO3Ratio
Increase, dielectric constant, the iron electric polarization remitted its fury of ferrous acid bismuthino ternary solid solution film, but dielectric loss is substantially reduced, absolutely
Edge and disruptive field intensity are obviously improved.With BaTiO3Ratio increase, dielectric constant, the iron of ferrous acid bismuthino ternary solid solution film
Electric polarization slightly weakens, but significant decrease is lost in the electric hysteresis under high electric field, and ferroelectricity loop line obviously attenuates.By regulating and controlling x and y
Value, ferrous acid bismuthino ternary solid solution film breakdown field strength is up to 3.0~5.3MV/cm, and energy storage density is up to 112J/cm3, and
With 80% high energy storage efficiency.Experiments have shown that this ferrous acid bismuthino ternary solid solution dielectric film material has both biggish dielectric
Constant, lesser dielectric loss, higher disruptive field intensity and excellent energy-storage property are that one kind is hopeful to be applied to embedded-type electric
Dielectrics energy storage field and the environment friendly materials such as container, electrostatic energy storage component, Pulse Power Techniques.It should be noted that
It is above-mentioned to be equally applicable to the preparation for feature and advantage described in ferrous acid bismuthino ternary solid solution dielectric film material and be used for
The method of the ferrous acid bismuthino ternary solid solution film of high density dielectric energy storage, details are not described herein again.
In an additional aspect of the present invention, the invention proposes a kind of energy storage devices, according to an embodiment of the invention, the storage
Energy device includes above-mentioned ferrous acid bismuthino ternary solid solution dielectric film material or prepares ferrous acid bismuthino ternary solid solution using above-mentioned
The ferrous acid bismuthino ternary solid solution dielectric film material that the method for dielectric film material obtains.It should be noted that above-mentioned be directed to
Institute in ferrous acid bismuthino ternary solid solution dielectric film material and the method for preparing ferrous acid bismuthino ternary solid solution dielectric film material
The feature and advantage of description are equally applicable to the energy storage device, and details are not described herein again.Specifically, the energy storage device can be dielectric
Capacitor, electrostatic energy storage component, pulse power element, embedded capacitor are further developed and are assembled based on above-mentioned device
Device.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
The test method of sample properties is as follows in following embodiments: in ferrous acid bismuthino ternary solid solution film upper surface
Prepare round metal electrode by d.c. sputtering method (diameter is 100~400 μm, thickness about 100nm).Dielectric properties test uses
The E4294A impedance analyzer of Agilent company of the U.S. production, ferroelectric hysteresis loop test use U.S. Radiant
The Precision Premier II ferroelectricity test platform of Technology company, energy storage density and efficiency are calculated by ferroelectric hysteresis loop
It obtains.
Embodiment 1
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.3, y=0.45) ingredient is carried out, wherein Bi2O3Raw material excessive 10%.Raw material is using dehydrated alcohol to dry after medium ball milling 8 hours
Dry, sieving, by obtained powder in 800 degrees Celsius pre-burning 2 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 12MPa tablet press machine, then with 25MPa isostatic cool pressing
Pressure maintaining 10 minutes, obtain the disk idiosome of about 1 inch of diameter, about 5 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried at 1100 degrees celsius 2 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.5 × 10-6mbar；Base reservoir temperature is 700 degrees Celsius when deposition, and cavity partial pressure of oxygen is 2.6Pa, and logical oxygen flow is
1.5sccm, laser energy 1.7J/cm2, frequency 10Hz.After deposition, film is in 500 degrees Celsius, 800mbar oxygen
Pressure annealing 20 minutes, is then cooled to room temperature with 10 degrees celsius/minute speed.
The thickness about 500nm, Fig. 3 of ferrous acid bismuthino ternary solid solution film obtained are ferrous acid bismuthino ternary solid solution film
Section transmission electron microscope picture, it can be found that film has good epitaxial quality, surface roughness small, film even compact is intact
It falls into.Fig. 4 illustrates dielectric constant and the dielectric loss tangent angle of ferrous acid bismuthino ternary solid solution film (x=0.3, y=0.45).
Fig. 5 a illustrates dielectric polarization of the ferrous acid bismuthino ternary solid solution film (x=0.3, y=0.45) under different electric field strengths and rings
It answers.The performance of the ferrous acid bismuthino ternary solid solution film reaches following index: dielectric constant and loss tangent angle point at 1 khz
Not Wei 266 and 0.015, disruptive field intensity 4.9MV/cm, polarize as 69 μ C/cm2, energy storage density reaches 112J/cm3, energy storage efficiency
It is 80%.
Embodiment 2
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.2, y=0.45) ingredient is carried out, wherein Bi2O3Raw material excessive 15%.Raw material is using dehydrated alcohol to dry after medium ball milling 8 hours
Dry, sieving, by obtained powder in 780 degrees Celsius pre-burning 2 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 12MPa tablet press machine, then with 25MPa isostatic cool pressing
Pressure maintaining 10 minutes, obtain the disk idiosome of about 1 inch of diameter, about 5 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried under 1080 degrees Celsius 1.5 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.5 × 10-6mbar；Base reservoir temperature is 700 degrees Celsius when deposition, and cavity partial pressure of oxygen is 2.6Pa, and logical oxygen flow is
1.75sccm, laser energy 1.7J/cm2, frequency 10Hz.After deposition, film is in 500 degrees Celsius, 800mbar oxygen
Pressure annealing 20 minutes, is then cooled to room temperature with 10 degrees celsius/minute speed.
The thickness about 500nm, Fig. 4 of ferrous acid bismuthino ternary solid solution film obtained illustrate ferrous acid bismuthino ternary solid solution
The dielectric constant of film (x=0.2, y=0.45) and dielectric loss tangent angle.It is thin that Fig. 5 b illustrates ferrous acid bismuthino ternary solid solution
Dielectric polarization response of the film (x=0.2, y=0.45) under different electric field strengths.The property of the ferrous acid bismuthino ternary solid solution film
Following index can be reached: dielectric constant and loss tangent angle are respectively 281 and 0.031, disruptive field intensity 4.4MV/ at 1 khz
Cm polarizes as 69 μ C/cm2, energy storage density reaches 96J/cm3, energy storage efficiency 79%.
Embodiment 3
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.1, y=0.45) ingredient is carried out, wherein Bi2O3Raw material excessive 15%.Raw material is using dehydrated alcohol to dry after medium ball milling 8 hours
Dry, sieving, by obtained powder in 750 degrees Celsius pre-burning 2 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 12MPa tablet press machine, then with 25MPa isostatic cool pressing
Pressure maintaining 10 minutes, obtain the disk idiosome of about 1 inch of diameter, about 5 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried under 1050 degrees Celsius 1.5 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.5 × 10-6mbar；Base reservoir temperature is 700 degrees Celsius when deposition, and cavity partial pressure of oxygen is 2.6Pa, and logical oxygen flow is
1.5sccm, laser energy 1.7J/cm2, frequency 10Hz.After deposition, film is in 500 degrees Celsius, 800mbar oxygen
Pressure annealing 20 minutes, is then cooled to room temperature with 10 degrees celsius/minute speed.
The thickness about 500nm, Fig. 4 of ferrous acid bismuthino ternary solid solution film obtained illustrate ferrous acid bismuthino ternary solid solution
The dielectric constant of film (x=0.1, y=0.45) and dielectric loss tangent angle.It is thin that Fig. 5 c illustrates ferrous acid bismuthino ternary solid solution
Dielectric polarization response of the film (x=0.1, y=0.45) under different electric field strengths.The property of the ferrous acid bismuthino ternary solid solution film
Following index can be reached: dielectric constant and loss tangent angle are respectively 312 and 0.039, disruptive field intensity 3.6MV/ at 1 khz
Cm polarizes as 66 μ C/cm2, energy storage density reaches 74J/cm3, energy storage efficiency 76%.
Embodiment 4
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.4, y=0.45) ingredient is carried out, wherein Bi2O3Raw material excessive 10%.Raw material is using dehydrated alcohol to dry after medium ball milling 8 hours
Dry, sieving, by obtained powder in 820 degrees Celsius pre-burning 2 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 12MPa tablet press machine, then with 25MPa isostatic cool pressing
Pressure maintaining 10 minutes, obtain the disk idiosome of about 1 inch of diameter, about 5 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried under 1200 degrees Celsius 2.5 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.5 × 10-6mbar；Base reservoir temperature is 700 degrees Celsius when deposition, and cavity partial pressure of oxygen is 2.6Pa, and logical oxygen flow is
1.5sccm, laser energy 1.7J/cm2, frequency 10Hz.After deposition, film is in 500 degrees Celsius, 800mbar oxygen
Pressure annealing 20 minutes, is then cooled to room temperature with 10 degrees celsius/minute speed.
The thickness about 500nm, Fig. 4 of ferrous acid bismuthino ternary solid solution film obtained illustrate ferrous acid bismuthino ternary solid solution
The dielectric constant of film (x=0.4, y=0.45) and dielectric loss tangent angle.It is thin that Fig. 5 d illustrates ferrous acid bismuthino ternary solid solution
Dielectric polarization response of the film (x=0.4, y=0.45) under different electric field strengths.The property of the ferrous acid bismuthino ternary solid solution film
Following index can be reached: dielectric constant and loss tangent angle are respectively 240 and 0.013, disruptive field intensity 5.3MV/ at 1 khz
Cm polarizes as 62 μ C/cm2, energy storage density reaches 110J/cm3, energy storage efficiency 81%.
Embodiment 5
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.3, y=0.3) ingredient is carried out, wherein Bi2O3Raw material excessive 15%.Raw material is using dehydrated alcohol to dry after medium ball milling 10 hours
Dry, sieving, by obtained powder in 750 degrees Celsius pre-burning 3 hours.It is dried after obtaining powder secondary ball milling 10 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 10MPa tablet press machine, then with 30MPa isostatic cool pressing
Pressure maintaining 15 minutes, obtain the disk idiosome of about 1 inch of diameter, about 7 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried at 1100 degrees celsius 1.5 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.0 × 10-6mbar；Base reservoir temperature is 700 degrees Celsius when deposition, and cavity partial pressure of oxygen is 4.0Pa, and leading to oxygen flow is 2sccm,
Laser energy is 2.5J/cm2, frequency 10Hz.After deposition, film is annealed under 550 degrees Celsius, 500mbar partial pressure of oxygen
30 minutes, room temperature then was cooled to 10 degrees celsius/minute speed.
The thickness about 400nm of ferrous acid bismuthino ternary solid solution film obtained, the ferrous acid bismuthino ternary solid solution film
Performance reaches following index: dielectric constant and loss tangent angle are respectively 310 and 0.042 at 1 khz, and disruptive field intensity is
3.3MV/cm polarizes as 56 μ C/cm2, energy storage density reaches 52J/cm3, energy storage efficiency 70%.
Embodiment 6
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.25, y=0.4) ingredient is carried out, wherein Bi2O3Raw material excessive 10%.Raw material is using dehydrated alcohol to dry after medium ball milling 8 hours
Dry, sieving, by obtained powder in 900 degrees Celsius pre-burning 2 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 5MPa tablet press machine, then is protected with 25MPa isostatic cool pressing
Pressure 20 minutes obtains the disk idiosome of about 1.5 inches of diameter, about 5 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome
Burning is buried under 1300 degrees Celsius 2.5 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.7 × 10-6mbar；Base reservoir temperature is 750 degrees Celsius when deposition, and cavity partial pressure of oxygen is 1.3Pa, and leading to oxygen flow is 2sccm,
Laser energy is 1.5J/cm2, frequency 10Hz.After deposition, film is annealed under 450 degrees Celsius, 400mbar partial pressure of oxygen
40 minutes, room temperature then was cooled to 10 degrees celsius/minute speed.
About 1.5 μm of the thickness of ferrous acid bismuthino ternary solid solution film obtained, the ferrous acid bismuthino ternary solid solution film
Performance reaches following index: dielectric constant and loss tangent angle are respectively 280 and 0.021 at 1 khz, and disruptive field intensity is
3.5MV/cm polarizes as 61 μ C/cm2, energy storage density reaches 67J/cm3, energy storage efficiency 83%.
Embodiment 7
By raw material Bi2O3、Fe2O3、BaCO3、SrCO3And TiO2By (1-x-y) BiFeO3-xBaTiO3-ySrTiO3(x=
0.2, y=0.6) ingredient is carried out, wherein Bi2O3Raw material excessive 10%.Raw material is using dehydrated alcohol to dry after medium ball milling 10 hours
Dry, sieving, by obtained powder in 780 degrees Celsius pre-burning 4 hours.It is dried after obtaining powder secondary ball milling 8 hours, is added 5%
The poly-vinyl alcohol solution of (mass percent) concentration is granulated, tabletted under 8MPa tablet press machine, then is protected with 40MPa isostatic cool pressing
Pressure 5 minutes obtains the disk idiosome of about 0.5 inch of diameter, about 4 millimeters of thickness.After heat preservation excludes polyvinyl alcohol, disk idiosome exists
Burning is buried under 1150 degrees Celsius 3 hours, obtain the ferrous acid bismuthino ternary solid solution ceramic target of high quality.
Using pulsed laser ablation ferrous acid bismuthino ternary solid solution ceramic target, burn target material composition stoichiometrically
Erosion, vaporization, form the plasma plume brightness of high temperature and pressure in vacuum cavity, and are diffused into the strontium titanates conductive single crystal of niobium doping
In substrate, deposition growing is high quality dielectric film.The parameter of pulsed laser deposition technique includes: reaction cavity background vacuum
It is 4.0 × 10-6mbar；Base reservoir temperature is 670 degrees Celsius when deposition, and cavity partial pressure of oxygen is 2.0Pa, and leading to oxygen flow is 5sccm,
Laser energy is 2.0J/cm2, frequency 5Hz.After deposition, film anneals 20 under 475 degrees Celsius, 600mbar partial pressure of oxygen
Minute, then room temperature is cooled to 10 degrees celsius/minute speed.
The thickness about 800nm of ferrous acid bismuthino ternary solid solution film obtained, the ferrous acid bismuthino ternary solid solution film
Performance reaches following index: dielectric constant and loss tangent angle are respectively 240 and 0.017 at 1 khz, and disruptive field intensity is
4.5MV/cm polarizes as 74 μ C/cm2, energy storage density reaches 92J/cm3, energy storage efficiency 84%.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
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|---|---|---|---|---|
| CN110511018A (en) * | 2019-08-13 | 2019-11-29 | 华南师范大学 | A kind of high energy storage density ceramic capacitor dielectric and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511018A (en) * | 2019-08-13 | 2019-11-29 | 华南师范大学 | A kind of high energy storage density ceramic capacitor dielectric and preparation method thereof |
| CN110511018B (en) * | 2019-08-13 | 2022-02-01 | 华南师范大学 | High-energy-storage-density ceramic capacitor dielectric and preparation method thereof |
| CN111362690A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Preparation method of bismuth ferrite-barium titanate composite piezoelectric ceramic |
| CN113773073A (en) * | 2021-09-18 | 2021-12-10 | 深圳先进电子材料国际创新研究院 | Strontium titanate-based ceramic material and preparation method and application thereof |
| CN115974163A (en) * | 2022-12-23 | 2023-04-18 | 山东省科学院新材料研究所 | Zinc and titanium co-doped bismuth ferrite film and preparation method thereof |
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| CN109912304B (en) | 2020-09-22 |
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