CN101348931A - Method for preparing uniform transparent zinc oxide nanorod array film by pulse electrodeposition - Google Patents
Method for preparing uniform transparent zinc oxide nanorod array film by pulse electrodeposition Download PDFInfo
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Abstract
The invention discloses a method for preparing a uniform transparent zinc oxide nano-rod array membrane by pulse electrodeposition, belonging to the preparation field of nano materials. The method comprises in turn the following steps: analytically pure zinc chloride and potassium chloride are dissolved in distilled water, and are stirred so as to obtain stable transparent solution; the the solution is fed into water bath with the temperature of between 60 and 80 DEG C so as to maintain a constant temperature, and oxygen is continuously fed into the solution; and in a three-electrode system, ITO conductive glass coated with a ZnO nano particle membrane is used as a cathode, while a platinum sheet is used as a counter electrode and a saturated calomel electrode is used as a reference electrode so as to carry out pulse electrodeposition to prepare a ZnO nano-rod array membrane under applied voltage of between 0.8 V below zero and 1.1V below zero with the on-off time ratio ton/toff controlled between 10s/10s and 1s/1s. Through adjusting the initial concentration of precursor and controlling factors such as the applied voltage of pulse electrodeposition, on-off time ratio of voltage and pulse frequency, the method prepares the transparent zinc oxide nano-rod array membrane with the diameter less than 50nm and uniform and controllable length, and effectively increases the quality of the membrane. The method has the advantages of simple process, strong controllability and less energy consumption, and can meet the requirements of mass production; moreover, the method has an enormous application prospect in the fields of solar battery, photoelectron, catalysis, and the like.
Description
Technical field
The invention belongs to field of nano material preparation, particularly aqueous solution electrodeposition prepares the zinc carbonate nano film material of diameter less than 50 nanometers, length homogeneous and controllable.
Background technology
ZnO is a kind of novel I I-VI family wide bandgap compound semiconductor material of hexagonal structure, and energy gap is 3.37eV under the room temperature, and exciton binding energy has possessed the supremacy clause of emission blue light or near-ultraviolet light up to 60meV.(Vapor-Liquid-Solid VLS) has prepared height-oriented ZnO nano-wire array and observe photic Ultra-Violet Laser emission phenomenon under the room temperature to calendar year 2001 Yang etc. with the VLS method; Konenkamp in 2005 etc. make further research the photoelectric properties of ZnO nanometer stick array, ZnO nano wire/excellent array that this achievement makes people recognize high-sequential has important significance for theories and application prospect at aspects such as development nanoelectronic of new generation, opto-electronic devices, so the preparation of the ZnO nano wire/excellent array of high-sequential and property research are becoming the new research focus of chemistry, physics and Materials science.In recent years, people attempt preparing with different physics and chemical process the ZnO nanometer stick array of excellent performance, wherein electrochemical deposition method since its reaction conditions gentleness, experiment parameter be easy to control, be easy to advantage such as mass industrialized production and more and more cause people's attention.In recent years, more international research groups adopt constant potential electrodip processes or continuous current electrodip process (for example: 1. Pauporte, T. to prepare the ZnO nanometer stick array; Lincot, D.Appl.Phys.Lett.1999,75,3817. 2. Illy, B.; Shollock, B.A.; MacManus-Driscoll J.L.; Ryan, M.P.Nanotechnology 2005,16,320. 3. Cao, B-Q.; Cai, W-P.; Zeng, H-B.; Duan, G-T.J.Appl.Phys.2006,99,073516.).
The subject matter that adopts electrodip process large-area preparation nanometic zinc oxide rod array to exist at present is: the nanometer rod diameter is bigger, reaches the hundreds of nanometer and does not wait, and the diameter of rod fails to be effectively controlled; In addition, the speed of growth difference of nanometer rod causes the length height of rod not wait resulting uneven film thickness one; Secondly, in deposition process, easily introduce impurity, cause product impure.Above-mentioned shortcoming has restricted electrodip process in ZnO nano-device Development Application.
Summary of the invention
The present invention proposes to adopt the method for square-wave pulse galvanic deposit,-0.8～-impressed voltage of 1.1V under, controlling factors such as the make-and-break time ratio of the starting point concentration by adjusting presoma and the impressed voltage of pulse electrodeposition, voltage, pulse-repetition, prepare the transparent film of diameter less than the nanometic zinc oxide rod array of 50nm, length homogeneous and controllable, improved the quality of nanometic zinc oxide rod array film effectively, not only can enhance productivity, energy efficient, and be easy to operate and control.
The method that the present invention's pulse electrodeposition in the aqueous solution prepares uniform transparent zinc oxide nanorod array film in turn includes the following steps:
(1) analytically pure zinc chloride and Repone K are used dissolved in distilled water in electrolyzer, stir the solution that obtains stable transparent, the concentration of described liquor zinci chloridi is 0.0005～0.001mol/L, and the concentration of Klorvess Liquid is 0.1～0.8mol/L;
(2) above-mentioned solution is placed water-bath constant temperature, bath temperature is 60～80 ℃;
(3) in above-mentioned solution, continue aerating oxygen;
(4) adopt three-electrode system to carry out the square-wave pulse galvanic deposit, ITO conductive glass with coating ZnO film of nanoparticles is a working electrode, platinized platinum is a counter electrode, saturated calomel electrode is a reference electrode, carry out square-wave pulse galvanic deposit ZnO, add square-wave voltage and be-0.8～-1.1V, the make-and-break time ratio of voltage is t
On/ t
Off=10s/10s～1s/1s;
(5) conductive glass is taken out, after washed with de-ionized water,, make uniform transparent zinc oxide nanorod array film in 60～80 ℃ of drying 30～60min of loft drier.
2, the method for preparing uniform transparent zinc oxide nanorod array film according to claim 1, it is characterized in that, described oxygen should feed in solution 10～15 minutes before pulse electrodeposition in advance, in the process of carrying out pulse electrodeposition, and aerating oxygen in solution always.
The present invention is by the impressed voltage of reasonable setting pulse galvanic deposit, the make-and-break time ratio of voltage, size, precursor liquid concentration, reaction times and the temperature of square-wave pulse frequency, controlled the size of nanometer rod diameter effectively, and the speed of growth of rod, finally obtained the transparent film of diameter less than the nanometic zinc oxide rod array of 50nm, length homogeneous and controllable, the homogeneity and the transparency of nanometic zinc oxide rod array have been guaranteed, improve production efficiency greatly, saved energy consumption; This method easy handling can be used for scale operation.
Description of drawings
Fig. 1 adopts the nanometic zinc oxide rod array SEM photo of square-wave pulse electro-deposition method preparation.
Fig. 2 adopts the nanometic zinc oxide rod array XRD figure of square-wave pulse electro-deposition method preparation.
Fig. 3 adopts the nanometic zinc oxide rod array transmitted light spectrogram of square-wave pulse electro-deposition method preparation.
Embodiment
Below in conjunction with example the present invention is set forth, but therefore do not limit the present invention within the example ranges.
With scanning electronic microscope (SEM), X-ray diffraction (XRD) and transmitted spectrum characterize structure, pattern and the transparency of the ZnO nanometer stick array prepared.
Embodiment 1:
(1) analytically pure zinc chloride and Repone K are used dissolved in distilled water in electrolyzer, stir the solution that obtains stable transparent, the concentration of liquor zinci chloridi is 0.0005mol/L, and the concentration of Klorvess Liquid is 0.1mol/L;
(2) get above-mentioned solution place 60 ℃ of constant temperature of water-bath to the reaction finish till;
(3) aerating oxygen 10 minutes in above-mentioned solution in advance before pulse electrodeposition, in the process of carrying out pulse electrodeposition, aerating oxygen in solution always;
(4) adopt three-electrode system to carry out the square-wave pulse galvanic deposit, ITO conductive glass with coating ZnO film of nanoparticles is working electrode (being negative electrode), and platinized platinum is counter electrode (being anode), and saturated calomel electrode is a reference electrode, under the impressed voltage of-0.8V, t is compared in control conduction time
On/ t
Off=10s/10s carries out pulse electrodeposition ZnO nanometer stick array;
(5) the ITO conductive glass is taken out, after washed with de-ionized water,, make uniform transparent zinc oxide nanorod array film in 60 ℃ of dry 60min of loft drier.
Embodiment 2:
(1) analytically pure zinc chloride and Repone K are used dissolved in distilled water in electrolyzer, stir the solution that obtains stable transparent, the concentration of liquor zinci chloridi is 0.0006mol/L, and the concentration of Klorvess Liquid is 0.4mol/L;
(2) get above-mentioned solution place 70 ℃ of constant temperature of water-bath to the reaction finish till;
(3) aerating oxygen 14 minutes in above-mentioned solution in advance before pulse electrodeposition, in the process of carrying out pulse electrodeposition, aerating oxygen in solution always;
(4) adopt three-electrode system to carry out the square-wave pulse galvanic deposit, ITO conductive glass with coating ZnO film of nanoparticles is working electrode (being negative electrode), and platinized platinum is counter electrode (being anode), and saturated calomel electrode is a reference electrode, under the impressed voltage of-1.0V, t is compared in control conduction time
On/ t
Off=5s/5s carries out pulse electrodeposition ZnO nanometer stick array;
(5) the ITO conductive glass is taken out, after washed with de-ionized water,, make uniform transparent zinc oxide nanorod array film in 70 ℃ of dry 40min of loft drier.
Embodiment 3:
(1) analytically pure zinc chloride and Repone K are used dissolved in distilled water in electrolyzer, stir the solution that obtains stable transparent, the concentration of liquor zinci chloridi is 0.0008mol/L, and the concentration of Klorvess Liquid is 0.8mol/L;
(2) get above-mentioned solution place 70 ℃ of constant temperature of water-bath to the reaction finish till;
(3) aerating oxygen 15 minutes in above-mentioned solution in advance before pulse electrodeposition, in the process of carrying out pulse electrodeposition, aerating oxygen in solution always;
(4) adopt three-electrode system to carry out the square-wave pulse galvanic deposit, ITO conductive glass with coating ZnO film of nanoparticles is working electrode (being negative electrode), and platinized platinum is counter electrode (being anode), and saturated calomel electrode is a reference electrode, under the impressed voltage of-1.1V, t is compared in control conduction time
On/ t
Off=1s/1s carries out pulse electrodeposition ZnO nanometer stick array;
(5) the ITO conductive glass is taken out, after washed with de-ionized water,, make uniform transparent zinc oxide nanorod array film in 80 ℃ of dry 30min of loft drier.
Concrete experimental result
Adopt the square-wave pulse electrodip process, under above-mentioned test conditions, prepare ZnO nanometer stick array transparent film in all can be on a large scale, wherein, the rod mean diameter all less than 50nm, the height unanimity of nanometer rod, perpendicular to substrate grown, as depicted in figs. 1 and 2.When lambda1-wavelength during greater than 400nm, the transmittance of ZnO nanometer stick array is all greater than 95%, as shown in Figure 3.
Detected result shows, adopt the method for square-wave pulse galvanic deposit, by the make-and-break time ratio of reasonable control impressed voltage, voltage, the size of square-wave pulse frequency, for constant potential and continuous current electro-deposition method, can control the size of nanometer rod diameter more effectively, especially Bang the speed of growth, finally prepare the transparent zinc oxide nanorod array film of diameter less than 50nm, length homogeneous and controllable, and do not have the existence of other impurity in the thin film composition that this method obtains, can be used for scale operation.
Claims (2)
1, a kind of pulse electrodeposition prepares the method for uniform transparent zinc oxide nanorod array film, it is characterized in that, in turn includes the following steps:
(1) analytically pure zinc chloride and Repone K are used dissolved in distilled water in electrolyzer, stir the solution that obtains stable transparent, the concentration of described liquor zinci chloridi is 0.0005～0.001mol/L, and the concentration of Klorvess Liquid is 0.1～0.8mol/L;
(2) above-mentioned solution is placed water-bath constant temperature, bath temperature is 60～80oC;
(3) in above-mentioned solution, continue aerating oxygen;
(4) adopt three-electrode system to carry out the square-wave pulse galvanic deposit, ITO conductive glass with coating ZnO film of nanoparticles is a working electrode, platinized platinum is a counter electrode, saturated calomel electrode is a reference electrode, carry out square-wave pulse galvanic deposit ZnO, add square-wave voltage and be-0.8～-1.1V, the make-and-break time ratio of voltage is ton/toff=10s/10s～1s/1s;
(5) conductive glass is taken out, after washed with de-ionized water,, make uniform transparent zinc oxide nanorod array film in 60～80 ℃ of drying 30～60min of loft drier.
2, the method for preparing uniform transparent zinc oxide nanorod array film according to claim 1, it is characterized in that, described oxygen should feed in solution 10～15 minutes before pulse electrodeposition in advance, in the process of carrying out pulse electrodeposition, and aerating oxygen in solution always.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2469869A (en) * | 2009-05-01 | 2010-11-03 | Univ Bolton | Continuous ZnO films |
| CN102388437A (en) * | 2009-02-11 | 2012-03-21 | 联合太阳能奥佛有限公司 | Solution based non-vacuum method and apparatus for preparing oxide materials |
| CN102507531A (en) * | 2011-10-28 | 2012-06-20 | 中国科学院理化技术研究所 | Raman scattering enhanced substrate of zinc oxide-based semiconductor and preparation method and application thereof |
| CN102747424A (en) * | 2012-08-06 | 2012-10-24 | 苏州汶颢芯片科技有限公司 | Method for preparing zinc oxide nano wire/pipe arrays with controllable diameters and heights on indium tin oxide (ITO) glass |
| CN103060909A (en) * | 2012-12-31 | 2013-04-24 | 苏州汶颢芯片科技有限公司 | Method for preparing ZnO nanowire/nanotube arrays with adjustable diameter and height on organic flexible substrate |
| CN103147130A (en) * | 2013-01-27 | 2013-06-12 | 浙江大学 | Preparation method of transition metal element doped zinc oxide (ZnO) nanometer array and semiconductor device with the same |
| CN103194784A (en) * | 2013-04-11 | 2013-07-10 | 江苏大学 | Method for preparing nano ZnO thin film through controlled electro-deposition by taking colloid as template |
| CN103320827A (en) * | 2013-06-13 | 2013-09-25 | 江苏大学 | Preparation method of inorganic-salt-doped nano zinc oxide film |
| CN103422129A (en) * | 2013-07-24 | 2013-12-04 | 浙江大学 | Method for changing appearance of ZnO by adding Ca<2+> |
| CN103469273A (en) * | 2013-08-29 | 2013-12-25 | 长春工程学院 | Method for preparing nano-zinc oxide |
| US9682346B1 (en) * | 2016-10-20 | 2017-06-20 | Sultan Qaboos University | Nanostructured zinc oxide membrane for separating oil from water |
| CN107460514A (en) * | 2017-06-27 | 2017-12-12 | 江苏大学 | A kind of simple method for preparing zinc oxide nano popped rice |
| CN108277462A (en) * | 2017-12-27 | 2018-07-13 | 浙江交通科技股份有限公司 | A kind of method that pulse electrodeposition prepares magnetic metal nanotube |
| CN108588778A (en) * | 2018-06-05 | 2018-09-28 | 北方民族大学 | A method of Low-temperature electro-deposition prepares orderly ZnO nanorod in flexible plastic substrates |
| CN113526541A (en) * | 2021-08-24 | 2021-10-22 | 郑州大学 | Method for preparing ultrathin zinc oxide nanosheet with assistance of electrochemical reduction |
| CN115501754A (en) * | 2022-08-19 | 2022-12-23 | 西安建筑科技大学 | Method and device for improving desalination performance of nano-channel membrane through external electric field regulation and control |
| CN116479498A (en) * | 2023-04-04 | 2023-07-25 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
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2008
- 2008-09-11 CN CNA2008101198103A patent/CN101348931A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102388437A (en) * | 2009-02-11 | 2012-03-21 | 联合太阳能奥佛有限公司 | Solution based non-vacuum method and apparatus for preparing oxide materials |
| GB2469869A (en) * | 2009-05-01 | 2010-11-03 | Univ Bolton | Continuous ZnO films |
| CN102507531A (en) * | 2011-10-28 | 2012-06-20 | 中国科学院理化技术研究所 | Raman scattering enhanced substrate of zinc oxide-based semiconductor and preparation method and application thereof |
| CN102747424A (en) * | 2012-08-06 | 2012-10-24 | 苏州汶颢芯片科技有限公司 | Method for preparing zinc oxide nano wire/pipe arrays with controllable diameters and heights on indium tin oxide (ITO) glass |
| CN103060909A (en) * | 2012-12-31 | 2013-04-24 | 苏州汶颢芯片科技有限公司 | Method for preparing ZnO nanowire/nanotube arrays with adjustable diameter and height on organic flexible substrate |
| CN103147130A (en) * | 2013-01-27 | 2013-06-12 | 浙江大学 | Preparation method of transition metal element doped zinc oxide (ZnO) nanometer array and semiconductor device with the same |
| CN103147130B (en) * | 2013-01-27 | 2016-05-11 | 浙江大学 | The preparation method of transition metal element doped ZnO nano array and comprise the semiconductor devices of this nano-array |
| CN103194784A (en) * | 2013-04-11 | 2013-07-10 | 江苏大学 | Method for preparing nano ZnO thin film through controlled electro-deposition by taking colloid as template |
| CN103194784B (en) * | 2013-04-11 | 2016-03-02 | 江苏大学 | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film |
| CN103320827B (en) * | 2013-06-13 | 2015-12-09 | 江苏大学 | A kind of preparation method of inorganic-salt-dopednano nano zinc oxide film |
| CN103320827A (en) * | 2013-06-13 | 2013-09-25 | 江苏大学 | Preparation method of inorganic-salt-doped nano zinc oxide film |
| CN103422129B (en) * | 2013-07-24 | 2015-09-30 | 浙江大学 | A kind of by adding Ca 2+change the method for appearance of ZnO |
| CN103422129A (en) * | 2013-07-24 | 2013-12-04 | 浙江大学 | Method for changing appearance of ZnO by adding Ca<2+> |
| CN103469273A (en) * | 2013-08-29 | 2013-12-25 | 长春工程学院 | Method for preparing nano-zinc oxide |
| US9682346B1 (en) * | 2016-10-20 | 2017-06-20 | Sultan Qaboos University | Nanostructured zinc oxide membrane for separating oil from water |
| CN107460514A (en) * | 2017-06-27 | 2017-12-12 | 江苏大学 | A kind of simple method for preparing zinc oxide nano popped rice |
| CN108277462A (en) * | 2017-12-27 | 2018-07-13 | 浙江交通科技股份有限公司 | A kind of method that pulse electrodeposition prepares magnetic metal nanotube |
| CN108588778A (en) * | 2018-06-05 | 2018-09-28 | 北方民族大学 | A method of Low-temperature electro-deposition prepares orderly ZnO nanorod in flexible plastic substrates |
| CN113526541A (en) * | 2021-08-24 | 2021-10-22 | 郑州大学 | Method for preparing ultrathin zinc oxide nanosheet with assistance of electrochemical reduction |
| CN113526541B (en) * | 2021-08-24 | 2022-08-02 | 郑州大学 | Method for preparing ultrathin zinc oxide nanosheet with assistance of electrochemical reduction |
| CN115501754A (en) * | 2022-08-19 | 2022-12-23 | 西安建筑科技大学 | Method and device for improving desalination performance of nano-channel membrane through external electric field regulation and control |
| CN116479498A (en) * | 2023-04-04 | 2023-07-25 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
| CN116479498B (en) * | 2023-04-04 | 2023-10-20 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
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