CN103074658A - Method for electrochemically preparing sea urchin-shaped zinc oxide nanowire array on indium tin oxide (ITO) glass - Google Patents
Method for electrochemically preparing sea urchin-shaped zinc oxide nanowire array on indium tin oxide (ITO) glass Download PDFInfo
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- CN103074658A CN103074658A CN2012105896793A CN201210589679A CN103074658A CN 103074658 A CN103074658 A CN 103074658A CN 2012105896793 A CN2012105896793 A CN 2012105896793A CN 201210589679 A CN201210589679 A CN 201210589679A CN 103074658 A CN103074658 A CN 103074658A
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Abstract
The invention relates to a method for electrochemically preparing a sea urchin-shaped zinc oxide nanowire array on indium tin oxide (ITO) glass. The method comprises the following steps: depositing single layer of sequential polystyrene microsphere on the ITO glass by a self-assembling method; and electrochemically depositing good sequential zinc oxide nanowire on the surface of microsphere so as to obtain the radial sea urchin-shaped zinc oxide nanowire array. The preparation method for the sea urchin-shaped zinc oxide nanowire array is cheap in required materials, environment-friendly, simple in equipment and step, short in preparation period and easy to synthesize. The prepared ZnO nanowire consists of ZnO nanocrystal, can regulate and control the height and the diameter, has excellent optical and electrical performance, and can be widely applied in the fields of nanocrystal solar batteries, nano sensors and the like.
Description
Technical field
The present invention relates to a kind ofly prepare the method for sea urchin shape zinc oxide nano-wire array at ito glass, this array film can be applicable to the fields such as nano-crystalline solar battery, nano-sensor.
Background technology
Zinc oxide (ZnO) at room temperature can obtain efficient excitonic luminescence as a kind of novel semiconductor material, and has strong free exciton transition luminescence at ultraviolet band.In various one/3-D nano, structures, because the surface-area of ZnO nano-wire is huge, thereby produce surface effects, small-size effect and macro quanta tunnel effect, have many properties and new purposes at aspects such as catalysis, photoelectricity, magnetic, sensitivities, add that raw material resources is abundant, low price, nontoxic to environment, be suitable for the epitaxy of film, have wide practical use at the information photoelectric field, become new in recent years study hotspot.
At present, the method for preparing three-dimensional ZnO array has chemical Vapor deposition process and liquid-phase growth method.Chemical Vapor deposition process usually with zinc powder or oxide powder and zinc as starting material, under comparatively high temps, by gas-phase transport, then in suitable warm area deposition, obtain at last the zinc oxide of different appearances.This method needs high temperature, sometimes also needs catalyzer, disadvantage to be wayward, the poor repeatability of process of growth.Liquid-phase growth method prepares the nanocrystalline as Seed Layer of one deck zinc oxide in substrate usually, then soaks for some time in 60～90 ℃ zinc solution, thereby obtains zinc oxide nano-wire array.The reaction conditions of the method is gentle, cost is low, product is even, but required precursor reagent relative complex, and product pollutes easily, is difficult for purifying, and crystallinity is not high.
Electrochemical synthesis is a kind of synthetic method that is widely used in recent years, it has environmental protection, reaction conditions is gentle, process is controlled, and is easy to the advantages such as automated operation, has become a kind of effective ways of synthesis of metal oxide nano wire, the ZnO nano-wire of preparation is comprised of the ZnO nano crystalline substance, height and diameter all can be regulated and control, and have good optics and electric property, can be widely used in the fields such as nano-crystalline solar battery, nano-sensor.
Summary of the invention
The present invention relates to utilize the method for electrochemical deposition, the processing parameter by the regulation and control electrochemical deposition comprises Repone K (KCl) and zinc oxide (ZnCl
2) concentration, and the electric weight of electrochemical deposition (Q) is regulated and control diameter and the height of nano-wire array, take the polystyrene microsphere array as template, at microsphere surface making ZnO nano wire, thereby obtains radial, sea urchin shape zinc oxide nano-wire array.By control deposition electric weight, can regulate and control continuously height and the diameter of ZnO nanowire array.
For achieving the above object, the present invention adopts following operation steps:
Adopt self-assembly method at ito glass preparation polystyrene microsphere array; In liquor zinci chloridi, prepare height-oriented ZnO nanowire array with electrochemical method at the micro-sphere array surface deposition, thereby obtain radial, sea urchin shape zinc oxide nano-wire array.
The described construction from part that picks up from prepares the method for polystyrene microsphere array at ito glass, adopts following steps:
1. under constant temperature 60-80 ℃, with ito glass substrate successively at trieline (C
2HCl
3), acetone (CH
3COCH
3), Virahol (CH
3CH (OH) CH) carries out ultrasonic cleaning 10-25min in the solvent, then rinse well with ultrapure water, dry up with nitrogen at last.
2. be the individual layer polystyrene microsphere of micron level at clean ito glass substrate with the self-assembly method sedimentation diameter, naturally dry in air with mera.
3. the ito glass substrate that will be attached with the polystyrene microsphere array immerses the ZnCl of 1-2M
2Take out after processing 45-60min in the solution, as the working electrode of electro deposition oxidation zinc nano wire.
Describedly in liquor zinci chloridi, prepare height-oriented ZnO nanowire array with electrochemical method at the micro-sphere array surface deposition, adopt following steps:
1. the three electrode electro-deposition system of employing standard is attached with the ito glass substrate of polystyrene microsphere array as working electrode, and platinum wire electrode is to electrode, and saturated calomel electrode is reference electrode.
2. dispose ZnO nano-wire electric depositing solution, 1-5x10
-4The ZnCl of M
2Be the galvanic deposit precursor, the KCl of 0.1-3.4M is supporting electrolyte.
3. before galvanic deposit began, solution led to oxygen 10-20min under 70-80 ℃ of constant temperature.In electrodeposition process, solution is done the logical oxygen of bubbling always and process.
4. working electrode is applied-1V vs saturated calomel electrode, deposition electric weight Q is 2.5-50C/cm
2, when Q surpassed set(ting)value, instrument quit work automatically.
5. taking-up sample after rinsing well with deionized water, dries up with nitrogen, makes radial, sea urchin shape zinc oxide nano-wire array.
Reaction on the working electrode is comprised of reaction (1), (2) and chemical reaction (3)
O
2+ 2H
2O+2e
-→ H
2O
2+ 2OH
-Reaction (1)
O
2+ 2H
2O+4e
-→ 4OH
-Reaction (2)
Zn
2++ 2OH
-→ ZnO+H
2O reacts (3)
The oxygen of working electrode surface is reduced to OH
-Ion, the zine ion of close electrode is assembled into ZnO nanowire array at working electrode surface automatically under the effect of electric field.
Among the present invention, a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass, be based on the method for electrochemical deposition principle.
Among the present invention, a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass, be take individual layer self-assembly polystyrene microsphere as template, in microsphere surface growth of zinc oxide nano linear array, the method for electrochemical deposition principle.
Among the present invention, a kind of have under the same diameter at the control ZnO nanowire array in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass, can regulate and control continuously the height of ZnO nanowire array.
Among the present invention, a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass, under control ZnO nanowire array equal height, can regulate and control continuously the ZnO nanowire array diameter.
What propose among the present invention is a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass, simple to operate, preparation time is short, and energy expenditure is low, output is higher, will obtain in fields such as nano-crystalline solar battery, nano-sensors to use widely.
Description of drawings
Fig. 1 is the field emission scanning electron microscope picture of self-assembly microspheres.
Fig. 2 is the field emission scanning electron microscope picture of sea urchin shape ZnO nanowire array.
Specific embodiments
Embodiment 1:
Successively at trieline (C
2HCl
3), acetone (CH
3COCH
3), Virahol (CH
3CH (OH) CH) Ultrasonic Heating (70 ℃) cleans ito glass substrate 15min in the solvent, then rinses well with ultrapure water to dry up with nitrogen afterwards.The self-assembly sedimentation diameter is 4 microns polystyrene microsphere on clean substrate, and depositional area is 1x2cm
2, the ito glass substrate that is attached with the polystyrene microsphere array immerses the ZnCl of 1M
2Take out after processing 45min in the solution, as the working electrode of electro deposition oxidation zinc nano wire.With 5x10
-4M ZnCl
2Be made into the ZnO electric depositing solution with 1M KCl, under 80 ℃ of constant temperature, solution leads to oxygen 10min.In electrodeposition process, solution is done the bubbling oxygenation always and process.The three electrode electro-deposition system of employing standard carries out electrochemical deposition, the ito glass of ZnO Seed Layer film is arranged as working electrode, and the platinum wire electrode conduct is to electrode, and saturated calomel electrode is as reference electrode.Working electrode is applied-1V vs saturated calomel electrode, and electric weight Q is set to 10C/cm
2, when Q surpasses 10C/cm
2The time, electrochemical workstation will stop galvanic deposit automatically.Take out sample, after rinsing well with deionized water, dry up with nitrogen, make sea urchin shape ZnO nanowire array.
Claims (7)
1. one kind in the power on method of chemical preparation sea urchin shape zinc oxide (ZnO) nano-wire array of ito glass substrate, it is characterized in that this preparation method at first adopts the orderly polystyrene microsphere of self-assembling method deposited monolayers on ito glass, deposit good in order zinc oxide nanowire at the microsphere surface electrochemistry subsequently, thereby obtain radial, sea urchin shape zinc oxide nano-wire array.
2. a kind ofly can regulate and control the method for the sea urchin shape zinc oxide nano-wire array of diameter and height in ito glass preparation by claimed in claim 1, it is characterized in that the preparation method comprises the steps:
1. adopt self-assembly method at the working electrode of ito glass preparation polystyrene microsphere array as electro deposition oxidation zinc nano wire, adopt following steps:
1) under constant temperature 60-80 ℃, with ito glass substrate successively at trieline (C
2HCl
3), acetone (CH
3COCH
3), Virahol (CH
3CH (OH) CH) carries out ultrasonic cleaning 10-25min in the solvent, then rinse well with ultrapure water, dry up with nitrogen at last.
2) be the individual layer polystyrene microsphere of micron level at clean ito glass substrate with the self-assembly method sedimentation diameter, naturally dry in air with mera.
The ito glass substrate that 3) will be attached with the polystyrene microsphere array immerses the ZnCl of 1-2M
2Take out after processing 45-60min in the solution, as the working electrode of electro deposition oxidation zinc nano wire.
2. in liquor zinci chloridi, prepare height-oriented ZnO nanowire array with electrochemical method in the microsphere surface deposition, adopt following steps:
1) the three electrode electro-deposition system of employing standard is coated with the ito glass of ZnO Seed Layer film as working electrode, and platinum wire electrode is to electrode, and saturated calomel electrode is reference electrode.
2) configuration ZnO nano-wire electric depositing solution, 1-5x10
-4The ZnCl of M
2Be the galvanic deposit precursor, the KCl of 0.1-3.4M is supporting electrolyte.
3) before galvanic deposit begins, solution leads to oxygen 10-20min under 70-80 ℃ of constant temperature.In electrodeposition process, solution is done the logical oxygen of bubbling always and process.
4) working electrode is applied-1V vs saturated calomel electrode, deposition electric weight Q is 2.5-50C/cm
2, when Q surpassed set(ting)value, instrument quit work automatically.
5) take out sample, after rinsing well with deionized water, dry up with nitrogen, make radial, sea urchin shape zinc oxide nano-wire array.
3. by claim 1 or 2 described a kind ofly it is characterized in that in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass substrate, assemble complete microballoon and put into 1-2M ZnCl
2Process for some time in the solution, make Surfaces of Polystyrene Microparticles have electrochemical activity.
4. by claim 1 or 2 described a kind ofly it is characterized in that in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass substrate, the ZnO nanowire array vertical-growth is in microsphere surface, thereby obtains radial, sea urchin shape zinc oxide nano-wire array.
5. describedly a kind ofly it is characterized in that in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass substrate the height of ZnO nano-wire is regulated and control by electric weight Q by claim 1 or 2; The diameter of ZnO nano-wire is by KCl, ZnCl
2Concentration regulate and control.
6. by claim 1 or 2 described a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass substrate, it is characterized in that, electro-deposition method making ZnO nano wire and ZnO nano pipe simple to operate, generated time is short, energy expenditure is low, and output is higher.
7. by claim 1 or 2 described a kind of in the power on method of chemical preparation sea urchin shape zinc oxide nano-wire array of ito glass substrate, it is characterized in that, the sea urchin shape ZnO nano-wire of preparation is comprised of the ZnO nano crystalline substance, have good optics and electric property, can be widely used in the fields such as nano-crystalline solar battery, nano-sensor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368710A (en) * | 2018-12-26 | 2019-02-22 | 台州学院 | A method of preparing Fe9Ni1P10S30 micron chip |
| CN109813776A (en) * | 2017-11-20 | 2019-05-28 | 天津师范大学 | Intermediate pore size porous silicon-base zinc oxide films film composite material gas sensor and its preparation method and application |
| US20220081312A1 (en) * | 2020-09-16 | 2022-03-17 | Industry-Academic Cooperation Foundation, Yonsei University | Method for preparing sea urchin-shaped zinc oxide nanowire |
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| CN109813776A (en) * | 2017-11-20 | 2019-05-28 | 天津师范大学 | Intermediate pore size porous silicon-base zinc oxide films film composite material gas sensor and its preparation method and application |
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| US20220081312A1 (en) * | 2020-09-16 | 2022-03-17 | Industry-Academic Cooperation Foundation, Yonsei University | Method for preparing sea urchin-shaped zinc oxide nanowire |
| US11685665B2 (en) * | 2020-09-16 | 2023-06-27 | Industry-Academic Cooperation Foundation, Yonsei University | Method for preparing sea urchin-shaped zinc oxide nanowire |
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Application publication date: 20130501 |