CN1257311C - Method for preparing nano zinc oxide film of high ultraviolet absorption - Google Patents
Method for preparing nano zinc oxide film of high ultraviolet absorption Download PDFInfo
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- CN1257311C CN1257311C CN 200410017849 CN200410017849A CN1257311C CN 1257311 C CN1257311 C CN 1257311C CN 200410017849 CN200410017849 CN 200410017849 CN 200410017849 A CN200410017849 A CN 200410017849A CN 1257311 C CN1257311 C CN 1257311C
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Abstract
The present invention relates to a preparing method of nanometer zinc oxide film with high ultraviolet absorption. Firstly, zinc nitrate hexahydrate and six sub-methyl tetramine with the molar concentration proportion of 1:1 are dissolved respectively in methanol solution for preparing reaction solution for the growth of the film; then, a pretreated base plate is immersed in the prepared reaction solution for the growth of the film for 30 to 60 minutes, and a reaction is carried out by heating to 95 to 100 DEG C for 2 to 3 hours to obtain the tight zinc oxide film. The method of the present invention has simple operation, low cost and short producing cycle; the prepared film is composed of spherical nanometer zinc oxide granules with the average granule size of 120 nanometer, and the film has strong ultraviolet absorption and good permeability of visible light.
Description
Technical field
The invention belongs to the preparation method of inorganic thin film, it is strong to relate to a kind of ultraviolet absorption, the preparation method of the Nano zinc oxide film that visible light permeability is good.Be specifically related to adopt chemical solution method to prepare Nano zinc oxide film.
Background technology
Zinc-oxide film is a kind of good semiconductor material, it has good photoelectric functional owing to having bigger energy gap width (similar with gan), thereby have a wide range of applications in fields such as gas sensitive, luminescent material, photoelectric conversion material, piezoelectrics, can be used as transparent conductor, luminous element, solar cell window, optical waveguide, monochromatic field emission display, high frequency piezoelectric transducer, micro sensor bulk acoustic wave material and give birth to film Resonator on the surface-duided wave material, wave filter etc.Less about the uv-absorbing of zinc oxide nano film and visible light transmissive performance report in the past, and synthesize strong uv-absorbing and have the nano film material of good perviousness that zinc oxide is applied on the photoelectric material to visible light.The preparation method of nano zinc oxide material can be divided into vapor phase process and solution method.Vapor phase process comprises chemical vapor deposition (CVD), magnetron sputtering method, spray pyrolysis, pulsed laser deposition (PLD), atomic-layer epitaxial growth method and molecular beam epitaxy etc.; Solution method comprises sol-gel method, hydrolysis method, hydrothermal method, antiphase emulsifiable method, the precipitator method and electrochemical deposition method.Report about the preparation method of zinc-oxide film in recent years more, but these methods overwhelming majority concentrates on gas phase synthesis method, for example.There are shortcomings such as temperature of reaction height, equipment complexity, cost height, efficient be low in these gas phase process.Under comparing, advantage simple to operate, that cost is low, efficient is high that the chemical solution rule has.But this method is mainly used in the preparation of Zinc oxide nanoparticle or powder at present, and the preparation for thin-film material mainly concentrates on the electrochemical deposition preparation, and adopts simple solution-deposition method and solvent thermal rule that report is seldom arranged.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, providing a kind of has strong absorption and good to visible light permeability, simple to operate to UV-light, the preparation method of the zinc-oxide film that temperature of reaction is low, cost is low, production efficiency is high.
For realizing such purpose, in the technical scheme of the present invention, adopt chemical solution method to prepare zinc-oxide film.Zinc salt and ammonia source are dissolved in the methanol solution according to certain concentration and ratio respectively, after the solution clarification, pour in the tetrafluoroethylene reactor, the substrate of handling is immersed in the reaction soln for preparing, in pre-soaking after 30～60 minutes, be warming up to 95-100 ℃, react and to obtain the compact nanometer zinc-oxide film in 2～3 hours.The zinc-oxide film of preparation is made up of the spheric Zinc oxide particles, and median size is 120nm.
Preparation method of the present invention comprises following concrete steps:
1. the preparation of film growth reaction solution: zinc salt and ammonia source are dissolved in the methanol solution according to certain concentration and ratio respectively, are stirred to the solution clarification, can be prepared into reaction soln.
The said zinc salt of the present invention is a zinc nitrate hexahydrate; The ammonia source is that (HMT is commonly called as six methylene radical four ammonia: urotropine).
The concentration of the said zinc salt of the present invention is 0.005M～0.0075M.
The concentration in the said ammonia of the present invention source is 0.005M～0.0075M.
The volumetric molar concentration ratio in said zinc salt of the present invention and ammonia source is 1: 1
2. the pre-treatment of substrate: at first substrate is cut into the thick 2mm of the wide 12mm of long 40mm according to the size of ultraviolet ware, so that measure its ultraviolet absorption characteristic, be immersed in then in the vitriol oil of ebullient 98% 5～10 hours, be immersed in again in the acetone ultrasonic 30～60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
The said substrate of the present invention is a quartz substrate.
3. Nano zinc oxide film is synthetic: the growth response solution of the above-mentioned zinc oxide nanocrystalline for preparing is poured in the tetrafluoroethylene reactor, substrate was soaked in the above-mentioned film growth reaction soln for preparing 30～60 minutes, closed reactor, be warming up to 95-100 ℃, reacted 2～3 hours, reaction naturally cools to normal temperature after finishing, and takes out a large amount of deionized water rinsings of sample, can obtain Nano zinc oxide film through drying naturally after repeatedly washing.
Excellent results of the present invention is:
1. the product Nano zinc oxide film can simply be controlled by the concentration of reactant (zinc nitrate hexahydrate and urotropine) the absorptive character of UV-light and visible light.
2. need not to add tensio-active agent or polymkeric substance, avoided the cumbersome process of aftertreatment, thereby reduced cost.
3. because HMT is a kind of ammonia source that is heated and slowly decomposes, can be uniformly and zinc nitrate react, thereby can on substrate, evenly generate the nano zine oxide crystal.
4. methyl alcohol is a kind of lower boiling solvent, has higher vapour pressure under lower temperature, makes reaction soln viscosity reduce, and provides condition for obtaining the less nanocrystal of particle diameter.
5. because the chemical solution method temperature of reaction that the present invention adopts is low, have only 95～100 ℃, reaction times is short, only need 2～3 hours, reaction raw materials is cheap, only need zinc salt and urotropine commonly used, solvent methanol is recyclable to be utilized again, reaction system is airtight, can not pollute, thereby the inventive method is simple to operate, cost is low, the efficient height, the nano zine oxide crystal of preparation all is monocrystalline, and particle diameter is 15 nanometers, and these little Zinc oxide single crystals are assembled into the spheroidal particle that particle diameter is 120 nanometers on substrate, these particles are grown in substrate surface with the form of individual layer, be evenly distributed and closely, make the Nano zinc oxide film material of prepared one-tenth strong absorption be arranged, and visible light is had the good transparency UV-light.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the embodiment of the invention 1 resulting Nano zinc oxide film.
Fig. 2 is the electron scanning micrograph of the embodiment of the invention 1 resulting Nano zinc oxide film.
Among Fig. 2, a is the large-area scanning Electronic Speculum picture of film, and b is the amplification picture of a figure.
Fig. 3 is the transmission electron microscope photo and the electron diffraction picture thereof of the embodiment of the invention 1 resulting nano zine oxide crystal grain.
Among Fig. 3, a is the transmission electron microscope photo, and b is the electron diffraction picture.
Fig. 4 is the uv-visible absorption spectroscopy figure of the Nano zinc oxide film that obtains under different reactant concns.
Among Fig. 4, curve a-e is 0.0025M corresponding to different reactant concns: a; B is 0.005M; C is 0.0075M; D is 0.01M; E is 0.02M.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
1. the preparation of reaction soln: 0.0005mol zinc nitrate, six methylene radical four ammonia of 0.0005mol are dissolved in the 100ml methanol solution, are stirred to the solution clarification, can be prepared into the reaction solution of zinc-oxide film growth.
2. quartz plate that will the thick 2mm of the wide 12mm of long 40mm is immersed in the ebullient vitriol oil, and soak and immerse again in the acetone soln after 10 hours, ultrasonic 30 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. Nano zinc oxide film is synthetic: above-mentioned growth response solution according to the zinc oxide nanocrystalline that 1. prepares is poured in the tetrafluoroethylene reactor, to soak into according to the quartz substrate that 2. step is handled in the above-mentioned film growth reaction soln for preparing 30 minutes, closed reactor, be warming up to 100 ℃, reacted 2 hours, reaction naturally cools to normal temperature after finishing, and takes out a large amount of deionized water rinsings of sample, can obtain Nano zinc oxide film through drying naturally after repeatedly washing.
X-ray diffraction spectrogram such as Fig. 1 of resultant zinc-oxide film, prepared as seen from Figure 1 zinc oxide are hexagonal crystal shape (36-1451).The particle diameter of the zincite crystal that calculates according to the Scherrer formula is 15 nanometers.Electron scanning micrograph such as Fig. 2, prepared as seen from Figure 2 zinc-oxide film spheroidal particle is formed, and the particulate diameter is 120 nanometers, the particle alignment densification.For further studying the structure of Zinc oxide nanoparticle on the film, we scrape the zinc oxide on the film, and have children outside the state plan dispersion by force, adopt projection electron microscope to observe its crystalline structure and pattern.As shown in Figure 3, the particle of zinc oxide is made up of the littler crystal of size, and the crystalline size is about 15 nanometers, and its electron-diffraction diagram shows its single crystal structure.The ultraviolet-visible absorbing properties of prepared Nano zinc oxide film adopts the ultraviolet-visible absorption spectrometer to test (Fig. 4 curve b), and as seen from the figure, this thin-film material has strong absorption in the ultraviolet region, and visible region has the good transparency.The ultraviolet-visible absorbing properties of the prepared zinc oxide nano film reactant concn used with preparing this film has confidential relation, as Fig. 4 curve a, c, d.The ultraviolet absorption performance of prepared zinc oxide nano film strengthens along with the increase of concentration of reactants, but surpasses 0.005M (zinc oxide), and the enhancing amplitude weakens; Simultaneously, the visible light of prepared zinc oxide nano film material also strengthens with the increase of concentration of reactants, but surpasses 0.005M (zinc oxide), and the enhancing amplitude is just strong.Under comprehensive the comparison, we find that when concentration of reactants was 0.005M-0.0075M, the over-all properties of thin-film material was best, and promptly prepared nano film material has strong absorption in the ultraviolet region, and visible region has the good transparency.
Embodiment 2:
1. the preparation of reaction soln: 0.00075mol zinc nitrate, six methylene radical four ammonia of 0.00075mol are dissolved in the 100ml methanol solution, are stirred to the solution clarification, can be prepared into the reaction solution of zinc-oxide film growth.
2. quartz plate that will the thick 2mm of the wide 12mm of long 40mm is immersed in the ebullient vitriol oil, and soak and immerse again in the acetone soln after 8 hours, ultrasonic 45 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. Nano zinc oxide film is synthetic: above-mentioned growth response solution according to the zinc oxide nanocrystalline that 1. prepares is poured in the tetrafluoroethylene reactor, to soak into according to the quartz substrate that 2. step is handled in the above-mentioned film growth reaction soln for preparing 45 minutes, closed reactor, be warming up to 100 ℃, reacted 2.5 hours, reaction naturally cools to normal temperature after finishing, and takes out a large amount of deionized water rinsings of sample, can obtain Nano zinc oxide film through drying naturally after repeatedly washing.
Embodiment 3:
1. the preparation of reaction soln: 0.0005mol zinc nitrate, six methylene radical four ammonia of 0.0005mol are dissolved in the 100ml methanol solution, are stirred to the solution clarification, can be prepared into the reaction solution of zinc-oxide film growth.
2. quartz plate that will the thick 2mm of the wide 12mm of long 40mm is immersed in the ebullient vitriol oil, and soak and immerse again in the acetone soln after 5 hours, ultrasonic 60 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. Nano zinc oxide film is synthetic: above-mentioned growth response solution according to the zinc oxide nanocrystalline that 1. prepares is poured in the tetrafluoroethylene reactor, to soak into according to the quartz substrate that 2. step is handled in the above-mentioned film growth reaction soln for preparing 60 minutes, closed reactor, be warming up to 95 ℃, reacted 3 hours, reaction naturally cools to normal temperature after finishing, and takes out a large amount of deionized water rinsings of sample, can obtain Nano zinc oxide film through drying naturally after repeatedly washing.
Claims (2)
1, a kind of preparation method of strong uv-absorbing Nano zinc oxide film, it is characterized in that comprising: with the volumetric molar concentration ratio is 1: the zinc nitrate hexahydrate of l and six methylene radical four ammonia are dissolved in the methanol solution respectively, described zinc nitrate hexahydrate is 0.005mol/l～0.0075mol/l with six relative concentration in methanol solution of methylene radical four ammonia zinc salts, be stirred to the solution clarification, be prepared into the film growth reaction soln; Substrate was immersed in the vitriol oil of ebullient 98% 5～10 hours, was immersed in again in the acetone ultrasonic 30～60 minutes, stand-by with in vacuum drying oven, drying behind the deionized water rinsing; The above-mentioned reaction soln for preparing is poured in the tetrafluoroethylene reactor, substrate was soaked in the reaction soln 30～60 minutes, closed reactor, be warming up to 95-100 ℃, reacted 2～3 hours, reaction naturally cools to normal temperature after finishing, and takes out the sample deionized water rinsing, dries naturally to obtain the Nano zinc oxide film that median size is 120nm.
2, the preparation method of strong uv-absorbing Nano zinc oxide film as claimed in claim 1 is characterized in that described substrate is a quartz plate.
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| CN100509998C (en) * | 2005-11-26 | 2009-07-08 | 中国科学院合肥物质科学研究院 | Zinc oxide nano sheet film materials with UV luminescent characteristics and method for preparing same |
| CN100376712C (en) * | 2006-01-24 | 2008-03-26 | 北京工业大学 | Method for preparing ZnO nanostructure photocatalytic film with p-n junction |
| CN105506584B (en) * | 2014-01-24 | 2018-04-13 | 重庆文理学院 | A kind of preparation method of electric thin |
| CN109968769A (en) * | 2019-03-29 | 2019-07-05 | 中国科学院上海技术物理研究所 | A kind of low-cost large-area Non-energy-consumption radiation refrigeration laminated film and preparation method |
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