CN105018918A - Growth method for ZnO nanotube array - Google Patents
Growth method for ZnO nanotube array Download PDFInfo
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- CN105018918A CN105018918A CN201510374900.7A CN201510374900A CN105018918A CN 105018918 A CN105018918 A CN 105018918A CN 201510374900 A CN201510374900 A CN 201510374900A CN 105018918 A CN105018918 A CN 105018918A
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Abstract
The invention relates to a growth method for a ZnO nanotube array. The method includes the steps that under the alkaline condition, the ZnO nanotube array is prepared through a hydrothermal synthesis method with a Zn piece as a substrate and a reaction source; and according to the formation of the ZnO nanotube array, ZnO nanometer pieces are firstly formed on the substrate and then grow into nanometer sticks, the centers of the nanometer sticks are eroded, and finally, the nanometer sticks are eroded into nanotubes. The hydrothermal method is low in growth temperature and cost, easy to operate and beneficial to large-scale growth; the controllable growth of the ZnO nanotube array can be successfully achieved by only regulating the growth time; and hope is brought to the low-cost large-scale production technology meeting the development requirement of novel devices and industries, and an effective backup method is provided for the size-controllable growth of other nanometer materials.
Description
Technical field
The invention belongs to Material Field, be specifically related to a kind of growth method of ZnO nanotube/array.
Background technology
Nano material is the novel material grown up the beginning of the eighties, there is the special performance not available for traditional material in magnetics, optics, electricity and catalysis etc., will play a very important role the future economy and social development, thus have broad application prospects, be described as cross-centennial novel material, cause the very big concern of scientific circles and business circles.Particularly to the research of nano material optical property, attract the extensive concern of domestic and international scientific worker especially.
ZnO as a kind of novel third generation semiconductor material, one of study hotspot becoming field of semiconductor materials.ZnO energy gap is at room temperature about 3.37eV, it is a kind of important semiconductor material with wide forbidden band, the photon wavelength of launching is in near-ultraviolet light wave band, its exciton bind energy is up to 60meV, far above the ionization energy 26meV that room temperature thermal excitation provides, make the exciton of ZnO can at room temperature stable existence.Therefore, ZnO material at room temperature or easily realize low excitation threshold and the Laser emission of greater efficiency under higher temperature.In addition, ZnO has raw material resources to be enriched, and cheap, capability of resistance to radiation is strong, and the advantages such as environmental protection, therefore, ZnO material has huge effect at field of photoelectric devices such as royal purple light-emitting diode, solar cell, laser apparatus, UV-light spies.
Because ZnO nano material has the incomparable excellent properties of block materials, thus the aspects such as detector, photocatalyst, transparency conductive electrode, voltage dependent resistor and optical transmitting set can be widely used in.The factors such as the structure of ZnO nano material, pattern and size produce difference to its optics, magnetics, electrology characteristic, thus have material impact to its application, can apply better to make ZnO, investigator is by regulating preparation condition, prepare various pattern, the ZnO nano-structure of various size, thus be applied more broadly in nano-device aspect.In the nanostructure of ZnO, the application of the special technique of nano tube structure gives the expectation of height, this is not only owing to their superior optical, electrical, heat and mechanical property, also depends on high porosity, high efficiency caused by large surface-area and high reactivity.Up to the present, the research of nano material has achieved sizable progress, but for how effectively controlling the pattern of nano material and the research of performance, still waits to further investigate.
Summary of the invention
For defect of the prior art and deficiency, the object of this invention is to provide a kind of growth method of ZnO nanotube/array, hydrothermal synthesis method is mainly adopted to prepare a kind of ZnO nanotube/array of special appearance at a lower temperature, effectively controlled the growth of ZnO nanotube/array by adjusting reaction time, for meet novel appts and industry development needed for the requirement of low cost mass production techniques bring hope.
For achieving the above object, the present invention adopts following scheme to realize:
A growth method for ZnO nanotube/array, the method comprises in the basic conditions, on Zn surface by hydrothermal synthesis method making ZnO nano-tube array.
Concrete, using Zn sheet as substrate and reaction source, react under 150 DEG C of insulations condition of 15 hours in the basic solution of pH=14.
More specifically, the thickness of described Zn sheet is 0.15 ~ 0.25mm.
Further, described basic solution is NaOH solution.
Further, the method specifically comprises sealed reactor after the NaOH solution in surface treated Zn sheet immersion reactor;
The reactor of sealing is cooled to room temperature 150 DEG C of insulations after 15 hours, by reacted Zn sheet cleaning post-drying.
The ZnO nanotube/array growth method of described ZnO nanotube/array grown out is for the preparation of the application of photoelectricity apparatus.
Advantage of the present invention and positively effect as follows:
(1) the present invention selects Hydrothermal Growth ZnO nanotube/array, and namely first on substrate, form ZnO nano sheet, then nanometer sheet grows into nanometer rod, and nanometer rod easily corrodes in centre, and finally corroding becomes nanotube;
(2) XRD figure (see Fig. 1) of ZnO nanotube/array of the present invention, in ZnO standard spectrum, (101) face diffraction peak is the strongest, is secondly (100) face diffraction peak, is then (002) face diffraction peak.ZnO nanotube/array (002) the face diffraction peak that the present invention prepares is the strongest, so we think that ZnO nanotube/array is mainly looked unfamiliar long along (002), namely preferentially tends to growth along C axle;
The Raman spectrogram (see Fig. 2) of ZnO nanotube/array, the Raman scattering peak that sample is the strongest appears at 438cm
-1, be the high frequency vibration modes E2 of ZnO, E2 belongs to Raman active, and what it represent wurtzite phase can be with feature;
Scanning electron microscope (SEM) figure (see Fig. 3) of ZnO nanotube/array, the ZnO nanotube/array that Zn sheet substrate rises to, its diameter is about 450nm, and nano-tube array growth tendency is vertical Z n sheet substrate growth, and this is consistent with XRD result;
The growth mechanism schematic diagram (see Fig. 4) of ZnO nanotube/array, the forming process of ZnO nanotube/array experienced by ZnO nano sheet, ZnO nanorod, the final process forming ZnO nanotube/array;
The photoluminescence spectrogram (see Fig. 5) of ZnO nanotube/array, ZnO nanotube/array has two emission bands, ultraviolet emission and VISIBLE LIGHT EMISSION, the photoluminescence spectra ultra-violet light-emitting of nanotube is very strong, defect luminescence is more weak, illustrate the optical property of this kind of nanotube and crystallinity all relatively good;
(3) not only growth temperature is low for hydrothermal method of the present invention, cost is low, and it is simple to operate, be convenient to grown on larger scale, the controllable growth of ZnO nanotube/array just successfully can be realized by means of only the growth regulation time, the present invention for meet novel appts and industry development needed for the requirement of low cost mass production techniques bring hope, for other nano material dimension controllable growth provide Preparation Method effectively.
Accompanying drawing explanation
Fig. 1 is the XRD figure of ZnO nanotube/array of the present invention;
Fig. 2 is the Raman spectrogram of ZnO nanotube/array of the present invention;
Fig. 3 is scanning electron microscope (SEM) figure of ZnO nanotube/array of the present invention, and (a) is low power enlarged view, (b) is high magnification map;
Fig. 4 is the growth mechanism schematic diagram of ZnO nanotube/array of the present invention;
Fig. 5 is the photoluminescence spectrogram of ZnO nanotube/array of the present invention;
Fig. 6 is the scanning electron microscope (SEM) photograph of material prepared by embodiment two;
Below in conjunction with specification drawings and specific embodiments, the present invention is illustrated.
Embodiment
The object of the present invention is achieved like this, first from hydroxide ion in the zine ion of zinc metal sheet and sodium hydroxide solution at zinc metal sheet Surface Creation zinc complex, in the basic conditions, zinc complex decomposes on the surface at zinc metal sheet and generates ZnO crystal seed.ZnO crystal seed on zinc metal sheet surface is at zinc metal sheet surface nucleation, and core grows up into hexagonal ZnO nano sheet.ZnO crystal surface is polarity in a direction, and it can attract more ZnO seed and have the surface formation of ion at it of opposite charges, facilitates ZnO and forms nanometer rod along other direction anisotropic growth.The direction of polarity is in metastable state, and under the condition of higher alkalescence, this direction easily suffers erosion, and therefore ZnO nanorod is etched into ZnO nanotube/, forms nano-tube array.
In following examples, zinc metal sheet used is the square lamellar body of 1cm*1cm, and the thickness of zinc metal sheet is 0.15 ~ 0.25mm, and the purity of zinc metal sheet is 99.9%, purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment one:
The concrete steps of the present embodiment making ZnO nano-tube array are as follows:
The pH regulator of NaOH solution is 14 by step one: be dissolved in completely by NaOH in a certain amount of deionized water;
Step 2: ready NaOH solution is transferred in the reactor of tetrafluoroethylene;
Step 3: zinc metal sheet is placed in the dilute hydrochloric acid 10s of 5%, remove surface oxide layer, three times are repeatedly rinsed with deionized water after taking-up, bottom the Zn sheet insertion reaction still of the 1cm*1cm specification handled well, (zinc metal sheet lies in bottom reactor, each reactor puts a zinc metal sheet, is immersed in completely in NaOH solution) sealed reactor;
Step 4: the reactor of sealing is put into drying baker 150 DEG C insulation 15 hours, then cooled in room temperature by reactor, takes out Zn sheet substrate;
Step 5: by the washed with de-ionized water three times of the zinc metal sheet substrate in step 4, dry at 70 DEG C in drying baker.
X-ray diffraction test, Raman spectrum test, scanning electron microscope test, photoluminescence test have been carried out to nano-tube array prepared by embodiment one; X-ray diffraction test adopts Japan, MAC Science, MXP18, Raman spectrum testing apparatus are JobinYvon HR800 raman microspectroscopy spectrometer, scanning electronic microscope is Hitachi, the LABRAM-UV Raman spectrometer that S-570, photoluminescence adopt JobinYvon company to produce, excitation light source is He-Cd laser apparatus, excitation wavelength is 325nm, and power is 46mW, and all tests all at room temperature complete;
The XRD figure (see Fig. 1) of ZnO nanotube/array prepared by embodiment one, in ZnO standard spectrum, (101) face diffraction peak is the strongest, next is (100) face diffraction peak, then be (002) face diffraction peak, visible ZnO nanotube/array (002) face diffraction peak is the strongest, so think that ZnO nanotube/array is mainly looked unfamiliar long along (002), namely preferentially tend to growth along C axle;
The Raman spectrogram (see Fig. 2) of ZnO nanotube/array, the Raman scattering peak that sample is the strongest appears at 438cm
-1, be the high frequency vibration modes E of ZnO
2, E
2belong to Raman active, what it represent wurtzite phase can be with feature;
Scanning electron microscope (SEM) figure (see Fig. 3) of ZnO nanotube/array, the ZnO nanotube/array of Zn sheet Grown, its diameter is about 450nm, and nano-tube array growth tendency is vertical Z n sheet substrate growth, and this is consistent with XRD result;
The growth mechanism schematic diagram (see Fig. 4) of ZnO nanotube/array, the forming process of ZnO nanotube/array experienced by ZnO crystal seed and (schemes a), ZnO nano sheet (is schemed b), (c), the final ZnO nanotube/array that formed (schemes process d) to figure to ZnO nanorod;
The photoluminescence spectrogram (see Fig. 5) of ZnO nanotube/array, ZnO nanotube/array has two emission bands, ultraviolet emission and VISIBLE LIGHT EMISSION, the photoluminescence spectra ultra-violet light-emitting of nanotube is very strong, defect luminescence is more weak, illustrate the optical property of this kind of nanotube and crystallinity all relatively good.
Embodiment two: comparative example
The pH regulator of NaOH solution, after abundant magnetic agitation, is 14 by step one: be dissolved in completely by NaOH in a certain amount of deionized water
Step 2: NaOH solution ready in step one is transferred in tetrafluoroethylene reactor;
Step 3: by bottom the Zn sheet insertion reaction still of 1cm*1cm specification handled well, each reactor puts a zinc metal sheet, is immersed in completely in NaOH solution, sealed reactor;
Step 4: the reactor of sealing is put into drying baker 80 DEG C insulation 24 hours, then cooled in room temperature by reactor, takes out Zn sheet substrate;
Step 5: by the washed with de-ionized water three times of the zinc metal sheet substrate in step 4, dry at 70 DEG C in drying baker.
Adopt Hitachi equally to material prepared by embodiment two, S-570 electron microscope carries out scanning and obtains scanning electron microscope (SEM) photograph and see Fig. 6; Can be found out by the scanning electron microscope diagram of comparison example one and example two, if the reaction conditions changed, the pattern of the sample obtained is completely different, and can be found out can not be grown into nanotube by the growth result in Fig. 6, is only some irregular nanometer rod.
Claims (6)
1. a growth method for ZnO nanotube/array, is characterized in that, the method comprises in the basic conditions, on Zn surface by hydrothermal synthesis method making ZnO nano-tube array.
2. the growth method of ZnO nanotube/array as claimed in claim 1, is characterized in that, using Zn sheet as substrate and reaction source, to react in the basic solution of pH=14 under 150 DEG C of insulations condition of 15 hours.
3. the growth method of ZnO nanotube/array as claimed in claim 2, it is characterized in that, the thickness of described Zn sheet is 0.15 ~ 0.25mm.
4. the growth method of ZnO nanotube/array as claimed in claim 2 or claim 3, it is characterized in that, described basic solution is NaOH solution.
5. the growth method of ZnO nanotube/array as claimed in claim 4, is characterized in that, the method specifically comprises sealed reactor after the NaOH solution in surface treated Zn sheet immersion reactor;
The reactor of sealing is cooled to room temperature 150 DEG C of insulations after 15 hours, by reacted Zn sheet cleaning post-drying.
6. the ZnO nanotube/array growth method of the ZnO nanotube/array described in claim 1,2,3,4 or 5 grown out is for the preparation of the application of photoelectricity apparatus.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017138890A1 (en) * | 2016-02-12 | 2017-08-17 | Agency For Science, Technology And Research | Anti-bacterial patterned surfaces and methods of making the same |
| CN109988551A (en) * | 2018-01-03 | 2019-07-09 | 中国科学院理化技术研究所 | A kind of electrochromic material and its preparation method and application |
| CN111204794A (en) * | 2020-01-17 | 2020-05-29 | 清华大学 | Preparation method of dendritic hollow zinc oxide nanorod array |
| CN113215559A (en) * | 2021-04-01 | 2021-08-06 | 北京科技大学 | Class I parallel orientation (Al-Co)xOyPreparation method of nanosheet |
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| CN101412533A (en) * | 2008-11-18 | 2009-04-22 | 北京科技大学 | Method for preparing uniform zinc oxide nano tube in water solution |
| CN101456579A (en) * | 2008-12-05 | 2009-06-17 | 天津大学 | Method for synthesizing zinc oxide nano tube array by low-temperature hydrothermal method |
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Patent Citations (2)
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| CN101412533A (en) * | 2008-11-18 | 2009-04-22 | 北京科技大学 | Method for preparing uniform zinc oxide nano tube in water solution |
| CN101456579A (en) * | 2008-12-05 | 2009-06-17 | 天津大学 | Method for synthesizing zinc oxide nano tube array by low-temperature hydrothermal method |
Non-Patent Citations (2)
| Title |
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| J. H. YANG，ET.AL.: "Solvothermal growth of highly oriented wurtzite-structured ZnO nanotube arrays on zinc foil", 《CRYST. RES. TECHNOL.》 * |
| M. M. MOMENI ET.AL.: "ZnO nanorod films fabricated on zinc foil for photoelectrochemical water splitting", 《SURFACE ENGINEERING》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017138890A1 (en) * | 2016-02-12 | 2017-08-17 | Agency For Science, Technology And Research | Anti-bacterial patterned surfaces and methods of making the same |
| CN109988551A (en) * | 2018-01-03 | 2019-07-09 | 中国科学院理化技术研究所 | A kind of electrochromic material and its preparation method and application |
| CN109988551B (en) * | 2018-01-03 | 2022-07-01 | 中国科学院理化技术研究所 | Electrochromic material and preparation method and application thereof |
| CN111204794A (en) * | 2020-01-17 | 2020-05-29 | 清华大学 | Preparation method of dendritic hollow zinc oxide nanorod array |
| CN113215559A (en) * | 2021-04-01 | 2021-08-06 | 北京科技大学 | Class I parallel orientation (Al-Co)xOyPreparation method of nanosheet |
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