Preparation method of metal hollow micro-nano structure

Abstract

The invention discloses a metal hollow micro-nano structure preparation method which comprises the following steps: S1, performing simulation deposition experiments on different deposition pulse voltage waveforms through COMSOL simulation software to obtain correlation characteristics of sine wave pulses and square wave pulses in deposition efficiency and deposition structure characteristic changes under the same voltage power; and S2, preparing the metal hollow micro-nano structure on the metal substrate through an MCED technology and an alternating current deposition voltage control strategy based on the correlation characteristics obtained in the S1. According to the preparation method of the metal hollow micro-nano structure, the MCED technology is adopted in the preparation process of the metal hollow micro-nano structure, preparation of a complex geometric structure and a space array structure can be effectively completed, and the application range of an existing self-template method is widened.

Description

Technical Field

[0001] The present invention relates to the field of metal micro-nanostructure preparation, and more specifically, to a method for preparing metal hollow micro-nanostructures using a meniscus confined electrochemical deposition (MCED) method. Background Art

[0002] Metal hollow microstructures are three-dimensional geometric structures with internal space. They have the advantages of large surface area, low density, and high load capacity. They are widely used in biomedicine, microsensors, nanoreactors, etc. 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 the majority of scientific researchers. At present, the rotating anode-based regional electrochemical deposition technology (LECD) has been used to prepare metal hollow microstructures with uniform wall thickness. However, this structure is limited by the LECD technology and has problems such as large size and low product strength. In addition, the atomic force microscope deposition technology (AFM-based TBN) has been used to prepare metal hollow micrometer copper tubes. However, the AFM-based TBN technology has problems such as expensive equipment and high working environment requirements, which is not conducive to large-scale promotion and application. Therefore, it is extremely necessary to develop a new synthesis method that can be used to cheaply and conveniently prepare metal hollow microstructures and has the ability to prepare complex microstructures and spatial array structures. This has a strong practical significance for enhancing the versatility of the self-template method and expanding the scope of application. Summary of the invention

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

[0004] In order to achieve these purposes and other advantages of the present invention, a method for preparing a metal hollow micro-nano structure is provided, comprising:

[0005] S1. Using COMSOL simulation software to 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;

[0006] S2. Based on the correlation characteristics obtained in S1, metal hollow micro-nanostructures are prepared on metal substrates through MCED technology and AC deposition voltage control strategy.

[0007] Preferably, in S1, the association characteristic is:

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

[0009] Under the same voltage power, based on the annular deposits prepared by square wave pulses, the deposits have an obvious tendency to form hollow structures after applying sinusoidal wave pulses.

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

[0011] 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 1Hz, so as to deposit an annular deposition band on the metal substrate;

[0012] S21, adjusting to obtain a sine wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz, so as to deposit on the annular deposition belt 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 ceramics in the MCED system to generate corresponding displacement on the platform.

[0014] The present invention has at least the following beneficial effects: firstly, 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] Secondly, the present invention focuses on and proposes for the first time an AC pulse deposition voltage control strategy, which can realize the stable and continuous preparation of metal hollow microstructures and has high application value;

[0016] Thirdly, the present invention proposes for the first time a method of using MCED technology in the preparation process of metal hollow micro-nanostructures, which can effectively complete the preparation of complex geometric structures and spatial array structures, and expand the application scope of the existing self-template method.

[0017] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0020] Figure 3 The metal hollow microstructure is directly obtained by square wave pulse deposition;

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

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

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

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

[0025] Figure 8 This is a schematic diagram of the present invention using a sinusoidal wave pulse. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0027] The present invention relates to a method for preparing a metal hollow microstructure. The central idea is to complete the preparation of the metal hollow microstructure based on the AC pulse deposition voltage control strategy of the MCED technology. The MCED system principle used in the present invention is as follows: Figure 2 As shown, it mainly includes a piezoelectric ceramic motion platform 1, a metal substrate 2 arranged on the piezoelectric ceramic motion platform 1, a glass microprobe 3 arranged above the metal substrate 2 and spaced at 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 of the scanning process is arranged on one side of the piezoelectric ceramic motion platform 1, and a light source board 9 matched with the optical microscope camera 5 is arranged on the other side of the piezoelectric ceramic motion platform 1, the optical microscope camera 5 is communicatively connected with a computer terminal 6 to observe the forming process in real time, and the Cu electrode 4 and the metal substrate 2 are electrically connected with a power supply 7 and an ion current controller 8 respectively to construct positive and negative electrodes for applying a square wave pulse waveform in the MCED system.

[0028] Specifically, the present invention firstly simulates deposition experiments on different deposition pulse voltage waveforms through COMSOL simulation software. Through analysis, it is found that sinusoidal pulses under the same voltage power have higher deposition efficiency than square wave pulses, and based on the annular deposits prepared by square wave pulses, the deposits have an obvious tendency to form hollow structures after applying sinusoidal pulses.

[0029] Before the preparation of the metal hollow microstructure, the present invention needs to perform corresponding surface treatment on the metal substrate to enhance the connection strength between the metal hollow microstructure and the substrate, and then prepare a metal hollow microstructure array with high uniformity and high surface quality on the metal substrate using the MCED technology using an AC deposition voltage control strategy. The AC pulse deposition voltage control strategy consists of a two-step AC pulse deposition process. First, a ring-shaped deposit is deposited on the metal substrate using 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. The ring-shaped deposit lays the foundation for the subsequent preparation of the metal hollow microstructure; secondly, a sine wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz is used on the annular deposition belt for deposition to prepare the metal hollow microstructure.

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

[0031] Example 1

[0032] like Figure 1 As shown, the AC pulse deposition voltage control strategy used in the present invention is divided into two steps for 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%. The square wave pulse waveform is applied to both sides of the positive and negative electrodes of the MCED system, so that the metal cations in the electrolyte solution form a ring-shaped metal structure on the metal substrate. The ring-shaped metal structure provides an important basis for the subsequent preparation of metal hollow microstructures.

[0034] Secondly, for the already formed annular metal structure, a sine wave pulse with a voltage amplitude of 1.8V (positive voltage cycle) / -0.28V (negative voltage cycle) and a frequency of 0.5Hz (positive voltage cycle) / 1Hz (negative voltage cycle) is used for further deposition, so that the annular metal structure is gradually formed as shown in the figure. Figure 4 Compared with the metal hollow microstructure prepared by square wave pulse, the metal hollow microstructure shown in Figure 3 As shown, the metal hollow microstructure prepared by the present invention has better surface quality. It should be noted that, after experiments, due to the different effects of the voltage at different times of the sine wave on the formation of the metal hollow structure, the sine wave is composed of sine waves with different voltage amplitudes and different frequencies, wherein the positive half cycle waveform of the sine wave pulse is as follows: Figure 7 The voltage amplitude shown is a sine wave pulse of 1.8V and a frequency of 0.5Hz, while the negative half cycle waveform adopts Figure 8The sine wave pulse with a voltage amplitude of -0.28V 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 contact 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. With the continuous accumulation of metal elements, 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, the metal deposition trajectory is guided, and then the metal hollow microstructure is prepared.

[0036] The process of preparing metal hollow microstructures by this AC pulse deposition voltage control strategy has high controllability and precision. By adjusting parameters such as voltage amplitude, frequency and pulse duty cycle, the rate, morphology and structural characteristics of metal deposition can be controlled, thereby achieving precise control of metal hollow microstructures. Figure 6-Figure 7 The process of preparing a metal hollow microstructure array using this method and the prepared metal hollow microstructure array are demonstrated. This process not only presents a novel method for preparing metal microstructures, but also provides a feasible technical route for the manufacture of complex functional microstructures, which has 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 replacement and / or modification can be performed 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 the embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily realized. Therefore, without departing from the general concept defined by the claims and equivalent scope, the present invention is not limited to the specific details and the illustrations shown and described here.

Claims

1. A method for preparing a metal hollow micro-nano structure, characterized in that: include: S1. Using COMSOL simulation software to 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 through MCED technology and AC deposition voltage control strategy.

2. The method for preparing a metal hollow micro-nano structure according to claim 1, characterized in that: In S1, the association characteristic is: Under the same voltage and power, the sine wave pulse has a higher deposition efficiency than the square wave pulse; Under the same voltage power, based on the annular deposits prepared by square wave pulses, the deposits have an obvious tendency to form hollow structures after applying sinusoidal wave pulses.

3. The method for preparing a metal hollow micro-nano structure according to claim 1, characterized in that: 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 1Hz, so as to deposit an annular deposition band on the metal substrate; S21, adjusting to obtain a sine wave pulse with a voltage amplitude of 1.8 / -0.28V and a frequency of 0.5Hz / 1Hz, so as to deposit on the annular deposition belt according to a predetermined metal deposition trajectory to prepare a metal hollow micro-nano structure.

4. The method for preparing a metal hollow micro-nano structure according to claim 3, characterized in that: In S21, the metal deposition trajectory is obtained by driving the piezoelectric ceramics in the MCED system to generate corresponding displacement on the platform.

Images