CN1291920C - Zinc oxide nano-wire and its preparation method and application - Google Patents

Zinc oxide nano-wire and its preparation method and application Download PDF

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CN1291920C
CN1291920C CN 200310113384 CN200310113384A CN1291920C CN 1291920 C CN1291920 C CN 1291920C CN 200310113384 CN200310113384 CN 200310113384 CN 200310113384 A CN200310113384 A CN 200310113384A CN 1291920 C CN1291920 C CN 1291920C
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tube furnace
metal grill
container
zno nano
powder
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CN1618738A (en
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张洪洲
徐向宇
俞大鹏
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Peking University
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Abstract

The present invention discloses a zinc oxide nanometer wire, and a preparation method and an application thereof, which has the aim of providing a zinc oxide nanometer wire and a preparation method thereof, and an array of the ZnO nanometer wires. The ZnO nanometer wire provided by the present invention has the diameter of 20 to 60 nm, and the tip curvature radius of 3 to 10 nm; the array of the ZnO nanometer wires, which is also provided by the present invention, is composed of the ZnO nanometer wires growing homogeneously on a mesh screen, and each of the ZnO nanometer wires has the diameter of 20 to 60 nm, and the tip curvature radius of 3 to 10 nm. In the method of the present invention, the ZnO nanometer wires with high orientation (perpendicular to the mesh screen), high purity, high density and uniform diameter can grow on a large area with the magnitude of centimeter.

Description

A kind of zinc oxide nanowire and preparation method thereof and application
Technical field
The present invention relates to a kind of nano wire and preparation method thereof and application, particularly relate to a kind of ZnO nano wire and preparation method thereof and ZnO nano-wire array.
Background technology
As wide bandgap semiconductor, ZnO has excellent characteristics such as optics, electricity, photoelectricity and piezoelectricity, has been widely used in transmitter, power device, ultraviolet light-emitting diode, solar cell, device (J.W.Tomm, B.UIIrich, X.G.Qiu such as chip integrated microphone and optical waveguides, Y.Segawa, A.Ohtomo, M.Kawasaki, and H.Koinuma.Optical and photoelectrical properties of oriented ZnO films.J.Appl.Phys, 87,4,2000; J.B.L.Martins, E.Longo, C.A.Taft.CO 2AndNH3 Interaction with ZnO Surface An AM1 Study.Inter.J.of Quan.Chem., 70,1998; T.Paul Chow and R.Tyagi.Wide bandgap compound semiconductors forsuperior high-voltage unipolar power devices.IEEE Tran.On Elect.Devices, 41,8,1994; H.Ohta, K.Kawamura, M.Orita, N.Sarukura, M.Hirano, and H.Hosono.UV-emitting diode composed of transparent oxidesemiconductors:p-SrCu202/n-ZnO.Electronics Letts, 36,11,2000; W.E.Devaney, W.S.Chen, J.M.Stewart, and R.A.Mickelsen.Structure and properties of highefficiency ZnO/CdZnS/CuInGaSe2 solar cells.IEEE Tran.On Electr.Devices, 37,2,1990; R.P.Ried, E.S.Kim, D.M.Hong, and R.S.Muller.Piezoelectricmicrophone with on-chip CMOS circuits.J.Micro.Sys., 2,3,1993).In recent years, about studies show that of nano level ZnO material, it is penetrated and there is huge potential using value in aspect such as field emission swashing, (M.H.Huang such as plane active illuminating light source for example, S.Mao, H.Feick, H.Yan, Y.Wu, H.Kind, E.Weber, R.Russo, and P.Yang.Science.292,1897 (2001)).The synthetic method of nano level ZnO material has physical evaporation method (Z.R.Dai, Z.W.Pan at present, Z.L. Wang.Novel nanostructures of functional oxides synthesized by thermalevaporation.Adv.Funct.Mater, 13,1,2003; B.D.Yao, Y.F.Chan, andN.Wang.Formation of ZnO nanostructures by a simple way of thermalevaporation.Appl.Phys.Lett., 81,4,2002; J.S.Lee, M.I.Kang, S.Kim, M.S.Lee, and Y.K.Lee.Growth of zinc oxide nanowires by thermal evaporationon vicinal Si (100) substrate.J.Crys.Growth, 249,2003), chemical vapour deposition (S.C.Lyu, Y.Zhang, H.Ruh, H.J.Lee, H.W.Shim, E.K.Suh, C.J.Lee.Lowtemperature growth and photoluminescence of well-aligned zinc oxidenanowires.Chem.Phys.Letts, 363,2002; J.J.Wu, and S.C.Liu.Low-temperature growth of well-aligned ZnO nanorods by chemical vapordeposition.Adv.Mater., 14,3,2002), molecular beam epitaxy (Y.W.Heo, V.Varadarajan, M.Kaufman, K.Kim, D.P.Norton, R.Ren, P.H.Fleming.Site-specific growthof ZnO nanorods using catalysis-driven molecular beam epitaxy.Appl.Phys.Lett., 81,16,2002), chemical vapor transportation (M.H.Huang, Y.Wu, H.Feick, N.Tran, E.Weber, and P.Yang.Catalytic growth of Zinc oxide nanowires by vaportransport.Adv.Mater.13,2,2001), solution method (K.Govender, D.S.Boyle, P.O ' Brien, D.Binks, D.West, and D.Coleman.Adv.Mater., 14,1221 (2002)) etc.These methods cut both ways.Though the physical evaporation method method is simple but controllability is relatively poor, the pattern of synthetic ZnO nano wire and quality are not high; The molecular beam epitaxial growth cost is too high, is not suitable for need of industrial production; Chemical vapour deposition is relative method preferably with chemical vapor transportation, but also need improve at (for example single pattern) aspect the controlledly synthesis of nanostructure; Use the solution method accurate one-dimentional structure of growing nano ZnO at a lower temperature, still, this technology and traditional semiconductor technology are incompatible.Therefore,, just need a kind of compatibility of development and the good technology of controllability, use this technology synthetic ZnO nanostructure should have specific structure and character simultaneously for making the further practicability of ZnO nanostructure.
The innovation and creation content
The purpose of this invention is to provide a kind of ZnO nano wire and preparation method thereof.
ZnO nano wire provided by the present invention, its diameter are 20-60nm, tip curvature radius 3-10nm.
Wherein, the diameter of this ZnO nano wire is preferably 30-50nm, and the tip curvature radius is preferably 5nm.
A kind of method for preparing above-mentioned ZnO nano wire may further comprise the steps:
1) metal grill that is the 15-25 micron with warp and parallel spacing is as substrate, and the catalyzer of plating one deck 10-100nm on described substrate, described catalyzer be golden, titanium or nickel;
2) metal grill that will handle through described step 1), the container that fills the container of Zn powder and fill the Se powder are all put into tube furnace; The container of described metal grill and the described Zn of filling powder all places in the flat-temperature zone of described tube furnace, and described metal grill places on the container of the described Zn of filling powder, and the spacing on described metal grill and described Zn powder surface is 2-5mm; The container of the described Se of filling powder places the inlet end of described tube furnace;
3) feeding flow to the inlet end of tube furnace is that the rare gas element of 60-140sccm makes the intraductal atmospheric pressure of described tube furnace maintain 0.001-0.005atm in reaction process; The inlet end temperature that makes described tube furnace was kept 30-60 minute at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature, obtained the ZnO nano wire.
Wherein, the warp of metal grill described in the step 1) and parallel spacing all are preferably 20 microns, and described metal grill can be the lower metal grill of vapour pressure under temperature of reaction such as stainless steel, copper or tungsten, is preferably stainless steel or copper mesh; The thickness of described catalyzer is preferably 40-60nm, and described catalyzer is preferably gold.Step 2) in, the stainless steel reaction pipe of quartz socket tube is arranged in described tube furnace can be, be respectively silica tube and the stainless steel tube of 3cm and 2.5cm as diameter.The spacing on described metal grill and Zn powder surface is preferably 3mm.The Ar gas that feeds described in the step 3) or the flow of other rare gas elementes are preferably 80-120sccm; In the reaction process, the intraductal atmospheric pressure of described tube furnace maintains 0.003atm; The inlet end temperature of described tube furnace is kept at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature and was benefit in 45 minutes.
The nano wire that exists with the form of array is with a wide range of applications, and another object of the present invention provides a kind of nano wire that exists with array format.
ZnO nano-wire array provided by the present invention is the ZnO nano wire of evenly growing at metal grill, and the diameter of this ZnO nano wire is 20-60nm, and its tip curvature radius is 3-10nm.Prepare through following method:
1) metal grill that is the 15-25 micron with warp and parallel spacing is as substrate, and the catalyzer of plating one deck 10-100nm on described substrate, described catalyzer be golden, titanium or nickel;
2) metal grill that will handle through described step 1), the container that fills the container of Zn powder and fill the Se powder are all put into tube furnace; The container of described metal grill and the described Zn of filling powder all places in the flat-temperature zone of described tube furnace, and described metal grill places on the container of the described Zn of filling powder, and the spacing on described metal grill and described Zn powder surface is 2-5mm; The container of the described Se of filling powder places the inlet end of described tube furnace;
3) feeding flow to the inlet end of tube furnace is that the rare gas element of 60-140sccm makes the intraductal atmospheric pressure of described tube furnace maintain 0.001-0.005atm in reaction process; The inlet end temperature that makes described tube furnace was kept 30-60 minute at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature, obtained described ZnO nano-wire array.
The present invention has synthesized ZnO nano wire and array by the improvement to each link of physical evaporation technology.Method of the present invention can be at the ZnO nano wire of the high orientation of the large area deposition on centimetre magnitude (perpendicular to metal grill), high purity, high-density and diameter homogeneous.With respect to several synthetic technologys of former report, outstanding contributions of the present invention are: (1) has improved the controllability of physical evaporation.Utilize the geometrical shape of metal grill that transporting of source steam limited, by adjusting its flow direction and concentration distribution, and then the transport of substances of vegetative point is controlled.Synthetic nano wire orientation is good like this.(2) adopt the method for electron beam deposition on metal grill, to deposit one deck catalyzer.Because of grid has certain thickness, be easy to realize the selection deposition of catalyzer at surface mesh.The thickness of catalyst layer is another controllable factor.These 2 homogeneity, selectivity and the high-density of determining the ZnO nano-wire array.(3) synthetic ZnO nanostructure only needs very low temperature of reaction.The substrate of other types, the glass required, no any infringement under this temperature as indicating meter.This synthetic technology can be used as a link in the conventional semiconductor processing, and harmless to whole technology.(4) method of the present invention is simple, and cost is low, and repeatability is fine.
The invention solves nano level ZnO use in essential controllability that solves of (especially for field emission displays spare) institute and big area low cost composition problem.Feds is that single radiator has very big aspect ratio for the requirement of radiator, and radiator is arranged in the suitable array of density, graphical controllable growth, the own conductivity of radiator good (preferably should be the n type for semi-conductor).ZnO nano wire of the present invention and ZnO nano-wire array meet these requirements of feds from pattern, and this technology realizes the special pattern growth easily, as long as the grid of design different-shape.The present invention also preliminary study the field emission performance of ZnO nano-wire array, its field emission performance can be comparable with CNT (carbon nano-tube).Plane technique of display based on the field emission performance of CNT (carbon nano-tube) has had prototype at present, has developed into the practicability stage.The practicability that the invention enables ratio nano carbon pipe to have the ZnO nano-wire array of more stable field emission performance becomes possibility.In addition, the technique influence that the present invention is more far-reaching is to can be used as the basis of studying and solving other nano-structure array synthetic technology, can smoothly be applied to have important significance for theories and practical significance in the solution of similar problem.
Description of drawings
Fig. 1 a is the stereoscan photograph in the big zone of ZnO nano-wire array
Fig. 1 b is the stereoscan photograph of the regional area on the single skeleton of ZnO nano-wire array
Fig. 2 a is the transmission electron microscope photo of ZnO nano-wire array
Fig. 2 b is the transmission electron microscope photo of single ZnO nano wire
Fig. 3 is the EDS spectrum of ZnO nano-wire array sample
Embodiment
The preparation of embodiment 1, ZnO nano wire and ZnO nano-wire array
1, adopt warp and parallel spacing to be 20 microns, the diameter of Stainless Steel Wire be 30 microns stainless steel grid as substrate, and be cut into the rectangle of 1cm * 5cm size.To grid, carry out following processing then as substrate: at first grid is cleaned successively with alcohol and deionized water, the mode of using e-beam induced deposition then at the golden film of an evaporation one layer thickness 40-60nm of grid as catalyzer.
2, take by weighing an amount of (can keep the reaction aequum with reactant is as the criterion) Zn powder and Se powder, they are placed respectively in two quartz boats.To ride on the boat that fills the Zn powder through the copper mesh that step 1 is handled, Zn powder surface is at a distance of 3mm in grid and the boat.Carefully Zn boat and Se boat are put into (west, ravine, Luoyang City refractory materials pilot plant is made 1200 ℃ of electric tube furnaces that are rapidly heated) in the tube furnace stainless steel reaction pipe of quartz socket tube (in have).During the placing response thing, the Se boat should place inlet end, and the Zn boat places the flat-temperature zone that is positioned at reaction tubes central tubular stove.
3, place appropriate after, with the tube furnace closed at both ends, inlet end passes to Ar gas, flow is 80-120sccm, bled by mechanical pump in the outlet side, pumping speed is reconciled by a needle-valve on the gas circuit between reaction tubes and the mechanical pump.Adjust the Ar airshed and the end valve door aperture of bleeding, make intraductal atmospheric pressure in reaction process, maintain 0.003atm.React required oxygen and derive from the system leak in the residual adsorption gas and reaction process in the system, if the air tight system of perfection then passes to the following oxygen flow of 5sccm.Then, begin to heat, should make the temperature of Se boat region be elevated to 355 ℃, the temperature (being temperature of reaction) of flat-temperature zone, Zn boat place fast and be elevated to 350 ℃ fast, keep 45mins.After reaction finishes, stop heating earlier, treat that furnace temperature drops to room temperature after, stop logical Ar gas and close mechanical pump.Open the reaction tubes sealing two ends, take out two quartz boats that fill reactant.At this moment on metal grill, can observe the alternate material of the yellow cyan of one deck.
4, the evaluation of ZnO nano wire and ZnO nano-wire array
Use is operated in the surface topography that Strata DB235-FIB nanometer workstation under the scan pattern (SEM) comes observing samples.The result is shown in Fig. 1 a and Fig. 1 b, and Fig. 1 a shows evenly covered the velvet-like thing of one deck on the skeleton of metal grill, illustrate this growth method can be on big area very even growth ZnO nano-array, white portion is the long copper mesh skeleton that nano wire is arranged among the figure; Fig. 1 b shows that these velvet-like things are shape homogeneous, the nano-wire array of marshalling, can read by the scale that shows among the figure, the diameter of these nano wires is greatly about 30-50nm, and their diameter is homogeneous very, simultaneously can see that the head of these nano wires all is shrunk to the tip that a radius-of-curvature is about 5nm.Structure and composition for further institute synthetic sample, scraping sample segment from grid is put into TEM micro grid and carries out TEM observation, use Tecnai F30 transmission electron microscope and built-in EDS analyser thereof further the microstructure and the composition of sample to be analyzed, result such as Fig. 2 a, Fig. 2 b and shown in Figure 3, Fig. 2 a shows the sample shape homogeneous, the orientation height, and diameter Distribution is between 30-50nm, there is a tip on each nano wire top, and the tip curvature radius is about 5nm; Fig. 2 b shows can know the atomic plane of seeing marshalling, and interplanar distance is about 0.52nm, and identical with [0001] crystal orientation of ZnO bulk, lattice fringe is apparent, and this interpret sample crystallization degree is fine; Visible significantly Zn peak and O peak among Fig. 3, interpret sample is mainly elementary composition by Zn and two kinds of O.In conjunction with high-resolution result (be that high resolution display surface spacing is 0.52nm, this [0001] crystal orientation in ZnO coincide), can determine that sample is the good ZnO nano wire of crystallization degree, wherein Cu and C peak derive from little grid.

Claims (9)

1, a kind of ZnO nano wire, its diameter is 20-60nm, tip curvature radius 3-10nm.
2, ZnO nano wire according to claim 1 is characterized in that: the diameter of described ZnO nano wire is 30-50nm, tip curvature radius 5nm.
3, a kind of method for preparing the described ZnO nano wire of claim 1 may further comprise the steps:
1) metal grill that is the 15-25 micron with warp and parallel spacing is as substrate, and the catalyzer of plating one deck 10-100nm on described substrate, described catalyzer be golden, titanium or nickel;
2) metal grill that will handle through described step 1), the container that fills the container of Zn powder and fill the Se powder are all put into tube furnace; The container of described metal grill and the described Zn of filling powder all places in the flat-temperature zone of described tube furnace, and described metal grill places on the container of the described Zn of filling powder, and the spacing on described metal grill and described Zn powder surface is 2-5mm; The container of the described Se of filling powder places the inlet end of described tube furnace;
3) feeding flow to the inlet end of tube furnace is that the rare gas element of 60-140 cubic centimetre/second makes the intraductal atmospheric pressure of described tube furnace maintain 0.001-0.005atm in reaction process; The inlet end temperature that makes described tube furnace was kept 30-60 minute at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature, obtained the ZnO nano wire.
4, method according to claim 3 is characterized in that: described metal grill is stainless steel, copper or tungsten grid; The warp of described metal grill and parallel spacing are 20 microns.
5, method according to claim 3 is characterized in that: the thickness of catalyzer described in the step 1) is 40-60nm, and described catalyzer is a gold.
6, method according to claim 3 is characterized in that: described tube furnace has the stainless steel reaction pipe of quartz socket tube in being.
7, method according to claim 3 is characterized in that: the spacing on described metal grill and Zn powder surface is 3mm.
8, method according to claim 3 is characterized in that: the flow of the rare gas element of described feeding is 80-120 cubic centimetre/second; In the reaction process, the intraductal atmospheric pressure of described tube furnace maintains 0.003atm; The inlet end temperature of described tube furnace was kept 45 minutes at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature.
9, a kind of ZnO nano-wire array is the ZnO nano wire of evenly growing at metal grill, and the diameter of described ZnO nano wire is 20-60nm, tip curvature radius 3-10nm; This ZnO nano-wire array is made by following method:
1) metal grill that is the 15-25 micron with warp and parallel spacing is as substrate, and the catalyzer of plating one deck 10-100nm on described substrate, described catalyzer be golden, titanium or nickel;
2) metal grill that will handle through described step 1), the container that fills the container of Zn powder and fill the Se powder are all put into tube furnace; The container of described metal grill and the described Zn of filling powder all places in the flat-temperature zone of described tube furnace, and described metal grill places on the container of the described Zn of filling powder, and the spacing on described metal grill and described Zn powder surface is 2-5mm; The container of the described Se of filling powder places the inlet end of described tube furnace;
3) feeding flow to the inlet end of tube furnace is that the rare gas element of 60-140 cubic centimetre/second makes the intraductal atmospheric pressure of described tube furnace maintain 0.001-0.005atm in reaction process; The inlet end temperature that makes described tube furnace was kept 30-60 minute at 300-400 ℃ at 350-360 ℃, flat-temperature zone temperature, obtained described ZnO nano-wire array.
CN 200310113384 2003-11-18 2003-11-18 Zinc oxide nano-wire and its preparation method and application Expired - Fee Related CN1291920C (en)

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Publication number Priority date Publication date Assignee Title
CN1313377C (en) * 2005-07-14 2007-05-02 天津大学 Method for large scale quick preparation of one-dimension zinc oxide array thin film in aqueous solution
CN100372776C (en) * 2005-12-30 2008-03-05 北京科技大学 Ultra-fine zinc oxide nonometer line and its preparation method
CN100396615C (en) * 2006-06-30 2008-06-25 华东师范大学 Process for preparing nano ZnO
CN101580267B (en) * 2009-02-23 2015-09-30 中山大学 The method of low-temperature heat zinc and catalyst growth nano structure of zinc oxide and application thereof
CN101997084B (en) * 2010-09-10 2012-11-07 江苏大学 CuPc/ZnO organic/inorganic compound solar battery and preparation method thereof
CN102476787A (en) * 2010-11-26 2012-05-30 海洋王照明科技股份有限公司 Preparation method of ZnO nanowire array
CN102539462B (en) * 2011-11-11 2014-04-16 中国科学院苏州纳米技术与纳米仿生研究所 In-situ characterization method for nano wires
CN102941079B (en) * 2012-11-07 2014-10-15 上海大学 Method for preparing photoelectric catalyst multilayer ZnO nanowire array
CN105220229B (en) * 2015-11-06 2018-08-24 中国科学院理化技术研究所 Preparation method of ZnO single crystal nanotube array
CN108821326B (en) * 2018-06-27 2020-05-12 五邑大学 ZnO nano material and preparation method thereof
CN112158875A (en) * 2020-10-09 2021-01-01 南京信息工程大学 Preparation method of isolated ZnO micron rod

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