CN108987560A - A kind of perovskite ferroelectric film and preparation method thereof with multistage multidomain nanostructure based on crystallography engineering - Google Patents
A kind of perovskite ferroelectric film and preparation method thereof with multistage multidomain nanostructure based on crystallography engineering Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 56
- 238000002050 diffraction method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 15
- 230000005684 electric field Effects 0.000 claims description 31
- 238000004549 pulsed laser deposition Methods 0.000 claims description 29
- 238000000151 deposition Methods 0.000 claims description 27
- 229910003421 Pb(Zr0.2Ti0.8)O3 Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910002353 SrRuO3 Inorganic materials 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910004121 SrRuO Inorganic materials 0.000 claims description 11
- 229910002367 SrTiO Inorganic materials 0.000 claims description 10
- 230000010287 polarization Effects 0.000 abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- 230000004044 response Effects 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 124
- 239000010936 titanium Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- 238000010586 diagram Methods 0.000 description 17
- 239000010409 thin film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000003917 TEM image Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910002370 SrTiO3 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/04—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning
- H10N30/045—Treatments to modify a piezoelectric or electrostrictive property, e.g. polarisation characteristics, vibration characteristics or mode tuning by polarising
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
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Abstract
What the present invention provides a kind of based on crystallography engineering has the perovskite ferroelectric film of multistage multidomain nanostructure, and the multistage multidomain nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, wherein and the perovskite ferroelectric film is the Pb (Zr of (111) orientation0.2Ti0.8)O3Epitaxial film.Multistage multidomain nanostructure in perovskite ferroelectric film provided by the invention is by single (a1, c) and/(a2, c) and multidomain band arranges, enhance the electrology characteristic of perovskite ferroelectric film, compared with the perovskite ferroelectric film of not multistage in this way multidomain nanostructure, other than reducing coercive field and enhancing dielectric response, iron electric polarization is also enhanced, and substantially increase fatigue durability.
Description
Technical field
The present invention relates to ferroelectric material technical fields, and in particular to a kind of based on crystallography engineering to there is multistage multidomain to receive
The perovskite ferroelectric film and preparation method thereof of rice structure.
Background technique
Ferroelectric material refers to a kind of material with ferroelectric effect, and in ferroelectric material, spontaneous polarization direction is identical micro-
Zonule forms ferroelectric domain (domain), and the boundary between adjacent ferroelectric farmland is domain wall.In the case where not adding external electric field, farmland
Orientation is arbitrary, and ferroelectric material does not show macroscopic polarization behavior.If applying external electric field to ferroelectric material, inside
Farmland may reorientation, the polarization direction on the farmland after reorientation has the tendency that being consistent with extra electric field direction as far as possible.
The ferroelectric domain that multiple and different orientations are generally included in one crystal grain, only in ferroelectric single crystal, entire crystal is just only by one
Farmland composition.Due to being likely to occur uneven components, impurity, interface and additional constraint condition etc. in material, in order to make entirely to be
The free energy of system reaches minimum value, so there have been the domain structure of different orientation, the ferroelectric material with multidomain structure due to
It attracts the concern of numerous researchers with superior physical characteristic and broad application prospect.
Engineering farmland refers to that crystal forms the farmland configuration of high, the difficult displacement of stability after non-polarized direction applies electric field.This
Kind engineering farmland can be generally improved the electromechanical properties of material, dielectric and piezoelectricity after piezoelectric strain and improvement including no lag
Coefficient.Further, since the thermodynamic stability of multidomain structure, these improvement are intrinsic, therefore for device application more
For ideal.It is worth noting that, engineering farmland generally require to be pre-formed in ferroelectric material three or four it is equivalent switching
Body.Although the geometrical condition of film is substantially identical as block materials, in the prior art almost without exploring work in the film
The report on journey farmland.This can be partly attributed to the particular form of the nanoscale self assembly of switching body in the case where two-dimentional mechanics constrains.
Therefore, it is necessary to which the nanometer farmland to thin-film material carries out crystallography design, to improve its electromechanical properties.
Summary of the invention
What the purpose of the present invention is to provide a kind of based on crystallography engineering has the perovskite of multistage multidomain nanostructure
Ferroelectric thin film and preparation method thereof, the multistage multidomain nanostructure in perovskite ferroelectric film provided by the invention is by single
(a1, c) and/(a2, c) and multidomain band arranges, and coercive field and enhancing dielectric response are reduced, enhances iron electric polarization, and mention significantly
High fatigue durability.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
What the present invention provides a kind of based on crystallography engineering has the perovskite ferroelectric film of multistage multidomain nanostructure,
It is characterized in that, the multistage multidomain nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, wherein the calcium
Titanium ore ferroelectric thin film is the Pb (Zr of (111) orientation0.2Ti0.8)O3Epitaxial film.
Preferably, thickness >=100nm of the perovskite ferroelectric film.
Preferably, the perovskite ferroelectric film with a thickness of 200~250nm.
The present invention provides the calcium with multistage multidomain nanostructure described in above-mentioned technical proposal based on crystallography engineering
The preparation method of titanium ore ferroelectric thin film, comprising the following steps:
(1) SrTiO being orientated using pulsed laser deposition in (111)3Single side epitaxial growth (111) orientation of substrate
SrRuO3Film hearth electrode；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth of film hearth electrode
(111) Pb (Zr being orientated0.2Ti0.8)O3Film；
(3) by Pb (Zr in the step (2)0.2Ti0.8)O3Film is with 50~60 DEG C of min-1Rate of temperature fall is cooled to room
Then temperature applies circulation external electric field, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film, is had
The perovskite ferroelectric film of multistage multidomain nanostructure.
Preferably, in the step (1) operating condition of pulsed laser deposition include: reaction chamber be evacuated to≤1 ×
10-6Pa；Depositing temperature is 650~700 DEG C；Depositing oxygen pressure is 50~100mtorr；Laser energy density is 1.7Jcm-2；Swash
Optical pulse frequency is 10Hz.
Preferably, the SrRuO3Film hearth electrode with a thickness of 5~25nm.
Preferably, in the step (2) operating condition of pulsed laser deposition include: reaction chamber be evacuated to≤1 ×
10-6Pa；Depositing temperature is 550~600 DEG C；Depositing oxygen pressure is 100~150mtorr；Laser energy density is 1.7Jcm-2；
Laser pulse frequency is 10Hz.
Preferably, in the step (3) voltage of circulation external electric field be +/- 5~+/- 8V.
Preferably, the application number of circulation external electric field is 3~7 times in the step (3).
What the present invention provides a kind of based on crystallography engineering has the perovskite ferroelectric film of multistage multidomain nanostructure,
The multistage multidomain nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, wherein and the perovskite ferroelectric is thin
Film is the Pb (Zr of (111) orientation0.2Ti0.8)O3Epitaxial film.Multistage multidomain in perovskite ferroelectric film provided by the invention
Nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, the electrology characteristic of perovskite ferroelectric film is enhanced, with
Compared without the perovskite ferroelectric film of so multistage multidomain nanostructure, in addition to reduce coercive field and enhancing dielectric response it
Outside, iron electric polarization is also enhanced, and substantially increases fatigue durability.In embodiment the experimental results showed that, by single multidomain band group
At (111) be orientated Pb (Zr0.2Ti0.8)O3Film possesses the smallest coercive electric field and maximum dielectric response；And by single more
(111) of farmland band composition are orientated Pb (Zr0.2Ti0.8)O3Film is orientated Pb compared to (111) being made of three kinds of multidomain bands
(Zr0.2Ti0.8)O3The residual polarization of film and dielectric constant have been respectively increased about 25% and 50%；In addition, by single multidomain band
(111) of composition are orientated Pb (Zr0.2Ti0.8)O3The fatigue durability of film is better than the calcium without so multistage multidomain nanostructure
The fatigue durability of titanium ore ferroelectric thin film.
The present invention also provides described, and the perovskite ferroelectric with multistage multidomain nanostructure based on crystallography engineering is thin
The preparation method of film, preparation method provided by the invention is easy to operate, by the method for rapid cooling in perovskite ferroelectric film
Then one asymmetric mechanic boundary condition of middle manufacture applies circulation external electric field in perovskite ferroelectric film again and carries out pole
Change, to be formed in perovskite ferroelectric film a kind of by single (a1, c) and/(a2, c) multidomain band arrangement made of multistage multidomain
Nanostructure.
Detailed description of the invention
The structural schematic diagram of multistage multidomain nanostructure in the perovskite ferroelectric film that Fig. 1 provides for embodiment 1；Wherein,
1、a2Farmland；2, the farmland c；3,a1Farmland；4, apply the probe of circulation external electric field；
The structural schematic diagram of multistage multidomain nanostructure in the common perovskite ferroelectric film that Fig. 2 comparative example 1 provides；Its
In, 1, a2Farmland；2, the farmland c；3,a1Farmland；4, apply the probe of circulation external electric field；
Fig. 3 is the PFM image of perovskite ferroelectric film in embodiment 1；Wherein (c), shape appearance figure；(d), amplitude image outside face；
(e), amplitude image in face；
Fig. 4 is the PFM image of perovskite ferroelectric film in comparative example 1；Wherein (f), shape appearance figure；(g), amplitude image outside face；
(h), amplitude image in face；
Fig. 5 is the TEM image of perovskite ferroelectric film in embodiment 1；Wherein (a), growth in situ perovskite ferroelectric film
The light field TEM image of cross section；(b), after electric polarization perovskite ferroelectric film cross section light field TEM image；(c), multistage more
The high-amplification-factor TEM image of farmland nanostructure (being derived from the region irised out in b)；(a) illustration in figure is that perovskite ferroelectric is thin
The selective electron diffraction figure of film；(b) illustration in figure is the PFM figure in the dark field TEM image (upper left) and face in same area
Picture；
Fig. 6 is the ferroelectric hysteresis loop comparison diagram of perovskite ferroelectric film prepared by embodiment 1 and comparative example 1~3；
Fig. 7 is the butterfly curve comparison figure of perovskite ferroelectric film prepared by embodiment 1 and comparative example 1~3；
Fig. 8 is the curve of fatigue comparison diagram of perovskite ferroelectric film in embodiment 1 and comparative example 1, and scheming interior illustration is to implement
The comparison diagram of ferroelectric hysteresis loop (i.e. PE) of the perovskite thin film before and after testing fatigue in example 1.
Fig. 9 is the curve of fatigue comparison diagram of perovskite ferroelectric film in comparative example 2 and comparative example 3, and scheming interior illustration is comparison
The comparison diagram of ferroelectric hysteresis loop (i.e. PE) of the perovskite thin film before and after testing fatigue in example 2 and comparative example 3.
Specific embodiment
What the present invention provides a kind of based on crystallography engineering has the perovskite ferroelectric film of multistage multidomain nanostructure,
The multistage multidomain nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, wherein and the perovskite ferroelectric is thin
Film is the Pb (Zr of (111) orientation0.2Ti0.8)O3Epitaxial film.In the present invention, the thickness of the perovskite ferroelectric film is preferred
>=100nm, more preferably 200~250nm.
The present invention provides the calcium with multistage multidomain nanostructure described in above-mentioned technical proposal based on crystallography engineering
The preparation method of titanium ore ferroelectric thin film, comprising the following steps:
(1) SrTiO being orientated using pulsed laser deposition in (111)3Single side epitaxial growth (111) orientation of substrate
SrRuO3Film hearth electrode；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth of film hearth electrode
(111) Pb (Zr being orientated0.2Ti0.8)O3Film；
(3) by Pb (Zr in the step (2)0.2Ti0.8)O3Film is with 50~60 DEG C of min-1Rate of temperature fall is cooled to room
Then temperature applies circulation external electric field, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film, is had
The perovskite ferroelectric film of multistage multidomain nanostructure.
The SrTiO that the present invention uses pulsed laser deposition to be orientated in (111)3The single side epitaxial growth (111) of substrate takes
To SrRuO3Film hearth electrode.The present invention is for the SrTiO3Substrate does not have special restriction, using those skilled in the art
The well known SrTiO with (111) orientation3Substrate commercial goods.In the present invention, SrTiO3Substrate and Pb
(Zr0.2Ti0.8)O3With similar lattice structure and good lattice, SrTiO3The stress regulation and control of substrate can pass through
SrRuO3Film is transmitted to Pb (Zr0.2Ti0.8)O3Film, and then can be in SrRuO3The upper surface epitaxial growth of film is high-quality out
Pb (the Zr of amount0.2Ti0.8)O3Film.
In the present invention, the operating condition of the pulsed laser deposition preferably includes: reaction chamber is evacuated to≤1 ×
10-6Pa；Depositing temperature is 650~700 DEG C；Depositing oxygen pressure is 50~100mtorr；Laser energy density is 1.7Jcm-2；Laser
Pulse frequency is 10Hz.
In the present invention, the SrRuO3The thickness of film hearth electrode is preferably 5~25nm.In the present invention, SrRuO3Tool
There are high conductivity, high chemical stability and thermal stability, with Pb (Zr0.2Ti0.8)O3With similar lattice structure and good
Lattice, can surface epitaxial growth on it go out the Pb (Zr of high quality0.2Ti0.8)O3Film.
In the SrTiO of (111) orientation3The single side epitaxial growth SrRuO of substrate3After film hearth electrode, the present invention uses pulse
Laser deposition is in the SrRuO3Pb (the Zr of upper surface epitaxial growth (111) orientation of film hearth electrode0.2Ti0.8)O3Film.
In the present invention, the operating condition of the pulsed laser deposition preferably includes: reaction chamber is evacuated to≤1 × 10-6Pa；Deposition
Temperature is 550~600 DEG C；Depositing oxygen pressure is 100~150mtorr；Laser energy density is 1.7Jcm-2；Laser pulse frequency
For 10Hz.
In the SrRuO3Pb (the Zr of upper surface epitaxial growth (111) orientation of film hearth electrode0.2Ti0.8)O3After film,
The present invention is by the Pb (Zr0.2Ti0.8)O3Film is with 50~60 DEG C of min-1Rate of temperature fall is cooled to room temperature, and then applies circulation
External electric field, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film, obtains that there is multistage multidomain nano junction
The perovskite ferroelectric film of structure.The present invention is by fast cooling, so that in Pb (Zr0.2Ti0.8)O3Mismatch in epitaxial film is answered
Power is preferentially discharged in the form of forming a variety of switching bodies；In Pb (Zr0.2Ti0.8)O3Initial mismatch should try hard to keep in epitaxial film
Hold it is constant in the case where, be most stable of along the farmland configuration that the crystallographic direction that strains with maximum mismatch is formed.
In the present invention, the voltage of the circulation external electric field be preferably +/- 5~+/- 8V, be specifically as follows +/- 5V, +/-
6V, +/- 7V or +/- 8V.In the present invention, the application number of the circulation external electric field is preferably 3~7 times.The present invention by pair
Pb (the Zr of (111) after cooling orientation0.2Ti0.8)O3Film applies circulation external electric field, the Pb (Zr for being orientated (111)0.2Ti0.8)
O3Unordered nanometer domain structure in film is changed into single (a1, c) and/(a2, c) multidomain band arrangement multistage multidomain nanostructure.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) SrTiO being orientated using pulsed laser deposition in (111)3The single side epitaxial growth of substrate is with a thickness of 5nm's
(111) SrRuO being orientated3Film hearth electrode；Wherein, the operating condition of the pulsed laser deposition includes: that reaction chamber is taken out very
Empty extremely≤1 × 10-6Pa, depositing temperature are 690 DEG C, and deposition oxygen pressure is 80mtorr, laser energy density 1.7Jcm-2, swash
Optical pulse frequency is 10Hz；
(2) pulsed laser deposition SrRuO in (1) is used3The upper surface epitaxial growth thickness of film hearth electrode
Pb (the Zr being orientated for (111) of 230nm0.2Ti0.8)O3Film；Wherein, the operating condition of the pulsed laser deposition includes:
Reaction chamber is evacuated to≤1 × 10-6Pa, depositing temperature are 600 DEG C, and deposition oxygen pressure is 100mtorr, and laser energy density is
1.7J·cm-2, laser pulse frequency 10Hz；
(3) with 50 DEG C of min-1Rate of temperature fall is by Pb (Zr in the step (2)0.2Ti0.8)O3Film cooling is to room temperature, so
Apply a +/- 6V afterwards and recycle external electric field, replaces the pole (+6V/-6V/+6V/-6V/+6V/-6V) three times in the circulation external electric field
Under change effect, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film to receive to get to multistage multidomain
The perovskite ferroelectric film of rice structure.
Pb (Zr manufactured in the present embodiment0.2Ti0.8)O3Multistage multidomain nanostructure is by a in film1Farmland, a2Farmland and the farmland c group
At, and the multistage multidomain nanostructure is by single (a1, c) and/(a2, c) and multidomain band arranges, the multistage multidomain nanometer
The structural schematic diagram of structure is as shown in Figure 1, wherein 1-a2Farmland；The farmland 2-c；3-a1Farmland；4- applies the probe of circulation external electric field.
Comparative example 1
(1) SrTiO being orientated using pulsed laser deposition in (111)3The single side epitaxial growth of substrate is with a thickness of 5nm's
(111) SrRuO being orientated3Film hearth electrode；Wherein, the operating condition of the pulsed laser deposition includes: that reaction chamber is taken out very
Empty extremely≤1 × 10-6Pa, depositing temperature are 690 DEG C, and deposition oxygen pressure is 80mtorr, laser energy density 1.7Jcm-2, swash
Optical pulse frequency is 10Hz；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth of film hearth electrode
Pb (the Zr being orientated with a thickness of (111) of 230nm0.2Ti0.8)O3Film；Wherein, the operating condition of the pulsed laser deposition
It include: that reaction chamber is evacuated to≤1 × 10-6Pa, depositing temperature are 600 DEG C, and deposition oxygen pressure is 100mtorr, laser energy density
For 1.7Jcm-2, laser pulse frequency 10Hz；
(3) with 5 DEG C of min-1Rate of temperature fall is by Pb (Zr in the step (2)0.2Ti0.8)O3Film cooling is to room temperature, so
Apply a +/- 7V afterwards and recycle external electric field, replaces the pole (+7V/-7V/+7V/-7V/+7V/-7V) three times in the circulation external electric field
Under change effect, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film to receive to get to multistage multidomain
The perovskite ferroelectric film of rice structure.
Pb (the Zr of this comparative example preparation0.2Ti0.8)O3Multistage multidomain nanostructure is by a in film1Farmland, a2Farmland and the farmland c group
At, and the multistage multidomain nanostructure is arranged by three kinds of multidomain bands, the structural representation of the multistage multidomain nanostructure
Figure is as shown in Figure 2, wherein 1-a2Farmland；The farmland 2-c；3-a1Farmland；4- applies the probe of circulation external electric field.
Comparative example 2
(1) SrTiO being orientated using pulsed laser deposition in (001)3The single side epitaxial growth of substrate is with a thickness of 10nm
(001) orientation SrRuO3Film hearth electrode；Wherein, the operating condition of the pulsed laser deposition includes: that reaction chamber is taken out
Vacuum extremely≤1 × 10-6Pa, depositing temperature are 690 DEG C, and deposition oxygen pressure is 80mtorr, laser energy density 1.7Jcm-2,
Laser pulse frequency is 10Hz；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth of film hearth electrode
Pb (the Zr being orientated with a thickness of (001) of 200nm0.2Ti0.8)O3Film；Wherein, the operating condition of the pulsed laser deposition
It include: that reaction chamber is evacuated to≤1 × 10-6Pa, depositing temperature are 600 DEG C, and deposition oxygen pressure is 100mtorr, laser energy density
For 1.7Jcm-2, laser pulse frequency 10Hz；
(3) with 50 DEG C of min-1Rate of temperature fall is by Pb (Zr in the step (2)0.2Ti0.8)O3Film cooling is to room temperature, so
Apply a +/- 6V afterwards and recycle external electric field, replaces the pole (+6V/-6V/+6V/-6V/+6V/-6V) three times in the circulation external electric field
Under change effect, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film to receive to get to multistage multidomain
The perovskite ferroelectric film of rice structure.
Comparative example 3
(1) SrTiO being orientated using pulsed laser deposition in (101)3The single side epitaxial growth of substrate is with a thickness of 8nm's
(101) SrRuO being orientated3Film hearth electrode；Wherein, the operating condition of the pulsed laser deposition includes: that reaction chamber is taken out very
Empty extremely≤1 × 10-6Pa, depositing temperature are 690 DEG C, and deposition oxygen pressure is 80mtorr, laser energy density 1.7Jcm-2, swash
Optical pulse frequency is 10Hz；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth of film hearth electrode
Pb (the Zr being orientated with a thickness of (101) of 210nm0.2Ti0.8)O3Film；Wherein, the operating condition of the pulsed laser deposition
It include: that reaction chamber is evacuated to≤1 × 10-6Pa, depositing temperature are 600 DEG C, and deposition oxygen pressure is 100mtorr, laser energy density
For 1.7Jcm-2, laser pulse frequency 10Hz；
(3) with 50 DEG C of min-1Rate of temperature fall is by Pb (Zr in the step (2)0.2Ti0.8)O3Film cooling is to room temperature, so
Apply a +/- 6V afterwards and recycle external electric field, replaces the pole (+6V/-6V/+6V/-6V/+6V/-6V) three times in the circulation external electric field
Under change effect, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film to receive to get to multistage multidomain
The perovskite ferroelectric film of rice structure.
Embodiment 2
To the structure of the perovskite ferroelectric film with multistage multidomain nanostructure prepared by embodiment 1 and comparative example 1~3
It is characterized, specific as follows:
Fig. 3 is the PFM image of perovskite ferroelectric film in embodiment 1, wherein (c), shape appearance figure, (d), amplitude image outside face,
(e), amplitude image in face；Fig. 4 be comparative example 1 in perovskite ferroelectric film PFM image, wherein (f), shape appearance figure, (g), outside face
Amplitude image, (h), amplitude image in face.As can be seen from figs. 3 and 4 the multistage for the perovskite ferroelectric film being quickly cooled down in embodiment 1
Multidomain nanostructure is by single (a1, c) and/(a2, c) mostly with farmland composition, i.e., as shown in Fig. 1 structural schematic diagram；And comparative example
The multistage multidomain nanostructure of the perovskite ferroelectric film obtained under conventional chilling rate in 1 is by-(a1,a2)/(a1, c),
(a1,a2)/(a2, c) and (a1,c)/(a2, c) more than three kinds with farmland composition, i.e., as shown in Fig. 2 structural schematic diagram.
Fig. 5 is the TEM image of perovskite ferroelectric film prepared by embodiment 1, wherein (a), growth in situ perovskite ferroelectric
The light field TEM image of film cross section, (b), after electric polarization perovskite ferroelectric film cross section light field TEM image, (c), more
The high-amplification-factor TEM image of grade multidomain nanostructure (being derived from the region irised out in b)；(a) illustration in figure is perovskite iron
The selective electron diffraction figure of conductive film；(b) illustration in figure is in the dark field TEM image (upper left) and face in same area
PFM image.As shown in figure 5, TEM image shows the Pb (Zr in embodiment 10.2Ti0.8)O3Film is heteroepitaxial growth, and should
Pb(Zr0.2Ti0.8)O3Film has complicated nano twin crystal domain structure pattern under primary metastable state, and outer in circulation
Under the action of electric field, the parallel multistage multidomain nanostructure with striated.The multistage multidomain nanostructure is by single
(a1, c) and/(a2, c) and multidomain band composition, i.e., as shown in Fig. 1 structural schematic diagram.Embodiment 1 is more determined in conjunction with PFM figure and TEM figure
In in prepared perovskite ferroelectric film multistage multidomain nanostructure by single (a1, c) and/(a2, c) and multidomain band composition (Fig. 1
It is shown).
To the electricity of the perovskite ferroelectric film with multistage multidomain nanostructure prepared by embodiment 1 and comparative example 1~3
Performance is characterized, specific as follows (wherein, in order to test the ferroelectric hysteresis loop (i.e. PE) and butterfly curve of perovskite ferroelectric film
(i.e. CE) needs to grow the point electrode of one layer of platinum on perovskite ferroelectric film):
Fig. 6 is ferroelectric hysteresis loop (i.e. PE) comparison diagram of perovskite ferroelectric film prepared by embodiment 1 and comparative example 1~3；Figure
Butterfly curve (i.e. CE) comparison diagram of the 7 perovskite ferroelectric films prepared for embodiment 1 and comparative example 1~3.By Fig. 6 and Fig. 7
It is found that (111) orientation Pb (Zr being made of single multidomain band in embodiment 10.2Ti0.8)O3Film is compared to comparative example 1~3
In three kinds of Pb (Zr0.2Ti0.8)O3Film possesses the smallest coercive electric field and maximum dielectric response.And in embodiment 1 by
(111) of single multidomain band composition are orientated Pb (Zr0.2Ti0.8)O3Film compared in comparative experiments 1 by three kinds of multidomain band groups
At (111) be orientated Pb (Zr0.2Ti0.8)O3The residual polarization of film and dielectric constant have been respectively increased about 25% and 50%.
Fig. 8 is the curve of fatigue comparison diagram of perovskite ferroelectric film in embodiment 1 and comparative example 1, and scheming interior illustration is to implement
The comparison diagram of ferroelectric hysteresis loop (i.e. PE) of the perovskite thin film before and after testing fatigue in example 1.As shown in figure 8, in embodiment 1 by
(111) of single multidomain band composition are orientated Pb (Zr0.2Ti0.8)O3The fatigue durability of film be better than in comparative example 1 by three kinds
(111) of multidomain band composition are orientated Pb (Zr0.2Ti0.8)O3The fatigue durability of film.Fig. 9 is calcium titanium in comparative example 2 and comparative example 3
The curve of fatigue comparison diagram of mine ferroelectric thin film, scheming interior illustration is perovskite thin film in comparative example 2 and comparative example 3 before testing fatigue
The comparison diagram of ferroelectric hysteresis loop (i.e. PE) afterwards.In conjunction with Fig. 8 and Fig. 9 it is found that being made of single multidomain band in embodiment 1
(111) it is orientated Pb (Zr0.2Ti0.8)O3The fatigue durability of film is better than Pb (Zr in comparative example 2 and comparative example 30.2Ti0.8)O3It is thin
The fatigue durability of film.
As seen from the above embodiment, the multistage multidomain nanostructure in perovskite ferroelectric film provided by the invention is by single
(a1, c) and/(a2, c) and multidomain band arranges, and enhances the electrology characteristic of perovskite ferroelectric film, and it is such multistage
The perovskite ferroelectric film of multidomain nanostructure is compared, and other than reducing coercive field and enhancing dielectric response, also enhances iron
Electric polarization, and substantially increase fatigue durability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of perovskite ferroelectric film with multistage multidomain nanostructure based on crystallography engineering, which is characterized in that institute
Multistage multidomain nanostructure is stated by single (a1, c) and/(a2, c) and multidomain band arranges, wherein the perovskite ferroelectric film
For the Pb (Zr of (111) orientation0.2Ti0.8)O3Epitaxial film.
2. the perovskite ferroelectric film with multistage multidomain nanostructure according to claim 1, which is characterized in that described
Thickness >=100nm of perovskite ferroelectric film.
3. the perovskite ferroelectric film with multistage multidomain nanostructure according to claim 2, which is characterized in that described
Perovskite ferroelectric film with a thickness of 200~250nm.
4. the perovskite ferroelectric with multistage multidomain nanostructure described in any one of claims 1 to 3 based on crystallography engineering
The preparation method of film, comprising the following steps:
(1) SrTiO being orientated using pulsed laser deposition in (111)3Single side epitaxial growth (111) orientation of substrate
SrRuO3Film hearth electrode；
(2) pulsed laser deposition SrRuO in the step (1) is used3The upper surface epitaxial growth (111) of film hearth electrode
Pb (the Zr of orientation0.2Ti0.8)O3Film；
(3) by Pb (Zr in the step (2)0.2Ti0.8)O3Film is with 50~60 DEG C of min-1Rate of temperature fall is cooled to room temperature, so
Apply circulation external electric field afterwards, in the Pb (Zr0.2Ti0.8)O3Multistage multidomain nanostructure is formed in film, obtains that there is multistage
The perovskite ferroelectric film of multidomain nanostructure.
5. the preparation method according to claim 4, which is characterized in that the behaviour of pulsed laser deposition in the step (1)
It include: that reaction chamber is evacuated to≤1 × 10 as condition-6Pa；Depositing temperature is 650~700 DEG C；Deposit oxygen pressure for 50~
100mtorr；Laser energy density is 1.7Jcm-2；Laser pulse frequency is 10Hz.
6. preparation method according to claim 4 or 5, which is characterized in that the SrRuO3Film hearth electrode with a thickness of 5
~25nm.
7. the preparation method according to claim 4, which is characterized in that the behaviour of pulsed laser deposition in the step (2)
It include: that reaction chamber is evacuated to≤1 × 10 as condition-6Pa；Depositing temperature is 550~600 DEG C；Deposit oxygen pressure for 100~
150mtorr；Laser energy density is 1.7Jcm-2；Laser pulse frequency is 10Hz.
8. the preparation method according to claim 4, which is characterized in that the voltage of circulation external electric field is in the step (3)
+/- 5~+/- 8V.
9. the preparation method according to claim 4 or 8, which is characterized in that the application of circulation external electric field in the step (3)
Number is 3~7 times.
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