CN108394928B - Preparation method of zinc oxide/zinc stannate core-shell structure heterojunction - Google Patents

Preparation method of zinc oxide/zinc stannate core-shell structure heterojunction Download PDF

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CN108394928B
CN108394928B CN201810252172.6A CN201810252172A CN108394928B CN 108394928 B CN108394928 B CN 108394928B CN 201810252172 A CN201810252172 A CN 201810252172A CN 108394928 B CN108394928 B CN 108394928B
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zinc oxide
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CN108394928A (en
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邹友生
刘舒婷
曾海波
刘佳欣
朱正峰
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Nanjing University of Science and Technology
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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Abstract

The invention discloses a preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction. According to the invention, a mode of combining atomic layer deposition, liquid phase laser ablation and a solvothermal method is adopted, a zinc oxide nanorod array is vertically grown on the surface of a flexible fibrous thin metal wire serving as a substrate, a high-purity metal tin target immersed in a solution is ablated by laser, a high-activity solvothermal precursor is obtained, and a zinc oxide/zinc stannate core-shell structure heterojunction is further grown on the zinc oxide array by the solvothermal method. The method adopted by the invention has the advantages of simple operation, mild reaction conditions, high purity, no impurity elements, no surfactant addition and the like, and the prepared zinc oxide/zinc stannate core-shell structure heterojunction has uniform appearance and size and good crystallinity. The zinc oxide/zinc stannate core-shell structure heterojunction prepared by the invention can be applied to a flexible fibrous ultraviolet photoelectric detector.

Description

Preparation method of zinc oxide/zinc stannate core-shell structure heterojunction
Technical Field
The invention relates to the technical field of metal oxide semiconductor nano material preparation, in particular to a preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction.
Background
Ultraviolet light detection has led to extensive research and application in the areas of stratospheric ozone monitoring, flame protection, fire protection, optical communication, and the like. And flexible fibrous ultraviolet photoelectric detector is owing to have characteristics such as flexibility, 360 degrees surveys, can weave and wearable, so survey ultraviolet light when can realize human wearing, has wider range of application than planar detector. At present, the material for preparing the flexible fiber-shaped ultraviolet photoelectric detector is mainly zinc oxide. As a binary metal oxide, zinc oxide has a defect that it is difficult to detect ultraviolet light having a shorter wavelength because its band gap is not wide enough (the band gap is about 3.37 eV). Compared with the binary metal oxide material, the ternary metal oxide zinc stannate has the advantages of high electron mobility, fast electron transfer and fast response speed. Meanwhile, zinc stannate is an important n-type semiconductor material with a band gap of about 3.64eV, the band gap can be widened by adjusting the component ratio, and the phase separation caused by doping zinc oxide is avoided, so that the zinc oxide detection range can be widened by constructing a zinc oxide/zinc stannate core-shell structure heterojunction, and the wide spectral response is realized.
At present, there are some reports in the literature on the preparation of zinc oxide/zinc stannate heterojunctions. Sunghoon Park et al (Ceramics International,2013,39(4):3539-2And synthesizing Zn by using graphite powder as raw material2SnO4Nano wire, depositing ZnO on the surface by atomic layer deposition technique to prepare zinc stannate (core)/zinc oxide (shell) heterojunction, and using the heterojunction in gas sensor2SnO4Nanowire comparison to NO2The response value of the gas is improved by five times. Cheng et al (ACS Applied Materials)&Interfaces,2014,6(6):4057-62) is treated with Zn (NO) by a sol-gel method3)2·6H2O、SnCl2·2H2O, citric acid and glycol are taken as raw materials to prepare the zinc oxide/zinc stannate heterojunction nanowire. However, a method combining liquid-phase laser ablation, atomic layer deposition and solvothermal is not available, and the zinc oxide/zinc stannate core-shell structure heterojunction capable of being used for weaving wearable flexible ultraviolet detection is prepared.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction.
The technical solution for realizing the purpose of the invention is as follows: a preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction is characterized in that a mode of combining atomic layer deposition, liquid phase laser ablation and a solvothermal method is adopted, a flexible fibrous thin metal wire is used as a substrate, a zinc oxide nanorod array vertically grows on the surface, a high-purity metal tin target immersed in a solution is further ablated by laser, a high-activity solvothermal precursor is obtained, and the zinc oxide/zinc stannate core-shell structure heterojunction grows on the zinc oxide array by the solvothermal method. The method specifically comprises the following steps:
step 1, ultrasonic cleaning and drying metal wires by using deionized water and absolute ethyl alcohol respectively;
step 2, depositing a zinc oxide film on the surface of the metal wire by using an atomic layer deposition method to serve as a seed layer;
step 3, growing a zinc oxide nanorod array on the surface of the seed layer along the vertical direction by a solvothermal method;
step 4, adding the prepared solution into a reaction container, placing a tin target into the solution, and soaking the surface of the target with the solution;
step 5, adjusting the light path of the pulse laser beam of the laser, focusing the laser beam on the target material below the liquid level of the solvent, selecting proper laser wavelength, frequency and energy, starting the pulse laser, and carrying out ablation reaction on the tin target in a liquid environment; continuously stirring the solution by using a magnetic stirrer in the laser ablation process until the ablation is finished;
step 6, taking out the tin target, adding an alkaline solution into the precursor solution obtained after laser ablation, and adjusting the solution to be alkaline; transferring the precursor solution and the zinc oxide nanorod array into a reaction kettle, heating to a set temperature, and preserving heat;
step 7, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 8, taking out the nanorod array, and cleaning by using an organic solvent and the like to obtain the zinc oxide/zinc stannate core-shell structure heterojunction.
Compared with the prior art, the invention has the following remarkable advantages: 1) the solvent thermal precursor containing the Sn source prepared by adopting liquid-phase laser ablation has ultrahigh activity, other impurity elements cannot be introduced, and the product is pure. 2) The zinc oxide/zinc stannate core-shell structure heterojunction prepared by the method has the advantages of uniform appearance and size, good crystallinity and widened detection range of zinc oxide. Meanwhile, the flexible fiber-shaped metal wire is used as a substrate, and the ultraviolet detector can be applied to weaving wearable ultraviolet detection.
Drawings
FIG. 1 shows ZnO/Zn as a product prepared in inventive example 12SnO4Overall view of core-shell structure heterojunction.
Fig. 2 is an SEM image of intermediate ZnO prepared in inventive example 1.
FIG. 3 shows ZnO/Zn as a product prepared in inventive example 12SnO4High power SEM images of core-shell structure heterojunctions.
FIG. 4 shows ZnO/Zn as a product prepared in inventive example 12SnO4Core-shell structure heterojunction cross sectionSEM image.
FIG. 5 shows ZnO/Zn as a product prepared in inventive example 12SnO4XRD pattern of core-shell structure heterojunction.
FIG. 6 shows ZnO/Zn as a product prepared in inventive example 22SnO4SEM image of core-shell structure heterojunction.
FIG. 7 shows ZnO/Zn as a product prepared in inventive example 22SnO4XRD pattern of core-shell structure heterojunction.
FIG. 8 shows ZnO/Zn as a product prepared in inventive example 32SnO4SEM image of core-shell structure heterojunction.
FIG. 9 shows ZnO/Zn as a product of invention example 42SnO4SEM image of core-shell structure heterojunction.
FIG. 10 shows ZnO/Zn as a product prepared in inventive example 52SnO4SEM image of core-shell structure heterojunction.
Detailed Description
With the attached drawings, the preparation method of the zinc oxide/zinc stannate core-shell structure heterojunction comprises the following steps:
step 1, respectively using deionized water and absolute ethyl alcohol to ultrasonically clean and dry flexible fibrous fine metal wires; the metal wires comprise titanium wires or zinc wires, and the diameter of each metal wire is 0.1-1 mm.
Step 2, depositing a zinc oxide film on the surface of the metal wire by using an atomic layer deposition method to serve as a seed layer; the thickness of the zinc oxide film deposited by the atomic layer is 50-200 nm.
Step 3, growing a zinc oxide nanorod array on the surface of the seed layer along the vertical direction by a solvothermal method; the hydrothermal temperature set by the solvothermal method is 90-120 ℃, and the hydrothermal time is 4-8 h.
Step 4, adding the prepared solution into a reaction container, placing the tin source target material into the solution, and enabling the solution to soak the surface of the target material; the prepared solution is a mixed solution of ethanol, deionized water and hydrogen peroxide, wherein the volume ratio of the ethanol to the deionized water is 0: 1-1: 1, the volume ratio of the deionized water to the hydrogen peroxide is 15: 1-120: 1, and the tin source target is a high-purity metal tin target with the purity of more than 99.9%.
Step 5, adjusting the light path of the pulse laser beam of the laser, focusing the laser beam on the tin source target material below the liquid level of the solvent, setting the laser wavelength, frequency and energy, starting the pulse laser, and carrying out ablation reaction on the tin source target material in the reaction container; continuously stirring the solution by using a magnetic stirrer in the laser ablation process until the ablation is finished; the laser is an Nd YAG solid laser, the pulse frequency is 5-10 Hz, the laser wavelength is 1064nm, the laser energy is 80-120 mJ, and the laser ablation time is 20-60 min.
Step 6, taking out the tin source target, and adding an auxiliary agent into the precursor solution obtained after laser ablation; transferring the precursor solution and the zinc oxide nanorod array into a reaction kettle, heating to a set temperature, and preserving heat; the auxiliary agent is ethanolamine with the concentration of 99.8%, and the volume ratio of the ethanolamine to the total solution is 1: 6-1: 12. The set temperature is 140-200 ℃, and the heat preservation time is 4-15 h.
Step 7, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 8, taking out the nanorod array, and cleaning by using an organic solvent to obtain the zinc oxide/zinc stannate core-shell structure heterojunction.
As described in more detail below:
the invention discloses a preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction, which adopts a mode of combining atomic layer deposition, liquid phase laser ablation and a solvothermal method, grows a zinc oxide nanorod array on the surface of a thin metal wire serving as a substrate along the vertical direction, further obtains a high-activity solvothermal precursor by laser ablation of a high-purity metal tin target immersed in a solution, and grows the zinc oxide/zinc stannate core-shell structure heterojunction on the zinc oxide array by the solvothermal method. The zinc oxide/zinc stannate core-shell structure heterojunction with different sizes and appearances is obtained by changing the laser ablation time, the addition amount of deionized water and auxiliary agents (ethanol, hydrogen peroxide and ethanolamine), the reaction temperature and the reaction time, and the method specifically comprises the following steps:
step 1, taking a fine metal wire, respectively ultrasonically cleaning the fine metal wire for 30 minutes by using deionized water and absolute ethyl alcohol, drying the fine metal wire, and then depositing a zinc oxide film with the thickness of 50-200 nm on the surface of the fine metal wire by using an atomic layer deposition technology. Then, growing a zinc oxide nanorod array on the surface in a vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 90-120 ℃, and the hydrothermal time is 4-8 h.
Step 2, adding the prepared solution into a reaction container, placing the tin source target material into the solution, and enabling the solution to soak the surface of the target material; the prepared solution is deionized water and hydrogen peroxide in a volume ratio of 15: 1-120: 1, and the tin source target is a high-purity metal tin target with the purity of more than 99.9%.
Step 3, adjusting the light path of the pulse laser beam of the laser to focus the laser beam on the target material below the liquid level of the solvent, selecting proper laser wavelength, frequency and energy, starting the pulse laser, and carrying out ablation reaction on the tin source target material in a liquid environment; continuously stirring the solution by using a magnetic stirrer in the laser ablation process until the ablation is finished; YAG solid laser, pulse frequency is 5-10 Hz, laser wavelength is 1064nm, laser energy is 80-120 mJ, and ablation time is 20-60 min.
Step 4, taking out the tin target, and adding an alkaline solution to make the solution alkaline; the alkaline solution is ethanolamine with the concentration of 99.8%, and the volume ratio of the ethanolamine to the solution is 1: 6-1: 12.
Step 5, transferring the precursor solution in the container to a reaction kettle, heating to a set temperature, and preserving heat; the set temperature is 160-180 ℃, and the heat preservation time is 4-15 h.
Step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 7, taking out the nanorod array, and cleaning the nanorod array by using an organic solvent and the like. The organic solvent used for cleaning is ethanol or methanol.
The solvothermal precursor prepared by liquid-phase laser ablation has ultrahigh activity, short solvothermal required time and low temperature, does not introduce other impurity elements, and obtains ZnO/Zn2SnO4The core-shell structure heterojunction has high purity and uniform appearance and size.
The present invention will be described in further detail with reference to examples.
Example 1
Synthesizing a ZnO nanorod array with uniform appearance and size by using a mode of combining atomic layer deposition, liquid-phase laser ablation and a solvothermal method through the atomic layer deposition and the solvothermal method; then, high-purity metallic tin targets immersed in the solution are ablated by laser to obtain high-activity solvent thermal precursors; then the ZnO/Zn with uniform size and appearance is synthesized by a solvothermal method and a zinc oxide array as a base under a mild condition2SnO4The core-shell structure heterojunction specifically comprises the following steps:
step 1, taking a zinc wire with the diameter of 0.5mm, respectively ultrasonically cleaning the zinc wire with deionized water and absolute ethyl alcohol for 30 minutes, drying the zinc wire, and then depositing a zinc oxide film with the thickness of 50nm on the surface of the metal zinc wire by utilizing an atomic layer deposition technology. Then growing a zinc oxide nanorod array on the surface in the vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 90 ℃ and the hydrothermal time is 4 hours;
step 2, adding 60mL of deionized water and 1mL of hydrogen peroxide into a reaction container, placing the tin target into the solution, and soaking the surface of the target with the solution;
step 3, using an Nd-YAG solid laser, ablating a tin target immersed in the solution for 35min, wherein the pulse frequency is 10Hz, the laser wavelength is 1064nm, and the laser energy is 100 mJ;
step 4, taking out the metallic tin target, and adding 7ml of ethanolamine into the solution;
step 5, transferring the precursor solution in the container and the zinc oxide nanorod array into a reaction kettle, heating to 160 ℃, and preserving heat for 9 hours;
step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 7, taking out the nanorod array, and cleaning the nanorod array by using ethanol and deionized water to obtain ZnO/Zn2SnO4A core-shell structure heterojunction array.
The products prepared were characterized as shown in FIGS. 1-5. The results show that ZnO/Zn can be obtained according to the process parameters of example 12SnO4A core-shell structure heterojunction array. FIG. 1 shows ZnO/Zn prepared2SnO4The overall picture of the core-shell structure heterojunction shows that the surface of the obtained material is neat and intact. FIG. 2 is a diagram of an intermediate ZnO array. The ZnO/Zn obtained can be seen in FIG. 3 and FIG. 42SnO4The heterojunction with the core-shell structure has uniform appearance and size and the diameter of about 350 nm. XRD (X-ray diffraction) pattern shows that the heterojunction with the core-shell structure is high-purity ZnO/Zn2SnO4。
Example 2
Synthesizing a ZnO nanorod array with uniform appearance and size by using a mode of combining atomic layer deposition, liquid-phase laser ablation and a solvothermal method through the atomic layer deposition and the solvothermal method; then, high-purity metallic tin targets immersed in the solution are ablated by laser to obtain high-activity solvent thermal precursors; then the ZnO/Zn with uniform size and appearance is synthesized by a solvothermal method and a zinc oxide array as a base under a mild condition2SnO4The core-shell structure heterojunction specifically comprises the following steps:
step 1, taking a titanium wire with the diameter of 0.1mm, respectively ultrasonically cleaning the titanium wire with deionized water and absolute ethyl alcohol for 30 minutes, drying the titanium wire, and then depositing a zinc oxide film with the thickness of 150nm on the surface of the metal titanium wire by utilizing an atomic layer deposition technology. Then growing a zinc oxide nanorod array on the surface in the vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 95 ℃ and the hydrothermal time is 6 hours;
step 2, adding 60mL of deionized water and 1.5mL of hydrogen peroxide into a reaction container, placing the tin target into the solution, and soaking the surface of the target with the solution;
step 3, using an Nd-YAG solid laser, ablating the tin target immersed in the solution for 20min, wherein the pulse frequency is 5Hz, the laser wavelength is 1064nm, and the laser energy is 120 mJ;
step 4, taking out the tin target, and adding 10ml of ethanolamine into the solution;
step 5, transferring the precursor solution in the container and the zinc oxide nanorod array into a reaction kettle, heating to 160 ℃, and preserving heat for 15 hours;
step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
step 7, taking out the nanorod array, and utilizing ethanol and deionizationWashing with water to obtain ZnO/Zn2SnO4A core-shell structure heterojunction array.
The prepared product was subjected to characterization analysis, as shown in fig. 6 and 7. The result shows that according to the process parameters of the embodiment 2, the core-shell structure heterojunction nanorod array with the length of about 350nm can be obtained, the shape and the size are uniform, and an XRD (X-ray diffraction) diagram shows that the core-shell structure heterojunction is ZnO/Zn2SnO4。
Example 3
Synthesizing a ZnO nanorod array with uniform appearance and size by using a mode of combining atomic layer deposition, liquid-phase laser ablation and a solvothermal method through the atomic layer deposition and the solvothermal method; then, high-purity metallic tin targets immersed in the solution are ablated by laser to obtain high-activity solvent thermal precursors; then the ZnO/Zn with uniform size and appearance is synthesized by a solvothermal method and a zinc oxide array as a base under a mild condition2SnO4The core-shell structure heterojunction specifically comprises the following steps:
step 1, taking a zinc wire with the diameter of 1mm, respectively ultrasonically cleaning the zinc wire for 30 minutes by using deionized water and absolute ethyl alcohol, drying the zinc wire, and then depositing a zinc oxide film with the thickness of 200nm on the surface of the metal zinc wire by utilizing an atomic layer deposition technology. Then growing a zinc oxide nanorod array on the surface in the vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 95 ℃ and the hydrothermal time is 6 hours;
step 2, adding 60mL of deionized water and 3mL of hydrogen peroxide into a reaction container, placing the tin target into the solution, and soaking the surface of the target with the solution;
step 3, using an Nd-YAG solid laser, ablating the tin target immersed in the solution for 60min, wherein the pulse frequency is 10Hz, the laser wavelength is 1064nm, and the laser energy is 110 mJ;
step 4, taking out the tin target, and adding 6ml of ethanolamine into the solution;
step 5, transferring the precursor solution in the container and the zinc oxide nanorod array into a reaction kettle, heating to 200 ℃, and preserving heat for 4 hours;
step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 7, taking out the nanorod array, and cleaning the nanorod array by using ethanol and deionized water to obtain ZnO/Zn2SnO4A core-shell structure heterojunction array.
The prepared product was subjected to characterization analysis as shown in fig. 8. The result shows that the core-shell structure heterojunction nanorod array with the length of about 350nm can be obtained according to the process parameters of the embodiment 3, and the shape and the size are uniform.
Example 4
Synthesizing a ZnO nanorod array with uniform appearance and size by using a mode of combining atomic layer deposition, liquid-phase laser ablation and a solvothermal method through the atomic layer deposition and the solvothermal method; then, high-purity metallic tin targets immersed in the solution are ablated by laser to obtain high-activity solvent thermal precursors; then the ZnO/Zn with uniform size and appearance is synthesized by a solvothermal method and a zinc oxide array as a base under a mild condition2SnO4The core-shell structure heterojunction specifically comprises the following steps:
step 1, taking a zinc wire with the diameter of 0.5mm, respectively ultrasonically cleaning the zinc wire with deionized water and absolute ethyl alcohol for 30 minutes, drying the zinc wire, and then depositing a zinc oxide film with the thickness of 100nm on the surface of the metal zinc wire by utilizing an atomic layer deposition technology. Then growing a zinc oxide nanorod array on the surface in the vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 100 ℃, and the hydrothermal time is 6 hours;
step 2, adding 60mL of deionized water and 0.5mL of hydrogen peroxide into a reaction container, placing the tin target into the solution, and soaking the surface of the target with the solution;
step 3, using an Nd-YAG solid laser, ablating a tin target immersed in the solution for 50min, wherein the pulse frequency is 10Hz, the laser wavelength is 1064nm, and the laser energy is 80 mJ;
step 4, taking out the tin target, and adding 8ml of ethanolamine into the solution;
step 5, transferring the precursor solution in the container and the zinc oxide nanorod array into a reaction kettle, heating to 140 ℃, and preserving heat for 12 hours;
step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
step (ii) of7. Taking out the nanorod array, and cleaning with ethanol and deionized water to obtain ZnO/Zn2SnO4A core-shell structure heterojunction array.
The prepared product was subjected to characterization analysis as shown in fig. 9. The result shows that the core-shell structure heterojunction nanorod array with uniform morphology and size can be obtained according to the process parameters of the embodiment 4.
Example 5
Synthesizing a ZnO nanorod array with uniform appearance and size by using a mode of combining atomic layer deposition, liquid-phase laser ablation and a solvothermal method through the atomic layer deposition and the solvothermal method; then, high-purity metallic tin targets immersed in the solution are ablated by laser to obtain high-activity solvent thermal precursors; then the ZnO/Zn with uniform size and appearance is synthesized by a solvothermal method and a zinc oxide array as a base under a mild condition2SnO4The core-shell structure heterojunction specifically comprises the following steps:
step 1, taking a zinc wire with the diameter of 0.5mm, respectively ultrasonically cleaning the zinc wire with deionized water and absolute ethyl alcohol for 30 minutes, drying the zinc wire, and then depositing a zinc oxide film with the thickness of 200nm on the surface of the metal zinc wire by utilizing an atomic layer deposition technology. Then growing a zinc oxide nanorod array on the surface in the vertical direction by a solvothermal method, wherein the set hydrothermal temperature is 120 ℃, and the hydrothermal time is 8 hours;
step 2, adding 60mL of deionized water and 4mL of hydrogen peroxide into a reaction container, placing the tin target into the solution, and soaking the surface of the target with the solution;
step 3, using an Nd-YAG solid laser, ablating the tin target immersed in the solution for 40min, wherein the pulse frequency is 5Hz, the laser wavelength is 1064nm, and the laser energy is 90 mJ;
step 4, taking out the tin target, and adding 12ml of ethanolamine into the solution;
step 5, transferring the precursor solution in the container and the zinc oxide nanorod array into a reaction kettle, heating to 180 ℃, and preserving heat for 6 hours;
step 6, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
step 7, taking out the nanorod array and utilizing BCleaning with alcohol and deionized water to obtain ZnO/Zn2SnO4A core-shell structure heterojunction array.
The prepared product was subjected to characterization analysis as shown in fig. 10. The result shows that the core-shell structure heterojunction nanorod array with uniform morphology and size can be obtained according to the process parameters of the embodiment 5.

Claims (6)

1. A preparation method of a zinc oxide/zinc stannate core-shell structure heterojunction is characterized by comprising the following steps:
step 1, respectively using deionized water and absolute ethyl alcohol to ultrasonically clean and dry flexible fibrous fine metal wires;
step 2, depositing a zinc oxide film on the surface of the metal wire by using an atomic layer deposition method to serve as a seed layer;
step 3, growing a zinc oxide nanorod array on the surface of the seed layer along the vertical direction by a solvothermal method;
step 4, adding the prepared solution into a reaction container, placing the tin source target material into the solution, and enabling the solution to soak the surface of the target material; the prepared solution is a mixed solution of ethanol, deionized water and hydrogen peroxide, wherein the volume ratio of the ethanol to the deionized water is 0: 1-1: 1, the volume ratio of the deionized water to the hydrogen peroxide is 15: 1-120: 1, and the tin source target is a high-purity metal tin target with the purity of more than 99.9%;
step 5, adjusting the light path of the pulse laser beam of the laser, focusing the laser beam on the tin source target below the liquid level of the solution, setting the laser wavelength, frequency and energy, starting the pulse laser, and carrying out ablation reaction on the tin source target in the reaction container; continuously stirring the solution by using a magnetic stirrer in the laser ablation process until the ablation is finished;
step 6, taking out the tin source target, and adding an auxiliary agent into the precursor solution obtained after laser ablation; transferring the precursor solution and the zinc oxide nanorod array into a reaction kettle, heating to a set temperature, and preserving heat; the auxiliary agent is ethanolamine with the concentration of 99.8%, and the volume ratio of the ethanolamine to the total solution is 1: 6-1: 12;
step 7, after the reaction is finished, cooling the reaction system to room temperature along with the furnace;
and 8, taking out the nanorod array, and cleaning by using an organic solvent to obtain the zinc oxide/zinc stannate core-shell structure heterojunction.
2. The preparation method of the zinc oxide/zinc stannate core-shell structure heterojunction as claimed in claim 1, wherein the metal wire in step 1 comprises a titanium wire or a zinc wire, and the diameter is 0.1-1 mm.
3. The method for preparing the zinc oxide/zinc stannate core-shell structure heterojunction as claimed in claim 1, wherein the thickness of the atomic layer deposited zinc oxide thin film in the step 2 is 50-200 nm.
4. The method for preparing a zinc oxide/zinc stannate core-shell structure heterojunction as claimed in claim 1, wherein the hydrothermal temperature set by the solvothermal method in step 3 is 90-120 ℃ and the hydrothermal time is 4-8 h.
5. The method for preparing a zinc oxide/zinc stannate core-shell structure heterojunction as claimed in claim 1, wherein the laser in step 5 is Nd-YAG solid laser, the pulse frequency is 5-10 Hz, the laser wavelength is 1064nm, the laser energy is 80-120 mJ, and the laser ablation time is 20-60 min.
6. The preparation method of the zinc oxide/zinc stannate core-shell structure heterojunction as claimed in claim 1, wherein the temperature in step 6 is set to be 140-200 ℃ and the heat preservation time is 4-15 h.
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