Flexible film preparation method and flexible film
By epitaxially growing a water-soluble sacrificial layer and a single-crystal nickel cobalt oxide film on a single-crystal substrate, and utilizing the dissolution of the sacrificial layer to achieve non-destructive transfer, the problems of poor crystal quality and low yield in flexible film preparation are solved, and high-quality flexible film transfer is achieved.
Patent Information
- Application Number
- CN202511572337.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-30
- Publication Date
- 2026-02-03
AI Technical Summary
In the preparation of flexible thin films, existing technologies often result in poor crystal quality and high defect density in polycrystalline or amorphous thin films. Furthermore, traditional mechanical peeling or chemical etching methods can easily introduce cracks and contamination, leading to low yields.
A water-soluble sacrificial layer and a single-crystal nickel cobalt oxide film are epitaxially grown on a single-crystal substrate. The water-soluble sacrificial layer is dissolved to achieve non-destructive transfer, resulting in a self-supporting single-crystal nickel cobalt oxide film, which is then transferred to a flexible substrate.
This technology enables the non-destructive transfer of flexible films, improving the crystal quality and yield of the films while avoiding damage caused by mechanical peeling or chemical corrosion.
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Figure CN121451284A_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of thin film technology, and in particular to a method for preparing a flexible thin film and a flexible thin film. Background Technology
[0002] Flexible electronics technology is an important direction for the development of future information devices. Among them, the key to realizing high-performance flexible devices is to make functional oxide thin films with excellent electrical and magnetic properties flexible. Perpendicular magnetic anisotropy (PMA) materials, especially oxides with inverse spinel structures, have broad application prospects in magnetic memory, sensors and other fields.
[0003] In the related technologies for preparing flexible thin films, one approach is to directly deposit functional thin films on flexible substrates. However, the resulting thin films are mostly polycrystalline or amorphous, and the resulting crystals have poor quality and high defect density. Their magnetic anisotropy, carrier mobility, and other properties are far inferior to those of single-crystal thin films. Another approach is to use the "post-growth transfer" technique. However, traditional mechanical peeling or chemical etching methods are prone to introducing cracks, contamination, or damage to the functional layer, resulting in a low yield.
[0004] Therefore, how to obtain flexible films through non-destructive transfer is an urgent problem to be solved. Summary of the Invention
[0005] Therefore, it is necessary to provide a method for preparing flexible thin films and a flexible thin film to address the above-mentioned technical problems, so as to achieve the acquisition of flexible thin films through non-destructive transfer.
[0006] In a first aspect, this application provides a method for preparing a flexible thin film, the method comprising:
[0007] Provide a single-crystal substrate;
[0008] A water-soluble sacrificial layer is epitaxially grown on a single-crystal substrate;
[0009] Epitaxial growth of single-crystal nickel cobalt oxide thin films on water-soluble sacrificial layers;
[0010] The sample with a single crystal nickel cobalt oxide film grown on it was immersed in the target solvent. After the water-soluble sacrificial layer was dissolved, the single crystal nickel cobalt oxide film was peeled off from the single crystal substrate to obtain a self-supporting single crystal nickel cobalt oxide film.
[0011] A self-supporting single-crystal nickel cobalt oxide film is transferred onto a target flexible substrate.
[0012] In one embodiment, epitaxially growing a water-soluble sacrificial layer on a single-crystal substrate includes: using pulsed laser deposition to bombard a target solution with a laser to obtain an epitaxially grown water-soluble sacrificial layer on the single-crystal substrate at a target growth temperature; wherein the target solution includes the components of the water-soluble sacrificial layer.
[0013] In one embodiment, epitaxial growth of a single-crystal nickel cobalt oxide film on a water-soluble sacrificial layer includes: using pulsed laser deposition to bombard a nickel cobalt oxide solution with a laser, and obtaining an epitaxially grown single-crystal nickel cobalt oxide film on a water-soluble sacrificial layer at a target growth temperature.
[0014] In one embodiment, the target growth temperature is 600-800°C.
[0015] In one embodiment, the water-soluble sacrificial layer is a strontium aluminate film; the thickness of the strontium aluminate film is 10nm-100nm.
[0016] In one embodiment, the target solvent is deionized water; the dissolution temperature of deionized water is 20-80°C.
[0017] In one embodiment, the thickness of the single-crystal nickel cobalt oxide film is 5nm-50nm.
[0018] In one embodiment, the material of the single-crystal substrate is magnesium aluminate or strontium titanate.
[0019] In one embodiment, the material of the target flexible substrate is polydimethylsiloxane, polyimide, or polyethylene terephthalate.
[0020] Secondly, this application provides a flexible film, which is obtained by the flexible film preparation method described in any embodiment of the first aspect.
[0021] The above-described flexible thin film preparation method and flexible thin film can provide a single-crystal substrate, on which a water-soluble sacrificial layer is epitaxially grown. A single-crystal nickel cobalt oxide thin film is then epitaxially grown on the water-soluble sacrificial layer. The sample with the grown single-crystal nickel cobalt oxide thin film is immersed in a target solvent to dissolve the water-soluble sacrificial layer. The single-crystal nickel cobalt oxide thin film is then peeled off from the single-crystal substrate to obtain a self-supporting single-crystal nickel cobalt oxide thin film. The self-supporting single-crystal nickel cobalt oxide thin film is then transferred to the target flexible substrate. In the above preparation process, after obtaining the single-crystal nickel cobalt oxide thin film on the water-soluble sacrificial layer, the water-soluble sacrificial layer is dissolved by immersing the sample with the grown single-crystal nickel cobalt oxide thin film in the target solvent, thus obtaining a non-destructive single-crystal nickel cobalt oxide thin film. The self-supporting single-crystal nickel cobalt oxide thin film can then be transferred to the target flexible substrate. Compared with the existing technology of peeling off flexible thin films by mechanical peeling or chemical etching, this method can achieve non-destructive transfer of flexible thin films. Attached Figure Description
[0022] To more clearly illustrate the technical solutions in the embodiments of this application or related technologies, the drawings used in the description of the embodiments of this application or related technologies will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.
[0023] Figure 1 This is a schematic flowchart of a flexible thin film preparation method in one embodiment;
[0024] Figure 2 This is a flowchart illustrating the epitaxial growth steps of a water-soluble sacrificial layer in one embodiment;
[0025] Figure 3 This is a schematic flowchart of the epitaxial growth steps of a single-crystal nickel cobalt oxide thin film in one embodiment;
[0026] Figure 4 This is a schematic flowchart of a flexible thin film preparation method in another embodiment;
[0027] Figure 5 This is a flowchart illustrating the flexible thin film preparation method in yet another embodiment;
[0028] Figure 6 The XRD diffraction patterns of nickel cobalt oxide films deposited at different temperatures in one embodiment are shown.
[0029] Figure 7 This is a schematic diagram of the magnetization intensity versus external magnetic field intensity curves of nickel cobalt oxide thin films deposited at different temperatures in one embodiment;
[0030] Figure 8 This is a structural block diagram of a flexible thin film fabrication apparatus in one embodiment;
[0031] Figure 9 This is an internal structural diagram of a computer device in one embodiment. Detailed Implementation
[0032] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.
[0033] In one exemplary embodiment, such as Figure 1 As shown, a method for preparing a flexible thin film is provided, comprising the following steps:
[0034] S110 provides a single-crystal substrate.
[0035] The single-crystal substrate is used to provide support for the growth of single-crystal nickel cobalt oxide (NiCo2O4, or NCO) thin films.
[0036] In one alternative embodiment, the material of the single-crystal substrate can be magnesium aluminate (MgAl2O4, or MAO) or strontium titanate (SrTiO3).
[0037] S120, an epitaxial growth of a water-soluble sacrificial layer on a single-crystal substrate.
[0038] The water-soluble sacrificial layer can be understood as a temporary layer used in the material preparation process, which releases the structure through dissolution.
[0039] In the embodiments of this application, the water-soluble sacrificial layer is used to provide temporary support for the growth of the monocrystalline nickel cobalt oxide film, and is used to obtain the monocrystalline nickel cobalt oxide film after removal.
[0040] In one optional embodiment, the water-soluble sacrificial layer can be a strontium aluminate (Sr3Al2O6, or SAO) film. In another optional embodiment, the thickness of the strontium aluminate film can be 10 nm to 100 nm.
[0041] S130, a single-crystal nickel cobalt oxide thin film is epitaxially grown on a water-soluble sacrificial layer.
[0042] Among them, single-crystal nickel cobalt oxide thin films can be understood as functional oxide thin films, used to provide different electrical, magnetic and other properties in flexible devices.
[0043] In one optional embodiment, the thickness of the single-crystal nickel cobalt oxide film obtained by epitaxial growth can be 5nm-50nm.
[0044] S140: Immerse the sample with the grown monocrystalline nickel cobalt oxide film in the target solvent. After the water-soluble sacrificial layer dissolves, the monocrystalline nickel cobalt oxide film is peeled off from the monocrystalline substrate to obtain a self-supporting monocrystalline nickel cobalt oxide film.
[0045] Among them, the sample with a single-crystal nickel cobalt oxide film can be understood as a sample on a single-crystal substrate with a water-soluble sacrificial layer and a single-crystal nickel cobalt oxide film epitaxially grown sequentially.
[0046] The target solvent is used to dissolve the water-soluble sacrificial layer so that the monocrystalline nickel cobalt oxide film can be peeled off from the monocrystalline substrate to obtain a self-supporting monocrystalline nickel cobalt oxide film.
[0047] In one optional embodiment, the target solvent may be deionized water. In another optional embodiment, the dissolution temperature of deionized water may be 20-80°C.
[0048] It is understandable that self-supporting monocrystalline nickel cobalt oxide films can independently maintain their shape and structural stability without relying on external support.
[0049] S150 transfers a self-supporting single-crystal nickel cobalt oxide film onto a target flexible substrate.
[0050] The target flexible substrate is used to provide support for the self-supporting single-crystal nickel cobalt oxide film.
[0051] In one alternative embodiment, the material of the target flexible substrate may be polydimethylsiloxane (PDMS), polyimide (PI), or polyethylene terephthalate (PET).
[0052] In the above-mentioned flexible thin film preparation method, after obtaining a single-crystal nickel cobalt oxide thin film on a water-soluble sacrificial layer, the water-soluble sacrificial layer is dissolved by immersing the sample with the grown single-crystal nickel cobalt oxide thin film in a target solvent, thereby obtaining a non-destructive single-crystal nickel cobalt oxide thin film. The self-supporting single-crystal nickel cobalt oxide thin film can then be transferred to a target flexible substrate. Compared with the existing technology of peeling off flexible thin films by mechanical peeling or chemical etching, this method can achieve non-destructive transfer to obtain flexible thin films.
[0053] Based on the technical solutions of the above embodiments, this application also provides another optional embodiment, in which the epitaxial growth step of the water-soluble sacrificial layer in S120 is refined.
[0054] See Figure 2 The illustrated epitaxial growth steps of the water-soluble sacrificial layer include:
[0055] S210 employs pulsed laser deposition to bombard a target solution with a laser to obtain an epitaxially grown water-soluble sacrificial layer on a single-crystal substrate at a target growth temperature; wherein the target solution contains the components of the water-soluble sacrificial layer.
[0056] It is understandable that by using pulsed laser deposition to bombard the target solution with laser, the components of the water-soluble sacrificial layer included in the target solution can be deposited on a single-crystal substrate, thereby obtaining a water-soluble sacrificial layer.
[0057] In one alternative embodiment, the target growth temperature can be 600-800°C.
[0058] In this embodiment, by using pulsed laser deposition to bombard the target solution with laser, the growth time of the water-soluble sacrificial layer can be shortened and the production efficiency improved.
[0059] Based on the technical solutions of the above embodiments, this application also provides another optional embodiment, in which the epitaxial growth step of single crystal nickel cobalt oxide thin film in S130 is refined.
[0060] See Figure 3 The epitaxial growth steps of the single-crystal nickel cobalt oxide thin film shown include:
[0061] S310 employs pulsed laser deposition to bombard a nickel cobalt oxide solution with a laser, resulting in an epitaxially grown single-crystal nickel cobalt oxide film on a water-soluble sacrificial layer at the target growth temperature.
[0062] It is understandable that by using pulsed laser deposition to bombard a nickel cobalt oxide solution with a laser, nickel cobalt oxide in the solution can be precipitated on a water-soluble sacrificial layer, thereby obtaining a single-crystal nickel cobalt oxide film.
[0063] In one alternative embodiment, the target growth temperature can be 600-800°C.
[0064] In this embodiment, by using pulsed laser deposition to bombard the nickel cobalt oxide solution with laser, the growth time of single-crystal nickel cobalt oxide thin films can be shortened and production efficiency improved.
[0065] Based on the technical solutions of the above embodiments, this application also provides another optional embodiment, in which the method for preparing flexible thin films is described in detail.
[0066] See Figure 4 and Figure 5 The method for preparing flexible thin films shown includes:
[0067] S410 provides a single-crystal substrate made of magnesium aluminate (MAO);
[0068] S420 employs pulsed laser deposition to bombard a strontium aluminate solution with laser to obtain an epitaxially grown strontium aluminate (SAO) film with a thickness of 10nm-100nm on a single crystal substrate in the
[001] direction at a growth temperature of 600-800℃.
[0069] S430 employs pulsed laser deposition to bombard a nickel cobalt oxide solution with a laser to obtain an epitaxially grown single-crystal nickel cobalt oxide (NCO) film on a strontium aluminate film at a growth temperature of 600-800℃.
[0070] S440 involves immersing a sample with a single-crystal nickel cobalt oxide film grown on it in deionized water at a dissolution temperature of 20-80℃. After the strontium aluminate film dissolves, the single-crystal nickel cobalt oxide film is peeled off from the single-crystal substrate to obtain a self-supporting single-crystal nickel cobalt oxide film with a thickness of 5nm-50nm.
[0071] S450 transfers a self-supporting single-crystal nickel cobalt oxide film onto a flexible substrate made of polydimethylsiloxane (PDMS).
[0072] S460 is used to perform voltage testing on a single-crystal nickel cobalt oxide thin film on a flexible substrate.
[0073] like Figure 6 As shown, this application also provides XRD diffraction patterns of nickel cobalt oxide films deposited at different temperatures. Figure 6 The XRD diffraction patterns of nickel cobalt oxide films deposited at different temperatures are shown below. These patterns were obtained by characterizing the nickel cobalt oxide films using X-ray diffraction at temperatures of 300℃, 325℃, 350℃, and 375℃. The vertical axis represents the intensity of the X-rays, and the horizontal axis represents the diffraction angle (2θ).
[0074] like Figure 7 As shown, this application also provides schematic diagrams of magnetization-external magnetic field strength curves for nickel cobalt oxide films deposited at different temperatures. Figure 7 The schematic diagrams showing the magnetization-external magnetic field strength curves of nickel cobalt oxide films deposited at different temperatures illustrate the variation of magnetization with external magnetic field strength at temperatures of 300℃, 325℃, 350℃, and 375℃. The vertical axis represents magnetization (M), and the horizontal axis represents external magnetic field strength (H).
[0075] It should be understood that although the steps in the flowcharts of the embodiments described above are shown sequentially according to the arrows, these steps are not necessarily executed in the order indicated by the arrows. Unless explicitly stated herein, there is no strict order restriction on the execution of these steps, and they can be executed in other orders. Moreover, at least some steps in the flowcharts of the embodiments described above may include multiple steps or multiple stages. These steps or stages are not necessarily completed at the same time, but can be executed at different times. The execution order of these steps or stages is not necessarily sequential, but can be performed alternately or in turn with other steps or at least some of the steps or stages of other steps.
[0076] This application also provides a flexible film, which is obtained by the flexible film preparation method as described in any of the above embodiments.
[0077] Based on the same inventive concept, this application also provides a flexible thin film preparation apparatus for implementing the flexible thin film preparation method described above. The solution provided by this apparatus is similar to the solution described in the above method; therefore, the specific limitations in one or more flexible thin film preparation apparatus embodiments provided below can be found in the limitations of the flexible thin film preparation method described above, and will not be repeated here.
[0078] In one exemplary embodiment, such as Figure 8 As shown, a flexible thin film fabrication apparatus is provided, comprising: a first growth module 810, a second generation module 820, a dissolution module 830, and a transfer module 840, wherein:
[0079] The first growth module 810 is used to epitaxially grow a water-soluble sacrificial layer on a single-crystal substrate;
[0080] The second generation module 820 is used for epitaxially growing a single-crystal nickel cobalt oxide thin film on the water-soluble sacrificial layer;
[0081] The dissolution module 830 is used to immerse the sample on which the single crystal nickel cobalt oxide film is grown into the target solvent, so that the water-soluble sacrificial layer is dissolved, and the single crystal nickel cobalt oxide film is peeled off from the single crystal substrate to obtain the self-supporting single crystal nickel cobalt oxide film.
[0082] The transfer module 840 is used to transfer the self-supporting single-crystal nickel cobalt oxide film onto the target flexible substrate.
[0083] In one embodiment, the first growth module 810 is specifically used to: bombard the target solution with a laser using a pulsed laser deposition method to obtain an epitaxially grown water-soluble sacrificial layer on a single crystal substrate at a target growth temperature; wherein the target solution includes the components of the water-soluble sacrificial layer.
[0084] In one embodiment, the second generation module 820 is specifically used to: bombard a nickel cobalt oxide solution with a laser using pulsed laser deposition, and obtain an epitaxially grown single-crystal nickel cobalt oxide film on a water-soluble sacrificial layer at a target growth temperature.
[0085] In one embodiment, the target growth temperature is 600-800°C.
[0086] In one embodiment, the water-soluble sacrificial layer is a strontium aluminate film; the thickness of the strontium aluminate film is 10nm-100nm.
[0087] In one embodiment, the target solvent is deionized water; the dissolution temperature of deionized water is 20-80°C.
[0088] In one embodiment, the thickness of the single-crystal nickel cobalt oxide film is 5nm-50nm.
[0089] In one embodiment, the material of the single-crystal substrate is magnesium aluminate or strontium titanate.
[0090] In one embodiment, the material of the target flexible substrate is polydimethylsiloxane, polyimide, or polyethylene terephthalate.
[0091] Each module in the aforementioned flexible thin film fabrication apparatus can be implemented entirely or partially through software, hardware, or a combination thereof. These modules can be embedded in or independent of the processor in a computer device, or stored in the memory of a computer device as software, so that the processor can call and execute the operations corresponding to each module.
[0092] In one exemplary embodiment, a computer device is provided, which may be a server, and its internal structure diagram may be as follows: Figure 9 As shown, this computer device includes a processor, memory, input / output (I / O) interfaces, and a communication interface. The processor, memory, and I / O interfaces are connected via a system bus, and the communication interface is also connected to the system bus via the I / O interfaces. The processor provides computational and control capabilities. The memory includes non-volatile storage media and internal memory. The non-volatile storage media stores the operating system, computer programs, and databases. The internal memory provides the environment for the operation of the operating system and computer programs stored in the non-volatile storage media. The I / O interfaces are used for exchanging information between the processor and external devices. The communication interface is used for communication with external terminals via a network connection. When the computer program is executed by the processor, it implements a flexible thin film fabrication method.
[0093] Those skilled in the art will understand that Figure 9 The structure shown is merely a block diagram of a portion of the structure related to the present application and does not constitute a limitation on the computer device to which the present application is applied. Specific computer devices may include more or fewer components than those shown in the figure, or combine certain components, or have different component arrangements.
[0094] In one exemplary embodiment, a computer device is provided, including a memory and a processor, wherein the memory stores a computer program, and the processor executes the computer program to implement the steps of the flexible thin film preparation method provided in any of the above embodiments.
[0095] In one embodiment, a computer-readable storage medium is provided having a computer program stored thereon, which, when executed by a processor, implements the steps of the flexible thin film preparation method provided in any of the above embodiments.
[0096] In one embodiment, a computer program product is provided, including a computer program that, when executed by a processor, implements the steps of the flexible thin film preparation method provided in any of the above embodiments.
[0097] Those skilled in the art will understand that all or part of the processes in the methods of the above embodiments can be implemented by a computer program instructing related hardware. The computer program can be stored in a non-volatile computer-readable storage medium, and when executed, it can include the processes of the embodiments of the above methods. Any references to memory, databases, or other media used in the embodiments provided in this application can include at least one of non-volatile memory and volatile memory. Non-volatile memory can include read-only memory (ROM), magnetic tape, floppy disk, flash memory, optical memory, high-density embedded non-volatile memory, resistive random access memory (ReRAM), magnetic random access memory (MRAM), ferroelectric random access memory (FRAM), phase change memory (PCM), graphene memory, etc. Volatile memory can include random access memory (RAM) or external cache memory, etc. By way of illustration and not limitation, RAM can take many forms, such as Static Random Access Memory (SRAM) or Dynamic Random Access Memory (DRAM). The databases involved in the embodiments provided in this application may include at least one type of relational database and non-relational database. Non-relational databases may include, but are not limited to, blockchain-based distributed databases. The processors involved in the embodiments provided in this application may be general-purpose processors, central processing units, graphics processing units, digital signal processors, programmable logic devices, quantum computing-based data processing logic devices, artificial intelligence (AI) processors, etc., and are not limited to these.
[0098] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this application.
[0099] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of this patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this application should be determined by the appended claims.
Claims
1. A method for preparing a flexible thin film, characterized in that, The method includes: Provide a single-crystal substrate; A water-soluble sacrificial layer is epitaxially grown on the single-crystal substrate; A single-crystal nickel cobalt oxide thin film is epitaxially grown on the water-soluble sacrificial layer; The sample with the grown monocrystalline nickel cobalt oxide film is immersed in the target solvent to dissolve the water-soluble sacrificial layer. The monocrystalline nickel cobalt oxide film is then peeled off from the monocrystalline substrate to obtain the self-supporting monocrystalline nickel cobalt oxide film. The self-supporting single-crystal nickel cobalt oxide film is transferred onto the target flexible substrate.
2. The method according to claim 1, characterized in that, The epitaxial growth of a water-soluble sacrificial layer on the single-crystal substrate includes: A pulsed laser deposition method is used to bombard the target solution with a laser to obtain the epitaxially grown water-soluble sacrificial layer on the single crystal substrate at the target growth temperature; wherein the target solution contains the components of the water-soluble sacrificial layer.
3. The method according to claim 1, characterized in that, The epitaxial growth of a single-crystal nickel cobalt oxide film on the water-soluble sacrificial layer includes: A single-crystal nickel cobalt oxide film was epitaxially grown on the water-soluble sacrificial layer by laser bombardment of a nickel cobalt oxide solution at a target growth temperature.
4. The method according to claim 2 or 3, characterized in that, The target growth temperature is 600-800℃.
5. The method according to any one of claims 1-3, characterized in that, The water-soluble sacrificial layer is a strontium aluminate film; the thickness of the strontium aluminate film is 10nm-100nm.
6. The method according to any one of claims 1-3, characterized in that, The target solvent is deionized water; the dissolution temperature of the deionized water is 20-80℃.
7. The method according to any one of claims 1-3, characterized in that, The thickness of the single-crystal nickel cobalt oxide film is 5nm-50nm.
8. The method according to any one of claims 1-3, characterized in that, The material of the single crystal substrate is magnesium aluminate or strontium titanate.
9. The method according to any one of claims 1-3, characterized in that, The material of the target flexible substrate is polydimethylsiloxane, polyimide, or polyethylene terephthalate.
10. A flexible film, characterized in that, The flexible thin film is prepared by any one of claims 1-9.