A peelable flexible Ga based on electrospinning (3x+2y) / 3N x O y Thin Films and Their Preparation Methods

Abstract

The application belongs to the technical field of semiconductor thin film materials and device preparation, and relates to a peelable flexible Ga (3x+2y) / 3 N x O y thin film based on electrostatic spinning and a preparation method thereof. The method takes metal as a substrate, and sequentially prepares a diffusion barrier layer, a Ga2O3 electrostatic spinning layer, a Ga-rich layer, a liquid Ga layer, a Ga (3m+2n) / 3 N m O n buffer layer and a Ga (3x+2y) / 3 N x O y growth layer on one side surface of the metal substrate. The diffusion barrier layer is prepared by a magnetron sputtering method, the Ga2O3 electrostatic spinning layer is prepared by an electrostatic spinning method combined with a sintering method, the liquid Ga layer is prepared by a spin coating method, and the remaining layers are prepared by an ECR-PEMOCVD method. The method can realize growth of a high-quality Ga (3x+2y) / 3 N x O y thin film, and the obtained thin film has flexibility and transferability and is suitable for fields of flexible display, optoelectronic devices and sensors.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor thin film material and device fabrication technology, specifically relating to a peelable flexible Ga based on electrospinning. (3x+2y) / 3 N x O y Thin films and their preparation methods. Background Technology

[0002] Gallium oxide (Ga₂O₃) and gallium nitride (GaN), as next-generation wide-bandgap semiconductor materials, have shown great application potential in optoelectronic devices, power electronic devices, ultraviolet detectors, and high-frequency communications due to their excellent optoelectronic properties, thermal stability, and high-voltage resistance. GaN has a wide direct bandgap of approximately 3.39 eV, high electron mobility, and good thermal conductivity, making it widely used in light-emitting diodes (LEDs), microwave power devices, and lasers. Ga₂O₃, on the other hand, has an even wider bandgap (approximately 4.8–5.3 eV) and also possesses high breakdown field strength, low power consumption, and tunability, demonstrating significant advantages in deep ultraviolet detectors, power devices, and high-performance optoelectronic devices. In recent years, with the increasing demand for bandgap tunability and multifunctional applications, the preparation of GaN by controlling the oxygen and nitrogen composition has become a focus. (3x+2y) / 3 N x O y Thin films combine the advantages of GaN and Ga2O3, enabling wide-range bandgap tuning while also possessing high crystallinity and excellent optoelectronic properties, thus becoming a cross-disciplinary research hotspot for third- and fourth-generation semiconductor materials.

[0003] Meanwhile, flexible electronics technology is developing rapidly, with emerging applications such as flexible displays, wearable devices, photodetectors, and flexible lighting devices constantly appearing, placing higher demands on high-performance, low-defect, and transferable flexible semiconductor thin films. An ideal flexible semiconductor thin film not only needs high crystallinity and tunable photoelectric properties, but also requires low-cost, controllable fabrication processes that are compatible with flexible device processing technologies. However, existing Ga... (3x+2y) / 3 N x O y The application of thin films in flexible electronics still faces many technical bottlenecks: In terms of fabrication processes, the epitaxy of high-quality thin films usually relies on rigid single-crystal substrates such as sapphire, SiC, or silicon. These substrates are expensive, have limited area, and their coefficients of thermal expansion differ significantly from those of the thin films, easily leading to high-density defects and stress warping during epitaxy. Furthermore, traditional MOCVD processes are mostly carried out at high temperatures, resulting in high energy consumption and the introduction of impurities. They also lack the ability to precisely control the oxygen-nitrogen ratio, making it difficult to achieve Ga… (3x+2y) / 3 N x O yThe composition and properties of thin films are continuously tunable. Furthermore, current flexible device fabrication processes often rely on laser ablation, chemical etching, or mechanical polishing. These methods are complex, inefficient, and prone to damaging the thin film or substrate, resulting in high costs and low yields. Regarding thin film materials, Ga… (3x+2y) / 3 N x O y Thin films on heterogeneous substrates often suffer from problems such as insufficient crystal quality and high defect density. Lattice mismatch and poor interfacial bonding further reduce their structural integrity and stability. At the same time, the control of oxygen and nitrogen composition is limited, which easily leads to uneven film composition and makes it difficult to obtain high-quality materials with controllable and reproducible performance. These factors restrict their widespread application in flexible electronic devices.

[0004] In summary, although Ga (3x+2y) / 3 N x O y Thin films have great potential in optoelectronics, power devices and flexible electronics, but existing technologies still have significant shortcomings in low-temperature epitaxial growth, low-stress thin film preparation, peelable flexible thin film preparation and low-cost mass production. There is an urgent need for a new preparation method to break through the above-mentioned technical bottlenecks. Summary of the Invention

[0005] The purpose of this invention is to overcome the limitations of existing Ga (3x+2y) / 3 N x O y The fabrication of thin films faces challenges such as high temperature requirements, high film stress, difficulty in precisely controlling oxygen and nitrogen composition, difficulty in film peeling, and limitations in flexible applications. To address these issues, a peelable flexible Ga film based on electrospinning is proposed. (3x+2y) / 3 N x O y Thin films and their preparation methods.

[0006] The main technical concept for achieving the purpose of this invention is as follows: using a low-cost metal material with excellent electrical and thermal conductivity and a thermal expansion coefficient matching that of the thin film as a substrate, a diffusion barrier layer, a Ga2O3 electrospun layer, a Ga-rich layer, a liquid Ga layer, and a Ga... (3m+2n) / 3 N m O n Buffer layer and Ga (3x+2y) / 3 N x O y The growth layer consists of a diffusion barrier layer to suppress inter-diffusion of atoms and impurity contamination at the interface; a Ga2O3 electrospinning layer forming an ordered array structure that serves as a template for oriented epitaxy and as a separation interface in subsequent growth processes; and a Ga-rich layer formed after plasma treatment that interacts with the spin-coated liquid Ga layer, improving the smoothness of the spinning surface and providing an active nucleation environment for epitaxial growth, which is gradually consumed during subsequent growth to avoid interface residue.(3m+2n) / 3 N m O n A buffer layer is epitaxially formed on a liquid Ga layer, serving to relieve stress and suppress defects, thereby providing Ga with a buffer layer. (3x+2y) / 3 N x O y High-quality deposition of the growth layer lays the foundation. This structural design enables precise control of oxygen and nitrogen components during low-temperature electron cyclotron resonance-plasma-enhanced metal-organic chemical vapor deposition (ECR-PEMOCVD), resulting in Ga with high crystallinity, low defect density, and tunable composition. (3x+2y) / 3 N x O y film.

[0007] In the preparation of Ga (3x+2y) / 3 N x O y Among the many methods for thin film deposition, the ECR-PEMOCVD method can provide a variety of highly active plasma sources without relying on high-temperature pyrolysis to generate reactive particles, thus enabling the deposition of Ga at relatively low temperatures. (3x+2y) / 3 N x O y Epitaxial growth of thin films. Low-temperature processes not only help reduce thermal stress caused by differences in thermal expansion coefficients between the metal substrate and the functional layers, but also effectively suppress impurities from the substrate to Ga. (3x+2y) / 3 N x O y Diffusion in thin films, thereby significantly improving Ga (3x+2y) / 3 N x O y The crystal quality of the thin film. More importantly, the ECR-PEMOCVD process can precisely control the ratio of oxygen to nitrogen sources and suppress the volatilization of oxygen and nitrogen through low-temperature manufacturing processes, thereby reducing the density of oxygen and nitrogen vacancies. This is beneficial for obtaining Ga with tunable oxygen and nitrogen composition and high crystallinity. (3x+2y) / 3 N x O y film.

[0008] Among various methods for preparing liquid Ga layers, spin coating offers advantages such as simple process, good film uniformity, and controllable liquid Ga layer thickness, making it particularly suitable for preparing uniform and continuous ultrathin liquid Ga layers. Using spin coating to form a liquid Ga layer on the surface of a Ga-rich layer not only ensures good wetting and spreading of the liquid Ga layer on Ga₂O₃ electrospinning, but also facilitates subsequent Ga… (3x+2y) / 3 N x O y Epitaxial growth of thin films provides a smooth and active reaction surface, which is beneficial for achieving high-quality thin film preparation.

[0009] The technical solution of this invention is:

[0010] A peelable flexible Ga based on electrospinning (3x+2y) / 3 N x O y thin film, the Ga (3x+2y) / 3 N x O y The thin film uses a metal substrate. On one side of the metal substrate, from the inside out, are a diffusion barrier layer, a Ga2O3 electrospun layer, a Ga-rich layer, a liquid Ga layer, and a Ga layer. (3m+2n) / 3 N m O n Buffer layer and Ga (3x+2y) / 3 N x O y Growth layer.

[0011] The metal substrate is made of an alloy composed of one or more of the following: silver (Ag), gold (Au), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), hafnium (Hf), iridium (Ir), molybdenum (Mo), nickel (Ni), niobium (Nb), platinum (Pt), ruthenium (Ru), titanium (Ti), tantalum (Ta), tungsten (W), and zirconium (Zr), with an overall thickness of 0.3–3 mm; the diffusion barrier layer is composed of an alloy composed of one or more of the following: chromium (Cr), hafnium (Hf), tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), titanium (Ti), zirconium (Zr), and carbon (C), or... The Ga₂O₃ electrospun layer is a nitride formed by at least one of the following elements: chromium (Cr), hafnium (Hf), tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), titanium (Ti), and zirconium (Zr), with an overall thickness of 5–100 nm; the Ga₂O₃ electrospun layer is a parallel ordered fiber array structure composed of Ga₂O₃ fibers with a diameter of 50–200 nm and a fiber spacing of 0.2–2 μm; the Ga-rich layer is composed of elemental Ga and Ga₂O, with a thickness of 1–20 nm; the liquid Ga layer is composed of liquid Ga with a uniform thickness and a purity of 6N or higher, with a thickness of 10–100 nm; the Ga… (3m+2n) / 3 N m O n The thickness of the buffer layer is 20nm to 100nm, Ga (3m+2n) / 3 N m O n The component values ​​of the buffer layer are controlled as follows: 0≤m≤1, 0≤n≤3; the Ga (3x+2y) / 3 N x O y The thickness of the growth layer is 500 nm to 5 μm, Ga (3x+2y) / 3 N x O yThe component values ​​of the growth layer are controlled as follows: 0≤x≤1, 0≤y≤3.

[0012] The above-mentioned peelable flexible Ga based on electrospinning (3x+2y) / 3 N x O y The thin film preparation method, using the ECR-PEMOCVD equipment described in invention patent 201210247144.8, includes the following steps: Step a, cleaning and drying a pretreated metal substrate; Step b, preparing a diffusion barrier layer by magnetron sputtering; Step c, preparing a Ga2O3 electrospun layer; Step d, ECR oxygen plasma oxidation treatment; Step e, ECR hydrogen plasma cleaning treatment; Step f, preparing a liquid Ga layer by spin coating; Step g, preparing a Ga layer by ECR-PEMOCVD. (3m+2n) / 3 N m O n Buffer layer; Step h, ECR-PEMOCVD method for preparing Ga (3x+2y) / 3N x O y Growth layer; Step i: Preparation of flexible Ga by mechanical exfoliation method (3x+2y) / 3 N x O y film.

[0013] Step a specifically involves: placing the metal substrate in acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning at least three times, rinsing it clean with deionized water, and then drying it with high-purity nitrogen gas with a purity greater than 5N.

[0014] Step b specifically involves: using a high-purity target material with an impurity content of less than 0.001%, and using high-purity argon gas with a purity greater than 6N as the sputtering gas. The metal substrate treated in step a is placed on the material stage within the coating chamber of the magnetron sputtering equipment. When the background pressure of the coating chamber is evacuated to 5 × 10⁻⁶... -4 Below Pa, heat the stage to 50-600℃. After the stage temperature stabilizes, introduce high-purity argon gas into the magnetron sputtering coating chamber at a flow rate of 40-100 sccm to control the pressure in the coating chamber to 0.1-5 Pa. After the pressure in the coating chamber stabilizes, set the power of the RF sputtering power supply for the target to 30-200W and turn on the RF sputtering power supply to begin sputtering and depositing a diffusion barrier layer on the surface of the metal substrate.

[0015] Step c specifically involves: using a polymer solution containing a Ga2O3 precursor as the spinning solution. The polymer solution is prepared by dissolving gallium acetate or gallium nitrate and polyvinylpyrrolidone in dimethylformamide (DMF) at a mass ratio of 1:5 to 4:5. The solution is stirred evenly and filtered through a 0.2 to 0.5 μm filter membrane. During the spinning process, a high-voltage electrostatic field traction process is used. Under the impingement of an injection pump, the spinning solution is sprayed from the needle tip at a rate of 0.2 to 1.0 mL / h, maintaining the distance between the needle tip and the diffusion barrier layer at 10 to 20 cm. A high-voltage power supply is applied with a voltage of 10 to 20 kV, and the environment... The temperature is controlled at 20–30℃ and the relative humidity does not exceed 40%. Under the action of an electric field, the spinning solution fibers are uniformly drawn and deposited along the surface direction of the diffusion barrier layer to form a parallel and ordered spinning solution fiber array. Then, the metal substrate with the diffusion barrier layer and the spinning solution fiber array is placed in an atmospheric pressure tube furnace and heat-treated in a high-purity oxygen atmosphere with a purity greater than 6N. The flow rate of the high-purity oxygen is 50–200 sccm, the heat treatment temperature is 800–1000℃, and the heat treatment time is 2–10 min, thereby obtaining a Ga2O3 electrospun layer on the diffusion barrier layer.

[0016] Step d specifically involves: transferring the metal substrate with the diffusion barrier layer and Ga2O3 electrospun layer from the atmospheric pressure tube furnace (after it has recovered to room temperature) to the metal substrate loading chamber of the ECR-PEMOCVD equipment, and then from the metal substrate loading chamber to the metal substrate platform in the reaction chamber. When the background pressure in the reaction chamber is evacuated to 1×10⁻⁶... -4 After the temperature of the metal substrate stage is below 25-400℃, the temperature of the metal substrate stage is heated to 25-400℃. After the temperature of the metal substrate stage is stable, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber through the first gas distribution valve of the discharge gas supply device. The second gas supply ring with several through holes along the circumference of the first gas distribution valve is introduced into the chamber. The flow rate of high-purity oxygen is 60-200 sccm, so that the gas pressure in the reaction chamber is controlled at 0.1-5Pa. After the gas pressure in the reaction chamber is stable, the microwave power supply is set to 300-1000W, the microwave source is turned on to discharge, and ECR oxygen plasma oxidation treatment is performed for 2-10 minutes.

[0017] The specific steps of step e are as follows: the high-purity oxygen discharge in the ECR-PEMOCVD equipment is switched to high-purity hydrogen discharge with a purity greater than 6N, the high-purity hydrogen flow rate is 50-200 sccm, the working pressure is controlled at 0.1-5 Pa, the microwave source power is maintained at 300-1000 W, and the time is controlled at 30s-30min, so as to form a Ga-rich layer rich in metallic Ga and Ga2O on the surface of Ga2O3 electrospinning.

[0018] Step f specifically involves: transferring the metal substrate with the Ga-rich layer to the glove box of the ECR-PEMOCVD equipment, followed by a liquid Ga spin-coating process. The Ga raw material used is high-purity liquid Ga with a purity higher than 6N. To avoid oxidation of the liquid Ga, the entire transfer and spin-coating process is carried out under a nitrogen or argon atmosphere with a purity higher than 6N. Before spin-coating, the metal substrate with the Ga-rich layer is fixed on a vacuum adsorption spin-coating stage, ensuring that the Ga-rich layer faces upwards. The spin-coating stage is preheated to 40–100°C. Then, high-purity liquid Ga is uniformly dropped onto the surface of the Ga-rich layer at a rate of 0.5–2.0 μL / mm² using a micro-injection needle. The spin-coating program is then started immediately, with the rotation speed starting slowly from 100–500 rpm for 5–10 seconds, then accelerated to 2000–4000 rpm and maintained for 50–100 seconds. After spin-coating, the spin-coating stage is slowly cooled to room temperature, resulting in a liquid Ga layer on the Ga-rich layer.

[0019] Step g specifically involves: transferring the metal substrate with the liquid Ga layer prepared from the glove box of the ECR-PEMOCVD equipment to the metal substrate loading chamber, and then from the metal substrate loading chamber to the metal substrate platform in the reaction chamber. When the background gas pressure in the reaction chamber is evacuated to 1×10⁻⁶... -4 After the temperature drops below Pa, the metal substrate stage is heated to 100–500°C. Once the temperature stabilizes, the first gas distribution valve of the discharge gas supply device is used to introduce one or more of the following gases—high-purity oxygen (greater than 6N), nitrogen, ammonia, nitrous oxide, nitric oxide, and nitrogen dioxide—through the second gas supply ring into the quartz cup discharge chamber. The total gas flow rate is controlled at 50–200 sccm, maintaining the gas pressure in the reaction chamber at 0.1–5 Pa. After the gas pressure in the reaction chamber stabilizes, the microwave source power is set to 300–1000 W, and the microwave power supply is turned on to discharge, generating oxygen plasma, nitrogen plasma, ammonia plasma, or a mixed plasma containing oxygen and nitrogen. After the microwave discharge stabilizes, trimethylgallium or triethylgallium is introduced into the reaction chamber as a gallium source to prepare Ga. (3m+2n) / 3 N m O n A buffer layer is used, in which hydrogen is the carrier gas for the gallium source, and the molar flow rate of the gallium source is controlled at 5.0 × 10⁻⁶. -7 ~5.0×10 -5 mol / min.

[0020] The specific step h is as follows: after heating the metal substrate stage to 300-800℃, the ECR-PEMOCVD method is used to process Ga... (3m+2n) / 3 N m O n Ga prepared on buffer layer (3x+2y) / 3 N x O yThe growth layer, including microwave discharge and gallium source introduction, follows the same process as step g. The Ga content is controlled by varying the flow rates and preparation time of each gas. (3x+2y) / 3 N x O y The thickness and composition of the growth layer.

[0021] Ga (3x+2y) / 3 N x O y After the growth layer is prepared, the gallium source is first turned off, and then the temperature of the metal substrate stage is set to 20°C to begin cooling. During the cooling process, the other preparation processes in step h are kept unchanged. When the temperature drops below 100°C, the microwave source and other gases are turned off, and then the sequential operation is performed to remove the Ga substrate. (3x+2y) / 3 N x O y The metal substrate for the growth layer was then systematically shut down the ECR-PEMOCVD equipment.

[0022] Step i specifically involves: fixing Ga... (3x+2y) / 3 N x O y The metal substrate for the growth layer is scribing its surrounding surface to expose the entire interface edge between the Ga2O3 electrospinning layer and the diffusion barrier layer. The Ga2O3 is then cleaned and dried. (3x+2y) / 3 N x O y On the surface of the growth layer, a piece of transparent tape with adhesive on one side is attached to Ga. (3x+2y) / 3 N x O y The upper surface edge of the growth layer is rolled with a pressure of 20–50 kPa, 2–3 times, and left to stand for 1–3 minutes. Under conditions of ambient temperature of 20–30°C and relative humidity below 40%, the peeling angle is controlled at 30–70° and the peeling speed at 10–100 mm / min. A total tensile force of 4–24 N is applied, and the layer is slowly lifted from the exposed edge to allow the Ga... (3x+2y) / 3 N x O y The entire growth layer to the Ga2O3 electrospinning layer was peeled off from the diffusion barrier layer and the metal substrate, ultimately yielding a flexible Ga... (3x+2y) / 3 N x O y film.

[0023] The beneficial effects of this invention are: by employing the ECR-PEMOCVD method and spin-coating liquid Ga process, the fabrication of each functional layer can be completed at a relatively low temperature, thereby reducing stress caused by thermal mismatch and minimizing the risk of interface cracking; the low-temperature deposition of ECR-PEMOCVD not only inhibits the volatilization of nitrogen and oxygen elements and the generation of vacancy defects during the growth process, but also achieves Ga… (3x+2y) / 3 N x O y Controllable adjustment of composition yields high-quality thin films with lower crystal defect density. The diffusion barrier layer constructed on a metal substrate in this invention effectively prevents atomic interdiffusion between the metal substrate and the Ga-containing film, reducing Gaa content. (3x+2y) / 3 N x O y The impurity content of the thin film; the prepared Ga2O3 electrospun layer and spin-coated liquid Ga layer, which are Ga... (3m+2n) / 3 N m O n Buffer layer and Ga (3x+2y) / 3 N x O y The growth layer provides an ordered, oriented epitaxial template, reducing film stress and improving crystal quality. More importantly, the Ga2O3 electrospinning layer ensures the Ga... (3x+2y) / 3 N x O y Lateral epitaxial growth of thin films within diffusion barrier layers can also serve as a separation layer, enabling convenient acquisition of flexible Ga films with low dislocation density and low warpage through mechanical exfoliation. (3x+2y) / 3 N x O y film.

[0024] The Ga prepared in this invention (3x+2y) / 3 N x O y Thin films can be directly attached to highly conductive metal substrates and diffusion barrier layers to construct vertically conductive semiconductor devices; alternatively, they can be peeled off and widely used as core materials for flexible electronic devices such as solar cells, photodetectors, and thin-film transistors, showing broad application prospects. Furthermore, the metal substrate and diffusion barrier layer can be reused after peeling, reducing Ga content. (3x+2y) / 3 N x O y The manufacturing cost of the thin film. Attached Figure Description

[0025] Figure 1 This invention relates to a peelable flexible Ga based on electrospinning. (3x+2y) / 3 N x O y A schematic diagram of the thin film structure.

[0026] Figure 2 This is a process flow diagram of the preparation method described in this invention.

[0027] Figure 3 This is a top view schematic diagram of the processing equipment of the present invention, which uses the equipment described in the invention patent "Equipment for preparing vertical GaN-based LED chips using metal substrates (Patent No.: ZL201210247144.8)".

[0028] Figure 4 yes Figure 3 AA sectional view.

[0029] In the figure: 1. Metal substrate; 2. Diffusion barrier layer; 3. Ga₂O₃ electrospun layer; 4. Ga-rich layer; 5. Liquid Ga layer; 6. Ga (3m+2n) / 3 N m O n Buffer layer; 7Ga (3x+2y) / 3 N x O y Growth layer;

[0030] 8. Glove box; 9. Photoelectric alarm; 10. Reflective high-energy electron diffractometer; 11. Fluorescent screen; 12. Faraday cylinder; 13. Electron probe; 14. Microwave source; 15. Waveguide; 16. Microwave coupling antenna; 17. Resonant cavity; 18. Piston short circuitr; 19. Permanent magnet ring; 20. Quartz cup discharge chamber; 21. Gas phase metal-organic compound supply device; 21-1 First gas supply ring; 22. Magnetic field coil support cylinder; 23. Lighting terminal; 24. Pressure gauge; 25. Venting valve; 26. Loading door; 27. Magnetic manipulator; 28. Observation window; 29. ​​Terminal; 30. First gas distribution valve; 30-1 Second gas supply ring; 31. Reaction chamber; 32. Metal substrate loading chamber; 32-1 Electric control gate valve; 33. Vacuum pumping equipment; 34. Pneumatic feeding device; 34-1 Feeding rod; 35. Metal substrate platform; 36. Plasma source supply device; 37. Second gas distribution valve; 38. Vacuum meter. Detailed Implementation

[0031] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings and technical solutions.

[0032] like Figure 1 The present invention relates to a peelable flexible Ga based on electrospinning. (3x+2y) / 3 N x O y thin film, the Ga (3x+2y) / 3 N x O y The thin film uses a metal substrate. On one side surface of the metal substrate 1, from the inside out, are: a diffusion barrier layer 2, a Ga2O3 electrospun layer 3, a Ga-rich layer 4, a liquid Ga layer 5, and a Ga...(3m+2n) / 3 N m O n Buffer layer 6 and Ga (3x+2y) / 3 N x O y Growth layer 7. Preparation process as follows: Figure 2 As shown, the ECR-PEMOCVD equipment used in the preparation (invention patent: ZL201210247144.8) is as follows: Figure 3 and Figure 4 As shown.

[0033] Example 1

[0034] The sequential process steps for fabricating peelable gallium nitride (GaN) films on molybdenum (Mo) substrates are as follows:

[0035] Step a: Clean and dry the pretreated metal substrate 1: Select a 20mm×20mm metal molybdenum (Mo) with a purity greater than 5N and a thickness of 0.3mm as the metal substrate 1. Place the metal substrate 1 in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning 3 times in turn. Finally, rinse it with deionized water and blow it dry with high-purity nitrogen gas with a purity greater than 5N.

[0036] Step b, Preparation of diffusion barrier layer 2 by magnetron sputtering: Tungsten (W) metal with a purity greater than 5N is selected as the target material. High-purity argon gas with a purity greater than 6N is used for sputtering. The metal substrate 1 treated in step a is placed on the material stage in the coating chamber of the magnetron sputtering equipment. When the background pressure of the coating chamber of the magnetron sputtering equipment is evacuated to 1×10⁻⁶... -4 When the pressure is Pa, heat the stage to 50°C. After the stage temperature stabilizes, introduce high-purity argon gas into the magnetron sputtering coating chamber at a flow rate of 40 sccm to control the pressure in the coating chamber to 0.1 Pa. After the pressure in the coating chamber stabilizes, set the power of the RF sputtering power supply for the required tungsten target to 30W and turn on the required RF sputtering power supply to begin sputtering and depositing the tungsten diffusion barrier layer 2 on the surface of the metal substrate 1, and control the thickness of the tungsten diffusion barrier layer 2 to 5 nm.

[0037] Step c, Preparation of Ga2O3 electrospinning layer 3: A polymer solution containing Ga2O3 precursor is used as the spinning solution. The solution is prepared by dissolving gallium acetate and polyvinylpyrrolidone in dimethylformamide (DMF) at a mass ratio of 1:5. After stirring evenly, the solution is filtered through a 0.2 μm filter membrane. During the spinning process, a high-voltage electrostatic field traction process is used. The spinning solution is sprayed from the needle tip at a rate of 0.2 mL / h under the push of an injection pump, keeping the distance between the needle tip and the diffusion barrier layer 2 at 10 cm. A high-voltage power supply of 10 kV is applied, the ambient temperature is controlled at 20℃, and the relative humidity is 35%. Under the action of the diffusion barrier layer 2, the spinning solution fibers are uniformly drawn and deposited along the surface direction of the diffusion barrier layer 2 to form a parallel and ordered spinning solution fiber array. Then, the metal substrate 1 with the diffusion barrier layer 2 and the spinning solution fiber array is placed in an atmospheric pressure tube furnace and heat-treated in a high-purity oxygen atmosphere with a purity greater than 6N. The high-purity oxygen flow rate is 50 sccm, the heat treatment temperature is 800℃, and the heat treatment time is 2 min, thereby obtaining a Ga2O3 electrospinning layer 3 on the diffusion barrier layer, so that the diameter of the Ga2O3 fiber is controlled to be 50 nm and the spacing between the Ga2O3 fibers is controlled to be 0.2 μm.

[0038] Step d, ECR oxygen plasma oxidation treatment: ECR oxygen plasma oxidation treatment is performed using an ECR-PEMOCVD device. A permanent magnet ring 19 is placed around the quartz cup discharge chamber 20 to provide the permanent magnetic field required for microwave electron cyclotron resonance (ECR). All circulating water supplies to the ECR-PEMOCVD device are turned on. Then, power is supplied to the lighting terminal 23 on the metal substrate loading chamber 32 via terminal 29 to turn on the lighting. The vertical position of the metal substrate stage 35 is observed through the observation window 28, ensuring that the metal substrate stage 35 is positioned to receive the metal substrate 1 with the diffusion barrier layer 2 and Ga2O3 electrospun layer 3. Then, power is supplied to the metal substrate loading chamber 32 via... The vent valve 25 is used to fill the metal substrate loading chamber 32 with high-purity nitrogen gas with a purity greater than 6N until the pressure gauge 24 on the metal substrate loading chamber 32 indicates one atmosphere. Then, the vent valve 25 on the metal substrate loading chamber 32 is closed, the loading door 26 is opened, and the metal substrate 1 with the diffusion barrier layer 2 and Ga2O3 electrospun layer 3 prepared is taken out from the atmospheric pressure tube furnace after it has been restored to room temperature. It is then placed on the support platform of the pneumatic feeding device 34, the loading door 26 is closed, and the bypass pipeline of the vacuum pumping device 33 is turned on to evacuate the metal substrate loading chamber 32. The pressure of the metal substrate loading chamber 32 is detected by the vacuum degree meter 38 on the metal substrate loading chamber 32. The pressure is evacuated until the background pressure of the metal substrate loading chamber 32 is 1×10⁻⁶. -4After Pa, open the electric control gate valve 32-1, and then transfer the metal substrate 1 with the diffusion barrier layer 2 and Ga2O3 electrospun layer 3 prepared through the pneumatic feeding device 34's feeding rod 34-1 and the magnetic manipulator 27 to the metal substrate loading chamber 31 via the metal substrate loading chamber 32 onto the metal substrate platform 35. Reset the pneumatic feeding device 34, feeding rod 34-1, and magnetic manipulator 27, turn off the electric control gate valve 32-1 and the lighting in the metal substrate loading chamber 32, stop the bypass evacuation of the vacuum equipment 33 to the metal substrate loading chamber 32, and switch to evacuating the reaction chamber 31. Detect the air pressure in the reaction chamber 31 through the vacuum gauge 38 on the reaction chamber 31. When the background air pressure in the reaction chamber 31 is evacuated to 1×10⁻⁶, the pressure is released. -5 After Pa, the temperature of the metal substrate stage 35 is heated to 25℃. Once the temperature of the metal substrate stage 35 stabilizes, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the first gas distribution valve 30 of the discharge gas supply device, via the second gas supply ring 30-1 with several through holes along the circumferential direction. The flow rate of the high-purity oxygen is 60 sccm, controlling the gas pressure in the reaction chamber 31 to 0.1 Pa. Once the gas pressure in the reaction chamber 31 stabilizes, the power supply of the magnetic field coil supporting cylinder 22 is turned on to provide a magnetic field for confining the plasma. The power of the microwave source 14 is set to 300W, and the microwave source 14 is turned on to discharge. The discharge process involves the microwave... The microwaves generated by source 14 are transmitted to microwave coupling antenna 16 through waveguide 15, and then coupled into resonant cavity 17 through microwave coupling antenna 16. The piston short circuit 18 is adjusted so that microwave source 14 can monitor microwave reflection power, so that plasma source supply device 36 generates oxygen plasma and starts ECR oxygen plasma oxidation treatment, with the time controlled at 10 minutes. During the entire ECR oxygen plasma oxidation treatment, photoelectric alarm 9 is activated to monitor the luminous brightness of oxygen plasma to provide microwave discharge extinguishing alarm. The ion energy in oxygen plasma is detected by Faraday cylinder 12, and the electron energy and electron density in oxygen plasma are detected by electron probe 13.

[0039] Step e, ECR hydrogen plasma cleaning treatment: After step d, the high-purity oxygen discharge in the ECR-PEMOCVD equipment is switched to high-purity hydrogen discharge with a purity greater than 6N. The high-purity hydrogen flow rate is 50 sccm, the working pressure is controlled at 0.1 Pa, the power of microwave source 14 is kept at 300W, the piston short circuit 18 is adjusted so that microwave source 14 can monitor microwave reflection power, and the time is controlled at 30s, so as to form a Ga-rich layer 4 rich in metallic Ga and Ga2O on the surface of Ga2O3 electrospinning, and the thickness of Ga-rich layer 4 is controlled at 1nm.

[0040] Step f, spin coating method for preparing liquid Ga layer 5: After step e, microwave source 14 and high-purity hydrogen are turned off in an orderly manner, and the background pressure of reaction chamber 31 is evacuated to 1×10 -3 After Pa, the high-energy reflection electron diffractometer 10 is turned on, and the high-energy reflection electron diffraction image of the liquid Ga layer is captured and recorded through the fluorescent screen 11 and the matching CCD camera. The high-energy reflection electron diffractometer 10 is turned off, the vacuum pump 33 is turned off to evacuate the reaction chamber 31, the electric control gate valve 32-1 is opened, and the metal substrate 1 with the Ga-rich layer 4 is transferred from the reaction chamber 31 to the metal substrate loading chamber 32 through the feeding rod 34-1 and the magnetic manipulator 27. The electric control gate valve 32-1 is turned off, and then high-purity nitrogen gas with a purity greater than 6N is introduced into the metal substrate loading chamber 32 through the vent valve 25 on the metal substrate loading chamber 32 to maintain the pressure gauge 24 on the metal substrate loading chamber 32 at one atmosphere. The connection between the metal substrate loading chamber 32 and the ECR-P is opened. The metal substrate 1 with the Ga-rich layer 4 is transferred from the sealed door of the glove box 8 of the EMOCVD equipment into the glove box 8. Then, a liquid Ga spin-coating process is performed using a spin coater. The Ga raw material used is high-purity liquid Ga with a purity higher than 6N. To avoid oxidation of the liquid Ga, the entire transfer and spin-coating process is maintained at one atmosphere and operated under a high-purity nitrogen atmosphere. Before spin-coating, the metal substrate 1 with the Ga-rich layer 4 is fixed on the vacuum adsorption spin-coating stage, ensuring that the Ga-rich layer 4 faces upwards. The spin-coating stage is preheated to 40°C, and the bypass evacuation line of the vacuum pump 33 is turned on to evacuate the vacuum adsorption line of the spin coater, so as to fix the metal substrate 1 with the Ga-rich layer 4 through vacuum adsorption. Then, high-purity liquid Ga is injected at a rate of 0.5 μL / mm using a micro-syringe. 2 The amount of liquid Ga was evenly dropped onto the surface of the Ga-rich layer 4, and then the spin coating program was started immediately. The speed was started slowly at 100 rpm and held for 5 seconds, then accelerated to 2000 rpm and held for 50 seconds. After the spin coating was completed, the bypass pumping line of the vacuum equipment 33 to the spin coater was turned off, and the spin coating stage was slowly cooled to room temperature to obtain a liquid Ga layer 5 on the Ga-rich layer 4. The thickness of the liquid Ga layer 5 was controlled to be 10 nm.

[0041] Step g: Preparation of Ga by ECR-PEMOCVD method (3m+2n) / 3 N m O n Buffer layer 6 (in this embodiment, Ga) (3m+2n) / 3 N m O nThe nitrogen and oxygen component values ​​in the buffer layer 6 material are set to m=1 and n=0, respectively, i.e., the product is GaN): The metal substrate 1 with the liquid Ga layer 5 is transferred from the glove box 8 of the ECR-PEMOCVD equipment to the metal substrate loading chamber 32, and then from the metal substrate loading chamber 32 to the metal substrate stage 35 in the reaction chamber 31. When the background gas pressure of the reaction chamber 31 is evacuated to 1×10 -5 After Pa, the temperature of the metal substrate stage 35 is heated to 100℃. Once the temperature of the metal substrate stage 35 stabilizes, high-purity ammonia gas with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of the high-purity ammonia gas is controlled at 50 sccm, and the gas pressure in the reaction chamber 31 is controlled at 0.1 Pa. Once the gas pressure in the reaction chamber 31 stabilizes, the power of the microwave source 14 is set to 300W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power and generate ammonia plasma. After the microwave discharge stabilizes, the second gas distribution valve 37 of the gas phase metal-organic compound supply device 21 is opened, and trimethylgallium is introduced into the reaction chamber 31 through the gas phase metal-organic compound supply device 21 and the first gas supply ring 21-1 of the gas phase metal-organic compound supply device 21 as a gallium source to prepare Ga. (3m+2n) / 3 N m O n Buffer layer 6, wherein the carrier gas for the gallium source is hydrogen, and the molar flow rate of the gallium source is controlled at 5.0 × 10⁻⁶. -7 mol / min, convert Ga (3m+2n) / 3 N m O n The thickness of buffer layer 6 is controlled to be 20nm;

[0042] Step h: Preparation of Ga by ECR-PEMOCVD method (3x+2y) / 3 N x O y Growth layer 7 (in this embodiment, Ga (3x+2y) / 3 N x O y The nitrogen and oxygen component values ​​in the growth layer 7 material are set to x=1 and y=0, respectively, i.e., the product is GaN: After heating the metal substrate stage 35 to 300℃, high-purity ammonia gas with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of the high-purity ammonia gas is controlled at 150 sccm, and the gas pressure in the reaction chamber 31 is controlled at 3Pa. After the gas pressure in the reaction chamber 31 stabilizes, the microwave power supply is set to 650W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power to generate ammonia plasma. After the microwave discharge stabilizes, trimethylgallium is introduced into the reaction chamber 31 as a gallium source using the gas phase metal-organic compound supply device 21 through the second gas distribution valve 37 and the first gas supply ring 21-1 to prepare Ga.(3x+2y) / 3 N x O y Growth layer 7, in which hydrogen is used as the carrier gas for the gallium source, and the molar flow rate of the gallium source is controlled at 7.0 × 10⁻⁶. - 6 mol / min, so that Ga (3x+2y) / 3 N x O y The thickness of growth layer 7 is controlled to be 500 nm;

[0043] Ga (3x+2y) / 3 N x O y After the growth layer 7 is prepared, the gallium source is first turned off, and then the temperature of the metal substrate stage 35 is set to 20°C to begin cooling. During the cooling process, the other preparation processes in step h are kept unchanged. When the temperature drops to 80°C, the microwave source 14 and other gases are turned off, and then the orderly operation is performed to remove the Ga substrate. (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is then sequentially shut down;

[0044] Step i: Preparation of flexible GaN thin films by mechanical exfoliation: GaN films are immobilized. (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is scribed, exposing the entire interface edge between the Ga2O3 electrospun layer 3 and the diffusion barrier layer 2. The Ga2O3 is then cleaned and dried. (3x+2y) / 3 N x O y On the surface of growth layer 7, a piece of transparent tape with adhesive on one side is attached to Ga. (3x+2y) / 3 N x O y The upper surface edge of growth layer 7 is rolled with a rolling pressure of 20 kPa, twice, and left to stand for 1 minute. Under the conditions of ambient temperature of 20°C and relative humidity of 30%, the peeling angle is controlled at 30° and the peeling speed at 10 mm / min. The layer is then slowly lifted from the exposed edge with a total tensile force of 4 N, allowing the Ga... (3x+2y) / 3 N x O y The entire growth layer 7 to Ga2O3 electrospinning layer 3 is peeled off from the diffusion barrier layer 2 / metal substrate 1.

[0045] Using the above steps, a wurtzite-phase Ga phase with a thickness of 500 nm was obtained. (3x+2y) / 3 N x O y Atomic force microscopy (AFM) analysis of the flexible GaN film grown in layer 7 showed that Ga... (3x+2y) / 3N x O y The root-mean-square roughness of the growth layer 7 is less than 3.6 nm; X-ray diffraction results show that Ga (3x+2y) / 3 N x O y The growth layer 7 is grown with a single c-axis orientation, and the full width at half maximum (FWHM) of the high-resolution X-ray diffraction curve of its GaN(002) crystal plane is less than 265 arcseconds.

[0046] Example 2

[0047] The continuous process steps for preparing a peelable gallium oxide (Ga2O3) thin film on a molybdenum-titanium alloy (Mo-Ti) substrate are as follows:

[0048] Step a: Cleaning and drying pre-treated metal substrate 1: Select a molybdenum-titanium alloy with a size of 20mm×20mm, a thickness of 3mm, a composition of Mo: 95wt%, Ti: 5wt%, and an impurity content of no more than 0.001% as metal substrate 1. Place the metal substrate 1 in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning 3 times in sequence. Finally, rinse it with deionized water and blow it dry with high-purity nitrogen gas with a purity greater than 5N.

[0049] Step b, Preparation of diffusion barrier layer 2 by magnetron sputtering: A tungsten-titanium alloy (W-Ti) with a composition of W: 90wt%, Ti: 10wt%, and impurity content less than 0.001% is selected as the target material. High-purity argon gas with a purity greater than 6N is used for sputtering. The metal substrate 1 treated in step a is arranged on the material stage in the coating chamber of the magnetron sputtering equipment. When the background gas pressure in the coating chamber of the magnetron sputtering equipment is evacuated to 1×10 -4 When the pressure is 5 Pa, heat the stage to 600℃. After the stage temperature stabilizes, introduce high-purity argon into the magnetron sputtering coating chamber at a flow rate of 100 sccm to control the pressure in the coating chamber to 5 Pa. After the pressure in the coating chamber stabilizes, set the power of the RF sputtering power supply for the required tungsten-titanium alloy target to 200W and turn on the required RF sputtering power supply to begin sputtering and depositing the tungsten-titanium alloy diffusion barrier layer 2 on the surface of the metal substrate 1, and control the thickness of the tungsten-titanium alloy diffusion barrier layer 2 to 100 nm.

[0050] Step c, Preparation of Ga2O3 electrospinning layer 3: A polymer solution containing Ga2O3 precursor was used as the spinning solution. The solution was prepared by dissolving gallium nitrate and polyvinylpyrrolidone in dimethylformamide (DMF) at a mass ratio of 4:5. After stirring evenly, the solution was filtered through a 0.5 μm filter membrane. During the spinning process, a high-voltage electrostatic field traction process was used. The spinning solution was sprayed from the needle tip at a rate of 1.0 mL / h under the push of an injection pump, keeping the distance between the needle tip and the diffusion barrier layer 2 at 20 cm. A high-voltage power supply of 20 kV was applied, and the ambient temperature was controlled at 30 °C and the relative humidity at 35%. In this process, the spinning solution fibers are uniformly drawn and deposited along the surface direction of the diffusion barrier layer 2 to form a parallel and ordered spinning solution fiber array. Then, the metal substrate 1 with the diffusion barrier layer 2 and the spinning solution fiber array is placed in an atmospheric pressure tube furnace and heat-treated in a high-purity oxygen atmosphere with a purity greater than 6N. The high-purity oxygen flow rate is 200 sccm, the heat treatment temperature is 1000℃, and the heat treatment time is 10 min, thereby obtaining a Ga2O3 electrospun layer 3 on the diffusion barrier layer, so that the Ga2O3 fiber diameter is controlled to be 200 nm and the Ga2O3 fiber spacing is controlled to be 2 μm.

[0051] Step d, ECR oxygen plasma oxidation treatment: The metal substrate 1 with the diffusion barrier layer 2 and Ga2O3 electrospun layer 3 prepared is transferred from the atmospheric pressure tube furnace after being restored to room temperature to the metal substrate loading chamber 32 in the ECR-PEMOCVD equipment, and then transferred from the metal substrate loading chamber 32 to the metal substrate stage 35 in the reaction chamber 31. When the background pressure of the reaction chamber 31 is evacuated to 1×10 -5 After Pa, the temperature of the metal substrate stage 35 is heated to 400℃. When the temperature of the metal substrate stage 35 stabilizes, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the first gas distribution valve 30 of the discharge gas supply device, from the second gas supply ring 30-1 with several through holes along the circumferential direction of the first gas distribution valve 30. The flow rate of high-purity oxygen is 200 sccm, so that the gas pressure of the reaction chamber 31 is controlled at 5Pa. When the gas pressure of the reaction chamber 31 stabilizes, the power of the microwave source 14 is set to 1000W, the microwave source 14 is turned on to discharge, the piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power, and ECR oxygen plasma oxidation treatment is performed for 2 minutes.

[0052] Step e, ECR hydrogen plasma cleaning treatment: After step d, the high-purity oxygen discharge in the ECR-PEMOCVD equipment is switched to high-purity hydrogen discharge with a purity greater than 6N. The high-purity hydrogen flow rate is 200 sccm, the working pressure is controlled at 5 Pa, the microwave source 14 power is kept at 1000W, and the time is controlled at 30 min, so as to form a Ga-rich layer 4 rich in metallic Ga and Ga2O on the surface of Ga2O3 electrospinning, and the thickness of the Ga-rich layer 4 is controlled at 20 nm.

[0053] Step f, preparation of liquid Ga layer 5 by spin coating: After step e, the metal substrate 1 with the Ga-rich layer 4 is transferred to the glove box 8 of the ECR-PEMOCVD equipment. Then, a liquid Ga spin coating process is performed using a spin coater. The Ga raw material used is high-purity liquid Ga with a purity higher than 6N. To avoid oxidation of the liquid Ga, the entire transfer and spin coating process is maintained at one atmosphere and operated under an argon atmosphere with a purity higher than 6N. Before spin coating, the metal substrate 1 with the Ga-rich layer 4 is fixed in a vacuum. On the adsorption spin coating stage, ensure that the Ga-rich layer 4 faces upward and preheat the spin coating stage to 100°C. Then, use a micro-syringe to uniformly drop high-purity liquid Ga onto the surface of the Ga-rich layer 4 at a rate of 2.0 μL / mm². Immediately afterward, start the spin coating program, starting slowly at 500 rpm for 10 seconds, then accelerating to 4000 rpm and holding for 100 seconds. After spin coating, slowly cool the spin coating stage to room temperature to obtain a liquid Ga layer 5 on the Ga-rich layer 4. Control the thickness of the liquid Ga layer 5 to be 100 nm.

[0054] Step g: Preparation of Ga by ECR-PEMOCVD method (3m+2n) / 3 N m O n Buffer layer 6 (in this embodiment, Ga) (3m+2n) / 3 N m O n The nitrogen and oxygen component values ​​in the buffer layer 6 material are set to m=0 and n=3, respectively, i.e., the product is Ga2O3): The metal substrate 1 with the liquid Ga layer 5 is transferred from the glove box 8 of the ECR-PEMOCVD equipment to the metal substrate loading chamber 32, and then from the metal substrate loading chamber 32 to the metal substrate stage 35 in the reaction chamber 31. When the background gas pressure of the reaction chamber 31 is evacuated to 1×10 -5After Pa, the temperature of the metal substrate stage 35 is heated to 400℃. Once the temperature of the metal substrate stage 35 stabilizes, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of the high-purity oxygen is controlled at 150 sccm, so that the gas pressure in the reaction chamber 31 is controlled at 4.5 Pa. After the gas pressure in the reaction chamber 31 stabilizes, the power of the microwave source 14 is set to 800W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power to generate oxygen plasma. After the microwave discharge stabilizes, triethylgallium is introduced into the reaction chamber 31 as a gallium source to prepare Ga. (3m+2n) / 3 N m O n Buffer layer 6, wherein the carrier gas for the gallium source is hydrogen, and the molar flow rate of the gallium source is controlled at 6.5 × 10⁻⁶. -6 mol / min, convert Ga (3m+2n) / 3 N m O n The thickness of buffer layer 6 is controlled to be 100nm;

[0055] Step h: Preparation of Ga by ECR-PEMOCVD method (3x+2y) / 3 N x O y Growth layer 7 (in this embodiment, Ga (3x+2y) / 3 N x O y The nitrogen and oxygen component values ​​in the growth layer 7 material are set to x=0 and y=3, respectively, i.e., the product is Ga2O3: After heating the metal substrate stage 35 to 500℃, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of high-purity oxygen is controlled at 200 sccm, and the gas pressure in the reaction chamber 31 is controlled at 5 Pa. After the gas pressure in the reaction chamber 31 stabilizes, the microwave power supply is set to 1000W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power to generate oxygen plasma. After the microwave discharge stabilizes, trimethylgallium is introduced into the reaction chamber 31 as a gallium source to prepare Ga. (3x+2y) / 3 N x O y Growth layer 7, in which hydrogen is used as the carrier gas for the gallium source, and the molar flow rate of the gallium source is controlled at 5.0 × 10⁻⁶. -5 mol / min, so that Ga (3x+2y) / 3 N x O y The thickness of growth layer 7 is controlled to be 5 μm;

[0056] Ga (3x+2y) / 3 N x O yAfter the growth layer 7 is prepared, the gallium source is first turned off, and then the temperature of the metal substrate stage 35 is set to 20°C to begin cooling. During the cooling process, the other preparation processes in step h are kept unchanged. When the temperature drops to 80°C, the microwave source 14 and other gases are turned off, and then the orderly operation is performed to remove the Ga substrate. (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is then sequentially shut down;

[0057] Step i: Preparation of flexible Ga2O3 thin film by mechanical exfoliation: Ga2O3 film is prepared by immobilization. (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is scribed, exposing the entire interface edge between the Ga2O3 electrospun layer 3 and the diffusion barrier layer 2. The Ga2O3 is then cleaned and dried. (3x+2y) / 3 N x O y On the surface of growth layer 7, a piece of transparent tape with adhesive on one side is attached to Ga. (3x+2y) / 3 N x O y The upper surface edge of growth layer 7 is rolled with a rolling pressure of 50 kPa, rolled 3 times, and left to stand for 3 minutes. Under the conditions of ambient temperature of 30°C and relative humidity of 30%, the peeling angle is controlled at 70° and the peeling speed at 100 mm / min. The layer is slowly lifted from the exposed edge with a total tensile force of 24 N, so that the Ga... (3x+2y) / 3 N x O y The entire growth layer 7 to Ga2O3 electrospinning layer 3 is peeled off from the diffusion barrier layer 2 / metal substrate 1.

[0058] Using the above steps, a monoclinic Ga phase with a thickness of 5 μm was obtained. (3x+2y) / 3 N x O y Atomic force microscopy (AFM) analysis of the flexible Ga2O3 film grown in layer 7 showed that Ga... (3x+2y) / 3 N x O y The root-mean-square roughness of the surface of growth layer 7 is less than 4.3 nm; X-ray diffraction results show that Ga (3x+2y) / 3 N x O y The growth layer 7 is grown with a single (002) plane orientation, and the full width at half maximum (FWHM) of the high-resolution X-ray diffraction curve of its β-Ga2O3 (002) crystal plane is less than 273 arcseconds.

[0059] Example 3

[0060] Preparation of peelable Ga on a tantalum (Ta) substrate 0.65 N 0.15 O 0.75 The continuous process steps for thin films are as follows:

[0061] Step a: Clean and dry the pretreated metal substrate 1: Select a tantalum (Ta) metal with a size of 20mm×20mm, a thickness of 2mm, and a purity greater than 5N as the metal substrate 1. Place the metal substrate 1 in acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning 3 times each. Finally, rinse it with deionized water and blow it dry with high-purity nitrogen gas with a purity greater than 5N.

[0062] Step b: Preparation of diffusion barrier layer by magnetron sputtering: Titanium nitride (TiN) with a total impurity content of less than 0.001% is selected as the target material. High-purity argon gas with a purity greater than 6N is used for sputtering. The metal substrate 1 treated in step a is arranged on the material stage in the coating chamber of the magnetron sputtering equipment. When the background gas pressure in the coating chamber of the magnetron sputtering equipment is evacuated to 1×10 -4 When the pressure is Pa, heat the stage to 300℃. After the stage temperature stabilizes, introduce high-purity argon gas into the magnetron sputtering coating chamber at a flow rate of 40 sccm to control the pressure in the coating chamber to 3.5 Pa. After the pressure in the coating chamber stabilizes, set the power of the radio frequency sputtering power supply for the required titanium nitride target to 120W and turn on the required radio frequency sputtering power supply to begin sputtering and depositing the titanium nitride diffusion barrier layer 2 on the surface of the metal substrate 1, and control the thickness of the titanium nitride diffusion barrier layer 2 to 20 nm.

[0063] Step c, Preparation of Ga2O3 electrospinning layer 3: A polymer solution containing Ga2O3 precursor was used as the spinning solution. The solution was prepared by dissolving gallium acetate and polyvinylpyrrolidone in dimethylformamide (DMF) at a mass ratio of 1:5. After stirring evenly, the solution was filtered through a 0.3 μm filter membrane. During the spinning process, a high-voltage electrostatic field traction process was adopted. The spinning solution was sprayed from the needle tip at a rate of 0.5 mL / h under the impetus of an injection pump, keeping the distance between the needle tip and the diffusion barrier layer 2 at 15 cm. A high-voltage power supply of 15 kV was applied, and the ambient temperature was controlled at 25 °C and the relative humidity at 35%. Under the action of the diffusion barrier layer 2, the spinning solution fibers are uniformly drawn and deposited along the surface direction of the diffusion barrier layer 2 to form a parallel and ordered spinning solution fiber array. Then, the metal substrate 1 with the diffusion barrier layer 2 and the spinning solution fiber array is placed in an atmospheric pressure tube furnace and heat-treated in a high-purity oxygen atmosphere with a purity greater than 6N. The oxygen flow rate is 150 sccm, the heat treatment temperature is 800℃, and the heat treatment time is 5 min, thereby obtaining a Ga2O3 electrospinning layer 3 on the diffusion barrier layer, so that the Ga2O3 fiber diameter is controlled to be 100 nm and the Ga2O3 fiber spacing is controlled to be 0.2 μm.

[0064] Step d, ECR oxygen plasma oxidation treatment: The metal substrate 1 with the diffusion barrier layer 2 and Ga2O3 electrospun layer 3 prepared is transferred from the atmospheric pressure tube furnace after being restored to room temperature to the metal substrate loading chamber 32 in the ECR-PEMOCVD equipment, and then transferred from the metal substrate loading chamber 32 to the metal substrate stage 35 in the reaction chamber 31. When the background pressure of the reaction chamber 31 is evacuated to 1×10 -5 After Pa, the temperature of the metal substrate stage 35 is heated to 300℃. When the temperature of the metal substrate stage 35 stabilizes, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber 20 through the first gas distribution valve 30 of the discharge gas supply device from the second gas supply ring 30-1 of the first gas distribution valve 30. The flow rate of high-purity oxygen is 100 sccm, so that the gas pressure of the reaction chamber 31 is controlled at 3Pa. When the gas pressure of the reaction chamber 31 stabilizes, the power of the microwave source 14 is set to 500W, the microwave source 14 is turned on to discharge, the piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power, and the ECR oxygen plasma oxidation treatment is started, with the time controlled at 5min.

[0065] Step e, ECR hydrogen plasma cleaning treatment: After step d, the high-purity oxygen discharge in the ECR-PEMOCVD equipment is switched to high-purity hydrogen discharge with a purity greater than 6N. The high-purity hydrogen flow rate is 190 sccm, the working pressure is controlled at 3 Pa, the power of microwave source 14 is kept at 600W, the piston short circuit 18 is adjusted so that microwave source 14 can monitor microwave reflection power, and the time is controlled at 10min, so as to form a Ga-rich layer 4 rich in metallic Ga and Ga2O on the surface of Ga2O3 electrospinning, and the thickness of Ga-rich layer 4 is controlled at 10nm.

[0066] Step f, preparation of liquid Ga layer 5 by spin coating: After step e, the metal substrate 1 with the Ga-rich layer 4 is transferred to the glove box 8 of the ECR-PEMOCVD equipment. Then, a liquid Ga spin coating process is performed using a spin coater. The Ga raw material used is high-purity liquid Ga with a purity higher than 6N. To avoid oxidation of the liquid Ga, the entire transfer and spin coating process is maintained at one atmosphere and operated under a nitrogen atmosphere with a purity higher than 6N. Before spin coating, the metal substrate 1 with the Ga-rich layer 4 is fixed on a vacuum gas cylinder. On the air adsorption spin coating stage, ensure that the Ga-rich layer 4 faces upward and preheat the spin coating stage to 60°C. Then, use a micro-injection needle to uniformly drop high-purity liquid Ga onto the surface of the Ga-rich layer 4 at a rate of 1.5 μL / mm². Immediately afterward, start the spin coating program, starting slowly at 300 rpm for 10 seconds, then accelerating to 3000 rpm and holding for 60 seconds. After spin coating, slowly cool the spin coating stage to room temperature to obtain a liquid Ga layer 5 on the Ga-rich layer 4. Control the thickness of the liquid Ga layer 5 to be 10 nm.

[0067] Step g: Preparation of Ga by ECR-PEMOCVD method (3m+2n) / 3 N m O n Buffer layer 6 (in this embodiment, Ga) (3m+2n) / 3 N m O n The nitrogen and oxygen component values ​​in buffer layer 6 are set to m=0.1 and n=0.9, respectively, meaning the product is Ga. 0.7 N 0.1 O 0.9 The metal substrate 1 with the liquid Ga layer 5 is transferred from the glove box 8 of the ECR-PEMOCVD equipment to the metal substrate loading chamber 32, and then from the metal substrate loading chamber 32 to the metal substrate stage 35 in the reaction chamber 31. When the background gas pressure of the reaction chamber 31 is reduced to 1×10 - 5 After Pa, the temperature of the metal substrate stage 35 is heated to 300℃. Once the temperature of the metal substrate stage 35 stabilizes, high-purity oxygen, high-purity ammonia, and high-purity nitric oxide with a purity greater than 6N are introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of high-purity oxygen is controlled at 90 sccm, the flow rate of high-purity ammonia is controlled at 25 sccm, and the flow rate of high-purity nitric oxide is controlled at 5 sccm, so that the gas pressure in the reaction chamber 31 is controlled at 4.5 Pa. Once the gas pressure in the reaction chamber 31 stabilizes, the power of the microwave source 14 is set to 700W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power, generating a mixed plasma containing oxygen and nitrogen. After the microwave discharge stabilizes, trimethylgallium is introduced into the reaction chamber 31 as a gallium source to prepare Ga. (3m+2n) / 3 N m O n Buffer layer 6, wherein the carrier gas for the gallium source is hydrogen, and the molar flow rate of the gallium source is controlled at 6.5 × 10⁻⁶. - 6 mol / min, convert Ga (3m+2n) / 3 N m O n The thickness of buffer layer 6 is controlled to be 80nm;

[0068] Step h: Preparation of Ga by ECR-PEMOCVD method (3x+2y) / 3 N x O y Growth layer 7 (in this embodiment, Ga (3x+2y) / 3 N x O y The nitrogen and oxygen component values ​​in the growth layer 7 material were set to x=0.15 and y=0.75, respectively, meaning the product was Ga. 0.65 N 0.15 O 0.75After heating the metal substrate stage 35 to 500℃, high-purity ammonia, high-purity oxygen, and high-purity nitric oxide (with a purity greater than 6N) are introduced into the quartz cup discharge chamber 20 through the second gas supply ring 30-1 using the first gas distribution valve 30. The flow rate of high-purity oxygen is controlled at 74 sccm, the flow rate of high-purity ammonia at 37 sccm, and the flow rate of high-purity nitric oxide at 9 sccm, so that the gas pressure in the reaction chamber 31 is controlled at 4.5 Pa. After the gas pressure in the reaction chamber 31 stabilizes, the microwave power supply is set to 700W, and the microwave power supply is turned on for discharge. The piston short circuit 18 is adjusted so that the microwave source 14 can monitor the microwave reflection power, generating a mixed plasma containing oxygen and nitrogen. After the microwave discharge stabilizes, trimethylgallium is introduced into the reaction chamber 31 as a gallium source to prepare Ga. (3x+2y) / 3 N x O y Growth layer 7, in which hydrogen is used as the carrier gas for the gallium source, and the molar flow rate of the gallium source is controlled at 7.0 × 10⁻⁶. -6 mol / min, convert Ga (3x+2y) / 3 N x O y The thickness of growth layer 7 is controlled to be 3 μm;

[0069] Ga (3x+2y) / 3 N x O y After the growth layer 7 is prepared, the gallium source is first turned off, and then the temperature of the metal substrate stage 35 is set to 20°C to begin cooling. During the cooling process, the other preparation processes in step h are kept unchanged. When the temperature drops to 80°C, the microwave source 14 and other gases are turned off, and then the orderly operation is performed to remove the Ga substrate. (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is then sequentially shut down;

[0070] Step i: Preparation of flexible Ga by mechanical exfoliation method 0.65 N 0.15 O 0.75 Thin film: prepared with Ga (3x+2y) / 3 N x O y The metal substrate 1 of the growth layer 7 is scribed, exposing the entire interface edge between the Ga2O3 electrospun layer 3 and the diffusion barrier layer 2. The Ga2O3 is then cleaned and dried. (3x+2y) / 3 N x O y On the surface of growth layer 7, a piece of transparent tape with adhesive on one side is attached to Ga. (3x+2y) / 3 N x O yThe upper surface edge of growth layer 7 is rolled with a rolling pressure of 30 kPa, rolled 3 times, and left to stand for 3 minutes. Under the conditions of ambient temperature of 25°C and relative humidity of 30%, the peeling angle is controlled at 30° and the peeling speed at 50 mm / min. The layer is slowly lifted from the exposed edge with a total tensile force of 20 N, so that the Ga... (3x+2y) / 3 N x O y The entire growth layer 7 to Ga2O3 electrospinning layer 3 is peeled off from the diffusion barrier layer 2 / metal substrate 1.

[0071] Using the above steps, a monoclinic Ga phase with a thickness of 3 μm was obtained. (3x+2y) / 3 N x O y Flexible Ga in growth layer 7 0.65 N 0.15 O 0.75 Thin film, AFM testing results show that Ga (3x+2y) / 3 N x O y The root-mean-square roughness of the growth layer 7 is less than 5.2 nm; X-ray diffraction results show that Ga (3x+2y) / 3 N x O y Growth layer 7 is grown with a single (002) face orientation, and its β-Ga 0.65 N 0.15 O 0.75 The full width at half maximum (FWHM) of the rocking curves of the high-resolution X-ray diffraction of the crystal plane is less than 306 arcseconds.

Claims

1. A peelable flexible Ga based on electrospinning (3x+2y) / 3 N x O y The thin film is characterized by, The Ga (3x+2y) / 3N x O y The thin film uses a metal substrate. On one side of the metal substrate, from the inside out, are a diffusion barrier layer, a Ga2O3 electrospun layer, a Ga-rich layer, a liquid Ga layer, and a Ga layer. (3m+2n) / 3 N m O n Buffer layer and Ga (3x+2y) / 3 N x O y Growth layer.

2. The peelable flexible Ga based on electrospinning according to claim 1 (3x+2y) / 3 N x O y The thin film is characterized by, The metal substrate is made of an alloy composed of one or more of the following: silver, gold, cobalt, chromium, copper, iron, hafnium, iridium, molybdenum, nickel, niobium, platinum, ruthenium, titanium, tantalum, tungsten, and zirconium; the diffusion barrier layer is composed of an alloy composed of one or more of the following: chromium, hafnium, tungsten, molybdenum, niobium, tantalum, titanium, zirconium, and carbon, or a nitride formed by at least one of the following elements: chromium, hafnium, tungsten, molybdenum, niobium, tantalum, titanium, and zirconium; the Ga2O3 electrospun layer is a parallel ordered fiber array structure composed of Ga2O3; the Ga-rich layer is composed of elemental Ga and Ga2O; the liquid Ga layer is composed of liquid Ga with a uniform thickness and a purity of 6N or higher; the Ga... (3m+2n) / 3 N m O n The component values ​​of the buffer layer are controlled as follows: 0≤m≤1, 0≤n≤3; the Ga (3x+2y) / 3 N x O y The component values ​​of the growth layer are controlled as follows: 0≤x≤1, 0≤y≤3.

3. A peelable flexible Ga based on electrospinning according to claim 1 (3x+2y) / 3 N x O y The thin film is characterized by, The thickness of the metal substrate is 0.3–3 mm; the thickness of the diffusion barrier layer is 5–100 nm; the Ga₂O₃ electrospun layer has Ga₂O₃ fibers with a diameter of 50–200 nm and a fiber spacing of 0.2–2 μm; the thickness of the Ga-rich layer is 1–20 nm; the thickness of the liquid Ga layer is 10–100 nm; the Ga… (3m+2n) / 3 N m O n The thickness of the buffer layer is 20nm to 100nm; the Ga (3x+2y) / 3 N x O y The thickness of the growth layer is 500 nm to 5 μm.

4. The peelable flexible Ga based on electrospinning according to any one of claims 1-3 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, The preparation was carried out using an ECR-PEMOCVD apparatus, including the following steps: Step a, cleaning and drying the pretreated metal substrate; Step b, preparing a diffusion barrier layer by magnetron sputtering; Step c, preparing a Ga2O3 electrospun layer; Step d, ECR oxygen plasma oxidation treatment; Step e, ECR hydrogen plasma cleaning treatment; Step f, preparing a liquid Ga layer by spin coating; Step g, preparing Ga by ECR-PEMOCVD. (3m+2n) / 3 N m O n Buffer layer; Step h, ECR-PEMOCVD method for preparing Ga (3x+2y) / 3 N x O y Growth layer; Step i: Preparation of flexible Ga by mechanical exfoliation method (3x+2y) / 3 N x O y film.

5. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, Step a specifically involves: placing the metal substrate in acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning at least three times, rinsing it clean with deionized water, and then drying it with high-purity nitrogen gas with a purity greater than 5N. Step b specifically involves: using a high-purity target material with an impurity content of less than 0.001%, and using high-purity argon gas with a purity greater than 6N as the sputtering gas. The metal substrate treated in step a is placed on the material stage within the coating chamber of the magnetron sputtering equipment. When the background pressure of the coating chamber is evacuated to 5 × 10⁻⁶... -4 Below Pa, heat the stage to 50-600℃. After the stage temperature stabilizes, introduce high-purity argon gas into the magnetron sputtering coating chamber at a flow rate of 40-100 sccm to control the coating chamber pressure at 0.1-5 Pa. After the coating chamber pressure stabilizes, set the power of the RF sputtering power supply for the target to 30-200W and turn on the RF sputtering power supply to begin sputtering and depositing a diffusion barrier layer on the surface of the metal substrate. Step c specifically involves: using a polymer solution containing a Ga2O3 precursor as the spinning solution. The polymer solution is prepared by dissolving gallium acetate or gallium nitrate and polyvinylpyrrolidone in dimethylformamide at a mass ratio of 1:5 to 4:

5. The solution is stirred evenly and filtered through a 0.2 to 0.5 μm filter membrane. During the spinning process, a high-voltage electrostatic field traction process is used. Under the impetus of an injection pump, the spinning solution is sprayed from the needle tip at a rate of 0.2 to 1.0 mL / h, maintaining the distance between the needle tip and the diffusion barrier layer at 10 to 20 cm. A high-voltage power supply is applied with a voltage of 10 to 20 kV, and the ambient temperature is controlled. At a temperature of 20–30°C and a relative humidity not exceeding 40%, under the influence of an electric field, the spinning solution fibers are uniformly drawn and deposited along the surface direction of the diffusion barrier layer, forming a parallel and ordered array of spinning solution fibers. Then, the metal substrate with the diffusion barrier layer and the spinning solution fiber array is placed in an atmospheric pressure tube furnace and heat-treated in a high-purity oxygen atmosphere with a purity greater than 6N. The flow rate of the high-purity oxygen is 50–200 sccm, the heat treatment temperature is 800–1000°C, and the heat treatment time is 2–10 min, thereby obtaining a Ga2O3 electrospun layer on the diffusion barrier layer.

6. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, Step d specifically involves: transferring the metal substrate with the diffusion barrier layer and Ga2O3 electrospun layer from the atmospheric pressure tube furnace (after it has recovered to room temperature) to the metal substrate loading chamber of the ECR-PEMOCVD equipment, and then from the metal substrate loading chamber to the metal substrate platform in the reaction chamber. When the background pressure in the reaction chamber is evacuated to 1×10⁻⁶... -4 After the temperature of the metal substrate stage is below Pa, heat the temperature to 25-400℃. When the temperature of the metal substrate stage is stable, high-purity oxygen with a purity greater than 6N is introduced into the quartz cup discharge chamber through the first gas distribution valve of the discharge gas supply device. The second gas supply ring with several through holes along the circumference of the first gas distribution valve is introduced into the chamber. The flow rate of high-purity oxygen is 60-200 sccm, so that the gas pressure in the reaction chamber is controlled at 0.1-5 Pa. When the gas pressure in the reaction chamber is stable, the microwave power supply is set to 300-1000W, the microwave source is turned on to discharge, and ECR oxygen plasma oxidation treatment is performed for 2-10 minutes. The specific steps of step e are as follows: the high-purity oxygen discharge in the ECR-PEMOCVD equipment is switched to high-purity hydrogen discharge with a purity greater than 6N, the high-purity hydrogen flow rate is 50-200 sccm, the working pressure is controlled at 0.1-5 Pa, the microwave source power is maintained at 300-1000 W, and the time is controlled at 30s-30min, so as to form a Ga-rich layer rich in metallic Ga and Ga2O on the surface of Ga2O3 electrospinning.

7. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, Step f specifically involves: transferring the metal substrate with the Ga-rich layer to the glove box of the ECR-PEMOCVD equipment, followed by a liquid Ga spin coating process. The Ga raw material used is high-purity liquid Ga with a purity higher than 6N. During the transfer and spin coating process, the operation is carried out under a nitrogen or argon atmosphere with a purity higher than 6N. Before spin coating, the metal substrate with the Ga-rich layer is fixed on the vacuum adsorption spin coating stage, ensuring that the Ga-rich layer faces upwards. The spin coating stage is preheated to 40-100°C. Then, high-purity liquid Ga is uniformly dropped onto the surface of the Ga-rich layer at a rate of 0.5-2.0 μL / mm² using a micro-injection needle. The spin coating program is then started immediately, with the rotation speed starting slowly from 100-500 rpm and continuing for 5-10 seconds. The speed is then accelerated to 2000-4000 rpm and maintained for 50-100 seconds. After spin coating, the spin coating stage is slowly cooled to room temperature, resulting in a liquid Ga layer on the Ga-rich layer.

8. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, Step g specifically involves: transferring the metal substrate with the liquid Ga layer prepared from the glove box of the ECR-PEMOCVD equipment to the metal substrate loading chamber, and then from the metal substrate loading chamber to the metal substrate platform in the reaction chamber. When the background gas pressure in the reaction chamber is evacuated to 1×10⁻⁶... -4 After the temperature drops below Pa, the metal substrate stage is heated to 100–500°C. Once the temperature stabilizes, the first gas distribution valve of the discharge gas supply device is used to introduce one or more of the following gases—high-purity oxygen (greater than 6N), nitrogen, ammonia, nitrous oxide, nitric oxide, and nitrogen dioxide—through the second gas supply ring into the quartz cup discharge chamber. The total gas flow rate is controlled at 50–200 sccm, maintaining the gas pressure in the reaction chamber at 0.1–5 Pa. After the gas pressure in the reaction chamber stabilizes, the microwave source power is set to 300–1000 W, and the microwave power supply is turned on to discharge, generating oxygen plasma, nitrogen plasma, ammonia plasma, or a mixed plasma containing oxygen and nitrogen. After the microwave discharge stabilizes, trimethylgallium or triethylgallium is introduced into the reaction chamber as a gallium source to prepare Ga. (3m+2n) / 3 N m O n A buffer layer is used, in which hydrogen is the carrier gas for the gallium source, and the molar flow rate of the gallium source is controlled at 5.0 × 10⁻⁶. -7 ~5.0×10 -5 mol / min.

9. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, The specific step h is as follows: after heating the metal substrate stage to 300-800℃, the ECR-PEMOCVD method is used to process Ga... (3m+2n) / 3 N m O n Ga prepared on buffer layer (3x+2y) / 3 N x O y The growth layer, including microwave discharge and gallium source introduction, follows the same process as step g. The Ga content is controlled by varying the flow rates and preparation time of each gas. (3x+2y) / 3 N x O y The thickness and composition of the growth layer; Ga (3x+2y) / 3 N x O y After the growth layer is prepared, the gallium source is first turned off, and then the temperature of the metal substrate stage is set to 20°C to begin cooling. During the cooling process, the other preparation processes in step h are kept unchanged. When the temperature drops below 100°C, the microwave source and other gases are turned off, and then the orderly operation is performed to remove the Ga substrate. (3x+2y) / 3 N x O y The metal substrate for growing the layer was then shut down in an orderly manner by the ECR-PEMOCVD equipment.

10. The peelable flexible Ga based on electrospinning according to claim 4 (3x+2y) / 3 N x O y A method for preparing a thin film, characterized in that, Step i specifically involves: fixing Ga... (3x+2y) / 3 N x O y The metal substrate for the growth layer is scribing its surrounding surface to expose the entire interface edge between the Ga2O3 electrospinning layer and the diffusion barrier layer. The Ga2O3 is then cleaned and dried. (3x+2y) / 3 N x O y On the surface of the growth layer, a piece of transparent tape with adhesive on one side is attached to Ga. (3x+2y) / 3 N x O y The upper surface edge of the growth layer is rolled with a pressure of 20–50 kPa, 2–3 times, and left to stand for 1–3 minutes. Under ambient temperature of 20–30°C and relative humidity below 40%, the peeling angle is controlled at 30–70° and the peeling speed at 10–100 mm / min. A total tensile force of 4–24 N is applied, and the layer is slowly lifted from the exposed edge to allow the Ga... (3x+2y) / 3 N x O y The entire growth layer to the Ga2O3 electrospinning layer was peeled off from the diffusion barrier layer and the metal substrate, ultimately yielding a flexible Ga... (3x+2y) / 3 N x O y film.

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