CN101319370B - Method for controlling orientation and profile characteristic of zinc oxide nano-stick/nano-tube array - Google Patents

Method for controlling orientation and profile characteristic of zinc oxide nano-stick/nano-tube array Download PDF

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CN101319370B
CN101319370B CN 200810016893 CN200810016893A CN101319370B CN 101319370 B CN101319370 B CN 101319370B CN 200810016893 CN200810016893 CN 200810016893 CN 200810016893 A CN200810016893 A CN 200810016893A CN 101319370 B CN101319370 B CN 101319370B
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seed layer
zno
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CN101319370A (en
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武卫兵
胡广达
崔守刚
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Jinan University
University of Jinan
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a method for synthesizing a ZnO nano-rod/nanotube array in a water solution. An array film can be applied in the aspects of ultraviolet lasing fluorescence, nano sensors, nanocrystal solar cells (including dye sensitization solar cells, inorganic ultrathin absorption layer solar cells and quantum-dot solar cells) and so on. The method comprises the following steps that: by adoption of the combination of the sol-gel spincoating method and the quick annealing technique, a (001) highly oriented solid or hollow ZnO seed layer film is deposited on various substrate surfaces; and the ZnO seed layer film is epitaxially grown in the zinc nitrate water solution, and then the highly oriented ZnO nano-rod/nanotube array film is obtained. The method can realize single-particle distribution of a seed layer and single-crystal growth of a nano-rod on a substrate, and can realize epitaxial growth of the ZnO nano-rod/nanotube and control of the shapes such as the diameter, the length and so on of the ZnO nano-rod/nanotube through control of the concentration, the compositions and the pH value of a growth solution and the growth time.

Description

The method of a kind of controlled oxidation zinc nanometer rod/nano-tube array orientation and shape characteristic
Technical field
The present invention relates to a kind of method of in the aqueous solution, synthesizing ZnO nanometer rod/nano-tube array, this array film can be applicable to luminous, the nano-sensor of Ultra-Violet Laser, nano-crystalline solar battery aspects such as (comprising dye sensitization solar battery, the inorganic solar cell of absorption layer as thin as a wafer and quantum dot solar cell).
Background technology
Zinc oxide is the semiconductor material of a kind of broad-band gap (3.37eV), has performances such as good photoelectricity, piezoelectricity, catalysis.In recent years, a large amount of researchs have been carried out both at home and abroad about one-dimension zinc oxide structures such as nanometer rod, nanometer rod and nanotubes.These One-Dimensional ZnO array structures are at transmitter, photoelectric device, and fields such as solar cell are with a wide range of applications.
The present existing method for preparing one-dimension zinc oxide array comprises chemical Vapor deposition process and liquid-phase growth method.Chemical gas-phase method such as U.S. Pat 6,036, the method of a kind of vapor phase process growing metal oxide nano-rod that 774 (making nanometic zinc oxide rod array perpendicular to the substrate on surface and preparation method thereof) provide, and chemical gas-phase method prepares the method for zinc oxide nano rod under a kind of 250 ℃ low temperature of providing of Chinese patent CN 1333117C (a kind of method at growing oriented aligning zinc oxide nanometer rod array on the silicon base).Prepare aspect ZnO nanometer rod/nanotube at liquid phase method, U.S. Pat 7,265,037B2 (nanometer stick array, nanometer rod solar cell and preparation method thereof) adopts the aqueous solution of the zinc nitrate that adds vulkacit H and polymine to prepare the ZnO nanometer stick array; It is the method that template prepares the ZnO nanometer rod that Chinese patent CN 1301217C (a kind of method of chemically preparing zinc oxide nanometer rod using low temperature wet) has provided a kind of Sodium dodecylbenzene sulfonate that adopts, and the nanometer rod diameter is 80-100nm, and length is 2 μ m; Recently, the patent " zinc oxide nano mitron and supersonically preparation method thereof " (200610150940.4) of the people such as Chen Yujin of Harbin Engineering University application has provided a kind of method that adopts Ultrasonic Wave-Assisted Preparation ZnO nanotube.But above-mentioned all methods adopt and the unmatched substrate of ZnO lattice mostly, and the orthostatic of One-Dimensional ZnO nanostructure is relatively poor.Be to guarantee orthostatic, some research adopt in substrate deposition one deck orientation and with the buffer layer of ZnO lattice match, but the existence of these buffer layers tends to bring disadvantageous effect to the application of following ZnO nanostructure.For satisfying the needs of following performance application, be necessary to invent a kind of new can be directly from the substrate the novel method of growing height orthostatic ZnO nano-structure array.
Summary of the invention
The object of the present invention is to provide the method for a kind of controlled oxidation zinc nanometer rod/nano-tube array orientation and shape characteristic, make the ZnO nanometer rod/nano-tube array that obtains have following character:
1.ZnO do not have nano particle to pile up between nanometer rod/nano-tube array and the substrate, but be grown directly upon in the substrate, so that electronics or photon can directly enter single crystal structure from deposition substrate, there are not electron trapping and photon scattering in the transmission course, speed is higher;
2.ZnO nanometer rod/nanotube should have good orthostatic, is beneficial to the homogeneity of later stage absorption layer when preparing devices such as solar cell;
3.ZnO the controllable diameter of nanometer rod/nanotube.To the application of nanocrystalline battery, wish its diameter between the 50-100 nanometer, required thickness requirement when setting up built in field to satisfy; To the application of ultra-violet light-emitting device, wish that its diameter is lower than 50 nanometers, to satisfy the required diameter dimension of quantum size effect;
4.ZnO the spacing of nanometer rod/nanotube is controlled.For different application, to the requirement difference of spacing.To nano-crystalline solar battery, spacing is preferably between the 50-150nm, to satisfy subsequent deposition sensitizing layer, p type layer or required space requirements such as ionogen filling, ion diffusion and liquid or gaseous diffusion; Wish then that for the application of ultra-violet light-emitting device its spacing is as far as possible little under mutual disjunct situation, to satisfy the density requirements of high luminous intensity;
5.ZnO the length controlled of nanometer rod/nanotube.For the application of nanocrystalline battery and senser element, wish its length between the 1.5-10 micron, satisfy the requirement of extinction and big interior surface area.
The present invention realizes by following technical measures:
The invention discloses the method for a kind of controlled oxidation zinc nanometer rod/nano-tube array orientation and shape characteristic, comprise the steps: to adopt sol-gel spin-coating method and rta technique to combine, at substrate surface deposition (001) height-oriented solid or hollow ZnO Seed Layer film, the epitaxy in zinc nitrate aqueous solution of ZnO Seed Layer film is obtained height-oriented ZnO nanometer rod/nano-pipe array thin film;
The method of the described solid or hollow ZnO Seed Layer film that height of deposition is orientated in substrate, adopt following steps:
A. prepare the Seed Layer precursor solution: will wait mole of acetic acid zinc and stablizer to be dissolved into successively in the ethanol, the acetate zinc concentration is 0.075～0.3M, and after fully stirring, the sealing homogenizing is made the Seed Layer precursor solution;
B. the cleaning of deposition substrate: substrate is thoroughly cleaned;
C. deposit the ZnO Seed Layer: the Seed Layer precursor solution is spun to substrate surface with the speed of 3000-7500 commentaries on classics/min;
D. with the substrate behind the gluing 180-300 ℃ of following solvent evaporated or more than the pyrolysis 5min; Transfer in the quick anneal oven, under 250-800 ℃ temperature, heat-treat, obtain solid or hollow ZnO Seed Layer film;
The described method that height-oriented ZnO nanometer rod/nano-pipe array thin film is prepared in epitaxy in solution, adopt following steps:
A. prepare epitaxy solution: used reagent is the Zn (NO of equimolar amount 3) 26H 2O and vulkacit H (C 6H 12N 4), its concentration is 0.01-0.1molL -1, add polymine ((CH 2CH 2NH) n, PEI) as the epitaxy conditioning agent of ZnO nanometer rod/nanotube, its concentration is 5-20mmolL -1
B. with in the encloses container of epitaxy solution under 85-95 ℃ preheating 0.5-5 hour;
C. adopt the downward mode of end face to put into epitaxial solution solid or hollow ZnO Seed Layer film and grow, growth time is 1-48 hour;
D. the film that will grow takes out, and keep facing down put into static immersions of deionized water 30min fast after, change over to and soak in the dehydrated alcohol more than the 30min, take out final vacuum rapid drying, preservation.
Method of the present invention, preparation process is as follows more specifically:
(1) preparation Seed Layer precursor solution: with equimolar amount zinc acetate and thanomin (0.3-0.075M) be dissolved into successively in the ethanol, drip the water with the zine ion equimolar amount, after fully stirring, the sealing homogenizing is more than 24 hours;
(2) cleaning of deposition substrate:, also dry with the ultrasonic cleaning of acetone, alcohol, deionized water successively with base materials such as silicate glass, ITO or FTO conductive glass, plating Pt silicon chip, monocrystalline silicon piece and sapphires;
(3) deposition ZnO Seed Layer: deposition substrate is transferred on the sol evenning machine, dripped the precursor solution of step (1) preparation, treat to rotate 30s with the speed of 3000-7500 commentaries on classics/min behind the homodisperse;
(4) substrate after the spin coating is transferred in the drying plant, at 280 ℃ of following evaporating solvents or more than the pyrolysis 5min;
(5) transfer in the quick anneal oven and handle, earlier more than 300 ℃ of following pyrolysis 5min, and then temperature is elevated to more than 500 ℃ of rapid thermal process 5min, obtain solid ZnO Seed Layer;
(6) temperature is continued to be elevated to more than 650 ℃, more than the thermal treatment 5min, obtain hollow ZnO Seed Layer;
(7) growing ZnO nanorod: the preparation epitaxial solution, wherein contain 0.01-0.1mol.L -1Zn (NO 3) 26H 2O and equimolar vulkacit H, 0-20mmol.L -1Polymine (PEI); Epitaxial solution at 85-95 ℃ of preheating 2-5 hour, is put into the solid ZnO Seed Layer top that obtains in the step (5) downwards, grown 1-48 hour down at 85-95 ℃;
(8) growth ZnO nanotube: the epitaxial solution in the step (7) is accurately regulated, by adding HNO 3Control pH value of solution value is between 5.6-7.5; , more than 3 hours the hollow ZnO Seed Layer top that obtains in the step (6) is put into downwards 85-95 ℃ of preheating; Grew 1-48 hour down at 85-95 ℃;
(9) clean ZnO nanometer rod/nano-tube film: the nanometer rod/nano-tube film of step (7) or (8) growth is taken out and keep pushing up and put into deionized water downwards fast from growth media, static immersion is more than the 30min, it is changed in the dehydrated alcohol, and keeping same way as to place, static immersion is more than the 30min; Taking out the final vacuum rapid evaporation preserves.
The preparation method who the invention has the beneficial effects as follows proposition is applicable to multiple deposition substrate, the orthostatic of ZnO nanometer rod/nanotube and the crystalline structure of substrate and orientation are irrelevant, the Seed Layer and the liquid growing technology that adopt are low-cost technologies, by control precursor strength of solution, spin speed and annealing schedule can realize that the single particle of Seed Layer distributes and nanometer rod in suprabasil single crystal growing; Can realize the epitaxy of ZnO nanometer rod/nanotube and the control of patterns such as diameter and length thereof by control growing liquid concentration, composition, pH value and growth time.
Description of drawings
Fig. 1 has provided atomic force microscope (AFM) picture on (001) of adopting sol-gel spin-coating method and short annealing technology to combine to obtain height-oriented ZnO Seed Layer surface and field emission scanning electron microscope (FESEM) picture of section.
Fig. 2 has provided X-ray diffraction (XRD) collection of illustrative plates of the height-oriented ZnO Seed Layer in (001) of adopting sol-gel spin-coating method and short annealing technology to obtain in various substrates such as silicate glass, ITO or FTO conductive glass, plating Pt silicon chip, monocrystalline silicon piece and sapphire.Ordinate zou is an X-ray diffraction intensity, and X-coordinate is a diffraction angle.
The ZnO Seed Layer (P2) that Fig. 3 has provided the ZnO Seed Layer (P1) of non-orientation and (001) orientation is containing 0.1M Zn (NO 3) 26H 2O and wait mole HMT and the growth media of 20mM PEI in grow for 95 ℃ times profile scanning electron microscope (SEM) picture of the ZnO nanometer stick array that obtains.
Fig. 4 has provided X-ray diffraction (XRD) collection of illustrative plates that adopts (001) height-oriented (P1) and the ZnO Seed Layer non-orientation (P2) that different sol-gel spin coating proceedings and rta technique prepare in the Si substrate.Ordinate zou is an X-ray diffraction intensity, and X-coordinate is a diffraction angle.
Fig. 5 has provided the Seed Layer among Fig. 1 is being higher than the hollow zinc oxide seed laminar surface (a) that obtains after handling 15 minutes under 650 ℃ the temperature and field emission scanning electron microscope (FESEM) picture of section (b).
Fig. 6 has provided 95 ℃ and has adopted hollow ZnO Seed Layer film down and containing the Zn (NO that waits mole (0.05M) 3) 26H 2Scanning electronic microscope (SEM) picture of the ZnO nano-tube array that the growth media growth of O and HMT and 10mM PEI obtained in 8 hours.
Fig. 7 has provided and has adopted solid ZnO Seed Layer and wait mole (0.02M Zn (NO containing 3) 26H 2O) and scanning electronic microscope (SEM) picture of HMT and the ZnO nanometer stick array that in not adding the growth media of PEI, obtains.
Fig. 8 has provided 85 ℃ and has adopted (001) height-oriented Seed Layer down and containing 0.1M Zn (NO 3) 26H 2O and wait mole HMT and grow scanning electronic microscope (SEM) picture of the ZnO nanometer stick array that obtains of the growth media of 20mM PEI.
Fig. 9 has provided 95 ℃ and has adopted (001) height-oriented solid ZnO Seed Layer down and wait mole (0.01mol.L -1) zinc nitrate and vulkacit H and add 50mmolL -1Scanning electronic microscope (SEM) picture of the ZnO nanometer stick array that obtained in 12 hours of the growth media growth of polymine;
Figure 10 has provided 95 ℃ and has adopted the Seed Layer of height (001) orientation down and containing the Zn (NO that waits mole (0.05M) 3) 26H 2O and HMT and 5mmolL -1Field emission scanning electron microscope (FESEM) picture of the ZnO nano-stick array thin film that obtained in 8 hours of the growth media growth of polymine.
Embodiment
Following example is intended to illustrate the present invention, rather than will limit the present invention by any way.
Embodiment 1
(1) preparation Seed Layer precursor solution: with equimolar amount zinc acetate and thanomin (0.3M) be dissolved in the ethanol; Fully stir after 1 hour sealing homogenizing 24 hours;
(2) clean deposition substrate: with ultrasonic cleaning and the oven dry one by one of silicate glass substrate acetone, alcohol, deionized water;
(3) spin coating precursor solution: deposition substrate is placed on the sol evenning machine, drips the Seed Layer precursor solution of preparation, with the speed spin coating 30s of 7500 commentaries on classics/min;
(4) solvent evaporation: the substrate after the spin coating transferred on 280 ℃ the hot plate and handle 5min;
(5) transfer in the quick anneal oven,, handle 5min 500 ℃ of short annealings again, obtain the ZnO Seed Layer earlier at 300 ℃ of pyrolysis 10min.Its surface and cross-section morphology as shown in Figure 1, seed grain is distributed in the substrate with single particle, and is full particle, particle size is about 30nm.Fig. 2 is the XRD figure spectrum of the Seed Layer that obtains in various substrates.As can be seen, ZnO Seed Layer film all is that (001) is height-oriented in various substrates, and the crystalline structure of orientation and substrate and crystalline orientation are irrelevant;
(6) above-mentioned solid ZnO Seed Layer is transferred to 3 hours the epitaxy growth from solution of preparing in advance of 95 ℃ of preheatings 12 hours, Seed Layer is placed by the downward mode in top.Mole (0.1mol.L such as contain in the epitaxy solution -1) Zn (NO 3) 26H 2O and vulkacit H, 20mmolL -1Polymine;
(7) nanometer rod/nano-tube film after will growing takes out and puts into fast deionized water from growth media, keeps downward static the immersions 30min in top, changes the static immersion of the above-mentioned modes of emplacement of maintenance 30min, rapid evaporation under vacuum then in the dehydrated alcohol over to.Fig. 3 a is the section SEM photo of the ZnO one-dimentional structure that grows.As can be seen, the epitaxy of solid ZnO seed obtains the ZnO nanometer rod, and the orthostatic of nanometer rod is better, and diameter is 50-60nm, and spacing is 60-80nm, and length is 6 μ m, and does not have particle packing between substrate and nanometer rod.After changing the Si substrate into ITO conductive glass or Pt/Si, the nanometer rod of acquisition has similar pattern.
Embodiment 2:
(1) preparation Seed Layer precursor solution: the zinc acetate and the thanomin (0.075M) of equimolar amount are dissolved in the ethanol; Fully stir after 1 hour sealing homogenizing 24 hours;
(2) clean deposition substrate: with ultrasonic cleaning and the oven dry one by one of monocrystalline silicon piece acetone, alcohol, deionized water;
(3) spin coating precursor solution: deposition substrate is placed on the sol evenning machine, drips the Seed Layer precursor solution of preparation, with the speed spin coating 30s of 3000 commentaries on classics/min;
(4) solvent evaporation: the substrate after the spin coating transferred on 280 ℃ the hot plate and handle 10min;
(5) change in the quick anneal oven, handle 10min at 300 ℃ earlier, handle 5min 500 ℃ of short annealings again.P2 is the XRD figure spectrum of the ZnO Seed Layer film of acquisition among Fig. 4.This Seed Layer is at (001), (100) and (101) direction random orientation;
(6) with the ZnO Seed Layer of the random orientation of above-mentioned acquisition 3 hours epitaxy growth from solution of 95 ℃ of preheatings 4 hours.Mole (0.1mol.L such as contain in the epitaxy solution -1) Zn (NO 3) 26H 2O and vulkacit H and 20mmolL -1Polymine;
(7) cleaning and the drying process such as the embodiment 1 of the nano-rod film after the growth.Fig. 3 b is the section SEM photo of this ZnO nanometer stick array.As can be seen, the diameter of nanometer rod is 50-60nm, and length is 1.5 μ m, but orthostatic is compared obvious variation with embodiment 1.The orientation that Seed Layer is described has directly determined excellent orthostatic.
Embodiment 3:
(1) preparation Seed Layer precursor solution: with equimolar amount zinc acetate and thanomin (0.15M) be dissolved in the ethanol; Fully stir after 1 hour sealing homogenizing 24 hours;
(2) clean deposition substrate: with ultrasonic cleaning and the oven dry one by one of monocrystalline silicon piece substrate acetone, alcohol, deionized water;
(3) spin coating precursor solution: deposition substrate is placed on the sol evenning machine, drips the Seed Layer precursor solution of preparation, with the speed spin coating 30s of 4500 commentaries on classics/min;
(4) substrate after the spin coating is transferred on 280 ℃ the hot plate and handled 5min;
(5) change quick anneal oven over to, earlier at 300 ℃ of pyrolysis 10min, more respectively at 500 ℃ and 650 ℃ of thermal treatment 5min.Fig. 5 is the surface (a) of the Seed Layer of acquisition and the FESEM picture of section (b).As can be seen, through high growth temperature, seed sizes is increasing perpendicular to the base plane direction, and direction reduces in face, causes grain spacing to become big.Importantly, the high energy centre rapid evaporation of ZnO nano particle has formed hollow nanocrystal structure under the high temperature;
(6) with the hollow ZnO Seed Layer of above-mentioned acquisition 3 hours epitaxy growth from solution of 95 ℃ of preheatings 8 hours.Mole (0.05mol.L such as contain in the epitaxy solution -1) Zn (NO 3) 26H 2O and vulkacit H and 10mmol.L -1Polymine is by adding HNO 3PH regulator to 6.7 with solution;
(7) cleaning and the drying process such as the embodiment 1 of growth rear film.Fig. 6 has provided the surperficial SEM picture of the ZnO nano structure membrane of growth.As can be seen, tangible nano tubular structure is arranged in the film, the shape basically identical of the shape of nanotube and hollow seed grain, wall thickness is approximately 10nm.
Embodiment 4:
(1) preparation Seed Layer precursor solution such as embodiment 2
(2) cleaning of monocrystal silicon substrate such as embodiment 1;
(3) the spin coating worker of precursor solution benefit is as embodiment 2;
(4) solvent evaporation and stoving process such as embodiment 1;
(5) annealing process of Seed Layer such as embodiment 1;
(6) the solid ZnO Seed Layer of above-mentioned acquisition was grown 4 hours in the growth media of 95 ℃ of preheating 30min.Epitaxy solution such as contains at mole (0.02mol.L -1) zinc nitrate and vulkacit H, do not add PEI in the solution;
(7) cleaning and the drying process such as the embodiment 1 of the nanometer stick array after the growth.Fig. 7 has provided the section SEM picture of the ZnO nano-stick array thin film that obtains.As can be seen, although the ZnO nanometer rod has high perpendicularity, diameter obviously is increased to 100-200nm, and interrod spacing is lower than 50nm, and length is 1.5 microns.Be apparent that more tangible nanocrystalline accumulation is arranged between nanometer rod and the deposition substrate, illustrate to have significantly nucleation process again in the process of growth, be the p-n growth.
Embodiment 5:
(1) Pei Zhi Seed Layer precursor solution such as embodiment 2;
(2) with the cleaning such as the embodiment 1 of monocrystal silicon substrate;
(3) even glue coating process such as embodiment 1;
(4) solvent evaporation and stoving process such as embodiment 1;
(5) annealing process of Seed Layer such as embodiment 1;
(6) above-mentioned solid ZnO Seed Layer is transferred to 5 hours epitaxy growth from solution of 85 ℃ of preheatings 12 hours, Seed Layer is placed by the downward mode in top.Mole (0.1mol.L such as contain in the epitaxy solution -1) Zn (NO 3) 26H 2O and vulkacit H, 20mmolL -1Polymine;
(7) cleaning and the drying process such as the embodiment 1 of the nanometer stick array after the growth.Fig. 8 has provided the section SEM picture of the ZnO nanometer stick array that obtains.As can be seen, the growth temperature reduction causes the ZnO nanometer rod obviously slack-off at the c direction of principal axis and the radial speed of growth, and the diameter of nanometer rod is approximately 20-40nm, and length is about 3 μ, do not have nano particle to pile up between monocrystal nano rod and the substrate, be the direct epitaxy of seed crystal grain.
Embodiment 6:
(1) preparation Seed Layer precursor solution such as embodiment 2;
(2) cleaning of monocrystal silicon substrate such as embodiment 1;
(3) even glue coating process such as embodiment 1;
(4) solvent evaporation and stoving process such as embodiment 1;
(5) annealing process of Seed Layer such as embodiment 1;
(6) growth technique of nanometer stick array such as embodiment 1.Wherein growth media is 0.01mol.L -1Zinc nitrate and vulkacit H, 5mmolL -1Polymine, 95 ℃ of preheatings 3 hours were grown 12 hours;
(7) cleaning of nanometer stick array and drying process such as embodiment 1.Fig. 9 has provided the ZnO nano-stick array thin film that obtains.As can be seen, lower zinc salt concentration causes the speed of growth of ZnO nanometer rod in c direction of principal axis and radially all obviously reductions, and the diameter of nanometer rod is about 10-20nm, and length is inhomogeneous.
Embodiment 7:
(1) preparation Seed Layer precursor solution such as embodiment 2;
(2) cleaning of monocrystal silicon substrate such as embodiment 1;
(3) even glue coating process such as embodiment 1;
(4) solvent evaporation and stoving process such as embodiment 1;
(5) annealing process of Seed Layer such as embodiment 1;
(6) above-mentioned solid ZnO Seed Layer is transferred to the film that 2 hours epitaxy growth from solution of 95 ℃ of preheatings obtained in 8 hours, Seed Layer is placed by the downward mode in top.Mole (0.05mol.L such as contain in the epitaxy solution -1) zinc nitrate and vulkacit H, 5mmol.L -1Polymine;
(7) cleaning of nanometer stick array and drying process such as embodiment 1.Figure 10 has provided the section FESEM picture of the ZnO nano-stick array thin film that obtains.As can be seen, lower PEI concentration causes the speed of growth of ZnO nanometer rod in c direction of principal axis and radially all obviously increases, and nanometer rod has extraordinary orthostatic, and the diameter of nanometer rod is about 100-150nm, and length reaches 8 μ m, and interrod spacing is less.

Claims (3)

1. the method for a controlled oxidation zinc nanometer rod/nano-tube array orientation and shape characteristic is characterized in that comprising the steps:
Adopt sol-gel spin-coating method and rta technique to combine, solid or hollow ZnO Seed Layer film in substrate surface height of deposition orientation obtains height-oriented ZnO nanometer rod/nano-pipe array thin film with the epitaxy in zinc nitrate aqueous solution of ZnO Seed Layer film;
The method of the described solid or hollow ZnO Seed Layer film that height of deposition is orientated in substrate, adopt following steps:
A. prepare the Seed Layer precursor solution: will wait mole of acetic acid zinc and stablizer to be dissolved into successively in the ethanol, the acetate zinc concentration is 0.075～0.3M, and after fully stirring, the sealing homogenizing is made the Seed Layer precursor solution;
B. the cleaning of deposition substrate: substrate is thoroughly cleaned;
C. deposit the ZnO Seed Layer: the Seed Layer precursor solution is spun to substrate surface with the speed of 3000-7500 commentaries on classics/min;
D. with the substrate behind the gluing 280 ℃ of following solvent evaporated or more than the pyrolysis 5min; Transfer in the quick anneal oven, under 300-800 ℃ temperature, heat-treat, obtain solid or hollow ZnO Seed Layer film;
The described method that height-oriented ZnO nanometer rod/nano-pipe array thin film is prepared in epitaxy in solution, adopt following steps:
A. prepare epitaxy solution: used reagent is the Zn (NO of equimolar amount 3) 26H 2O and vulkacit H, its concentration are 0.01-0.1molL -1, add the epitaxy conditioning agent of polymine as ZnO nanometer rod/nanotube, its concentration is 5-20mmolL -1
B. with in the encloses container of epitaxy solution under 85-95 ℃ preheating 0.5-5 hour;
C. adopt the downward mode of end face to put into epitaxial solution solid or hollow ZnO Seed Layer film and grow, growth time is 1-48 hour;
D. the film that will grow takes out, and keep facing down put into static immersions of deionized water 30min fast after, change over to and soak in the dehydrated alcohol more than the 30min, take out final vacuum rapid drying, preservation;
Described thermal treatment is: handling under 300 ℃ the air conditions more than the 5min, handling more than the 5min under 500 ℃ of air conditionses, obtain solid ZnO Seed Layer film; Again with solid ZnO Seed Layer film handling under the temperature more than 650 ℃ more than the 5min, obtain hollow ZnO Seed Layer film.
2. the method for claim 1, it is characterized in that: described stablizer is a monoethanolamine.
3. the method for claim 1 is characterized in that: described substrate is simple glass, ITO or FTO conductive glass, plating Pt silicon chip, monocrystalline silicon piece or sapphire.
CN 200810016893 2008-06-24 2008-06-24 Method for controlling orientation and profile characteristic of zinc oxide nano-stick/nano-tube array Expired - Fee Related CN101319370B (en)

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