Iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin films

Abstract

This application proposes a strong ferromagnetic ceramic thin film based on iron-tin co-doped amorphous gallium oxide, belonging to the technical field of magnetic semiconductor ceramic materials. The invention involves thoroughly mixing Ga, Fe, and Sn organic precursor solutions in a specific ratio to form a GaFeSn organic precursor solution; spin-coating the GaFeSn organic precursor solution onto a cleaned single-crystal alumina substrate; then placing the resulting GaFeSn organic precursor film into a single-temperature tube furnace; under an air atmosphere, slowly raising the furnace temperature to 550°C at a rate of 5°C / min, and annealing at 550°C for 1 hour to prepare a uniformly thick amorphous GaFeSnO magnetic ceramic thin film with strong ferromagnetism. This invention excites strong ferromagnetism in the film with a relatively low iron doping concentration (10%), solving the problem of low conductivity caused by transition metal doping in magnetic ceramic thin films. The amorphous GaFeSnO magnetic ceramic thin film prepared by this invention exhibits a conductivity of 170 emu / cm² at 2K. 3 90 emu / cm at 300K 3 It has strong ferromagnetism and a Curie temperature as high as 335K.

Description

Technical Field

[0001] This application belongs to the field of magnetic semiconductor ceramic materials technology, and in particular relates to an iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film. Background Technology

[0002] Gallium oxide (Ga2O3) possesses advantages such as a wide bandgap, high thermal stability, and high power density, making it widely used in high-frequency, high-temperature electronic devices, RF power amplifiers, and ultraviolet photodetectors, especially suitable for high-efficiency applications in extreme environments. Now, as traditional electronics faces challenges in size and energy efficiency, researchers are seeking new ways to achieve more efficient and lower-power devices. Therefore, spintronic devices, with their unique advantages of non-volatility, low power consumption, and high-speed operation, have begun to be developed.

[0003] The ferromagnetism of gallium oxide (GaO) can be achieved by doping it with different transition metals, a discovery that quickly sparked great interest in GaO-based dilute magnetic semiconductors and their potential in spintronics applications. Practical applications of dilute magnetic semiconductors require at least three key requirements: high Curie temperature, strong saturation magnetization, and good conductivity. The Curie temperature needs to be above 300 K to ensure that dilute magnetic semiconductor-based devices can operate normally at room temperature. Furthermore, saturation magnetization is closely related to the switching speed of free-layer magnetization in spin-transfer torque (STM), and stronger saturation magnetization can significantly improve the read / write performance of STM-based magnetic random access memory (MRAM). Good conductivity is a fundamental requirement for device fabrication.

[0004] Currently, dilute magnetic semiconductors are generally achieved at room temperature by doping with various transition metals. However, doped dilute magnetic semiconductors often suffer from low saturation magnetization and an exponential decrease in conductivity with increasing transition metal doping concentration, which greatly limits the practical application of spintronic devices based on dilute magnetic semiconductors. Therefore, it is necessary to fabricate gallium oxide-based dilute magnetic semiconductors with high Curie temperature, strong saturation magnetization, and good conductivity through a simple and feasible method for future application in spintronic devices. Summary of the Invention

[0005] The purpose of this application is to provide an iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film and its preparation method, aiming to solve the problems of low saturation magnetization and exponential decrease in conductivity with increasing transition metal doping concentration in existing dilute magnetic semiconductors.

[0006] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows:

[0007] In a first aspect, this application provides an iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film, wherein the preparation method of the iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film includes the following steps:

[0008] S1: Preparation of GaFeSn organic precursor solution: Add 10 parts by mass of Fe organic precursor solution and 7-30 parts by mass of Sn organic precursor solution to 100 parts by mass of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0009] S2: Cleaning the substrate surface: Using single-crystal alumina as the substrate, clean it with ultrasonic waves for 5-15 minutes in acetone, alcohol and deionized water respectively, and finally dry it with a nitrogen gun.

[0010] S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate described in step S2 to obtain a GaFeSn organic precursor film.

[0011] S4: Growth and heat treatment: The GaFeSn organic precursor film obtained in step S3 is placed in a single-temperature zone tube furnace; under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, and heat-treated at 550℃ for annealing. Finally, it is cooled to room temperature to prepare a GaFeSnO magnetic ceramic film. The GaFeSnO magnetic ceramic film is an amorphous phase and has both room-temperature ferromagnetism and conductivity. The saturation magnetization and conductivity of the GaFeSnO magnetic ceramic film both increase with the increase of Sn concentration.

[0012] In some embodiments, in step S1, the method for preparing the Sn organic precursor solution includes: adding 2-15 parts by mass of polyethyleneimine to 40 ml of deionized water, stirring thoroughly with a magnetic stirrer until clear to obtain a polymer solution, then adding 1-10 parts by mass of soluble tin salt dropwise to the polymer solution and stirring thoroughly until homogeneous, and then obtaining a Sn organic precursor solution with a molecular weight greater than 10000 g / mol by ultrafiltration.

[0013] In some embodiments, the soluble tin salt includes tin tetrachloride hydrate.

[0014] In some embodiments, the method for preparing the Ga organic precursor solution in step S1 includes:

[0015] Add 2-15 parts by mass of polyethyleneimine and 1.5-15 parts by mass of ethylenediaminetetraacetic acid to 40 ml of deionized water, and stir thoroughly with a magnetic stirrer until transparent to obtain a polymer solution. Then, add 1-10 parts by mass of soluble gallium salt dropwise to the polymer solution and stir thoroughly. Finally, obtain a Ga organic precursor solution with a molecular weight greater than 10,000 g / mol by ultrafiltration.

[0016] The preparation method of the Fe organic precursor solution includes: adding 2-15 parts by mass of polyethyleneimine and 1.5-15 parts by mass of ethylenediaminetetraacetic acid to 40 ml of deionized water, stirring thoroughly with a magnetic stirrer until clear to obtain a polymer solution, then adding 1-10 parts by mass of soluble iron salt dropwise to the polymer solution and stirring thoroughly, and then obtaining an Fe organic precursor solution with a molecular weight greater than 10000 g / mol by ultrafiltration.

[0017] In some embodiments, the soluble gallium salt includes gallium nitrate hydrate, and the soluble iron salt includes ferric nitrate hydrate.

[0018] In some embodiments, in step S3, the spin coating step further includes: adjusting the thickness of the prepared GaFeSn organic precursor film by adjusting the spin coating speed and the number of spin coatings.

[0019] Based on the above technical solution, the iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film provided in this application has at least the following technical effects:

[0020] The preparation method of this invention involves thoroughly mixing Ga, Fe, and Sn organic precursor solutions in a certain proportion to form a GaFeSn organic precursor solution. This solution is then spin-coated onto a cleaned single-crystal alumina substrate. The temperature of the tube furnace is then increased to 550°C at a rate of 5°C / min under air atmosphere, and annealed at this temperature for 1 hour. After cooling to room temperature, a uniformly thick GaFeSnO magnetic ceramic thin film with strong ferromagnetism is prepared. This method has low environmental requirements, as the reaction can occur in air, eliminating the need for a vacuum or sealed environment, thus significantly reducing costs. The air-atmosphere growth and amorphous properties result in a film with numerous oxygen vacancies. Furthermore, Fe doping imparts a stable long-range ferromagnetic order to the gallium oxide film, while co-doping with Sn as a donor increases the number of free electrons in the film. These increased free electrons enhance the film's conductivity (increasing current by 10%). 4On the one hand, the increased number of electrons increases the number of hydrogen-like orbitals of the bound magnetic polarons, allowing them to occupy more space and thus promoting overlap between adjacent bound magnetic polarons. This significantly strengthens ferromagnetic coupling, resulting in a substantial increase in the Curie temperature and saturation magnetization of the thin film (both increasing by approximately 3.4 times). The fabrication method of this invention is simple and easy to implement, has broad application prospects in the field of spintronic devices, and simultaneously opens up new design ideas for improving the ferromagnetism of materials.

[0021] On the other hand, the GaFeSnO magnetic ceramic thin film prepared by this invention has good conductivity and uniform thickness, and also exhibits a conductivity of 170 emu / cm at 2K. 3 90 emu / cm at 300K 3 It has strong ferromagnetism and a Curie temperature as high as 335K. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 The X-ray diffraction (XRD) patterns of GaFeO magnetic ceramic films and GaFeSnO magnetic ceramic films prepared in air atmosphere in Examples 1-6 of this invention are obtained on Al2O3 single crystal substrates with (0001) crystal planes.

[0024] Figure 2 This is a high-resolution transmission electron microscope (HRTEM) image of an amorphous GaFeSnO magnetic ceramic thin film prepared in air atmosphere on an Al2O3 single crystal substrate with a (0001) crystal plane according to Example 3 of the present invention. Figure 2 (a) is a high-resolution transmission electron microscope (HRTEM) image of the GaFeSnO magnetic ceramic thin film prepared in Example 3. Figure 2 (b) is Figure 2 (a) Enlarged view of part A1, Figure 2 (c) is Figure 2 (a) Enlarged view of part A2.

[0025] Figure 3 This is an elemental mapping image of an amorphous GaFeSnO magnetic ceramic thin film prepared on an Al2O3 substrate with a (0001) crystal plane in an air atmosphere according to Example 3 of the present invention.

[0026] Figure 4 The X-ray photoelectron spectroscopy (XPS) spectra of the amorphous GaFeSnO magnetic ceramic thin films prepared on an Al2O3 substrate with a (0001) crystal plane in air atmosphere after heat treatment at 550°C in Examples 2 and 6 of the present invention are shown in the O 1s spectra.

[0027] Figure 5 The X-ray photoelectron spectroscopy (XPS) spectra of the Fe 2p of the amorphous GaFeSnO magnetic ceramic thin film prepared on an Al2O3 substrate with a (0001) crystal plane in air atmosphere after heat treatment at 550°C in Examples 2 and 6 of the present invention.

[0028] Figure 6 The X-ray photoelectron spectroscopy (XPS) spectra of the Sn 3d of GaSnO ceramic thin films and GaFeSnO magnetic ceramic thin films prepared on Al2O3 substrates with (0001) crystal planes in air atmosphere after heat treatment at 550°C in Examples 2-7 of this invention.

[0029] Figure 7 The temperature relationship curves of magnetization intensity of amorphous GaSnO ceramic thin films, GaFeO magnetic ceramic thin films and GaFeSnO magnetic ceramic thin films prepared on Al2O3 substrates with (0001) crystal planes in air atmosphere after heat treatment at 550°C in Examples 1-7 of the present invention.

[0030] Figure 8 The Curie temperature and saturation magnetization of amorphous GaFeO and GaFeSnO magnetic ceramic films prepared on Al2O3 substrates with (0001) crystal planes in air atmosphere after heat treatment at 550°C in Examples 1-6 of this invention are line graphs showing the variation of Sn element doping concentration.

[0031] Figure 9 The hysteresis loops perpendicular to the film direction are obtained by heat treatment at 550°C on an Al2O3 substrate with (0001) crystal plane in air atmosphere for Embodiments 1 and 6 of the present invention.

[0032] Figure 10 The hysteresis loops parallel to the film direction at room temperature are obtained by heat treatment at 550°C on an Al2O3 substrate with (0001) crystal plane in air atmosphere after embodiment 4-6 of the present invention.

[0033] Figure 11The current-voltage curves of amorphous GaFeO magnetic ceramic thin films and GaFeSnO magnetic ceramic thin films prepared in air atmosphere on Al2O3 substrates with (0001) crystal planes on Examples 1-6 of the present invention were obtained by heat treatment at 550°C.

[0034] Figure 12 These are the XRD diffraction patterns of the amorphous gallium oxide thin films prepared in Examples 1 to 6 of this application and the crystalline gallium oxide thin film prepared in Example 8.

[0035] Figure 13 These are the O 1s spectra of the X-ray photoelectron spectroscopy (XPS) spectra of the amorphous gallium oxide thin film prepared in Example 5 and the crystalline gallium oxide thin film prepared in Example 8 of this application.

[0036] Figure 14 This is a temperature relationship curve of the magnetization intensity of the amorphous gallium oxide thin film prepared in Example 5 and the crystalline gallium oxide thin film prepared in Example 8 of this application. Detailed Implementation

[0037] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0038] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0039] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0040] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0041] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0042] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0043] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0044] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass described in the embodiments of this application can be a well-known unit of mass in the chemical industry, such as µg, mg, g, or kg.

[0045] Example 1

[0046] This embodiment 1 provides a method for preparing Fe-doped amorphous gallium oxide-based magnetic ceramic thin films, the specific steps of which are as follows:

[0047] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa, to obtain the Ga organic precursor solution.

[0048] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0049] Preparation of GaFe organic precursor solution: Add 10 parts of Fe organic precursor solution to 100 parts of Ga organic precursor solution and stir thoroughly to obtain GaFe organic precursor solution.

[0050] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0051] Step S3: Spin coating: Spin coat the Ga organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0052] Step S4: Heat treatment: The GaFe organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFe organic precursor film is heated to 550°C at a rate of 5°C / min, then held at that temperature for 1 hour for annealing, and finally cooled to room temperature to prepare a GaFeO magnetic ceramic film, named S1.

[0053] Example 2

[0054] This embodiment 2 provides a method for preparing iron-tin co-doped amorphous gallium oxide-based strongly ferromagnetic ceramic thin films, the specific steps of which are as follows:

[0055] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0056] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0057] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0058] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 7 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0059] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0060] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0061] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, then held at that temperature for 1h for annealing, and finally cooled to room temperature to prepare a GaFeSnO magnetic ceramic film, named S2.

[0062] Example 3

[0063] This embodiment 3 provides a method for preparing iron-tin co-doped amorphous gallium oxide-based strongly ferromagnetic ceramic thin films, the specific steps of which are as follows:

[0064] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0065] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0066] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0067] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 15 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0068] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0069] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0070] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, then held at that temperature for 1h for annealing, and finally cooled to room temperature to prepare a GaFeSnO magnetic ceramic film, named S3.

[0071] Example 4

[0072] This embodiment 4 provides a method for preparing iron-tin co-doped amorphous gallium oxide-based strongly ferromagnetic ceramic thin films, the specific steps of which are as follows:

[0073] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0074] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0075] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0076] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 20 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0077] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0078] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0079] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, then held at that temperature for 1h for annealing, and finally cooled to room temperature to prepare a GaFeSnO magnetic ceramic film, named S4.

[0080] Example 5

[0081] This embodiment 5 provides a method for preparing iron-tin co-doped amorphous gallium oxide-based strongly ferromagnetic ceramic thin films, the specific steps of which are as follows:

[0082] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0083] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0084] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0085] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 25 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0086] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0087] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0088] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, then held at that temperature for 1h for annealing, and finally cooled to room temperature to prepare a GaFeSnO magnetic ceramic film, named S5.

[0089] Example 6

[0090] This embodiment 6 provides a method for preparing iron-tin co-doped amorphous gallium oxide-based strongly ferromagnetic ceramic thin films, the specific steps of which are as follows:

[0091] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0092] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0093] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0094] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 30 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0095] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0096] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0097] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 550℃ at a rate of 5℃ / min, then held at that temperature for 1h for annealing, and finally cooled to room temperature to prepare a GaFeSnO magnetic ceramic film, named S6.

[0098] Example 7

[0099] This embodiment 7 provides a method for preparing Sn-doped amorphous gallium oxide-based magnetic ceramic thin films, the specific steps of which are as follows:

[0100] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa, to obtain the Ga organic precursor solution.

[0101] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0102] Preparation of GaSn organic precursor solution: Add 5 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution and stir thoroughly to obtain GaSn organic precursor solution.

[0103] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0104] Step S3: Spin coating: Spin coat the GaSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0105] Step S4: Heat treatment: The GaSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaSn organic precursor film is heated to 550°C at a rate of 5°C / min, then held at that temperature for 1 hour for annealing, and finally cooled to room temperature to prepare a GaSnO ceramic film, named S7.

[0106] Example 8

[0107] This embodiment 8 provides a method for preparing a strong ferromagnetic ceramic thin film based on iron-tin co-doped crystalline gallium oxide, the specific steps of which are as follows:

[0108] Step S1: Preparation of Ga organic precursor solution: Add 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) to 40 mL of deionized water, stir to dissolve, and then add 1.5 g of gallium nitrate hydrate (Ga(NO3)3·xH2O) and stir for more than 6 h. Use an ultrafiltration cup stirrer to ultrafilter the above solution, removing compounds with molecular weights below 10000 g / mol under a pressure of 0.2 MPa.

[0109] Preparation of Fe organic precursor solution: 2 g of polyethylenediamine (PEI) and 1.5 g of ethylenediaminetetraacetic acid (EDTA) were added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of ferric nitrate hydrate hydrate (FeN3O9·9H2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer at a pressure of 0.2 MPa to remove compounds with molecular weights below 10000 g / mol.

[0110] Preparation of Sn organic precursor solution: 2 g of polyethylenediamine (PEI) was added to 40 mL of deionized water and stirred until dissolved. Then, 1.5 g of tin tetrachloride hydrate (SnCl4·xH2O) was added and stirred for at least 6 h. The solution was then ultrafiltered using an ultrafiltration cup stirrer to remove compounds with molecular weights below 10000 g / mol at a pressure of 0.2 MPa.

[0111] Preparation of GaFeSn organic precursor solution: Add 10 parts of Fe organic precursor solution and 25 parts of Sn organic precursor solution to 100 parts of Ga organic precursor solution, and stir thoroughly to obtain GaFeSn organic precursor solution.

[0112] Step S2: Cleaning the substrate surface: Select single-crystal Al2O3 as the substrate, and clean it with ultrasonic waves in acetone, alcohol and deionized water for 15 min in sequence to remove organic matter and dust from the surface. Finally, blow it dry with a nitrogen gun.

[0113] Step S3: Spin coating: Spin coat the GaFeSn organic precursor solution obtained in step S1 onto the substrate cleaned in step S2. During spin coating, the spin coater speed is set to 3000 r / min and the spin coating time is 30 s.

[0114] Step S4: Heat treatment: The GaFeSn organic precursor film obtained by spin coating in step S3 is placed in a single-temperature zone tube furnace. Under an air atmosphere, the GaFeSn organic precursor film is heated to 750°C at a rate of 5°C / min, then held at that temperature for 1 hour for annealing, and finally cooled to room temperature to prepare a crystalline GaFeSnO magnetic ceramic film, named S8.

[0115] result:

[0116] This application used X-ray diffraction (XRD) to detect the phase composition of the GaFeO magnetic ceramic films prepared in air atmosphere in Example 1 and the GaFeSnO magnetic ceramic films prepared in air atmosphere in Examples 2-6. The XRD diffraction patterns are shown below. Figure 1 As shown. Figure 1 The XRD patterns only showed peaks in the Al2O3 substrate, indicating that the GaFeO and GaFeSnO magnetic ceramic films prepared in this invention are both amorphous phases.

[0117] Figure 2 This is a high-resolution transmission electron microscope (HRTEM) image of an amorphous GaFeSnO magnetic ceramic thin film prepared on an Al2O3 single-crystal substrate with a (0001) crystal plane according to Example 3 of the present invention. Figure 2 As can be seen, the thickness of the prepared GaFeSnO magnetic ceramic film is very uniform, approximately 30 nm. Figure 2 b and 2c are respectively Figure 2 Enlarged view of parts A1 and A2 in a. Figure 2 b shows the interface between the amorphous GaFeSnO thin film and the Al2O3 single crystal substrate. No long-range ordered lattice structure similar to that of the Al2O3 single crystal substrate was observed in the amorphous GaFeSnO thin film. Figure 2 c shows an enlarged HRTEM image of the amorphous GaFeSnO thin film in region A2, compared with... Figure 2 The FFT image with scattered spots in the illustration of c reveals the disordered arrangement of atoms.

[0118] Figure 3This is an elemental mapping image of an amorphous GaFeSnO magnetic ceramic thin film prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane according to Embodiment 3 of the present invention. Figure 3 The image shows that the Ga, O, Sn and Fe elements in the amorphous GaFeSnO magnetic ceramic film are distributed very uniformly, all on the upper side of the Al2O3 substrate with (0001) crystal plane, with clear boundaries, and there is no agglomeration of Fe and Sn elements.

[0119] Figure 4 This is the O 1s spectrum of the X-ray photoelectron spectroscopy (XPS) spectrum of amorphous GaFeSnO magnetic ceramic thin films prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane after heat treatment at 550°C according to Examples 2 and 6 of the present invention. Figure 4 It can be observed that the O 1s spectrum can be divided into two subpeaks, located at approximately 530.70 eV and 532.10 eV, respectively, corresponding to lattice oxygen atoms and oxygen vacancies. From Figure 4 A comparison of Example 2 (top) and Example 6 (bottom) shows that as the Sn doping concentration increases, the oxygen vacancy content of the amorphous GaFeSnO magnetic ceramic film gradually decreases, while the lattice oxygen content gradually increases.

[0120] Figure 5 The X-ray photoelectron spectroscopy (XPS) spectra of the Fe 2p of the amorphous GaFeSnO magnetic ceramic thin film prepared on an Al2O3 substrate with a (0001) crystal plane in air atmosphere after heat treatment at 550°C according to Embodiments 2 and 6 of the present invention. Figure 5 The spectra show that both the Fe 2p 1 / 2 and Fe 2p 3 / 2 spectra can be divided into two Fe subpeaks, corresponding to Fe 2p 1 / 2 and Fe 2p 3 / 2 respectively. 2+ and Fe 3+ There is a Sn 3p diffraction peak interspersed in the middle. When the Fe doping concentration remains constant, but the Sn doping concentration increases, Fe... 2+ and Fe 3+ The proportion of Fe in Examples 2 (upper side) and 6 (lower side) continued to increase. 2+ and Fe 3+ The contents were 52:48 and 64:36, respectively. Fe 2+ The magnetic moment is 4 μB, which is less than that of Fe. 3+ The magnetic moment of (5uB) explains why the saturation magnetization and Curie temperature eventually stabilize: more Fe 3+ It was converted into Fe 2+ This limits the further increase in saturation magnetization and Curie temperature.

[0121] Figure 6 This is the Sn 3d spectrum of the X-ray photoelectron spectroscopy (XPS) spectra of amorphous GaSnO ceramic thin films and GaFeSnO magnetic ceramic thin films prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane after heat treatment at 550°C according to Examples 2-7 of the present invention. Figure 6 It can be observed that the Sn 3d spectrum can be divided into two subpeaks located at approximately 495.50 eV and 487.00 eV, corresponding to Sn 3d3 / 2 and Sn 3d5 / 2 respectively, with an Auger peak of gallium interspersed in between. Figure 6 As can be seen, when the Fe element concentration remains constant while the Sn element concentration continuously increases, the intensity of the Sn 3d peak in the GaFeSnO magnetic ceramic film continuously increases, while its position remains unchanged from that in the Sn-doped amorphous gallium oxide film of Example 7. This means that the Sn element continuously increases in intensity. 4+ The state exists.

[0122] Figure 7 These are temperature-dependent magnetization curves of amorphous GaSnO ceramic films, GaFeO magnetic ceramic films, and GaFeSnO magnetic ceramic films prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane under heat treatment at 550°C in Examples 1-7 of this invention. Figure 7 It can be seen that the amorphous GaSnO ceramic thin film doped only with Sn (Example 7) does not exhibit ferromagnetism. For Examples 1-6, as the Sn doping concentration increases, the magnetization and Curie temperature of the amorphous GaFeSnO magnetic ceramic thin film also increase. Among them, the amorphous GaFeSnO magnetic ceramic thin films of Examples 5-6 have Curie temperatures exceeding room temperature. Example 6 has a Curie temperature of 335 K.

[0123] Figure 8 This is a line graph showing the Curie temperature and saturation magnetization of amorphous GaFeO and GaFeSnO magnetic ceramic films prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane after heat treatment at 550°C according to Examples 1-6 of the present invention, as a function of Sn doping concentration. Figure 8 It can be seen that, while keeping the iron doping concentration constant, as the Sn doping concentration increases, the saturation magnetization and Curie temperature first increase linearly, and then tend to saturate. Examples 5 and 6 have very similar saturation magnetization and Curie temperature.

[0124] Figure 9The hysteresis loops parallel to the film direction at 2K are obtained by heat treatment at 550°C on an Al2O3 substrate with a (0001) crystal plane and in air atmosphere for amorphous GaFeO magnetic ceramic films and GaFeSnO magnetic ceramic films. This is based on Embodiments 1 and 6 of the present invention. Figure 9 It can be seen that the saturation magnetization of Examples 1 and 6 prepared in air at 2K is 52.0 emu / cm, respectively. 3 and 175.0 emu / cm 3 The saturation magnetization of Example 6 is about 3.4 times that of Example 1, indicating that the incorporation of Sn greatly enhances its ferromagnetism.

[0125] Figure 10 The hysteresis loops parallel to the film direction at room temperature are obtained by heat treatment at 550°C on an Al2O3 substrate with a (0001) crystal plane in air atmosphere, as described in Examples 4-6 of this invention. Figure 10 It can be seen that the amorphous GaFeSnO magnetic ceramic films prepared in air in Examples 4-6 have a saturation magnetization of 10 emu / cm at room temperature (300K). 3 55 emu / cm 3 and 90 emu / cm 3 . Figure 10 The illustration shows the hysteresis loops parallel to and perpendicular to the film direction at room temperature in Example 4. They almost completely overlap, indicating that Example 5 has typical amorphous characteristics. The amorphous GaFeSnO magnetic ceramic film lacks magnetic anisotropy. Figure 10 This invention demonstrates that the amorphous GaFeSnO magnetic ceramic films prepared in Examples 4-6 exhibit strong ferromagnetism at room temperature, and that the saturation magnetization of the amorphous GaFeSnO magnetic ceramic films at room temperature (300K) increases with increasing Sn concentration.

[0126] Figure 11 The figures show the current-voltage curves of amorphous GaFeO and GaFeSnO magnetic ceramic films prepared in air atmosphere on an Al2O3 substrate with a (0001) crystal plane under heat treatment at 550°C according to Examples 1-6 of the present invention. Figure 11 It can be seen that while keeping the iron doping concentration constant, the current signal of the amorphous GaFeSnO magnetic ceramic thin film continuously increases as the Sn doping concentration is increased. The current signal intensity of Example 6 can reach 10 times that of Example 1. 4 The result shows that the incorporation of Sn greatly improves the conductivity of the amorphous GaFeSnO magnetic ceramic film, and the conductivity of the amorphous GaFeSnO magnetic ceramic film increases with the increase of Sn doping concentration.

[0127] Figure 12 The XRD diffraction patterns are those of the amorphous gallium oxide thin films prepared in Examples 1 to 6 and the crystalline gallium oxide thin films prepared in Example 8 of this application. The upper curve represents the crystalline gallium oxide thin film of Example 8, and the lower curve represents the amorphous gallium oxide thin films of Examples 1 to 6. It can be seen that the two have completely different crystal structures.

[0128] Figure 13 The images show the O 1s spectra of the X-ray photoelectron spectroscopy (XPS) spectra of the amorphous gallium oxide thin film prepared in Example 5 and the crystalline gallium oxide thin film prepared in Example 8 of this application. The upper image shows the crystalline gallium oxide thin film of Example 8 with 24% oxygen vacancies, while the lower image shows the amorphous gallium oxide thin film of Example 5 with 42% oxygen vacancies. This indicates that the difference in oxygen vacancies between the Fe / Sn co-doped gallium oxide and the crystalline structure is significant.

[0129] Figure 14 This is a temperature relationship curve of the magnetization intensity of the amorphous gallium oxide thin film prepared in Example 5 and the crystalline gallium oxide thin film prepared in Example 8 of this application. The upper curve represents the magnetization temperature (MT) of the amorphous gallium oxide in Example 5, and the lower curve represents the MT of the crystalline gallium oxide in Example 8. Both have the same doping concentration, but the significant difference in oxygen vacancies leads to a significant difference in magnetic properties. The Curie temperature T of the crystalline gallium oxide thin film prepared in Example 8 is... C The saturation magnetization at 138 K (below room temperature) is 62 emu / cm at 2 K. 3 The Curie temperature of amorphous gallium oxide in Example 5 is 323 K (above room temperature), and the saturation magnetization at 2 K is 157 emu / cm. 3 .

[0130] In summary, the amorphous GaFeSnO magnetic ceramic thin film prepared by the method of this invention possesses abundant oxygen vacancies and uniform thickness, along with high saturation magnetization and a Curie temperature as high as 335 K. The incorporation of Sn element can simultaneously achieve strong ferromagnetism in the film with a relatively low iron doping concentration (10%), and solve the problem of low conductivity caused by transition metal doping in magnetic ceramic thin films, thereby increasing the current of the amorphous GaFeSnO magnetic ceramic thin film by 10%. 4 The preparation method of this invention has low environmental requirements, requiring no vacuum or sealed environment, and can react in air, thus greatly reducing costs and having broad application prospects.

[0131] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. An iron tin co-doped amorphous gallium oxide based strong ferromagnetic ceramic thin film, characterized in that, The preparation method of the iron-tin co-doped amorphous gallium oxide-based strong ferromagnetic ceramic film comprises the following steps: S1: preparing a GaFeSn organic precursor solution: adding 10 parts by mass of the Fe organic precursor solution and 7-30 parts by mass of the Sn organic precursor solution into 100 parts by mass of the Ga organic precursor solution, and fully stirring to obtain the GaFeSn organic precursor solution; The preparation method of the Sn organic precursor solution comprises the following steps: adding 2-15 parts by mass of polyethyleneimine into 40 ml of deionized water, fully stirring to obtain a polymer solution by using a magnetic stirrer until the solution is clear, then adding 1-10 parts by mass of a soluble tin salt drop by drop into the polymer solution, fully stirring until the solution is uniform, and then obtaining the Sn organic precursor solution with a molecular weight greater than 10000 g / mol by ultrafiltration; S2: cleaning the surface of the substrate: taking single-crystal alumina as the substrate, cleaning the substrate in acetone, alcohol and deionized water respectively by using ultrasonic cleaning for 5-15 min, and finally blowing dry by using a nitrogen gun; S3: spin coating: spin coating the GaFeSn organic precursor solution obtained in step S1 onto the substrate in step S2 to obtain a GaFeSn organic precursor film; S4: growth and heat treatment: placing the GaFeSn organic precursor film obtained in step S3 into a single-temperature-zone tube furnace; under an air atmosphere, heating the GaFeSn organic precursor film to 550 DEG C at a rate of 5 DEG C / min, heat-treating the film at 550 DEG C, annealing for 1 h, and finally cooling to room temperature, to prepare a GaFeSnO magnetic ceramic film; the GaFeSnO magnetic ceramic film is in an amorphous phase, has room-temperature ferromagnetism and conductivity, and the saturation magnetization and conductivity of the GaFeSnO magnetic ceramic film are enhanced with the increase of the Sn concentration.

2. The Fe and Sn co-doped amorphous gallium oxide-based strong ferromagnetic ceramic thin film according to claim 1, characterized in that, The soluble tin salt comprises stannic chloride hydrate.

3. The Fe and Sn co-doped amorphous gallium oxide-based ferromagnetic ceramic thin film according to claim 1, wherein, In step S1, the preparation method of the Ga organic precursor solution comprises the following steps: In 40 ml of deionized water, adding 2-15 parts by mass of polyethyleneimine and 1.5-15 parts by mass of ethylenediaminetetraacetic acid, fully stirring to obtain a polymer solution by using a magnetic stirrer until the solution is transparent, then adding 1-10 parts by mass of a soluble gallium salt drop by drop into the polymer solution, fully stirring until the solution is uniform, and then obtaining the Ga organic precursor solution with a molecular weight greater than 10000 g / mol by ultrafiltration; The preparation method of the Fe organic precursor solution comprises the following steps: adding 2-15 parts by mass of polyethyleneimine and 1.5-15 parts by mass of ethylenediaminetetraacetic acid into 40 ml of deionized water, fully stirring to obtain a polymer solution by using a magnetic stirrer until the solution is clear, then adding 1-10 parts by mass of a soluble iron salt drop by drop into the polymer solution, fully stirring until the solution is uniform, and then obtaining the Fe organic precursor solution with a molecular weight greater than 10000 g / mol by ultrafiltration.

4. The Fe and Sn co-doped amorphous gallium oxide-based ferromagnetic ceramic thin film according to claim 3, characterized in that, The soluble gallium salt comprises gallium nitrate hydrate, and the soluble iron salt comprises ferric nitrate hydrate.

5. The Fe and Sn co-doped amorphous gallium oxide based strong ferromagnetic ceramic thin film according to claim 1, wherein, In step S3, the spin-coating step further comprises: adjusting the thickness of the prepared GaFeSn organic precursor film by adjusting the rotation speed and the number of times of spin-coating.

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