CN103058264A - Method for preparing double-layer zinc oxide nanowire array by chemical vapor deposition - Google Patents
Method for preparing double-layer zinc oxide nanowire array by chemical vapor deposition Download PDFInfo
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- CN103058264A CN103058264A CN2012104401276A CN201210440127A CN103058264A CN 103058264 A CN103058264 A CN 103058264A CN 2012104401276 A CN2012104401276 A CN 2012104401276A CN 201210440127 A CN201210440127 A CN 201210440127A CN 103058264 A CN103058264 A CN 103058264A
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Abstract
The invention relates to a preparation method of a double-layer zinc oxide nanowire array. The method comprises the following steps: by using a silicon wafer coated with a zinc oxide crystal seed layer as a substrate, inducing growth of a ZnO nanowire array by chemical vapor deposition; and spin-coating a ZnO nano crystal seed layer on the top end of the primarily grown ZnO nanowire to carry out gas-phase secondary growth of the ZnO nanowire array, thereby obtaining the double-layer superlong ZnO nanowire array. The method has the advantage of simple preparation process; and the prepared double-layer ZnO nanowire array has the advantages of obviously higher length-to-diameter ratio, small starting electric field, and obviously enhanced field emission properties.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide nano-wire array, particularly a kind of preparation method of layer zinc oxide nano-wire array.
Background technology
ZnO has higher electron-hole in conjunction with energy (60 meV) as a wide bandgap semiconductor materials, is widely used in the fields such as electron device, optics, photoelectric device, laser apparatus, photodiode.The piezoelectricity of ZnO and pyroelecthc properties make it have huge application prospect at aspects such as sensor, generator, photochemical catalysis hydrolytic hydrogen productions.Simultaneously, ZnO or a kind of green material, it has biocompatibility, biodegradability and non-toxic nature, thereby can be applied to field of medicaments and environmental science.The one-dimensional ZnO nanowires structure has the position with the one-dimensional silicon nanostructure equal importance, and aspect the development nanometer science and technology, it is bringing into play more and more crucial effect.In current research, carbon nanotube, silicon nanowires, ZnO nanowire array are most important monodimension nanometer materials.The ZnO nano-wire of one dimension can prepare at multiple substrate by methods such as high temperature vapour deposition process and low temperature liquid polymerization processes.
The field emission performance of ZnO one-dimensional nano line and the length-to-diameter ratio of material exist closely related, and the larger improvement to field emission performance of length-to-diameter ratio is more favourable, have at present a large amount of research work to be devoted to improve the length-to-diameter ratio of ZnO nano-wire.The J.B.Cui of U.S. Dartmouth College etc. the have adopted Liquid preparation methods ZnO nanowire array of different lengths, experimental result shows along with ZnO nano-wire length increases to 1.3 μ m by 200 nm, length-to-diameter ratio increases to 8 from 5.7, the unlatching electric field of nano wire is decreased to 5.7 V/ μ m from 8V/ μ m, and field enhancement factor has increased 30 %.Liu seminar of NUS adopts liquid phase method, take ITO as substrate, changes a solution in per 3.5 hours, and having prepared length is the nano-wire array of 33 μ m.But fusion to a certain degree can occur in the nano wire bottom of this method preparation.Merge for the nano-wire array bottom that prevents the repetition Liquid preparation methods, one deck self-assembled monolayer has adhered at nano wire in Gao seminar of Univ. of Pittsburgh, and four layers of synthetic ZnO nanowire array length have reached 40 μ m.Although self-assembled monolayer has reduced to a certain extent the bottom of nano-wire array and has merged,, this kind method preparation process is comparatively loaded down with trivial details.2010, the Kevin of NUS etc. covered one deck organic membrane at the nano-wire array of a liquid growth, and when again carrying out liquid growth, the nano wire that is exposed at the film outside can carry out the secondary liquid growth.But some nano wire has carried out the secondary liquid growth in the nano-wire array that this method is synthesized, and the diameter of the nano wire of diauxic growth is larger than the nanowire diameter of a secondary growth, is unfavorable for the raising of field emission performance.2011, Hefei material science research institute of Chinese Academy of Sciences Zhu seminar is at first at silicon chip substrates layer of ZnO nano-wire array, then evaporation layer of Au particle on the array that is synthesized, take ZnS as source material, on the basis of galvanic deposit ZnO nanowire array, adopt double-deck nano-wire array of vapor phase process preparation.Although this method can improve the length of ZnO nanowire array, the nanowire length of vapor phase growth preparation only has several microns, the total length of nano-wire array do not have be improved significantly.And the top of prepared nano wire has metallic particles to adhere to, and can the performance of nano-wire array be impacted to a certain extent.The preparation method of development and perfection ZnO nanowire array, the preparation length-to-diameter ratio is large, perpendicularity good, the ZnO nanowire array of top catalyst-free has great importance for the research of field emission device.
Summary of the invention
The object of the present invention is to provide the method for the standby double-deck ZnO nanowire array of a kind of chemical vapor deposition growth legal system.
For achieving the above object, reaction mechanism of the present invention is as follows:
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of chemical Vapor deposition process prepares the method for layer zinc oxide nano-wire array, it is characterized in that having following preparation process and step:
A. the silicon chip with single-sided polishing carries out pre-treatment;
B. two hydration zinc acetates are dissolved in and are mixed with the solution that concentration is 0.01-0.02 M in the ethanol, then be spin-coated on the step a gained silicon chip oven dry 15-20 time;
C. Graphite Powder 99 and zinc oxide are pressed 1:1 mass ratio grind, after it is fully mixed, the silicon chip that step b gained surface is scribbled zinc oxide crystal seed be placed on powder directly over, adopt chemical Vapor deposition process, under 400mbar vacuum tightness, the flow velocity that passes into argon gas and 1-2 sccm with the flow velocity of 35-70 sccm passes into oxygen, and temperature is 900-950 ℃, be incubated 30 minutes, after temperature is down to room temperature, take out sample;
D. repeating step b and step c finally obtain the layer zinc oxide nano-wire array.
The pretreatment process of above-mentioned step a is: 100 silicon chips of single-sided polishing were put into ethanol, acetone soln each ultrasonic 0.5 hour, then put into the vitriol oil and hydrogen peroxide by the mixing solutions of 3:1 volume ratio, 80 ℃ were heated 1 hour, and the silicon chip after processing was put into ultrapure water ultrasonic 0.5 hour.
Characteristics and the advantage of the inventive method are as follows: the present invention adopts time chemical Vapor deposition process to prepare that perpendicularity is good, the double-deck ZnO nanowire array of top catalyst-free.The top end diameter decrease of double-deck ZnO nanowire array, mean diameter is reduced to 300 nm by 2 μ m.The length of double-deck ZnO nanowire array doubles, and length-to-diameter ratio increases to 100 by 7.5.
The ZnO nanowire array of the ZnO nanowire array of bilayer and individual layer has been carried out field emission performance ground, result of study shows that the unlatching electric field of double-deck ZnO nanowire array is less, and field emission performance is significantly improved.
Adopt chemical Vapor deposition process to prepare the method that double-deck ZnO nanowire array is a kind of novelty, the double-deck ZnO nanowire array that can prepare that perpendicularity is good, top catalyst-free and field emission performance is improved.
Description of drawings
Fig. 1 is individual layer ZnO nanowire array front scan Electronic Speculum figure;
Fig. 2 is double-deck ZnO nanowire array front scan Electronic Speculum figure of the present invention;
Fig. 3 is double-deck ZnO nanowire array of the present invention side scanning electron microscope (SEM) photograph;
Fig. 4 is the X ray diffracting spectrum of individual layer ZnO nanowire array and double-deck ZnO nanowire array.
Fig. 5 is the electronic field emission J-E curve of individual layer and double-deck ZnO nanowire array.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment one: the preparation of double-deck ZnO nanowire array
Concrete preparation process of the present invention is as follows:
(1) silicon wafer N (100) of single-sided polishing was put into ethanol, acetone soln each ultrasonic 0.5 hour, remove the silicon chip surface organism, then put into the vitriol oil, hydrogen peroxide (volume ratio 3:1) mixing solutions, 80 ℃ were heated 1 hour, the oxide compound of removal silicon face, metallic impurity etc.Silicon chip after processing is put into ultrapure water ultrasonic 0.5 hour, remove the remained on surface acid solution;
(2) take by weighing 0.1098 g, two hydration zinc acetates and join in the 25 mL ethanolic solns, be stirred to whole dissolvings.Spin coating zinc acetate ethanolic soln is put into 100 ℃ of loft drier oven dry 20 minutes for several times after each spin coating on silicon chip;
(3) take by weighing 0.5 g Graphite Powder 99 and 0.5 g ZnO, grind and to put into quartz boat after it is fully mixed, the silicon chip that the surface is scribbled the ZnO crystal seed be placed on powder directly over, quartz boat is put into the center warm area of tube furnace.Start vacuum pump, close vacuum pump after reaction chamber is evacuated to vacuum state.In reaction chamber, pass into argon gas (flow velocity is 70 sccm) and oxygen (flow velocity is 2 sccm), when vacuum tightness reaches 400 mbar in the reaction chamber, again start vacuum pump, guarantee that the vacuum tightness perseverance is 400 mbar in the reaction chamber.Start temperature elevation system, rise to 950 ℃ with 24 ℃/min after insulation 30 minutes.Keep gas flow rate constant, after the tube furnace temperature is down to room temperature, take out sample;
(4) sample surfaces again spin coating zinc acetate ethanolic soln for several times put into 100 ℃ of baking ovens oven dry 1 hour;
(5) take by weighing 0.5 g Graphite Powder 99 and 0.5 g ZnO, grinding is put into quartz boat after it is fully mixed, the sample of step 4 preparation is placed on apart from the 3 mm places of wind direction under the powder, quartz boat is put into the center warm area of tube furnace, be 70 sccm at the argon gas flow velocity, oxygen gas flow rate is 2 sccm, and vacuum tightness is under the condition of 400 mbar, and 950 ℃ are incubated 30 minutes.Keep gas flow rate constant, after the tube furnace temperature is down to room temperature naturally, take out sample.
Prepared sample detects through instrument and characterizes and field emission performance can be tested in above-described embodiment, and its result is as follows:
1. by Fig. 1 and Fig. 2 as can be known, the nanowire diameter of the secondary vapor phase growth of double-deck ZnO nanowire array is given birth to than a gas phase
Long nano wire top end diameter is little, and mean diameter is reduced to 300 nm from 2 μ m.As shown in Figure 3, double-deck ZnO nanowire array length is for increasing to 30 m, and length-to-diameter ratio increases to 100, twice vapor phase growths by 7.5 partly obvious boundary.Fig. 4 as can be known, double-deck ZnO nanowire array is consistent with the XRD spectra of individual layer ZnO nanowire array, is typical hexagonal wurtzite structure, lattice parameter is a=0.325 nm, c=0.521 nm.Diffraction peak appears at 2 θ=31.75 °, 34.39 °, 36.24 °, 47.54 °, 62.86 ° of (100) that correspond respectively to the ZnO Wurzite structure, (002), (101), (102), (103) crystal face, (JCPDS card 36-1451) is consistent with body phase ZnO standard value.Simultaneously, the diffraction peak peak width at half height is very little, illustrates that the ZnO crystal crystallinity is better.
2. known by Fig. 5 that the unlatching electric field of individual layer ZnO nanowire array and double-deck ZnO nanowire array is respectively 3.15 μ A/cm
2With 2.23 μ A/cm
2The unlatching electric field of double-deck ZnO nanowire array obviously reduces than the unlatching electric field of individual layer ZnO nanowire array, and field emission performance is significantly improved, and this is because due to the length-to-diameter ratio increase of double-deck ZnO nanowire array.
Claims (2)
1. a chemical Vapor deposition process prepares the method for layer zinc oxide nano-wire array, it is characterized in that having following preparation process and step:
A. the silicon chip with single-sided polishing carries out pre-treatment;
B. two hydration zinc acetates are dissolved in and are mixed with the solution that concentration is 0.01-0.02 M in the ethanol, then be spin-coated on the step a gained silicon chip oven dry 15-20 time;
C. Graphite Powder 99 and zinc oxide are pressed 1:1 mass ratio grind, after it is fully mixed, the silicon chip that step b gained surface is scribbled zinc oxide crystal seed be placed on powder directly over, adopt chemical Vapor deposition process, under 400mbar vacuum tightness, the flow velocity that passes into argon gas and 1-2 sccm with the flow velocity of 35-70 sccm passes into oxygen, and temperature is 900-950 ℃, be incubated 30 minutes, after temperature is down to room temperature, take out sample;
D. repeating step b and step c finally obtain the layer zinc oxide nano-wire array.
2. chemical Vapor deposition process according to claim 1 prepares the method for layer zinc oxide nano-wire array, the pretreatment process that it is characterized in that described step a is: 100 silicon chips of single-sided polishing were put into ethanol, acetone soln each ultrasonic 0.5 hour, then put into the vitriol oil and hydrogen peroxide by the mixing solutions of 3:1 volume ratio, 80 ℃ were heated 1 hour, and the silicon chip after processing was put into ultrapure water ultrasonic 0.5 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109019663A (en) * | 2017-06-08 | 2018-12-18 | Tcl集团股份有限公司 | A kind of ZnO nanorod, QLED device and preparation method thereof |
| CN110127733A (en) * | 2019-05-21 | 2019-08-16 | 中国科学院重庆绿色智能技术研究院 | The preparation method of bitter earth nano gauze |
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| CN1769545A (en) * | 2004-11-02 | 2006-05-10 | 清华大学 | Method for developping directionally aligning zinc oxide nanometer rod array on silicon substrate |
| CN102534780A (en) * | 2012-01-12 | 2012-07-04 | 西安交通大学 | Multiple epitaxial growth method for realizing big length-to-diameter ratio ZnO nanowire array film based on low-temperature hydrothermal method |
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| CN1769545A (en) * | 2004-11-02 | 2006-05-10 | 清华大学 | Method for developping directionally aligning zinc oxide nanometer rod array on silicon substrate |
| CN102534780A (en) * | 2012-01-12 | 2012-07-04 | 西安交通大学 | Multiple epitaxial growth method for realizing big length-to-diameter ratio ZnO nanowire array film based on low-temperature hydrothermal method |
Non-Patent Citations (1)
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| 方耀国: "硅基ZnO纳米结构的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 07, 15 July 2012 (2012-07-15), pages 24 - 34 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109019663A (en) * | 2017-06-08 | 2018-12-18 | Tcl集团股份有限公司 | A kind of ZnO nanorod, QLED device and preparation method thereof |
| CN109019663B (en) * | 2017-06-08 | 2021-02-19 | Tcl科技集团股份有限公司 | ZnO nanorod, QLED device and preparation method thereof |
| CN110127733A (en) * | 2019-05-21 | 2019-08-16 | 中国科学院重庆绿色智能技术研究院 | The preparation method of bitter earth nano gauze |
| CN110127733B (en) * | 2019-05-21 | 2022-05-10 | 中国科学院重庆绿色智能技术研究院 | Preparation method of magnesium oxide nanowire net |
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