CN102553588B - Catalyst for zinc oxide nanowire growth, and application of catalyst - Google Patents
Catalyst for zinc oxide nanowire growth, and application of catalyst Download PDFInfo
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- CN102553588B CN102553588B CN201210008229.0A CN201210008229A CN102553588B CN 102553588 B CN102553588 B CN 102553588B CN 201210008229 A CN201210008229 A CN 201210008229A CN 102553588 B CN102553588 B CN 102553588B
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Abstract
The invention discloses a catalyst for a zinc oxide nanowire and application of the catalyst in growth of the zinc oxide nanowire. The catalyst for the zinc oxide nanowire is an Au/M multilayer film or an Au-M alloy film formed by metal Au and metal M with a mass ratio of 0.2 to 5:1, wherein M is a metal, the eutectic point of which and Zn is below 500 DEG C, preferably, M is a metal, the eutectic point of which and Zn is below 300 DEG C. Compared with gold as a catalyst under similar conditions, the catalyst is used for the growth of the zinc oxide nanowire, and the higher growth rate of the zinc oxide nanowire can be obviously obtained, the density of arrays of the prepared zinc oxide nanowire is larger, the diameter and the length of the nanowire are more uniform, and the grown zinc oxide nanowire has higher crystalline quality.
Description
Technical field
The present invention relates to the preparation field of nano material, particularly grow catalyst used and application thereof of a kind of zinc oxide nanowire orthogonal array.
Background technology
One dimension oxidisability nano wire has large draw ratio, and large exciton bind energy at room temperature has large energy gap.Therefore there is excellent photoelectric characteristic, aspect nano laser, field emitting electronic source, solar cell and gas sensitive device, having broad application prospects.And controllably synthesizing zinc oxide nano wire is the basis of its device application.
Chemical vapour deposition technique is to prepare one of the most frequently used method of zinc oxide nanowire, and this method is compared with other method, and the zinc oxide nanowire of growing has best crystalline quality and orientation.But chemical vapour deposition technique needs very high synthesis temperature (500 ℃ of >) conventionally, simultaneously, the gold of take is prepared the problem of diameter that zinc oxide nanowire also exists nano wire, length, Density Distribution inequality as catalyst, and this gives, and device is integrated has caused great difficulty.
The present invention intends in traditional Au catalyst film, mixing the metal of low melting point, with Au-M alloy, does catalyst film, makes the zinc oxide nanowire of preparation have better Density Distribution and pattern.In nano wire gas-liquid-solid method growth course, catalyst and reactant need to form the catalyst drop of congruent melting, drip gauge mask has higher coefficient of viscosity, be conducive to adsorb vapor-phase reactant, when absorption reactant in drop after hypersaturated state, will from drop, separate out, because reactant is constantly separated out deposition, nano wire is constantly growth just.The eutectic point of gold-zinc is more than 400 ℃, so the temperature of zinc oxide nanowire growth is conventionally all higher, and this has limited the practical application of nano-material greatly.And in gold thin film, sneak into low melting point and can form with zinc the metal of eutectic point, can greatly reduce the synthesis temperature of zinc oxide nanowire.
Summary of the invention
The object of the invention is, in order to address the above problem, provides a kind of catalyst of zinc oxide nanowire growth
The application of the catalyst that above-mentioned a kind of zinc oxide nanowire growth is provided for 2 o'clock of object of the present invention aspect zinc oxide nanowire growth.
Adopt new catalyst formulation, it can effectively control its density and pattern in preparing the growth course of zinc oxide nanowire.
Technical scheme of the present invention
A kind of zinc oxide (ZnO) nanowire growth catalyst used, for being that Au:M is the formed Au/M multilayer film of 0.2～5:1, Au-M alloy firm in mass ratio by metal A u and metal M, wherein M is eutectic point with the Zn metal below 500 degree, be preferably eutectic point with the Zn metal below 300 degree, as gallium.
Above-mentioned a kind of ZnO nano-wire catalyst used of growing, the preparation method of Au/M multilayer film, Au-M alloy firm, adopts electron-beam vapor deposition method, specifically comprises the steps:
The preparation of Au/M multilayer film:
Take simple metal Au and simple metal Ga is evaporation source, at a-face Al
2o
3or c-face Al
2o
3on backing material, first deposit one deck Ga, and then deposition layer of Au, so hocket, topmost one deck is Au metallic film, finally obtains the catalyst A u/M multilayer film of zinc oxide nanowire; It is 5 kW that above-mentioned deposition process is controlled beam power, and sedimentation rate is 0.01A/s, and gross thickness is 1.5-10nm, and thickness in monolayer is adjustable, and the proportion control of Au and Ga is between 0.2～5:1;
The preparation of Au-M alloy firm:
Take pure Au and pure Ga metal is evaporation source, adopts the method preparation of codeposition, simultaneously by Au and Ga thin film deposition to a-face Al
2o
3or c-face Al
2o
3on backing material, thickness is 1.5-10nm, and the ratio between Au and Ga is by regulating Au film and Ga thin film evaporation speed to regulate, and ultimate constituent proportioning is between 0.2～5:1, and the evaporation rate of Au film and Ga film is by regulating beam power to regulate.
In addition, catalyst A u/M multilayer film, the Au-M alloy firm of above-mentioned zinc oxide nanowire can also adopt ionic-implantation, control accelerating potential 30kV, and line size is 0.19nA, and the time is 70ms.
Utilize above-mentioned a kind of ZnO nano-wire catalyst used of growing to carry out the growth of ZnO nano-wire, step is as follows:
(1), by etc. zinc oxide nano powder and the graphite powder of mass ratio fully grind, pack in quartz boat;
Described graphite powder is preferably crossed 300 mesh sieves;
(2), the a-face Al of Au/M multilayer film or Au-M alloy firm catalyst will be coated with
2o
3or c-face Al
2o
3backing material is put on the powder of quartz boat;
(3), quartz boat is put in quartz glass tube, then quartz glass tube is put into tube furnace, and make quartz boat
Aim at tube furnace centre;
(4), to control heating rate be that 10-60 ℃/min is warming up to after 880-1200 ℃, passes into 10-120 Sccm Ar gas, keeps 1-60min, stops Ar, naturally cools to room temperature, the a-face Al of gained
2o
3or c-face Al
2o
3the grey matter of substrate surface is ZnO nano-wire.
Above-mentioned a kind of ZnO nano-wire catalyst used of growing, is applicable to the growth preparation of all kinds of zinc oxide nanowires based on gas-liquid-solid principle.
Beneficial effect of the present invention
A kind of ZnO nano-wire of the present invention catalyst used of growing, owing to containing M metal, as gallium, make it when growing for ZnO nano-wire, the growth rate of ZnO nano-wire is greatly improved, in a preferred embodiment of the present invention, the growth rate of ZnO nano-wire than use pure Au to grow used as ZnO nano-wire catalyst time growth rate provide 4 times.
In addition, due to a kind of ZnO nano-wire of the present invention catalyst used of growing, owing to containing M metal, make it when growing for ZnO nano-wire, the ZnO nano-wire of growing in unit are is more, and stand density is large, in a preferred embodiment of the present invention, the stand density of ZnO nano-wire than use pure Au to grow used as ZnO nano-wire catalyst time stand density improved 33.3%, and diameter narrow distribution range, generally all in 100nm left and right.
Accompanying drawing explanation
The photo of the ESEM of the ZnO nano-wire of Fig. 1, embodiment 1 gained;
The photo of the ESEM of the ZnO nano-wire of Fig. 2, comparative example's 1 gained;
In Fig. 3, embodiment 2, surface is coated with the a-face Al of Au/Ga alloy firm catalyst
2o
3the EDX of backing material
Power spectrum;
The stereoscan photograph of the ZnO nano-wire top view of Fig. 4, embodiment 2 gained under low power lens (4500 times);
The ZnO nano-wire side view of Fig. 5, embodiment 2 gained is at the stereoscan photograph of high power lens (40000 times);
The ZnO nano-wire top view of Fig. 6, embodiment 2 gained is at the stereoscan photograph of high power lens (40000 times);
The curve map that the diameter of the ZnO nano-wire of Fig. 7, embodiment 2 gained distributes;
The ZnO nano-wire side view of Fig. 8, embodiment 3 gained is at the stereoscan photograph of high power lens (12000 times);
The ZnO nano-wire top view of Fig. 9, embodiment 3 gained is at the stereoscan photograph of high power lens (8000 times).
The specific embodiment
Below by embodiment, also by reference to the accompanying drawings the present invention is further set forth, but do not limit the present invention.
The present invention's nanowire deposition used Lindberg tube furnace, manufacturer is U.S. Thermo Scientific company;
ESEM adopts Quanta FEG type field emission scanning electron microscope, and manufacturer is FEI Co.;
Focused-ion-beam lithography adopts DualBeam type focused-ion-beam lithography system, WeiFEI company of growth producer;
Electron beam evaporation deposition adopts Explorer 14 type electron beam evaporation deposition instrument, and manufacturer is the U.S.
Denton company.
embodiment 1
A catalyst for zinc oxide nanowire growth, for being that Au:Ga is the formed Au/Ga duplicature of 1.5:1 in mass ratio by metal A u and metal Ga;
The preparation method of the catalyst A u/Ga duplicature of above-mentioned a kind of zinc oxide nanowire growth is as follows:
Adopt a-face Al
2o
3as backing material, deposited by electron beam evaporation method plates the gallium layer of 1nm on substrate, evaporation rate be 0.01A/s again on substrate deposited by electron beam evaporation method plate the gold layer of 1.5nm, evaporation rate is 0.01A/s.
The a-face Al processing with above-mentioned employing electron evaporation method
2o
3for backing material, with chemical vapour deposition technique growth of zinc oxide nano line, detailed process is as follows:
(1), by etc. the zinc oxide nano powder of mass ratio and the graphite powder of crossing 300 mesh sieves fully grind, pack in quartz boat;
(2), by the a-face Al of the catalyst A u/Ga duplicature that is coated with zinc oxide nanowire growth that adopts electron-beam vapor deposition method to obtain
2o
3backing material is put on the powder of quartz boat;
(3), quartz boat is put in quartz glass tube, then quartz glass tube is put into tube furnace, and make quartz boat aim at stove centre;
(4), to control heating rate be that 50 ℃/min is warming up to after 910 ℃, passes into 12 Sccm Ar gas, keeps 5min, stops, with as Ar gas, naturally cooling to room temperature, the substrate surface grey matter finally obtaining is ZnO nano-wire.
comparative example 1
As a comparison, under chemical vapor deposition method condition similarly to Example 1, the simple metal Au that the thickness of usining is 2.5nm is as the catalyst ZnO nano-wire of also having grown.
With ESEM, two ZnO nano-wire samples of embodiment 1 and comparative example's 1 gained are observed to sign respectively, result as shown in Figure 3 and Figure 4.From Fig. 3 and Fig. 4, can find out, under identical growth technique condition, it is very long as the ZnO nano-wire of catalyst growth that the Au/M multilayer film of take in embodiment 1 is Au/Ga multilayer film, to such an extent as to is mutually wound around.And the ZnO nano-wire sample length of growing while making catalyst with pure Au in comparative example 1 is short a lot, illustrate when the surface of growth substrate exists gallium, the growth rate of ZnO nano-wire greatly improves.
Under identical preparation process condition, the ZnO nano-wire sample average density that the Au-Ga of take is catalyst growth is 9/um
2; The ZnO nano-wire sample average density that the Au of take is catalyst growth is 6/um
2, density has improved 33.3%.The growth rate that the Au-Ga of take is the ZnO nano-wire of catalyst growth is 2um/min, and the growth rate that Au is the ZnO nano-wire of catalyst growth is 500nm/min, and growth rate has improved 4 times.
embodiment 2
First deposited by electron beam evaporation method is at a-face Al
2o
3on substrate, plate the Au film that one deck 1.5nm is thick, then use focused-ion-beam lithography (FIB) method to carry out the implantation of local Ga ion, ion beam milling condition is: accelerating potential 30kV, and line size is 0.19nA, etching period is 70ms, the circle that etch areas size is 20um for diameter.As shown in Figure 3, as can be seen from Figure 3, there is the peak of Ga in the Au thin film electronic energy dispersive spectrum (EDS) that the Ga+ of focused-ion-beam lithography rear region implants, illustrate that Ga is successfully implanted in Au film in EDS collection of illustrative plates.
The a face Al processing with FIB
2o
3for backing material, use chemical vapour deposition technique growing ZnO nano-wire, concrete growth course is as follows:
(1), by etc. the zinc oxide nano powder of mass ratio and the graphite powder of crossing 300 mesh sieves fully grind, pack in quartz boat;
(2), by the a-face Al of the catalyst A u/Ga alloy firm that is coated with zinc oxide nanowire growth that adopts ionic-implantation to obtain
2o
3substrate is put on the powder of quartz boat;
(3), quartz boat is put in quartz glass, then quartz glass tube is put into tube furnace, and make quartz boat aim at stove centre;
(4), to control heating rate be that 50 ℃/min is warming up to after 910 ℃, passes into 12 Sccm Ar gas, keeps 2min, stops Ar, naturally cools to room temperature, the substrate surface grey matter finally obtaining is ZnO nano-wire.
The stereoscan photograph of the ZnO nano-wire of gained under low power lens is 4500 times is shown in Fig. 4, as can be seen from Figure 4, the region of crossing at ion beam etching, ZnO nano-wire is fine and close and even, the orientation that has preferred growth, and around etch areas, the growth of ZnO nano-wire is suppressed greatly, the ZnO nano-wire of growth is thin and short, and density is low.The doping of this explanation Ga makes ZnO nano-wire have preferential growth trend.
Fig. 5,6 is respectively side view and the stereoscan photograph of top view under high power lens is 40000 times of the ZnO nano-wire of gained.From Fig. 5, Fig. 6, can find out the region of processing at FIB, ZnO nano-wire preferred growth, ZnO nano-wire length and diameter uniformity are all better.
Fig. 7 is the curve map that the diameter of the ZnO nano-wire of gained distributes.As can be seen from Figure 7, the region ZnO nano-wire of processing through FIB has good uniformity, and diameter narrow distribution range, generally all in 100nm left and right.
embodiment 3
With c face Al
2o
3for substrate, 1.5nm Au film is catalyst, with FIB technology Local treatment catalyst film, carries out the implantation of local Ga ion, ion beam milling condition is accelerating potential 30kV, line size is 0.19nA, and etching period is 70ms, the circle that etch areas size is 20um for diameter.
The c face Al processing with FIB
2o
3for backing material, use chemical vapour deposition technique growing ZnO nano-wire, concrete growth course is as follows:
(1), by etc. the zinc oxide nano powder of mass ratio and the graphite powder of crossing 300 mesh sieves fully grind, pack in quartz boat;
(2), by the c face Al of the catalyst A u/Ga alloy firm that is coated with zinc oxide nanowire growth that adopts ionic-implantation to obtain
2o
3substrate is put on the powder of quartz boat;
(3), quartz boat is put in quartz glass tube, then quartz glass tube is put into tube furnace, and make quartz boat aim at stove centre;
(4), to control heating rate be that 50 ℃/min is warming up to after 910 ℃, passes into 12 Sccm Ar gas, keeps 1min, stops Ar, naturally cools to room temperature, the substrate surface grey matter finally obtaining is ZnO nano-wire.The side view of the ZnO nanowire array of gained growth and the top view stereoscan photograph under low power lens is 12000 times and 8000 times, respectively as Fig. 8, shown in Fig. 9.From Fig. 8 and Fig. 9, can find out that the region of metal Ga, ZnO nano-wire vertical-growth are contained in the region of processing at FIB; And in the region of unprocessed mistake, not containing the region of metal Ga, the direction of growth of ZnO nano-wire is disorderly and unsystematic orientation.Illustrate that after substrate implantation Ga, the direction of growth of ZnO nano-wire also can change.
Foregoing is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (4)
1. a kind of utilize catalyst of zinc oxide nanowire growth to carry out zinc oxide nanowire growth method, the catalyst of described zinc oxide nanowire growth is for being that Au:M is the formed Au/M multilayer film of 0.2～5:1 or Au-M alloy firm in mass ratio by metal A u and metal M;
Wherein M is eutectic point with the Zn gallium below 500 degree, it is characterized in that step is as follows:
(1), the preparation of catalyst;
Adopt electron-beam vapor deposition method or magnetron sputtering method, at a-face Al
2o
3or c-face Al
2o
3on backing material, preparing thickness is Au/M multilayer film or the Au-M alloy firm catalyst film of 1.5-10nm, and film deposition rate is 0.01-0.05A/s;
(2), the growth of zinc oxide nanowire
1., by etc. zinc oxide nano powder and the graphite powder of mass ratio fully grind, pack in quartz boat;
2., step (1) is coated with to the a-face Al of Au/M multilayer film or Au-M alloy firm catalyst
2o
3or c-face Al
2o
3backing material is put on the powder of quartz boat;
3., quartz boat is put in quartz glass tube, then quartz glass tube is put into tube furnace, and make quartz boat aim at tube furnace centre;
4., to control heating rate be that 10-60 ℃/min is warming up to after 880-1200 ℃, passes into 10-120 Sccm Ar gas, keeps 1-60min, stops Ar, naturally cools to room temperature, the a-face Al of gained
2o
3or c-face Al
2o
3the surperficial grey matter of backing material is zinc oxide nanowire.
2. the method for claim 1, it is characterized in that the catalyst A u/M multilayer film of the zinc oxide nanowire in step (1) or the preparation of Au-M alloy firm adopt ionic-implantation to replace electron-beam vapor deposition method or magnetron sputtering method, in preparation process, control accelerating potential 30kV, line size is 0.19nA, and the time is 70ms.
3. method as claimed in claim 2, it is characterized in that in step (2) 1. described in graphite powder cross 300 mesh sieves.
4. the method for claim 1, is characterized in that described metal A u and metal M are that Au:M is 1.5:1 in mass ratio.
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| US11370023B2 (en) | 2019-01-28 | 2022-06-28 | Global Graphene Group, Inc. | Production of metal nanowires directly from metal particles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208094B2 (en) * | 2003-12-17 | 2007-04-24 | Hewlett-Packard Development Company, L.P. | Methods of bridging lateral nanowires and device using same |
| CN101407335A (en) * | 2008-08-27 | 2009-04-15 | 上海理工大学 | Method for preparing zinc oxide nano-wire by using zinc nano-particle |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208094B2 (en) * | 2003-12-17 | 2007-04-24 | Hewlett-Packard Development Company, L.P. | Methods of bridging lateral nanowires and device using same |
| CN101407335A (en) * | 2008-08-27 | 2009-04-15 | 上海理工大学 | Method for preparing zinc oxide nano-wire by using zinc nano-particle |
Non-Patent Citations (2)
| Title |
|---|
| "气-液-固法在半导体纳米线生长中的应用";彭英才等;《功能材料与器件学报》;20081031;第14卷(第5期);第867页最后一段 * |
| 彭英才等."气-液-固法在半导体纳米线生长中的应用".《功能材料与器件学报》.2008,第14卷(第5期),第867页最后一段. |
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