Preparation Method of Metal Hollow Micro-Nano Structure

Abstract

The present invention discloses a method for preparing a metal hollow micro-nano structure, comprising: S1, performing simulation deposition experiments on different deposition pulse voltage waveforms through COMSOL simulation software to obtain the correlation characteristics of sine wave pulses and square wave pulses in terms of deposition efficiency and deposition structure characteristics change under the same voltage power; S2, based on the correlation characteristics obtained in S1, preparing a metal hollow micro-nano structure on a metal substrate through MCED technology and an AC deposition voltage control strategy. The present invention provides a method for preparing a metal hollow micro-nano structure. By adopting MCED technology in the process of preparing the metal hollow micro-nano structure, the preparation of complex geometric structures and spatial array structures can be effectively completed, expanding the application scope of the existing self-template method.

Description

Technical Field

[0001] The present invention relates to the field of preparation of metal micro-nano structures. More specifically, the present invention relates to a method for preparing metal hollow micro-nano structures using Meniscus Confined Electrodeposition (MCED). Background Art

[0002] Metal hollow microstructures are three-dimensional geometric structures with internal spaces, which have advantages such as large surface area, low density, and high load capacity, and are widely used in fields such as biomedicine, micro sensors, and nano reactors. Traditional methods for preparing metal hollow microstructures include hard template method, soft template method, and self-template method. Among them, the self-template method has the advantages of simple synthesis steps, low cost, and good product uniformity, and is favored by many researchers. At present, metal hollow microstructures with uniform wall thickness have been prepared using the Localized Electrochemical Deposition (LECD) technique based on a rotating anode. However, due to the limitations of the LECD technique, this structure has problems such as relatively large size and low product strength. In addition, metal hollow micro copper tubes have been prepared using the Atomic Force Microscope Deposition Technique (AFM-based TBN). However, the AFM-based TBN technique has problems such as expensive equipment and high requirements for the working environment, which is not conducive to large-scale popularization and application. Therefore, there is an urgent need to develop a new synthesis method that can cheaply and conveniently prepare metal hollow microstructures and has the ability to prepare complex microstructures and spatial array structures, which has strong practical significance for enhancing the versatility of the self-template method and expanding its application scope. Summary of the Invention

[0003] An object of the present invention is to solve at least the above problems and / or defects and provide at least the advantages described hereinafter.

[0004] To achieve these objects and other advantages of the present invention, there is provided a method for preparing a metal hollow micro-nano structure, including:

[0005] S1. Perform simulation deposition experiments on different deposition pulse voltage waveforms through COMSOL simulation software to obtain the correlation characteristics of sine wave pulses and square wave pulses in terms of deposition efficiency and deposition structure characteristics under the same voltage power;

[0006] S2. Based on the correlation characteristics obtained in S1, prepare metal hollow micro-nano structures on a metal substrate through the MCED technique and an alternating current deposition voltage control strategy.

[0007] Preferably, in S1, the correlation characteristics are:

[0008] At the same voltage and power, the sine wave pulse has a higher deposition efficiency than the square wave pulse;

[0009] At the same voltage and power, based on the annular deposit prepared by the square wave pulse, after applying the sine wave pulse, the deposit has an obvious tendency to form a hollow structure.

[0010] Preferably, the AC deposition voltage control strategy includes:

[0011] S20. Adjust to obtain a square wave pulse with a voltage amplitude of 0.9 / -0.8V, a positive voltage duty cycle of 0.3, and a frequency of 1Hz to deposit an annular deposition zone on the metal substrate;

[0012] S21. Adjust to obtain a sine wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz to deposit on the annular deposition zone according to a predetermined metal deposition trajectory to prepare a metal hollow micro-nano structure.

[0013] Preferably, in S21, the metal deposition trajectory is obtained by driving the piezoelectric ceramic in the MCED system to generate a corresponding displacement on the platform.

[0014] The present invention has at least the following beneficial effects: First, compared with other existing methods for preparing metal hollow microstructures, the present invention can quickly prepare metal hollow microstructures and has the ability to prepare complex microstructures and spatial array structures;

[0015] Second, the present invention first focuses on and proposes an AC pulse deposition voltage control strategy, which can achieve stable and continuous preparation of metal hollow microstructures and has high application value;

[0016] Third, the present invention first proposes to use the MCED technology in the process of preparing metal hollow micro-nano structures, which can effectively complete the preparation of complex geometric structures and spatial array structures and expand the application range of the existing self-template method.

[0017] Other advantages, objectives and features of the present invention will be partially reflected by the following description and partially understood by those skilled in the art through the research and practice of the present invention. Description of the Drawings

[0018] Figure 1 Schematic diagram of the deposition steps for preparing a hollow microstructure by the MCED method of the present invention;

[0019] Figure 2 Schematic diagram of the MCED deposition system used in the present invention;

[0020] Figure 3 Metal hollow microstructures directly deposited by square wave pulses;

[0021] Figure 4 is a metal hollow microstructure deposited by using the method of the present invention;

[0022] Figure 5 is a process schematic diagram of preparing a metal hollow microstructure array by using the method of the present invention;

[0023] Figure 6 is a metal hollow microstructure array prepared by using the method of the present invention.

[0024] Figure 7 is a schematic diagram of the square wave pulse adopted by the present invention;

[0025] Figure 8 is a schematic diagram of the sine wave pulse adopted by the present invention. Specific Embodiments

[0026] The following further describes the present invention in detail with reference to the accompanying drawings, so that those skilled in the art can implement it according to the description in the specification.

[0027] The present invention relates to a research on a preparation method for metal hollow microstructures. The central idea is to complete the preparation of metal hollow microstructures based on the AC pulse deposition voltage control strategy of the MCED technology. The principle of the MCED system used in the present invention is as Figure 2 shown, mainly including a piezoelectric ceramic moving platform 1, a metal substrate 2 disposed on the piezoelectric ceramic moving platform 1, a glass microprobe 3 disposed above the metal substrate 2 and spaced a predetermined distance, and the glass microprobe contains an electrolyte solution and a Cu electrode 4. An optical microscope camera 5 for real-time detection during the scanning process is disposed on one side of the piezoelectric ceramic moving platform 1, and a light source board 9 cooperating with the optical microscope camera 5 is disposed on the other side of the piezoelectric ceramic moving platform 1. The optical microscope camera 5 is communicatively connected to a computer terminal 6 to observe the forming process in real time. The Cu electrode 4 and the metal substrate 2 are respectively electrically connected to a power supply 7 and an ion current controller 8 to construct the anode and cathode electrodes for applying a square wave pulse waveform of the MCED system.

[0028] Specifically, the present invention first conducts simulation deposition experiments on different deposition pulse voltage waveforms through COMSOL simulation software. It is found through analysis that the sine wave pulse has a higher deposition efficiency than the square wave pulse under the same voltage power, and based on the annular deposits prepared by the square wave pulse, after applying the sine wave pulse, the deposits have an obvious tendency to form a hollow structure.

[0029] Before starting the preparation of metal hollow microstructures, the metal substrate needs to be subjected to corresponding surface treatment to enhance the connection strength between the metal hollow microstructures and the substrate. Then, through the MCED technology, an AC deposition voltage control strategy is used to prepare a metal hollow microstructure array with high uniformity and high surface quality on the metal substrate. This AC pulse deposition voltage control strategy consists of two-step AC pulse deposition processes. First, a square wave pulse with a voltage amplitude of 0.9 / -0.8V, a positive voltage duty cycle of 0.3, and a frequency of 1Hz is used to deposit a ring-shaped deposit on the metal substrate, which lays the foundation for the subsequent preparation of metal hollow microstructures. Second, a sine wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz is used for deposition on the ring-shaped deposition zone to prepare metal hollow microstructures.

[0030] The present invention can achieve stable and continuous preparation of metal hollow microstructures and has high application value.

[0031] Example 1

[0032] As Figure 1 shown, the AC pulse deposition voltage control strategy used in the present invention is divided into two-step deposition:

[0033] First, an ion current controller is used to generate a square wave pulse waveform with a voltage amplitude of 0.9 (positive voltage) / 0.8V (negative voltage), a frequency of 1Hz, and a positive voltage duty cycle of 30%. This square wave pulse waveform is applied to both sides of the anode and cathode of the MCED system, so that metal cations in the electrolyte solution form a ring-shaped metal structure on the metal substrate. This ring-shaped metal structure provides an important basis for the subsequent preparation of metal hollow microstructures.

[0034] Second, for the formed ring-shaped metal structure, a sine wave pulse with a voltage amplitude of 1.8V (positive voltage period) / -0.28V (negative voltage period) and a frequency of 0.5Hz (positive voltage period) / 1Hz (negative voltage period) is used for further deposition, so that a metal hollow microstructure as shown in Figure 4 is gradually formed on the ring-shaped metal structure. Compared with the metal hollow microstructures prepared by square wave pulses as shown in Figure 3 , the metal hollow microstructures prepared by the present invention have better surface quality. It should be noted that through experiments, due to the different effects of the voltage at different times of the sine wave on the formation of metal hollow structures, the sine wave consists of sine waves with different voltage amplitudes and different frequencies. Among them, the positive half-cycle waveform of the sine wave pulse uses a sine wave pulse with a voltage amplitude of 1.8V and a frequency of 0.5Hz as shown in Figure 7 , while the negative half-cycle waveform uses a sine wave as shown in Figure 8The sine wave pulse with a voltage amplitude of -0.28 V and a frequency of 1 Hz is more stable and beneficial to the metal hollow microstructure (or metal micro-nanostructure) of the present invention.

[0035] It should be noted that the generation principle of the metal hollow microstructure prepared by the present invention is the redox reaction in electrochemistry. Specifically, in this process, the glass microprobe contains an electrolyte solution, which is close to a conductive substrate with a gold-plated surface. Due to the capillary effect, tiny droplets will gather at the tip of the probe. After these droplets come into contact with the conductive substrate, a droplet bridge will be formed between the tip of the glass microprobe and the conductive substrate. This MCED system completes the circuit. Then, by applying a positive voltage to the electrodes of the MCED experimental system and a negative voltage to the substrate, the metal cations in the electrolyte solution undergo a reduction reaction on the surface of the substrate, and then the metal cations are reduced to metal elements. As the metal elements continue to accumulate, the metal deposition layer continues to gradually thicken and the metal structure continues to increase. At this time, the piezoelectric ceramic displacement platform is driven to move, guiding the metal deposition trajectory, and then the metal hollow microstructure is prepared.

[0036] This AC pulse deposition voltage control strategy allows for highly controlled and precise fabrication of hollow metal microstructures. By adjusting parameters such as voltage amplitude, frequency, and pulse duty cycle, the rate, morphology, and structural properties of metal deposition can be tuned, achieving precise control of the resulting hollow metal microstructures. Figures 6 - 7 The process of fabricating a metal hollow microstructure array using this method and the resulting metal hollow microstructure array are demonstrated. This process not only presents a novel method for fabricating metal microstructures, but also provides a feasible technical route for the manufacture of complex functional microstructures, with broad application prospects.

[0037] The above solution is only an illustration of a preferred embodiment, but is not limited thereto. When implementing the present invention, appropriate replacements and / or modifications can be made according to user needs.

[0038] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and exemplary embodiments. They can be applied to a variety of fields suitable for the present invention. Further modifications will be readily apparent to those skilled in the art. Therefore, the present invention is not limited to the specific details and illustrations shown and described herein without departing from the general concept defined by the claims and their equivalents.

Claims

1. A method for preparing a metal hollow micro-nanostructure, characterized in that: include: S1. Using COMSOL simulation software, simulate deposition experiments with different deposition pulse voltage waveforms to obtain the correlation characteristics of sine wave pulses and square wave pulses in deposition efficiency and deposition structure characteristics under the same voltage power; S2. Based on the correlation characteristics obtained in S1, metal hollow micro-nanostructures are prepared on metal substrates using MCED technology and AC deposition voltage control strategy; In S1, the associated characteristics are: Under the same voltage and power, the sine wave pulse has higher deposition efficiency than the square wave pulse; Under the same voltage power, based on the ring-shaped deposits prepared by square wave pulses, the deposits have an obvious tendency to form hollow structures after applying sine wave pulses; The AC deposition voltage control strategy includes: S20, adjusting to obtain a square wave pulse with a voltage amplitude of 0.9 / -0.8V, a positive voltage duty cycle of 0.3, and a frequency of 1 Hz, so as to deposit an annular deposition band on the metal substrate; S21. Adjust to obtain a sinusoidal wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz, so as to deposit a metal according to a predetermined metal deposition trajectory on the annular deposition belt to prepare a metal hollow micro-nanostructure.

2. The method for preparing a metal hollow micro-nanostructure according to claim 1, wherein: In S21 , the metal deposition trajectory is obtained by driving the piezoelectric ceramics in the MCED system to generate corresponding displacement on the platform.

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