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Preparation method of zinc oxide nanorod array thin film

A technology of zinc oxide nanorods and nanorod arrays, which is applied in the field of preparation of zinc oxide nanorod array thin films, can solve the problems of inability to meet the performance requirements of ZnO nanorod array thin film devices, poor crystal quality, weak emission peaks, etc., and achieve improved Photoluminescent properties, improved crystal quality, effects of uniform diameter and length

Inactive Publication Date: 2016-04-27
UNIV OF JINAN
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Problems solved by technology

[0004] In the applicant's previous patent (a method for controlling the orientation and morphology of zinc oxide nanorods and nanotube arrays, CN200810016893.3), a method for preparing ZnO nanorods / nanotubes by a liquid phase method was proposed, but water The thermal reaction temperature is below 100°C, grow for 2-12 hours to obtain a vertically grown ZnO nanorod array film, the length of ZnO nanorods does not exceed 10 μm, and the crystal quality is poor, making its photoluminescence performance at 500 There is an obvious defect emission peak in the -700nm range, and the intrinsic emission peak is relatively weak, which cannot meet the performance requirements of ZnO nanorod array thin film devices
[0005] At present, there are many reports on ultra-long ZnO nanorod array films. For example, L.Wen, et al. successfully prepared 180 μm ultra-long ZnO nanorod array films on silicon wafers by chemical vapor phase method at a high temperature of 950 ° C. (L.Wen, K.M.Wong, Y.Fang, M.Wu, Y.Lei.Fabrication and characterization of well-aligned, high density Zn Onano wire arrays and their realizations in Schottky devices applications using a two-step approach, J. Mater. Chem., 2011, 21, 7090-7097), DiGao et al. (82-87 degrees) The hydrothermal method successfully prepared a 30 μm ZnO nanorod array film, (C.XuandD.Gao.Two-StageHydrothermalGrowthofLongZnONanowiresforEfficientTiO2Nanotube-BasedDye-SensitizedSolarCells, J.Phys.Chem.C,2012,116(12): 7236–7241.), JijunQiu et al. used low-temperature hydrothermal method to prepare 40 μm high aspect ratio ultra-long ZnO nanorod array film, (J.Qiu, X.Li, W.He, S.J.Park, H.K.Kim, Y.H.Hwang, J.H.Lee, Y.D.Kim.ThegrowthmechanismandopticalpropertiesofultralongZnOnanorodarrayswithahighaspectratiobyapreheatinghydrothermalmethod,2009,20(15):155603.) However, in their work, they failed to obtain ZnO nanowire array films with high crystalline quality and high ultraviolet light emission, so they synthesized high crystalline quality and low ZnO nanorod array film with surface defects is of great significance for its application in optoelectronic devices

Method used

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  • Preparation method of zinc oxide nanorod array thin film
  • Preparation method of zinc oxide nanorod array thin film
  • Preparation method of zinc oxide nanorod array thin film

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] (1) Prepare the seed layer precursor solution: Dissolve equimolar amounts of zinc acetate and ethanolamine 0.3M in sequence in ethanol, stir well, seal and homogenize for more than 4 hours;

[0059] (2) Cleaning of the deposition substrate: The ITO conductive glass was ultrasonically cleaned for 30 minutes with a 1:1:1 solution of ethanol:isopropanol:acetone, then ultrasonically cleaned with deionized water for 10 minutes and dried.

[0060] (3) Spin-coating ZnO precursor solution: transfer the deposition substrate to a homogenizer, add the precursor solution prepared in step (1) dropwise, and spin at a speed of 6000 rpm for 30 seconds after uniform dispersion.

[0061] (4) Evaporation of the solvent: transfer the spin-coated substrate to an electric heating plate, and evaporate the solvent or pyrolyze it at 180-300° C. for more than 5 minutes.

[0062] (5) Crystallization of the ZnO seed layer thin film: transfer to a rapid annealing furnace, perform rapid heat treatme...

Embodiment 2

[0069] The preparation method and test are the same as in Example 1, but the programmed heating process is changed, as Figure 7 Schematic diagram of step heating. Figure 8 is in equimolar amount of Zn(NO 3 ) 2 ·6H 2 O and hexamethylenetetramine at a concentration of 0.15 mol L -1 , add 60mmol·L -1 Polyethylenimine growth solution, using Figure 7 According to the step heating process, the FESEM image of the cross-section of the obtained ZnO nanorod array film was grown under the condition of 80-150°C step heating for 16 hours. The ZnO nanorods prepared by the method have a diameter of 50-150 nm and a length of about 50 μm. It shows that the length of ZnO nanorods will decrease if the temperature rises too fast.

[0070] The photoluminescent performance of the ZnO nanorods obtained by this method is the same as that of the ZnO nanorods array thin film obtained by step heating in Example 1, which has good high intrinsic emission.

Embodiment 3

[0072] Preparation method and test are identical with embodiment 1, but the concentration of growth solution is 3 times of embodiment 1, the Zn(NO 3 ) 2 ·6H 2 O and hexamethylenetetramine at a concentration of 0.15 mol L -1 , add 60mmol·L -1 Polyethyleneimine as epitaxial growth regulator of ZnO nanorods. Figure 9 For the cross-sectional FESEM diagram of the ZnO array film prepared by this method, the diameter of the ZnO nanorods is 100-250nm and the length is about 150 μm, indicating that increasing the concentration is beneficial to the increase of the length of the ZnO nanorods, but the diameter of the ZnO nanorods also increases.

[0073] The photoluminescent performance of the ZnO nanorods obtained by this method is the same as that of the ZnO nanorods array thin film obtained by step heating in Example 1, which has good high intrinsic emission.

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Abstract

The invention belongs to the technical field of semiconductor film preparation, and particularly relates to a preparation method of a zinc-oxide nanorod array film. The technical scheme adopted by the invention is as follows: the preparation method comprises the following steps of: (1) on the basis of adopting height (001)-oriented ZnO as a seed layer, putting the ZnO seed layer into an aqueous solution of zinc nitrate (Zn(NO3)2), polyethyleneimine (PEI) and hexamethylenetetramine (HMT) for epitaxial growth to obtain a (001) preferred-orientation ultralong ZnO nanorod array film; (2) carrying out fast annealing treatment on the film, and improving the photoluminescence performance of the ZnO array film. The technology has the advantages that the continuous growth of the ZnO nanorod at the temperature higher than 100 DEG C can be realized; due to the high-temperature growth condition, the crystallization quality of the nanorod is improved, the internal defects are obviously reduced; the zinc-oxide nanorod array film has excellent photoelectric performance, and is more conductive to being applied in photoelectric devices such as dye-sensitized solar batteries, ultraviolet detectors, field-effect transistors, light-emitting diodes and nanogenerators.

Description

technical field [0001] The invention belongs to the technical field of semiconductor film preparation, and in particular relates to a preparation method of a zinc oxide nanorod array film. Background technique [0002] Zinc oxide is a wide bandgap (3.37eV) semiconductor material with good photoelectric, piezoelectric, catalytic and other properties. In recent years, with the development of nanotechnology, scientists have discovered that the one-dimensional ZnO array structure has good development prospects in the fields of sensors, light-emitting diodes, solar cells, and nanogenerators. Zinc oxide is one of the research hotspots at home and abroad. [0003] As a wide bandgap transparent semiconductor material, ZnO has an exciton binding energy as high as 60meV, and has excellent exciton recombination luminescence performance, and is suitable for the development of ultraviolet lasers. [0004] In the applicant's previous patent (a method for controlling the orientation and ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C30B29/16C30B19/00C30B29/62C30B33/02
Inventor 武卫兵刘宽菲张楠楠陈晓东陈宝龙
Owner UNIV OF JINAN
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