CN105463564A - ZnO nanorod and ZnO cluster composite structure and preparation method thereof - Google Patents
ZnO nanorod and ZnO cluster composite structure and preparation method thereof Download PDFInfo
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- CN105463564A CN105463564A CN201510859333.4A CN201510859333A CN105463564A CN 105463564 A CN105463564 A CN 105463564A CN 201510859333 A CN201510859333 A CN 201510859333A CN 105463564 A CN105463564 A CN 105463564A
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- C30—CRYSTAL GROWTH
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Abstract
The invention relates to a ZnO nanorod and ZnO cluster composite structure and a preparation method thereof. According to the technology, the surface of a copper sheet is spin-coated with a photoresist with thickness of 1-20 mu m and the like, or the surface of a copper sheet is soaked and modified with a 0.1wt%-1.0wt% fluoroalkyl silane ethanol solution, a hydrophobic surface is formed, then the ZnO nanorod and ZnO cluster composite structure is grown with a wet chemical method through a pre-prepared crystal seed layer and is different from a ZnO nanorod array generally grown on a bare metal surface, and the cluster ZnO nano-composite structure has special optical and electrical characteristics, a wetting characteristic and other characteristics. The preparation method is simple in process and easy to operate, has low energy consumption and low cost and is applicable to popularization and application; ZnO nanorods and ZnO clusters prepared with the technology have special morphology, and reference is provided for follow-up preparation of ZnO nanorod and ZnO cluster composite structures with special morphology.
Description
Technical field
The present invention relates to a kind of zinc oxide nano rod and cluster composite structure technology of preparing thereof.This kind of technology of preparing, in hydrophobic metallic surface growing ZnO nanorod and cluster thereof, arrives to obtain the different zinc oxide nano rod of pattern.
Background technology
ZnO has the direct broad-band gap (3.37eV of wurtzite structure as II-VI race, 300K) compound semiconductor materials, because of the physicochemical property of its excellence, as high Young's modulus, extremely low thermal expansivity, high thermostability, large exciton bind energy and negative electron affinity energy etc., at numerous areas such as sensor, UV transmitting, opto-electronic conversion, super-hydrophobic interface, photochemical catalysis and photodiodes, there is potential application, in recent years, worldwide showing great attention to is received.
Up to now, the preparation method of ZnO one-dimensional nano structure material mainly contains: template assisting growth method, metal organic vapor method (MOVPE), pulsed laser deposition (PLD), chemical Vapor deposition process (CVD), electrochemical vapor deposition and wet chemistry method etc.For One-Dimensional ZnO nano-array, gas-phase reaction method is a main preparation method, the ZnO nano array that gas-phase reaction prepares has very high crystal property and quality, but energy consumption is large, the equipment needing costliness, harsh processing condition, is not suitable for scale operation.Wet chemistry method desired reaction temperature lower (compared with vapor phase process), simple to operate, equipment requirements is low, and preparation cost is low, is applicable to the advantages such as scale operation, becomes the focus that everybody studies concern.Due to before general all using hydrophilic materials such as naked metal, naked glass or silicon chips as substrate, and growing ZnO nanorod is also seldom used for for hydrophobic or the surface of super-hydrophobicity.
Summary of the invention
The invention provides a kind of zinc oxide nano rod and cluster composite structure and preparation method thereof thereof, simply effective, with low cost.
The present invention adopts following technical scheme: a kind of zinc oxide nano rod and cluster composite structure thereof, hydrophobization process is carried out on the copper sheet surface of cleaning, the prefabricated ZnO crystal seed layer in surface after treatment, adopts method of reverse deduction to grow in the solution and obtains zinc oxide nano rod and cluster composite structure thereof.
Described hydrophobization process modifies silicon fluoride after being included in copper sheet surface-coated ultraviolet photoresist, copper sheet surface roughening again.
The preparation method of described zinc oxide nano rod and cluster composite structure thereof, hydrophobization process is carried out on the copper sheet surface of cleaning, the prefabricated ZnO crystal seed layer in surface after treatment, adopts method of reverse deduction to grow in the solution and obtains zinc oxide nano rod and cluster composite structure thereof.
The preparation method of described zinc oxide nano rod and cluster composite structure thereof, comprises the following steps:
(1) copper sheet surface preparation: pure copper sheet through acetone, ethanol and deionized water ultrasonic cleaning, dry up after immerse in diluted acid and clean, obtain clean copper sheet after then drying up with washed with de-ionized water cold wind for subsequent use;
(2) surface hydrophobicity process: adopt spin coating plating method, at the copper sheet surface-coated ultraviolet photoresist of cleaning, or adopts silicon fluoride to modify method, by the process of clean copper sheet silicon fluoride ethanolic soln surface hydrophobicity;
(3) prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness of acquisition is 50-500nm;
(4) composite structure growth: growth media is poured in reaction vessel, then will the copper sheet surface of crystal seed layer be had to face down, be suspended in growth media, afterwards good seal reaction vessel, water-bath growth afterwash dries and obtains zinc oxide nano rod and cluster composite structure thereof.
Step (2) medium ultraviolet photoresist material thickness is 1 ~ 20 μm.
When in step (2), silicon fluoride modifies method, copper sheet that is bright and clean or roughened is put into the silicon fluoride ethanolic soln of 0.1-1.0wt.%, 30-80 DEG C of water bath heat preservation 30min ~ 2h, the cleaning of taking-up hot ethanol dries up, and takes out after being then placed in 80 DEG C of oven drying 1h.
Seed-solution described in step (3) is that the NaOH methanol solution of 0.03mol/L is joined in the hydration zinc acetate methanol solution of 0.01mol/L, obtains after 60 DEG C of stirring 2h
In step (4), bath temperature is 35-90 DEG C, and the time is 1-12h.
Growth media described in step (4) is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Beneficial effect:
(1) by hydrophobization process, can make copper sheet surface presentation hydrophobicity, can promote the nonuniform deposition of crystal seed layer, hydrophobicity is stronger, and ununiformity is larger;
(2) hydrophobicity adjusted by photoresist material thickness and the silicon fluoride time of modifying, and also by the pre-roughening in copper sheet surface, then modify silicon fluoride, increase hydrophobicity further, contact angle can regulate arbitrarily between 90-170 °;
(3) uneven crystal seed layer, when the solution growth zinc oxide carried out further, impels surface to define nanometer rod and cluster composite structure thereof, without hydrophobization process, after the two-step approach process of copper sheet surface, the array zinc oxide perpendicular to substrate arrangement can only be obtained, not there is composite structure;
(4) during composite structure growth, adopt method of reverse deduction, particles of solute can be avoided in solution at sample surfaces formation of deposits grain-like zinc-oxide, also can the too fast growth of inhibited oxidation zinc;
(5) cluster-shaped zinc-oxide nano composite structure has special optics, electricity and the characteristic such as wetting.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscopic picture of the prefabricated ZnO crystal seed layer in copper sheet surface in embodiment 1.
The scanning electron microscopic picture of copper sheet surface recombination structure in Fig. 2 embodiment 1.
Fig. 3 is the partial enlargement scanning electron microscopic picture of copper sheet surface recombination structure in embodiment 1.
Fig. 4 is the XRD figure spectrum of copper sheet surface recombination structure in embodiment 1.
Fig. 5 is without hydrophobic treatment copper sheet surface scan electromicroscopic photograph in embodiment 4.
Fig. 6 is without hydrophobic treatment copper sheet surface partial enlargement stereoscan photograph in embodiment 4.
Fig. 7 is the form of water droplet after silicon fluoride surface modification after growing nano cluster in embodiment 1.
Embodiment
A technology of preparing for anisotropy super hydrophobic surface, comprises following treatment step:
(1) copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
(2) surface hydrophobicity process: adopt spin coating plating method, at cleaned copper sheet surface spin coating one deck ultraviolet photoresist, thickness is 1 ~ 20 μm, or, adopt silicon fluoride to modify method, copper sheet is put into the silicon fluoride ethanolic soln of 0.1-1.0wt.%, 30-80 DEG C of water bath heat preservation 30min ~ 2h, the cleaning of taking-up hot ethanol dries up, and takes out after being then placed in 80 DEG C of oven drying 1h;
(3) prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 50-500nm, described seed-solution is that the NaOH-methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
(4) composite structure growth: growth media being poured in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 35-90 DEG C of water bath condition, growth 1-12h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, can obtain zinc oxide nano rod and cluster composite structure thereof, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 1
Copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
Surface hydrophobicity process: adopt spin coating plating method, at cleaned copper sheet surface spin coating one deck ultraviolet photoresist, thickness is 1 μm;
Prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 50nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtain after 60 DEG C of stirring 2h, now the SEM pattern on surface as shown in Figure 1.
Composite structure grows: poured into by growth media in reaction vessel, then will the copper sheet surface of crystal seed layer be had to face down, be suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 35 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, and can obtain nanometer rod and cluster composite structure thereof, as shown in Figures 2 and 3, the XRD figure spectrum that Fig. 4 provides illustrates, the composite structure grown is zinc oxide and cluster thereof, and described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 2
Copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
Surface hydrophobicity process: adopt spin coating plating method, at cleaned copper sheet surface spin coating one deck ultraviolet photoresist, thickness is 10 μm;
Prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 120nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
Composite structure grows: being poured into by growth media in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 35 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, can obtain zinc oxide nano rod and cluster composite structure thereof, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 3
(1) copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
(2) surface hydrophobicity process: adopt spin coating plating method, at cleaned copper sheet surface spin coating one deck ultraviolet photoresist, thickness is 20 μm;
(3) prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 320nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
(4) composite structure growth: growth media being poured in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 35 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, can obtain zinc oxide nano rod and cluster composite structure thereof, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 4
Copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
Prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 100nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
Composite structure grows: being poured into by growth media in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, is placed in electric heating constant temperature tank, under 90 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, room temperature is dried, can obtain the zinc oxide array nanorod structure perpendicular to substrate grown, as shown in Figure 5 and Figure 6, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 5
Copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
Surface hydrophobicity process: adopt silicon fluoride to modify method, copper sheet is put into the silicon fluoride ethanolic soln of 0.1wt.%, 60 DEG C of water bath heat preservation 2h, the cleaning of taking-up hot ethanol dries up, and takes out after being then placed in 80 DEG C of oven drying 1h;
Prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 100nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
Composite structure grows: being poured into by growth media in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 90 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, can obtain zinc oxide nano rod and cluster composite structure thereof, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Embodiment 6
(1) copper sheet surface preparation: pure copper sheet is cut into the pat that size is 2cm × 3cm, through acetone, ethanol and each 5min of deionized water ultrasonic cleaning, drying up rear immersion volume fraction is 60s in rare HCl solution of 10%, then dries up rear for subsequent use with washed with de-ionized water cold wind;
(2) surface hydrophobicity process: adopt silicon fluoride to modify method, copper sheet is put into the silicon fluoride ethanolic soln of 1wt.%, 60 DEG C of water bath heat preservation 2h, the cleaning of taking-up hot ethanol dries up, and takes out after being then placed in 80 DEG C of oven drying 1h;
(3) prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness obtained is 500nm, described seed-solution is that the NaOH methanol solution of 0.03mol/L is joined in the methanol solution of hydration zinc acetate of 0.01mol/L, obtains after 60 DEG C of stirring 2h;
(4) composite structure growth: growth media being poured in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 90 DEG C of water bath condition, growth 6h, after taking-up, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature is dried, can obtain zinc oxide nano rod and cluster composite structure thereof, described growth media is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
Claims (9)
1. a zinc oxide nano rod and cluster composite structure thereof, it is characterized in that, carry out hydrophobization process on the copper sheet surface of cleaning, the prefabricated ZnO crystal seed layer in surface after treatment, adopt method of reverse deduction to grow in the solution and obtain zinc oxide nano rod and cluster composite structure thereof.
2. zinc oxide nano rod as claimed in claim 1 and cluster composite structure thereof, it is characterized in that, described hydrophobization process modifies silicon fluoride after being included in copper sheet surface-coated ultraviolet photoresist, copper sheet surface roughening again.
3. the preparation method of the zinc oxide nano rod described in claim 1 or 2 and cluster composite structure thereof, it is characterized in that, hydrophobization process is carried out on the copper sheet surface of cleaning, the prefabricated ZnO crystal seed layer in surface after treatment, adopts method of reverse deduction to grow in the solution and obtains zinc oxide nano rod and cluster composite structure thereof.
4. the preparation method of zinc oxide nano rod as claimed in claim 3 and cluster composite structure thereof, is characterized in that, comprise the following steps:
(1) copper sheet surface preparation: pure copper sheet through acetone, ethanol and deionized water ultrasonic cleaning, dry up after immerse in diluted acid and clean, obtain clean copper sheet after then drying up with washed with de-ionized water cold wind for subsequent use;
(2) surface hydrophobicity process: adopt spin coating plating method, at the copper sheet surface-coated ultraviolet photoresist of cleaning, or adopts silicon fluoride to modify method, by the process of clean copper sheet silicon fluoride ethanolic soln surface hydrophobicity;
(3) prefabricated crystal seed layer: utilize sol evenning machine that the ZnO seed-solution prepared is spun on the copper sheet of hydrophobic treatment, the seed layer thickness of acquisition is 50-500nm;
(4) composite structure growth: being poured into by growth media in reaction vessel, then by there being the copper sheet surface of crystal seed layer to face down, being suspended in growth media, afterwards good seal reaction vessel, water-bath growth afterwash dries and obtains zinc oxide nano rod and cluster composite structure thereof.
5. the preparation method of zinc oxide nano rod as claimed in claim 4 and cluster composite structure thereof, it is characterized in that, step (2) medium ultraviolet photoresist material thickness is 1 ~ 20 μm.
6. the preparation method of zinc oxide nano rod as claimed in claim 4 and cluster composite structure thereof, it is characterized in that, when in step (2), silicon fluoride modifies method, copper sheet that is bright and clean or roughened is put into the silicon fluoride ethanolic soln of 0.1-1.0wt.%, 30-80 DEG C of water bath heat preservation 30min ~ 2h, the cleaning of taking-up hot ethanol dries up, and takes out after being then placed in 80 DEG C of oven drying 1h.
7. the preparation method of zinc oxide nano rod as claimed in claim 4 and cluster composite structure thereof, it is characterized in that, seed-solution described in step (3) is that the NaOH methanol solution of 0.03mol/L is joined in the hydration zinc acetate methanol solution of 0.01mol/L, obtains after 60 DEG C of stirring 2h.
8. the preparation method of zinc oxide nano rod as claimed in claim 4 and cluster composite structure thereof, is characterized in that, in step (4), bath temperature is 35-90 DEG C, and the time is 1-12h.
9. the preparation method of zinc oxide nano rod as claimed in claim 4 and cluster composite structure thereof, is characterized in that, growth media described in step (4) is with KOH and Zn (NO
3)
2compound concentration is 0.1molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12, abundant magnetic agitation, the settled solution obtained.
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| CN106430287A (en) * | 2016-09-21 | 2017-02-22 | 苏州大学 | Low-temperature hydro-thermal synthesis method for three-dimensional dandelion-shaped zinc oxide |
| CN117299217A (en) * | 2023-09-27 | 2023-12-29 | 暨南大学 | Preparation method and application of fleshy zinc oxide composite micro-motor |
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| CN117299217A (en) * | 2023-09-27 | 2023-12-29 | 暨南大学 | Preparation method and application of fleshy zinc oxide composite micro-motor |
| CN117299217B (en) * | 2023-09-27 | 2024-03-22 | 暨南大学 | Preparation method and application of fleshy zinc oxide composite micro-motor |
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