CN109056068A - A kind of unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system and preparation method thereof - Google Patents
A kind of unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system and preparation method thereof Download PDFInfo
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Abstract
The invention discloses unleaded single crystal epitaxial multilayer energy storage films of a kind of BCT/BZT system and preparation method thereof；This method uses radiofrequency magnetron sputtering technology, BCT/BZT plural layers have been obtained on substrate to the bombardment of target by plasma, by the sputtering time for adjusting two kinds of targets, prepare the film of different cycles under same thickness, film obtained is capable of forming the heterogeneous structure of epitaxial multilayer, interface can make portion of electrical current path terminate at interface, effectively inhibit the generation of breakdown；And as inhibition of the increase at interface to material internal electric current branch enhances, while reaching huge energy storage density, the energy storage film that the present invention prepares possesses high energy efficiency, wherein the energy efficiency in 8 periods is 65% or more, major part is 70% or more, and the efficiency of 4 period samples can largely be greater than 80%.
Description
Technical field
The present invention relates to energy storage thin film materials arts, and in particular to a kind of unleaded single crystal epitaxial multilayer storage of BCT/BZT system
Energy film and preparation method thereof.
Background technique
BT- based dielectric material is widely used in always in the electronic material component in various fields, passes through different members
The doping or compound with other materials of element, BTO based dielectric material have become one of current Material Field it is important
Research direction.It is PLZT ceramics (PLZT) system that energy storage density is highest in film energy storage material, and energy storage density reaches
67J/cm is arrived3, however due to the harm to natural environment and human body in production of its lead poisoning, it limits it and uses neck
Domain.(Ba,Ca)(Zr,Ti)O3(BCZT) system ceramic material is a very important branch in BT sill, while by
The trend for replacing lead-containing materials has been gradually appeared at many aspects in its good piezoelectric property.Pass through investigation of materials person in recent years
Deepen continuously, by the techniques such as doping vario-property and composite optimization, so that piezoelectricity system of the BCTZ ceramics at its quasi- homotype phase boundary
Number has reached 600pCN.It is contemplated that BCTZ system will also have bigger research space.
With the micromation of various electronic equipments, integrated and multifunction, is required to the size of electronic component also day
It is beneficial severe.Thin-film material faced blocks material has apparent size advantage, it is often more important that: as thin-film material is increasingly deep
Research and discovery, the physical characteristic not having with many block materials.Maximum possessed by two-dimensional film material is excellent
Gesture is exactly its interfacial effect and dimensional effect, and is studied so far, these effects play greatly the performance of thin-film material
Improvement result.
In formula, W is energy storage density, J/cm3, PmaxFor maximum polarization, μ C/cm2, Pr is spontaneous polarization strength, μ C/
cm2；P is polarization intensity, μ C/cm2, E is electric field strength, MV/cm；From (1) formula: the energy storage density of material mainly by it most
Big polarizability and maximum disruptive field intensity determine that the disruptive field intensity for improving material is a weight for increasing energy storage material energy storage density
Want means；On the other hand, almost all of electricity device will appear fever phenomenon when in use to influence the performance of device,
The energy storage efficiency and thermal stability of material are problems urgently to be resolved at present.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, a kind of unleaded monocrystalline of BCT/BZT system is provided
Energy storage film is made using radio-frequency magnetron sputter method in epitaxial multilayer energy storage film and preparation method thereof, and the film is in energy storage density
While high, energy efficiency is high.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system, comprising the following steps:
(1) by Ba0.7Ca0.3TiO3Ceramic target and BaZr0.2Ti0.8O3Ceramic target is mounted in magnetic control sputtering system not
On same target position；
(2) substrate is put into the deposit cavity in magnetic control sputtering system after cleaning substrate；
(3) magnetic control sputtering system precondition substrate: is evacuated to 10-5-10-4Mbar is passed through oxygen and argon gas gaseous mixture
Body, heated baking substrate；
(4) pre-sputtering ceramic target: pre-sputtering BCT ceramic target and BZT ceramic target respectively；
(5) it sputters ceramic target: according to the film target number of plies, determining the period N of thin film sputtering, successively staggeredly sputter BCT
Layer and BZT layer, while on substrate progress epitaxial film growth；A cycle is one BCT layers and one BZT layers of sputtering, and N is
2,4 or 8；
(6) film that annealing process step (5) generates；The unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system is made.
A further improvement of the present invention is that:
Preferably, in step (1), use purity grade for the BaCO of 4~5N3Powder, CaCO3Powder and TiO2Powder preparation
Ba0.7Ca0.3TiO3Ceramic target；Use purity grade for the BaCO of 4~5N3Powder, ZrO2Powder and TiO2Powder preparation
BaZr0.2Ti0.8O3Ceramics.
Preferably, in step (1), Ba0.7Ca0.3TiO3Ceramic target and BaZr0.2Ti0.8O3Ceramic target passes through respectively
Ball milling, pre-sintering, secondary ball milling, granulation, molding and sintering are prepared.
Preferably, in step (2), substrate uses the conductive single crystal SrTiO of (001) oriented growth3Substrate；Substrate first passes through
Ultrasonic vibration cleans 3~5min and places into the deposit cavity of magnetic control sputtering system.
Preferably, the specific steps of step (3) are as follows: the air pressure in magnetic control sputtering system is evacuated to 10-5-10-4Mbar leads to
Enter the mixed gas of oxygen and argon gas, until the air pressure in magnetic control sputtering system is 400mbar, begins to warm up substrate；Substrate heating
To 850 DEG C, the air pressure in magnetic control sputtering system is evacuated to 10 again-5-10-4Mbar is passed through the mixed gas of oxygen and argon gas,
Air pressure in magnetic control sputtering system is 200mbar；Oxygen and argon gas volume ratio are in the mixed gas of the oxygen and argon gas
1:1。
Preferably, in step (4), the pre-sputtering atmosphere of each ceramic target is mixed-gas atmosphere, mixed gas by
The oxygen and argon gas of volume ratio 1:1 forms；The distance between sputtering target and substrate are 55mm；Pre-sputtering power is 100W；It splashes in advance
Penetrating the time is 10min.
Preferably, in step (5), when N=2, each BCT layers of sputtering time is 83-103min, with a thickness of 12-
18nm, each BZT layers of sputtering time is 242-262min, with a thickness of 32-38nm；When N=4, each BCT layers of sputtering
Time is 36-56min, and with a thickness of 5.5-9.5nm, each BZT layers of sputtering time is 116-136min, with a thickness of 15.5-
19.5nm；When N=8, each BCT layers of sputtering time is 18-28min, and with a thickness of 3.7-3.9nm, each BZT layers splashes
Penetrating the time is 58-68min, 8.7-8.9nm.
Preferably, in step (5), the sputtering atmosphere of each ceramic target is mixed-gas atmosphere, and mixed gas is by body
Oxygen of the product than 1:1 and argon gas composition；The distance between sputtering target and substrate are 55mm；Pre-sputtering power is 100W.
Preferably, in step (6), annealing atmosphere is mixed-gas atmosphere, mixed gas by volume ratio 1:1 oxygen and argon
Gas composition；Annealing gas pressure is 400mbar, and annealing temperature is 850 DEG C, annealing time 15min.
Utilize the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system made from the preparation method.
Compared with prior art, the invention has the following beneficial technical effects:
The invention discloses a kind of preparation methods of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system；This method
Using radiofrequency magnetron sputtering technology, BCT/BZT plural layers have been obtained to the bombardment of target on substrate by plasma；It is logical
The target number of plies is crossed, determines the different sputtering periods, film obtained is made to be capable of forming the heterogeneous structure of epitaxial multilayer, interface can be with
So that portion of electrical current path is terminated at interface, effectively inhibits the generation of breakdown；And as the increase at interface is to material internal electricity
The inhibition enhancing of branch is flowed, while reaching huge energy storage density, the energy storage film that the present invention prepares possesses high
Energy efficiency.
Further, the conventional solid preparation process point that preparation method of the invention uses high-purity powder first, passes through ceramics
Do not synthesize BCT and BZT ceramic target, recycles radiofrequency magnetron sputtering technology, pass through plasma under high temperature, high oxygen pressure environment
Body realizes the epitaxial growth film on substrate to the bombardment of target；By adjusting the sputtering time of two kinds of targets, realize identical
The film of different cycles under thickness, and realize to thickness in monolayer, the i.e. control of component, so that the performance to the energy storage film carries out
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 it
Energy storage density makes its energy storage density reach current BaTiO3(BTO)-base energy storage film maximum value, can be with plumbum-based material phase
Analogy.
The invention also discloses a kind of unleaded single crystal epitaxial multilayer energy storage films of BCT/BZT system；The energy storage film has
Good thermal stability, wherein the sample of N=4 still has excellent energy storage characteristic under room temperature to 140 DEG C of temperature ranges；
The energy storage film energy efficiency with higher prepared through the invention simultaneously, is in particular in its ferroelectric hysteresis loop " narrow thin "
Shape, the energy efficiency in 8 period of energy storage film is 65% or more, and major part is 70% or more, and the efficiency of 4 period samples is big
Part can be greater than 80%.The unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system of the present invention, in the feelings for keeping same thickness
The film that the Lead-free Environment close friend of huge energy storage density can be prepared under condition by the optimization film period, can be widely used in Jie
The fields such as electricity, ferroelectricity, piezoelectric material.The invention belongs to BTO base energy storage film, avoid traditional Pb base energy storage film to environment with
And the harm of human body, meet the requirement in current industrial production to environmental protection.
Detailed description of the invention
Fig. 1 is that θ -2 θ for the different cycles BCT/BZT single crystal epitaxial multilayer energy storage film that embodiment 1,2 and 3 is prepared is swept
Tracing；
The phi- for the different cycles BCT/BZT single crystal epitaxial multilayer energy storage film that Fig. 2 embodiment 1,2 and 3 is prepared is scanned
Figure；
Fig. 3 is the cross sectional transmission electron microscope photo of N=8 sample prepared by embodiment 3；
Fig. 4 is the electron diffraction pattern of N=8 sample prepared by embodiment 3；
Fig. 5 is the cross sectional transmission electron microscope photo of N=4 sample prepared by embodiment 2；
Fig. 6 is the electron diffraction pattern of N=4 sample prepared by embodiment 2；
Fig. 7 is the cross sectional transmission electron microscope photo of N=2 sample prepared by embodiment 1；
Fig. 8 is the electron diffraction pattern of N=2 sample prepared by embodiment 1；
Fig. 9 is the film performance figure that the present invention implements 1,2 and 3 preparations；Wherein figure (a) is that energy storage density shows with energy efficiency
It is intended to；Scheme in (b) present invention ferroelectric hysteresis loop under embodiment 1,2 and 3 corresponding different cycles sample maximum breakdown voltages；Scheme (c)
Embodiment 1,2 and energy storage density and energy efficiency and electric field pass under 3 corresponding different cycles sample different voltages in the present invention
System；Figure (d) is the comparison of the energy storage density of material involved in the present invention and current energy storage film.
Figure 10 is the stability diagram of sample, wherein figure (a) is the N=4 sample of the preparation of embodiment 2 in room temperature to 140 DEG C of models
Energy storage density and energy efficiency in enclosing；Figure (b) is storage of the N=8 sample of the preparation of embodiment 3 within the scope of room temperature to 140 DEG C
It can density and energy efficiency.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawing.
The preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system of the present invention is specific as follows:
(1) first, in accordance with Ba0.7Ca0.3TiO3(BCT) and BaZr0.2Ti0.8O3(BZT) stoichiometric ratio weighs pure respectively
Spend the BaCO that circle is 4~5N rank3Powder, CaCO3Powder and TiO2Powder synthesizes BCT ceramic target mixture, weighs BaCO3Powder,
ZrO2Powder, TiO2Powder synthesizes BZT ceramic target mixture；The mixture of each target successively passes through ball milling, pre-sintering, two
Secondary ball milling, granulation, molding and sintering process obtain the Ba of sheet0.7Ca0.3TiO3(BCT) ceramic target and BaZr0.2Ti0.8O3
(BZT) ceramic target.Wherein ball milling is identical as the procedure parameter of secondary ball milling, specifically: the quality of ballstone, mixture and alcohol
Than for 2:1:1, rotational speed of ball-mill 400r/min, Ball-milling Time 6h；Pre-sintering temperature is 900 DEG C, the pre-sintering time is 4h；At
Type selects tablet press machine, and the pressure in forming process is 40Mpa, dwell time 5min；Sintering temperature in sintering process is
1050 DEG C, sintering time 4h.
(2) cleaning substrate: by the conductive single crystal SrTiO of (001) oriented growth3(STO) substrate immerses in alcohol, with ultrasound
Cleaning equipment carries out concussion 3~5min of cleaning, and the substrate after cleaning is immediately placed in magnetic control sputtering system with after being dried with nitrogen
Deposit cavity in.
(3) precondition substrate；BZT ceramic target and BCT ceramic target air the purging removal that step (1) is prepared
After surface impurity, it is installed on rf magnetron sputtering target position different in magnetic control sputtering system；First with mechanical pump and molecule
Pump group closes the multistage extract system constituted and air pressure in deposition chamber is evacuated to 10-5-10-4Mbar is then charged with oxygen and argon gas
Mixed gas (volume ratio 1:1) begins to warm up substrate, so that substrate is at this until the intracorporal air pressure of deposit cavity is 400mbar at this time
It is toasted under air pressure conditions, to remove substrate surface attachment and defect；When substrate temperature rises to 850 DEG C, again by deposit cavity
Internal air pressure is evacuated to 10-5-10-4Then mbar is filled with the mixed gas (volume ratio 1:1) of oxygen and argon gas in deposition chamber,
It is 200mbar to the intracorporal air pressure of deposit cavity.
(4) pre-sputtering BCT and BZT ceramic target: under conditions of air pressure is 200mbar, pre-sputtering BCT ceramic target first
Material after pre-sputtering BCT ceramic target, rotates mechanical arm, so that the target position and substrate of BZT ceramic target are corresponding, starts to splash in advance
Penetrate BZT ceramic target；The pre-sputtering parameter of two kinds of ceramic targets is identical, and specially sputtering atmosphere is oxygen and argon gas volume ratio is
The mixed gas of 1:1, target spacing are 55mm, and sputtering power 100W, the pre-sputtering time of each ceramic target is 10min.
(5) staggeredly sputter BCT and BZT ceramic target, form plural layers: adjustment sputtering parameter, sputtering pressure are first
200mbar, the mixed gas that sputtering atmosphere is oxygen and argon gas volume ratio is 1:1, after conditional stability, according to required component, week
Phase adjusts target location and growth time respectively；A cycle is to sputter to generate one BCT layers and one BZT layers；With
The increase of target period, a kind of growth time reduction of ceramic target；It is two growth cycles (N=2) when film has 4 layers,
The structure of target multi layer film are as follows: substrate/BCT/BZT/BCT/BZT, sputtering prepare different films and pass through on mobile mechanical arm
Target location realizes, wherein BCT layer and BZT layers of growth time are respectively 83-103min and 242-262min, single layer BCT and
BZT thickness is respectively 12-18nm and 32-38nm；It is 4 periods (N=4), in multilayer film growth course when film has 8 layers
BCT layers staggeredly grow with BZT layers, and growth time is respectively 36-56min and 116-136min, and single layer BCT and BZT thickness are distinguished
For 5.5-9.5nm and 15.5-19.5nm；It is 8 periods (N=8), at BCT layers of multilayer film growth course when film has 16 layers
It is staggeredly grown with BZT layers, growth time is respectively 18-28min and 58-68min, and single layer BCT and BZT thickness are respectively 3.7-
3.9nm and 8.7-8.9nm；Ultimately form process layer；Target spacing when every kind of thin film sputtering is 55min, and sputtering power is
100W；Mismatch relative to BZT, BCT and STO substrate is smaller, therefore first grows BCT layers, BZT layers of regrowth in the present invention.
(6) after process layer growth, it is passed through the mixed gas of oxygen and argon gas that volume ratio is 1:1, arrives cavity
Up to the air pressure of 400mbar；Make annealing treatment film at 850 DEG C, annealing time 15min is lacked to fill up oxygen in sample
It falls into, is down to room temperature to temperature after annealing, obtains a kind of unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system.It will
Sample takes out, and carries out structured testing.
The sample being grown on conductive STO substrate is subjected to part polishing, selects the rectangular gold,platinized electrode of 100 purposes, into
The test of row Electronic Speculum and electric performance test.
Fig. 1-Fig. 8 is the BCT/BZT single crystal epitaxial multilayer for the different cycles that the embodiment of the present invention 1- embodiment 3 is prepared
The high-resolution XRD diagram picture and TEM picture of energy storage film.Wherein Fig. 1 is the BCT/BZT single crystal epitaxial of embodiment 1-3 prepared
θ -2 θ of multilayer energy storage film is scanned, it can be seen that when N is 2, it is compound to show two-phase for sample, and working as N increases to 4 and 8, figure
As showing apparent satellites, show that superlattice structure has been presented in sample at this time；Phi-scan in Fig. 2 shows three kinds of samples
It is four sub-symmetry structures along (001) mirror surface；Fig. 3, Fig. 5 and Fig. 7 are the cross sectional transmission electron microscope photo of low resolution, clearly
Show multi-layer compound film structure；Fig. 4, Fig. 6 and Fig. 8 are the electron diffraction pattern of sample, show that three kinds of samples are list
Brilliant epitaxial film.
It is that ferroelectric material energy storage density and energy efficiency calculate schematic diagram that (a) is schemed in Fig. 9, and figure (b) is involved in the present invention
Ferroelectric hysteresis loop of three kinds of different cycles samples under maximum breakdown voltage, the period 2,4,8 is calculated by Weibull distribution
The disruptive field intensity of sample is respectively 3.3MV/cm, 4.3MV/cm and 4.7MV/cm, but due to the disruptive field intensity in actual test
Stepping is 0.5MV/cm, and the maximum breakdown voltage used when calculating is 3.0MV/cm, 4.0MV/cm and 4.5MV/cm.It is " narrow
It is thin " loop shape show its energy efficiency with higher.Scheme the energy storage density that (c) is three samples according to the present invention
Change curve is being pressed with electric field with energy efficiency.It can be seen that with the increase of extra electric field, the energy storage density of three is showed
The trend increased out.The wherein energy efficiency highest in 4 periods；(d) is schemed for BCT/BZT single crystal epitaxial multilayer involved in the present invention storage
The comparison of energy film and current Pb- base and unleaded energy storage thin-film material in terms of energy storage density and energy efficiency: discovery is of the invention
Related material reaches maximum value in lead-free field and can compare favourably with Pb sill；Energy dose-effect with higher simultaneously
Rate.
Figure 10 indicates the temperature stability of sample, wherein figure (a) and figure (b) respectively indicate the sample of N=4 and N=8 in room
Temperature is to 110 DEG C of energy storage densities and energy efficiency with 140 DEG C.It can be seen that the sample of N=4 is in room temperature to 140 DEG C of temperature ranges
Its energy storage density has reached 35J/cm in range3, while its energy efficiency is maintained at 75% or more.And in room temperature to 110 DEG C of models
In enclosing, the energy storage density of N=8 sample is up to 40J/cm3, energy density is maintained at 65%.Therefore, prepared by the present invention
Unleaded extension energy storage film can keep excellent energy storage characteristic at high temperature.
Embodiment 1
(1) first, in accordance with Ba0.7Ca0.3TiO3(BCT) and BaZr0.2Ti0.8O3(BZT) stoichiometric ratio weighs 4 respectively
The BaCO of~5N rank3High-purity powder, ZrO2High-purity powder, TiO2High-purity powder synthesizes BaZr0.2Ti0.8O3(BZT) ceramic target mixes
Object weighs BaCO3High-purity powder, CaCO3High-purity powder and TiO2High-purity powder synthesizes Ba0.7Ca0.3TiO3(BCT) ceramic target mixture；
The mixture of each target successively passes through ball milling, pre-sintering, secondary ball milling, granulation, molding and sintering process, obtains sheet
BCT and BZT ceramic target.Wherein ball milling is identical as the procedure parameter of secondary ball milling, specifically: ballstone, mixture and alcohol
Mass ratio be 2:1:1, rotational speed of ball-mill 400r/min, Ball-milling Time 6h；Pre-sintering temperature is 900 DEG C, is pre-sintered the time
For 4h；It is formed by tablet press machine, the pressure in forming process is 40Mpa, dwell time 5min；Sintering temperature in sintering process
Degree is 1050 DEG C, sintering time 4h.
(2) cleaning substrate: by the conductive single crystal SrTiO of (001) oriented growth3(STO) substrate immerses in alcohol, with ultrasound
Cleaning equipment carries out concussion cleaning 4min, and the substrate after cleaning is heavy in magnetic control sputtering system with being immediately placed in after being dried with nitrogen
In product chamber.
(3) precondition substrate；BZT ceramic target and BCT ceramic target air the purging removal that step (1) is prepared
After surface impurity, it is installed on rf magnetron sputtering target position different in magnetic control sputtering system；Air pressure in cavity is evacuated to air pressure
It is 10-5Mbar is then charged with the mixed gas (volume ratio 1:1) of oxygen and argon gas, until the intracorporal air pressure of chamber is 400mbar, this
When begin to warm up substrate, when substrate temperature rises to 850 DEG C, air pressure in cavity is evacuated to 10 again-5Mbar, then in the cavity
It is filled with the mixed gas (volume ratio 1:1) of oxygen and argon gas, until the intracorporal air pressure of chamber is 200mbar.
(4) pre-sputtering BCT and BZT ceramic target: under conditions of air pressure is 200mbar, pre-sputtering BCT ceramic target first
Material after pre-sputtering BCT ceramic target, rotates mechanical arm, so that the target position and substrate of BZT ceramic target are corresponding, starts to splash in advance
Penetrate BZT ceramic target；The pre-sputtering parameter of two kinds of ceramic targets is identical, and specially sputtering atmosphere is oxygen and argon gas volume ratio is
The mixed gas of 1:1, target spacing are 55mm, and sputtering power 100W, the pre-sputtering time of each ceramic target is 10min.
(5) staggeredly sputter BCT and BZT ceramic target, form plural layers: adjustment sputtering parameter, sputtering pressure are first
200mbar, the mixed gas that sputtering atmosphere is oxygen and argon gas volume ratio is 1:1, after conditional stability；The film of N=2 is prepared,
BCT, BZT, BCT and BZT are sequentially prepared on substrate；Wherein single layer BCT layers of growth time is 93min, with a thickness of 15nm；It is single
The growth time of BZT layers of layer is 252min, with a thickness of 35nm；Target spacing when every kind of thin film sputtering is 55min, and sputtering power is
100W；Staggeredly prepare forming process film after 2 periods.
(6) after process layer growth, it is passed through the mixed gas of oxygen and argon gas that volume ratio is 1:1, arrives cavity
Up to the air pressure of 400mbar；Make annealing treatment film at 850 DEG C, annealing time 15min obtains a kind of BCT/BZT
The unleaded single crystal epitaxial multilayer energy storage film of system.
Embodiment 2
In the present embodiment, in step 2, the ultrasonic cleaning time is 3min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-5Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-5mbar；In step (5), preparation
The film of N=4, the growth time that BCT layers of single layer is 46min, with a thickness of 7.5nm；BZT layers of growth time is 126min, thick
Degree is 17.5nm；Staggeredly prepare forming process film after 4 periods；Remaining step is same as Example 1.
Embodiment 3
In the present embodiment, in step 2, the ultrasonic cleaning time is 4min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-4Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-5mbar；In step (5), preparation
The film of N=8, the growth time that BCT layers of single layer is 23min, with a thickness of 3.8nm；The growth time that BZT layers of single layer is 63min,
With a thickness of 8.8nm；Staggeredly prepare forming process film after 8 periods；Remaining step is same as Example 1.
Embodiment 4
In the present embodiment, in step 2, the ultrasonic cleaning time is 5min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-4Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-4mbar；In step (5), preparation
The film of N=2, the growth time that BCT layers of single layer is 83min, with a thickness of 12nm；The growth time that BZT layers of single layer is 242min,
With a thickness of 32nm；Staggeredly prepare forming process film after 2 periods；Remaining step is same as Example 1.
Embodiment 5
In the present embodiment, in step 2, the ultrasonic cleaning time is 5min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-5Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-4mbar；In step (5), preparation
The film of N=4, the growth time that BCT layers of single layer is 36min, with a thickness of 5.5nm；The growth time that BZT layers of single layer is
116min, with a thickness of 15.5nm；Staggeredly prepare forming process film after 4 periods；Remaining step is same as Example 1.
Embodiment 6
In the present embodiment, in step 2, the ultrasonic cleaning time is 3min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-5Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-5mbar；In step (5), preparation
The film of N=8, the growth time that BCT layers of single layer is 18min, with a thickness of 3.7nm；The growth time that BZT layers of single layer is 58min,
With a thickness of 8.7nm；Staggeredly prepare forming process film after 8 periods；Remaining step is same as Example 1.
Embodiment 7
In the present embodiment, in step 2, the ultrasonic cleaning time is 4min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-4Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-4mbar；In step (5), preparation
The film of N=2, the growth time that BCT layers of single layer is 103min, with a thickness of 18nm；The growth time that BZT layers of single layer is
262min, with a thickness of 38nm；Staggeredly prepare forming process film after 2 periods；Remaining step is same as Example 1.
Embodiment 8
In the present embodiment, in step 2, the ultrasonic cleaning time is 4min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-5Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-5mbar；In step (5), preparation
The film of N=4, the growth time that BCT layers of single layer is 56min, with a thickness of 9.5nm；The growth time that BZT layers of single layer is
136min, with a thickness of 19.5nm；Staggeredly prepare forming process film after 4 periods；Remaining step is same as Example 1.
Embodiment 9
In the present embodiment, in step 2, the ultrasonic cleaning time is 4min；In step (3), air pressure in cavity is evacuated to first
Air pressure is 10-4Air pressure in cavity is evacuated to 10 again when substrate temperature is 850 DEG C by mbar-4mbar；In step (5), preparation
The film of N=8, the growth time that BCT layers of single layer is 28min, with a thickness of 3.9nm；The growth time that BZT layers of single layer is 68min,
With a thickness of 8.9nm；Staggeredly prepare forming process film after 8 periods；Remaining step is same as Example 1.
(Ba, Ca) TiO provided by the invention3(BCT)/Ba(Zr,Ti)O3(BZT) the unleaded single crystal epitaxial multilayer energy storage of system
Film is the BCT/BZT multilayer obtained on substrate by plasma to the bombardment of target using radiofrequency magnetron sputtering technology
Film.BCT and BZT ceramic target, then benefit are respectively synthesized out using high-purity powder, by the conventional solid preparation process of ceramics first
With radiofrequency magnetron sputtering technology, the bombardment of target is realized outside on substrate by plasma under high temperature, high oxygen pressure environment
Prolong growing film；It is realized simultaneously by adjusting the sputtering time of two kinds of targets to thickness in monolayer, the i.e. control of component, thus to this
The performance of energy storage film is predicted and is regulated and controled.By adjusting the period of multilayer film under condition of equivalent thickness, hitting for film is improved
Field strength is worn to increase its energy storage density, its energy storage density is made to have reached current BaTiO3(BTO)-base energy storage film maximum
Value, can be comparable with plumbum-based material.The use of this material in the industrial production will avoid Pb to natural environment and human health
Bring harm.The energy storage film energy efficiency with higher prepared through the invention simultaneously, is in particular in its electric hysteresis
The shape of loop line " narrow thin ".
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 the statistics of the test and Weibull distribution of sample ferroelectric properties, discovery periodicity is respectively its disruptive field intensity of 2,4,8 sample
Respectively 3.3,4.3,4.7MV/cm.This is because the increase with interface increases the inhibition of material internal electric current branch
By force, show that its energy storage density is respectively 22~27J/cm by integral calculation3, 40~45J/cm3With 50~55J/cm3.Reaching
While huge energy storage density, energy storage film according to the present invention possesses high energy efficiency, wherein the big portion of the efficiency in 8 periods
It is divided into 70% or more and the efficiency of 4 period samples is most of 80% or more.
The advantages of BCT/BZT system of the invention unleaded single crystal 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
BCT and BZT layers of interface number, can play the inhibition to electric branch extensions path, to increase the breakdown of plural layers
Field strength.Higher disruptive field intensity induces higher spontaneous polarization simultaneously, according to formula:
The energy storage density being calculated is close with the energy storage density of plumbum-based material phase.
(2) using suitable BCT layers and BZT layers of ratio, higher pole is kept while so that not reducing disruptive field intensity
Rate, 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 preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system, it is characterised in that: including following step
It is rapid:
(1) by Ba0.7Ca0.3TiO3Ceramic target and BaZr0.2Ti0.8O3Ceramic target is mounted on different in magnetic control sputtering system
On target position；
(2) substrate is put into the deposit cavity in magnetic control sputtering system after cleaning substrate；
(3) magnetic control sputtering system precondition substrate: is evacuated to 10-5-10-4Mbar is passed through oxygen and argon gas mixed gas, adds
Heat baking substrate；
(4) pre-sputtering ceramic target: pre-sputtering BCT ceramic target and BZT ceramic target respectively；
(5) sputter ceramic target: according to the film target number of plies, determine the period N of thin film sputtering, successively staggeredly sputtering BCT layer with
BZT layers, while the growth of epitaxial film is carried out on substrate；A cycle is one BCT layers and one BZT layers of sputtering, N 2,4
Or 8；
(6) film that annealing process step (5) generates；The unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system is made.
2. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
It is characterized in that: in step (1), using purity grade for the BaCO of 4~5N3Powder, CaCO3Powder and TiO2Powder preparation
Ba0.7Ca0.3TiO3Ceramic target；Use purity grade for the BaCO of 4~5N3Powder, ZrO2Powder and TiO2Powder preparation
BaZr0.2Ti0.8O3Ceramics.
3. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 2,
It is characterized in that: in step (1), Ba0.7Ca0.3TiO3Ceramic target and BaZr0.2Ti0.8O3Ceramic target is respectively by ball milling, pre-
Sintering, secondary ball milling, granulation, molding and sintering are prepared.
4. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
Be characterized in that: in step (2), substrate uses the conductive single crystal SrTiO of (001) oriented growth3Substrate；Substrate first passes through ultrasonic shake
3~5min of cleaning is swung to place into the deposit cavity of magnetic control sputtering system.
5. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
It is characterized in that: the specific steps of step (3) are as follows: the air pressure in magnetic control sputtering system is evacuated to 10-5-10-4Mbar is passed through oxygen
Substrate is begun to warm up until the air pressure in magnetic control sputtering system is 400mbar with the mixed gas of argon gas；Substrate is heated to 850
DEG C, the air pressure in magnetic control sputtering system is evacuated to 10 again-5-10-4Mbar is passed through the mixed gas of oxygen and argon gas, until magnetic control
Air pressure in sputtering system is 200mbar；Oxygen and argon gas volume ratio are 1:1 in the mixed gas of the oxygen and argon gas.
6. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
Be characterized in that: in step (4), the pre-sputtering atmosphere of each ceramic target is mixed-gas atmosphere, and mixed gas is by volume ratio
The oxygen and argon gas of 1:1 forms；The distance between sputtering target and substrate are 55mm；Pre-sputtering power is 100W；The pre-sputtering time
For 10min.
7. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
Be characterized in that: in step (5), when N=2, each BCT layers of sputtering time is 83-103min, each with a thickness of 12-18nm
A BZT layers of sputtering time is 242-262min, with a thickness of 32-38nm；When N=4, each BCT layers of sputtering time is 36-
56min, with a thickness of 5.5-9.5nm, each BZT layers of sputtering time is 116-136min, with a thickness of 15.5-19.5nm；N=
When 8, each BCT layers of sputtering time is 18-28min, and with a thickness of 3.7-3.9nm, each BZT layers of sputtering time is
58-68min, 8.7-8.9nm.
8. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
Be characterized in that: in step (5), the sputtering atmosphere of each ceramic target is mixed-gas atmosphere, and mixed gas is by volume ratio 1:1
Oxygen and argon gas composition；The distance between sputtering target and substrate are 55mm；Pre-sputtering power is 100W.
9. a kind of preparation method of the unleaded single crystal epitaxial multilayer energy storage film of BCT/BZT system according to claim 1,
Be characterized in that: in step (6), annealing atmosphere is mixed-gas atmosphere, mixed gas by volume ratio 1:1 oxygen and argon gas group
At；Annealing gas pressure is 400mbar, and annealing temperature is 850 DEG C, annealing time 15min.
10. being stored up using the unleaded single crystal epitaxial multilayer of BCT/BZT system made from preparation method described in claim 1-9 any one
It can film.
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