CN101608305B - Method for preparing ZnO nanowire array - Google Patents
Method for preparing ZnO nanowire array Download PDFInfo
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- CN101608305B CN101608305B CN200910203556XA CN200910203556A CN101608305B CN 101608305 B CN101608305 B CN 101608305B CN 200910203556X A CN200910203556X A CN 200910203556XA CN 200910203556 A CN200910203556 A CN 200910203556A CN 101608305 B CN101608305 B CN 101608305B
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Abstract
The invention relates to a controllable preparation method of needle-shaped and hexagonal columnar ZnO nanowire arrays in the technical field of ZnO nano-material preparation. The method for preparing a ZnO film comprises the following steps of: firstly preparing a silver film or a copper film on the substrate material, and then immersing the substrate into 5-120mM zinc nitrate aqueous solution and 10-30mM dimethyl amine boron alkane aqueous solution, the total volume of which is 50ml, keeping the temperature of the solution within 60-90 DEG C, and finally obtaining a zinc oxide film on the substrate after full reaction. The preparation method can realize the forming of the copper or silver film on the substrate with a magnetron sputtering method, or a vacuum evaporation method, or a vacuum sputtering method, and can also polish the surface of the substrate of copper so as to obtain a surface on which zinc oxide Nazi arrays can grow.
Description
Technical field
The present invention relates to the preparation method of ZnO film, particularly the controllable method for preparing of needle-like in the preparing technical field of ZnO nano material and hexagonal column ZnO nano-wire array.
Background technology
The One-Dimensional ZnO nano material has unique electricity, optics, photoelectricity and piezoelectric property; Especially the ZnO nano-wire array that exists with array format is with a wide range of applications, for example in fields such as nano generator, solar cell, field emission electron body, photochemical catalysis, transmitter and laser apparatus.The optics of ZnO nano material and electrical properties and the microstructure of self are very responsive, and therefore effectively the growth of control ZnO nano wire and microstructure thereof are just very important.
The One-Dimensional ZnO preparation of nanomaterials is divided into vapor phase process and liquid phase method two big classes, and wherein vapor phase process comprises magnetron sputtering, chemical vapour deposition, pulsed laser deposition and molecular beam epitaxy etc.; Liquid phase method comprises hydrothermal method, template, microemulsion method, thermal decomposition method and catalytic growth method etc.Two big types of preparing methods respectively have advantage, but compare vapor phase process, advantage such as liquid phase method has that synthesis temperature is low, equipment is simple, easy-regulating and high deposition rate and receive investigator's attention.
The controlled ZnO of preparing nano-wire array is design and the prerequisite for preparing various devices on specific substrate.The prior art disclosed method is the sublayer that is pre-formed ZnO film in substrate material surface, then substrate is immersed in the mixing solutions of the zinc salt prepare and amine tensio-active agent, can on the ZnO sublayer, grow the ZnO nano wire.Adopt laser deposition or ion sputtering method to form the ZnO sublayer respectively like Chinese invention patent 200810028488.3 and 200810122113.3 in substrate material surface; Then substrate is inserted in the mixing solutions of zinc salt and amine tensio-active agent, grow the ZnO nano-wire array at substrate surface.From the technology of these preparation ZnO nano-wire arrays, all exist the reaction times long, sedimentation rate is not high, need shortcomings such as HTHP and microstructure be wayward.In addition, mostly prior art is preparation ZnO nano wire on the substrate of ZnO sublayer, because the sublayer is a semi-conductor, this structure may receive certain restriction in application.
Summary of the invention
The present invention provide can overcome prior art insufficient a kind of easy, effectively control the method for ZnO nano-wire array structure.
Method of the present invention is that the substrate surface with copper carries out polished finish; Then substrate is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 5～120mM that TV is 50ml; Keeping solution temperature is 60～90 ℃, fully can on substrate, obtain zinc-oxide film after the reaction.
Another kind of method of the present invention is at first at glass, silicon; The sublayer of perhaps preparing silver or copper on the substrate material such as pottery; Then substrate is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 5～120mM that TV is 50ml; Keeping solution temperature is 60～90 ℃, fully can on substrate, obtain zinc-oxide film after the reaction.
The present invention forms the sublayer of silver or copper on substrate material method can be vacuum evaporation, perhaps method such as vacuum sputtering.
The present invention also can adopt chemical method to form the sublayer of silver at substrate surface on glass substrate material.
Adopt chemical method to be at the preferred method that substrate material surface forms the sublayer of silver:
A. glass substrate ultrasonic cleaning in zero(ppm) water, alcohol, acetone soln respectively, remove impurity, the oil stain on surface;
B. be immersed in cleaned substrate at normal temperatures the SnCl of 5-10g/l
2In the mixed in hydrochloric acid sensitized solution of 0.08M, soaked 0.5 to 5 minute;
C. after taking out, be immersed in the zero(ppm) water about 2 to 20 seconds;
D. take out then, be immersed in glass substrate the normal temperature AgNO of 1-10g/l again
3In the treating water solution, soaked 1 to 6 minute;
E. repeating step b-d is become dark brown until glass substrate material for several times by clear transparent.
Adopt the present invention; Different concns through the control zinc nitrate aqueous solution; Can obtain the zinc-oxide film of different shape; For example: will have in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of the substrate material of silver or copper or 5～10mM that copper sheet is immersed in 50ml and handle, and can obtain needle-like ZnO nano-wire array; To have in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of the substrate material of silver or copper or 20～70mM that copper sheet is immersed in 50ml and handle, can obtain the cross section is hexagonal column ZnO nano-wire array; To have in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of the substrate material of silver or copper or 80～120mM that copper sheet is immersed in 50ml and handle, can obtain the ZnO film of sheet or polycrystalline structure.
Method operation of the present invention is extremely easy, and sedimentation rate is high, and cost is low, can on conductive substrates, large-area preparation go out the ZnO nano-wire array, helps suitability for industrialized production and the application in field of electronic devices.Adopt chemical method on Ag, Cu substrate, to prepare the controlled ZnO nano-wire array of microstructure.Ag, Cu are modal conduction and electrode materials, prepare the ZnO nano wire above that and compare with preparation ZnO nano wire on the substrate of ZnO sublayer, and the present invention more helps the application of ZnO nano-wire array in electron device.
Description of drawings
Fig. 1 plates the stereoscan photograph of Ag glass substrate.
Fig. 2 plates the X-ray diffraction spectrum of the needle-like ZnO nano-wire array of growing on the Ag glass substrate.
Fig. 3 plates the ESEM Photomicrograph of the acicular ZnO nano-wire array of growing on the Ag glass substrate.
Fig. 4 plates the ESEM Photomicrograph of the ZnO nano-wire array of the hexagonal column of growing on the Ag glass substrate.
The ESEM Photomicrograph of the needle-like ZnO nano-wire array of Fig. 5 Cu sheet substrate surface growth.
The ESEM Photomicrograph of the needle-like ZnO nano-wire array of Fig. 6 SiCu substrate surface growth.
Embodiment
Through embodiment method of the present invention is further specified below.
Embodiment 1
Glass is cut into the substrate of 12 * 24 * 0.5mm size, is plating Ag on the glass substrate as follows: glass substrate ultrasonic cleaning in zero(ppm) water, alcohol, acetone soln respectively, remove impurity, the oil stain on surface;
Be immersed in cleaned substrate at normal temperatures the SnCl of 5-10g/l
2In the mixed in hydrochloric acid sensitized solution of 0.08M, soaked 0.5 to 8 minute;
After the taking-up, be immersed in the zero(ppm) water about 2 to 40 seconds;
Take out then, be immersed in glass substrate the normal temperature AgNO of 1-10g/l again
3In the activated water solution, soaked 1 to 10 minute;
Repeating step b-d is for several times become dark brownly by clear transparent until glass substrate material, show the activation success.
The core of above-mentioned steps is to take place a Sn
2+Reduction Ag
+Redox reaction for Ag simple substance.The active substrate stereoscan photograph of plating Ag is seen Fig. 1, and visible its surface is by the Ag granulometric composition of 10-20nm.
Preparation 10mM Zn (NO
3)
2With 30mM DMAB mixing solutions 50ml; Place 90 ℃ of water-baths, will plate the Ag substrate and immerse in the mixing solutions, react and to generate acicular ZnO nano-wire array in 30 minutes; Referring to accompanying drawing 2; Its X-ray diffraction spectrum is seen accompanying drawing 2, and (0002) diffraction peak is a highest peak, shows to tend to grow perpendicular to substrate surface in [0001] crystal orientation of ZnO.Stereoscan photograph is seen accompanying drawing 3, and visible ZnO has acicular structure, and mean diameter is 40nm, and length is about 300nm.The sedimentation velocity that also can estimate the ZnO nano-wire array is about 10nm/min.
Zn (the NO of lower concentration
3)
2Help generating acicular structure.Zn (the NO of 5-10mM
3)
2Concentration is the top condition of preparation needle-like ZnO nano-wire array on the Ag substrate.
Embodiment 2
The preparation of plating Ag glass substrate is identical with example 1.
Preparation 50mM Zn (NO
3)
2With 10mM DMAB mixing solutions 50ml, place 90 ℃ of water-baths, substrate immerses wherein, reacts 30 minutes, can generate hexagonal column ZnO nano-wire array.Stereoscan photograph is seen accompanying drawing 4, and the diameter of visible nano wire is 80nm, the about 300nm of length.
The condition that generates hexagonal column ZnO nano-wire array is control Zn (NO
3)
2Concentration is between 20-70mM.We test discovery, greater than the Zn (NO of 80mM
3)
2Concentration is unfavorable for obtaining nano-wire array, and can prepares sheet or polycrystalline ZnO film.
Embodiment 3
(15 * 15 * 0.7mm) immerse in the embodiment 1 described solution Cu sheet of 1500 order sand paper polishing, and insulation is 30 minutes in 90 ℃ of water-baths.Stereoscan photograph is seen accompanying drawing 5, and the surface of lint shape is exactly acicular ZnO nano-wire array, mean diameter 40nm, and length is about 300nm.
Embodiment 4
(the thick Cu of magnetron sputtering method sputter one deck 50nm is adopted on 10 * 10mm) surfaces, and this substrate is immersed in the embodiment 1 described solution, and insulation is 30 minutes in 90 ℃ of water-baths at (111) Si sheet.Stereoscan photograph is seen accompanying drawing 6, the about 30nm of the mean diameter of acicular ZnO nano-wire array, and length is about 300nm.Because the surface of Si substrate of plating Cu is very smooth, therefore, can prepare uniform more ZnO nano-wire array with embodiment 3 contrasts.
Related experiment also shows, when the concentration of the zinc nitrate aqueous solution that is used to handle substrate during at 80～120mM, can on substrate, obtain the ZnO film of sheet or polycrystalline structure.
Claims (7)
1. the method for preparing ZnO film; It is characterized in that at first on substrate material, preparing the sublayer of silver; Then substrate is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 5～120mM that TV is 50mL; Keeping solution temperature is 60～90 ℃, fully can on substrate, obtain zinc-oxide film after the reaction.
2. method according to claim 1 is characterized in that the method for vacuum evaporation, and perhaps the method for vacuum sputtering forms the sublayer of silver on substrate.
3. method according to claim 1 is characterized in that adopting chemical method to form the sublayer of silver at glass substrate surface.
4. method according to claim 3 is characterized in that used chemical method in the method that substrate surface forms the sublayer of silver is:
A. glass substrate ultrasonic cleaning in zero(ppm) water, alcohol, acetone soln respectively, remove impurity, the oil stain on surface;
B. be immersed in cleaned substrate at normal temperatures the SnCl of 5-10g/L
2In the mixed in hydrochloric acid sensitized solution of 0.08M, soaked 0.5 to 5 minute;
C. after taking out, be immersed in the zero(ppm) water 2 to 20 seconds;
D. take out then, be immersed in glass substrate the normal temperature AgNO of 1-10g/L again
3In the treating water solution, soaked 1 to 6 minute;
E. repeating step b-d is become dark brown until glass substrate material for several times by clear transparent.
5. according to the described arbitrary method of claim 1 to 4, it is characterized in that the substrate material that has silver is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 5～10mM of 50mL and handle, obtain needle-like ZnO nano-wire array.
6. according to the described arbitrary method of claim 1 to 4; The substrate material that it is characterized in that having silver is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 20～70mM of 50mL and handles, and obtaining the cross section is hexagonal column ZnO nano-wire array.
7. according to the described arbitrary method of claim 1 to 4; The substrate material that it is characterized in that having silver is immersed in the dimethyamine borane aqueous solution of zinc nitrate aqueous solution and 10～30mM of 80～120mM of 50mL and handles, and obtains the ZnO film of sheet or polycrystalline structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101853973A (en) * | 2010-05-07 | 2010-10-06 | 北京理工大学 | Photo-electrochemical cell with nanostructure for solar hydrogen production and preparation method thereof |
| CN101962269B (en) * | 2010-09-14 | 2012-11-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of superhydrophobic antireflection zinc oxide nano needle array |
| CN102092774B (en) * | 2010-12-28 | 2012-05-23 | 电子科技大学 | Preparation method of zinc oxide nano linear array |
| CN102503550B (en) * | 2011-11-07 | 2013-05-08 | 上海交通大学 | Method for preparing zinc oxide nanowire film |
| CN103569953B (en) * | 2013-11-12 | 2016-01-20 | 无锡英普林纳米科技有限公司 | The preparation method of the polymer fiber bundle that cross section is cross |
| CN115518641A (en) * | 2022-10-10 | 2022-12-27 | 西南交通大学 | Preparation method and application of foam nickel/zinc oxide nano-array photocatalytic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736876A (en) * | 2005-07-14 | 2006-02-22 | 天津大学 | Method for large scale quick preparation of one-dimension zinc oxide array thin film in aqueous solution |
| CN101045991A (en) * | 2007-04-30 | 2007-10-03 | 四川大学 | Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film |
| CN101234855A (en) * | 2007-02-01 | 2008-08-06 | 四川大学 | On-site chemical modification method for preparing zinc oxide nano-stick array thin film and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736876A (en) * | 2005-07-14 | 2006-02-22 | 天津大学 | Method for large scale quick preparation of one-dimension zinc oxide array thin film in aqueous solution |
| CN101234855A (en) * | 2007-02-01 | 2008-08-06 | 四川大学 | On-site chemical modification method for preparing zinc oxide nano-stick array thin film and use thereof |
| CN101045991A (en) * | 2007-04-30 | 2007-10-03 | 四川大学 | Transition metal salt dopping process for preparing magnetic nanometic zinc oxide rod array film |
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