CN116722076A - Ce-doped ZnO nano-pillar array and preparation method thereof - Google Patents
Ce-doped ZnO nano-pillar array and preparation method thereof Download PDFInfo
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- 239000002061 nanopillar Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000243 solution Substances 0.000 claims abstract description 79
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000004246 zinc acetate Substances 0.000 claims abstract description 49
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 42
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 22
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 230000032683 aging Effects 0.000 claims abstract description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 19
- 238000004528 spin coating Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 abstract description 49
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 14
- 239000004020 conductor Substances 0.000 description 11
- 238000003491 array Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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Abstract
The application belongs to the technical field of nano materials, and particularly relates to a Ce-doped ZnO nano column array and a preparation method thereof, wherein the preparation method comprises the steps of adding ethanolamine and polyvinylpyrrolidone into an aqueous solution of zinc acetate and cerium nitrate, stirring at constant temperature, and aging to form a mixed solution; spin-coating the mixed solution on a substrate, performing heat treatment at a first temperature, and performing annealing treatment at a second temperature to form a Ce-doped ZnO seed layer, wherein the second temperature is higher than the first temperature; and performing hydrothermal reaction on the Ce-doped ZnO seed layer and a reaction solution to form a Ce-doped ZnO nano-pillar array, wherein the reaction solution is an aqueous solution of zinc acetate, cerium nitrate and hexamethylenetetramine. The method has the advantages of simple preparation process, low equipment requirement, high controllable degree, uniform obtained product, excellent transmittance and wide application in energy and environmental protection industries.
Description
Technical Field
The application belongs to the technical field of nano materials, and particularly relates to a Ce-doped ZnO nano-pillar array and a preparation method thereof.
Background
With the increasing development of the optoelectronic industry, the wide application of Transparent Conductive Oxide (TCO) films as transparent electrode materials in electroluminescent devices, solar cells, transparent thin film transistors and flat panel displays has become a hot spot of current research. Indium Tin Oxide (ITO) is the most widely used commercially transparent conductive film, and its expensive raw materials and fewer resources on earth limit its future applications, although it has optical properties of high conductivity and high transmittance. Meanwhile, the continuous development of optoelectronic technology places higher demands on the performance of transparent electrodes in flexible displays. The above situation has attracted attention and importance to the research of ITO substitutes. As a wide-bandgap semiconductor metal oxide, the ZnO film is a very promising TCO film material because of the cheap raw materials, abundant reserves, no toxicity, easy bending, and the capability of being used for flexible substrates, and the characteristic of realizing high transmittance and low resistance through doping.
Disclosure of Invention
The primary technical problem to be solved by the application is to provide the Ce-doped ZnO nano-pillar array with simple process and low cost and the preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the application comprises the following steps: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: adding ethanolamine and polyvinylpyrrolidone into an aqueous solution of zinc acetate and cerium nitrate, stirring at constant temperature, and aging to form a mixed solution; spin-coating the mixed solution on a substrate, performing heat treatment at a first temperature, and performing annealing treatment at a second temperature to form a Ce-doped ZnO seed layer, wherein the second temperature is higher than the first temperature; and performing hydrothermal reaction on the Ce-doped ZnO seed layer and a reaction solution to form a Ce-doped ZnO nano-pillar array, wherein the reaction solution is an aqueous solution of zinc acetate, cerium nitrate and hexamethylenetetramine.
Wherein the first temperature of the heat treatment at the first temperature is 270-350 ℃, and the heat treatment time is 5-10min; the number of heat treatments at the first temperature is 3-5.
Wherein, the second temperature in the annealing treatment at the second temperature is 450-550 ℃; the annealing time is 60-90 minutes.
Wherein the temperature of the hydrothermal reaction is 90-110 ℃; the hydrothermal reaction time is 90-120min.
Wherein, in the aqueous solution of zinc acetate and cerium nitrate, the molar ratio of zinc acetate to cerium nitrate is 100:1-100:3, and the concentration of the aqueous solution of zinc acetate and cerium nitrate is 0.5-0.75mol/L.
Wherein, the aqueous solution of zinc acetate and cerium nitrate is formed by respectively adding zinc acetate and cerium nitrate into deionized water and stirring for 60-90min.
Wherein the substrate comprises quartz glass.
Wherein the mol ratio of the ethanolamine to the polyvinylpyrrolidone is 1:1-3:1; the constant temperature stirring temperature is 40-60 ℃, and the stirring time is 60-90min.
Wherein the aging time is 12-48 hours.
Wherein, in the aqueous solution of zinc acetate, cerium nitrate and hexamethylenetetramine, the molar ratio of the zinc acetate to the cerium nitrate to the hexamethylenetetramine is 100:1:20-100:3:20.
The application also comprises a second technical scheme, namely the Ce-doped ZnO nano-pillar array, which is prepared by the preparation method.
The Ce-doped ZnO nano-pillar array comprises a plurality of Ce-doped ZnO nano-pillars, wherein the diameter of each Ce-doped ZnO nano-pillar is 200-250 nm, and the length of each nano-pillar is 350-400nm.
The application has the beneficial effects that:
(1) The preparation method of the Ce-doped ZnO nano-pillar array does not need expensive instruments and equipment, and realizes the preparation of the Ce-ZnO nano-pillar array through reasonable process control. The application has the advantages of cheap and easily obtained raw materials, simple synthesis process, low cost, short reaction period and no pollution to the environment. The Ce-doped ZnO nano-pillar array prepared by the preparation method of the Ce-doped ZnO nano-pillar array has the advantages of uniform size, adjustable size and good dispersion.
(2) The Ce-doped ZnO nano-pillar array prepared by the preparation method provided by the application has higher visible light transmittance, higher ultraviolet absorptivity and better conductivity, and can be applied to the fields of catalysis, photoelectric devices, military and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) front view of the Ce-doped ZnO nanopillar array of example 1 of the present application.
Fig. 2 is a Scanning Electron Microscope (SEM) cross-sectional photograph of another Ce-doped ZnO nanopillar array of example 1 of the present application.
Fig. 3 is a graph of transmittance contrast of Ce doped ZnO nanopillar arrays of the present application versus undoped ZnO arrays.
Fig. 4 is a graph comparing absorbance of Ce doped ZnO nanopillar arrays of the present application with undoped ZnO arrays.
Fig. 5 is a graphical representation of X-ray diffractometer (XRD) contrast of Ce doped ZnO nanopillar arrays of the present application with undoped ZnO arrays.
Fig. 6 is an electrochemical impedance contrast diagram of Ce doped ZnO nanopillar arrays of the present application and undoped ZnO arrays.
Detailed Description
The following examples are presented to further illustrate the methods of the present application, but are not meant to limit the application thereto.
Example 1:
a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form an aqueous solution of zinc acetate and cerium nitrate, which is called a mixed solution A for convenience of description, wherein the concentration of the solution A is 0.773mol/L. And step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B. And thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours. Spin-coating the aged solution B on quartz glass, and performing heat treatment at 300 ℃ for 10min for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and seventhly, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant-temperature oven, and performing constant-temperature hydrothermal reaction at 90 ℃ for 90min to obtain the compact Ce: znO nano column array with high transmittance. In the preparation method of the embodiment of the application, the diameter of the Ce-ZnO nano-pillar array can be controlled by controlling the amount of hexamethylenetetramine, and the length of the Ce-doped ZnO (Ce-ZnO) nano-pillar array can be controlled by controlling the hydrothermal time length.
As shown in fig. 1 and fig. 2, the Ce doped ZnO nano-pillar array prepared by the embodiment of the present application includes a plurality of Ce doped ZnO nano-pillars, where the diameter of the Ce doped ZnO nano-pillars is 200nm-250nm, and the length of the nano-pillars is 350-400nm. The ZnO nano-pillar array is uniformly distributed. As can be seen from fig. 1, the Ce doped ZnO nanopillar array film is dense and has a relatively uniform size.
As shown in FIG. 3, the Ce-doped ZnO nano-pillar array prepared by the embodiment of the application has the light transmittance reaching 90% under the condition of 500nm wavelength, and the light transmittance is increased after the Ce-doped ZnO is adopted. As shown in fig. 4, the Ce doped ZnO nanopillar array of the embodiment of the present application. As shown in FIG. 4, the ultraviolet-visible absorption diagram of the Ce-doped ZnO nano-pillar array prepared by the embodiment of the application shows that the Ce-doped ZnO nano-pillar array has lower absorbance in the visible light range (380 nm < wavelength < 800 nm) and higher absorbance in the ultraviolet light range (wavelength < 380 nm), thereby being more beneficial to the wide application in transparent photoelectric devices. As shown in FIG. 5, the XRD patterns of the Ce-doped ZnO nanopillar arrays prepared in the examples of the present application, it can be seen from the patterns that the diffraction peaks at (100), (101) and (002) are matched with those of ZnO, and since Ce doping cannot be represented in XRD, the Ce-doped ZnO nanopillar arrays show the same diffraction peaks as ZnO. As shown in fig. 6, in the electrochemical impedance diagram of the Ce doped ZnO nano-pillar array prepared according to the embodiment of the present application, the impedance of the ZnO thin film 4380 Ω is measured by zsimemo 3.30d software analysis, and the impedance of the Ce doped ZnO array is 1800 Ω. The impedance of the Ce doped ZnO nano-pillar array is obviously reduced, and the migration/diffusion of interface carriers is effectively improved. The impedance of the Ce-doped ZnO nano-pillar array prepared by the embodiment of the application is obviously smaller than that of ZnO, which indicates that the conductivity of the Ce-doped ZnO nano-pillar array is improved.
Example 2:
this example differs from example 1 in that the amount of cerium nitrate in step one was changed to 0.00015mol, and otherwise the same as example 1, specifically as follows: a Ce-doped ZnO nano-column array preparation method comprises the steps of firstly, dissolving 0.015mol of zinc acetate and 0.00015mol of cerium nitrate in 20ml of deionized water, and stirring to form a mixed solution A, wherein the concentration of the solution A is 0.758mol/L; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 3:
this example differs from example 1 in that the amount of ethanolamine in step two was changed to 0.0042mol, and otherwise the same as in example 1, specifically as follows: a Ce-doped ZnO nano-column array preparation method comprises the steps of firstly, dissolving 0.015mol of zinc acetate and 0.00045mol of cerium nitrate in 20ml of deionized water, and stirring to form a mixed solution A; step two, adding 0.0042mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 4:
this example differs from example 1 in that in step two the stirring temperature was changed to 60℃and the stirring time was changed to 90min, otherwise the same as example 1, and the following is specifically mentioned: a Ce-doped ZnO nano-column array preparation method comprises the steps of firstly, dissolving 0.015mol of zinc acetate and 0.00045mol of cerium nitrate in 20ml of deionized water, and stirring to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 60 ℃ for 90min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times;
step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.01035mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 5:
this example differs from example 1 in that the reaction temperature in step four was changed to 350 ℃, and otherwise the same as example 1, specifically as follows: step one, a Ce-doped ZnO nano column array preparation method comprises the following steps of firstly, dissolving 0.015mol of zinc acetate and 0.00045mol of cerium nitrate in 20ml of deionized water, and stirring to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on the quartz glass which is fully washed, and performing heat treatment for 10min at 350 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 6:
this example differs from example 1 in that the reaction time in step four was changed to 5min, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 5min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 7:
this example differs from example 1 in that the number of reactions in step four was changed to 5, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 5 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 8:
this example differs from example 1 in that the reaction temperature in step five was changed to 450 ℃, and otherwise the same as example 1, in particular, as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at the temperature of 450 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 9:
this example differs from example 1 in that the reaction time in step five was changed to 90min, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 90min to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 10:
this example differs from example 1 in that the amount of cerium nitrate in the step was changed to 0.00015mol, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00015mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 11:
this example differs from example 1 in that the reaction temperature in step seven was changed to 110 ℃, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A, wherein the concentration of the mixed solution A is 0.075mol/L; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 110 ℃ for 90min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 12:
this example differs from example 1 in that the reaction time in step seven was changed to 110min, and otherwise the same as example 1, specifically as follows: a preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.00045mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred to form a mixed solution A; step two, adding 0.0014mol of ethanolamine and 0.0014mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 40 ℃ for 60min to obtain a solution B; thirdly, standing the stirred solution for a plurality of hours, and aging for 24 hours; spin-coating the prepared solution on quartz glass which is fully washed, and performing heat treatment for 10min at 300 ℃ for 3 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 550 ℃, and keeping the temperature for 60 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00135mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and step seven, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant temperature oven, and reacting at a constant temperature of 90 ℃ for 110min to obtain the compact Ce: znO nano column array transparent conductive material with high transmittance.
Example 13
A preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.0003mol of cerium nitrate are dissolved in 20ml of deionized water, and stirred for 60 minutes to form an aqueous solution of zinc acetate and cerium nitrate, which is called a mixed solution A for convenience of description, and the concentration of the solution A is 0.5mol/L. And step two, adding 0.0014mol of ethanolamine and 0.00047mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 60 ℃ for 90min to obtain a solution B. And thirdly, standing the stirred solution for a plurality of hours, and aging for 12 hours. Spin-coating the aged solution B on quartz glass, and performing heat treatment at 270 ℃ for 8min, wherein the heat treatment times are 5 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at the temperature of 450 ℃, and keeping the temperature for 90 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00045mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and seventhly, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant-temperature oven, and performing constant-temperature hydrothermal reaction at 90 ℃ for 120min to obtain the compact Ce: znO nano array with high transmittance.
Example 14
A preparation method of a Ce-doped ZnO nano-pillar array comprises the following steps: step one, 0.015mol of zinc acetate and 0.0003mol of cerium nitrate were dissolved in 20ml of deionized water, and stirred for 80 minutes to form an aqueous solution of zinc acetate and cerium nitrate, which is referred to as a mixed solution a for convenience of description. And step two, adding 0.0014mol of ethanolamine and 0.0007mol of polyvinylpyrrolidone into the mixed solution A, and stirring at a constant temperature of 50 ℃ for 80min to obtain a solution B. And thirdly, standing the stirred solution for a plurality of hours, and aging for 48 hours. Spin-coating the aged solution B on quartz glass, and performing heat treatment at 350 ℃ for 10min, wherein the repeated heat treatment times are 4 times; step five, placing the spin-coated quartz glass in a muffle furnace for annealing at 500 ℃, and keeping the temperature for 80 minutes to obtain a compact Ce: znO seed layer with good transmittance; step six, adding 0.045mol of zinc acetate, 0.00045mol of cerium nitrate and 0.009mol of hexamethylenetetramine into 100ml of deionized water, and stirring to obtain a solution C; and seventhly, placing the compact Ce: znO seed layer with good transmittance into a tetrafluoroethylene reaction kettle, adding the solution C, placing the reaction kettle into a constant-temperature oven, and performing constant-temperature hydrothermal reaction for 90min at 100 ℃ to obtain the compact Ce: znO nano array with high transmittance.
Claims (10)
1. The preparation method of the Ce-doped ZnO nano-pillar array is characterized by comprising the following steps of:
adding ethanolamine and polyvinylpyrrolidone into an aqueous solution of zinc acetate and cerium nitrate, stirring at constant temperature, and aging to form a mixed solution;
spin-coating the mixed solution on a substrate, performing heat treatment at a first temperature, and performing annealing treatment at a second temperature to form a Ce-doped ZnO seed layer, wherein the second temperature is higher than the first temperature;
and carrying out hydrothermal reaction on the Ce-doped ZnO seed layer and a reaction solution to form a Ce-doped ZnO nano-pillar array, wherein the reaction solution is an aqueous solution of zinc acetate, cerium nitrate and hexamethylenetetramine.
2. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
the first temperature of the heat treatment at the first temperature is 270-350 ℃, and the heat treatment time is 5-10min; the number of heat treatments at the first temperature is 3-5.
3. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
the second temperature in the annealing treatment at the second temperature is 450-550 ℃; the annealing time is 60-90 minutes.
4. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
the temperature of the hydrothermal reaction is 90-110 ℃; the hydrothermal reaction time is 90-120min.
5. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
in the aqueous solution of zinc acetate and cerium nitrate, the molar ratio of the zinc acetate to the cerium nitrate is 100:1-100:3, and the concentration of the aqueous solution of the zinc acetate and the cerium nitrate is 0.5-0.773mol/L.
6. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
the mol ratio of the ethanolamine to the polyvinylpyrrolidone is 1:1-3:1; the constant temperature stirring temperature is 40-60 ℃, and the stirring time is 60-90min.
7. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
the aging time is 12-48 hours.
8. The method for preparing the Ce-doped ZnO nanopillar array according to claim 1, wherein,
in the aqueous solution of zinc acetate, cerium nitrate and hexamethylenetetramine, the molar ratio of the zinc acetate to the cerium nitrate to the hexamethylenetetramine is 100:1:20-100:3:20.
9. A Ce doped ZnO nanopillar array prepared by the preparation method of any one of claims 1-8.
10. The Ce-doped ZnO nanopillar array of claim 9, wherein the Ce-doped ZnO nanopillar array comprises a plurality of Ce-doped ZnO nanopillars having a diameter of 200nm-250nm and a length of 350-400nm.
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