CN101994149A - Size-controllable growth method for ZnO nanorod array - Google Patents
Size-controllable growth method for ZnO nanorod array Download PDFInfo
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- CN101994149A CN101994149A CN 200910067407 CN200910067407A CN101994149A CN 101994149 A CN101994149 A CN 101994149A CN 200910067407 CN200910067407 CN 200910067407 CN 200910067407 A CN200910067407 A CN 200910067407A CN 101994149 A CN101994149 A CN 101994149A
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Abstract
The invention relates to a size-controllable growth method for a ZnO nanorod array. The method comprises the following steps of: preparing a ZnO crystal nucleus layer on a substrate; and growing the nanorod array by using a chemical water bath deposition method, wherein the diameter size of the ZnO nanorod array is controlled by changing the density and the size of ZnO nanoparticles. In the method, a two-step chemical water bath deposition method is adopted, so that the method is easy to operate, grows the array at the low temperature of 93 DEG C, has low cost, is suitable for growing the array on any substrate apart from plastic and is easy to realize mass production and the like. The growth of the ZnO nanorod array with controllable diameter size is successfully realized by adjusting the density and the size of the ZnO nanorod particles of the crystal nucleus layer. The method provides an effective standby method for the size-controllable growth of other nanomaterials.
Description
Technical field
The present invention relates to a kind of method of ZnO nanometer stick array controllable size growth.
Background technology
The one dimension semiconductor nano material has non-linear optical property, photoluminescence, high-luminous-efficiency, lower Laser emission threshold value because of its two-dimentional quantum confinement effect, and good physicalies such as superelevation physical strength, high chemical stability and thermostability are arranged, show huge application potential in a lot of fields, be the important materials of making nano photoelectronic devices such as short wavelength's nano laser, field-effect transistor, ultraviolet nanometer size gas detector and nanometer resonator, have broad application prospects.
Along with the rise of nanotechnology, the various performances of ZnO display especially comprehensively: from material essence, it is the wide band gap semiconducter photoelectric material; On performance, it is that semi-conductor adds piezoelectrics; From physically, it is a material that is applied to spintronics; From biology, it has nontoxicity, biodegradability; Prior, on nanostructure, it is the extraordinary material of plasticity-, can make various forms, and all can synthesize under high temperature and cold condition, and the very big advantage that combines with semi-conductor industry is arranged.These excellent properties have constantly excited people's research interest, have brought the research boom of one powerful nano-ZnO thus.Published the report of relevant specific form nano-ZnO on calendar year 2001 " Science " continuously, so far, the preparation of relevant Nano ZnO and the report of performance just emerge in an endless stream always.In the last few years, one-dimensional nano structure material, as nanotube, nano wire, nanometer rod, nano belt etc., because of its in the importance of basic physics research and at nanoelectronic, the potential application of aspects such as nanometer mechanics has constantly excited people's research interest.The One-Dimensional ZnO nanometer rod with the character of ZnO excellence and the combination of low dimensional structures, demonstrates huge potential using value in field of optoelectronic devices.
Up to now, people adopt the gas phase transmission method, pulsed laser deposition, and chemical Vapor deposition process, and electrochemical deposition method can obtain the One-Dimensional ZnO nanometer rod.Yet these methods all need special instrument usually, under the pyritous condition, just can prepare material through the complicated operations process.
Therefore, chemical bath deposition enjoys people's favor because of it is simple to operate in numerous preparation methods.The more important thing is that this method can just can be prepared sample under 95 ℃ of cryogenic conditions.But, adopt this method growing ZnO nanorod on Si, be difficult to control diameter and orientation usually, and repeatability is bad.At present, also nobody adopts this method to control the diameter of nanometer stick array.Yet with regard to the chemical bath deposition method, be divided into nucleation and two processes of growth, nucleation process is directly determining the growth conditions of nanometer rod.As everyone knows, nucleation has very big randomness and complicacy on the different interfaces, and density, size and the distribution of wanting to control nucleation acquire a certain degree of difficulty.But on different substrates, still be relatively easy to the relative homogeneous nucleation of heterogeneous nucleation.Therefore we select two step chemical bath deposition growing ZnO nanorod arrays, promptly earlier form crystal nucleation layer on substrate, adopt chemical bath deposition to carry out the growth of nanometer stick array again.For this method, situations such as the density of nucleus, size and distribution just directly affect the growth of nanometer stick array on the substrate.That is to say conditions such as density by regulating nucleus on the substrate, size, just might control the diameter of nanometer stick array.Therefore, we expect to reach by this method the purpose of ZnO nanometer stick array controllable growth.
Summary of the invention
The objective of the invention is to provide a kind of ZnO nanometer stick array controllable size growth method, this method adopts two step chemical bath depositions, on substrate, form earlier crystal nucleation layer, adopt chemical bath deposition to carry out the growth of nanometer stick array again, by the density of change ZnO nano particle and the diameter of size control ZnO nanometer stick array, overcome the shortcoming and defect of prior art.
The object of the present invention is achieved like this, this method is to prepare the ZnO crystal nucleation layer earlier on substrate, utilize chemical bath deposition to carry out the growth of nanometer stick array again, thereby by the density of change ZnO nano particle and the diameter of size control ZnO nanometer stick array;
Its concrete steps are as follows:
The first step: the preparation of ZnO crystal nucleation layer
1., configuration Zn (OOCCH
3)
22H
2O spirituous solution, volumetric molar concentration are 0.005M.65 ℃ of heating magnetic agitation 1h form colourless transparent solution.
2., the Si substrate is successively placed on ethanol and deionized water for ultrasonic was handled 20 minutes, dries stand-by in air.
3., use the spin coating instrument that the colourless transparent solution of step in 1. is spin-coated on the Si substrate, 30 seconds spin coating time, 2000 revolutions per seconds of spin speed, after spin coating 1 or 2 or 3 or 4 times, 250 ℃ of sintering 30 minutes;
4., repeat above-mentioned steps 3. once, finally on the Si substrate, generated ZnO nano particle crystal nucleation layer.
Above-mentioned 3., 4. along with the change of spin coating number of times, the density of ZnO nano particle will change, and when keeping the spin coating number of times constant, change 250 ℃ or 500 ℃ or 600 ℃ of sintering temperature T, the big young pathbreaker of ZnO nano particle changes;
Second step: the preparation of ZnO nanometer stick array
1., with zinc nitrate (Zn (NO
3)
26H
2O) and hexamethylenetetramine (C
6H
12N
4) with etc. mol ratio (1: 1) be dissolved in the deionized water, zinc nitrate and hexamethylenetetramine concentration are all 1M.The reaction soln for preparing is put in the beaker.
2., the Si substrate tilting that will be coated with ZnO nano particle crystal nucleation layer places the beaker bottom (45～70 ° at pitch angle) that fills reaction soln, puts into Reaktionsofen (93 ℃), growth 2h.
3., after the reaction, substrate is taken out, clean up, dry and get final product with deionized water.
The ZnO nanoparticle density is greater than threshold value 2.3 * 10 on substrate
8Cm
-2The time, realize the controllable growth of ZnO nanometer stick array by 40nm～150nm.
Advantage of the present invention and positively effect are as follows:
1, the present invention selects two step chemical bath deposition growing ZnO nanorod arrays, promptly on substrate, form ZnO nano particle crystal nucleation layer earlier, adopt chemical bath deposition to carry out the growth of nanometer stick array again, by regulating conditions such as grain density, size on the substrate, realize the controllable growth of ZnO nanometer stick array diameter.
2, atomic force microscope (AFM) the figure (see figure 1) of the crystal nucleation layer of the scanning electron microscope of ZnO nanometer stick array of the present invention (SEM) figure and correspondence thereof shows, by changing density and the size that the spin coating number of times of zinc acetate solution on substrate changes the ZnO nano particle, effectively controlled the size of ZnO nanometer stick array, realized the controllable growth of diameter by 40nm to 150nm, Fig. 2 has provided the density of crystal nucleation layer and the statistics of ZnO nanometer stick array diameter.In addition, by changing the sintering temperature of crystal nucleation layer, changed the big or small (see figure 3) of ZnO nano particle on the substrate, the AFM figure of the SEM figure of contrast ZnO nanometer stick array and corresponding crystal nucleation layer thereof, by analysis, the density of ZnO nano particle and size are determining the diameter of ZnO nanometer stick array jointly on the substrate, but work as nanoparticle density greater than threshold value 2.3 * 10
8Cm
-2The time, density plays main effect in the control of ZnO nanometer stick array size.
3, the present invention two step chemical bath deposition not only have simple to operate, 93 ℃ of low-temperature epitaxies, low cost is suitable for growing on any substrate except that plastics, is easy to realize advantages such as scale operation.And, successfully realized ZnO nanometer stick array diameter controllable growth by regulating the density and the size of crystal nucleation layer ZnO nano particle.The present invention provides effective back Preparation Method for other nano material controllable size growths.
Description of drawings
Fig. 1 is the SEM image of different diameter size ZnO nanometer stick array of the present invention and the afm image on the respective substrate.
Fig. 2 is the graph of a relation of ZnO nanoparticle density on ZnO nanometer stick array diameter of the present invention and the substrate.
Fig. 3 is the afm image of differing temps sintering back substrate and the SEM image of corresponding ZnO nanometer stick array.
Embodiment
In accompanying drawing 1: the diameter of the density of nano particle and ZnO nanometer stick array is respectively on the substrate: (a), 4.9 * 10
7Cm
-2, 200nm; (b), 9.52 * 10
8Cm
-2, 90nm; (c), 2.51 * 10
9Cm
-2, 40nm.
In accompanying drawing 3: sintering temperature, ZnO nanoparticle density and ZnO nanometer stick array diameter are respectively: (a), 250 ℃, 2.02 * 10
9Cm
-2, 50nm; (b), 500 ℃, 1.38 * 10
9Cm
-2, 70nm; (c), 600 ℃, 1.35 * 10
9Cm
-2, 70nm.
Concrete operations step of the present invention is as follows:
The first step: the preparation of ZnO crystal nucleation layer
1., configuration Zn (OOCCH
3)
22H
2O spirituous solution, volumetric molar concentration are 0.005M.65 ℃ of heating magnetic agitation 1h form colourless transparent solution.
2., the Si substrate is successively placed on ethanol and deionized water for ultrasonic was handled 20 minutes, dries stand-by in air.
3., use the spin coating instrument that the colourless transparent solution of step in 1. is spin-coated on the Si substrate, 30 seconds spin coating time, 2000 revolutions per seconds of spin speed, after spin coating 1 or 2 or 3 or 4 times, 250 ℃ of sintering 30 minutes;
4., repeat above-mentioned steps 3. once, finally on the Si substrate, generated ZnO nano particle crystal nucleation layer.
Keep sintering temperature constant (250 ℃), change spin coating number of times (N=1,2,3,4), the changing conditions of nanoparticle density is summarized in table 1 according to Fig. 1:
Table 1 spin coating number of times is to the influence of ZnO pellet density on the substrate and ZnO nanometer rod diameter
| The spin coating number of times | ZnO pellet density * 10 8cm -2 | ZnO nanometer rod diameter nm |
| 1 | 0.49 | 200 |
| 2 | 2.30 | 150 |
| 3 | 9.52 | 90 |
| 4 | 25.1 | 40 |
Keep spin coating number of times constant (4 times), the change sintering temperature (T=250 ℃, 500 ℃, 600 ℃), the change situation of nano particle size and density is summarized in table 2 according to Fig. 3:
Table 2 thermal treatment is to the influence of ZnO pellet density, size and ZnO nanometer rod diameter on the substrate
| Thermal treatment temp | ZnO pellet density * 10 9cm -2 | ZnO granular size nm | ZnO nanometer rod diameter nm |
| 250℃ | 2.02 | 35 | 50 |
| 500℃ | 1.38 | 47 | 70 |
| 600℃ | 1.35 | 60 | 70 |
Second step: the preparation of ZnO nanometer stick array
1., with zinc nitrate (Zn (NO
3)
26H
2O) and hexamethylenetetramine (C
6H
12N
4) with etc. mol ratio (1: 1) be dissolved in the deionized water, zinc nitrate and hexamethylenetetramine concentration are all 1M.The reaction soln for preparing is put in the beaker.
2., the Si substrate tilting that will be coated with ZnO nano particle crystal nucleation layer places the beaker bottom (45～70 ° at pitch angle) that fills reaction soln, puts into Reaktionsofen (93 ℃), growth 2h.
3., after the reaction, substrate is taken out, clean up, dry and get final product with deionized water.
The ZnO nanoparticle density is greater than threshold value 2.3 * 10 on substrate
8Cm
-2The time, realize the controllable growth of ZnO nanometer stick array, as depicted in figs. 1 and 2 by 40nm～150nm.
Claims (2)
1. ZnO nanometer stick array controllable size growth method, it is characterized in that: this method is to prepare the ZnO crystal nucleation layer earlier on substrate, utilize chemical bath deposition to carry out the growth of nanometer stick array again, thereby by the density of change ZnO nano particle and the diameter of size control ZnO nanometer stick array;
Its concrete steps are as follows:
The first step: the preparation of ZnO crystal nucleation layer
1., configuration Zn (OOCCH
3)
22H
2O spirituous solution, volumetric molar concentration are 0.005M, and 65 ℃ of heating magnetic agitation 1h form colourless transparent solution;
2., the Si substrate be successively placed on dehydrated alcohol and deionized water for ultrasonic handled 20 minutes, in air, dry stand-by;
3., use the spin coating instrument that the colourless transparent solution of step in 1. is spin-coated on the Si substrate, 30 seconds spin coating time, 2000 revolutions per seconds of spin speed, after spin coating 1 or 2 or 3 or 4 times, 250 ℃ of sintering 30 minutes;
4., repeat above-mentioned steps 3. once, finally on the Si substrate, generated ZnO nano particle crystal nucleation layer,
Above-mentioned 3., 4. along with the change of spin coating number of times, the density of ZnO nano particle will change, and when keeping the spin coating number of times constant, change 250 ℃ or 500 ℃ or 600 ℃ of sintering temperature T, the big young pathbreaker of ZnO nano particle changes;
Second step: the preparation of ZnO nanometer stick array
1., with zinc nitrate and hexamethylenetetramine with etc. mol ratio be dissolved at 1: 1 in the deionized water, zinc nitrate and hexamethylenetetramine concentration are all 1M, the reaction soln for preparing is put in the beaker;
2., the Si substrate tilting that will be coated with ZnO nano particle crystal nucleation layer places and fills the 1. beaker bottom of reaction soln, puts into 93 ℃ Reaktionsofen, growth 2h;
3., after the reaction, substrate is taken out, clean up, dry and get final product with deionized water;
The ZnO nanoparticle density is greater than threshold value 2.3 * 10 on substrate
8Cm
-2The time, realize the controllable growth of ZnO nanometer stick array by 40nm～150nm.
2. a kind of ZnO nanometer stick array controllable size growth method according to claim 1 is characterized in that: the angle that described Si substrate and beaker bottom tilt is 45～70 °.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066154A (en) * | 2012-12-31 | 2013-04-24 | 东华大学 | Preparation method for ZnO / CdS / Cu2ZnSnS4 pn junction nanorod arrays |
| CN104882287A (en) * | 2014-02-28 | 2015-09-02 | 吉林师范大学 | Method for improving photoelectric conversion efficiency of quantum dot sensitized solar cell |
| CN106986373A (en) * | 2017-04-26 | 2017-07-28 | 武汉理工大学 | A kind of preparation method of ZnO nanorod |
| CN110261366A (en) * | 2019-07-09 | 2019-09-20 | 吉林师范大学 | Have both the preparation method of the difunctional micro-composites of detection and degrading pesticide |
-
2009
- 2009-08-12 CN CN 200910067407 patent/CN101994149A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066154A (en) * | 2012-12-31 | 2013-04-24 | 东华大学 | Preparation method for ZnO / CdS / Cu2ZnSnS4 pn junction nanorod arrays |
| CN103066154B (en) * | 2012-12-31 | 2015-11-11 | 东华大学 | A kind of ZnO/CdS/Cu 2znSnS 4pn ties the preparation method of nanometer stick array |
| CN104882287A (en) * | 2014-02-28 | 2015-09-02 | 吉林师范大学 | Method for improving photoelectric conversion efficiency of quantum dot sensitized solar cell |
| CN104882287B (en) * | 2014-02-28 | 2017-11-07 | 吉林师范大学 | A kind of method for improving quantum dot sensitized solar cell photoelectric conversion efficiency |
| CN106986373A (en) * | 2017-04-26 | 2017-07-28 | 武汉理工大学 | A kind of preparation method of ZnO nanorod |
| CN110261366A (en) * | 2019-07-09 | 2019-09-20 | 吉林师范大学 | Have both the preparation method of the difunctional micro-composites of detection and degrading pesticide |
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Application publication date: 20110330 |