CN101823759A - Continuous large-area zinc oxide nano-sheet and preparation method thereof - Google Patents
Continuous large-area zinc oxide nano-sheet and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002135 nanosheet Substances 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000002127 nanobelt Substances 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000005468 ion implantation Methods 0.000 claims description 4
- 239000002096 quantum dot Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 238000006263 metalation reaction Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract 2
- 239000012528 membrane Substances 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract 1
- 239000004312 hexamethylene tetramine Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 42
- 239000011701 zinc Substances 0.000 description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 31
- 229910052725 zinc Inorganic materials 0.000 description 31
- 239000010408 film Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000005498 polishing Methods 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 241000446313 Lamella Species 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 photoelectric device Substances 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to continuous large-area zinc oxide nano sheets and a preparation method thereof, belonging to the technical field of nano material. The preparation method comprises the following steps: building a micro-nano structure on a metal and metal oxide substrate as required; dispersing zinc nitrate and hexamethylenetetramine in deionized water by use of the hydrothermal synthesis method, and softly stirring for dissolution; subsequently, reacting at a constant temperature of 70 to 110 DEG C for 10 minutes to 10 hours, taking out the sample, cleaning and drying to obtain a continuous porous membrane consisting of zinc oxide nano sheets on the substrate. The thickness of the obtained zinc oxide nano sheets is between 1 to 100 nanometers, and the nano sheets are connected with each other on the substrate to form a porous structure, wherein the aperture of the porous structure is between 0.5 to 3 mu m and the total thickness of the porous zinc oxide layer is between 100 nm to 50 mu m. Such continuous zinc oxide porous membrane can form a free independent structure after the substrate is removed, and the application field thereof includes gas sensor, solar battery material, surface coating, nano photoelectric device and so on.
Description
Technical field
The present invention relates to large-area, successive porous-film technology of preparing that a kind of zinc oxide nano-sheet is formed, belong to technical field of nano material, its Application Areas comprises aspects such as gas sensor, solar cell material, top coat and nano photoelectric device.
Technical background
Zinc oxide, owing to have excellent photoelectric characteristic, thermostability and chemical stability etc. apply on the high-tech products such as photoelectric device, gas sensor, piezoelectric transducer widely.The exploitation nano structure of zinc oxide both can further be studied the performance of zinc oxide on the low-dimensional yardstick, again can the development of new device.Invention about nano structure of zinc oxide is a lot, and the nano structure of zinc oxide overwhelming majority of report is the structure than big L/D ratio of having of growing fast and forming along [0001] direction, as nanometer rod, nano wire etc.Different with it is, if along [0110] direction, promptly with [0001] vertical direction, growth velocity comparatively fast then can form nano belt or nano flake, and such nano belt or nanometer sheet are hopeful to form the successive vesicular structure.Successive porous zinc bloom film can form independently film after having certain thickness, does not need the support of substrate, and the more applications scope can be arranged.Wang Zhonglin seminar has reported in calendar year 2001 and has utilized thermal evaporation deposition process to obtain spiral nanometer band and the nano-rings structure (W.P.Zheng that grows fast along [0110] direction, et al., Science 291 (2001) 1947), though these structural tables reveal particular performances, on technology, there is not the large-area preparation of implementation rule.Chinese invention patent application specification CN1970683A has disclosed with hydrothermal method depositing zinc oxide on silicon substrate, the preparation zinc oxide nano-sheet.But illustrated in this patent what prepare with silicon substrate is the sexangle zinc oxide thin slice that is separated from each other, and does not form the successive structure.The vesicular structure that laminar zinc oxide is formed is not seen patent or patent application.
Literature search is found, the paper that people such as Z.H.Jing deliver " Fabrication and Gas-Sensing Properties ofPorous ZnO Nanoplates; Adv.Mater.20 (2008) 4547 ", and the paper " Effective electron collection in highly (110)-oriented ZnO porous nanosheet frameworkphotoanode; Nanotechnology 21 (2010) 065703 " delivered of people such as X.Y.Wang, respectively under 400 and 500 ℃ of high temperature, the thermal treatment precursor obtains lamella zinc oxide structure, on each sheet zinc oxide, a lot of holes are arranged, with the present patent application to form vesicular structure by a lot of zinc oxide thin slices different, and complicated process of preparation.And this successive vesicular structure of present patent application is compared with most of existing dispersive nano structure of zinc oxide, in application such as gas sensor, piezoelectric device and combustion sensitized solar battery very big advantage is arranged.
On the other hand, for the application of zinc-oxide nano device, large-area (more than 1 square centimeter), repeatably nanostructure preparation technology is particularly important.The preparation technology of present nano structure of zinc oxide can be divided into vapour deposition and liquid deposition.Vapour deposition comprises laser molecular beam epitaxy, microwave magnetron sputtering, pulsed laser deposition, spraying high temperature pyrolysis, metal organic vapor phase epitaxy (MOCVD) and thermal evaporation etc., these methods can obtain the big area sample, but the growth velocity of film is slow, thickness is limited, and is with high costs.For example Chinese patent application CN200710176926.6 utilizes carrier gas to feed the zinc source in MOCVD equipment, growth one deck zinc sealing coat on substrate, utilize carrier gas to feed zinc source and oxygen, make on the zinc sealing coat, to obtain nanometic zinc oxide rod array epitaxial film, complex process.Chinese patent CN200810071953.1 utilizes thermal evaporation to obtain the dispersive zinc oxide nano-sheet, and this method controllability and repeatability are not enough.Liquid phase process can be realized multiple different low dimensional structures, but mostly is the dispersive powder and often multiple low dimensional structures is mixed in together, and this has limited the application of this method greatly.Chinese patent CN200910048958.7 utilizes solvent thermal reaction, under 110-150 ℃ temperature, react 6-12h, dry 5～12h at 40～60 ℃ after being cooled to room temperature, the product centrifugation is washed, obtain the ZnO nanometer rod, complex process, and product is the powder that disperses, and the pattern of powder is difficult to consistent with size.Other patents relevant with nano structure of zinc oxide also have similar problem, as Chinese patent CN200910113962.7 (nano wire) and Chinese patent CN200810153801.6 (nanotube) or the like.Therefore, in order to overcome the expensive and low growth velocity of vapour deposition, overcome the discontinuity and the low repeatability of liquid deposition, need a kind of preparation technology that can realize big area, successive nano structure of zinc oxide of exploitation, this technology itself has advantages such as the technology of liquid phase method is simple, with low cost simultaneously, also has the characteristics such as continuous film structure, repeatability of present vapor phase process.
Summary of the invention
What the present invention is directed in the technical background to be set forth lacks the successive nano structure of zinc oxide, and can't realize large-area, repeatably, weak point such as preparation technology cheaply, propose a kind ofly in metal base and metal oxide substrate, to utilize suitable Hydrothermal Preparation technology to realize large-area, the successive porous zinc bloom film of forming by zinc oxide nano-sheet.
Large-area, successive zinc oxide method for preparing porous film: the first step: ultrasonic cleaning metal base or metal oxide substrate; Second step: utilize hydrothermal synthesis method, zinc nitrate and vulkacit H are dispersed in the deionized water, the add-on of zinc nitrate is at 0.005-0.05mol/l, the vulkacit H add-on is at 0.005-0.05mol/l, zinc nitrate and vulkacit H mol ratio are controlled between the 0.5-2.0, after the gentle agitation dissolving, the baking oven of putting into 70-110 ℃ heats 10min-10h, taking out sample cleans and dries, obtain sheet thickness between the 1-100 nanometer, the continuous poriferous Zinc oxide film of aperture between 0.5-3 μ m.
Described metal and metal oxide substrate include but not limited to metallic aluminium, titanium and copper etc., and metal oxide includes but not limited to aluminum oxide, titanium oxide and cupric oxide etc.
Described preparation method before hydro-thermal is synthetic, constructs low dimensional structures in metal base or metal oxide substrate.
Describedly constructing low dimensional structures in metal substrate surface, is to realize low dimensional structures in the metallic surface by technologies such as chemical rightenning, electrochemical etching and etchings, comprises nano dot, nano belt and micron ledge structure etc.
Metal oxide obtains in the following way: the layer of oxide layer that obtains in corresponding metallic surface by the metallic surface anodic oxidation, or the zone of oxidation that realizes by thermooxidizing metal or ion implantation metallic surface, or metal oxide powder compression and agglomerating bulk, if construct low dimensional structures at the metal oxide substrate surface, be when obtaining metal oxide, to form low dimensional structures, promptly directly obtain the zone of oxidation that the surface has low dimensional structures by the metallic surface anodic oxidation, or by the surperficial zone of oxidation that has nanostructure of powder sintering technology realization, or by thermooxidizing metal or the surperficial zone of oxidation that has nanostructure of ion implantation metallic surface realization.Described low dimensional structures comprises nanoporous, nano dot and nano-wire array structure etc.
Described hydrothermal method synthesis technique, its temperature of reaction between 70-110 ℃, hydro-thermal synthetic Zn (OH) in such temperature range
2Can decompose generation ZnO, prepare the ZnO nano thin-film.
Described hydrothermal method synthesis technique, its reaction times is between 10 minutes to 10 hours, because vulkacit H is a weak base, OH
-Slowly discharge in reaction, the longest 10 hours is can react fully completely in order to allow to solvent.The shortest ten minutes reaction times can obtain thin porous zinc bloom film.
Described hydrothermal method synthesis technique, the total thickness of prepared porous zinc bloom layer is between 100nm-50 μ m, and thickness depends on total zinc ion content, temperature of reaction and reaction times.
Described vesicular structure is meant the vesicular structure that zinc oxide nano-sheet is interconnected to form, rather than tightly packed formation dense structure, neither not have the dispersed texture that connects each other.Single zinc oxide nano-sheet thickness is between 1-100nm, and the aperture of vesicular structure is at 0.5-3 μ m.Sheet thickness is relevant with selected substrate with hydro-thermal technology with the vesicular structure pore size that thin slice connects into.
Described successive, large-area preparation technology are meant that selected area of base is big, at 1-100cm
2Between, and porous zinc bloom grows on such area that to obtain film be uniformly, continuous uninterrupted.
The preparation method of large-area, successive zinc oxide vesicular structure of the present invention, selecting has better coupling metal and metal oxide with zinc oxide, less just because of the lattice mismatch between substrate and the zinc oxide, the easy nucleating growth of ZnO utilizes metal and metal oxide as base material, and the film that grows is even continuously, after experiment finishes, solution presents transparence, and does not precipitate, and zinc oxide is long all in substrate.And, this growth that in metal and metal oxide substrate, realizes fast, fixes a point, to metal and metal oxide substrate require low, in the substrate of various patterns, comprise a micron step, nanoporous, nano wire etc., can both realize large-area, successive porous zinc bloom nanostructure.Same technology on glass and silicon, is difficult to obtain similar structures in other substrates, and growth velocity is very low simultaneously.Compared with prior art, coating growth speed of the present invention is fast, productive rate is high, hydro-thermal technology is simpler, and can realize in multiple substrate.Resulting zinc oxide thin slice has only 5-100nm thickness, and these thin slices can be formed vesicular structure again, and this provides convenience for the application of nano structure of zinc oxide.
Description of drawings
Fig. 1 is the sem photograph of the porous zinc bloom that obtains of embodiment 1
Fig. 2 is the atomic force microscope photo of embodiment 2 substrates
Fig. 3 is the sem photograph of the porous zinc bloom that obtains of embodiment 2
Fig. 4 is the sem photograph of embodiment 3 substrates
Fig. 5 is the sem photograph of the porous zinc bloom that obtains of embodiment 3
Fig. 6 is the sem photograph of the porous zinc bloom that obtains of embodiment 3
Fig. 7 is the sem photograph of embodiment 6 substrates
Fig. 8 is the sem photograph of the porous zinc bloom that obtains of embodiment 6
Fig. 9 is the sem photograph of the porous zinc bloom that obtains of embodiment 6
Figure 10 is the sem photograph of the porous zinc bloom that obtains of embodiment 7
Embodiment
Further specify content of the present invention below in conjunction with example:
Case one: do not constructing the metallic aluminium surface preparation porous zinc bloom film of nanostructure
With surface-area is 100cm
2Commercial-purity aluminium, trade mark 1A95 soaked in acetone 10 minutes, behind the deionized water rinsing, the mixed solution of putting into 60 ℃ 6.0% weight percent phosphoric acid and 1.8% weight percent chromic acid soaks removed surface oxide layer in 30 minutes.
Aluminium substrate is put into beaker, add 0.005mol Zn (NO
3)
2, the 0.005mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 100 ℃ heats 1h, reaction is taken out sample after finishing from beaker, the baking oven of putting into 60 ℃ is dried.The porous zinc bloom surface topography that obtains as shown in Figure 1.The about 10-20nm of the thickness of zinc oxide lamella, a lot of zinc oxide thin slices are interconnected to form the vesicular structure film of successive pore size between 0.5-2 μ m.
Case two: have the metal titanium surface preparation porous zinc bloom film of nano belt structure
With area is 50cm
2, thickness is the high purity titanium sheet (99.5wt%) of 200 μ m, is hydrofluoric acid in volume ratio: nitric acid: polishing is 2 minutes in the polishing solution of water=1.5: 12: 6, and polish temperature is 10 ℃, and the polishing fluid cumulative volume is 200ml, and flushing is oven dry also.Utilize atomic force microscope test surfaces structure, as shown in Figure 2, obtain the nano strip surface tissue.
The titanium metal substrate that will have banded nanostructure is put into beaker, adds 0.02mol Zn (NO
3)
2, the 0.02mol vulkacit H, pour the solution that deionized water is made into 1000ml into, the baking oven of putting into 90 ℃ heats 3h, after reaction finishes sample is taken out from beaker, the baking oven of putting into 60 ℃ is dried.The porous zinc bloom surface topography that obtains as shown in Figure 2, the about 30-50nm of the thickness of zinc oxide lamella, a lot of zinc oxide thin slices are interconnected to form the vesicular structure film of successive pore size between 0.5-2 μ m.
Case three: have the metallic aluminium surface preparation porous zinc bloom film of micron ledge structure
With purity 99.999% thickness 200 μ m area 20cm
2High-purity aluminum foil, in acetone, soaked 10 minutes, behind the deionized water rinsing, directly put into electrolyzer as anode, be negative electrode with the graphite cake, the ratio of cathode area and annode area is 2: 1.Electrolytic solution consists of 0.1MNaCl and 0.1M oxalic acid, and temperature is 10 ℃, and the cumulative volume of electrolytic solution is 500ml in the electrolyzer, and electrolyzer places the low temperature thermostat bath of 2L.Anodizing time is 15 minutes, cleans.The ledge structure that obtains as shown in Figure 4.
Beaker is put in the metallic aluminium substrate that will have micron ledge structure, adds 0.30mol Zn (NO
3)
2, the 0.15mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 80 ℃ heats 1h, reaction is taken out alumina formwork after finishing from beaker, the baking oven of putting into 60 ℃ is dried.The porous zinc bloom surface topography that obtains as shown in Figure 5, the about 20-40nm of the thickness of zinc oxide lamella, a lot of zinc oxide thin slices are interconnected to form the vesicular structure film of successive pore size between 0.5-2 μ m.The step that Fig. 6 shows micrometer structure still is influential to the pattern of porous zinc bloom film, the successive porous-film also can rise and fall along with the fluctuating of step, obtain more complicated composite structure, the thin slice that reaches Nano grade on the microcosmic is interconnected to form the continuous film of vesicular structure, and continuous film has the same fluctuating in entablement rank at micro-meter scale.
Case four: prepare porous zinc bloom at the copper surface of not constructing low dimensional structures
With area is that 10 square centimeters, thickness are the industrial pure copper of 200 μ m, and at mixed polishing solution, it consists of the hydrogen peroxide of 650ml/l, the sulfuric acid of 30g/l, the ethylene glycol of 100g/l, 1g/l tensio-active agent OP-10 and 5g/l brightening agent, 20 ℃ of polishings 5 minutes, obtain the copper sheet of surfacing light.
The titanium oxide that will have nanohole array is put into beaker together with the titanium substrate, adds 0.05mol Zn (NO
3)
2, the 0.05mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 70 ℃ heats 9h, reaction is taken out alumina formwork after finishing from beaker, the baking oven of putting into 60 ℃ is dried.Resulting porous zinc bloom structure is similar to Fig. 5.
Case five: have the aluminium surface preparation porous zinc bloom of nano particle
With purity 99.999% thickness 200 μ m area 20cm
2High-purity aluminum foil, in acetone, soaked 10 minutes, behind the deionized water rinsing, directly put into electrolyzer as anode, be negative electrode with the graphite cake, the ratio of cathode area and annode area is 2: 1.Electrolytic solution consists of 0.03M oxalic acid, and temperature is 10 ℃, and the cumulative volume of electrolytic solution is 500ml in the electrolyzer, and electrolyzer places the low temperature thermostat bath of 2L.Anodizing time is 10 seconds, cleans.Obtain uniform nano particle respectively on its surface.
Add 0.01mol Zn (NO
3)
2, the 0.02mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 90 ℃ heats 30min, reaction is taken out sample after finishing from beaker, the baking oven of putting into 60 ℃ is dried.Resulting porous zinc bloom structure is similar to Fig. 1.
Case six: prepare porous zinc bloom at alumina surface with nanohole array
With purity 99.999% thickness 200 μ m area 40cm
2High-purity aluminum foil, in acetone, soaked 10 minutes, behind the deionized water rinsing, directly put into electrolyzer as anode, be negative electrode with the graphite cake, the ratio of cathode area and annode area is 2: 1.Electrolytic solution consists of 0.3M oxalic acid, and electrolysis voltage is 40V, and the cumulative volume of electrolytic solution is two liters in the electrolyzer, and electrolyzer places the water bath with thermostatic control of 5L, and the water bath with thermostatic control design temperature is 0 ℃.Anodizing time is 2 hours, puts into 60 ℃ the 6.0% weight percent phosphoric acid and the mixed solution of 1.8% weight percent chromic acid after the cleaning and soaks 4 hours removal zone of oxidation, and taking-up is cleaned standby.Will be through once electrolytic and the aluminium foil after removing zone of oxidation carry out re-electrolysis, electrolysis time is 1 hour, other conditions are constant, form the layer of even vesicular structure on the surface of metallic aluminium, the aperture is 40nm, oxidated layer thickness is 3 μ m.The microstructure of porous alumina as shown in Figure 7.
The aluminum oxide that will have nanohole array is put into beaker together with aluminium substrate, adds 0.01mol Zn (NO
3)
2, the 0.01mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 110 ℃ heats 8h, reaction is taken out sample after finishing from beaker, the baking oven of putting into 60 ℃ is dried.The porous zinc bloom surface topography that obtains such as Fig. 8 and shown in Figure 9.Fig. 8 shows, the about 40-80nm of the thickness of zinc oxide lamella.Fig. 9 shows that a lot of zinc oxide thin slices are at 3600 μ m
2Area on be interconnected to form the vesicular structure film of successive pore size between 0.5-3 μ m.
Case seven: prepare porous zinc bloom in titania surface with nanohole array
With area is 50cm
2, thickness is the high purity titanium sheet (99.5wt%) of 200 μ m, is hydrofluoric acid in volume ratio: nitric acid: polishing is 3 minutes in the polishing solution of water=1.5: 12: 6, and polish temperature is 0 ℃, and the polishing fluid cumulative volume is 200ml, and flushing is oven dry also.Porous titanium oxide is at NH
440V in the electrolytic solution that F (0.5wt%) and ethylene glycol are formed, 10 ℃ of electrolysis 2h obtain.Aperture 100nm, oxidated layer thickness are 2 μ m.
The titanium oxide that will have nanohole array is put into beaker together with the titanium substrate, adds 0.015mol Zn (NO
3)
2, the 0.015mol vulkacit H is mixed with the solution of 1000ml, the baking oven of putting into 90 ℃ heats 4h, reaction will be taken out in the sample beaker after finishing, the baking oven of putting into 60 ℃ is dried.As shown in figure 10, the about 50-100nm of the thickness of zinc oxide lamella, a lot of zinc oxide thin slices are interconnected to form the vesicular structure film of successive pore size between 0.5-2 μ m.
Claims (10)
1. continuous large-area zinc oxide nano-sheet, it is characterized in that: the vesicular structure that described zinc oxide nano-sheet is interconnected to form is not tightly packed formation dense structure, neither not have the dispersed texture that connects each other.
2. the described zinc oxide nano-sheet of claim 1, it is characterized in that: the aperture of vesicular structure is at 0.5-3 μ m, and the total thickness of zinc oxide nano-sheet is between 100nm-50 μ m, and single zinc oxide nano-sheet thickness is between 1-100nm.
3. the preparation method of the described zinc oxide nano-sheet of claim 1, it is characterized in that: described preparation method was divided into for two steps: (1) ultrasonic cleaning metal base or metal oxide substrate; (2) zinc nitrate and vulkacit H are dispersed in deionized water, gentle agitation dissolving back forms mixing solutions, metal base or metal oxide substrate inserted carry out the thermostat(t)ed water thermal response in the mixing solutions, take out sample and clean and dry, in metal base or metal oxide substrate, obtain the continuous poriferous film of forming by zinc oxide nano-sheet.
4. the described preparation method of claim 3 is characterized in that: before hydro-thermal is synthetic, construct low dimensional structures in metal base or metal oxide substrate.
5. the described preparation method of claim 4, it is characterized in that: describedly construct low dimensional structures in metal substrate surface, be to realize low dimensional structures in the metallic surface by technologies such as chemical rightenning, electrochemical etching and etchings, low dimensional structures comprises nano dot, nano belt and micron ledge structure.
6. the described preparation method of claim 3, it is characterized in that: metal oxide obtains in the following way: the zone of oxidation that obtains in corresponding metallic surface by anodic oxidation, or the zone of oxidation that realizes by thermooxidizing metal or ion implantation metallic surface, or metal oxide powder agglomerating bulk.
7. the described preparation method of claim 4, it is characterized in that: describedly construct low dimensional structures at the metal oxide substrate surface, be when obtaining metal oxide, to form low dimensional structures, promptly directly obtain the zone of oxidation that the surface has low dimensional structures by the metallic surface anodic oxidation, or by the surperficial zone of oxidation that has nanostructure of powder sintering technology realization, or by thermooxidizing metal or the surperficial zone of oxidation that has nanostructure of ion implantation metallic surface realization, low dimensional structures comprises nanoporous, nano dot and nano-wire array structure etc.
8. the described preparation method of claim 3, it is characterized in that: the volumetric molar concentration of zinc nitrate is 0.005-0.05mol/l, and the vulkacit H volumetric molar concentration is 0.005-0.05mol/l, and zinc nitrate and vulkacit H mol ratio are controlled at 0.5-2.0: between 1.
9. the described preparation method of claim 3, it is characterized in that: the temperature of reaction of thermostat(t)ed water thermal response is between 70-110 ℃, and the reaction times is between 10 minutes to 10 hours.
10. the described preparation method of claim 3, it is characterized in that: the metal as substrate includes but not limited to metallic aluminium, titanium and copper, includes but not limited to aluminum oxide, titanium oxide and cupric oxide, area of base 1-100cm as the metal oxide of substrate
2Between.
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