CN1487108A - Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process - Google Patents
Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process Download PDFInfo
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- CN1487108A CN1487108A CNA031317731A CN03131773A CN1487108A CN 1487108 A CN1487108 A CN 1487108A CN A031317731 A CNA031317731 A CN A031317731A CN 03131773 A CN03131773 A CN 03131773A CN 1487108 A CN1487108 A CN 1487108A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000004005 microsphere Substances 0.000 claims abstract description 38
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000004793 Polystyrene Substances 0.000 claims abstract description 25
- 229920002223 polystyrene Polymers 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 17
- 125000006850 spacer group Chemical group 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000011805 ball Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011806 microball Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 238000007772 electroless plating Methods 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 206010070834 Sensitisation Diseases 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008313 sensitization Effects 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001311 chemical methods and process Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- -1 silver ions Chemical class 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 13
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- 239000000839 emulsion Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 17
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- 238000010586 diagram Methods 0.000 description 6
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- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
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- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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Abstract
During the preparation of ordered nano structure metal material, correponding colloid crystal template is first prepared via capillary abstraction self-assembling method. Spacer is set between two parallel plates to form micro passage in the same thickness as the spacer, one end of the micro passage is soaked into microsphere emulsion so that the emulsion is driven by capillary effect to the micro passage to form ordered arrangement. The bottom of the micro passage is then soaked into sensitizing stannous ion solution, so that the surface of the microsphere has one layer of sensitizing stannous ion adsorbed and is sensitized. The present invention features the surface seed growing method and colloidal crystal of polystyrene microsphere as template. When the template is set inside chemical plating solution, some interval is formed between microspheres owing to electrostatic repulsion, and the interval permits forming metal shell in the outer surface of the medium microsphere.
Description
One, technical field
The present invention relates to the ordered nano-structure metallic substance, especially two and three dimensions ordered nano-structure metallic substance and the related preparation technology that is formed by the hollow metal sphere solid matter.
Two, background of invention
The nano porous metal material has many important use at aspects such as porous electrode, fuel cell, transmitter, catalysis and electrochemical capacitors.
In recent years, the science researcher began the preparation of the orderly nano porous metal material of special concern.It is found that this class material except the characteristic with general porous metal material, also has special optical property.For example, people such as Tessire find: adopt ordered nano porous structure gold film as substrate, Raman scattering is had tangible surperficial reinforcing effect.They find: this reinforcing effect result from fully material nano ordered feature (referring to Tessier, P.M.; Velev, O.D.; Kalambur, A.T.J.Am.Chem.Soc.2000,122,9554.) Wang Zhenlin etc. also predicts this class material and may become the preferred material of preparation infrared region broad-band gap photonic crystal (referring to Z.L.Wang, C.T.Chan, W.Y.Zhang, N.B.Ming, and Ping Sheng, Phys.Rev.B 2001,64,113108).
The preparation of micro-nanometer ordered structure metallic substance generally is to adopt following operation.At first monodispersed medium ball (commonly used is silicon-dioxide or polystyrene microsphere) is passed through process of self-organization, form the colloidal crystal of orderly structural arrangement; With such crystal is template, inserts the respective metal material by physics or chemical process in its space, adopts appropriate means to remove template at last, just obtains nanoporous ordered structure metallic substance.Here, the size in aperture depends on the size of the microballoon that forms template, can be from tens nanometer to several microns.The advantage that adopts this method is to guarantee fully that institute's duplicating material has the high-sequential constitutional features.This method cost is low simultaneously, the efficient height, and the material that is obtained has very high specific surface area.
Because the space of template is the three-dimensional space of a nanoscale, bending, different with growing metal film on flat substrate, growing metal is owing to being subjected to many constraints to seem difficult unusually in such nanometer space.By years of researches, the scientific research personnel has explored and has developed some otherwise effective technique and prepared orderly nano structure metal materials.
Prior art one: deposition/chemical conversion process, referring to Yan, H.W.; Blanford, C.F.; Holland, B.T.Adv.Mater.1999,11,1003.The synoptic diagram of this method is seen Figure 1A.At first adopt monodispersed polystyrene microsphere or silicon dioxide microsphere to be self-assembled into colloidal crystal; Then the metal ion precursor solution is penetrated in the colloidal crystal template space.In order fully to guarantee the moistening of solution and microballoon, need choose appropriate solvent.Solution is penetrated in the nanometer space by the capillary force effect.Then, in the space of template, introduce oxalic acid, generate the lower metal-salt of solubleness by precipitin reaction.These metal-salts that are deposited in the stencil apertures have formed orderly skeleton structure, become the precursor of porous metal material.Then, sample is heated (for polystyrene microsphere, template is also removed simultaneously) in air, metal alkoxide is converted into metal oxide.By the reduction reaction under hydrogen atmosphere, metal oxide is reduced into metal, thereby forms orderly nano-porous structure metallic substance at last.
Prior art two: adopt the minimum nano-metal particle of size directly to insert stencil apertures, referring to Velev, O.D.; Tessier, P.M.; Lenhoff, A.M.Nature 1999,401, and 548.Its synoptic diagram is seen Figure 1B.This method is to prepare the very little metal nanoparticle of size earlier, then it is mixed with the colloid micro ball latax; Under action of gravity, when colloid micro ball was self-assembled into colloidal crystal, these nano-metal particles also deposited in the space of template simultaneously.Remove template by appropriate means and just obtain required orderly nano structure metal materials afterwards.
Prior art three: electrochemical method, referring to Wijnhoven, J.E.G.J.; Zevenhuuizen, S.J.M.; Hendriks, M.A.Adv.Mater.2000,12,888.Its synoptic diagram is seen Fig. 1 C.It is template that this method adopts the opal crystal that is formed by silicon dioxide microsphere, by electrochemical method growing metal in the space of template.In order to guarantee that formwork structure is unlikely destroyed in the process of metallic growth, need template is carried out anneal before metal filled carrying out, so that form " neck " that links to each other between ball and the ball.Simultaneously, in the process of metallic growth, must remain close contacting between template and the electrode, in the space of template, grow to guarantee metal.Adopt hydrofluoric acid that silica template is corroded at last, obtain desired ordered nano-structure material.
Prior art four: chemical plating method, referring to Jiang, P.; Cizeron, J.; Bertone, J.F.J.Am.Chem.Soc.1999,121,7957.) template that this method adopted is identical with existing technology three; Template is positioned in the chemical plating fluid, and chemistry crosses in the space that liquid is penetrated into template under the capillary force effect, is implemented in metal filled in the space by electroless plating.
Above-mentioned these methods can be implemented in and insert metal in the stencil apertures fully.Therefore after removing template, resulting structure is identical, is and template antipodal ordered porous (mutually together with) nano structural material.
Three, summary of the invention:
The present invention proposes a kind of two and three dimensions ordered nano-structure metallic substance and preparation method who is made up of the medium ball or the hollow metal spherical shell of metal parcel.
The present invention seeks to realize like this: have the sequential 2 D nano structure metal materials, on smooth substrate, arrange according to the close heap mode of hexagonal by the medium ball or the hollow metal sphere of metal parcel.
Has the three-dimensional order nano structure metal materials, the three-dimensional structure that on smooth substrate, forms by the medium ball or the hollow metal sphere of metal parcel according to close heap mode.
Above-mentioned ordered nano-structure metallic substance preparation method at first adopts the colloid micro ball self-assembling method under the capillary attraction, and preparing corresponding colloidal crystal is template.Specifically be promptly to have adopted by place spacer between two smooth, form a microchannel identical with spacer thickness, the end with the microchannel is immersed in the latex solution of microballoon then; Latax is inhaled into the microchannel under capillary force drives, the top in the microchannel, microballoon self-organization and form ordered arrangement in inside microchannels; Owing to moisture evaporation in the microchannel, in the microchannel, form liquid stream from bottom to top simultaneously; Liquid stream constantly takes the microballoon in the latax in the passage to; Driving colloid micro ball simultaneously together to tip motions.After colloid micro ball outreached, its motion was restricted.These microballoons finally form close pile structure on the top of microchannel according to the minimum principle of system capacity.Through promptly preparing the single domain colloidal crystal of desired size behind the reasonable time.
The present invention can prepare the individual layer and the orderly colloidal crystal template of multiwalled of large-area single-domain.By spacer thickness in the control microchannel, can very conveniently get the thickness of accurately controlling colloidal crystal.To given colloid micro ball diameter d, in order in the microchannel, to grow the colloidal crystal that the number of plies is number of plies N, the thickness H of microchannel
NMust satisfy:
Two smooth substrates that the present invention is adopted during template by preparation form the protection to colloidal crystal template naturally.In the metallic growth process, template is limited between two substrates all the time.Although colloidal crystal template when drying regime, is in contact with one another between the adjacent polystyrene sphere; But in case template is immersed in the aqueous solution, because mutual Coulomb repulsion effect, these balls are not just in contact.Therefore adopt such substrate constraint not only can make template in whole process of preparation, keep ordered structure, allow also that simultaneously the spacing between ball and the ball has certain stretching, contract.
The present invention carries out sensitization to the surface of colloid micro ball and handles after template forms, and makes the growth of nano-metal particle from microsphere surface.Can guarantee like this can both form the metal spherical shell on the surface of each microballoon; Entire structure then is the nano structure metal materials of the high-sequential that formed by the medium ball of metal parcel or hollow metal spherical shell (removing the back in template).Sensitizing is as follows: after template is made, keep under the prerequisite of two smooth substrate interlinear notes templates, the bottom of microchannel is immersed in the pre-configured stannous ion sensitized solution; Sensitized solution is inhaled in the microchannel under the capillary force effect, makes surface adsorption one deck stannous ion of microballoon by sensitization.
Template by sensitization, drying after, the bottom, microchannel is immersed in the distilled water, removed chlorion, prevent from subsequent step, to form silver chloride with the silver ions reaction.Simultaneously behind the stannous ion hydrolysis reaction with Sn (OH) Cl, Sn (OH)
2, and Sn
2(OH)
3The Cl form is adsorbed on the surface of PS ball.To from distilled water, propose from the microchannel after the cleaning, and at air drying.
Template immerses the lower end, microchannel in the silver plating liquid after being cleaned by sensitization, distilled water, by seed induce/the electroless plating process is at the surface growth metal spherical shell of fulcrum ball.Obtain the ordered nano-structure metallic substance that the medium microsphere by argent parcel is arranged in.Chemical plating fluid, prepared ordered nano metallic substance can be gold and silver, copper, aluminium etc.
If what adopt is that polystyrene microsphere is as supporting kernel, after medium ball in template is cleaned by metal spherical shell parcel, distilled water, the bottom of microchannel is immersed in the mixed solution of the methyl alcohol that configures and benzene, removed polystyrene microsphere as template by chemical process; Perhaps with template together with the fixed substrate be heated to 100 ℃ or more than, the kernel by sintering process remove to support finally obtains the ordered nano-structure metallic substance that is arranged in by hollow ping-pong ball.
If what adopt is that silicon dioxide microsphere is as supporting kernel, after medium ball in template is cleaned by metal spherical shell parcel, distilled water, the bottom of microchannel is immersed in the hydrofluoric acid solution that configures, remove silicon dioxide microsphere by chemical process, finally obtain the ordered nano-structure metallic substance that is arranged in by hollow ping-pong ball.
The present invention can control the internal diameter of metal spherical shell by selecting the support kernel of different size for use; And the spherical shell external diameter is by the time control of the concentration or the electroless plating of chemical plating bath; The number of plies of structure is determined by the thickness of the spacer that forms the microchannel and ratio as the microsphere diameter of kernel.
Characteristics of the present invention are to adopt surperficial seed growth method, and this is different from deposition/chemical conversion, the direct metal nano particle is filled or electrochemical growth, and these methods all can't form the Metal Ball shell structure on Supporting Media ball surface.On the other hand, the colloidal crystal that is made of polystyrene microsphere that the present invention adopts is a template, when template was in chemistry and crosses in the liquid, because of there is certain clearance in Coulomb repulsion between them, such interval allowed to form metal casing at the outside surface of each medium ball between ball and the ball.
What existing electrochemistry or electroless plating technology adopted is the ordered structure that silicon dioxide microsphere forms, and these methods need be to template annealing, and are unlikely destroyed in the material preparation process to guarantee template.The stability of the template among the present invention is to form naturally template protection by needed substrate when the template growth; this method also allows the spacing between ball and the ball suitable contraction (template is at air drying) to be arranged and expand (template is placed in the solution) in the protection template.
The unit that constitutes orderly nanometer metal structure material among the present invention both can be the polystyrene microsphere of metal parcel, also can be hollow metal spherical shell; And being these unit, entire structure arranges according to the close heap mode of the most stable hexagonal in the space.
The yardstick of the nanostructure among the present invention depends mainly on the yardstick that microballoon is supported in the conduct of being adopted; The thickness of metal spherical shell then depends on concentration of reactants in the electroless plating; For same electroless plating liquid bath, the shell thickness that is obtained depends on the time of electroless plating.
Characteristics of the present invention are: this is a kind of ordered nano structural metallic materials that is become by the medium ball or the hollow metal sphere hull shape of metal parcel.This pattern is different from the ordered porous nano structure metal materials that prior art obtains.Structural stability that the present invention obtains is better than the resulting micro-nanometer ordered structure metallic substance of prior art.Nano material of the present invention has bigger specific surface area.
Four, description of drawings:
Below in conjunction with accompanying drawing, the present invention will be further described.
Fig. 1 is existing three kinds of synoptic diagram that prepare ordered nano-structure metallic substance method.1A is a deposition/chemical conversion process; 1B is that nano-metal particle is directly inserted stencil apertures; 1C is an electrochemical method.
Fig. 2 is a process flow diagram of the present invention.
Fig. 3 adopts regional area scanning electron microscopy (SEM) photo of the two-dimensional colloidal crystal template that the monodisperse polystyrene microsphere of 1.6 microns of diameters makes for the present invention.
Fig. 4 adopts three-dimensional colloidal crystal template that the monodisperse polystyrene microsphere of diameter 610 nanometers makes at dried SEM photo for the present invention.The spacer thickness that is adopted during template growth is 1.8 microns.The crack of the dry sample of being seen from figure can find out clearly that template is made of three layers of close heap microballoon.
Fig. 5 A two-dimensional colloidal crystal shown in Figure 3 for the present invention adopts is template, the SEM photo of the sequential 2 D nano structure metal materials that is made of hollow ping-pong ball that is obtained.
Fig. 5 B is the SEM photo at the edge of the sequential 2 D nano structure metal materials sample shown in Fig. 5 A.Can be clearly seen that from figure: this material is made up of the hollow ping-pong ball of individual layer.Two among the figure have the hollow structure that the microballoon that opening is arranged shows these Metal Ball clearly.
Fig. 5 C is the X-ray diffraction analysis result of the sequential 2 D nanostructured metal silver shown in Fig. 5 A of the present invention.The position at the diffractive features peak of diffraction peak among the figure and crystallization silver fits like a glove, and this explanation is made up of crystallization silver institute having removed the spherical shell that stays behind the fulcrum ball.
Fig. 6 A three-dimensional colloidal crystal shown in Figure 4 for the present invention adopts is template, the SEM photo of the three-dimensional order nano structure metal materials that is made of hollow ping-pong ball that is obtained.
Fig. 6 B is the SEM photo of surface under (20,000 times) under the higher magnification of Fig. 6 A sample.
The cave in SEM photo in ping-pong ball shell zone of the existence that Fig. 6 C is observed for Fig. 6 A sample surfaces.
Five, embodiment
The synoptic diagram of technical process of the present invention is seen Fig. 2.
The present invention chooses a wave plate as substrate, and it is kept flat.Then with two identical, have that certain thickness separator is parallel to be placed on the wave plate.Cover an onesize wave plate more thereon.Under the relative position that keeps two wave plates, they are fixed up at last.
Separator among the present invention can be that cylinder shape or square section are the orthogonal dielectric rod.The material selection of spacer can be born certain extruding and indeformable dielectric material.
The present invention also can adopt monodispersed silica spheres as spacer.Distance between two smooth substrates equals the silicon-dioxide spherical diameter.
The present invention is immersed in an end of prepared microchannel in the colloid micro emulsion glue that configures., after needed size, the microchannel is proposed from latax in colloidal growth.
The present invention is in order to protect template, and the substrate that is adopted is the interlinear notes template in the preparation process of material, just can take apart after the ordered nano-structure metallic substance forms.
The present invention implements to stir to the colloid latax in the process of colloidal crystal growth simultaneously, can prevent that like this colloid micro ball deposits to the latax bottom in the long-time process of growth of crystal.The stirring of latax does not influence the quality of template.
As the example of preparation colloidal crystal template, (being of a size of and adopting thickness between the 1.6cm * 2.5cm) is 1.8 microns spacer, clamps the slide both sides with two clips, and forming a thickness is 1.8 microns microchannels at two slides.Preparation colloid micro ball latax is 15mL, and the capacity of putting into is the crucible of 20mL, carries out magnetic and stirs.
Fig. 3 is the dried regional area SEM of the two-dimensional colloidal crystal template photo that the present invention adopts 1.6 microns polystyrene microspheres of diameter to make.Polystyrene microsphere is arranged in the close pile structure of hexagonal of high-sequential.
It is regional area SEM photo after the three-dimensional colloidal crystal template drying made of the polystyrene microsphere of 610 nanometers that Fig. 4 the present invention adopts diameter.As can be seen, no matter be that template all has the preface structure on surface or inner.
The present invention under the prerequisite that keeps two thin glass plate substrate interlinear notes, is immersed the template bottom in the pre-configured sensitized solution after template is made.Because capillary force, sensitized solution is inhaled in the interlayer of two slides.The purpose of sensitization is exactly for can be at polystyrene spheres surface adsorption one deck stannous ion.
As an example, sensitized solution of the present invention is by the 2.5g tin protochloride, 10mL hydrochloric acid, and the distilled water of 3.0g tin particles and 140mL mixes.This process continues 3-4 and divides clock time.Propose from sensitizing solution from the microchannel then, and at air drying.
The present invention is then immersed the bottom, microchannel in the distilled water, has removed chlorion simultaneously, prevents to form silver chloride with the silver ions reaction in subsequent step.Simultaneously behind the stannous ion hydrolysis reaction with Sn (0H) Cl, Sn (OH)
2, andSn
2(OH)
3The Cl form is adsorbed on the surface of PS ball, and we can adsorb on the slide top with filter paper, to accelerate the cleaning process in the slide interlayer.To from distilled water, propose from the microchannel after the cleaning, and at air drying.
The present invention is immersed the lower end, microchannel in the silver plating liquid, by seed induce/the electroless plating process shows the growing metal spherical shell fulcrum ball.As an example, the used plating bath of the present invention is to be mixed according to the equal-volume ratio before use by two kinds of solution of first, second.First solution is the Silver Nitrate by 2.0g, and the distilled water of 100mL and the ammoniacal liquor of 2.1mL mix.Second solution is to be dissolved in the 100mL distilled water formulated by the 10g Seignette salt.Template is in case by the submergence of silver plating liquid institute, because microsphere surface is charged, mutual repulsion makes and produces small separating between ball and the ball.The size of separating depend on each microsphere surface with electric density, generally at tens nanometer.In the template two kinds of reactions take place in succession simultaneously.At first be that stannous ion attached to the polystyrene microsphere surface directly is reduced into silver-colored simple substance with the silver ions in the solution and attached to the surface of ball.Next, the silver-colored simple substance that has formed makes that as catalytic surface the silver ions in the solution is reduced into silver by the Seignette salt in the solution, and this is similar to the seed growth process.Through this process, just formed one deck silver of parcel continuously on the surface of polystyrene spheres.Can adsorb on the top with filter paper equally, accelerate plating bath and enter inside microchannels.
Template of the present invention through after the appropriate time plating, proposes the microchannel in silver plating liquid from plating bath, and immerses in the distilled water once more and clean, and obtains the ordered nano-structure metallic substance that the polystyrene microsphere by the argent parcel is arranged in.
At last the bottom of microchannel is immersed in the mixed solution of the methyl alcohol that configures and benzene, removed polystyrene microsphere as template by chemical process.Finally obtain the ordered nano-structure metallic substance that is arranged in by hollow ping-pong ball.
As an example, Fig. 5 A is a template for the present invention adopts the two-dimensional colloidal crystal (see figure 3), the SEM photo by the sequential 2 D nano structure metal materials that is obtained.This material is made up of according to the hexagonal solid matter the hollow ping-pong ball of same size.Fig. 5 B is an edge of materials region S EM photo.Fig. 5 C is the X-ray diffraction analysis result of material.The characteristic diffraction peak of diffraction peak that is observed and crystallization silver is in full accord, has shown the existence of argent in the spherical shell.
As an example, three-dimensional colloidal crystal is the SEM photo by the three-dimensional order nano structure metal materials that the template (see figure 4) is obtained to Fig. 6 A for the present invention adopts.This material is arranged institute in the space according to close heap mode by hollow ping-pong ball and is formed.Fig. 6 B is the SEM photo under high-amplification-factor more; Fig. 6 C is at the photo that supports the metal spherical shell that caves in that is observed after microballoon is removed.
The size of hollow core metallic microspheres internal diameter of the present invention is determined by the support adhesive member diameter of micro ball that is adopted.The thickness of spherical shell depends on concentration of reactants in the metal plating liquid.For adopting same bath trough, the thickness of spherical shell depends on the time of electroless plating.
Metallic substance among the present invention is not limited to silver, can be gold, copper, aluminium, nickel; And the colloid micro ball that is used for the support metal spherical shell is not limited to monodispersed polystyrene, can be monodispersed silicon dioxide microsphere.
Claims (10)
1, a kind of sequential 2 D nano structure metal materials that is made of hollow metal sphere is characterized in that being arranged according to the close heap mode of hexagonal on smooth substrate by the medium ball or the hollow metal sphere of metal parcel.
2, a kind of three-dimensional order nano structure metal materials that is made of hollow metal sphere is characterized in that the three-dimensional structure that medium ball or hollow metal sphere by metal parcel form according to close heap mode on smooth substrate.
3, by right 1 or the 2 described ordered nano-structure metallic substance preparation methods that are made of hollow metal sphere, it is characterized in that at first adopting the capillary attraction self-assembling method, preparing corresponding colloidal crystal is template.Specifically be promptly to have adopted by place spacer between two smooth, form a microchannel identical with spacer thickness, the end with the microchannel is immersed in the latex solution of microballoon then; Latax is inhaled into the microchannel under capillary force drives, the top in the microchannel, microballoon self-organization and form ordered arrangement in inside microchannels; Owing to moisture evaporation in the microchannel, in the microchannel, form liquid stream from bottom to top simultaneously; Liquid stream constantly takes the microballoon in the latax in the passage to; These microballoons form close pile structure according to the minimum principle of system capacity in the microchannel.
4, by right 3 described ordered nano-structure metallic substance preparation methods, it is characterized in that the preparation of colloidal crystal template constitutes in the following manner, the number of plies of microballoon is regulated by the thickness of the spacer of formation microchannel in the template.If diameter of micro ball is d, in the microchannel, grow the template that the number of plies is N, the thickness H of spacer
NMust satisfy:
5, by the preparation method of right 1 or 2 described ordered nano-structure metallic substance, it is characterized in that after template is made, keep under the prerequisite of two smooth substrate interlinear notes templates, the bottom of microchannel is immersed in the pre-configured stannous ion sensitized solution; Sensitized solution is inhaled in the microchannel under the capillary force effect, makes surface adsorption one deck stannous ion of microballoon by sensitization.
6, by the preparation method of right 1 or 2 described ordered nano-structure metallic substance, it is characterized in that after template is by sensitization, drying, the bottom, microchannel is immersed in the distilled water, removed chlorion, prevent from subsequent step, to form silver chloride with the silver ions reaction.Simultaneously behind the stannous ion hydrolysis reaction with Sn (OH) Cl, Sn (OH)
2, andSn
2(OH)
3The Cl form is adsorbed on the surface of PS ball.To from distilled water, propose from the microchannel after the cleaning, and at air drying.
7, by the preparation method of right 1 or 2 described ordered nano-structure metallic substance, it is characterized in that after template is cleaned by sensitization, distilled water, the lower end, microchannel is immersed in the silver plating liquid, by seed induce/the electroless plating process shows the growing metal spherical shell fulcrum ball.Obtain the ordered nano-structure metallic substance that the medium microsphere by argent parcel is arranged in.Chemical plating fluid, prepared ordered nano metallic substance can be gold and silver, copper, aluminium etc.
8, by the preparation method of right 1,2 desired ordered nano-structure metallic substance, it is characterized in that if what adopt is polystyrene microsphere as supporting kernel, after medium ball in template is cleaned by metal spherical shell parcel, distilled water, the bottom of microchannel is immersed in the mixed solution of the methyl alcohol that configures and benzene, removed polystyrene microsphere as template by chemical process; Perhaps template is heated to 100 ℃ together with the fixed substrate, removes the kernel that supports, finally obtain the ordered nano-structure metallic substance that is arranged in by hollow ping-pong ball by sintering process.
9, by the preparation method of right 1,2 desired ordered nano-structure metallic substance, it is characterized in that if what adopt is silicon dioxide microsphere as supporting kernel, after medium ball in template is cleaned by metal spherical shell parcel, distilled water, the bottom of microchannel is immersed in the hydrofluoric acid solution that configures, remove silicon dioxide microsphere by chemical process, finally obtain the ordered nano-structure metallic substance that is arranged in by hollow ping-pong ball.
10, by right 1,2 desired ordered nano-structure metallic substance, its feature is controlled the internal diameter of metal spherical shell by selecting the support kernel of different size for use; And the spherical shell external diameter is by the time control of the concentration or the electroless plating of chemical plating bath; The number of plies of structure is determined by the thickness of the spacer that forms the microchannel and ratio as the microsphere diameter of kernel.
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