CN109082642A - A kind of unleaded epitaxial multilayer film and preparation method thereof with high energy storage density and excellent heat stability - Google Patents
A kind of unleaded epitaxial multilayer film and preparation method thereof with high energy storage density and excellent heat stability Download PDFInfo
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- CN109082642A CN109082642A CN201810988745.1A CN201810988745A CN109082642A CN 109082642 A CN109082642 A CN 109082642A CN 201810988745 A CN201810988745 A CN 201810988745A CN 109082642 A CN109082642 A CN 109082642A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/088—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or Pb and B representing a refractory or rare earth metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
Abstract
The present invention relates to energy storage thin film materials arts, and in particular to a kind of unleaded epitaxial multilayer film and preparation method thereof with high energy storage density and excellent heat stability, unleaded epitaxial multilayer film of the invention, including Nb:SrTiO3Substrate and layer structure, layered structure setting is in Nb:SrTiO3The upper surface of substrate；Layered structure includes the first layer structure that several layers stack gradually setting, and the first layer structure includes the BaZr for stacking gradually setting from bottom to top0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer；For film of the invention while energy storage density is high, energy efficiency is high, excellent heat stability.
Description
Technical field
The present invention relates to energy storage thin film materials arts, and in particular to a kind of with high energy storage density and excellent heat stability
Unleaded epitaxial multilayer film and preparation method thereof.
Background technique
As the mankind are to the growing of renewable energy demand, energy storage technology is faced with bigger challenge.Instantly
Energy storage material has very much, such as lithium battery, fuel cell, supercapacitor, ceramic energy-storage capacitor, however quickly fills
The excellent properties such as discharge time, higher energy storage density and good energy-storing efficiency provide for energy-storage capacitor
Huge application prospect.In recent years, with the micromation of various electronic equipments, integrated and multifunction, to electronic component
Size require it is also increasingly serious.And the appearance of thin-film material not only meets requirement of the device to micromation, simultaneously because its
Controllable crystalline orientation and excellent physicochemical property (such as dimensional effect and interfacial effect), are not replaced with block materials
Advantage has great potentiality in energy storage material field, is also increasingly becoming a big hot spot of Material Field.
In general, the energy storage density for improving thin-film material should improve its disruptive field intensity and dielectric from two aspects
Constant (polarization intensity).And the two is often two conflicting parameters, that is, possess larger dielectric constant material its hit
Wear field strength smaller (such as CCTO huge dielectric constant system) and its dielectric constant of the biggish material of disruptive field intensity very low (such as crystallite is made pottery
Porcelain body system).Have much to the research work of energy storage film at present, such as by doping, substitution, core-shell structure mode, but it is led
Purport is pointedly to improve another parameter in the case where keeping one of parameter constant, to improve the energy storage of material
Density.
In addition, the important parameter as characterization energy storage material, in addition to the energy storage density of material, energy storage efficiency and temperature are stablized
Property equally be characterize thin-film material energy storage characteristic important parameter.These three parameters are mutually indepedent but mutually restrict.How to make
The standby energy storage thin film capacitor for providing high energy storage density and excellent wide warm stability become the bottleneck studied at present and
The difficult point for needing to capture.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, provide it is a kind of have high energy storage density with it is excellent
Unleaded epitaxial multilayer film of thermal stability and preparation method thereof, film of the invention, can dose-effects while energy storage density is high
Rate is high, excellent heat stability.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability, including Nb:SrTiO3Substrate
And layer structure, layered structure setting is in Nb:SrTiO3The upper surface of substrate；Layered structure include several layers successively
The first layer structure of setting is stacked, the first layer structure includes the BaZr for stacking gradually setting from bottom to top0.15Ti0.85O3Layer
And BaZr0.35Ti0.65O3Layer.
Layered structure with a thickness of 260nm, wherein the thickness of all first layer structures is identical, every layer of first layer
In shape structure, BaZr0.15Ti0.85O3The thickness and BaZr of layer0.35Ti0.65O3The thickness of layer is identical.
Nb:SrTiO3Substrate is the monocrystalline Nb:SrTiO of (001) oriented growth3Substrate.
Described 2~12 layers of first stratiform structure setting.
The number of plies of first layer structure is 2,3,6,8 or 12.
A kind of preparation method of the unleaded epitaxial multilayer film with high energy storage density and excellent heat stability, process is such as
Under:
In Nb:SrTiO3Substrate upper surface is repeated in preparation BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer,
In, BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3The number of plies of layer is identical.
BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3The overall thickness of layer is 260nm, BaZr0.15Ti0.85O3The thickness of layer
And BaZr0.35Ti0.65O3The thickness of layer is identical.
Nb:SrTiO3Substrate is the monocrystalline Nb:SrTiO of (001) oriented growth3Substrate.
In Nb:SrTiO3Substrate upper surface is repeated in preparation BaZr by magnetron sputtering0.15Ti0.85O3Layer and
BaZr0.35Ti0.65O3Layer, magnetron sputtering use BaZr0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3Ceramic target.
When magnetron sputtering, first the deposit cavity of magnetic control sputtering system is vacuumized, so that vacuum degree is not less than 10 in deposit cavity- 5mbar；It is 1/1 mixed gas mixed that argon gas and oxygen are passed through into deposit cavity again according to volume ratio, at this time deposit cavity
Interior air pressure is 400mbar；Heater is opened again, deposit cavity temperature is increased to 850 DEG C, then by Nb:SrTiO3Substrate is 850
DEG C, baking 10min is carried out under 400mbar air pressure, remove Nb:SrTiO3The attachment of substrate surface；Deposit cavity is vacuumized again,
Make the vacuum degree of deposit cavity not less than 10-5mbar；It slowly is passed through the mixed gas to deposit cavity again, and adjusts magnetron sputtering system
The mass flowmenter of system is to required growth air pressure 0.2mbar；
After stable gas pressure in chamber to be deposited, BaZr is alternately adjusted0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3
The position of ceramic target and growth time, in Nb:SrTiO3The epitaxial film of different cycles under same thickness is realized on substrate
Growth；
After growth, the mixed gas is passed through into deposit cavity, make deposit cavity air pressure reach 400mbar, and
Annealing 15min is carried out to sample under the air pressure；Heater is closed after annealing, is down to room temperature to temperature and is obtained that there is high energy storage
The unleaded epitaxial multilayer film of density and excellent heat stability.
In magnetic control sputtering system, target spacing is 55mm, carries out pre-sputtering 10 first by mixed gas under room temperature environment
~12h removes target material surface impurity；Wherein, mixed gas is the mixed gas of argon gas and oxygen, and argon gas is with oxygen volume ratio
1/1。
BaZr0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3Ceramic target uses purity grade for 4~5N's
BaCO3Powder, ZrO2Powder and TiO2Powder is prepared；Pass through BaCO3Powder, ZrO2Powder and TiO2Powder prepares BaZr respectively0.15Ti0.85O3
Ceramic target and BaZr0.35Ti0.65O3When ceramic target, sintering temperature is below each system into 100~200 DEG C of phase temperature.
The BaZr0.15Ti0.85O3The number of plies or BaZr of layer0.35Ti0.65O3The number of plies of layer is 2~12.
The BaZr0.15Ti0.85O3The number of plies or BaZr of layer0.35Ti0.65O3The number of plies of layer is 2,3,6,8 or 12.
Compared with prior art, the invention has the following beneficial technical effects:
The layer structure of film of the invention stacks gradually to be formed by the first layer structure of several layers, every layer of first stratiform
Structure includes the BaZr for stacking gradually setting from bottom to top0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer, the film are capable of forming
The structure of the heterogeneous section of epitaxial multilayer, interface can make portion of electrical current path terminate at interface, effectively inhibit the generation of breakdown；
Improve the disruptive field intensity of material, to obtain huge energy storage density and excellent power density, while the material possess it is high
Energy efficiency.Film of the invention belongs to BTO base energy storage film, avoids traditional Pb base energy storage film to environment and human body
Harm, meet the requirement in current industrial produce to environmental protection.
By the beneficial effect of film of the present invention it is found that the film that preparation method of the present invention is prepared has energy storage close
The characteristics of degree is high, energy efficiency is high and excellent heat stability.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the film that the layer structure number of plies of the present invention is 2.
Fig. 2 is the structural schematic diagram for the film that the layer structure number of plies of the present invention is 3.
Fig. 3 is the structural schematic diagram for the film that the layer structure number of plies of the present invention is 6.
Fig. 4 is the structural schematic diagram for the film that the layer structure number of plies of the present invention is 8.
Fig. 5 is the structural schematic diagram for the film that the layer structure number of plies of the present invention is 12.
Fig. 6 is the θ -2 θ scanning figure of film of the present invention.
Fig. 7 is the θ -2 θ scanning figure that film of the present invention (001) peak nearby amplifies.
Fig. 8 is the phi- scanning figure of film of the present invention.
Fig. 9 is the cross sectional transmission electron microscope photo for the film that the layer structure number of plies of the present invention is 6.
Figure 10 is the electron diffraction pattern of film shown in Fig. 9.
Figure 11 is the cross sectional transmission electron microscope photo for the film that the layer structure number of plies of the present invention is 8.
Figure 12 is the electron diffraction pattern of film shown in Figure 11.
Figure 13 is the cross sectional transmission electron microscope photo for the film that the layer structure number of plies of the present invention is 12.
Figure 14 is the electron diffraction pattern of film shown in Figure 13.
Figure 15 is the disruptive field intensity figure of film of the present invention.
Figure 16 is the energy storage density of film of the present invention and energy efficiency figure at room temperature.
Figure 17 is the film discharge energy density at room temperature and the relationship of time that the layer structure number of plies of the present invention is 6
Figure.
Figure 18 is the comparison of film of the present invention and super capacitor, the energy density of battery and fuel cell and power density
Figure.
Figure 19 is energy storage density and energy of the film within the scope of -100 DEG C to 200 DEG C that the layer structure number of plies of the present invention is 6
Amount efficiency figure.
Figure 20 be the layer structure number of plies of the present invention be 6 film in wide temperature range, material involved in the present invention and current
The comparison of the energy storage density of energy storage film.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawings and examples.
Unleaded epitaxial multilayer film with high energy storage density and excellent heat stability of the invention is BZT15/BZT35 body
It is unleaded epitaxial multilayer energy storage film, preparation method is specific as follows:
(1) first according to chemical formula BaZr0.15Ti0.85O3(i.e. BZT15) and BaZr0.35Ti0.65O3(i.e. BZT35), respectively
Weigh suitable 4~5N rank BaCO3High-purity powder, ZrO2High-purity powder and TiO2High-purity powder, to the mixture of above-mentioned three kinds of high-purity powder
The techniques such as ball milling, pre-burning, granulation, molding and sintering are carried out, ceramics preparation process is prepared into BZT15 ceramic target using conventional solid
Material and BZT35 ceramic target.During preparing ceramic target, sintering temperature is below system into 100~200 DEG C of phase temperature.
(2) prepared ceramic target is installed to magnetron sputtering first with sand paper polishing again with behind the peace and quiet surface of air gun
It is 55mm, argon gas/oxygen (Ar/O in target spacing in system2) mixed gas be 1/1 room temperature sputter environment under, carry out first
10~12h of pre-sputtering removes target material surface impurity.
(3) the monocrystalline Nb:SrTiO of (001) oriented growth is selected3Substrate (i.e. Nb:STO substrate) carries out the deposition of film,
Nb:STO substrate is immersed in alcohol, concussion 3~5min of cleaning is carried out with ultrasonic cleaning device, by the Nb:STO substrate after cleaning
It is immediately placed in the deposit cavity of magnetic control sputtering system with after being dried with nitrogen.
(4) combined using mechanical pump with molecular pump the multistage extract system constituted air pressure in deposit cavity is evacuated to it is one higher
Vacuum degree, at this time vacuum degree be not less than 10-5mbar；Argon gas/oxygen mixture needed for being passed through growing film to deposit cavity again
Body, Ar/O in mixed gas2Volume ratio is 1:1, and intracavitary air pressure at this time is 400mbar；Then by Nb:STO substrate 850 DEG C,
Baking 10min is carried out under 400mbar air pressure, removes Nb:STO substrate surface attachment；Deposit cavity is vacuumized again, makes vacuum degree
Not less than 10-5mbar；It is finally slowly introducing argon gas/oxygen mixed gas and adjusts mass flowmenter to required growth air pressure
0.2mbar。
(5) after stable gas pressure, the structural schematic diagram according to FIG. 1 to FIG. 5 alternately adjusts target location and growth
Time realizes the growth of the epitaxial film of different cycles under same thickness on Nb:STO substrate.Relative to BZT35, BZT15 with
The mismatch of Nb:STO substrate is smaller, therefore first grows BZT15 layers, BZT35 layers of regrowth in the present invention.
(6) after growing, being passed through mixed gas makes the air pressure of deposit cavity reach 400mbar, and to sample under the air pressure
Product carry out annealing 15min；It is down to room temperature to temperature after annealing, sample is taken out, obtains of the invention having high energy storage close
The unleaded epitaxial multilayer film of degree and excellent heat stability.
The present invention uses radiofrequency magnetron sputtering technology, is obtained on substrate by plasma to the bombardment of target
BZT15/BZT35 plural layers realize the thin of different cycles under same thickness by adjusting the sputtering time of two kinds of targets
Film, film obtained are capable of forming the structure of the heterogeneous section of epitaxial multilayer, and interface can make portion of electrical current path terminate at interface,
Effectively inhibit the generation of breakdown；And while obtaining huge energy storage density and excellent power density when periodicity is 6, gather around
There is high energy efficiency.
Unleaded epitaxial multilayer energy storage film prepared by the present invention has good thermal stability, wherein the sample of N=6
In -100 DEG C to 200 DEG C temperature ranges, still there is excellent energy storage characteristic.BZT15/BZT35 system of the present invention is unleaded outer
Prolong multilayer energy storage film, the unleaded of huge energy storage density can be prepared by increasing the film period in the case where keeping same thickness
Environmental-friendly film can be widely used in the fields such as dielectric, ferroelectricity, piezoelectric material.The invention belongs to BTO base energy storage is thin
Film avoids harm of traditional Pb base energy storage film to environment and human body, meets the requirement in current industrial production to environmental protection.
After obtaining the unleaded epitaxial multilayer film with high energy storage density and excellent heat stability of the invention, it is carried out
The sample being wherein grown on conductive Nb:STO substrate when test, is carried out part polishing, selects 100 destination party by structured testing
Shape platinum plating gold electrode carries out Electronic Speculum test and electric performance test.
Obtained material property:
Fig. 6 is that θ -2 θ of the unleaded epitaxial multilayer film with high energy storage density and excellent heat stability of the invention is scanned
Figure；Fig. 7 is the θ -2 θ scanning figure that (001) peak nearby amplifies, it can be seen that when periodicity is that 2 and 3 (i.e. the number of plies of layer structure is
2 and 3) when, it is compound that film sample shows two-phase, and when periodicity increases to 6,8 and 12, and image table reveals apparent satellite
Peak shows that superlattice structure has been presented in sample at this time；Phi- scanning in Fig. 8 shows that sample edge (022) crystal face is right four times
Claim structure.
Multi-layer compound film structure can clearly be shown by Fig. 9, Figure 11 and Figure 13；Figure 10, Figure 12 and Figure 14 show
Three kinds of samples are the plural layers of epitaxial growth.
Figure 15 is the disruptive field intensity that different cycles sample according to the present invention is calculated by Weibull distribution,
Middle periodicity is that the disruptive field intensity of 2,3,6,8 and 12 samples is respectively 5.4MV/cm, 6.5MV/cm, 8.3MV/cm, 7.5MV/cm
With 7.3MV/cm.Figure 16 is the energy storage density of different cycles sample according to the present invention and energy efficiency changes with periodicity
Relational graph, it can be seen that with the increase of periodicity, the energy storage density of plural layers first increases to be reduced afterwards, in periodicity N=6
When, plural layers obtain best energy storage characteristic, and energy storage density at room temperature is 83.9J/cm3, energy storage efficiency 78.4%.
Figure 17 is the discharge energy density and the relational graph of time that periodicity is N=6 sample at room temperature, power density 1.47MW/
cm3.Figure 18 is BZT15/BZT35 epitaxial multilayer energy storage material involved in the present invention and current common energy storage material at room temperature
The comparison of energy density and power density shows that the multilayered memory system not only has high energy storage density, and has height
Power density.
Figure 19 indicates energy storage of the sample of periodicity N=6 in the case where extra electric field is 6.4MV/cm, from -100 DEG C to 200 DEG C
Density and energy efficiency variation with temperature relationship.As can be seen that the sample within the scope of -100 DEG C to 200 DEG C temperature ranges its
Energy storage density has reached 63.2J/cm3, while its energy efficiency is maintained at 67% or more.Therefore, the nothing prepared by the present invention
Lead extension energy storage film can keep excellent energy storage characteristic at high temperature.
Figure 20 is in wide temperature range, BZT15/BZT35 epitaxial multilayer energy storage film involved in the present invention and current Pb- base with
Comparison of the unleaded energy storage thin-film material in terms of energy storage density and energy efficiency: find material according to the present invention compared to nothing
Lead and plumbum-based material all have more excellent energy storage characteristic, show the BZT15/BZT35 multilayer energy storage film tool in this research
The great potential and advantage of substituted lead base energy storage material.
Unleaded energy storage film according to the present invention makes current unleaded energy storage density reach a new height, so far for
The peak in film energy storage material only is PLZT system, and energy storage density has reached 67J/cm3, however due to its lead poisoning
In production to the harm of natural environment and human body, limits it and use field.Therefore energy storage film according to the present invention
With great potential.
The unleaded epitaxial multilayer energy storage film of BZT15/BZT35 system provided by the invention is using rf magnetron sputtering skill
Art, the BZT15/BZT35 plural layers that the bombardment of target is obtained on substrate by plasma.First using high-purity powder,
It is respectively synthesized out BZT15 and BZT35 ceramic target by the conventional solid preparation process of ceramics, recycles rf magnetron sputtering skill
Art realizes the epitaxial growth film on substrate to the bombardment of target by plasma under high temperature, high oxygen pressure environment；Lead to simultaneously
The sputtering time for overregulating two kinds of targets realizes to thickness in monolayer, the i.e. control of component, thus to the performance of the energy storage film into
Row prediction and regulation.By adjusting the period of multilayer film under condition of equivalent thickness, the disruptive field intensity of film is improved to increase
Its energy storage density makes its energy storage density reach current BaTiO3(BTO)-base energy storage film maximum value, can be with plumbum-based material
It is comparable.The use of this material in the industrial production will avoid Pb from endangering to natural environment and human health bring.Simultaneously
The energy storage film energy efficiency with higher prepared through the invention.
The present invention realizes the film of different cycles under same thickness by the sputtering time of two kinds of targets of adjusting.Pass through
To sample ferroelectric properties test with Weibull distribution statistics, discovery periodicity be respectively 2,3,6,8,12 sample its hit
Wearing field strength is respectively 5.4,6.5,8.3,7.5,7.3MV/cm.This is because on the one hand as the increase at interface is to material internal electricity
The inhibition enhancing for flowing branch, on the other hand as every a layer thickness reduces, interface coupling effect enhancing causes interface to be hit
The effect of wearing is more significant.Show that periodicity is that the energy storage density of N=6 sample is up to 83.9J/cm by integral calculation3While,
Efficiency is up to 78.4%.
The advantages of BZT15/BZT35 system of the invention unleaded epitaxial multilayer energy storage film, at least there are also following sides
Face:
(1) structure for using multilayer makes the biography for effectively hindering electric branch before breakdown occurs by increasing interface number
It broadcasts and extends, increase the disruptive field intensity of material.
Bombarding target by energetic ion makes it be deposited on the epitaxial growth of realization film on the substrate of orientation.Pass through increase
BZT15 and BZT35 layers of interface number, can play the inhibition to electric branch extensions path, to increase plural layers
Disruptive field intensity.Higher disruptive field intensity induces higher spontaneous polarization simultaneously, according to formula:
The available and comparable energy storage density of plumbum-based material and higher efficiency.
(2) ratio of suitable BZT15 layers with BZT35 layers are used, so that keeping while not reducing disruptive field intensity higher
Polarizability, to obtain ideal energy storage density.
(3) material is free of lead, can be widely used in every field.
Claims (10)
1. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability, which is characterized in that including Nb:
SrTiO3Substrate and layer structure, layered structure setting is in Nb:SrTiO3The upper surface of substrate；Layered structure includes
Several layers stack gradually the first layer structure of setting, and the first layer structure includes stacking gradually setting from bottom to top
BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer.
2. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 1,
It is characterized in that, Nb:SrTiO3Substrate is the monocrystalline Nb:SrTiO of (001) oriented growth3Substrate, the thickness of layered structure
For 260nm, wherein the thickness of all first layer structures is identical, in every layer of first layer structure, BaZr0.15Ti0.85O3Layer
Thickness and BaZr0.35Ti0.65O3The thickness of layer is identical.
3. a kind of unleaded epitaxial multilayer with high energy storage density and excellent heat stability according to claim 1 or 2 is thin
Film, which is characterized in that described 2~12 layers of first stratiform structure setting.
4. a kind of preparation method of the unleaded epitaxial multilayer film with high energy storage density and excellent heat stability, feature exist
In process is as follows:
In Nb:SrTiO3Substrate upper surface is repeated in preparation BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer, wherein
BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3The number of plies of layer is identical.
5. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 4
Preparation method, which is characterized in that in Nb:SrTiO3Substrate upper surface is repeated in preparation by magnetron sputtering
BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3Layer, magnetron sputtering use BaZr0.15Ti0.85O3Ceramic target with
BaZr0.35Ti0.65O3Ceramic target.
6. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 5
Preparation method, which is characterized in that when magnetron sputtering, first the deposit cavity of magnetic control sputtering system is vacuumized, so that true in deposit cavity
Reciprocal of duty cycle is not less than 10-5mbar；It is 1/1 gaseous mixture mixed that argon gas and oxygen are passed through into deposit cavity again according to volume ratio
Body, air pressure is 400mbar in deposit cavity at this time；Deposit cavity temperature is set to be increased to 850 DEG C again, then by Nb:SrTiO3Substrate exists
850 DEG C, baking 10min is carried out under 400mbar air pressure, remove Nb:SrTiO3The attachment of substrate surface；Deposit cavity is taken out again true
Sky makes the vacuum degree of deposit cavity not less than 10-5mbar；It slowly is passed through the mixed gas to deposit cavity again, makes institute in deposit cavity
It is 0.2mbar that air pressure, which need to be grown,；
After stable gas pressure in chamber to be deposited, BaZr is alternately adjusted0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3Ceramics
The position of target and growth time, in Nb:SrTiO3The life of the epitaxial film of different cycles under same thickness is realized on substrate
It is long；
After growth, it is passed through the mixed gas into deposit cavity, so that the air pressure of deposit cavity is reached 400mbar, and in the gas
Pressure carries out annealing 15min to sample；After annealing to temperature be down to room temperature obtain it is steady with high energy storage density and excellent heat
Qualitative unleaded epitaxial multilayer film.
7. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 5
Preparation method, which is characterized in that in magnetic control sputtering system, target spacing is 55mm, under room temperature environment first by mixed gas
10~12h of pre-sputtering is carried out, target material surface impurity is removed；Wherein, mixed gas be argon gas and oxygen mixed gas, argon gas with
Oxygen volume ratio is 1/1.
8. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 5
Preparation method, which is characterized in that BaZr0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3Ceramic target uses purity grade
For the BaCO of 4~5N3Powder, ZrO2Powder and TiO2Powder is prepared；Pass through BaCO3Powder, ZrO2Powder and TiO2Powder is prepared respectively
BaZr0.15Ti0.85O3Ceramic target and BaZr0.35Ti0.65O3When ceramic target, sintering temperature is below each system into phase temperature
100~200 DEG C.
9. a kind of unleaded extension with high energy storage density and excellent heat stability according to claim 4-8 any one
The preparation method of plural layers, which is characterized in that Nb:SrTiO3Substrate is the monocrystalline Nb:SrTiO of (001) oriented growth3Substrate,
BaZr0.15Ti0.85O3Layer and BaZr0.35Ti0.65O3The overall thickness of layer is 260nm, BaZr0.15Ti0.85O3Layer thickness and
BaZr0.35Ti0.65O3The thickness of layer is identical.
10. a kind of unleaded epitaxial multilayer film with high energy storage density and excellent heat stability according to claim 9
Preparation method, which is characterized in that the BaZr0.15Ti0.85O3The number of plies or BaZr of layer0.35Ti0.65O3Layer the number of plies be 2~
12。
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