Preparation method of hydrogen-responsive composite multilayer magnesium-based film surface self-wrinkled pattern

Abstract

The invention discloses a preparation method of a hydrogen-responsive composite multilayer magnesium-based film surface self-wrinkle pattern. The preparation method comprises the following steps: A, preparing a polymer elastic layer on the surface of a supporting substrate; b, depositing a plurality of layers of metal-based films on the polymer elastic layer by adopting a magnetron sputtering method; and C, exposing the prepared sample in a hydrogen-containing atmosphere, and forming a wrinkle pattern of which the recognizable size is in a range of 10nm-1000mu m on the surface through hydrogenation reaction at normal temperature. According to the method, the surface of the thin film can be deformed by exposing the thin film to the hydrogen-containing atmosphere environment, so that the three-dimensional wrinkle texture can be quickly realized, and the three-dimensional wrinkle morphology can be accurately regulated and controlled by adjusting the element components, sputtering time, sputtering power, working gas flow and hydrogen treatment parameters of the magnesium or magnesium alloy hydrogen-sensitive reaction film layer. The pattern features of the prepared wrinkle pattern can be recognized through characterization means such as an optical microscope, a scanning electron microscope, an atomic force microscope or a diffraction light-variable device.

Description

Technical Field

[0001] This invention relates to the field of functional material surface micro / nano structure preparation technology, specifically to a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern. Background Technology

[0002] Surface patterning technology is a core research direction in the fields of micro / nano fabrication and functional materials, with wide applications in optical devices, flexible electronics, biosensing, and intelligent bionics. Traditional patterning techniques, such as photolithography and electron beam etching, while offering high precision, typically involve complex processes, expensive equipment, and harsh processing environments, and struggle to achieve dynamic and reversible pattern control on flexible or sensitive substrates. In recent years, surface self-folding technology based on the stress mismatch principle has provided a new approach to solving these problems. This technology utilizes the compressive stress generated in the thin-film-substrate system under external stimuli to spontaneously form micro / nano wrinkled patterns, offering advantages such as simple processing, low cost, and suitability for large-area fabrication. Magnesium and magnesium alloy thin films are highly promising hydrogen-responsive materials, undergoing hydrogenation reactions in a hydrogen atmosphere accompanied by phase transitions and volume changes. Currently, they are mainly used in hydrogen sensors, and there are no reports of their application in the fabrication of surface self-folded micro / nano structure patterns. Therefore, developing a method for preparing hydrogen-responsive self-wrinkling surfaces based on a composite multilayer structure design that can achieve rapid, stable, controllable preparation without complex pre-patterning is of great significance for the development of novel smart surfaces and can be applied to the preparation of anti-counterfeiting pattern markings, identity verification markings, etc. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a method for preparing self-wrinkled patterns on the surface of hydrogen-responsive composite multilayer magnesium-based thin films. This method involves designing a multilayer thin film system comprising a metal catalytic film layer, a magnesium or magnesium alloy hydrogen-sensitive reactive film layer, a polymer elastic layer, and a supporting substrate. Utilizing the volume expansion effect generated by the hydrogen-responsive magnesium hydrogenation reaction (Mg + H₂ → MgH₂), wrinkled patterns spontaneously form on the surface of the elastic film layer. This method has the advantages of being simple and effective, capable of large-area production, and having a concise process. The objective of this invention is achieved through the following technical solution: In a first aspect, the present invention provides a method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film, comprising the following steps: A. Prepare a polymer elastic layer on the surface of the supporting substrate; B. A multilayer metal-based thin film is deposited on the polymer elastic layer using magnetron sputtering; C. The multilayer metal-based thin film is exposed to a hydrogen-containing atmosphere, and a recognizable wrinkle pattern with a size in the range of 10 nm to 1000 μm is formed on the surface by hydrogenation at room temperature.

[0004] Preferably, in step A, the thickness of the supporting substrate is not particularly limited, as long as it can achieve the supporting function. The present invention does not particularly limit the length and width of the supporting substrate; they can be selected according to actual needs.

[0005] Preferably, the material of the polymer elastic layer is selected from polymers with low elastic modulus. The low elastic modulus polymer refers to an elastomer with an elastic modulus in the range of 0.1-1000 MPa, capable of elastic deformation, including thermosetting elastomers, thermoplastic elastomers, and hydrogel elastomers, such as polysiloxane elastomers, polyurethane elastomers, polyester elastomers, polystyrene elastomers, polyvinyl chloride elastomers, ethylene-vinyl acetate copolymer elastomers, flexible epoxy resins, styrene-butadiene rubber, natural rubber, ethylene-propylene rubber, chloroprene rubber, nitrile rubber, silicone rubber, fluororubber, and polyacrylamide hydrogels. Preferably, the thickness of the polymer elastic layer is 50–2000 μm.

[0006] Preferably, in step B, the multilayer metal-based thin film includes a magnesium or magnesium alloy hydrogen-sensitive reaction film layer and a metal catalytic film layer sequentially disposed on a polymer elastic layer.

[0007] Preferably, in the magnesium alloy hydrogen-sensitive reaction film layer, the magnesium alloy composition is Mg. n -X 1-n The magnesium alloy comprises any one of magnesium-alkali metals, magnesium-alkaline earth metals, magnesium-rare earth metals, magnesium-transition metals, and magnesium-transition metal oxides. X can be any one of Sc, Gd, Ti, Mn, Fe, Co, Y, Nb, Ru, Zr, Ca, Ba, La, Sm, Al, TiO2, Nb2O5, and V2O5. More preferably, the magnesium alloy is any one of a magnesium-scandium film, a magnesium-yttrium film, and a magnesium-gadolinium film.

[0008] Preferably, the metal catalytic film layer includes at least one of a platinum catalytic film layer, a palladium catalytic film layer, or a palladium alloy catalytic film layer.

[0009] Preferably, the thickness of the magnesium or magnesium alloy hydrogen-sensitive reaction film is 10–500 nm, more preferably 45–200 nm.

[0010] The thickness of the metal catalytic film is 3–200 nm, more preferably 5–10 nm.

[0011] Preferably, in the step of depositing multilayer metal substrate thin films by magnetron sputtering, the working gas used for depositing each layer is argon, the target sputtering power is 40-500W, and the sputtering time is 10-600s.

[0012] Preferably, the multilayer metal-based thin film further includes a fluorocarbon protective film layer formed on the metal catalytic film layer, which can block water vapor permeation; the fluorocarbon protective film layer is prepared by inductively coupled plasma-enhanced chemical vapor deposition technology; the thickness of the fluorocarbon protective film layer is 5-500 nm.

[0013] Preferably, in step C, the hydrogen-containing atmosphere is a mixture of hydrogen and an inert gas, such as a mixture of hydrogen and argon. The volume concentration of hydrogen is greater than 0 and less than or equal to 100%. More preferably, the volume concentration of hydrogen is 1–50%, even more preferably 1–30%, and most preferably 2–10%.

[0014] Preferably, in step C, the multilayer metal-based thin film is exposed to a hydrogen-containing atmosphere for 5 to 50 minutes, more preferably 10 to 30 minutes.

[0015] Preferably, in step C, the formed fold pattern is a disordered or ordered fold pattern.

[0016] Preferably, the pleated pattern includes either a periodic wavy structure or a maze-like structure, and the characteristic dimensions of the pattern are adjustable.

[0017] Secondly, the present invention provides a wrinkled pattern prepared according to the aforementioned method. The wrinkled pattern prepared by the present invention can be characterized by means of optical microscopy, atomic force microscopy, scanning electron microscopy or diffraction optical variable devices to identify pattern features.

[0018] Thirdly, the present invention provides an application of the aforementioned folded pattern in the fabrication of micro / nano surface structures.

[0019] Preferably, the pleated pattern is used as an anti-counterfeiting pattern in the preparation of anti-counterfeiting labels, or as an identity verification mark in the process of identity verification.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1) This invention prepares multilayer metal-based films (including metal catalytic films and magnesium or magnesium alloy hydrogen-sensitive reaction films) using magnetron sputtering technology. This preparation process is stable, easy to control, and produces films with high density and good uniformity. The three-dimensional wrinkled morphology (ripples / maze) can be precisely controlled by adjusting the elemental composition of the magnesium or magnesium alloy hydrogen-sensitive reaction film, sputtering time, sputtering power, and working gas flow rate.

[0021] 2) This invention enables rapid deformation of the thin film surface to achieve wrinkled textures through exposure to a hydrogen environment. The wrinkled pattern can be controlled by adjusting the hydrogen treatment parameters. This method is simple and fast. Under the catalysis of a metal catalytic thin film layer, the magnesium-based metal layer and hydrogen react at room temperature. The magnesium or magnesium alloy hydrogen-sensitive reactive film layer undergoes a phase transition, causing volume expansion. Part of the energy input from this volume expansion is converted into the elastic potential energy of the polymer elastic layer. Since the polymer elastic layer is confined to a rigid, flat supporting substrate, pressure is generated along the top layer of the film, resulting in a three-dimensional wrinkled texture. The use of hydrogen treatment provides a new approach for constructing stimulus-responsive smart interfaces.

[0022] 3) The process of this invention is simple, requiring only three main steps: coating, sputtering and hydrogen treatment. It does not require complex equipment, has low production costs, is easy to implement on a large scale, and is suitable for industrial production. Attached Figure Description

[0023] Other features, objects, and advantages of the present invention will become more apparent from the following detailed description of non-limiting embodiments with reference to the accompanying drawings: Figure 1 This is a schematic diagram of the preparation process (polymer layer preparation on substrate → multilayer metal-based thin film → H2-containing atmosphere treatment to form wrinkled patterns). Figure 2 This is a schematic diagram of the structure of the self-wrinkled composite multilayer magnesium-based thin film prepared in this invention. Figure 3 This is an AFM morphology image of the folds formed according to the present invention; wherein Figure 3 (a) is the wavy texture formed in Example 1; Figure 3 (b) The maze-like texture formed in Example 3; Figure 4 These are microscopic images of the multilayered films formed in this invention under an optical microscope; wherein... Figure 4 (a) The wavy texture formed after hydrogenation in Example 5 Figure 4 (b) is the pattern formed when the hydrogenated magnesium-based thin film sample is placed in air again. Detailed Implementation

[0024] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0025] Example 1 This embodiment provides a method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film, as shown in the schematic diagram below. Figure 1 As shown, the specific method includes the following steps: (1) High-purity quartz glass was selected as the substrate and pre-cleaned. Polydimethylsiloxane prepolymer (Dow Corning Sylgard PDMS184, Agent A) and curing agent (Slygard PDMS184, Agent B) were mixed evenly at a ratio of 10:1 and stirred thoroughly for 10 minutes. The mixed solution was placed in a vacuum pump and vacuumed for degassing for 10 minutes. The degassed solution was evenly drop-coated onto the treated quartz glass sheet and cured in an oven at 60℃ for 6 hours to obtain a polymer PDMS elastic layer with a thickness of 300 μm. (2) The PDMS / quartz glass sample was placed on the sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was turned on to perform vacuuming. Argon gas was introduced at a flow rate of 40 sccm. After the gas pressure stabilized, the power supply to the magnesium and scandium targets was turned on, the baffle in front of the targets was turned off, and the targets were pre-sputtered and cleaned for 5 min. Then the co-sputtering process was set, the baffle in front of the targets was turned on, the sputtering power of the magnesium and scandium targets was 40W and 100W respectively, the co-sputtering time was 150s, and a magnesium-scandium alloy thin film with a thickness of 50nm was deposited. Then the sputtering process of the palladium layer was loaded, the sputtering power of the palladium target was 80W, the sputtering time was 14s, and a palladium film with a thickness of 5nm was deposited.

[0026] (3) The composite multilayer magnesium-based thin film fabricated (structural schematic diagram as shown in the figure) Figure 2 (As shown) The gas was placed in a gas flow chamber, and a 4% hydrogen-argon mixture (a mixture of hydrogen and argon with a volume ratio of 4:96) was introduced for 10 minutes to obtain a three-dimensional wrinkled pattern with an ordered arrangement structure, as shown. Figure 3 As shown in (a), the vertical height dimension of the three-dimensional fold is 450 nm.

[0027] Example 2 This embodiment provides a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern, including the following steps: (1) Float soda-lime silica glass was selected as the substrate. Silicone rubber liquid A (Ecoflex 00-10 A) and liquid B (Ecoflex 00-10 B) were mixed and stirred uniformly at a ratio of 1:1 for 10 min. The mixed solution was placed in a vacuum pump for degassing treatment for 10 min. The degassed solution was uniformly drop-coated onto the treated glass slide and cured at 60°C for 24 hours to obtain a rubber elastic layer with a thickness of 100 μm. (2) The sample containing the structure of silicone rubber / sodium-calcium silicate glass was placed in the sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was turned on to perform vacuuming. Argon working gas was introduced at a flow rate of 30 sccm. After the gas pressure stabilized, the power supplies for the magnesium and scandium targets were turned on, the target baffles were turned off, and the targets were pre-sputtered and cleaned for 5 minutes. Then the sputtering process program was set, the target baffles were turned on, and the sputtering power of the magnesium and scandium targets was 50W and 80W, respectively, with a sputtering time of 100s. A magnesium thin film with a thickness of 45nm was deposited. Then the sputtering process program for the palladium layer was loaded. The sputtering power of the palladium target was 80W, the sputtering time was 20s, and a palladium film with a thickness of 6nm was deposited.

[0028] (3) The composite multilayer magnesium-based thin film (structure of Pd / Mg-Sc / silicone rubber / sodium calcium silicate glass) was placed in a gas flow chamber and 2% hydrogen-argon mixture (mixed gas of hydrogen and argon with a volume ratio of 2:98) was introduced for 10 minutes to obtain a three-dimensional wrinkled pattern with an ordered arrangement structure. The pattern is similar to the pattern generated in Example 1, and the longitudinal height dimension of the wrinkles is 200 nm.

[0029] Example 3 This embodiment provides a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern, including the following steps: (1) Using polymethyl methacrylate (PMMA) acrylic glass as the substrate, polydimethylsiloxane prepolymer (Dow Corning Sylgard PDMS184, Agent A) and curing agent (Slygard PDMS184, Agent B) were mixed evenly in a 9:1 ratio and stirred thoroughly for 10 minutes. The mixture was then placed in a vacuum pump for degassing treatment for 10 minutes. The degassed solution was then evenly drop-coated onto the treated glass slide and cured at room temperature for 24 hours to obtain a polymer PDMS elastic layer with a thickness of 300 μm. (2) The PDMS / PMMA sample was placed on a sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was turned on to evacuate the sample, and argon (Ar) working gas was introduced at a flow rate of 20 sccm. After the gas pressure stabilized, the power to the magnesium and scandium targets was turned on, the baffle in front of the targets was turned off, and the targets were pre-sputtered and cleaned for 5 minutes. Then, the co-sputtering process was set up, the baffle in front of the targets was turned on, the sputtering power of the magnesium and yttrium targets was 40W and 100W respectively, and the co-sputtering time was 100s, depositing a magnesium-yttrium alloy thin film with a thickness of 50nm. Then, the sputtering process for the palladium layer was loaded, the sputtering power of the palladium target was 80W, the sputtering time was 14s, and a palladium film with a thickness of 5nm was deposited.

[0030] (3) The prepared composite multilayer magnesium-based film (structure: Pd / Mg-Y / PDMS / PMMA) was placed in a gas flow chamber and a 4% hydrogen-argon mixture (a mixture of hydrogen and argon with a volume ratio of 4:96) was introduced for 10 minutes to obtain a three-dimensional wrinkled pattern with disordered arrangement, such as... Figure 3 As shown in (b), the longitudinal height dimension of the folds is between 50 and 400 nm.

[0031] Example 4 This embodiment provides a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern, including the following steps: (1) Using transparent calcium fluoride ceramic material as the substrate, the flexible epoxy resin A (HASUNCAST, 3016A) and B (HASUNCAST, 3016B) were mixed evenly in a 1:1 ratio and stirred thoroughly for 10 minutes. The mixture was then placed in a vacuum pump for degassing treatment for 10 minutes. The degassed solution was then evenly drop-coated onto the treated glass slide and cured at room temperature for 24 hours to obtain a resin elastic layer with a thickness of 50 μm. (2) The sample, consisting of a resin / transparent calcium fluoride ceramic material, was placed in the center of the sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was then activated for evacuation. Argon gas (Ar) was introduced at a flow rate of 60 sccm. After the pressure stabilized, the power to the magnesium and scandium targets was turned on, and the baffles in front of the targets were closed. The targets were pre-sputtered and cleaned for 5 minutes. Then, the co-sputtering process was set up, with the baffles in front of the targets turned on. The sputtering power for the magnesium and scandium targets was 40W and 100W, respectively, and the co-sputtering time was 100s, depositing a magnesium-scandium alloy thin film with a thickness of 50nm. Next, the sputtering process for the palladium layer was initiated, with the palladium target sputtering power at 80W and the sputtering time at 14s, depositing a palladium film with a thickness of 5nm. (5) The composite multilayer magnesium-based film (structure is Pd / Mg-Sc / resin / transparent calcium fluoride ceramic material) was placed in a gas flow chamber and 4% hydrogen-argon mixture (mixed gas of hydrogen and argon with a volume ratio of 4:96) was introduced for 30 minutes to obtain a three-dimensional wrinkled pattern with an ordered arrangement. The pattern is similar to the pattern generated in Example 1, and the vertical height of the three-dimensional wrinkles is 300 nm.

[0032] Example 5 This embodiment provides a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern, including the following steps: (1) Float soda-lime silica glass was selected as the substrate. Polydimethylsiloxane prepolymer (Dow Corning Sylgard PDMS184, Agent A) and curing agent (Slygard PDMS184, Agent B) were mixed uniformly at a ratio of 9:1 and stirred thoroughly for 10 minutes. The mixture was then placed in a vacuum pump for degassing treatment for 10 minutes. The degassed solution was then uniformly drop-coated onto the treated glass slide and cured at room temperature for 24 hours to obtain a 200 μm thick polymer PDMS elastic layer. The PDMS film was then peeled off from the soda-lime silica film.

[0033] (2) The prepared PDMS sample was placed in the center of the sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was turned on to perform vacuuming. Argon working gas was introduced at a flow rate of 30 sccm. After the gas pressure stabilized, the magnesium target power was turned on, the target baffle was turned off, and the target was pre-sputtered and cleaned for 5 min. Then the sputtering process program was set, the target baffle was turned on, the magnesium target sputtering power was 40W, the sputtering time was 300s, and a magnesium thin film with a thickness of 140nm was deposited. Then the sputtering process program for the palladium layer was loaded, the palladium target sputtering power was 80W, the sputtering time was 20s, and a palladium film with a thickness of 6nm was deposited. Then, a fluorocarbon protective film with a thickness of 20nm was prepared on the surface using inductively coupled plasma-enhanced chemical vapor deposition. (3) The prepared composite multilayer magnesium-based thin film (structure FC / Pd / Mg / PDMS) was placed in a gas flow chamber and a 10% hydrogen-argon mixture (a mixture of hydrogen and argon with a volume ratio of 10:90) was introduced for 10 minutes, resulting in a three-dimensional wrinkled pattern with periodic wavy arrangement and a labyrinthine structure, such as... Figure 4 (a) The vertical height of the three-dimensional wrinkles is 100-400 nm. When the hydrogenated magnesium-based thin film sample is placed in air, the film pattern disappears because there is no substrate material to constrain it, as shown in the image. Figure 4 (b).

[0034] Example 6 This embodiment provides a method for preparing a hydrogen-responsive composite multilayer magnesium-based thin film surface self-wrinkled pattern, including the following steps: (1) Float soda-lime silica glass was selected as the substrate. Polydimethylsiloxane prepolymer (Dow Corning Sylgard PDMS184, Agent A) and curing agent (Slygard PDMS184, Agent B) were mixed uniformly at a ratio of 15:1 and stirred thoroughly for 10 minutes. The mixture was then placed in a vacuum pump for degassing treatment for 10 minutes. The degassed solution was then uniformly drop-coated onto the treated glass slide and cured at room temperature for 24 hours to obtain a polymer PDMS elastic layer with a thickness of 50 μm. (2) The sample containing the polymer PDMS elastic layer was placed on the sample tray and transferred to the main chamber of the magnetron sputtering equipment. The vacuum system was turned on to perform vacuuming. Argon working gas was introduced at a flow rate of 30 sccm. After the gas pressure stabilized, the magnesium-gadolinium alloy target power was turned on, and the target was pre-sputtered and cleaned for 30 s. Then the sputtering process program was set, and the magnesium-gadolinium alloy target was used for sputtering at a power of 50 W and a sputtering time of 300 s to deposit a magnesium-gadolinium alloy thin film with a thickness of 200 nm. Then the sputtering process program for the palladium layer was loaded, and the palladium target sputtering power was 80 W and the sputtering time was 20 s to deposit a palladium film with a thickness of 6 nm.

[0035] (3) The composite multilayer magnesium-based film (structure is Pd / Mg-Gd / PDMS / sodium calcium silicate glass) was placed in a gas flow chamber and 4% hydrogen-argon mixture (mixed gas of hydrogen and argon with a volume ratio of 4:96) was introduced for 20 minutes to obtain a three-dimensional wrinkled pattern with disordered arrangement. This pattern is similar to the pattern generated in Example 3, with a longitudinal height scale between 50-500 nm.

[0036] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film, characterized in that, Includes the following steps: A. Prepare a polymer elastic layer on the surface of the supporting substrate; B. A multilayer metal-based thin film is deposited on the polymer elastic layer using magnetron sputtering; C. The multilayer metal-based thin film is exposed to a hydrogen-containing atmosphere, and a recognizable wrinkle pattern with a size in the range of 10 nm to 1000 μm is formed on the surface by hydrogenation at room temperature.

2. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 1, characterized in that, In step A, the polymer elastic layer is selected from polymer materials with an elastic modulus in the range of 0.1 to 1000 MPa.

3. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 1, characterized in that, In step B, the multilayer metal-based thin film includes a magnesium or magnesium alloy hydrogen-sensitive reaction film layer and a metal catalytic film layer sequentially disposed on a polymer elastic layer; The thickness of the magnesium or magnesium alloy hydrogen-sensitive reaction film is 10–500 nm, and the thickness of the metal catalytic film is 3–200 nm.

4. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 3, characterized in that, In the magnesium alloy hydrogen-sensitive reaction film layer, the magnesium alloy is selected from any one of magnesium-alkali metal, magnesium-alkaline earth metal, magnesium-rare earth metal, magnesium-transition metal, and magnesium-transition metal oxide. The metal catalytic film layer includes at least one of a platinum catalytic film layer, a palladium catalytic film layer, or a palladium alloy catalytic film layer.

5. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 1, characterized in that, In step C, the hydrogen-containing atmosphere is a mixture of hydrogen and inert gas, wherein the volume concentration of hydrogen is greater than 0 and less than or equal to 100%.

6. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 1, characterized in that, In step C, the resulting fold pattern can be either disordered or ordered.

7. The method for preparing a self-wrinkled pattern on the surface of a hydrogen-responsive composite multilayer magnesium-based thin film according to claim 1 or 6, characterized in that, The pleated pattern includes either a periodic wavy structure or a maze-like structure, and the characteristic dimensions of the pattern are adjustable.

8. A pleated pattern prepared by the method according to any one of claims 1-7.

9. An application of the pleated pattern according to claim 8 in the fabrication of micro / nano surface structures.

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