CN115321582A - Preparation method and application of single-orientation ZnO nano array - Google Patents
Preparation method and application of single-orientation ZnO nano array Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 41
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
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- 238000009987 spinning Methods 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 abstract description 27
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- 230000008025 crystallization Effects 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 157
- 239000011787 zinc oxide Substances 0.000 description 77
- 239000002070 nanowire Substances 0.000 description 8
- 229960004011 methenamine Drugs 0.000 description 7
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
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Abstract
The invention relates to a preparation method and application of a single-orientation ZnO nano-array, wherein zinc acetate and polyvinyl alcohol are used as raw materials, the raw materials are mixed with deionized water and then are magnetically stirred to form zinc salt sol, a rotary coating technology is adopted to coat the zinc salt sol on an ITO substrate in a rotating mode, then heat treatment is carried out in the air atmosphere to obtain ZnO seed crystals, and on the basis of the ZnO seed crystals, a hydrothermal method is adopted, zinc nitrate and hexamethylenetetramine are used as raw materials, and a special substrate support is adopted to prepare the orderly-arranged ZnO nano-array on the ZnO seed crystals. The method has the advantages of simple process, mild preparation conditions and easy operation, and the prepared ZnO nanorods are orderly arranged and have good crystallization quality, thus being a substrate material of nano photoelectric devices with great development potential.
Description
Technical Field
The invention relates to the technical field of preparation of nano inorganic non-metallic semiconductor materials, in particular to a preparation method and application of a single-orientation ZnO nano array.
Background
As a third generation wide band gap semiconductor material, zinc oxide (ZnO) has unique electrical, optical, magnetic, mechanical and chemical properties, and has great application potential in the fields of microelectronic devices, photoelectric devices and the like. The performance of the ZnO material not only depends on the composition, structure and dimension of the ZnO material, but also depends on the dimension and form of the ZnO material, so that the structure, components, shape, dimension and position of the ZnO material are controlled to grow in the growth process of the ZnO material, the performance of the ZnO material can be designed and selectively assembled, and the ZnO material has important application value for developing various functions of the ZnO material. The one-dimensional nano material has obvious quantum effect and electron conduction effect, and is a main element of a nano device system. Therefore, the zinc oxide nanowire has good application prospects in the fields of electronic devices, photoelectric devices, electrochemical devices and the like, and solar cells, ultraviolet detectors, nanogenerators, photodiodes and the like are prepared by using the zinc oxide nanowire. At present, there are many methods for preparing ZnO nanowire arrays, such as Chemical Vapor Deposition (CVD), electrochemical Deposition (ED), vapor-liquid-solid growth (VLS), and hydrothermal methods, which require precise instruments and harsh growth conditions, but compared with the former methods, the hydrothermal methods are considered to be ideal methods for synthesizing ZnO nanoparticles because of their characteristics of simple equipment, low cost, and environmental friendliness, but the ZnO nanowire arrays prepared by the hydrothermal methods have the problem of irregular arrangement.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of a single-orientation ZnO nano-array. The method has simple process and easy operation, and the prepared ZnO nanowire array is orderly arranged and has good performance and can be used as a substrate material of a nano photoelectric device.
One of the purposes of the invention is to provide a preparation method of a single-orientation ZnO nano array, which specifically comprises the following steps:
(1) Preparing ZnO seed crystal: 3.3g of zinc acetate and 4.0g of polyvinyl alcohol (PVA) are respectively weighed and added into a beaker filled with 40ml of deionized water; placing the beaker on a heating magnetic stirrer, heating to 80 ℃ while stirring, continuing to stir at the constant temperature of 80 ℃ for 1 hour to form zinc salt sol, cooling the sol to room temperature, and then fixing the volume with deionized water to finally form transparent homogeneous sol with the zinc ion concentration of 0.6 mol/L; preparing seed crystals by adopting a rotary coating technology, directly placing a cleaned ITO substrate on a substrate support of a spin coater without drying, immediately spin-coating, and uniformly coating the prepared transparent homogeneous sol on an ITO substrate; drying the sample subjected to whirl coating in an oven at 100 ℃ for 10min; the whirl coating process comprises a drying process after whirl coating, the whirl coating process is repeated for 3 times, so that a film is finally formed on the ITO substrate, the obtained ITO substrate coated with the film is placed into a tubular furnace and is subjected to heat treatment for 2 hours in an air atmosphere at 300 ℃, and the ITO substrate with ZnO seed crystals is obtained;
(2) Preparing a ZnO nano array: dissolving a certain amount of zinc nitrate and hexamethylenetetramine in deionized water to prepare 100mL of solution with zinc ion concentration of 0.01-0.04 mol/L, uniformly stirring, transferring the solution into a hydrothermal reaction kettle lined with a polytetrafluoroethylene lining, sequentially and vertically placing a special substrate support and the ITO substrate with ZnO seed crystals obtained in the step (1) into the hydrothermal reaction kettle, wherein the side with the ZnO seed crystals faces downwards when the ITO substrate is placed, the ITO substrate is not immersed in the solution in the hydrothermal reaction kettle, and tightly sealing and covering the hydrothermal reaction kettle; and transferring the sealed hydrothermal reaction kettle to a muffle furnace at 95 ℃. Keeping the temperature for 4-12 h, closing the muffle furnace, naturally cooling to room temperature, taking out the hydrothermal reaction kettle, taking out a product from the hydrothermal reaction kettle, washing the product with deionized water and alcohol for several times, and drying the product in a tubular furnace at 300 ℃ for 1h to obtain a ZnO nanorod array;
preferably, the spin coating in step (1) is performed by rotating at 600rpm for 5 seconds and then at 3000rpm for 20 seconds.
Preferably, the thickness of the ZnO seed crystal on the ITO substrate grown with the ZnO seed crystal in the step (1) is 200nm.
Preferably, the mass ratio of the zinc nitrate to the hexamethylenetetramine in the step (2) is 1:1.
Preferably, the substrate support specially made in the step (2) is formed by etching polytetrafluoroethylene, and comprises a circular plane and two supporting legs, wherein the circular plane is matched with the inside of the hydrothermal reaction kettle, and the substrate support can be just placed in the middle of the hydrothermal reaction kettle when horizontally placed.
The invention also aims to provide a single-orientation ZnO nano array prepared by the method and application of the ZnO nano array in nano photoelectric devices.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method comprises the steps of mixing zinc acetate and polyvinyl alcohol serving as raw materials with deionized water, magnetically stirring to form zinc salt sol, coating the zinc salt sol on an ITO substrate in a spinning mode by adopting a spin coating technology, carrying out heat treatment in air atmosphere to obtain ZnO seed crystals, and preparing the regularly arranged ZnO nanorod array on the ZnO seed crystals by adopting a hydrothermal method and a special substrate support on the basis of the ZnO seed crystals by adopting zinc nitrate and hexamethylenetetramine as raw materials.
(2) The invention adopts homogeneous buffer layer technology, effectively improves the crystallization quality of ZnO nano-rods, and adopts a special substrate bracket to prepare a nano-rod array which is integrally arranged.
(3) The invention adopts sol-gel to prepare ZnO seed crystals, which can effectively improve the adhesiveness of ZnO nano arrays.
(4) The method has the advantages of simple process, mild preparation conditions and easy operation, and the prepared ZnO nanorods are orderly arranged and have good crystallization quality, thereby being a substrate material of nano photoelectric devices with very great development potential.
Drawings
FIG. 1 is an XRD pattern of a ZnO seed crystal prepared in example 1 of the present invention;
FIG. 2 is an AFM of a ZnO seed crystal prepared according to example 1 of the present invention;
FIG. 3 is an XRD pattern of ZnO nanorods prepared in example 1 of the present invention;
FIG. 4 is an SEM photograph of ZnO nanorods prepared in example 1 of the present invention;
FIG. 5 is a PL spectrum of a ZnO nanorod prepared in example 1 of the present invention;
FIG. 6 is a transmission spectrum of ZnO nanorods prepared in example 1 of the present invention;
FIG. 7 is an XRD pattern of ZnO nanorods prepared in example 2 of the present invention;
FIG. 8 is an SEM image of ZnO nanorods prepared in example 2 of the invention.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following examples taken in conjunction with the accompanying drawings. The following examples are given to illustrate detailed embodiments and procedures based on the technology of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) Preparation of ZnO seed crystal
1) 3.3g of zinc acetate and 4.0g of polyvinyl alcohol (PVA) are weighed on an electro-optical analytical balance respectively and added into a beaker filled with 40ml of deionized water;
2) Placing the beaker on a heating magnetic stirrer, heating to 80 ℃ while stirring, continuing to stir at the constant temperature of 80 ℃ for 1 hour to form zinc salt sol, cooling the sol to room temperature, and then fixing the volume with deionized water to finally form transparent homogeneous sol with the zinc ion concentration of 0.6 mol/L;
3) Preparing seed crystals by adopting a spin coating technology, directly placing a cleaned ITO substrate on a substrate support of a spin coater without drying, immediately spin-coating, uniformly coating the transparent homogeneous sol prepared in the step 2) on the ITO substrate, and firstly rotating at a low speed of 600rpm (revolutions per minute) for 5 seconds and then rotating at a high speed of 3000rpm for 20 seconds during spin-coating;
4) Drying the sample subjected to the spin coating in the step 3) in an oven at 100 ℃ for 10min;
5) And (3) marking the whirl coating step in the step 3) and the drying step after whirl coating in the step 4) as a complete whirl coating process, repeating the whirl coating process for 3 times, finally forming a film on the ITO substrate, putting the obtained ITO substrate coated with the film into a tubular furnace, and carrying out heat treatment for 2 hours in an air atmosphere at 300 ℃ to obtain the ZnO seed crystal with the thickness of 200nm.
FIG. 1 is an XRD pattern of the ZnO seed crystal prepared in this example, from which it can be seen that the ZnO seed crystal prepared in this example is a wurtzite structure with a preferred orientation in the c-axis direction;
FIG. 2 is an AFM image of the ZnO seed crystal prepared in this example, from which it can be seen that the ZnO seed crystal prepared in this example has a smooth and uniform surface, and is suitable for the next step of preparing ZnO nanorods.
(2) Preparation of ZnO nano-array
1) Dissolving a certain amount of zinc nitrate and hexamethylenetetramine in deionized water to prepare 100mL of solution with zinc ion concentration of 0.03mol/L, wherein the mass ratio of the zinc nitrate to the hexamethylenetetramine is 1:1, uniformly stirring, transferring the solution into a hydrothermal reaction kettle lined with polytetrafluoroethylene lining, sequentially and vertically placing a special substrate support and the ITO substrate with ZnO seed crystals obtained in the step (1) into the hydrothermal reaction kettle, wherein the side with the ZnO seed crystals faces downwards when the ITO substrate is placed, the solution in the hydrothermal reaction kettle does not immerse the ITO substrate, and tightly sealing and covering the hydrothermal reaction kettle;
2) Transferring the sealed hydrothermal reaction kettle in the step 1) to a muffle furnace at 95 ℃. And (3) keeping the temperature for 12h, closing the muffle furnace, naturally cooling to room temperature, taking out the hydrothermal reaction kettle, taking out a product from the hydrothermal reaction kettle, washing the product with deionized water and alcohol for several times, and drying the product in a tubular furnace at 300 ℃ for 1h to obtain the ZnO nanorod array.
The special substrate support in the step (2) is formed by etching polytetrafluoroethylene, and comprises a circular plane and two supporting legs, wherein the circular plane is matched with the interior of the hydrothermal reaction kettle and can be just placed in the middle of the hydrothermal reaction kettle when being horizontally placed.
Fig. 3 is an XRD pattern of the ZnO nanorods prepared in this example, and it can be seen from fig. 3 that the diffraction intensity of the sample is the largest at 2 θ =34.22 °, and the diffraction peak corresponds to the (002) crystal plane of the ZnO wurtzite structure, which indicates that the one-dimensional ZnO nanorods prepared in this example have a standard hexagonal wurtzite structure and the ZnO nanowires grow preferentially in the (002) direction.
FIG. 4 is an SEM image of the ZnO nanorods prepared in this example, and it can be seen that the ZnO nanorods array prepared in this example has a good orientation, and the nanorods all grow along the c-axis and are substantially perpendicular to the substrate surface.
FIG. 5 is a PL spectrum of the ZnO nanorod prepared in this example; from the figure, it can be seen that the ZnO nanowire has an ultraviolet excitation peak at 380nm (3.24 eV), which is smaller than the band gap width of ZnO by 3.37eV, and the ultraviolet luminescence in the ZnO nanowire is derived from band-edge exciton level transition and interband exciton recombination in the nanowire.
FIG. 6 is a transmission spectrum of the ZnO nanorod prepared in this example, and the result shows that the transmittance of the ZnO nanorod prepared in the visible light range is 80%.
Example 2:
(1) Preparation of ZnO seed crystal
1) 3.3g of zinc acetate and 4.0g of polyvinyl alcohol (PVA) are weighed on an electro-optical analytical balance respectively and added into a beaker filled with 40ml of deionized water;
2) Placing the beaker on a heating magnetic stirrer, heating to 80 ℃ while stirring, continuing to stir at the constant temperature of 80 ℃ for 1 hour to form zinc salt sol, cooling the sol to room temperature, and then fixing the volume with deionized water to finally form transparent homogeneous sol with the zinc ion concentration of 0.6 mol/L;
3) Preparing seed crystals by adopting a spin coating technology, directly placing a cleaned ITO substrate on a substrate support of a spin coater without drying, immediately spin-coating, uniformly coating the transparent homogeneous sol prepared in the step 2) on the ITO substrate, and firstly rotating at a low speed of 600rpm (revolutions per minute) for 5 seconds and then rotating at a high speed of 3000rpm for 20 seconds during spin-coating;
4) Drying the sample subjected to the spin coating in the step 3) in an oven at 100 ℃ for 10min;
5) And (4) recording the whirl coating step in the step 3) and the drying step after whirl coating in the step 4) as a complete whirl coating process, repeating the whirl coating process for 3 times, finally forming a film on the ITO substrate, putting the obtained ITO substrate coated with the film into a tubular furnace, and carrying out heat treatment for 2 hours in an air atmosphere at 300 ℃ to obtain the ZnO seed crystal with the thickness of 200nm.
(2) Preparation of ZnO nano-array
1) Dissolving a certain amount of zinc nitrate and hexamethylene tetramine in deionized water to prepare 100mL of solution with zinc ion concentration of 0.04mol/L, wherein the mass ratio of the zinc nitrate to the hexamethylene tetramine is 1:1, uniformly stirring, transferring the solution into a hydrothermal reaction kettle lined with a polytetrafluoroethylene lining, sequentially and vertically placing a special substrate support and the ITO substrate with ZnO seed crystals obtained in the step (1) into the hydrothermal reaction kettle, wherein the side with the ZnO seed crystals faces downwards when the ITO substrate is placed, the solution in the hydrothermal reaction kettle does not immerse the ITO substrate, and tightly sealing and covering the hydrothermal reaction kettle;
2) Transferring the sealed hydrothermal reaction kettle in the step 1) to a muffle furnace at 95 ℃. And (3) keeping the temperature for 4 hours, closing the muffle furnace, naturally cooling to room temperature, taking out the hydrothermal reaction kettle, taking out a product from the hydrothermal reaction kettle, washing the product with deionized water and alcohol for several times, and drying the product in a tubular furnace at 300 ℃ for 1 hour to obtain the ZnO nanorod array.
The special substrate support in the step (2) is formed by etching polytetrafluoroethylene, and comprises a circular plane and two supporting legs, wherein the circular plane is matched with the interior of the hydrothermal reaction kettle and can be just placed in the middle of the hydrothermal reaction kettle when being horizontally placed.
Fig. 7 is an XRD pattern of the ZnO nanorods prepared in this example, and a diffraction peak was observed only at 2 θ =34.22 °, corresponding to the (002) crystal plane of the ZnO wurtzite structure, indicating that the ZnO nanorods at this time have a standard hexagonal wurtzite structure, and the ZnO nanowires grow preferentially in the (002) direction.
FIG. 8 is an SEM photograph of the ZnO nanorods prepared according to the example, and it can be seen that the ZnO nanorods prepared have good array orientation, and all grow along the c-axis and perpendicular to the substrate surface.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (7)
1. A preparation method of a single-orientation ZnO nano array is characterized by comprising the following steps:
(1) Preparing ZnO seed crystal: 3.3g of zinc acetate and 4.0g of polyvinyl alcohol are respectively weighed and added into a beaker filled with 40ml of deionized water; placing the beaker on a heating magnetic stirrer, heating to 80 ℃ while stirring, continuing to stir at the constant temperature of 80 ℃ for 1 hour to form zinc salt sol, cooling the sol to room temperature, and then fixing the volume with deionized water to finally form transparent homogeneous sol with the zinc ion concentration of 0.6 mol/L; preparing seed crystals by adopting a rotary coating technology, directly placing a cleaned ITO substrate on a substrate support of a spin coater without drying, immediately spin-coating, and uniformly coating the prepared transparent homogeneous sol on an ITO substrate; drying the sample subjected to whirl coating in an oven at 100 ℃ for 10min; repeating the whirl coating process for 3 times, wherein the whirl coating process comprises a drying process after whirl coating, finally forming a film on the ITO substrate, putting the obtained ITO substrate coated with the film into a tubular furnace, and carrying out heat treatment for 2 hours in an air atmosphere at 300 ℃ to obtain the ITO substrate with ZnO seed crystals;
(2) Preparing a ZnO nano array: dissolving a certain amount of zinc nitrate and hexamethylenetetramine in deionized water, uniformly stirring, transferring the solution into a hydrothermal reaction kettle lined with a polytetrafluoroethylene lining, sequentially and vertically placing a substrate support and the ITO substrate with the ZnO seed crystals obtained in the step (1) into the hydrothermal reaction kettle, wherein the side with the ZnO seed crystals faces downwards when the ITO substrate is placed, the ITO substrate is not immersed in the solution in the hydrothermal reaction kettle, and the hydrothermal reaction kettle is sealed and covered tightly; transferring the sealed hydrothermal reaction kettle to a muffle furnace at the temperature of 95 ℃; and (3) keeping the temperature for 4-12 h, closing the muffle furnace, naturally cooling to room temperature, taking out the hydrothermal reaction kettle, taking out a product from the hydrothermal reaction kettle, washing the product with deionized water and alcohol for several times, and drying the product in a tubular furnace at 300 ℃ for 1h to obtain the single-orientation ZnO nano array.
2. The method for preparing a mono-oriented ZnO nano-array according to claim 1, wherein the spinning in the step (1) is performed by rotating at a rotation speed of 600rpm for 5 seconds and then at a rotation speed of 3000rpm for 20 seconds.
3. The method of preparing a mono-oriented ZnO nanoarray as claimed in claim 1, wherein the ZnO seeds on the ITO substrate on which the ZnO seeds are grown in step (1) have a thickness of 200nm.
4. The method for preparing a mono-oriented ZnO nano-array according to claim 1, wherein the mass ratio of the zinc nitrate to the hexamethylenetetramine in the step (2) is 1:1, the volume of the solution of the zinc nitrate and the hexamethylenetetramine is 100mL, and the concentration of zinc ions in the solution is 0.01 mol/L-0.04 mol/L.
5. The method for preparing a mono-oriented ZnO nanoarray as claimed in claim 1, wherein the substrate support specially made in step (2) is formed by etching ptfe, and the substrate support includes a circular plane and two support legs, the circular plane is fitted with the interior of the hydrothermal reaction vessel, and the substrate support can be placed in the middle of the hydrothermal reaction vessel when horizontally placed.
6. A mono-oriented ZnO nano-array prepared by the preparation method as claimed in any one of claims 1 to 5.
7. Use of a mono-oriented ZnO nanoarray as claimed in claim 6 in a nano-optoelectronic device.
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