CN113363376B - Magnetic controllable adjusting method for two-dimensional ferromagnetic material - Google Patents
Magnetic controllable adjusting method for two-dimensional ferromagnetic material Download PDFInfo
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Abstract
The invention relates to the field of two-dimensional magnetic materials, and discloses a controllable magnetic adjusting method of a two-dimensional ferromagnetic material, aiming at the defects of weak magnetism, poor repeatability and poor reversibility of the existing two-dimensional ferromagnetic material in a method for optimizing magnetism through ion grid regulation and the like, which comprises the steps of placing a two-dimensional ferromagnetic material sheet on a hard substrate; preparing a high-modulus polymer compact film coated with a two-dimensional ferromagnetic material; adhering a high-molecular flexible substrate on the surface of the high-molecular compact film, and then peeling the high-molecular flexible substrate together with the high-molecular compact film and the two-dimensional ferromagnetic material from the hard substrate to obtain a flexible substrate; and applying bending stress to the flexible substrate at the side of the polymer flexible substrate, and regulating the bending radius of the flexible substrate to continuously and controllably regulate the magnetism of the two-dimensional ferromagnetic material. The method can realize controllable, reversible and continuous magnetic adjustment of the two-dimensional ferromagnetic material, the magnetic strength of the two-dimensional ferromagnetic material is high, and the Curie temperature can be increased.
Description
Technical Field
The invention relates to the field of two-dimensional magnetic materials, in particular to a magnetic controllable adjusting method of a two-dimensional ferromagnetic material.
Background
The two-dimensional material is a layered or laminated-like material with electrons confined on a two-dimensional scale, has a plurality of unique physical and chemical properties, such as mechanical flexibility caused by ultrathin size, catalytic activity caused by large specific surface, energy band change induced by stacking mode and the like, is a popular direction for the research of functional materials at present, and has wide application prospect in the fields of photoelectricity, energy, information science and the like. In recent years, research on two-dimensional magnetic materials has been gradually developed, and the two-dimensional magnetic materials are expected to be applied to next-generation spintronics devices due to the two properties of spin and charge.
Scientists successively found in 2014 that two-dimensional chromium germanium tellurium and chromium iodide materials have intrinsic two-dimensional ferromagnetic characteristics, which is a major challenge to the classical magnetic theory, and the heat tide for the academic world to develop novel two-dimensional magnetic materials from an experimental point of view is triggered. Two-dimensional magnetism is generally introduced by means of magnetic doping, but is influenced by a magnetic second phase, so that the origin of magnetism is not revealed, and not only is the generated magnetism weak, but also the repeatability is poor.
Meanwhile, the intrinsic two-dimensional magnetic material has a low Curie temperature (usually far lower than room temperature), and the Curie temperature becomes lower due to the influence of factors such as thermal disturbance after being thinned to an atomic scale, so that the stability is worsened, and the room temperature application of the intrinsic two-dimensional magnetic material is restricted. The two-dimensional iron-germanium-tellurium material is a two-dimensional ferromagnetic material with the highest Curie temperature reported at present, the Curie temperature is up to 230 Kelvin, and the Curie temperature can be reduced to 130 Kelvin along with the reduction of the thickness of the material (the thickness is about 0.8 nanometer corresponding to the case of a single layer). Meanwhile, the magnetic characteristics of the thin-layer iron-germanium-tellurium material are optimized mainly by methods such as ion gate regulation, heterojunction epitaxy, exchange bias, ion beam focusing, non-stoichiometric ratio regulation and the like, but the repeatability, reversibility and enhanced level of magnetic regulation are in urgent need of improvement.
Disclosure of Invention
Aiming at the defects of weak magnetism, poor repeatability and poor reversibility of the conventional method for optimizing the magnetism of a two-dimensional ferromagnetic material through ion grid regulation and the like, the invention aims to provide a controllable magnetic regulation method of the two-dimensional ferromagnetic material so as to realize controllable, reversible and continuous magnetic regulation of the two-dimensional ferromagnetic material, and the two-dimensional ferromagnetic material has high magnetic strength.
The invention provides the following technical scheme:
a magnetically controllable tuning method of a two-dimensional ferromagnetic material, comprising the steps of:
(1) Placing a two-dimensional ferromagnetic material sheet on a hard substrate;
(2) Coating a high molecular polymer solution on a hard substrate dispersed with two-dimensional ferromagnetic material sheets, and then drying and dehydrating to form a high-modulus high molecular compact film coated with the two-dimensional ferromagnetic material;
(3) Adhering a high-molecular flexible substrate on the surface of the high-molecular compact film, and then peeling the high-molecular flexible substrate together with the high-molecular compact film and the two-dimensional ferromagnetic material from the hard substrate to obtain a flexible substrate;
(4) And applying bending stress to the flexible substrate at the side of the polymer flexible substrate, and regulating the bending radius of the flexible substrate to continuously and controllably regulate the magnetism of the two-dimensional ferromagnetic material.
The current research shows that the two-dimensional material can resist the strain of about 10 percent, but the performance control of the two-dimensional ferromagnetic material by directly applying the strain on the two-dimensional ferromagnetic material sheet is very difficult, and particularly, the effective application and transmission of the stress can be realized under the atomic thickness limit. Meanwhile, research on regulation and control of the magnetic property of the two-dimensional ferromagnetic material through strain application research is very few, and research on optimization of the magnetism by carrying out strain on the two-dimensional magnetic material is urgently needed. The utility model provides a technical scheme encapsulates two-dimensional ferromagnetic material in the fine and close membrane of polymer, and the adhesion is in order to increase thickness on the flexible substrate of polymer, through applying mechanical stress to whole flexible base plate in can effectually transmitting the crystal lattice of two-dimensional ferromagnetic material, avoided producing relative slip and decoupling zero between the fine and close membrane of two-dimensional ferromagnetic material and polymer simultaneously, realize the continuous controllable regulation of magnetism to two-dimensional ferromagnetic material through the continuous regulation and control that corresponds the grow, and the curie temperature of two-dimensional ferromagnetic material also can obtain obvious promotion, very effectual application prospect who expands two-dimensional ferromagnetic material. The whole method is simple and easy to operate, the defects of single effect, poor controllability and complex doping mode of the current carrier doping regulation and control method are overcome, the problem of slippage and decoupling caused by stress application in the traditional mode is solved, and the concept of the whole technical scheme is ingenious.
Preferably, the two-dimensional ferromagnetic material flakes are two-dimensional iron-germanium-tellurium flakes; the thickness of the two-dimensional ferromagnetic material sheet is less than or equal to 30nm, and the transverse size of the two-dimensional ferromagnetic material sheet is less than or equal to 20 mu m. The two-dimensional ferromagnetic material slice can be obtained by mechanical stripping, liquid phase stripping and the like, and is efficiently transferred to any flexible substrate, so the method is not limited to the application of the two-dimensional iron-germanium-tellurium slice.
Preferably, the hard substrate is a silicon wafer provided with a silicon oxide layer; the thickness of the silicon oxide layer is 100 to 300nm.
Preferably, the molecular weight of the high molecular weight polymer is 80000 to 150000g/mol.
Preferably, the concentration of the high molecular polymer solution is 5 to 20 percent; the high molecular polymer is polyvinyl alcohol.
The film formed by the material has higher Young modulus which can reach the GPa grade and is equivalent to the Young modulus of two-dimensional iron germanium tellurium, and is beneficial to the transmission of mechanical stress.
The preferable method of the invention is that the coating is spin coating, the spin coating speed is 500 to 2000rpm, and the spin coating time is 30 to 60 s; the drying temperature is 60 to 80 ℃, and the drying time is 1 to 5min. The two-dimensional iron germanium tellurium slice is coated in the high polymer material by a spin coating method, so that a strong bonding force can be formed between the high polymer material and the two-dimensional iron germanium tellurium slice, thereby avoiding relative slippage between the slice and the high polymer substrate and improving the stress transfer efficiency.
Preferably, the thickness of the polymer dense film is 50 to 100 μm. The two-dimensional ferromagnetic material sheet is encapsulated in the polymer film, which is beneficial to enhancing the stability of the two-dimensional sheet.
Preferably, the thickness of the polymer flexible substrate is 100 to 150 mu m; the polymer flexible substrate is a PET substrate; the thickness of the flexible substrate is less than or equal to 300 mu m.
As a preferred method of the present invention, a bending stress is applied to the flexible substrate by a three-point bending method. The stress application method is simple and feasible, and the bending stress can be applied by a four-point bending method.
Preferably, the strain range of the flexible substrate is 7% or less. The strain imposed on the flexible substrate can be determined by the equationɛ= τ/RIs calculated, wherein 2τIs the thickness of the flexible substrate,Rthe radius of curvature of the flexible substrate, the thickness of the flexible substrate and the radius of curvature of the flexible substrate are all passed through by lightThe microscope is used for accurate measurement.
The invention has the following beneficial effects:
firstly, compared with the existing magnetic adjusting method, the method realizes the aim of continuously, reversibly and repeatedly adjusting the magnetism of the two-dimensional ferromagnetic material through continuously changing the stress, and has high magnetic strength. Secondly, the method can realize the continuous magnetic regulation and control of various two-dimensional magnetic materials including two-dimensional iron, germanium and tellurium materials, and has the advantages of simple method, simple and convenient operation and ingenious conception. And thirdly, the aim of increasing the Curie temperature of the two-dimensional ferromagnetic material is fulfilled, and the Curie temperature can be increased to be higher than the room temperature by taking the two-dimensional iron-germanium-tellurium material as an example, so that the requirements of the research on the next-generation flexible spintronics device are met.
Drawings
FIG. 1 is a schematic diagram of the preparation of a two-dimensional Fe-Ge-Te sheet/PVA/PET composite flexible substrate of the invention.
FIG. 2 is a schematic illustration of the three point bending process applied stress of the present invention.
Fig. 3 shows the hysteresis loop (a) and magnetization-temperature curve (b) of the two-dimensional fe-ge-te sheet prepared in example 1 after 6.8% strain is applied to the two-dimensional fe-ge-te sheet and the original two-dimensional fe-ge-te sheet at 300K.
Fig. 4 shows the hysteresis loop (a) and magnetization-temperature curve (b) at 300K of the two-dimensional fe-ge-te sheet prepared in example 2 and example 5 after applying 5% strain to the flexible substrate.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art unless otherwise specified, and the methods in the following examples are conventional in the art unless otherwise specified.
In the following examples, two-dimensional fe-ge-te flakes are exemplified.
Example 1
A method for magnetically controllable tuning of a two-dimensional ferromagnetic material, comprising the steps of:
(1) By usingSpecial adhesive tape for mechanical stripping, namely blue film pair Fe-Ge-Te-Fe 3 GeTe 2 Peeling the single crystal, transferring the peeled two-dimensional iron-germanium-tellurium slice to a cleaned silicon chip coated with a silicon oxide layer, and arranging the silicon oxide layer on the silicon oxide layer, wherein the thickness of the silicon oxide layer is 300nm; the thickness of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 30nm, and the transverse size of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 20 mu m;
(2) Mixing PVA with the molecular weight of 130000g/mol and deionized water according to the mass ratio of 1:9, stirring and heating to 60 ℃ to obtain PVA water solution; placing the silicon wafer on a spin coater, and dripping a PVA solution on the two-dimensional iron germanium tellurium thin sheet for spin coating to form a film, wherein the rotation speed of the spin coater is 1000rpm, the rotation time is 40s, and the silicon wafer is placed in a vacuum drying oven for drying at 70 ℃ for 1min to form a compact PVA thin film coated with the two-dimensional iron germanium tellurium thin sheet, and the thickness of the compact PVA thin film is 70 mu m;
(3) Adhering a PET substrate on the compact PVA film by using glue, wherein the thickness of the PET substrate is 125 mu m, and the thickness of the glue is about 15 mu m, as shown in figure 1 (a); slowly peeling off the PET substrate from the substrate by using non-magnetic tweezers, and driving the two-dimensional iron, germanium and tellurium sheets to be separated from the silicon oxide wafer in the process, as shown in figure 1 (b), so as to obtain a flexible substrate, wherein the thickness of the flexible substrate is less than or equal to 300 mu m; (4) As shown in fig. 2, a three-point method is adopted to apply bending stress to the flexible substrate on the PET substrate side, so that the flexible substrate is bent to generate 6.8% strain, thereby realizing the adjustment of the magnetism of the two-dimensional iron-germanium-tellurium sheet.
Example 2
A method for magnetically controlling a two-dimensional ferromagnetic material, which is different from example 1 in that a flexible substrate is subjected to a strain of 5% by a three-point bending method in step (4).
Example 3
A magnetically controllable tuning method of a two-dimensional ferromagnetic material, comprising the steps of:
(1) Stripping the iron germanium tellurium monocrystal by using a mechanical stripping special adhesive tape, namely a blue film, transferring a stripped two-dimensional iron germanium tellurium slice to a cleaned silicon chip coated with a silicon oxide layer, and arranging the silicon oxide layer on the silicon oxide layer, wherein the thickness of the silicon oxide layer is 100nm; the thickness of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 30nm, and the transverse size of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 20 mu m;
(2) Mixing PVA with the molecular weight of 80000g/mol and deionized water according to the mass ratio of 2:8, stirring and heating to 60 ℃ to obtain a PVA aqueous solution; placing the silicon wafer on a spin coater, and dropwise coating a PVA solution on the two-dimensional iron germanium tellurium thin sheet for spin coating to form a film, wherein the rotation speed of the spin coater is 2000rpm, the rotation time is 30s, and the silicon wafer is placed in a vacuum drying oven for drying at 80 ℃ for 1min to form a compact PVA thin film coated with the two-dimensional iron germanium tellurium thin sheet, and the thickness of the compact PVA thin film is 50 mu m;
(3) Adhering a PET substrate on the compact PVA film by using glue, wherein the thickness of the PET substrate is 100 mu m, and the thickness of the glue is about 15 mu m; slowly peeling off the PET substrate from the substrate by using non-magnetic tweezers, and driving the two-dimensional iron, germanium and tellurium sheets to be separated from the silicon oxide wafer in the process, so that a flexible substrate is obtained, wherein the thickness of the flexible substrate is less than or equal to 300 mu m;
(4) And applying bending stress to the flexible substrate on the PET substrate side by adopting a three-point method to enable the flexible substrate to bend and generate 3% strain, thereby realizing the adjustment of the magnetism of the two-dimensional iron-germanium-tellurium slice.
Example 4
A magnetically controllable tuning method of a two-dimensional ferromagnetic material, comprising the steps of:
(1) Stripping the iron germanium tellurium monocrystal by using a mechanical stripping special adhesive tape, namely a blue film, transferring a stripped two-dimensional iron germanium tellurium slice to a cleaned silicon chip coated with a silicon oxide layer, and arranging the silicon oxide layer on the silicon oxide layer, wherein the thickness of the silicon oxide layer is 200nm; the thickness of the two-dimensional iron, germanium and tellurium slice is less than or equal to 30nm, and the transverse size is less than or equal to 20 mu m;
(2) Mixing PVA with the molecular weight of 150000g/mol and deionized water according to the mass ratio of 0.5; placing the silicon wafer on a spin coater, and dropwise coating a PVA solution on the two-dimensional iron germanium tellurium thin sheet for spin coating to form a film, wherein the rotation speed of the spin coater is 500rpm, the rotation time is 60s, and the silicon wafer is placed in a vacuum drying oven for drying at 60 ℃ for 5min to form a compact PVA thin film coated with the two-dimensional iron germanium tellurium thin sheet, and the thickness of the compact PVA thin film is 100 mu m;
(3) Adhering a PET substrate to the compact PVA film by using glue, wherein the thickness of the PET substrate is 150 mu m, and the thickness of the glue is about 15 mu m; slowly peeling off the PET substrate from the substrate by using non-magnetic tweezers, and driving the two-dimensional iron, germanium and tellurium sheets to be separated from the silicon oxide wafer in the process, so that a flexible substrate is obtained, wherein the thickness of the flexible substrate is less than or equal to 300 mu m;
(4) Bending stress is applied to the flexible substrate on the side of the PET substrate by adopting a three-point method, and the flexible substrate is bent to generate 7% strain, so that the magnetism of the two-dimensional iron-germanium-tellurium slice is adjusted.
Example 5
A method for magnetically controllable tuning of a two-dimensional ferromagnetic material, comprising the steps of:
(1) Stripping the iron germanium tellurium monocrystal by using a mechanical stripping special adhesive tape, namely a blue film, transferring a stripped two-dimensional iron germanium tellurium slice to a cleaned silicon chip coated with a silicon oxide layer, and arranging the silicon oxide layer on the silicon oxide layer, wherein the thickness of the silicon oxide layer is 300nm; the thickness of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 30nm, and the transverse size of the two-dimensional iron, germanium and tellurium sheets is less than or equal to 20 mu m;
(2) Mixing a main agent and a curing agent according to a mass ratio of 10 to 1 to prepare a polydimethylsiloxane PDMS precursor solution, wherein the solution is a mixed solution with medium viscosity, and the PDMS is Dow Corning 184PDMS; then, the silicon wafer is placed on a spin coater, a PDMS precursor solution is dropwise coated on the two-dimensional iron germanium tellurium sheet for spin coating film formation, wherein the rotation speed of the spin coater is 1000rpm, the rotation time is 40s, and the silicon wafer is placed in a vacuum drying oven for drying at 70 ℃ for 5min to form a compact PDMS film coated with the two-dimensional iron germanium tellurium sheet, and the thickness of the PDMS film is 70 mu m;
(3) Adhering a PET substrate to the compact PDMS film by using glue, wherein the thickness of the PET substrate is 125 mu m, and the thickness of the glue is about 15 mu m; slowly peeling off the PET substrate from the substrate by using non-magnetic tweezers, and driving the two-dimensional iron, germanium and tellurium slices to be separated from the silicon oxide wafer in the process, so that a flexible substrate is obtained, wherein the thickness of the flexible substrate is less than or equal to 300 mu m;
(4) Bending stress is applied to the flexible substrate on the side of the PET substrate by adopting a three-point method, so that the flexible substrate is bent to generate 5% strain, and the magnetism of the two-dimensional iron-germanium-tellurium slice is adjusted.
Testing magnetic strength and Curie temperature change of regulated two-dimensional iron-germanium-tellurium thin sheet
1. Example 1 the two-dimensional fe-ge-te sheet after 6.8% strain and the original two-dimensional fe-ge-te sheet obtained in step (1) have the hysteresis lines and magnetic strength-temperature curves at 300K shown in fig. 3 (a) and 3 (b).
As can be seen from FIG. 3, the regulation and control method provided by the invention can significantly improve the magnetic performance of the two-dimensional Fe-Ge-Te thin slice at room temperature, realize controllable, continuous and repeated regulation of the magnetism of the two-dimensional Fe-Ge-Te thin slice, and significantly improve the Curie temperature of the two-dimensional Fe-Ge-Te thin slice, wherein the Curie temperature is higher than the room temperature.
2. The magnetic hysteresis lines and the magnetic strength-temperature curves at 300K of the two-dimensional iron-germanium-tellurium sheets after 5% strain of example 2 and example 5 are shown in fig. 4 (a) and fig. 4 (b).
It can be seen from the figure that the transfer efficiency of the stress is significantly higher when spin coating is performed with the aqueous solution of PVA than when PDMS is used. The reason is that the Young modulus of a compact film formed by selecting PVA is high, can reach a GPa level, is equivalent to that of two-dimensional iron germanium tellurium, and is beneficial to the transmission of mechanical stress, and the Young modulus of PDMS is in a megapascal (MPa) level, so that the stress transmission effect is poor.
Claims (10)
1. A method for the magnetically controllable adjustment of a two-dimensional ferromagnetic material, comprising the steps of:
(1) Placing a two-dimensional ferromagnetic material sheet on a hard substrate;
(2) Coating a high molecular polymer solution on a hard substrate dispersed with two-dimensional ferromagnetic material sheets, and then drying and dehydrating to form a high-modulus high molecular compact film coated with the two-dimensional ferromagnetic material;
(3) Adhering a high-molecular flexible substrate on the surface of the high-molecular compact film, and then peeling the high-molecular flexible substrate together with the high-molecular compact film and the two-dimensional ferromagnetic material from the hard substrate to obtain a flexible substrate;
(4) Applying bending stress to the flexible substrate at the side of the polymer flexible substrate, and regulating the bending radius of the flexible substrate to continuously and controllably regulate the magnetism of the two-dimensional ferromagnetic material;
the high molecular polymer is polyvinyl alcohol;
the coating is spin coating, the spin coating speed is 500 to 2000rpm, and the spin coating time is 30 to 60 s.
2. A method for magnetically controllable tuning of a two-dimensional ferromagnetic material as claimed in claim 1, wherein said two-dimensional ferromagnetic material flakes are two-dimensional iron germanium tellurium flakes; the thickness of the two-dimensional ferromagnetic material sheet is less than or equal to 30nm, and the transverse size of the two-dimensional ferromagnetic material sheet is less than or equal to 20 mu m.
3. The method for controllably adjusting the magnetism of a two-dimensional ferromagnetic material according to claim 1, wherein the hard substrate is a silicon wafer provided with a silicon oxide layer; the thickness of the silicon oxide layer is 100 to 300nm.
4. The magnetically controllable adjusting method of a two-dimensional ferromagnetic material according to claim 1, wherein the molecular weight of the high molecular polymer is 80000-150000 g/mol.
5. The controllable magnetic adjustment method for the two-dimensional ferromagnetic material according to claim 1 or 4, wherein the concentration of the high molecular polymer solution is 5-20%.
6. The controllable magnetic adjustment method for the two-dimensional ferromagnetic material according to claim 1, wherein the drying temperature is 60 to 80 ℃ and the drying time is 1 to 5min.
7. The controllable magnetic adjustment method for the two-dimensional ferromagnetic material according to claim 1 or 6, wherein the thickness of the polymer dense film is 50 to 100 μm.
8. The controllable magnetic adjustment method for the two-dimensional ferromagnetic material according to claim 1, wherein the thickness of the polymer flexible substrate is 100 to 150 μm; the polymer flexible substrate is a PET substrate; the thickness of the flexible substrate is less than or equal to 300 mu m.
9. A method for magnetically controllable tuning of a two-dimensional ferrimagnetic material according to claim 1, wherein the flexible substrate is subjected to a bending stress by a three-point bending method.
10. A method for magnetically controllable tuning of a two-dimensional ferromagnetic material as in claim 1 or 9, wherein the flexible substrate has a strain in the range of 7% or less.
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