CN110904417B - Flexible epitaxial Fe with stress-regulated magnetization intensity4N film and preparation method - Google Patents

Flexible epitaxial Fe with stress-regulated magnetization intensity4N film and preparation method Download PDF

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CN110904417B
CN110904417B CN201911126079.1A CN201911126079A CN110904417B CN 110904417 B CN110904417 B CN 110904417B CN 201911126079 A CN201911126079 A CN 201911126079A CN 110904417 B CN110904417 B CN 110904417B
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mica
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米文博
史晓慧
王立英
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0005—Separation of the coating from the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides

Abstract

The invention relates to a flexible epitaxial Fe with stress controlled magnetization intensity4N film and preparation method; the substrate is mica substrate with thickness of 40-60 μm, area of 4mm × 4mm, and Fe4The thickness of the N thin film is 3-48 nm. From the industrial production angle and the practical application angle, the invention adopts the opposite target reaction magnetron sputtering method to prepare the flexible epitaxial Fe with the film tightly combined with the substrate and good process repeatability by using the opposite target magnetron sputtering method4N film; when the sputtering current is 0.05-0.10A, the sputtering voltage is 750-850V, the sputtering pressure is 0.5-1.0Pa, and the substrate temperature is 400-500 ℃, the prepared flexible epitaxial Fe4The N film regulates and controls the magnetization intensity through the stress generated by bending, the relative change of the maximum magnetization intensity reaches 120 percent, and the N film has important application value on a flexible spin electronic device.

Description

Flexible epitaxial Fe with stress-regulated magnetization intensity4N film and preparation method
Technical Field
The invention relates to flexible epitaxial Fe with stress regulation and control4N film and a preparation method. More specifically, it is a flexible epitaxial Fe which can generate stress by bending and regulate and control magnetism by stress4N film and a preparation method thereof.
Background
With the application of wearable electronic devices in flexible circuit boards, solar cells and display devices, flexible electronic devices with the advantages of crimpability, portability and the like are widely concerned by people and become research hotspots in the fields of material science, condensed physical science, microelectronic science and the like. In flexible electronics, people have paid more attention to high-speed electronics and optoelectronic devices in the early days, and recently, magnetic functional characteristics are considered, namely, magnetic materials and devices are applied to flexible electronics, so that a new research field, namely flexible spintronics, is formed. Flexible spintronics devices require ferromagnetic electrode materials with high spin polarizability.
Cubic anti-perovskite Fe4N has the advantages of simple structure, easy preparation, corrosion resistance, oxidation resistance, good thermal stability, high saturation magnetization, high Curie temperature and the like, so that the N has wide application prospect in the spintronics device.
At present, there is no flexible Fe in the world4Preparation of N film and research of stress regulation and control magnetism. Ferromagnetic thin films prepared in flexible magnetic thin films and heterostructures are mostly polycrystalline or amorphous thin films [ APPLIED PHYSICS LETTERS 100,122407, 122407 (2012); APPLIED PHYSICS LETTERS 105,103504, 103504 (2014); ACS APPLIED MATERIALS&INTERFACES 10,42698-42705(2018)]And the research on the epitaxial ferromagnetic films is few, and the relative change of the magnetization intensity of stress regulation is small. In flexible spintronics devices, more flexible ferromagnetic films with stress-controlled magnetization change are needed. In addition, in the stress-controlled flexible spintronics device, a ferromagnetic thin film material is mainly used, and a sputtering method is mostly adopted in the preparation method.
Disclosure of Invention
From the perspective of industrial production and practical application, a low-cost magnetron sputtering method is needed to prepare a ferromagnetic thin film sample; the sample to be prepared has an epitaxial structure; and the relative change in magnetization for stress regulation is large. The invention prepares epitaxial Fe on a flexible mica substrate by adopting an opposite target reaction magnetron sputtering method through a large amount of experimental researches4The magnetization intensity of the N flexible thin film is regulated and controlled through stress generated by bending, the maximum relative change of the magnetization intensity reaches 120%, and the N flexible thin film has important application value on flexible spin electronics.
The technical scheme of the invention is as follows:
flexible epitaxial Fe with stress-regulated magnetization intensity4N film; the film is of an epitaxial Fe 4N/mica structure, Fe4The thickness of the N film is 3-18nm, and the thickness of the mica is 40-60 μm.
The invention relates to stress-controlled magnetization intensity flexible epitaxial Fe4The preparation method of the N film comprises the following steps:
1) adopting a vacuum opposite-target magnetron sputtering coating machine, wherein the substrate material is a mica sheet; two Fe targets with the purity of 99.99 percent are used and are arranged on a target pair head, wherein one end is used as the N pole of a magnetic line, and the other end is used as the S pole; the thickness of the target material is 3mm, and the diameter is 60 mm; the distance between the two targets is 60-90mm, and the distance between the axis of the targets and the substrate frame containing the mica substrate material is 60-90 mm;
2) fixing four corners of a mica sheet on a substrate frame by adopting silver glue, enabling the mica sheet to be tightly attached to the substrate frame, placing the mica sheet behind a baffle plate, and closing a vacuum chamber;
3) starting a vacuum system of the ultrahigh vacuum facing target magnetron sputtering film coating machine, vacuumizing until the back vacuum degree of the sputtering chamber is more than or equal to 2 multiplied by 10–5Pa；
4) Simultaneously introducing Ar gas of sputtering gas with the purity of 99.999 percent and reaction gas N into the vacuum chamber2Gas, Ar gas and N2The flow ratio of gas is 5: 1-4: 1, keeping the vacuum degree at 0.5-1.0 Pa;
5) uniformly heating the substrate to 400-500 ℃, wherein the heating rate is 10 ℃/min;
6) starting a sputtering power supply, applying 0.30-0.50A of current and 1000-1200V of direct current voltage on a pair of Fe targets, pre-sputtering for 5 minutes, and waiting for the sputtering current and voltage to be stable;
7) applying a current of 0.05-0.10A and a DC voltage of 750-850V to a pair of Fe targets, opening the baffle plate on the substrate holder to start sputtering, and reactively sputtering Fe4In the N film process, the position of the mica sheet is fixed;
8) sputtering to Fe4The thickness of the N film is 3-18 nm; closing the baffle plate on the substrate holder, then closing the sputtering power supply, and stopping introducing Ar gas and N2Completely opening a gate valve, continuously vacuumizing, and uniformly cooling the substrate to room temperature at a cooling rate of 2 ℃/min by using a temperature control system;
10) the vacuum system was turned off, the vacuum chamber was opened and the prepared epitaxial Fe grown on a 180 μm thick mica substrate was removed4N film;
11) epitaxial Fe grown on a 180 μm thick mica substrate4Film of N in sulfuric acidCutting the paper with scalpel in the direction parallel to mica surface, and tearing with forceps to obtain Fe growing on 40-60 μm thick mica substrate4N film; thereby obtaining flexible Fe4And N epitaxial thin film.
The concrete description is as follows:
(1) the invention designs flexible epitaxial Fe with stress-regulated magnetization intensity4And (6) N thin films. Fe4N is an N atom inserted into the body center position of the face-centered cubic Fe, so that the crystal lattice of the face-centered cubic Fe expands to cause ferromagnetic interaction, and the non-ferromagnetic face-centered cubic Fe is converted into ferromagnetism. Thus, Fe4Both expansion and compression of the N lattice can affect its magnetic properties. High spin polarization Fe under applied stress4The lattice of N is distorted, resulting in a change in the interaction, further affecting its magnetic properties. Further, Fe4N has good lattice match with Mica (Mica), and can form epitaxial Fe4N flexible film, influencing Fe by stress generated by bending4And the magnetization intensity of the N flexible thin film is realized, so that the regulation and control of the stress on the magnetism are realized.
(2) The invention adopts an opposite target reaction magnetron sputtering method, takes a pure Fe target as a raw material, introduces mixed gas of argon and oxygen in the sputtering process, and prepares epitaxial Fe on a thick mica substrate with the thickness of 180 mu m by changing sputtering current, sputtering voltage, sputtering pressure, sputtering temperature and cooling time in the sputtering process4N film, and obtaining epitaxial flexible Fe by mechanical stripping method4N film, Fe prepared4The thickness of the N film is 3-18nm, and the thickness of the stripped substrate is 40-60 μm.
(3) The invention finds that the vacuum degree of the back bottom is lower than 2 multiplied by 10–5Pa, the sputtering current is 0.05-0.10A, the sputtering voltage is 750-850V, the sputtering pressure is 0.5-1.0Pa, the substrate temperature is 400-500 ℃, and the flow ratio of argon to nitrogen is 5: 1-4: 1, the temperature rising rate is 10 ℃/min, the temperature reduction rate is 2 ℃/min, and the flexible Fe can be prepared under the conditions that the deposition rate of the film is 1.8-2.6nm/min4And N epitaxial thin film.
(4) The invention is used for preparing the gamma' -Fe4When the film is subjected to N epitaxy, the substrate is a mica sheet,the thickness is 180 μm, and the area is 4mm × 4 mm; obtaining a substrate thickness of 40-60 μm by peeling, Fe4And N is a flexible film with the thickness of 3-18 nm. Stress is applied through bending, tensile stress and compressive stress can be generated respectively, and the bending radius is 2 mm, 3mm and 5 mm; the direction of the applied magnetic field is parallel to the film face, along the axial direction of the curved face. The maximum relative change of the magnetization intensity of the flexible ferromagnetic film can reach 35 to 120 percent at room temperature under the magnetic field of 4000 Oe.
Flexible Fe according to the invention4The N epitaxial film has application value in flexible spintronics devices, for example, the N epitaxial film can be used as a storage unit of a flexible memory and an electrode of a logic device, the magnetron sputtering method adopted by the invention is a common method for producing film materials industrially, and the used Fe target has the advantages of simple target material selection, high target material utilization rate and the like.
To confirm the best embodiment of the invention, we prepared the flexible Fe of the invention4The N epitaxial film is subjected to X-ray diffraction, high-resolution transmission electron microscope characterization and stress control magnetism measurement.
Flexible Fe prepared from the present invention4On the X-ray diffraction pattern of the N-epitaxial film, it can be seen by comparing the uncoated mica substrate with the Fe-coated mica substrate4X-ray diffraction pattern of N film sample, Fe4The N film only presents a cubic anti-perovskite structure Fe4The diffraction peak of the (002) crystal face of N indicates Fe4N film edge [002]Directionally oriented growth, as shown in FIG. 1.
Flexible Fe prepared from the present invention4It can be seen from the pole figure of the N epitaxial thin film that only Fe4N appears<111>Diffraction peaks of the lattice plane family indicating Fe4The N film is an epitaxial film as shown in fig. 2.
Flexible Fe prepared from the present invention4It can be seen from the transmission electron microscope image of the N epitaxial film and the Fourier transform of the selected area that the film only grows along one crystal direction, further showing that Fe4The N film is an epitaxial film as shown in fig. 3.
The invention measures the flexibility of 18nm thickness under different bending radiiFe (Fe) property4The magnetization intensity of the N epitaxial film is changed along with the external magnetic field, and the direction of the magnetic field is parallel to the axial direction of the bending surface and the surface of the film. From the measurement results, it can be seen that the flexible Fe is 18nm thick4When the N epitaxial thin film was bent at a radius of 3mm, the magnetization of the sample was 135% of that of the unbent sample, and the relative change was 35%, as shown in fig. 4.
The invention measures the 3 nm-thick flexible Fe under different bending radii4The magnetization intensity of the N epitaxial film is changed along with the external magnetic field, and the direction of the magnetic field is parallel to the axial direction of the bending surface and the surface of the film. From the measurement results, it can be seen that the flexible Fe is 3nm thick4When the bending radius of the N-epitaxial thin film was 3mm, the magnetization of the sample was 220% of that of the unbent sample, and the relative change was 120%, as shown in fig. 5.
The invention measures the flexible Fe with the thickness of 6nm under different bending radii4The magnetization intensity of the N epitaxial film is changed along with the external magnetic field, and the direction of the magnetic field is parallel to the axial direction of the bending surface and the surface of the film. As can be seen from the measurement results, flexible Fe of 6nm thickness4When the N epitaxial thin film was bent at a radius of 3mm, the magnetization of the sample was 150% of that of the unbent sample, and the relative change was 50%, as shown in fig. 6.
Compared with the method for preparing the flexible ferromagnetic film by other methods, the method for preparing the ferromagnetic Fe film by the invention4The N film is epitaxially grown, and the stress can regulate and control flexible epitaxial Fe4The magnetization intensity of the N film is simple and practical, and the method is favorable for popularization in industrial production. The method comprises the following specific steps:
1) although flexible ferromagnetic films are reported internationally, most of the prepared ferromagnetic films are polycrystalline or amorphous, so that the stress of the ferromagnetic films has small regulation on the magnetization of a sample, which limits the practical application of the ferromagnetic films.
2) In the flexible ferromagnetic thin film prepared internationally at present, the relative change of the stress control magnetization intensity reaches up to 30 percent. The flexible epitaxy Fe prepared by the method4N filmThe relative change of the stress control magnetization reaches 35-120 percent;
3) because the main method adopted by the current industrial production is a sputtering method, the magnetron sputtering method adopted by the invention has obvious advantages in the industrial production compared with a molecular beam epitaxy method and a chemical method.
Drawings
FIG. 1 shows a flexible Fe prepared in the present invention4The X-ray diffraction pattern of the N epitaxial film comprises an uncoated mica substrate and Fe grown on the mica substrate4X-ray diffraction patterns of two samples of N thin films.
FIG. 2 shows a flexible Fe prepared in the present invention4Pole figure of N epitaxial thin film.
FIG. 3 shows a flexible Fe prepared in the present invention4Transmission electron microscope images of the N-epitaxial films and fourier transforms of the corresponding selected regions.
FIG. 4 shows the 18nm thick flexible Fe prepared in the present invention4The magnetization intensity of the N epitaxial film under different bending radii is in a change relation with a magnetic field. Wherein, Fe4The N epitaxial thin film is arranged on the outer surface of the bent sample.
FIG. 5 shows the 3nm thick flexible Fe prepared in the present invention4The magnetization intensity of the N epitaxial film under different bending radii is in a change relation with a magnetic field. Wherein, Fe4The N epitaxial thin film is arranged on the outer surface of the bent sample.
FIG. 6 shows a 6nm thick flexible Fe prepared in the present invention4The magnetization intensity of the N epitaxial film under different bending radii is in a change relation with a magnetic field. Wherein, Fe4The N epitaxial thin film is arranged on the outer surface of the bent sample.
Detailed Description
According to the results of our structural and property analyses on the samples prepared in the present invention, the following method will prepare flexible epitaxial Fe by the opposite-target reactive magnetron sputtering method4The best mode of the N film will be described in detail:
embodiment mode 1
1) The ultrahigh vacuum facing target magnetron sputtering film coating machine produced by Shenyang scientific instrument development center of Chinese academy of sciences is adopted, and the substrate material is a mica sheet with the thickness of 180 mu m. Two Fe targets with the purity of 99.99 percent are used and are arranged on a target pair head, wherein one end is used as the N pole of a magnetic line, and the other end is used as the S pole; the thickness of the target material is 3mm, and the diameter is 60 mm; the distance between the two targets is 90mm, and the distance between the axis of the targets and the substrate holder containing the mica substrate material is 60 mm;
2) firstly, placing mica sheets on a substrate frame, fixing four corners of the silver colloid mica sheets on the substrate frame to enable the mica sheets to be tightly attached to the substrate frame, preventing the substrate from being heated unevenly in the heating process, placing the mica sheets behind a baffle, and closing a vacuum chamber;
3) starting a vacuum system of the ultrahigh vacuum facing target magnetron sputtering film plating machine, vacuumizing until the back vacuum degree of the sputtering chamber is better than 2 multiplied by 10–5Pa；
4) Simultaneously introducing Ar gas of sputtering gas with the purity of 99.999 percent and reaction gas N into the vacuum chamber2Gas, Ar gas and N2The flow ratio of gas is 4: 1, keeping the vacuum degree at 1.0 Pa;
5) uniformly heating the substrate to 500 ℃, wherein the heating rate is 10 ℃/min;
6) starting a sputtering power supply, applying 0.50A current and 1200V direct current voltage on a pair of Fe targets, pre-sputtering for 5 minutes, and waiting for the sputtering current and voltage to be stable;
7) applying a current of 0.10A and a DC voltage of 850V to a pair of Fe targets, opening the shutter on the substrate holder to start sputtering, and reactively sputtering Fe4In the N film process, the position of the mica sheet is fixed;
8) control of Fe by varying sputter time4The thickness of the N thin film is 18 nm;
9) after sputtering is finished, the baffle plate on the substrate frame is closed, then the sputtering power supply is closed, and the introduction of Ar gas and N is stopped2Completely opening a gate valve, continuously vacuumizing, and uniformly cooling the substrate to room temperature at a cooling rate of 2 ℃/min by using a temperature control system;
10) the vacuum system was turned off, the vacuum chamber was opened and the prepared epitaxial Fe grown on a 180 μm thick mica substrate was removed4N film;
11) epitaxial Fe grown on a 180 μm thick mica substrate4Cutting N film on parchment paper along the direction parallel to mica surface with scalpel, and tearing with tweezers to obtain Fe grown on 60 μm thick mica substrate4And (6) N thin films. Thereby obtaining flexible Fe4And N epitaxial thin film.
Prepared flexible Fe4The X-ray diffraction pattern of the N-epitaxial film is shown in FIG. 1 by comparing an uncoated mica substrate with Fe-coated mica4X-ray diffraction pattern of N film sample, Fe4The N thin films only have a cubic anti-perovskite structure Fe4The diffraction peak of the (002) crystal face of N indicates Fe4N film edge [002]And (4) directionally growing. Prepared flexible Fe4A pole figure of an N-epitaxial film is shown in fig. 2. It can be seen from the figure that only Fe4N is present<111>Diffraction peaks of the lattice plane family indicating Fe4The N film is an epitaxial film. Prepared flexible Fe4A transmission electron microscope image of the N-epitaxial film and a fourier transform plot of selected areas are shown in fig. 3. As can be seen from the figure, the film grows in only one crystal direction, further indicating Fe4The N film is an epitaxial film. 18nm thick flexible Fe at different bend radii4The variation of the magnetization of the N-epitaxial thin film with the applied magnetic field is shown in fig. 4. During the measurement, the magnetic field direction is parallel to the axial direction of the curved surface and parallel to the film surface. As can be seen from the figure, the 18nm thick flexible Fe4Under the action of tensile stress with the bending radius of 3mm, the magnetization intensity of the N epitaxial film sample is 135% of that of an unbent sample, and the relative variation is 35%.
Embodiment mode 2
1) The ultrahigh vacuum facing target magnetron sputtering film coating machine produced by Shenyang scientific instrument development center of Chinese academy of sciences is adopted, and the substrate material is a mica sheet with the thickness of 180 mu m. Two Fe targets with the purity of 99.99 percent are used and are arranged on a target pair head, wherein one end is used as the N pole of a magnetic line, and the other end is used as the S pole; the thickness of the target material is 3mm, and the diameter is 60 mm; the distance between the two targets is 60mm, and the distance between the axis of the targets and the substrate holder containing the mica substrate material is 90 mm;
2) firstly, placing mica sheets on a substrate frame, fixing four corners of the silver colloid mica sheets on the substrate frame to enable the mica sheets to be tightly attached to the substrate frame, preventing the substrate from being heated unevenly in the heating process, placing the mica sheets behind a baffle, and closing a vacuum chamber;
3) starting a vacuum system of the ultrahigh vacuum facing target magnetron sputtering film coating machine, vacuumizing until the back vacuum degree of the sputtering chamber is more than or equal to 2 multiplied by 10–5Pa；
4) Simultaneously introducing Ar gas of sputtering gas with the purity of 99.999 percent and reaction gas N into the vacuum chamber2Gas, Ar gas and N2The flow ratio of gas is 4: 1, keeping the vacuum degree at 1.0 Pa;
5) uniformly heating the substrate to 400 ℃, wherein the heating rate is 10 ℃/min;
6) starting a sputtering power supply, applying 0.30A current and 1000V direct current voltage on a pair of Fe targets, pre-sputtering for 5 minutes, and waiting for the sputtering current and voltage to be stable;
7) applying a current of 0.05A and a DC voltage of 750V to a pair of Fe targets, opening a baffle plate on a substrate holder to start sputtering, and reactively sputtering Fe4In the N film process, the position of the mica sheet is fixed;
8) control of Fe by varying sputter time4The thickness of the N thin film is 3 nm;
9) after sputtering is finished, the baffle plate on the substrate frame is closed, then the sputtering power supply is closed, and the introduction of Ar gas and N is stopped2Completely opening a gate valve, continuously vacuumizing, and uniformly cooling the substrate to room temperature at a cooling rate of 2 ℃/min by using a temperature control system;
10) the vacuum system was turned off, the vacuum chamber was opened and the prepared epitaxial Fe grown on a 180 μm thick mica substrate was removed4N film;
11) epitaxial Fe grown on a 180 μm thick mica substrate4Cutting N film on parchment paper along direction parallel to mica surface with scalpel, and tearing with tweezers to obtain Fe grown on 40 μm thick mica substrate4And (6) N thin films. Thereby obtaining flexible Fe4And N epitaxial thin film.
3nm thick flexible Fe at different bend radii4Magnetization of N epitaxial filmThe variation of the applied magnetic field is shown in fig. 5. During the measurement, the magnetic field direction is parallel to the axial direction of the curved surface and parallel to the film surface. As can be seen from the figure, the 3nm thick flexible Fe4When the bending radius of the N epitaxial thin film is 3mm, the magnetization intensity of the sample is 220% of that of the unbent sample, and the relative change amount is 120%.
Embodiment 3
1) The ultrahigh vacuum facing target magnetron sputtering film coating machine produced by Shenyang scientific instrument development center of Chinese academy of sciences is adopted, and the substrate material is a mica sheet with the thickness of 180 mu m. Two Fe targets with the purity of 99.99 percent are used and are arranged on a target pair head, wherein one end is used as the N pole of a magnetic line, and the other end is used as the S pole; the thickness of the target material is 3mm, and the diameter is 60 mm; the distance between the two targets is 80mm, and the distance between the axis of the targets and the substrate frame containing the mica substrate material is 80 mm;
2) firstly, placing mica sheets on a substrate frame, fixing four corners of the silver colloid mica sheets on the substrate frame to enable the mica sheets to be tightly attached to the substrate frame, preventing the substrate from being heated unevenly in the heating process, placing the mica sheets behind a baffle, and closing a vacuum chamber;
3) starting a vacuum system of the ultrahigh vacuum facing target magnetron sputtering film plating machine, vacuumizing until the back vacuum degree of the sputtering chamber is better than 2 multiplied by 10–5Pa；
4) Simultaneously introducing Ar gas of sputtering gas with the purity of 99.999 percent and reaction gas N into the vacuum chamber2Gas, Ar gas and N2The flow ratio of gas is 4.5: 1, keeping the vacuum degree at 0.8 Pa;
5) uniformly heating the substrate to 450 ℃, wherein the heating rate is 10 ℃/min;
6) starting a sputtering power supply, applying 0.40A current and 1100V direct current voltage on a pair of Fe targets, pre-sputtering for 5 minutes, and waiting for the sputtering current and voltage to be stable;
7) applying a current of 0.07A and a DC voltage of 800V to a pair of Fe targets, opening a baffle plate on a substrate holder to start sputtering, and reactively sputtering Fe4In the N film process, the position of the mica sheet is fixed;
8) control of Fe by varying sputter time4The thickness of the N film is 6 nm;
9) after sputtering is finished, the baffle plate on the substrate frame is closed, then the sputtering power supply is closed, and the introduction of Ar gas and N is stopped2Completely opening a gate valve, continuously vacuumizing, and uniformly cooling the substrate to room temperature at a cooling rate of 2 ℃/min by using a temperature control system;
10) the vacuum system was turned off, the vacuum chamber was opened and the prepared epitaxial Fe grown on a 180 μm thick mica substrate was removed4N film;
11) epitaxial Fe grown on a 180 μm thick mica substrate4Cutting N film on parchment paper along direction parallel to mica surface with scalpel, and tearing with tweezers to obtain Fe grown on 50 μm thick mica substrate4And (6) N thin films. Thereby obtaining flexible Fe4And N epitaxial thin film.
Flexible Fe with thickness of 6nm under different bending radii4The variation of the magnetization of the N-epitaxial thin film with the applied magnetic field is shown in fig. 6. During the measurement, the magnetic field direction is parallel to the axial direction of the curved surface and parallel to the film surface. As can be seen from the figure, the flexible Fe is 6nm thick4Under the action of tensile stress with the bending radius of 3mm, the magnetization intensity of the N epitaxial film sample is 150% of that of the unbent sample, and the relative variation is 50%.
The invention discloses and provides a flexible epitaxial Fe with stress regulation and control4N thin films and methods of preparation, those skilled in the art can implement the methods and techniques of the present invention by referring to the contents herein, and changing the conditions and routes as appropriate, and although the methods and techniques of the present invention have been described with reference to preferred embodiments, it will be apparent to those skilled in the art that the methods and techniques described herein can be modified or re-combined to implement the final techniques of preparation without departing from the contents, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (2)

1. Flexible epitaxial Fe with stress-regulated magnetization intensity4N film; it is characterized in thatThe film is epitaxial Fe4N/mica structure, Fe4The thickness of the N film is 3-18nm, and the thickness of the mica is 40-60 μm.
2. Flexible epitaxial Fe of stress modulated magnetization according to claim 14The preparation method of the N film is characterized by comprising the following steps:
1) adopting a vacuum opposite-target magnetron sputtering coating machine, wherein the substrate material is a mica sheet; two Fe targets with the purity of 99.99 percent are used and are arranged on a target pair head, wherein one end is used as the N pole of a magnetic line, and the other end is used as the S pole; the thickness of the target material is 3mm, and the diameter is 60 mm; the distance between the two targets is 60-90mm, and the distance between the axis of the targets and the substrate frame containing the mica substrate material is 60-90 mm;
2) fixing four corners of a mica sheet on a substrate frame by adopting silver glue, enabling the mica sheet to be tightly attached to the substrate frame, placing the mica sheet behind a baffle plate, and closing a vacuum chamber;
3) starting a vacuum system of the ultrahigh vacuum facing target magnetron sputtering film coating machine, vacuumizing until the back vacuum degree of the sputtering chamber is more than or equal to 2 multiplied by 10–5Pa；
4) Simultaneously introducing Ar gas of sputtering gas with the purity of 99.999 percent and reaction gas N into the vacuum chamber2Gas, Ar gas and N2The flow ratio of gas is 5: 1-4: 1, keeping the vacuum degree at 0.5-1.0 Pa;
5) uniformly heating the substrate to 400-500 ℃, wherein the heating rate is 10 ℃/min;
6) starting a sputtering power supply, applying 0.30-0.50A of current and 1000-1200V of direct current voltage on a pair of Fe targets, pre-sputtering for 5 minutes, and waiting for the sputtering current and voltage to be stable;
7) applying a current of 0.05-0.10A and a DC voltage of 750-850V to a pair of Fe targets, opening the baffle plate on the substrate holder to start sputtering, and reactively sputtering Fe4In the N film process, the position of the mica sheet is fixed;
8) sputtering to Fe4The thickness of the N film is 3-18 nm; closing the baffle plate on the substrate holder, then closing the sputtering power supply, and stopping introducing Ar gas and N2Gas, open the gate valve completely, continue to vacuumize, utilize the temperature control system to make the substrate drop at uniform velocityCooling to room temperature at a rate of 2 ℃/min;
10) the vacuum system was turned off, the vacuum chamber was opened and the prepared epitaxial Fe grown on a 180 μm thick mica substrate was removed4N film;
11) epitaxial Fe grown on a 180 μm thick mica substrate4Cutting N film on parchment paper along direction parallel to mica surface with scalpel, and tearing with tweezers to obtain Fe growing on 40-60 μm thick mica substrate4N film; thereby obtaining flexible Fe4And N epitaxial thin film.
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