CN113745092A - Preparation method of flexible self-supporting perovskite oxide single crystal thin film with different crystal orientations - Google Patents
Preparation method of flexible self-supporting perovskite oxide single crystal thin film with different crystal orientations Download PDFInfo
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Abstract
The invention provides a preparation method of a flexible self-supporting perovskite oxide single crystal film with different crystal orientations. The method adopts soluble substances as sacrificial layers, firstly, the sacrificial layers are prepared on substrates with different crystal orientations, then, perovskite oxide single crystal thin films are prepared on the surfaces of the sacrificial layers, and finally, the sacrificial layers are dissolved by using solvents to obtain the flexible self-supporting perovskite oxide single crystal thin films with different crystal orientations. The method is simple, rapid and environment-friendly, can realize the flexibility of the ultrathin perovskite oxide single crystal film, and has important significance for regulating and controlling the physical properties of the flexible self-supporting perovskite oxide single crystal film and further integrally preparing heterogeneous structures with different crystal orientations.
Description
Technical Field
The invention belongs to the technical field of flexible electronics, and particularly relates to a preparation method of a flexible self-supporting perovskite oxide single crystal film with different crystal orientations.
Background
Flexible electronics as an emerging discipline, one of the important research directions is the development of novel multifunctional flexible materials andan electronic device. In the past decade, graphene and MoS have been used2And the traditional two-dimensional materials are taken as representative flexible self-supporting (freestanding) materials, so that the method is widely researched, and shows great application potential in the field of flexible electronics. Transition Metal Oxides (TMOs) are important functional materials, and due to the abundant physical properties of TMOs, the selection range of flexible functional materials is greatly enriched if the flexible application is realized, and a new opportunity is provided for the development of flexible electronics.
Compared with the characteristic of single crystal orientation of traditional flexible materials such as graphene, the TMOs film can realize controllable preparation of different crystal orientations. It is well known that the physical properties of perovskites are closely related to the crystallographic orientation. For example, in bulk BiFeO3And SrRuO3There are ferroelectric anisotropy and magnetic anisotropy associated with the crystal orientation. More importantly, in the two-dimensional oxide interface, due to the extreme particularity of interface symmetry, surface polarity, oxygen octahedron coupling and the like compared with the bulk phase, the orientation of crystals greatly influences the properties of the oxide heterostructure. For example, Gibert et al found [111]]Crystal orientation LaNiO3-LaMnO3The superlattice has a large exchange bias, and [001]]This phenomenon is not observed in a superlattice of crystal orientations. Furthermore, Catalano et al in NdNiO3Metal-insulator transitions associated with the crystal orientation are also observed in the thin film.
Therefore, the crystal orientation is one of important parameters influencing the properties of the perovskite oxide thin film, so that the preparation of the self-supporting perovskite oxide single crystal thin film with different crystal orientations is expected to provide a new degree of freedom for regulating and controlling the physical properties of the self-supporting TMOs thin film material, and is of great significance for further integrated preparation of heterostructures and improvement of the functionality of TMOs thin film-based flexible devices.
Disclosure of Invention
Aiming at the current situation, the invention aims to provide a preparation method of a flexible self-supporting perovskite oxide single crystal film with different crystal orientations, which has the advantages of simplicity, easiness in operation, recyclable substrate, no damage to a functional layer and the like.
In order to achieve the technical purpose, the inventor finds out through a large number of experiments that soluble substances are firstly prepared on substrates with different crystal orientations to be used as sacrificial layers, perovskite oxide single crystal thin films are prepared on the sacrificial layers, and then the sacrificial layers are dissolved by using solvents to obtain flexible self-supporting perovskite oxide single crystal thin films with different crystal orientations.
The technical scheme of the invention is as follows: a preparation method of flexible self-supporting perovskite oxide single crystal films with different crystal orientations is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing soluble substance films as sacrificial layers on substrates with different crystal directions, wherein the soluble substances are perovskite-like oxides or perovskite oxides;
(2) preparing a perovskite oxide single crystal film on the surface of the soluble substance film;
(3) and (3) dissolving the sacrificial layer by using a solvent, and taking out the perovskite oxide single crystal film to obtain the flexible self-supporting perovskite oxide single crystal film with different crystal orientations.
The substrate material is not limited and comprises SrTiO3(STO)、Nb-SrTiO3、LaAlO3、SrLaGaO4、SrLaAlO4、DyScO3、GdScO3、BaTiO3、LiNbO3One or more of MgO, PMN-PT and the like.
Preferably, a substrate having a lattice constant matching the lattice constant of the sacrificial layer is used. In view of the capability of matching the lattice constant of the perovskite oxide single crystal thin film with that of the substrate, the substrate having a lattice constant matching that of the perovskite oxide single crystal thin film is preferably selected.
For example, La2/3Sr1/3MnO3(LSMO) has a lattice constant of
Has room temperature ferromagnetism. STO has a cubic structure with a lattice constant of
STO can be used as a substrate for preparing the flexible self-supporting LSMO single crystal thin film.
Sr3Al2O6(SAO) is a perovskite-like oxide having a cubic structure and a lattice constant of
About four times of STO lattice constant, namely one SAO unit cell is matched with four STO unit cells in crystal face, can be well epitaxially grown, and SAO is easy to dissolve in water. Thus, when STO is used as a substrate to prepare a flexible self-supporting thin film of LSMO single crystal, SAO is a preferred material as a sacrificial layer.
The crystal orientation of the substrate includes but is not limited to one of [100], [110], [111], and the like.
Preferably, in the step (1), the surface of the substrate is pretreated first, and then a sacrificial layer is prepared on the substrate. The pretreatment method is not limited and comprises one or more of hydrofluoric acid corrosion, hydrochloric acid corrosion, helium ion bombardment, high-temperature annealing and the like.
The soluble substance includes but is not limited to Sr3Al2O6(SAO)、Ca3-xSrxAl2O6(CSAO)、La1-xSrxMnO3(LSMO) and the like.
The solvent dissolves soluble substances but does not react with the perovskite oxide single crystal thin film and the substrate. The solvent includes, but is not limited to, one of deionized water, potassium iodide, hydrochloric acid, and the like. The preparation method of the sacrificial layer is not limited, and includes one or more of Pulse Laser Deposition (PLD), magnetron Sputtering (Sputtering), Molecular Beam Epitaxy (MBE), and other preparation methods.
The preparation method of the perovskite oxide single crystal film is not limited, and comprises one or more of Pulse Laser Deposition (PLD), magnetron Sputtering (Sputtering), Molecular Beam Epitaxy (MBE) and other preparation methods.
In the step (3), after the sacrificial layer is dissolved by using the solvent, the perovskite oxide single crystal thin film is still attached to the substrate, and the LSMO thin film may be broken and incomplete after being directly taken out, for this reason, in the step (2), after the perovskite oxide single crystal thin film is prepared on the surface of the soluble substance thin film, a flexible substance is preferably coated or stuck on the surface of the perovskite oxide single crystal thin film, so that the perovskite oxide single crystal thin film can be prevented from being broken when the perovskite oxide single crystal thin film is taken out in the step (3), and the integrity of the perovskite oxide single crystal thin film can be improved.
The flexible material is not limited, and includes but is not limited to one or more of Polyimide (PI), cloth-based adhesive tape, polyethylene terephthalate (PET), Polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA), and the like.
The method for obtaining the flexible single crystal film by transferring is not limited, and comprises one or more of methods of dissolving the flexible substance by a solution, heating to release the flexible substance and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, a soluble perovskite-like oxide thin film or a perovskite oxide thin film is introduced between a substrate and a perovskite oxide single crystal thin film to serve as a sacrificial layer, and the sacrificial layer is dissolved by using a solvent, so that the flexible self-supporting perovskite oxide single crystal thin film is obtained.
(2) The method can prepare self-supporting flexible perovskite oxide single crystal films with different crystal orientations by controlling the crystal orientation of the substrate to control the crystal orientation of the perovskite oxide single crystal film; the perovskite oxide single crystal thin film has good crystallization quality, compared with the perovskite oxide single crystal thin film before self-supporting, the magnetic and electric properties of the perovskite oxide single crystal thin film are not obviously changed, and the stress from the substrate and the sacrificial layer is released, so that the lattice constant is enlarged and is close to the bulk phase lattice constant.
(3) The method is simple, rapid and environment-friendly, the substrate can be recycled, the functional layer of the flexible perovskite oxide is not damaged, and the flexibility of the ultrathin perovskite oxide single crystal film can be realized under the condition of not damaging the perovskite oxide single crystal film, so that the magnetic and electrical properties of the flexible perovskite oxide single crystal film can be researched.
(4) The method can stack the self-supporting perovskite oxide single crystal films with different crystal orientations so as to prepare the flexible self-supporting perovskite oxide heterostructure films with different crystal orientations, has important significance for regulating and controlling novel physical properties of the flexible perovskite oxide film, and provides a feasible scheme for preparing new functional devices.
Drawings
FIG. 1 is a surface topography of a [001] crystal orientation SAO/LSMO heterostructure thin film in example 1 of the present invention, wherein the inset is a reflection high energy electron diffraction pattern.
FIG. 2 is a diagram of a [001] crystal orientation flexible self-supporting LSMO single crystal thin film entity in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of the [001] orientation LSMO single crystal thin film before and after its flexibility in example 1 of the present invention.
FIG. 4 is a hysteresis loop of the LSMO single crystal thin film with the [001] crystal orientation before and after being subjected to the flexibilization in example 1 of the present invention.
FIG. 5 is a graph showing the temperature-dependent change in magnetization of the [001] orientation LSMO single crystal thin film before and after it is made flexible in example 1 of the present invention.
FIG. 6 is a temperature-dependent resistance curve of the [001] orientation LSMO single crystal thin film before and after its flexibility in example 1 of the present invention.
FIG. 7 is an X-ray diffraction pattern of the [110] orientation LSMO single crystal thin film of example 2 of the present invention before and after its being subjected to flexibilization.
FIG. 8 is a hysteresis loop of the [110] orientation LSMO single crystal thin film before and after its flexibility in example 2 of the present invention.
FIG. 9 is a graph showing the temperature dependence of magnetization before and after the [110] orientation LSMO single crystal thin film is made flexible in example 2 of the present invention.
FIG. 10 is a graph showing the temperature-dependent change in resistance of the [110] orientation LSMO single crystal thin film before and after it is subjected to the flexibilization in example 2 of the present invention.
FIG. 11 is an X-ray diffraction pattern of the [111] orientation LSMO single crystal thin film before and after its flexibility in example 3 of the present invention.
FIG. 12 is a hysteresis loop of the LSMO single crystal thin film with crystal orientation [111] before and after being flexible in example 3 of the present invention.
FIG. 13 is a graph showing the temperature-dependent change in magnetization of the [111] orientation LSMO single crystal thin film before and after it is made flexible in example 3 of the present invention.
FIG. 14 is a graph showing the temperature-dependent change in resistance of the [111] orientation LSMO single crystal thin film before and after it is subjected to the flexibilization in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
Example 1:
this example prepares a flexible self-supporting LSMO single crystal thin film with a [001] crystal orientation by the following method:
(1) selecting an STO substrate with a [001] crystal orientation as a substrate, and preparing an SAO film on the substrate as a sacrificial layer, wherein the method specifically comprises the following steps:
(1-1) the [001] as described]The area of the crystal orientation STO substrate is 5 x 5mm2The thickness is 0.5 mm; etching with hydrofluoric acid buffer [001]]A crystal orientation STO substrate, which is used for obtaining a surface with straight steps and a width of about 200 nm;
(1-2) in [001]Preparing SAO film with thickness of 6 unit cell layers on crystal orientation STO substrate, wherein the required pulse number of each unit cell is 80, the substrate temperature is 700 ℃ and the oxygen pressure is 1 multiplied by 10 when preparing SAO film by using pulse laser deposition system-3mbar, pulse laser energy density of 1.3J/cm2The pulse laser frequency was 2 Hz.
(2) Preparing an LSMO thin film on the SAO thin film to obtain an SAO/LSMO heterostructure thin film, which comprises the following steps:
preparing LSMO single crystal thin film with the thickness of 80 unit cell layers on the SAO thin film, wherein the required pulse number of each unit cell thickness is 58, the substrate temperature in the step of depositing the LSMO thin film is 700 ℃, and the oxygen pressure is 1 multiplied by 10-1mbar, pulse laser energy density of 1.3J/cm2The frequency of the pulse laser is 2 Hz;
FIG. 1 is a surface topography of the SAO/LSMO heterostructure thin film prepared as described above, with inset reflection high energy electron diffraction patterns. As can be seen from fig. 1, the film has a good surface topography.
(3) And flatly sticking a Polyimide (PI) adhesive tape on the surface of the SAO/LSMO heterostructure film to prevent the LSMO film from cracking.
(4) And (4) immersing the heterostructure film obtained in the step (3) in deionized water for 30 minutes, hydrolyzing the SAO sacrificial layer, and then taking out by using tweezers to obtain the flexible self-supporting LSMO single crystal film shown in figure 2.
FIG. 3 is an X-ray diffraction pattern of the LSMO single crystal thin film of [001] crystal orientation before and after the flexibility of the LSMO single crystal thin film in example 1 of the present invention, namely, the LSMO single crystal thin film on the SAO sacrificial layer obtained in step (2) (referred to as "initial state") and the flexible self-supporting LSMO single crystal thin film obtained in step (4) (referred to as "self-supporting").
As can be seen from fig. 3, the LSMO film has good crystalline quality, and after the LSMO film is flexible, the lattice constant c becomes large and close to the bulk lattice constant, indicating that the stress from the substrate and the sacrificial layer is released.
The magnetic and electrical properties of the LSMO single crystal thin film on the SAO sacrificial layer prepared in step (2) and the flexible self-supporting LSMO single crystal thin film prepared in step (4) are tested by using a magnetic measurement system (MPMS) and a comprehensive physical property test system (PPMS), and as a result, as shown in fig. 4, 5, and 6, it can be seen from fig. 4, 5, and 6 that the properties of the "initial state" and the "self-supporting" LSMO single crystal thin film are not significantly changed and are both room-temperature ferromagnetic metallic, and simultaneously the curie temperature of the "self-supporting" LSMO single crystal thin film is increased due to stress release.
Example 2:
this example prepared a flexible self-supporting LSMO single crystal thin film of [110] crystal orientation in substantially the same manner as in example 1, except that:
(1) in this embodiment, a [110] crystal orientation STO substrate is selected as a substrate;
(2) in the step (1-2), the substrate temperature is kept at 850 ℃ for about 30 minutes under the atmosphere of 1mbar of oxygen pressure to obtain a substrate with better surface appearance;
(3) in step (2), the substrate temperature in the step of depositing the LSMO thin film was 600 ℃.
Fig. 7 is an X-ray diffraction pattern of the LSMO single crystal thin film of [110] crystal orientation in this example before and after the flexibility, and it can be seen from fig. 7 that the LSMO thin film has good crystalline quality, and after the flexibility of the LSMO thin film, the lattice constant c becomes large and close to the bulk lattice constant, indicating that the stress from the substrate and the sacrificial layer is released.
Fig. 8, 9 and 10 show the magnetic and electrical properties of the [110] crystal orientation LSMO single crystal thin film of the present embodiment before and after being flexible, which are measured by a magnetic measurement system (MPMS) and a comprehensive Physical Property Measurement System (PPMS), and it can be seen from fig. 8, 9 and 10 that the flexible LSMO thin film maintains good room temperature ferromagnetism, and the curie temperature of the thin film is increased due to stress release.
Example 3:
this example prepared a flexible self-supporting LSMO single crystal thin film of [111] crystal orientation in substantially the same manner as in example 1, except that:
(1) in this embodiment, a [111] crystal orientation STO substrate is selected as a substrate;
(2) in the step (1-2): keeping the temperature of the substrate at 850 ℃ for about 30 minutes under the atmosphere of 1mbar of oxygen gas pressure to obtain the substrate with better surface appearance;
(3) in step (2), the substrate temperature in the step of depositing the LSMO thin film was 600 ℃.
Fig. 11 is an X-ray diffraction pattern of the LSMO single crystal thin film of [111] crystal orientation in this example before and after the flexibility, and it can be seen from fig. 11 that the LSMO thin film has good crystalline quality, and after the flexibility of the LSMO thin film, the lattice constant c becomes large and close to the bulk lattice constant, which shows that the stress from the substrate and the sacrificial layer is released.
Fig. 12, 13, and 14 show the magnetic and electrical properties of the [111] crystal orientation LSMO single crystal thin film of the present embodiment before and after being flexible, which are obtained by using a magnetic measurement system (MPMS) and a comprehensive physical property testing system (PPMS), and it can be seen from fig. 12, 13, and 14 that the flexible LSMO thin film maintains good room temperature ferromagnetism, and the curie temperature of the thin film is increased due to stress release.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of flexible self-supporting perovskite oxide single crystal films with different crystal orientations is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing soluble substance films as sacrificial layers on substrates with different crystal directions, wherein the soluble substances are perovskite-like oxides or perovskite oxides;
(2) preparing a perovskite oxide single crystal film on the surface of the soluble substance film;
(3) and dissolving the sacrificial layer by using a solvent, and taking out the perovskite oxide single crystal film to obtain the flexible self-supporting perovskite oxide single crystal film with different crystal orientations.
2. The method of claim 1, wherein: the substrate material comprises SrTiO3、Nb-SrTiO3、LaAlO3、SrLaGaO4、SrLaAlO4、DyScO3、GdScO3、BaTiO3、LiNbO3One or more of MgO and PMN-PT.
3. The method of claim 1, wherein: the soluble substance comprises Sr3Al2O6、Ca1.5Sr1.5Al2O6、La0.67Sr0.33MnO3One or more of them.
4. The method of claim 1, wherein: the solvent comprises one of deionized water, potassium iodide and hydrochloric acid.
5. The process according to claim 1, whereinCharacterized in that: the perovskite oxide is La2/3Sr1/3MnO3The substrate material is SrTiO3The soluble substance is Sr3Al2O6。
6. The method of claim 1, wherein: the crystal orientation of the substrate comprises one of [100], [110] and [111 ].
7. The method of claim 1, wherein: in the step (1), firstly, the surface of a substrate is pretreated, and then a sacrificial layer is prepared on the substrate;
preferably, the pretreatment method comprises one or more of hydrofluoric acid corrosion, hydrochloric acid corrosion, helium ion bombardment and high-temperature annealing.
8. The method of claim 1, wherein: the preparation method of the sacrificial layer comprises one or more of pulsed laser deposition, magnetron sputtering and molecular beam epitaxy;
preferably, the preparation method of the perovskite oxide single crystal film comprises one or more of pulse laser deposition, magnetron sputtering and molecular beam epitaxy.
9. The method of claim 1, wherein: in the step (2), after the perovskite oxide single crystal thin film is prepared on the surface of the soluble substance thin film, a flexible substance is coated or pasted on the surface of the perovskite oxide single crystal thin film;
preferably, the flexible substance material comprises one or more of polyimide, cloth-based adhesive tape, polyethylene terephthalate, polydimethylsiloxane and polymethyl methacrylate.
10. The process according to any one of claims 1 to 9, characterized in that: the crystal orientation of the perovskite oxide single crystal thin film is controlled by controlling the crystal orientation of the substrate.
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Cited By (3)
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| CN114197035A (en) * | 2021-12-08 | 2022-03-18 | 电子科技大学长三角研究院(湖州) | Perovskite thin film and epitaxial preparation method thereof |
| CN115182034A (en) * | 2022-06-17 | 2022-10-14 | 北京科技大学 | Chemical method-based preparation of self-supporting BaTiO 3 Process for preparing single crystal thin film |
| WO2024103780A1 (en) * | 2022-11-18 | 2024-05-23 | 电子科技大学长三角研究院(湖州) | Self-standing perovskite oxide thin film, and preparation method therefor and use thereof |
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| CN103774227A (en) * | 2014-01-20 | 2014-05-07 | 华东师范大学 | Manganite epitaxial thin film and preparation method thereof |
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| CN103774227A (en) * | 2014-01-20 | 2014-05-07 | 华东师范大学 | Manganite epitaxial thin film and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114197035A (en) * | 2021-12-08 | 2022-03-18 | 电子科技大学长三角研究院(湖州) | Perovskite thin film and epitaxial preparation method thereof |
| CN115182034A (en) * | 2022-06-17 | 2022-10-14 | 北京科技大学 | Chemical method-based preparation of self-supporting BaTiO 3 Process for preparing single crystal thin film |
| WO2024103780A1 (en) * | 2022-11-18 | 2024-05-23 | 电子科技大学长三角研究院(湖州) | Self-standing perovskite oxide thin film, and preparation method therefor and use thereof |
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