CN102864448B - Method for directly preparing ZnO nanometer grain film by using common Zn powder - Google Patents
Method for directly preparing ZnO nanometer grain film by using common Zn powder Download PDFInfo
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- CN102864448B CN102864448B CN201210339344.6A CN201210339344A CN102864448B CN 102864448 B CN102864448 B CN 102864448B CN 201210339344 A CN201210339344 A CN 201210339344A CN 102864448 B CN102864448 B CN 102864448B
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Abstract
The invention relates to a method for directly preparing a ZnO nanometer grain film by using common Zn powder, which comprises the following steps: pre-processing micron-scale Zn powder to nanoscale Zn powder by using a rolling vibration mill under an argon atmosphere and storing in a darkroom at normal temperature; mixing an organic solvent cyclohexane with a frequently used inorganic solution H2O, thereby preparing into an oil-phase/water-phase disperse system, wherein the volume ratio of cyclohexane to H2O is 1:19; weighting the preprocessed nanoscale Zn powder according to the weight ratio of 1:100, placing the nanoscale Zn powder into the prepared oil-phase/water-phase disperse system, and fully stirring and dispersing, thereby obtaining a mixed solution; placing the mixed solution into an ultrasonic cleaner, ultrasonically dispersing for 8h at room temperature, and stirring the mixed solution at a 2h interval, thereby ensuring the full dispersing of the Zn powder; and extracting the liquid from a supernatant layer of the mixed solution by using a dropper, dropwise adding to a clean silicon wafer and placing into a drier, and drying at the lower temperature below 50 DEG C, thereby obtaining the ZnO nanometer grain film. The method provided by the invention has the advantages that the preparation process is simple, the cost is low, the product performance is promoted and the method can be applied to large-scale production.
Description
Technical field
The present invention relates to the method for the direct making ZnO nanometer particle film of the common Zn powder of a kind of use.Belong to nano-particular film preparing technical field.
Background technology
Nano material is an important field of research in current scientific and technical research, and the nano material of different structure size is subject to people's attention because of its unique physical and chemical performance and in the potential application of the aspects such as optics, electricity, magnetics.ZnO is II-VI family semiconductor material of a kind of broad stopband direct band gap, under room temperature, can band gap be 3.37eV, exciton bind energy 60meV, its near ultraviolet region transmitting and transparent electric conductivity, biocompatibility, photocatalysis performance make it have application prospect widely, as: ultraviolet lasing device, photocatalysis treatment sewage apparatus, glucolase sensor.ZnO nano crystal has the special performance that is different from body phase material, and research report synthetic about it and aspect of performance is a lot of at present.
The preparation method of known Zinc oxide nanoparticle film is varied, mainly comprises: hydrothermal method, sol-gel method, reaction magnetocontrol sputtering, pulsed electron beam deposition method etc.Their experience years development comparative maturities, but these technology ubiquities complicated process of preparation, consume energy high, the defect such as yield poorly.Taking reaction magnetocontrol sputtering making ZnO nanometer particle film as example, (1) is from economic costs angle: magnetron sputtering equipment domestic equipment price is 40～1,500,000 yuan, at least 300 ten thousand yuan of import equipments, and instrument is expensive; (2) from technique means, implementation step angle: first magnetically controlled sputter method making ZnO nanometer particle film must use magnetron sputtering equipment, before each use, all need preheating, consume energy high and can not work long hours.Secondly, experiment need to be prepared high purity (99.99%) target, and target diameter and thickness will strictly be controlled; In reaction process, need strictly to control high purity Ar and O
2mixing gas component, keeps atmosphere stable; When reaction, keep high vacuum 2x10
-3pa, more crucial is to be subject to above all condition restriction, causes magnetically controlled sputter method making ZnO nanometer particle film to accomplish without any letup, and if this preparation technology will batch production can greatly reduce life-span of magnetron sputtering apparatus.
Summary of the invention
In order to reduce the preparation cost of Zinc oxide nanoparticle film in prior art, fall and can lower consumption, simplify preparation technology, improve the quality of products and preparation efficiency, the invention discloses the method for the direct making ZnO nanometer particle film of the common Zn powder of a kind of use, the present invention is under ambient temperature, adopt mechanical process directly to prepare Zinc oxide nanoparticle film by zinc powder, not only production technique is simple, and preparation cost is low, is suitable for large-scale industrial production.
Technical solution of the present invention is achieved in that
A method for the direct making ZnO nanometer particle film of the common Zn powder of use, adopt rolling-vibrating grinding machine under argon atmosphere to the pre-treatment of micron order zinc powder to nano level, and nano zinc powder normal temperature after treatment is stored in darkroom, carry out in accordance with the following steps:
A) by organic solvent hexanaphthene and conventional inorganic solution H
2o is mixedly configured into oil phase/water phase dispersion system, wherein hexanaphthene and H
2the volume ratio of O is 1:19;
B) take pretreated nano zinc powder according to nano zinc powder and oil phase/water phase dispersion system weight ratio 1:100, put into through steps A) the oil phase/water phase dispersion system that configures, fully dispersed with stirring, obtains mixed solution;
C) by step B) mixed solution that obtains is placed in ultrasonic cleaning machine, and at room temperature ultrasonic dispersion 8h, is uniformly mixed liquid every 2h during this time, ensures that zinc powder fully disperses;
D) utilize dropper to take out liquid from the supernatant liquid of mixed solution, be added drop-wise on clean silicon chip and be placed in drying machine, at 50 DEG C, oven drying at low temperature obtains Zinc oxide nanoparticle film.
The present invention adopts roll extrusion vibration mill pre-treatment zinc powder not only can obtain nano level zinc powder, and can improve the activity of zinc powder; Adopt oil phase/water phase dispersion system as tensio-active agent, be conducive to nanoparticulate dispersed; Adopt the ultrasonic cleaning machine ultrasonic dispersion of timing and be interrupted and stir, making oxidizing reaction more abundant.
The present invention compared with prior art has the following advantages:
1, the inventive method can be proceeded in two phases: first process common zinc powder and preserve to nano level darkroom normal temperature, the rear Zinc oxide nanoparticle film of preparing; Preparation process one gas is synthetic, has improved the operability of producing;
2, the present invention adopts the rolling-vibrating grinding machine with independent intellectual property right to prepare zinc nanoparticles, can significantly reduce energy consumption, not only cost is low, and preparation technology is easy, and can improve the activity of zinc powder, be conducive to nanometer Zn and change Zinc oxide nanoparticle film into;
3, adopt oil phase/water phase dispersion system as tensio-active agent, be conducive to nanoparticulate dispersed and Zinc oxide nanoparticle film preparation;
4, adopt the ultrasonic cleaning machine ultrasonic dispersion of timing and be interrupted and stir, making oxidizing reaction more abundant;
5, processing step is simple, easy handling, and product performance improve, and only need to configure the ultrasonic cleaner of rolling-vibrating grinding machine and some amount, can expand the scale of production.
Brief description of the drawings
Fig. 1 is the ZnO nano particle film sample prepared of the present invention and the X-ray diffraction analysis figure of Zn powder;
Wherein: the XRD figure spectrum that Fig. 1 (a) grinds ZnO nano particle film sample prepared by zinc powder 1h, 5h, 13h for roll extrusion vibration mill;
Fig. 1 (b) is the XRD figure spectrum of raw material Zn powder.
ZnO in figure (002): show that X-ray diffraction peak shows that this sample is that ZnO composition and this ZnO grow along (002) crystal orientation; Occurring that Si (111) is because base material is silicon, be not the product that the present invention comprises, and this Si grows along (111) crystal orientation; Occurring that Al (111) is because the material of testing tool sample table is aluminium, be not the product that the present invention comprises, and this Al grows along (111) crystal orientation.In collection of illustrative plates, as above, just crystal is grown along different crystal orientations in the lexical or textual analysis at other peaks.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.These embodiment are only for explaining the present invention instead of for limiting the present invention.The same or analogous method of all employings and the present invention, or the equivalent modifications of making, all should fall into protection domain of the present invention.
In the present invention, zinc powder material is ground to equipment used, all utilize rolling-vibrating grinding machine (Chinese patent CN99112092.2) dry process in batches under room temperature and shielding gas atmosphere.Raw material is common Zn powder, and before pre-treatment, median particle diameter is 50 microns, and its XRD figure is composed as shown in Fig. 1 (b).
Embodiment 1
A) utilize the common zinc powder of rolling-vibrating grinding machine pre-treatment 1 hour, when roll extrusion vibration mill milled processed, keep argon atmosphere, in process of lapping, while reaching 1h, stop grinding, material is carried out to stress relief; Darkroom normal temperature is preserved pretreated zinc powder;
B) adopt organic solvent hexanaphthene and conventional inorganic solution H
2o mixes formation oil phase/water phase dispersion system, and volume ratio is hexanaphthene: H
2o=1:19, gets 20ml; Take pretreated zinc powder 0.2g and put into ready oil phase/water phase dispersion system, fully the pretreated zinc powder of dispersed with stirring;
C) adopt ultrasonic cleaning machine to carry out ultrasonic dispersion to the oil phase/water phase dispersion system that tentatively disperses pre-treatment zinc powder, ambient temperature, ultrasonic dispersion 8h, during this time every 2h dispersed with stirring liquid, ensures that zinc powder fully disperses not precipitate;
D) utilize dropper to take out liquid from supernatant liquid, be added drop-wise on clean silicon chip, be placed in 50 DEG C of oven drying at low temperatures of drying machine, obtain Zinc oxide nanoparticle film.
The present embodiment adopts roll extrusion vibration mill to carry out 1h pre-treatment to zinc powder, taking oil phase/water phase system as medium, is aided with ultrasonic dispersion and prepares ZnO nano particle film.The XRD figure of its ZnO nano particle film is composed as shown in Fig. 1 (a).The granular size of the nanometer particle film that this embodiment prepares is about 300 nanometers, and the nanometer particle film particle size (5 nanometer～100 nanometer) of preparing than ordinary method is many greatly; Surface potential is up to 49.7mv, and surface can be higher.
Embodiment 2
A) utilize the common zinc powder of rolling-vibrating grinding machine pre-treatment 5 hours, when roll extrusion vibration mill milled processed, keep argon atmosphere, in process of lapping, while reaching 1h, 2h, 3h, 5h, stop grinding 1 hour, material is carried out to stress relief; Darkroom normal temperature is preserved pretreated zinc powder;
B) adopt organic solvent hexanaphthene and conventional inorganic solution H
2o mixes formation oil phase/water phase dispersion system, and volume ratio is hexanaphthene: H
2o=1:19, gets 20ml; Take pretreated zinc powder 0.2g and put into ready oil phase/water phase dispersion system, fully the pretreated zinc powder of dispersed with stirring;
C) adopt ultrasonic cleaning machine to carry out ultrasonic dispersion to the oil phase/water phase dispersion system that tentatively disperses pre-treatment zinc powder, ambient temperature, ultrasonic dispersion 8h, during this time every 2h dispersed with stirring liquid, ensures that zinc powder fully disperses not precipitate;
D) utilize dropper to take out liquid from supernatant liquid, be added drop-wise on clean silicon chip, be placed in 50 DEG C of oven drying at low temperatures of drying machine and obtain Zinc oxide nanoparticle film.
The present embodiment adopts roll extrusion vibration mill to carry out 5h pre-treatment to zinc powder, taking oil phase/water phase system as medium, is aided with ultrasonic dispersion and prepares ZnO nano particle film.The granular size of the nanometer particle film that this embodiment prepares is about 100 nanometers, relatively approaches the nanometer particle film particle size (5 nanometer～100 nanometer) that ordinary method is prepared; And surface potential is up to 63.3mV, the surface of the ZnO nano particle film of preparing than pre-treatment 1hZn can be high.
Embodiment 3
A) utilize the common zinc powder of rolling-vibrating grinding machine pre-treatment 13 hours, when roll extrusion vibration mill milled processed, keep argon atmosphere, in process of lapping, reach 1h, 2h, 3h, 5h, 7h, 9h, 11h, 13h, time and stop grinding 1 hour, material is carried out to stress relief; Darkroom normal temperature is preserved pretreated zinc powder;
B) adopt organic solvent hexanaphthene and conventional inorganic solution H
2o mixes formation oil phase/water phase dispersion system, and volume ratio is hexanaphthene: H
2o=1:19, gets 20ml; Take pretreated zinc powder 0.2g and put into ready oil phase/water phase dispersion system, fully the pretreated zinc powder of dispersed with stirring;
C) adopt ultrasonic cleaning machine to carry out ultrasonic dispersion to the oil phase/water phase dispersion system that tentatively disperses pre-treatment zinc powder, ambient temperature, ultrasonic dispersion 8h, during this time every 2h dispersed with stirring liquid, ensures that zinc powder fully disperses not precipitate;
D) utilize dropper to take out liquid from supernatant liquid, be added drop-wise on clean silicon chip, be placed in drying machine, 50 DEG C of oven drying at low temperatures obtain Zinc oxide nanoparticle film.
The present embodiment adopts roll extrusion vibration mill to carry out 13h pre-treatment to zinc powder, taking oil phase/water phase system as medium, is aided with ultrasonic dispersion and prepares ZnO nano particle film.The granular size of the nanometer particle film that this embodiment prepares is about 60 nanometers, relatively approaches the nanometer particle film particle size (5 nanometer～100 nanometer) that ordinary method is prepared; And surface potential is up to 80.0mV, the surface of the ZnO nano particle film of preparing than pre-treatment 1h, 5hZn can be high.
Embodiment 4
A) utilize the common zinc powder of rolling-vibrating grinding machine pre-treatment 13 hours, when roll extrusion vibration mill milled processed, keep argon atmosphere, in process of lapping, reach 1h, 2h, 3h, 5h, 7h, 9h, 11h, 13h, time and stop grinding 1 hour, material is carried out to stress relief; Darkroom normal temperature is preserved pretreated zinc powder;
B) adopt organic solvent hexanaphthene and conventional inorganic solution H
2o mixes formation oil phase/water phase dispersion system, and volume ratio is hexanaphthene: H
2o=1:1, gets 20ml; Take pretreated zinc powder 0.2g and put into ready oil phase/water phase dispersion system, fully the pretreated zinc powder of dispersed with stirring;
C) adopt ultrasonic cleaning machine to carry out ultrasonic dispersion to the oil phase/water phase dispersion system that tentatively disperses pre-treatment zinc powder, ambient temperature, ultrasonic dispersion 8h, during this time every 2h dispersed with stirring liquid, ensures that zinc powder fully disperses not precipitate;
D) utilize dropper from dispersion liquid, to take out liquid, be added drop-wise on clean silicon chip, be placed in 50 DEG C of oven drying at low temperatures of drying machine and obtain Zinc oxide nanoparticle film.
The present embodiment adopts roll extrusion vibration mill to carry out 13h pre-treatment to zinc powder, taking oil phase/water phase system as medium, is aided with ultrasonic dispersion making ZnO nanometer particle film.The granular size inequality of the nanometer particle film that this embodiment prepares, impurity is more, can not form uniform film, this is because nano grain surface can be very high, in oil phase/water phase system, can play the effect of tensio-active agent, the different ratios of oil phase/water phase has formed the microemulsion of different-shape, causes granular size inhomogeneous, is not easy to control.
Claims (1)
1. the method with the direct making ZnO nanometer particle film of common Zn powder, adopt rolling-vibrating grinding machine under argon atmosphere to the pre-treatment of micron order zinc powder to nano level, and nano zinc powder normal temperature after treatment is stored in darkroom, it is characterized in that carrying out in accordance with the following steps:
A) by organic solvent hexanaphthene and conventional inorganic solution H
2o is mixedly configured into oil phase/water phase dispersion system, wherein hexanaphthene and H
2the volume ratio of O is 1:19;
B) take pretreated nano zinc powder according to nano zinc powder and oil phase/water phase dispersion system weight ratio 1:100, put into through steps A) the oil phase/water phase dispersion system that configures, fully dispersed with stirring obtains mixed solution;
C) by step B) mixed solution that obtains is placed in ultrasonic cleaning machine, ambient temperature, ultrasonic dispersion 8h, is uniformly mixed liquid every 2h during this time, ensures that zinc powder fully disperses;
D) utilize dropper to take out liquid from the supernatant liquid of mixed solution, be added drop-wise on clean silicon chip and be placed in drying machine, at 50 DEG C, oven drying at low temperature obtains Zinc oxide nanoparticle film.
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| CN106861670A (en) * | 2017-01-20 | 2017-06-20 | 上海理工大学 | A kind of method for improving nano zero-valence zinc catalysis activity |
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| US20110268963A1 (en) * | 2008-06-27 | 2011-11-03 | National instutute of advanced industrial science and technology | Method of producing structural member having prussian blue-type metal complex nanoparticles, structural member obtained by the method, substrate, electrochromic device, rectifying device, and photo responding device, using the structural member |
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Patent Citations (5)
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| CN101054267A (en) * | 2007-02-02 | 2007-10-17 | 广州菲迪材料科技研究有限公司 | Preparation method for ITO thin film |
| CN101229584A (en) * | 2008-02-27 | 2008-07-30 | 上海工程技术大学 | Process of preparing oxide layer on nanometer prill surface and uses thereof |
| US20110268963A1 (en) * | 2008-06-27 | 2011-11-03 | National instutute of advanced industrial science and technology | Method of producing structural member having prussian blue-type metal complex nanoparticles, structural member obtained by the method, substrate, electrochromic device, rectifying device, and photo responding device, using the structural member |
| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
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