CN108987560B - Perovskite ferroelectric film with multilevel multi-domain nano structure based on crystallography engineering and preparation method thereof - Google Patents
Perovskite ferroelectric film with multilevel multi-domain nano structure based on crystallography engineering and preparation method thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims description 10
- 238000002050 diffraction method Methods 0.000 title claims description 6
- 238000012407 engineering method Methods 0.000 title description 2
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- 230000008021 deposition Effects 0.000 claims description 25
- 238000004549 pulsed laser deposition Methods 0.000 claims description 20
- 229910004121 SrRuO Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 11
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- 238000003917 TEM image Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
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- 125000004122 cyclic group Chemical group 0.000 description 7
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Abstract
本发明提供了一种基于结晶学工程的具有多级多畴纳米结构的钙钛矿铁电薄膜，所述多级多畴纳米结构由单一的(a1，c)/(a2，c)多畴带排列而成，其中，所述钙钛矿铁电薄膜为(111)取向的Pb(Zr0.2Ti0.8)O3外延薄膜。本发明提供的钙钛矿铁电薄膜中的多级多畴纳米结构由单一的(a1，c)/(a2，c)多畴带排列而成，增强了钙钛矿铁电薄膜的电学特性，与没有这样多级多畴纳米结构的钙钛矿铁电薄膜相比，除了降低矫顽场和增强介电响应之外，还增强了铁电极化，并大大提高了耐疲劳性。
The present invention provides a perovskite ferroelectric thin film with a multi-level multi-domain nanostructure based on crystallographic engineering, and the multi-level multi-domain nanostructure is composed of a single (a 1 , c)/(a 2 , c) The multi-domain bands are arranged, wherein the perovskite ferroelectric thin film is a (111) oriented Pb(Zr 0.2 Ti 0.8 )O 3 epitaxial thin film. The multi-level multi-domain nanostructure in the perovskite ferroelectric thin film provided by the present invention is formed by a single (a 1 , c)/(a 2 , c) multi-domain band, which enhances the perovskite ferroelectric thin film. The electrical properties, in addition to reducing the coercive field and enhancing the dielectric response, also enhance the ferroelectric polarization and greatly improve the fatigue resistance compared to perovskite ferroelectric films without such hierarchical multi-domain nanostructures.
Description
Technical Field
The invention relates to the technical field of ferroelectric materials, in particular to a perovskite ferroelectric film with a multi-level and multi-domain nano structure based on crystallographic engineering and a preparation method thereof.
Background
The ferroelectric material is a material having a ferroelectric effect, in which minute regions having the same spontaneous polarization direction form ferroelectric domains (domains), and the boundary between adjacent ferroelectric domains is a domain wall. In the absence of an applied electric field, the orientation of the domains is arbitrary and the ferroelectric material does not show macroscopic polarization behavior. If an external electric field is applied to the ferroelectric material, the internal domains thereof may be reoriented, and the reoriented domains tend to have a polarization direction as consistent as possible with the direction of the applied electric field. A crystal grain usually includes a plurality of ferroelectric domains of different orientations, and only in the ferroelectric single crystal, the entire crystal is composed of one domain. Since the material may have composition non-uniformity, impurities, interfaces, external constraint conditions and the like, and the free energy of the whole system reaches the minimum value, domain structures with different orientations appear, and the ferroelectric material with the multi-domain structure attracts the attention of a plurality of scientific researchers because of excellent physical properties and wide application prospect.
The engineered domain refers to a domain configuration which is high in stability and difficult to displace and is formed after an electric field is applied to a crystal in a non-polarization direction. Such engineered domains can generally improve the electromechanical properties of the material, including piezoelectric strain without hysteresis and improved dielectric and piezoelectric coefficients. Furthermore, these improvements are inherent due to the thermodynamic stability of the multi-domain structure and are therefore more desirable for device applications. Notably, engineering domains often requires the ability to pre-form three or four equivalent domain variants in the ferroelectric material. Although the geometry of the film is essentially the same as that of the bulk material, there are few reports in the prior art of exploring engineered domains in films. This may be due in part to the particular manner of nanoscale self-assembly of domain variants under two-dimensional mechanical constraints.
Therefore, it is necessary to perform crystallographic design on the nano-domains of the thin film material to improve the electromechanical properties thereof.
Disclosure of Invention
The invention aims to provide a perovskite ferroelectric thin film with a multi-level multi-domain nano structure based on crystallographic engineering and a preparation method thereof1，c)/(a2And c) the multi-domain strips are arranged, so that the coercive field is reduced, the dielectric response is enhanced, the ferroelectric polarization is enhanced, and the fatigue resistance is greatly improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a perovskite ferroelectric film with a multi-stage multi-domain nano structure based on crystallography engineering, which is characterized in that the multi-stage multi-domain nano structure is composed of a single (a)1，c)/(a2C) a multi-domain band arrangement, wherein the perovskite ferroelectric thin film is (111) oriented Pb (Zr)0.2Ti0.8)O3And (3) epitaxial thin films.
Preferably, the thickness of the perovskite ferroelectric thin film is more than or equal to 100 nm.
Preferably, the thickness of the perovskite ferroelectric thin film is 200-250 nm.
The invention provides a preparation method of a perovskite ferroelectric film with a multilevel and multidomain nano structure based on crystallographic engineering, which comprises the following steps:
(1) pulsed laser deposition of (111) -oriented SrTiO3Single-sided epitaxial growth of (111) oriented SrRuO on substrates3A thin film bottom electrode;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (111) -oriented Pb (Zr) on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film;
(3) adding Pb (Zr) in the step (2)0.2Ti0.8)O3The film is heated at 50-60 ℃ per minute-1Cooling to room temperature at a cooling rate, and applying a circulating external electric field to the Pb (Zr)0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
Preferably, the operating conditions of the pulsed laser deposition method in step (1) include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 650-700 ℃; the deposition oxygen pressure is 50-100 mtorr; the laser energy density is 1.7 J.cm-2(ii) a The laser pulse frequency was 10 Hz.
Preferably, the SrRuO3The thickness of the film bottom electrode is 5-25 nm.
Preferably, the operating conditions of the pulsed laser deposition method in step (2) include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 550-600 ℃; the oxygen pressure of the deposit is 100-150 mtorr; the laser energy density is 1.7 J.cm-2(ii) a The laser pulse frequency was 10 Hz.
Preferably, the voltage of the circulating external electric field in the step (3) is +/-5 to +/-8V.
Preferably, the application times of the external electric field in the circulation in the step (3) are 3-7 times.
The invention provides a perovskite ferroelectric thin film with a multi-stage multi-domain nano structure based on crystallography engineering, wherein the multi-stage multi-domain nano structure is composed of a single (a)1，c)/(a2C) a multi-domain band arrangement, wherein the perovskite ferroelectric thin film is (111) oriented Pb (Zr)0.2Ti0.8)O3And (3) epitaxial thin films. The multi-stage multi-domain nano structure in the perovskite ferroelectric thin film provided by the invention is composed of single (a)1，c)/(a2And c) the multi-domain zones are arranged, so that the electrical property of the perovskite ferroelectric film is enhanced, and compared with the perovskite ferroelectric film without the multi-stage multi-domain nano structure, the ferroelectric polarization is enhanced besides the coercive field reduction and the dielectric response enhancement, and the fatigue resistance is greatly improved. The experimental results in the examples show that (111) oriented Pb (Zr) consisting of a single multi-domain band0.2Ti0.8)O3The film has the minimum coercive electric field and the maximum dielectric response; and consisting of a single multi-domain band of (111) -oriented Pb (Zr)0.2Ti0.8)O3The film is compared with (111) oriented Pb (Zr) composed of three multi-domain bands0.2Ti0.8)O3The remanent polarization and the dielectric constant of the film are respectively improved by about 25 percent and 50 percent; further, (111) oriented Pb (Zr) consisting of single multi-domain band0.2Ti0.8)O3The fatigue resistance of the film is better than that of the perovskite ferroelectric film without the multi-stage multi-domain nano structure.
The invention also provides a preparation method of the perovskite ferroelectric film with the multilevel multi-domain nano structure based on the crystallographic engineering, the preparation method provided by the invention is simple to operate, an asymmetric mechanical boundary condition is manufactured in the perovskite ferroelectric film by a rapid cooling method, and then a cyclic external electric field is applied to the perovskite ferroelectric film for polarization, so that a single (a) phase is formed in the perovskite ferroelectric film1，c)/(a2And c) a multi-level multi-domain nano structure formed by arranging multi-domain zones.
Drawings
FIG. 1 is a schematic structural diagram of a multi-level multi-domain nanostructure in a perovskite ferroelectric thin film provided in example 1; wherein, 1, a2A domain; 2. c domain; 3. a is1A domain; 4. a probe for applying a cyclic external electric field;
FIG. 2 is a schematic structural diagram of a multi-level multi-domain nanostructure in a conventional perovskite ferroelectric thin film provided in comparative example 1; wherein, 1, a2A domain; 2. c domain; 3. a is1A domain; 4. a probe for applying a cyclic external electric field;
FIG. 3 is a PFM image of the perovskite ferroelectric thin film of example 1; wherein (c) a topography map; (d) an out-of-plane amplitude map; (e) an in-plane amplitude map;
FIG. 4 is a PFM image of the perovskite ferroelectric thin film in comparative example 1; wherein (f) is a topography; (g) an out-of-plane amplitude map; (h) an in-plane amplitude map;
FIG. 5 is a TEM image of the perovskite ferroelectric thin film in example 1; wherein (a) bright field TEM image of the cross section of the in-situ grown perovskite ferroelectric thin film; (b) bright field TEM image of the cross section of the perovskite ferroelectric thin film after electric polarization; (c) high magnification TEM images of multi-stage multi-domain nanostructures (taken from the area circled in b); (a) the inset in the figure is the selected region electron diffraction pattern of the perovskite ferroelectric thin film; (b) inset in the figure is a dark field TEM image (top left) and an in-plane PFM image within the same region;
FIG. 6 is a graph comparing the hysteresis loops of the perovskite ferroelectric thin films prepared in example 1 and comparative examples 1 to 3;
FIG. 7 is a comparison of butterfly curves for perovskite ferroelectric thin films prepared in example 1 and comparative examples 1 to 3;
fig. 8 is a graph comparing fatigue curves of the perovskite ferroelectric thin films of example 1 and comparative example 1, and the inset is a graph comparing the hysteresis loops (i.e., PE) of the perovskite thin films of example 1 before and after the fatigue test.
Fig. 9 is a graph comparing fatigue curves of the perovskite ferroelectric thin films of comparative examples 2 and 3, and the inset is a graph comparing hysteresis loops (i.e., PE) of the perovskite thin films of comparative examples 2 and 3 before and after the fatigue test.
Detailed Description
The invention provides a perovskite ferroelectric thin film with a multi-stage multi-domain nano structure based on crystallography engineering, wherein the multi-stage multi-domain nano structure is composed of a single (a)1，c)/(a2C) a multi-domain band arrangement, wherein the perovskite ferroelectric thin film is (111) oriented Pb (Zr)0.2Ti0.8)O3And (3) epitaxial thin films. In the invention, the thickness of the perovskite ferroelectric thin film is preferably not less than 100nm, and more preferably 200-250 nm.
The invention provides a preparation method of a perovskite ferroelectric film with a multilevel and multidomain nano structure based on crystallographic engineering, which comprises the following steps:
(1) pulsed laser deposition of (111) -oriented SrTiO3Single-sided epitaxial growth of (111) oriented SrRuO on substrates3A thin film bottom electrode;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (111) -oriented Pb (Zr) on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film;
(3) the P in the step (2)b(Zr0.2Ti0.8)O3The film is heated at 50-60 ℃ per minute-1Cooling to room temperature at a cooling rate, and applying a circulating external electric field to the Pb (Zr)0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
The invention adopts a pulse laser deposition method to prepare (111) -oriented SrTiO3Single-sided epitaxial growth of (111) oriented SrRuO on substrates3A thin film bottom electrode. The invention is directed to said SrTiO3The substrate is not particularly limited, and SrTiO having (111) orientation well known to those skilled in the art is used3The substrate is commercially available. In the present invention, SrTiO3Substrate and Pb (Zr)0.2Ti0.8)O3Having a similar lattice structure and good lattice matching, SrTiO3Stress regulation of the substrate will be via SrRuO3Film conduction to Pb (Zr)0.2Ti0.8)O3Thin film, further capable of being in SrRuO3Growing high-quality Pb (Zr) epitaxially on the upper surface of the film0.2Ti0.8)O3A film.
In the present invention, the operating conditions of the pulsed laser deposition method preferably include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 650-700 ℃; the deposition oxygen pressure is 50-100 mtorr; the laser energy density is 1.7Jcm-2(ii) a The laser pulse frequency was 10 Hz.
In the present invention, the SrRuO3The thickness of the thin film bottom electrode is preferably 5-25 nm. In the present invention, SrRuO3Has high conductivity, high chemical stability and thermal stability, and is compatible with Pb (Zr)0.2Ti0.8)O3Has similar lattice structure and good lattice matching property, and can epitaxially grow high-quality Pb (Zr) on the upper surface of the crystal0.2Ti0.8)O3A film.
SrTiO in (111) orientation3Single-sided epitaxial growth of SrRuO on a substrate3After the film bottom electrode, the invention adopts a pulse laser deposition method to deposit SrRuO3With (111) orientation of epitaxial growth on the upper surface of the thin film bottom electrodePb(Zr0.2Ti0.8)O3A film. In the present invention, the operating conditions of the pulsed laser deposition method preferably include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 550-600 ℃; the oxygen pressure of the deposit is 100-150 mtorr; the laser energy density is 1.7 J.cm-2(ii) a The laser pulse frequency was 10 Hz.
In the SrRuO3Epitaxially growing (111) -oriented Pb (Zr) on the upper surface of the thin film bottom electrode0.2Ti0.8)O3After the film is formed, the invention uses the Pb (Zr)0.2Ti0.8)O3The film is heated at 50-60 ℃ per minute-1Cooling to room temperature at a cooling rate, and applying a circulating external electric field to the Pb (Zr)0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure. The invention leads the Pb (Zr) to be in the Pb (Zr) through rapid cooling0.2Ti0.8)O3Mismatch stress in the epitaxial film, preferentially released in the form of formation of multiple domain variants; at Pb (Zr)0.2Ti0.8)O3The domain configuration formed along the crystal direction with the greatest mismatch strain is most stable with the initial mismatch stress in the epitaxial film remaining constant.
In the present invention, the voltage of the cyclic external electric field is preferably +/-5 to +/-8V, and may be +/-5V, +/-6V, +/-7V or +/-8V. In the present invention, the number of times of application of the external electric field for the cycle is preferably 3 to 7 times. The invention is to (111) oriented Pb (Zr) after cooling0.2Ti0.8)O3Applying cyclic external electric field to the film to make the (111) oriented Pb (Zr)0.2Ti0.8)O3The disordered nano-domain structure in the thin film is converted to a single (a)1，c)/(a2And c) a multi-domain nano structure with multiple domains arranged in a band.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Pulsed laser deposition of (111) -oriented SrTiO3Single-sided epitaxial growth of (111) -oriented SrRuO with thickness of 5nm3A thin film bottom electrode; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature 690 deg.C, deposition oxygen pressure 80mtorr, laser energy density 1.7J · cm-2The laser pulse frequency is 10 Hz;
(2) SrRuO in the (1) by adopting a pulse laser deposition method3Epitaxially growing (111) -oriented Pb (Zr) with a thickness of 230nm on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature of 600 deg.C, deposition oxygen pressure of 100mtorr, and laser energy density of 1.7J · cm-2The laser pulse frequency is 10 Hz;
(3) at 50 ℃ min-1Temperature reduction rate of Pb (Zr) in the step (2)0.2Ti0.8)O3The film was cooled to room temperature and then subjected to an external electric field of +/-6V cycles, under three alternating (+6V/-6V/+6V/-6V/+6V/-6V) polarizations of the external electric field in the Pb (Zr) phase0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
Pb (Zr) prepared in this example0.2Ti0.8)O3The multi-level multi-domain nano structure in the film is formed by1Domain, a2Domains and c-domains, and the multi-level multi-domain nanostructure is composed of a single (a)1，c)/(a2C) multi-domain bands are arranged, the structural schematic diagram of the multi-level multi-domain nano structure is shown in figure 1, wherein 1-a2A domain; 2-c domain; 3-a1A domain; 4-Probe applying a cyclic external electric field.
Comparative example 1
(1) By pulsed laser depositionMethod of making (111) -oriented SrTiO3Single-sided epitaxial growth of (111) -oriented SrRuO with thickness of 5nm3A thin film bottom electrode; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature 690 deg.C, deposition oxygen pressure 80mtorr, laser energy density 1.7J · cm-2The laser pulse frequency is 10 Hz;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (111) -oriented Pb (Zr) with a thickness of 230nm on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature of 600 deg.C, deposition oxygen pressure of 100mtorr, and laser energy density of 1.7J · cm-2The laser pulse frequency is 10 Hz;
(3) at 5 ℃ min-1Temperature reduction rate of Pb (Zr) in the step (2)0.2Ti0.8)O3The film was cooled to room temperature and then subjected to an external electric field of +/-7V cycles, under three alternating (+7V/-7V/+7V/-7V/+7V/-7V) polarizations of the external electric field in the Pb (Zr) phase0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
Pb (Zr) prepared by this comparative example0.2Ti0.8)O3The multi-level multi-domain nano structure in the film is formed by1Domain, a2The structure of the multilevel multi-domain nanostructure is shown in figure 2, wherein 1-a2A domain; 2-c domain; 3-a1A domain; 4-Probe applying a cyclic external electric field.
Comparative example 2
(1) Pulsed laser deposition of (001) -oriented SrTiO3Single-sided epitaxial growth of (001) -oriented SrRuO with thickness of 10nm3A thin film bottom electrode; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperatureThe temperature is 690 ℃, the deposition oxygen pressure is 80mtorr, and the laser energy density is 1.7J · cm-2The laser pulse frequency is 10 Hz;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (001) -oriented Pb (Zr) with a thickness of 200nm on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature of 600 deg.C, deposition oxygen pressure of 100mtorr, and laser energy density of 1.7J · cm-2The laser pulse frequency is 10 Hz;
(3) at 50 ℃ min-1Temperature reduction rate of Pb (Zr) in the step (2)0.2Ti0.8)O3The film was cooled to room temperature and then subjected to an external electric field of +/-6V cycles, under three alternating (+6V/-6V/+6V/-6V/+6V/-6V) polarizations of the external electric field in the Pb (Zr) phase0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
Comparative example 3
(1) Pulsed laser deposition of (101) -oriented SrTiO3Single-sided epitaxial growth of (101) -oriented SrRuO with thickness of 8nm3A thin film bottom electrode; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature 690 deg.C, deposition oxygen pressure 80mtorr, laser energy density 1.7J · cm-2The laser pulse frequency is 10 Hz;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (101) -oriented Pb (Zr) with a thickness of 210nm on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film; wherein the operating conditions of the pulsed laser deposition method include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa, deposition temperature of 600 deg.C, deposition oxygen pressure of 100mtorr, and laser energy density of 1.7J · cm-2The laser pulse frequency is 10 Hz;
(3) at 50 ℃ min-1Rate of temperature decrease willPb (Zr) in step (2)0.2Ti0.8)O3The film was cooled to room temperature and then subjected to an external electric field of +/-6V cycles, under three alternating (+6V/-6V/+6V/-6V/+6V/-6V) polarizations of the external electric field in the Pb (Zr) phase0.2Ti0.8)O3And forming a multilevel multi-domain nano structure in the film to obtain the perovskite ferroelectric film with the multilevel multi-domain nano structure.
Example 2
The structures of the perovskite ferroelectric thin films with the multi-stage multi-domain nano structures prepared in the embodiment 1 and the comparative examples 1 to 3 are characterized as follows:
FIG. 3 is a PFM image of the perovskite ferroelectric thin film of example 1, wherein (c), the topography, (d), the out-of-plane amplitude plot, (e), the in-plane amplitude plot; FIG. 4 is a PFM image of the perovskite ferroelectric thin film in comparative example 1, wherein (f), the morphology map, (g), the out-of-plane amplitude map, (h), the in-plane amplitude map. As can be seen from FIGS. 3 and 4, the multi-level multi-domain nanostructure of the rapidly cooled perovskite ferroelectric thin film in example 1 is composed of a single (a)1，c)/(a2C) multi-band domain composition, i.e. as shown in the structural diagram of fig. 1; while the multi-level multi-domain nano structure of the perovskite ferroelectric thin film obtained in the comparative example 1 at the conventional cooling rate is formed by (a)1,a2)/(a1,c)，(a1,a2)/(a2C) and (a)1,c)/(a2And c) three kinds of multi-band domains, namely as shown in the structural schematic diagram of FIG. 2.
FIG. 5 is a TEM image of the perovskite ferroelectric thin film prepared in example 1, wherein (a) is a bright field TEM image of a cross section of the in-situ grown perovskite ferroelectric thin film, (b) is a bright field TEM image of a cross section of the perovskite ferroelectric thin film after electric polarization, (c) is a high magnification TEM image of a multi-level multi-domain nanostructure (taken from the region circled in b); (a) the inset in the figure is the selected region electron diffraction pattern of the perovskite ferroelectric thin film; (b) the inset in the figure is a dark field TEM image (top left) and an in-plane PFM image in the same region. As shown in FIG. 5, the TEM image shows Pb (Zr) in example 10.2Ti0.8)O3The film is heteroepitaxially grown, and the Pb (Zr)0.2Ti0.8)O3The film has a complex nano twin domain structure pattern in a primary metastable state, and has a striped parallel multi-level multi-domain nano structure under the action of an external circulating electric field. The multi-level multi-domain nanostructure is composed of a single (a)1，c)/(a2And c) the multi-domain band composition is shown as the structural schematic diagram of FIG. 1. It was further confirmed by combining PFM and TEM images that the multi-level multi-domain nanostructure in the perovskite ferroelectric thin film prepared in example 1 consists of single (a)1，c)/(a2And c) multi-domain band composition (shown in FIG. 1).
The electrical properties of the perovskite ferroelectric thin films with the multi-stage multi-domain nano-structure prepared in example 1 and comparative examples 1 to 3 are characterized as follows (wherein, in order to test the hysteresis loop (i.e. PE) and the butterfly curve (i.e. CE) of the perovskite ferroelectric thin film, a platinum layer of point electrode needs to be grown on the perovskite ferroelectric thin film):
FIG. 6 is a graph comparing the hysteresis loops (i.e., PE) of the perovskite ferroelectric thin films prepared in example 1 and comparative examples 1 to 3; FIG. 7 is a comparison of butterfly curves (i.e., CEs) for the perovskite ferroelectric thin films prepared in example 1 and comparative examples 1-3. As can be seen from FIGS. 6 and 7, the (111) oriented Pb (Zr) composed of a single multi-domain band in example 10.2Ti0.8)O3The film was compared to three Pb (Zr) in comparative examples 1 to 30.2Ti0.8)O3The film has the minimum coercive electric field and the maximum dielectric response. And (111) oriented Pb (Zr) consisting of a single multi-domain band in example 10.2Ti0.8)O3The film was compared to (111) oriented Pb (Zr) consisting of three multi-domain bands in comparative experiment 10.2Ti0.8)O3The remanent polarization and the dielectric constant of the film are improved by about 25% and 50%, respectively.
Fig. 8 is a graph comparing fatigue curves of the perovskite ferroelectric thin films of example 1 and comparative example 1, and the inset is a graph comparing the hysteresis loops (i.e., PE) of the perovskite thin films of example 1 before and after the fatigue test. As shown in FIG. 8, the (111) orientation Pb (Zr) composed of a single multi-domain band in example 10.2Ti0.8)O3The fatigue resistance of the film was better than that of the (111) oriented Pb (Zr) composed of three kinds of multi-domain stripes in comparative example 10.2Ti0.8)O3Fatigue resistance of the film. Fig. 9 is a graph comparing fatigue curves of the perovskite ferroelectric thin films of comparative examples 2 and 3, and the inset is a graph comparing hysteresis loops (i.e., PE) of the perovskite thin films of comparative examples 2 and 3 before and after the fatigue test. As can be seen from FIGS. 8 and 9, the (111) oriented Pb (Zr) composed of a single multi-domain band in example 10.2Ti0.8)O3The fatigue resistance of the film is better than that of Pb (Zr) in comparative example 2 and comparative example 30.2Ti0.8)O3Fatigue resistance of the film.
As can be seen from the above examples, the present invention provides a perovskite ferroelectric thin film in which the multi-level multi-domain nanostructure is composed of a single (a)1，c)/(a2And c) the multi-domain zones are arranged, so that the electrical property of the perovskite ferroelectric film is enhanced, and compared with the perovskite ferroelectric film without the multi-stage multi-domain nano structure, the ferroelectric polarization is enhanced besides the reduction of coercive field and the enhancement of dielectric response, and the fatigue resistance is greatly improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of perovskite ferroelectric thin film with multi-level and multi-domain nano structure based on crystallography engineering comprises the following steps:
(1) pulsed laser deposition of (111) -oriented SrTiO3Single-sided epitaxial growth of (111) oriented SrRuO on substrates3A thin film bottom electrode;
(2) SrRuO in the step (1) by adopting a pulse laser deposition method3Epitaxially growing (111) -oriented Pb (Zr) on the upper surface of the thin film bottom electrode0.2Ti0.8)O3A film;
(3) adding Pb (Zr) in the step (2)0.2Ti0.8)O3The film is heated at 50-60 ℃ per minute-1Cooling down to room temperature at a cooling rate and then applying cyclesAn electric field outside the ring at said Pb (Zr)0.2Ti0.8)O3Forming a multilevel multi-domain nano structure in the film to obtain a perovskite ferroelectric film with the multilevel multi-domain nano structure;
the multilevel multidomain nano structure is formed by arranging single (a1, c)/(a2, c) multidomain bands, wherein the perovskite ferroelectric thin film is (111) oriented Pb (Zr)0.2Ti0.8)O3And (3) epitaxial thin films.
2. The method according to claim 1, wherein the operating conditions of the pulsed laser deposition method in the step (1) include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 650-700 ℃; the deposition oxygen pressure is 50-100 mtorr; the laser energy density is 1.7 J.cm-2(ii) a The laser pulse frequency was 10 Hz.
3. The preparation method according to claim 1 or 2, wherein the SrRuO is3The thickness of the film bottom electrode is 5-25 nm.
4. The method according to claim 1, wherein the operating conditions of the pulsed laser deposition method in the step (2) include: the reaction chamber is vacuumized to be less than or equal to 1 multiplied by 10-6Pa; the deposition temperature is 550-600 ℃; the oxygen pressure of the deposit is 100-150 mtorr; the laser energy density is 1.7 J.cm-2(ii) a The laser pulse frequency was 10 Hz.
5. The production method according to claim 1, wherein the voltage of the external electric field for the cycle in the step (3) is +/-5 to +/-8V.
6. The production method according to claim 1 or 5, wherein the number of times of application of the external electric field is circulated in the step (3) is 3 to 7 times.
7. The method according to claim 1, wherein the thickness of the perovskite ferroelectric thin film is not less than 100 nm.
8. The production method according to claim 1, wherein the thickness of the perovskite ferroelectric thin film is 200 to 250 nm.
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