CN103276445A - Method for liquid-phase synthesis of one-dimensional nano array ZnO thin film by using seed auxiliary method - Google Patents
Method for liquid-phase synthesis of one-dimensional nano array ZnO thin film by using seed auxiliary method Download PDFInfo
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Abstract
The invention discloses a method for liquid-phase synthesis of a one-dimensional nano array ZnO thin film by using a seed auxiliary method. The method substantially comprises the following two steps of: (1) sputtering a layer of Zn (50-200nm) on FTO conductive glass with a clean surface, calcining in a muffle furnace at 300-500 DEG C to obtain a dense ZnO seed layer; and (2) placing the FTO with the seed layer obtained in the step (1) in a zinc salt solution and further hydrolyzing to obtain the required one-dimensional nano array ZnO. According to the method, the seed layer can be prepared without configuring and spinning the solution, the problem of uneven film formation is solved, the required ZnO can be synthesized in a short time during the subsequent hydrolysis, and the obtained ZnO has good crystallinity. The method is simple and suitable for large-scale production.
Description
Technical field
The invention belongs to material chemistry technical field, relate in particular to a kind of method with the synthetic ZnO film of seed auxiliary law liquid phase.
Background technology
ZnO is a kind of important II-VI direct band gap semiconductor material with wide forbidden band.Under room temperature, can band gap be 3.37eV, exciton bind energy, up to 60meV, be conducive to realize efficient Laser emission, and material has the characteristics such as nontoxic, environmental protection and wide material sources.Nano level ZnO compares with common ZnO, nano-ZnO shows many excellences and special performance, as piezoelectric property, luminescence, transparent conductivity, biological safety and adaptability etc., make it in fields such as piezoelectric, ultraviolet light detector, field effect transistor, surface acoustic wave, solar cell, gas sensor, biosensors, gather around and have broad application prospects.
At present, the preparation method of nano zinc oxide material mainly contains chemical Vapor deposition process, metal organic vapor growth method, radio-frequency magnetron sputter method, hydrothermal method, template, microemulsion method etc.According to feed states, the preparation method mainly is divided into two kinds of vapor phase process and liquid phase methods.
The Dou of Oceanography Institute Of Zhejiang opens to rise and delivered " the synthetic ZnO nanorod of seed auxiliary chemical method and sign thereof " literary composition in " semiconductor technology ", and the author first uses Zn (CH
3cOO)
22H
2o, CH
3oH, KOH reaction obtains the ZnO seed, then uses Zn (NO
3)
26H
2o, PVA, DTA and deionized water are made into mixing solutions, and the ZnO seed that finally will obtain before joins in this mixing solutions and obtains ZnO nanorod.But prepared ZnO is powder, need further spin coating calcining film forming just can make solar cell device.Fenghua Zhao etc. delivers " Complex ZnO nanotree arrays with tunable top; stem and branch structures " literary composition in " Nanoscale ", and in literary composition, the author synthesizes the controlled graded structure of pattern by the concentration of controlling ethylenediamine solution in the zinc metal sheet substrate.S.Sarkar etc. deliver in " A low temperature in situ facile technique to enhance ultraviolet emission of zinc oxide nanorods and its mechanistic insights " literary composition on " Chemical Physics Letters ", at first sputter one deck zinc oxide seed layer on substrate of glass, then utilize this zinc oxide seed layer and Zn (CH
3cOO)
22H
2o, zinc powder, HMT(vulkacit H) and the CTAB(cetyl trimethylammonium bromide) in 80 ℃ of deionized waters, react 12 hours, the nanometer rod zinc-oxide film obtained.Jinping Liu etc. delivers " Vertically Aligned 1D ZnO Nanostructures on Bulk Alloy Substrates:Direct Solution Synthesis; Photoluminescence; and Field Emission " on " J. Phys. Chem. C ", and in literary composition, the author uses Zn (NO
3)
26H
2o and ammoniacal liquor synthesize the zinc oxide of the patterns such as nanometer rod, nanometer pencil under 70 ℃ by the concentration that changes ammoniacal liquor.Junsheng Yu etc. delivers " Size-selected growth of transparent well-aligned ZnO nanowire arrays " in " Nanoscale ", in literary composition, zinc acetate is dissolved in ethanolic soln and obtains mixing solutions, this solution is spun in the ITO substrate, then under 350 ℃, calcining 20min obtains the ZnO Seed Layer again.Use subsequently Zn (NO
3)
26H
2o, HMT generate ZnO nano-wire at the enterprising one-step hydrolysis of ZnO Seed Layer.But the dependence tensio-active agent, the treatment step that in aforesaid method, exist are loaded down with trivial details, in reactant containing toxic substance, the product shortcoming such as pure and mild complex process not.Therefore, urgently developing green environmental protection, process are simple, the nano-array ZnO film synthetic technology of operational safety.
Summary of the invention
The object of the present invention is to provide a kind of method that equipment is simple, technique is controlled, environmental friendliness prepares the one-dimensional nano-array ZnO film with excellent properties.
Problem to be solved by this invention is: overcome that the dependence tensio-active agent, the treatment step that exist in current making ZnO crystal method are loaded down with trivial details, in reactant containing toxic substance, the product shortcoming such as pure and mild complex process not, a kind of method with seed auxiliary law liquid phase synthesizing one-dimensional nano-array ZnO film is provided.
The present invention is with liquid phase synthesizing one-dimensional nano-array ZnO film under seed auxiliary law low temperature, and its concrete steps that prepare are:
The first step: sputter thickness 50 ~ 200nmZn in the FTO substrate, put into the retort furnace calcining and obtain the ZnO Seed Layer;
Second step: 0.035 ~ 0.05mol/L zinc solution is stirred and splashes into ammoniacal liquor until the solution clarification;
The 3rd step: mixing solutions is transferred in reactor, the ZnO Seed Layer is placed in to solution, react 3～10h and get final product in 50 ~ 90 ℃ of baking ovens;
The 4th step: the product that reaction is obtained takes out, cleans, dries.
FTO substrate described in the first step is the fin oxide condutire glass of mixing fluorine; Described calcining temperature is 300～500 ℃.
Zinc salt described in second step is soluble zinc salt, is selected from one or more in zinc acetate, zinc nitrate or zinc sulfate etc.; The mixing solutions that the solvent of described zinc solution is water or water and dehydrated alcohol; The volume ratio of described ammoniacal liquor and zinc solution is (1-3): 20; The concentration of described ammoniacal liquor is 25wt%.
The reactor that reactor described in the 3rd step is tetrafluoroethylene.
Bake out temperature described in the 4th step is below 60 ℃.
advantage of the present invention:
1, simple, the environmental protection of preparation method.Remove the preparation of Seed Layer, the preparation of follow-up ZnO array is carried out under low temperature (50 ~ 90 ℃), and the reaction times does not need very long, generally about half hour, can generate required array, and reaction conditions is gentleer.
2, pattern is controlled.By changing composition, temperature and the reaction times of solvent in reaction system, reach the control to the ZnO pattern in experiment.
3, product pattern looks perfection, good crystallinity, repetition rate is high.By the resulting ZnO of seed auxiliary law, be the one-dimensional nano-array array, diameter range is 60 ~ 200nm, and length range is 100nm ~ 1 μ m, and pattern is even and fine and close, length-to-diameter ratio is large, the uniform particle diameter degree is high; And obviously, peak intensity is very strong, good crystallinity for orientation on (002) direction.
4, raw material is cheap, is applicable to scale operation.Can one time to produce a large amount of Seed Layer is stand-by, and in experiment, required raw material is all very cheap, and source is wide, can scale operation, be convenient to industrialization and technology popularization.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
The XRD figure spectrum of the one-dimensional nano-array ZnO film that Fig. 2 is embodiment 1 preparation.
The SEM photo (a is 3h, and b is 6h, and c is 10h) of the one-dimensional nano-array ZnO film that Fig. 3 is embodiment 1 preparation.
The XRD figure spectrum of the one-dimensional nano-array ZnO film that Fig. 4 is embodiment 4 preparations.
The SEM photo (a is 50 ℃, and b is 70 ℃, and c is 90 ℃) of the one-dimensional nano-array ZnO film that Fig. 5 is embodiment 4 preparations.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
In Fig. 1, a kind of method for preparing the one-dimensional nano-array ZnO film of the present invention comprises following concrete steps:
One, the Zn that sputter thickness is 50-200nm in clean FTO substrate, put into retort furnace and calcine the ZnO Seed Layer that obtains one deck densification under 300-500 ℃;
Two, configure zinc acetate, zinc nitrate or the solution of zinc sulfate 20ml of 0.035 ~ 0.05mol/L in beaker, beaker is placed on magnetic stirring apparatus and stirs, splash into the commercially available 25wt% ammoniacal liquor of 1-3mL when stirring, in whipping process, mixing solutions can become clarification by muddiness;
Three, mixing solutions is transferred in the tetrafluoroethylene reactor of 28mL, will be had subsequently the FTO glass of Seed Layer to put into reactor, put into baking oven and react 3～10h get final product under 50 ~ 90 ℃ of low temperature;
Four, product reaction obtained takes out, and in deionized water and ethanol solution, cleans respectively, under 60 ℃, dries subsequently.
Further illustrate the preparation method of one-dimensional nano-array ZnO film below by embodiment
.
embodiment 1
1, the cleaning of FTO conductive glass, specifically be divided into following step.
ultrasonic cleaning 15min in liquid detergent solution;
deionized water for ultrasonic 5min, this step repeats twice;
at hydrogen peroxide: 80 ℃ of lower water-baths in the mixing solutions of ammoniacal liquor: deionized water=1:1:2, until there is no Bubble formation;
deionized water for ultrasonic 5min, repeat twice equally;
under 60 ℃, dry stand-by;
2, the Zn of sputter 100nm in the FTO substrate, put into 400 ℃ of retort furnaces and calcined, and obtains the ZnO Seed Layer of one deck densification;
3, the zinc salt solution 20mL of 3 groups of 0.05mol/L of configuration in beaker, be placed in magnetic stirring apparatus and stir.In the process stirred, slowly splash into the commercially available about 1mL of 25wt% ammoniacal liquor, now solution can be by the muddiness clarification that becomes.Subsequently mixing solutions is transferred in the reactor of 28mL tetrafluoroethylene, then will be had the FTO substrate of Seed Layer to put into reactor, in 70 ℃ of baking ovens, react respectively 3h (Fig. 3 a), 6h (Fig. 3 b), 10h (Fig. 3 c);
4, after reacting end, take out the gained sample, carry out respectively rinsing in deionized water and dehydrated alcohol, dry in the constant temperature blast drying oven of 60 ℃ afterwards, it is to be tested that after drying, the sample hose preservation is put in taking-up.Afterwards 3 groups of samples are carried out to XRD and SEM and characterize, XRD and SEM the results are shown in Figure 2 and Fig. 3.
1, the cleaning of FTO conductive glass, with embodiment 1;
2, the Zn of sputter 50nm in the FTO substrate, put into 300 ℃ of retort furnaces and calcined, and obtains the ZnO Seed Layer of one deck densification;
3, the zinc salt solution 20mL of 3 groups of 0.035mol/L of configuration in beaker, be placed in magnetic stirring apparatus and stir.In the process stirred, slowly splash into the commercially available about 2mL of 25% ammoniacal liquor, now solution can be by the muddiness clarification that becomes.Subsequently mixing solutions is transferred in the reactor of 28mL tetrafluoroethylene, then will be had the FTO substrate of Seed Layer to put into reactor, in 70 ℃ of baking ovens, react respectively 3h, 6h, 10h;
4, after reaction finishes, take out the gained sample, carry out respectively rinsing in deionized water and dehydrated alcohol, dry in the constant temperature blast drying oven of 60 ℃ afterwards, after drying, take out, obtain the one-dimensional nano-array ZnO film of different hydrothermal treatment consists under the time.
1, the cleaning of FTO conductive glass, with embodiment 1;
2, the Zn of sputter 200nm in the FTO substrate, put into 500 ℃ of retort furnaces and calcined, and obtains the ZnO Seed Layer of one deck densification;
3, the zinc salt solution 20mL of 3 groups of 0.05mol/L of configuration in beaker, be placed in magnetic stirring apparatus and stir.In the process stirred, slowly splash into the commercially available about 3mL of 25% ammoniacal liquor, now solution can be by the muddiness clarification that becomes.Subsequently mixing solutions is transferred in the reactor of 28mL tetrafluoroethylene, then will be had the FTO substrate of Seed Layer to put into reactor, react 3h respectively in the baking oven of 50 ℃, 70 ℃, 90 ℃;
4, after reacting end, take out the gained sample, carry out respectively rinsing in deionized water and dehydrated alcohol, dry in the constant temperature blast drying oven of 60 ℃ afterwards, it is to be tested that after drying, the sample hose preservation is put in taking-up.Obtain the one-dimensional nano-array ZnO film under different hydrothermal temperatures.
embodiment 4
1, the cleaning of FTO conductive glass, with embodiment 1;
2, the Zn of sputter 100nm in the FTO substrate, put into 400 ℃ of retort furnaces and calcined, and obtains the ZnO Seed Layer of one deck densification;
3, in beaker the configuration 3 groups of 0.045mol/L zinc solution 20mL (solvent is 10mLH
2o and 10mL dehydrated alcohol), be placed in magnetic stirring apparatus and stir.In the process stirred, slowly splash into the commercially available about 1mL of 25% ammoniacal liquor, now solution can be by the muddiness clarification that becomes.Subsequently mixing solutions is transferred in the reactor of 28mL tetrafluoroethylene, then will be had the FTO substrate of Seed Layer to put into reactor, at 50 ℃, (Fig. 5 a), react 3h in the baking oven of 70 ℃ (Fig. 5 b), 90 ℃ (Fig. 5 c) respectively;
4, after reaction finishes, take out the gained sample, carry out respectively rinsing in deionized water and dehydrated alcohol, dry in the constant temperature blast drying oven of 60 ℃ afterwards, after drying, take out, put into sample hose and preserve to be tested.Afterwards 3 groups of samples are carried out to XRD and SEM sign, XRD and SEM the results are shown in Figure 4 Fig. 5.
From Fig. 2-5, the ZnO of the synthetic gained of the auxiliary liquid phase of the seed adopted in the present invention is orientated obviously on (002) direction, and crystallinity is better, and pattern is one-dimensional nano-array.By to solvent system and the change of temperature of reaction and time, reached the purpose that the ZnO pattern is changed.
Claims (7)
1. a seed is assisted liquid phase synthesizing one-dimensional nano-array ZnO film method, it is characterized in that comprising following concrete steps:
The first step: sputter thickness 50 ~ 200nmZn in the FTO substrate, put into the retort furnace calcining and obtain the ZnO Seed Layer;
Second step: 0.035 ~ 0.05mol/L zinc solution is stirred and splashes into ammoniacal liquor until the solution clarification;
The 3rd step: mixing solutions is transferred in reactor, the ZnO Seed Layer is placed in to solution, react 3～10h and get final product in 50 ~ 90 ℃ of baking ovens;
The 4th step: the product that reaction is obtained takes out, cleans, dries.
2. the auxiliary liquid phase synthesizing one-dimensional nano-array ZnO film method of seed according to claim 1, is characterized in that the FTO substrate described in the first step is the fin oxide condutire glass of mixing fluorine; Described calcining temperature is 300～500 ℃.
3. the auxiliary liquid phase synthesizing one-dimensional nano-array ZnO film method of seed according to claim 1, is characterized in that the zinc salt described in second step is soluble zinc salt.
4. according to the auxiliary liquid phase synthesizing one-dimensional nano-array ZnO film method of the described seed of claim 1 or 3, it is characterized in that described zinc salt is selected from one or more in zinc acetate, zinc nitrate or zinc sulfate.
5. seed according to claim 1 is assisted liquid phase synthesizing one-dimensional nano-array ZnO film method, the mixing solutions that the solvent that it is characterized in that the zinc solution described in second step is water or water and dehydrated alcohol; The volume ratio of described ammoniacal liquor and zinc solution is (1-3): 20; The concentration of described ammoniacal liquor is 25wt%.
6. the auxiliary liquid phase synthesizing one-dimensional nano-array ZnO film method of seed according to claim 1, is characterized in that the reactor that the reactor described in the 3rd step is tetrafluoroethylene.
7. the auxiliary liquid phase synthesizing one-dimensional nano-array ZnO film method of seed according to claim 1, is characterized in that the bake out temperature described in the 4th step is below 60 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105859155A (en) * | 2016-05-23 | 2016-08-17 | 天津城建大学 | Method for preparing super-hydrophobic self-cleaning glass based on seed layer structure control |
| CN108893728A (en) * | 2018-09-06 | 2018-11-27 | 黑龙江省科学院高技术研究院 | The preparation method of ultra-thin ZnO nano chip arrays with high-specific surface area |
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| CN1995481A (en) * | 2006-12-13 | 2007-07-11 | 天津大学 | Method for preparing diverse microcosmic appearance zinc oxide film |
| US20090235862A1 (en) * | 2008-03-24 | 2009-09-24 | Samsung Electronics Co., Ltd. | Method of manufacturing zinc oxide nanowires |
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| CN1995481A (en) * | 2006-12-13 | 2007-07-11 | 天津大学 | Method for preparing diverse microcosmic appearance zinc oxide film |
| US20090235862A1 (en) * | 2008-03-24 | 2009-09-24 | Samsung Electronics Co., Ltd. | Method of manufacturing zinc oxide nanowires |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105859155A (en) * | 2016-05-23 | 2016-08-17 | 天津城建大学 | Method for preparing super-hydrophobic self-cleaning glass based on seed layer structure control |
| CN105859155B (en) * | 2016-05-23 | 2019-05-28 | 天津城建大学 | The preparation method of super-hydrophobic automatic cleaning glass based on seed layer structure control |
| CN108893728A (en) * | 2018-09-06 | 2018-11-27 | 黑龙江省科学院高技术研究院 | The preparation method of ultra-thin ZnO nano chip arrays with high-specific surface area |
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Application publication date: 20130904 |