Method for controllably preparing copper oxide micro-nano structure in solution

Abstract

The invention discloses a method for controllably preparing a copper oxide micro-nano structure in a solution, and belongs to the technical field of preparation of semiconductor material micro-nano structures, and the method comprises the following steps: firstly, preparing a complexing solution of copper sulfate and polyethyleneimine; and then putting a glass sample with a gold film deposited on the surface into the complexing solution. The continuous wave laser is focused and irradiated to the upper surface of the glass sample, and at the moment, local high temperature is formed at a laser spot on the upper surface of the glass sample. Under the effect of the local high temperature, the solution is subjected to chemical reaction to generate copper oxide micro-nano particles which are continuously deposited on the surface of the sample. And after irradiating for a period of time, taking out the glass sample, washing with a large amount of ethanol, and blow-drying with nitrogen, thereby obtaining the copper oxide micro-nano structure on the surface of the glass sample. The preparation process is very simple, complex equipment operation and tedious process steps are not needed, and the controllability of the position, size and morphology of the copper oxide micro-nano structure is good.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor material micro-nano structure preparation, and particularly relates to a method for controllably preparing copper oxide micro-nano structures in a solution. Background Art

[0002] As an important semiconductor material, copper oxide micro-nanostructures have broad application prospects in energy conversion, energy storage, photocatalysis, gas sensing and other fields. Currently, the methods for preparing copper oxide micro-nanostructures mainly include hydrothermal method, high-energy beam technology, chemical vapor deposition, sol-gel method and electrochemical deposition method. The hydrothermal method is relatively simple to operate and suitable for large-scale production, but it is difficult to quickly control the morphology and size. It generally requires equipment such as a high-pressure reactor, and cannot accurately control the forming process and forming position of the structure. Although high-energy beam technology can accurately control the structure, the equipment is expensive, the maintenance cost is high, and the operator requirements are strict. Chemical vapor deposition can produce high-quality structures, but the equipment is complex and the cost is high. The sol-gel method is simple to operate and suitable for the preparation of thin films and nanoparticles, but uniformity is difficult to ensure and the morphology control is insufficient. The electrochemical deposition method is simple to operate and suitable for the preparation of thin films and nanowires, but morphology and size control are difficult and uniformity is difficult to ensure.

[0003] In summary, while existing methods for preparing copper oxide micro- and nanostructures each have their own advantages, they also share some common limitations, such as strong equipment dependence, complex operations, high costs, and difficulty in controlling morphology and size. Therefore, developing a simple, efficient, and low-cost method that can precisely control the morphology, size, and position of copper oxide micro- and nanostructures has important scientific significance and application value. Summary of the Invention

[0004] The purpose of the present invention is to address the shortcomings of the above-mentioned existing methods for preparing copper oxide micro-nanostructures, and to propose a method for controllably preparing copper oxide micro-nanostructures in solution using continuous wave laser, thereby providing a new technical approach for the controllable preparation of copper oxide micro-nanostructures.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A method for controllably preparing copper oxide micro-nanostructures in a solution comprises the following steps:

[0007] (1) preparing a complex solution of copper sulfate CuSO4 and polyethyleneimine PEI;

[0008] (2) placing the glass sample with the gold film deposited on the surface into the complexing solution prepared in step (1);

[0009] (3) Focusing a continuous wave laser onto the upper surface of the glass sample, a localized high temperature is formed at the laser spot on the upper surface of the glass sample. Under the action of the localized high temperature, the solution undergoes a chemical reaction to produce copper oxide micro-nanoparticles that are continuously deposited on the surface of the glass sample.

[0010] (4) According to the preparation requirements, after irradiating the upper surface of the glass sample with a continuous wave laser for a period of time, the glass sample is taken out, rinsed with ethanol, and then blown dry with nitrogen, thereby obtaining a copper oxide micro-nanostructure on the surface of the glass sample.

[0011] Furthermore, in step (1), the process of preparing the complex solution is as follows: adding copper sulfate CuSO4 solid particles to the polyethyleneimine PEI solution, accompanied by ultrasonic oscillation for 5 minutes, and the Cu 2 + Complexation reaction occurs with the amino group of PEI to form a stable complex and obtain a complex solution.

[0012] Furthermore, the power range of the continuous wave laser is 10mW-100mW, and the magnification of the focusing lens is 5-100 times.

[0013] Furthermore, in step (4), the generation position of the copper oxide micro-nanostructure can be quickly regulated by regulating the irradiation position of the continuous wave laser.

[0014] Furthermore, in step (4), the size and morphology of the copper oxide micro-nanostructure are regulated by regulating the irradiation time and irradiation power of the continuous wave laser.

[0015] Furthermore, in step (2), the preparation process of the glass sample with the gold film deposited thereon is as follows: a piece of glass sample is taken for cleaning, dried after cleaning, and then 10 nm thick gold nanoparticles are deposited on the surface of the glass sample by magnetron sputtering, and then placed in a muffle furnace for annealing at 1000° C. for 1 hour, and then taken out and the glass sample is returned to room temperature for use.

[0016] Furthermore, the glass sample is fused quartz glass.

[0017] Furthermore, the complex solution is contained in a glass cuvette.

[0018] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0019] 1. The present invention places a glass sample with a gold film deposited on its surface into a configured complexing solution, and then achieves controllable preparation of copper oxide micro-nanostructures by controlling the irradiation position, irradiation time, and irradiation power of a continuous wave laser. This method does not require complex equipment operation and tedious process steps. Compared with currently commonly used hydrothermal methods, high-energy beam technology, chemical vapor deposition, sol-gel methods, and electrochemical deposition methods, it does not rely on expensive instruments and complex chemical reagent processing processes, simplifies the operation process, does not require harsh conditions such as high temperature and high pressure, reduces energy consumption and safety risks, and is more environmentally friendly and energy-saving. By precisely controlling the irradiation parameters of the continuous wave laser, the position, size, and morphology of the copper oxide micro-nanostructures can be precisely controlled.

[0020] 2. The present invention can rapidly generate copper oxide micro-nanostructures. The generated location, size, and morphology of the structures are completely dependent on the location, duration, and energy parameters of continuous wave laser irradiation on the sample surface. By varying the irradiation position of the continuous wave laser, the generated location of the copper oxide micro-nanostructures can be precisely controlled. By varying the irradiation time and energy parameters of the continuous wave laser, the size and morphology of the copper oxide micro-nanostructures can be precisely controlled. This allows the preparation of copper oxide micro-nanostructures with specific distribution, size, and morphology according to actual needs, achieving a high degree of controllability in the preparation of copper oxide micro-nanostructures on the sample surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and should not be considered as limiting the scope. A person of ordinary skill in the art can also derive other relevant drawings based on these drawings without inventive effort, among which:

[0022] Figure 1 Schematic diagram of the preparation process of copper oxide micro-nanostructures of the present invention;

[0023] Figure 2 Schematic diagram of a scanning electron microscope sample of copper oxide micro-nanostructures prepared under different continuous wave laser irradiation times in Example 1 of the present invention;

[0024] Figure 3 This is a comparison of scanning electron microscope samples of copper oxide micro-nanostructures prepared by irradiation with continuous wave laser at different powers in Example 2 of the present invention. DETAILED DESCRIPTION

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings herein can be arranged and designed in various different configurations.

[0026] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but rather merely represents selected embodiments of the present invention. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are intended to fall within the scope of protection of the present invention.

[0027] It should be noted that reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, it does not require further definition or explanation in subsequent drawings.

[0028] In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer" and the like indicate positions or locations based on the positions shown in the accompanying drawings, or the positions or locations in which the inventive product is typically placed when in use. These terms are intended merely to simplify the description of the present invention and do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed, or operate in a specific orientation. Therefore, they should not be construed as limitations on the present invention. Furthermore, the terms "first," "second," and "third," etc., are used solely to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0029] Furthermore, terms such as "horizontal" and "vertical" do not necessarily mean that a component must be absolutely horizontal or overhanging, but rather that it can be slightly tilted. For example, "horizontal" simply means that its direction is more horizontal than "vertical," and does not mean that the structure must be completely horizontal, but rather that it can be slightly tilted.

[0030] In the description of the present invention, it should also be noted that, unless otherwise expressly specified or limited, the terms "disposed," "installed," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed, detachable, or integral connections; mechanical or electrical connections; direct or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention in specific contexts.

[0031] In conjunction with the instructions Figure 1-3 ,

[0032] A method for controllably preparing copper oxide micro-nanostructures in a solution comprises the following steps:

[0033] (1) Prepare the pre-complexation solution, dissolve a certain mass ratio of copper sulfate solid particles in the polyethyleneimine solution, and oscillate with ultrasound for 5 minutes. Since the polyethyleneimine PEI molecular chain contains a large number of amino groups, the nitrogen atoms in these amino groups have lone pairs of electrons, which can react with copper ions Cu 2 + occurs coordination. Therefore, Cu 2 + It reacts with the amine group of PEI to form a stable complex, and the solution appears dark blue;

[0034] (2) preparing a substrate sample, taking a glass sample, cleaning it, drying it after cleaning, and then depositing 10 nm thick gold nanoparticles on the surface of the glass sample by magnetron sputtering, and then placing it in a muffle furnace for annealing at 1000° C. for 1 hour and then taking it out, and waiting for the glass sample to return to room temperature for use; wherein the glass sample is fused quartz glass;

[0035] (3) filling a glass cuvette with the complexing solution prepared in step (1), and placing the glass sample on which the gold film was deposited prepared in step (2) into the complexing solution;

[0036] (4) Figure 1 As shown in (a), the continuous wave laser is turned on and focused onto the upper surface of the glass sample for irradiation, forming a local high temperature at the laser spot;

[0037] (5) Figure 1 As shown in (b), under the continuous and stable thermal effect of a certain power laser, the complex in the solution partially decomposes under the photochemical action, releasing metallic copper Cu, which is then oxidized to produce copper oxide CuO micro-nanoparticles;

[0038] (6) Figure 1 As shown in (c), as copper oxide micro-nanoparticles continue to deposit to form copper oxide micro-nanostructures, the characteristics of the copper oxide micro-nanostructures can be regulated by controlling the position, irradiation time, and energy of the continuous wave laser.

[0039] (7) Figure 1 As shown in (d), after the continuous wave laser is continuously irradiated for a period of time, the continuous wave laser is turned off, and then the glass sample is taken out of the glass cuvette, cleaned with a large amount of ethanol, and then blown dry with nitrogen gas, thereby preparing copper oxide micro-nanostructures on the surface of the glass sample.

[0040] By adjusting the laser parameters, the position, size and morphology of copper oxide micro-nanostructures can be controlled. Specific control cases are as follows:

[0041] Example 1: Using laser irradiation position to control the formation position of copper oxide micro-nanostructures

[0042] like Figure 2 As shown in the figure, after the glass sample is placed in the complex solution, a 100x focusing objective is used, and the continuous wave laser power is set to 10.5mW. First, the continuous wave laser is focused to position 1 on the upper surface of the sample, irradiated for 10 seconds, and then the continuous wave laser is turned off to obtain a copper oxide micro-nanostructure. The glass sample is moved, and the laser is focused to position 2 of the glass sample, irradiated for 20 seconds, and then the continuous wave laser is turned off to obtain another copper oxide micro-nanostructure. The sample is continued to be moved, and the laser is focused to position 3 of the glass sample, irradiated for 50 seconds, and then the continuous wave laser is turned off to obtain a copper oxide micro-nanostructure, and so on. After obtaining multiple copper oxide micro-nanostructures at different positions, the glass sample is removed from the cuvette, washed with a large amount of ethanol, and then blown dry with nitrogen gas. This can achieve the preparation of multiple position-controllable copper oxide micro-nanostructures on the sample surface.

[0043] Example 2: Using laser irradiation power to control the size and morphology of copper oxide micro-nanostructures

[0044] like Figure 3 As shown in the figure, after the glass sample is placed in the complexing solution, a 20x focusing objective is used. The continuous wave laser power is first set to 20mW. The continuous wave laser is focused on position 1 on the sample surface and irradiated for 500 seconds. The continuous wave laser is then turned off to obtain a copper oxide micro-nanostructure. The sample is then moved, and the laser is focused on position 2 on the glass sample. The continuous wave laser power is adjusted to 40mW, irradiated for 500 seconds, and then turned off to obtain a copper oxide micro-nanostructure. The sample is then moved again, and the laser is focused on position 3 on the glass sample. The continuous wave laser power is adjusted to 50mW, irradiated for 500 seconds, and then turned off to obtain a copper oxide micro-nanostructure. Finally, the glass sample is removed from the cuvette, rinsed with a large amount of ethanol, and then blown dry with nitrogen. Multiple copper oxide micro-nanostructures with controllable size and morphology are thus prepared on the sample surface.

[0045] The above are the embodiments of the present invention. The foregoing are the preferred embodiments of the present invention. If the preferred implementation methods in each preferred embodiment are not obviously self-contradictory or based on a certain preferred implementation method, each preferred implementation method can be arbitrarily superimposed and used in combination. The embodiments and the specific parameters in the embodiments are only for the purpose of clearly describing the verification process of the invention, and are not intended to limit the scope of patent protection of the present invention. The scope of patent protection of the present invention is still subject to its claims. Any equivalent structural changes made by using the contents of the description and drawings of the present invention should also be included in the scope of protection of the present invention.

Claims

1. A method for controllably preparing copper oxide micro-nanostructures in a solution, characterized in that: The following steps are involved: (1) preparing a complex solution of copper sulfate CuSO4 and polyethyleneimine PEI; (2) placing the glass sample with the gold film deposited on the surface into the complexing solution prepared in step (1); (3) Focusing a continuous wave laser onto the upper surface of the glass sample, a localized high temperature is formed at the laser spot on the upper surface of the glass sample. Under the action of the localized high temperature, the solution undergoes a chemical reaction to produce copper oxide micro-nanoparticles that are continuously deposited on the surface of the glass sample. (4) According to the preparation requirements, after irradiating the upper surface of the glass sample with a continuous wave laser for a period of time, the glass sample is taken out, rinsed with ethanol, and then blown dry with nitrogen, thereby obtaining a copper oxide micro-nanostructure on the surface of the glass sample.

2. A method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, characterized in that: In the step (1), the process of preparing the complex solution is as follows: adding copper sulfate CuSO4 solid particles to the polyethyleneimine PEI solution, accompanied by ultrasonic oscillation for 5 minutes, and the Cu 2 + Complexation reaction occurs with the amino group of PEI to form a stable complex and obtain a complex solution.

3. The method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, wherein: The power range of the continuous wave laser is 10mW-100mW, and the magnification of the focusing lens is 5-100 times.

4. The method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, wherein: In the step (4), the generation position of the copper oxide micro-nanostructure can be quickly regulated by regulating the irradiation position of the continuous wave laser.

5. The method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, wherein: In the step (4), the size and morphology of the copper oxide micro-nanostructure are regulated by regulating the irradiation time and irradiation power of the continuous wave laser.

6. The method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, wherein: In the step (2), the preparation process of the glass sample with the gold film deposited thereon is as follows: a piece of glass sample is taken for cleaning, and then dried after cleaning, and then 10 nm thick gold nanoparticles are deposited on the surface of the glass sample by magnetron sputtering, and then the glass sample is placed in a muffle furnace for annealing at 1000° C. for 1 hour and then taken out and the glass sample is allowed to return to room temperature for use.

7. A method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1 or 6, characterized in that: The glass sample is fused silica glass.

8. The method for controllably preparing copper oxide micro-nanostructures in a solution according to claim 1, characterized in that: The complex solution is contained in a glass cuvette.

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