CN101024483B

CN101024483B - Constituting method for metal ordered structure surface reinforced base

Info

Publication number: CN101024483B
Application number: CN2007100554534A
Authority: CN
Inventors: 吕男; 杨秉杰; 黄春玉; 迟力峰
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2007-03-27
Filing date: 2007-03-27
Publication date: 2010-12-29
Anticipated expiration: 2027-03-27
Also published as: CN101024483A

Abstract

The invention relates to a method to construct ordered structure on base, and the application of using the base to construct metal ordered structure. The method includes the following steps: adopting inorganic base or polymer base, taking base surface process to make it could conduct electricity, construct ordered microstructure of different functional group or macromolecule barrier layer; assembling the metal nanometer particle into the ordered structure to gain metal nanometer ordered structure. The invention could be widely used in making high sensitive metal sensor and detector.

Description

Metal ordered structure surface strengthens the construction method of substrate

Technical field

The invention belongs to the ordered micro structure technology, be specifically related to construct surperficial ordered structure and construct metal ordered structure with this ordered structure substrate as template in substrate, this metal ordered structure has the application of obvious enhancing probe molecule signal in the Raman detection process.

Background technology

Traditional method of constructing micro-structural mainly comprises: photoetching, electron beam lithography, self-assembled monolayer, chemical vapour deposition technique etc.; In this patent, related unorthodox method comprises: nanometer embossing, and the LB self-assembling technique, and the method for the auxiliary electrochemical oxidation of atomic force etc.

Report is in order to realize constructing of metal structure in the document, the Science and Technology workers have carried out a lot of research work, wherein with strongest influence power is the method for electron beam lithography, utilize the method for electron beam lithography to realize the constructing of gold point battle array (Squarearrays of20～35nm-diam gold particles with50nm spacing were formed on thicksapphire substrates by electron beam lithography, Appl.Phys.Lett.44 (12) 1984) of 20～35nm as far back as H.G.Craighead in 1984 and G.A.Niklasson.Though the method for electron beam lithography has high accuracy, advantages such as high-resolution are because shortcoming such as instrument costliness, efficient be lower has limited it and used widely.Multiple method of constructing metal structure has appearred subsequently, as Nano microsphere array, self assembly and photoetching method (J.AM.CHEM.SOC.2002,124, the 10596-10604 in conjunction with electro-deposition; NANO LETT.2005,5,1503; Electrochimica Acta2003,48,3107; J.AM.CHEM.SOC.2006,128,13342).

People such as Tarcha utilized Raman to strengthen the detection (U.S.Pat.No5,266,498.) that has realized part first in 1993, and his used substrate is the silver colloid particle, and coarse silver surface.The substrate surface that people such as Cotton in 1998 are coupled between based on silver particles in silver-colored island structure is realized the measuring ability (U.S.Pat.No5,837,552.) that Raman strengthens.People such as Natan had constructed Raman enhanced activity substrate (the Surface enhanced Raman scattering from metalnanoparticle-analyte-nobl emetal substrate sandwiches of metal nanoparticle-analyte-noble metal structures in 2000, U.S.Pat.No6,149,868.).People such as Farquharso utilized sol-gel technique to realize construct (U.S.Pat.No6,610,351) of Raman enhanced activity substrate in 2003.People such as Natan utilize azanol and metal ion reaction, on golden nanometer particle monofilm surface, have realized the preparation (U.S.Pat.No6,624,886) of Raman enhanced activity substrate.

2004, people such as the Du Zuliang of He'nan University described in Chinese patent (CN1699966): the substrate surface of handling through sulfhydrylation obtains deposition Ag nano particle decorative layer by silver mirror reaction.The preparation method of this substrate comprises the steps such as formation of the processing of substrate hydroxylating, substrate sulfhydrylation and substrate surface Ag nano particle decorative layer.Realize constructing of surface-enhanced Raman scattering activity substrate, be suitable in water, carrying out the Raman signal measurement of monofilm.

Along with the appearance of various Raman enhanced activity substrate construction methods, also will be widely used based on the detection of Raman enhanced spectrum.People such as Martin Moskovits think: the very potential Single Molecule Detection that is applied to of detection method that Raman strengthens.

Summary of the invention

The purpose of this invention is to provide a kind of methods such as electrochemical oxidation of assisting and construct orderly surperficial nano/micron structure by photoetching, electron beam lithography, nano impression, self-assembled monolayer, chemical vapour deposition technique and atomic force, and be template with this body structure surface, carry out electrochemical reaction, realize constructing of orderly metal nano/micron structure.

The orderly metal structure of utilizing this patent method to construct, in Raman detection, signal to noise ratio, selectivity and sensitivity are all better, and the method is applicable to the preparation based on the sensor of Raman detection.

We find that after deliberation metal Nano structure has good optical and electric property in order, and its optics is different with the structural change of metal nanoparticle with electric property, therefore, finally can realize coming by control structure the purpose of accommodation property.As metal ordered structure fluorescent surface is strengthened more than 30 times, can improve luminous efficiency effectively, this enhancing is that the ordered structure of metal surface causes, and it strengthens the plasma resonance that principle is the metal surface.In order to realize the resonance of metal surface plasma body effectively, utilize accurately controlled advantage of electrochemical deposition, metal nanoparticle is deposited on the template surface of constructing ordered structure, thereby realizes constructing of orderly metal structure.

Adopt this method can realize economy, fast, large tracts of land constructs orderly metal nano/micron structure (array) (constructing the substrate that can reach 1cm * 1cm, shown in embodiment 1).In conjunction with the characteristics of construction method, it is very high that its resolution ratio can reach, and its resolution ratio of construction method that impresses as combining nano can reach 2～8nm, so just can control the spectrum function characteristic by control structure.Because the Raman enhancer can reach 10 ¹²More than, therefore can pass through the Raman enhanced spectrum, reflect that unimolecule is in suprabasil behavior.Therefore this orderly nanostructured substrate has very big application potential, is detection means with the Raman enhancing, realizes unimolecule spectrum, constructs high sensor, has great practical value.

The approach of constructing ordered structure surface mainly comprises two kinds: ordered structure surface that the employing different functional groups is constructed and the ordered structure surface that adopts barrier layer polymer to construct.

Construct the ordered structure surface formed by different functional groups mainly by following method: the method that self-assembled monolayer, vapour deposition process, LB technology and other (as photoetching, nano impression, scan-probe lithographic technique etc.) technology of constructing combine; Utilize barrier layer polymer to construct ordered structure and mainly comprise methods such as photoetching, electron beam lithography and nano impression.

The described employing barrier layer polymer of this patent is constructed the method that metal ordered structure surface strengthens the Raman substrate, comprises the steps:

A, choose inorganic substrates or polymeric substrates, after the cleaning conductive processing is carried out on its surface and obtain conductive substrates;

B, the method by photoetching, electron beam lithography, nano impression, (to the method for photoetching: the thickness on barrier layer is generally at 1～4 μ m to go out barrier layer polymer at the surface construction of conductive substrates; Method to electron beam lithography and nano impression: generally in 200～500nm) the orderly nano/micron structures that distribute alternately with conductive substrates, the nano/micron structure is adjustable to 25 μ m from 100nm for the thickness on barrier layer;

C, in electrolytic cell with the conductive substrates of the above-mentioned steps preparation electrode of working, do auxiliary electrode with another conductive substrates, at constant voltage mode (voltage swing 0.1～20v, time be 0.1～12h) or constant current mode (electric current is 0.1～5A, time is to carry out electrochemical deposition under 0.1～12h), under the inducing action of orderly nano/micron body structure surface, the metal nanoparticle that electrochemical reaction is obtained is assembled into working electrode surface in an orderly manner in situ, thereby realizes the metal ordered nano particle structure array that barrier layer polymer and metal nanoparticle distribute alternately;

D, the working electrode conductive substrates that above-mentioned steps is obtained are immersed in organic solvent (as acetone, chloroform, oxolane etc.) carry out wash-out in to remove barrier layer polymer, after repeating 3～4 times, utilize high purity nitrogen to dry up, finally obtain conductive substrates and metal nanoparticle metal ordered structure surface alternately and strengthen substrate.

The described employing different functional groups of this patent is constructed the method that orderly metal structure surface strengthens the Raman substrate, comprises the steps:

A, choose inorganic substrates or polymeric substrates, it is carried out again conductive processing being carried out on its surface after the cleaning;

B, the method that combines with scan-probe lithographic technique, photoetching or nanometer embossing by self-assembled monolayer, vapour deposition or LB technology go out the monofilm that different functional groups distributes in order at the surface construction of conductive substrates;

C, in electrolytic cell with the conductive substrates of the above-mentioned steps preparation electrode of working, do auxiliary electrode with another conductive substrates, at constant voltage mode (voltage swing 0.1～20v, time be 0.1～12h) or constant current mode (electric current is 0.1～5A, time is to carry out electrochemical deposition under 0.1～12h), because different functional groups plays the effect of inducing the metal nanoparticle nucleation, therefore under electrochemical action, along with the growth of metal nucleus, form metal ordered nano particle structure array on working electrode conductive substrates surface;

D, utilize high purity nitrogen to dry up conductive substrates, finally obtain metal ordered structure surface and strengthen substrate as working electrode.

Need to prove, for the metallic ordered structure of on different functional groups, constructing, because the functional group monomolecular film can be induced the nucleation of metal (silver) nano particle and be assembled growth, after metal nano particles array forms, functional group monomolecular film (decorative layer) is below metal nanoparticle, even (thickness of monomolecular film is generally 2～5nm), also can not influence the application of metal nanoparticle ordered structure array not remove monomolecular film.

The metal ordered structure surface that described in front two kinds of methods obtain strengthens substrate, adopting probe molecule (4-mercaptopyridine, pyridine or rhodamine etc.) to carry out the Raman enhanced activity measures, can observe Raman signal and greatly strengthen, Raman strengthens the signal homogeneous, and has high selectivity.

Inorganic substrates described in the said method comprises two large divisions at the bottom of conductor (containing semi-conducting material) substrate and the insulator-base.The conductor substrate comprises ito glass, silicon chip (comprising monocrystalline silicon piece, n-silicon, P-silicon etc.) and metallic substrates.Wherein metallic substrates comprises metal simple-substance (gold, silver, platinum, copper, cobalt, nickel, aluminium, cadmium etc.) and metal oxide (zinc oxide, aluminium oxide, chromium oxide, titanium oxide, zirconia etc.).Comprise quartz, glass, mica sheet, silica, calcirm-fluoride, ruby etc. at the bottom of the insulator-base.Polymeric substrates comprises dimethyl silicone polymer (PDMS), polyurethane (PU), polyvinyl chloride (PVC), PETG (PET), polystyrene (PS), polyethylene (PE), polypropylene (PP), conducting high polymers thing (polyaniline, polypyrrole) etc.

The cleaning of substrate: can handle respectively according to concrete substrate, to at first handling with oxygen plasma system his-and-hers watches face at the bottom of the insulator-base, purpose is to remove surperficial adsorbed organic matter, oxygen gas flow rate 80～200ml/min, power 100～300mW, processing time 1～15min; Use the high purity water ultrasonic cleaning again 2～3 times, each time is 3～5min, makes thoroughly cleaning of surface.Acetone, chloroform, absolute ethyl alcohol, high purity water ultrasonic cleaning 2～15min are used in the conductor substrate successively; Polymeric substrates is with after dipping in the absorbent cotton wiping of absolute ethyl alcohol, with high purity water ultrasonic cleaning 2～15min.

The conductive processing of substrate: at the bottom of the insulator-base and polymeric substrates (as quartz, glass, dimethyl silicone polymer (PDMS), polyurethane (PU), polyvinyl chloride (PVC), PETG (PET), polystyrene (PS), polyethylene (PE), polypropylene (PP) etc.), by physical method vacuum evaporation metal or make its conduction in substrate by chemical method (as electrochemical polymerization method, chemical oxidative polymerization, metal catalytic coupling polymerization method, solid-state coupling polymerization method etc.) growth conducting polymer composite.

Self-assembled monolayer: the method is applicable to foregoing glass, quartzy, silicon, the silica-based end, carry out cleaning, with the oxygen plasma system substrate surface is handled then, make the substrate surface oxidation produce silicon oxygen bond, the cleaning that to handle then, after immersing target solution of silane 20s～24h that concentration is 0.1～10 μ g/ml, dry and substrate conduction takes out, with toluene is solvent washing 3～5 times, sample is preserved 3～8h in 80～200 ℃ baking oven, immerse concentration once more and be to soak in the above-mentioned target solution of silane of 0.1～10 μ g/ml to take out behind 20s～24h and use corresponding solvent, as toluene, chloroform, organic solvent such as ethanol or oxolane ultrasonic cleaning 3～5 times, each 2～15min, use the deionized water ultrasonic cleaning again 3～5 times, each 2～15min, dry up with nitrogen then, (its thickness is 2～5nm) picture on surface (shown in Figure 14 (A)) thereby obtain the modified monolayer film in substrate.

On this monofilm, utilize the scan-probe lithographic technique, can obtain orderly structure, shown in Figure 14 (B).The scan-probe lithographic technique promptly adopts the atomic force needle point of titanizing or platinum plating, on atomic force instrument (Dimension3100 of DI company), needle point and sample are applied the voltage of 0.2～12V, monofilm partial oxygen through the making alive oxidation changes into carboxyl functional group, by programming and location translation, can in substrate, obtain the orderly pattern that carboxylic acid functional and target silane functional distribute alternately.

Target solution of silane recited above is silicol (silanol etc.), alkyl silane (n-octyl dichlorosilane, octadecyl trichlorosilane etc.), amino silane (aminopropyl triethoxysilane, hmds etc.), halogeno-group silane (tert-butyl diphenyl chlorosilane, trichlorosilane etc.), thiazolinyl silane (VTES etc.), fluorine substituted alkyl silane (perfluoro n-hexane base trichlorosilane etc.) etc.

Vapour deposition process: the method is applicable to the glass in the foregoing substrate, quartzy, silicon, silica, drip 2～20 μ l target silylating reagents in the vial in vacuum desiccator, with the cleaning of handling, dry and above-mentioned substrate conduction is fixed on the interior specimen holder of vacuum desiccator, make the vacuum in the vacuum desiccator remain on 0.01～0.015Mpa then, behind 15min～4h, take out sample, with deionized water ultrasonic cleaning 2～3 times, each 2～15min, dry up with nitrogen then, obtain single-layer membrane structure, its thickness is 1～3nm, and picture on surface and Figure 14 (A) are similar.On this monofilm, utilize the atomic force needle point of titanizing or platinum plating, on the atomic force instrument, needle point and sample are applied the voltage of 0.2～12V, by programming and location translation, obtain the orderly pattern that carboxylic acid functional and target silane functional distribute alternately, similar with Figure 14 (B).

The LB technology: the method is applicable to monocrystalline silicon piece, quartz plate, mica sheet, be that two palmitic acid phosphatid ylcholines, the concentration of 0.1～10mg/ml is the amphiphilic straight chain molecule mixed solution of the palmitic acid of 0.1～10mg/ml and the tar acid that holds with both hands with both hands with micro syringe with 2～50 μ l concentration respectively, together spread on the high purity water parfacies, the ratio of the mole dosage of alkali and mixed acid is 1:1, the mol ratio of two kinds of acid is 1～10:1 in the mixed acid, treat that solvent volatilizees behind 10min～24h naturally, on the LB film balance, use baffle plate with 5～30cm ²The speed of/min is compressed, obtain the Π～A curve of this sample, measure the surface pressure of film in the compression process with the Wihelmy film balance, select suitable shift pressure according to Π～A curve then, pressure 10min～the 24h that keeps 1～30mN/m, with vertical czochralski method on the mica sheet of newly peeling off of water flushing or on the above-mentioned cleaning crossed of oxygen plasma system handles, dry substrate, lift individual layer Langmuir film, putting forward film speed is 1～50mm/min, and whole process system temperature is controlled at room temperature.By control transition temperature, film transfer velocity and shift pressure, can obtain the ribbon structure of cycle 100nm～4 μ m, shown in Figure 13 (A).Constructed structure is the structure that the gas-liquid interface assembling obtains, and (constructs back 4～5 hours) template that can be directly used in electro-deposition at short notice certainly.As wanting long-time back to use, need the LB structure is further modified.

In order can to use for a long time, comprise two kinds of methods as the further modification of LB technology, a kind of method be surface by forming ribbon structure at the film that lifts through evaporation gold, silver or aluminum metal, the surface of film is further modified.Other method is by soak 1～3h in toluene, toluene is full of after the pore on the band, silylating reagent (silylating reagent used with the method for self-assembled monolayer is identical) is utilized the method for self-assembled monolayer, grow in the groove structure of LB film, utilize the method for ultrasonic cleaning to remove two palmitic acid phosphatidylcholine molecules and obtain monocrystalline silicon (quartz plate or mica sheet) surface and silylating reagent functional group orderly ribbon structure alternately, figure and Figure 13 (A) are similar.

The nano impression legal system is equipped with the alternate nano/micron body structure surface with substrate of polymer, and the method is applicable to foregoing all substrates, the steps include:

A. make with the method for photoetching or electron beam lithography and have micron rigid template of sub-micron micro-structural, be impressed into this rigid template in foregoing all substrates such as quartz, glass, ito glass, metal, silicon chip, silica, metal or conducting high polymers thing on spin on polymers barrier layer;

B. keep-up pressure 10～70Bar, heating under the condition that is higher than 30～100 ℃ of barrier polymers glass transition temperatures (Tg), keep 2～30min, molten polymer is flowed in the groove of rigid template;

C. reduce temperature to polymer glass conversion temperature (Tg), rigid template is peeled off;

D. remove residual layer in the polymer barrier layer groove with plasma etching again, in substrate, obtain polymer nano/micrometer structure surface with the rigid template complementary structure.

The polymer that is fit to do barrier material comprises that (main component is the polymethyl methacrylate of modification to thermoplastic polymer MR-17030, purchase in Germany, its molecular weight is 90000, and glass transition temperature Tg is 90 ℃), polymethyl methacrylate (PMMA), polystyrene (PS), polyurethane (PU), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), dibutene, polyvinyl alcohol (PVA), polystyrene butadiene copolymer (SBS), poly-to styrene polyoxyethylene alkene copolymer (PPVPE), ABS resin, the MEH-PPV of polyphenylene ethylene class (PPV), BEH-PPV and BuEH-PPV, poly-branch subchains such as PPP to the benzene class have flexibility, can spin-coating film, glass transition temperature tg is at the OK range polymeric material of (not being higher than 200 ℃).

The nano/micron ordered structure of photoetching process preparation: the method is applicable to foregoing all substrates, adopts the method for spin coating that the plus or minus photoresist film is spun in foregoing all substrates of handling, and spin speed is 10008000rpm.The chromium dioxide nano/micron ordered structure of constructing with employing deep ultraviolet lithographic method is a baffle plate, the substrate of the photoresist that spin coating is good places under the baffle plate, behind the 20s～20min that exposes under the ultraviolet light of 390nm with corresponding developer solution wash-out after, obtain the structure with the complementation of chromium dioxide ordered structure baffle plate, thereby construct the substrate of cashier/micro ordered structure.

The nano/micron ordered structure of electron beam lithography method preparation: this kind method is applicable to monocrystal silicon substrate.The method that adopts spin coating is that the PMMA barrier layer of 50K is spun on monocrystalline silicon sheet surface with molecular weight.Spin speed is 3000～8000rpm, and the spin coating thickness is 60～300nm.On hot platform, heat 180 ℃ then, 3min, fully solvent flashing also makes surfacing.Utilize JEOL JBX-5000LS electron beam lithography system.Electron beam intensity is 100 μ C/cm ²The monocrystalline silicon surface of handling well is carried out electron beam lithography, according to the program of setting, select the electron beam exposure that carries out of row, can obtain the nano-structure array of different structure, its resolution ratio can reach 2nm.

Utilize photoetching to prepare the method that different functional groups distributes alternately: to utilize the method for photoetching to obtain the nano/micron body structure surface with the method that self-assembled monolayer (or CVD method) combines, with this substrate as self assembly, drip 2～20 μ l target silylating reagents in the vial in vacuum desiccator, with receive/the micro-structure surface substrate is fixed on the specimen holder in the vacuum desiccator, make the vacuum in the vacuum desiccator remain on 0.01～0.015Mpa then, behind 15min～4h, take out sample, with deionized water ultrasonic cleaning 2～3 times, each 2～15min, dry up with nitrogen then, behind eluent (acetone, organic solvents such as oxolane) immersion 20s～15min, flush away photoresist barrier layer, obtain the structure that substrate surface and silylating reagent modification of surfaces distribute alternately, it is consistent that plate is covered in its structure and size and photoetching.

Utilize nano impression to prepare the method that different functional groups distributes alternately: to utilize the method for nano impression to be received/micro-structure surface with the method that self-assembled monolayer (or CVD method) combines, with of the substrate of this surface as self assembly, drip 2～20 μ l target silylating reagents in the vial in vacuum desiccator, to there be the substrate of micro-structure surface to be fixed on the interior specimen holder of vacuum desiccator, make the vacuum in the vacuum desiccator remain on 0.01～0.015Mpa then, behind 15min～4h, take out sample, with deionized water ultrasonic cleaning 2～3 times, each 2～15min, dry up with nitrogen then, with organic solvent (acetone, chloroform or oxolane etc.) wash-out removes high molecular barrier layer, obtain the structure that surface that substrate surface and silylating reagent modify distributes alternately, its structure is consistent with the template of nano impression with size.

This method can be used for constructing of most of metal ordered structures, is not only to be applicable to silver, and be that example is studied just with silver.The construction method that metal ordered structure surface strengthens substrate also is widely used in other metal material (gold, copper, cobalt, nickel, platinum, silver, cadmium, indium and germanium etc.) the constructing of micro-structural, also can be used for the constructing and the plating and the wash-out of film of electrophoresis, ordered structure of biomolecule, dye molecule.

Metal ordered structure is at preparation high sensitivity metal sensor and detector (J.AM.CHEM.SOC.2002,124,10596-10604, J.Phys.Chem.B2005,109,20522-20528), preparation Raman substrate and (J.Phys.Chem.B2003 in Raman detection, 107,1772-1780) have application widely.

Description of drawings

Fig. 1: the key step schematic diagram of constructing orderly metal nanometer micrometer structure with polymer barrier layer;

Fig. 2: the described electro-chemical systems of this patent (electrolytic cell) structural representation;

Fig. 3: the nano impression method prepares polymer ordered micro-structure surface process schematic diagram;

Fig. 4: the ESEM picture of the Nano silver grain ordered structure of in the ITO substrate, constructing;

A, B figure are the ESEM picture of the Nano silver grain ordered structure of two kinds of lattice structures;

C figure is the ESEM picture of the Nano silver grain of ribbon structure;

D figure is the ESEM picture of the Nano silver grain that deposits on the blank substrate;

Fig. 5: the light microscope picture of the Nano silver grain ordered structure of in the ITO substrate, constructing;

A figure is the light microscope picture of the Nano silver grain of lattice structure;

B figure is the light microscope picture of the Nano silver grain of ribbon structure;

Fig. 6: at the Raman enhanced spectrum of the orderly Nano silver grain absorption in ITO surface 4-mercaptopyridine monofilm;

Fig. 7 (A): the ESEM picture of the orderly Nano silver grain of lattice structure for preparing in the ITO substrate;

Fig. 7 (B): with the picture under the Raman scan pattern at 1099 wave number places behind the corresponding absorption of the A figure 4-mercaptopyridine monofilm;

Fig. 8 (A): the ESEM picture of the orderly Nano silver grain of ribbon structure that on monocrystal silicon substrate, prepares;

Fig. 8 (B): with the corresponding picture under the Raman scan pattern at 1099 wave number places of A figure;

Fig. 8 (C): the sem photograph of the orderly Nano silver grain of lattice structure that on monocrystal silicon substrate, prepares;

Fig. 8 (D): with the corresponding picture under the Raman scan pattern at 1099 wave number places of C figure;

Fig. 9: the Raman enhanced spectrum of the orderly Nano silver grain absorption of monocrystalline silicon surface 4-mercaptopyridine monofilm;

Figure 10: utilize the method for self-assembled monolayer to construct out the structure sem photograph of the silicon face depositing silver nano particle that the silylating reagent monofilm modifies;

Figure 11: the ESEM picture of the golden nanometer particle of in the ITO substrate, constructing;

A, C figure are the ESEM picture of the Nano silver grain of lattice structure;

B, D figure are the ESEM picture of the Nano silver grain of ribbon structure;

Figure 12: utilize the method for nano impression and self-assembled monolayer to combine, construct out the monofilm surface that structure is arranged of silylating reagent modified, the AFM picture of the Nano silver grain that deposition obtains;

Figure 13 (A): the ordered structure surface that utilizes the LB technology to construct;

Figure 13 (B): the body structure surface of constructing in the LB technology carries out the atomic force picture that electro-deposition obtains;

Figure 14 (A): utilize the method for self-assembled monolayer, the modification of constructing the surface of monofilm of silylating reagent;

Figure 14 (B): after utilizing the scan-probe lithographic technique that monofilm is applied the voltage oxidation, obtain the atomic force picture that different functional groups distributes in order;

Figure 15: after the scan-probe oxide etch, on the different functional groups surface that obtains, behind the electrochemical deposition Ag nano particles array, the surface is the Raman enhanced spectrum of Nano silver grain absorption 4-mercaptopyridine monofilm in order.

As shown in Figure 1, on conductive substrates, construct the key step schematic diagram of orderly metal nanometer micrometer structure with polymer barrier layer. The A step be spin coating barrier layer polymer 12 on conductive substrates, 11 are the conductive substrates that need to construct nanometer micrometer structure, 12 is the polymer barrier layer material; The B step is for utilizing nano impression to construct orderly nanometer micrometer structure, and 13 is the rigid template of nano impression, and its material can be the rigid materials such as silicon, silicon nitride, quartz and nickel; Can oneself utilize the methods such as electron beam lithography and photoetching to construct, also can commercially buy. After impression is finished, utilize oxygen plasma to remove the interior polymer residue layer of groove, expose conductive substrates, thereby obtain polymer barrier layer and conductive substrates surface ordered structure alternately. Step C is in the electrolytic cell of our designed, designed, utilizes the method for electro-deposition, further constructs out the ordered structure that barrier layer polymer and metal (silver) nano particle distribute alternately on the conductive substrates surface, and 14 is metal (silver) nano particle. Step D removes barrier layer polymer for utilizing organic solvent, thereby obtains the orderly array of metal (silver) nano particle on the surface of conductive substrates.

As shown in Figure 2, this electro-chemical systems (electrolytic cell) be with two conductive substrates (22 and 24 parts among the figure, two conductive substrates can be identical, also can be not identical, 24 conductive substrates for the nano/micron ordered structure of this patent preparation wherein are as working electrode; 22 for conductive substrates as auxiliary electrode) construct out parallel electric field, and be that reference electrode is (in the not high test of precision with simple substance silver strip (23 parts among the figure), can be without reference, still realize constructing by structural substrates), construct out micro reaction pool (this micro reaction pool is airtight). 26 is the external power supply part, and w connects working electrode (being negative pole), and s connects reference electrode, and a connects auxiliary electrode (namely anodal). Which kind of metal ordered structure electrolyte (is constructed, is adopted corresponding metal salt solution, as construct silver-colored ordered structure, adopt liquor argenti nitratis ophthalmicus; Construct golden ordered structure, adopt chlorauric acid solution; As construct the copper ordered structure, adopt copper-bath; As construct the nickel ordered structure, adopt Nickel Chloride solution etc.) volume at 10～500 μ l. And by controlling the thickness of plastic sandwich (21 parts among the figure), the field intensity between control electrode realizes controllable electric field. By applying different deposition voltages, electric current, sedimentation time, electrolyte concentration, stabilizing agent is (such as sodium ethylene diamine tetracetate EDTA, the macromolecules such as PVP PVP, can play the effect of stabilized nanoscale particle, make the uniform particle diameter of particle), the roughness of substrate (is not the structural parameters of constructed structure, but the intrinsic parameter of substrate, but can be by artificial method, substrate surface is polished or coarse processing, affect electrochemical nu-cleation, realize the control to the metal array structure) and the structure of the factor controlling metal ions such as structure of ordered structure substrate, pattern and size. Constructing of the micro-structurals such as this chemical bath not only can be used for deposition and the stripping of metal, also can be applicable to other biomolecule, dye molecule and film.

As shown in Figure 3, the standby polymer ordered micro-structure surface process schematic diagram of nano impression legal system, the B step in the corresponding diagram 1. 31 is the rigid template (11 in the corresponding diagram 1) of nano impression, and 32 is polymer barrier layer (12 in the corresponding diagram 1), and 33 is the substrate (13 in the corresponding diagram 1) of nano impression.

As shown in Figure 4, the ESEM picture of the Nano silver grain that embodiment 1 constructs in the ITO substrate, wherein bright part (light colour part) is Nano silver grain, dark part (dark colour part) is the ITO substrate surface, A figure is corresponding four kinds of dots structures from left to right, the size of its point is followed successively by 800nm * 800nm, 2 μ m * 2 μ m, 2 μ m * 2 μ m and 5 μ m * 5 μ m, and the spacing of point is to be followed successively by 1 μ m, 2 μ m, 8 μ m and 1 μ m; The corresponding first of enlarged drawing lattice structure among the figure A. The point size of B figure is 6 μ m * 6 μ m, and spacing is 2 μ m. The strip width of C figure is 800nm, and live width is 3 μ m. D figure is that its particle diameter is 200～300nm in blank ITO (not carrying out polymerization barrier material and monofilm modifies) the metallic structure that deposition obtains.

As shown in Figure 5, embodiment 1 is at the light microscope picture of the Nano silver grain that the ITO substrate is constructed (among the figure a, b and c partly respectively A, B and C in the ESEM picture in the corresponding diagram 4). Part (dark colour part) dark among the figure is Nano silver grain, and bright part (light colour part) is the ITO surface. A figure is the picture of different dot matrix size and spacing, from left to right increase, the size of whole points is from 800nm to 10 μ m, per 3 arrays of spacing are one-period, B figure is the picture of different live widths and distance between centers of tracks, every group of live width and distance between centers of tracks from left to right increase, and entire infrastructure is that 800nm is to 10 μ m.

As shown in Figure 6, corresponding embodiment 1, the Raman enhanced spectrum of ITO surface Ordered Silver nano particle absorption 4-mercaptopyridine monofilm, a curve is the Raman enhanced spectrum that 4-mercaptopyridine monofilm is adsorbed in the silver nanoparticle lattice structure; The b curve is the Raman enhanced spectrum that 4-mercaptopyridine monofilm is adsorbed in the Nano silver grain ribbon structure; The c curve is the Raman enhanced spectrum that 4-mercaptopyridine monofilm is adsorbed in disordered structure on the blank substrate. As seen in the orderly metal structure substrate of lattice structure and ribbon structure, the Raman spectrum of same probe molecule significantly strengthens.

As shown in Figure 7, A figure is the ESEM picture of the lattice structure of ITO surface Nano silver grain, and the size of its point is 6 μ m * 6 μ m, and spacing is 2 μ m. B figure is with it the picture under the Raman scan pattern at 1099 wave number places behind the corresponding absorption 4-mercaptopyridine monofilm.

As shown in Figure 8, A figure is the ESEM picture of the ribbon structure of silicon base surface Nano silver grain, and the width of its band is 1 μ m, and spacing is 1 μ m. B figure is the picture under the Raman scan pattern at 1099 wave number places behind the absorption 4-mercaptopyridine monofilm corresponding with A figure. C figure is the ESEM picture of the lattice structure of silicon base surface Nano silver grain, and the size of its point is 3 μ m * 3 μ m, and spacing is 7 μ m. D figure is the picture under the Raman scan pattern at 1099 wave number places behind the absorption 4-mercaptopyridine monofilm corresponding with C figure.

As shown in Figure 9, the Raman enhanced spectrum of silicon face Ordered Silver nano particle absorption 4-mercaptopyridine monofilm, the a curve is the Raman enhanced spectrum that 4-mercaptopyridine monofilm is adsorbed in the silver nanoparticle lattice structure, and the b curve is the Raman enhanced spectrum that 4-mercaptopyridine monofilm is adsorbed in the Nano silver grain ribbon structure. The c curve is a Raman spectrum at Adsorption On Silicon Surfaces 4-mercaptopyridine monofilm.

As shown in figure 10, the nano grain of silver minor structure of the silicon face deposition of liquid phase assembling silylating reagent modified, its particle diameter is 20～30nm.

As shown in figure 11, the ESEM picture of the golden nanometer particle of constructing in the ITO substrate, bright part is Nano silver grain, dark part is the ITO surface. A figure lattice structure, the size of its point are 4 μ m * 4 μ m, and spacing is 6 μ m, and among the B figure, strip width is 2 μ m, and distance between centers of tracks from left to right is 1 μ m～10 μ m. C figure lattice structure, the size of its point are 10 μ m * 10 μ m, and spacing is 25 μ m, and among the D figure, strip width is 8 μ m, and distance between centers of tracks from left to right is 1 μ m～15 μ m.

As shown in figure 12, the method by nano impression and self-assembled monolayer combines, and that constructs has a body structure surface. At this monofilm surface of structure is arranged, the AFM picture of the Nano silver grain that electrochemical deposition obtains. Its sweep limits is 15 μ m * 15 μ m. The A graph structure is that the size of point is 6 μ m * 6 μ m, and spacing is 2 μ m. The B graph structure is that the size of point is 2 μ m * 2 μ m, and spacing is 1 μ m.

As shown in figure 13, the body structure surface of constructing at LB carries out the atomic force picture that electro-deposition obtains, and its sweep limits is 7.5 μ m * 7.5 μ m. A figure is the ribbon structure (structure when not carrying out electro-deposition) that the method for LB is constructed, its strip width is 200nm, and spacing is 200nm, and B figure is the structure substrates at A figure, the ribbon structure of the argent nano particle that obtains, its particle diameter are 80～100nm.

As shown in figure 14, utilize the scan-probe lithographic technique that monofilm is applied atomic force picture before and after the voltage oxidation, its sweep limits is 5 μ m * 5 μ m. A figure is the silicon face of the method assembling silylating reagent modified of self-assembled monolayer. B figure applies the ribbon structure that voltage obtains after to the monofilm oxidation through the scan-probe lithographic technique. Bright part is the part that is oxidized to carboxylic acid functional group, the surface that the target silylating reagent of dark part is modified. Its live width can be led to snperoxiaized Control of Voltage, is under the 8v voltage among the figure, and live width is 100nm, and spacing can be by the size control of program or translational movement, and spacing is 500nm among the figure.

As shown in figure 15, corresponding embodiment 14, a curve are after the scan-probe oxide etch, on the different functional groups surface that obtains, and behind the electrochemical deposition Ag nano particles array, the Raman enhanced spectrum of surperficial Ordered Silver nano particle absorption 4-mercaptopyridine monofilm. The b curve behind the depositing silver nano particle, adsorbs the Raman spectrum of 4-mercaptopyridine monofilm on the silicon base of modifying.

The specific embodiment

Further illustrate the inventive method and application below by embodiment, rather than will limit the present invention with these embodiment.It is electrolyte that the present invention has mainly adopted silver nitrate, on the surface that has macromolecular structure of nano impression, realizes that the ordered structure of Nano silver grain is constructed.Equally also can be widely used in other the constructing of metal material (gold, copper, cobalt, nickel platinum, silver, indium and germanium etc.) micro-structural.

Embodiment 1:

Thermoplastics type's high molecular polymer MRI-7030 (Micro Resist company takes a morsel, Germany) be spun on the ITO surface of handling well, spin coating thickness is about 300nm, processing method is that ITO is cut into 2cm * 2cm size, use acetone, ethanol and high purity water ultrasonic cleaning 5min successively, after drying up with high pure nitrogen, utilize the body of oxygen plasma with the power of 200mW, handle 3min, make the ITO surface active.Utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the template of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, and the spacing dimension scope of point is 800nm～10 μ m; Another part is the strip-type structure, and its live width and distance between centers of tracks are 800nm～10 μ m) construct out the ordered structure of high molecular polymer and formwork structure complementation, promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma to remove polymer barrier layer between bar interband and dot matrix, expose the conductive surface of ITO, thereby obtain the ITO ordered structure alternate with polymer barrier layer.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this structural substrates, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus of the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 2h with 300mv, obtain the ordered structure that Nano silver grain and polymer barrier layer distribute alternately, in acetone, immerse three times, each 5min, remove polymer barrier layer MRI-7030, and dry up with high pure nitrogen, just obtained surface with the complementation of silicon nitride formwork structure, this surface is that (thickness of Nano silver grain is 200nm～250nm to Nano silver grain, thickness increases with the prolongation of sedimentation time, thickness is little to the effect of signals of Raman, but the influence of particle diameter is bigger) ordered structure alternate with ITO, whole process is as shown in Figure 1.

Fig. 4 and Fig. 5 are the pictures that obtains with ESEM and light microscope respectively, utilize this method as can be seen, the disposable large tracts of land that obtained, the structure of the orderly Nano silver grain of different structure.

Utilize the burnt Raman spectrometer System1000 of Britain Renishaw copolymerization to measure, behind absorption 4-mercaptopyridine in the substrate with Nano silver grain ordered micro structure, Raman spectrum strengthens, and enhancer is 10 ⁴More than.As shown in Figure 6, which kind of structure no matter, the raman scattering intensity of dot matrix is higher than the raman scattering intensity of band, in lattice structure, and its raman scattering intensity, size with structure changes, structure dimension is more little, and raman scattering intensity increases to some extent, fluctuates near the curve a that always gives in Fig. 6, ribbon structure also is similar, fluctuates near the curve b that gives in Fig. 6.Curve a and b are a kind of average results.From the scan pattern of Raman, can see that Raman is enhanced propertied and have a high homogeneity, as shown in Figure 7.

Embodiment 2:

The polymetylmethacrylate (sigma-aldrich) that takes a morsel is spun on the ITO surface of handling well, spin coating thickness is about 300nm, processing method is that ITO is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min, after drying up with high pure nitrogen, utilize the body of oxygen plasma with the power of 200mW, handle 3min, make the ITO surface active.Utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the template of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the conductive surface of ITO and the ordered structure that the barrier layer distributes alternately.We carry out electro-deposition in the designed electrolytic cell voluntarily, are working electrode with this structural substrates, are auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus of the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 2h with 300mv, obtain the ordered structure that Nano silver grain and polymer barrier layer distribute alternately, by immersing chloroform 3 times, each 5min, remove polymer barrier layer PMMA, and dry up with high pure nitrogen, (thickness of Nano silver grain is the ordered structure alternate with ITO of 200nm～250nm), with shown in Figure 4 similar just to have obtained surface with the complementation of silicon nitride formwork structure and be Nano silver grain.

Embodiment 3

The polystyrene PS (sigma-aldrich) that takes a morsel is spun on the ITO surface of handling well, spin coating thickness is about 300nm, processing method is that ITO is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min, after drying up with high pure nitrogen, utilize the body of oxygen plasma with the power of 200mW, handle 3min, make the ITO surface active.Utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the masterplate of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the conductive surface of ITO and the ordered structure that the barrier layer distributes alternately.We carry out electro-deposition in the designed electrolytic cell voluntarily, are working electrode with this structural substrates, are auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 2h with 300mv, obtain the ordered structure that Nano silver grain and polymer barrier layer distribute alternately, by immersing oxolane 3 times, each 5min, remove polymer barrier layer PS, and dry up with high pure nitrogen, the surface that has just obtained with the complementation of silicon nitride formwork structure is the alternate ordered structure of Nano silver grain and ITO, with shown in Figure 4 similar.

Embodiment 4

At aluminium flake, (acetone is used in substrate respectively to the level and smooth metallic substrates of cleanings such as silver strip, chloroform, ethanol, deionized water ultrasonic cleaning 5min, dry up with nitrogen, oven dry then) on, the polymetylmethacrylate (sigma-aldrich) that takes a morsel is spun on the metal substrate surface of handling well, spin coating thickness is about 300nm, method by nano impression, (method by electron beam lithography is constructed with the masterplate of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process as shown in Figure 3, utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, obtained the ordered structure that polymeric layer and bare metal substrate distribute alternately.In this substrate, carry out electro-deposition.With this structural substrates is working electrode, is auxiliary electrode with Pt, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.With the constant voltage of 300mv deposition 1h, by immersing chloroform 3 times, each 5min, remove barrier layer polymer after, just obtained the ordered structure that Nano silver grain and metallic substrates distribute alternately, with shown in Figure 4 similar.

Embodiment 5

Surface at monocrystalline silicon, pass through oxygen plasma respectively, acetone, ethanol and high purity water are handled (though the silicon oxide layer of monocrystalline silicon sheet surface has reduced its electric conductivity, but the metal nanoparticle that does not influence in this patent forms, so monocrystalline silicon be need not to do conductive processing), and after drying up with high pure nitrogen, thermal plastic polymer MRI-7030 (Micro Resist company takes a morsel, Germany) be spun on the silicon face of handling well, spin coating thickness is about 300nm, utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the masterplate of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, and its live width and distance between centers of tracks are 800nm～10 μ m.In this example, the width of its band is 1 μ m, and spacing is 1 μ m; The size of dot matrix is 3 μ m * 3 μ m, and spacing is 7 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the conductive surface of silicon and the ordered structure that the barrier layer distributes alternately.

Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this structural substrates, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 2h with 300mv, obtain the ordered structure that Nano silver grain and polymer barrier layer distribute alternately, by immersing in the acetone 3 times, each 5min, remove polymer barrier layer MRI-7030, and dry up with high pure nitrogen, just the surface that has obtained with the complementation of silicon nitride formwork structure is the alternate ordered structure of Nano silver grain and monocrystalline silicon, shown in the sem photograph of Fig. 8 (A), Fig. 8 (C).

Utilize the burnt Raman spectrometer system1000 of Britain Renishaw copolymerization, measure, behind the surface of orderly Nano silver grain absorption 4-mercaptopyridine, the Raman enhanced spectrum reflects that high-intensity Raman strengthens, and enhancer is 10 ⁴More than (as shown in Figure 9), its picture under the Raman scan pattern is shown in Fig. 8 (B), Fig. 8 (D).

Embodiment 6

On glass or quartz, and the method by gas phase or self-assembled monolayer (small, 2005,1,520-524), the conductive layer of the about 10～80nm of assembling last layer conducting polymer (polyaniline or polypyrrole).Thermal plastic polymer MRI-7030 (Micro Resist company takes a morsel, Germany) be spun in this substrate, spin coating thickness is about 300nm, utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the masterplate of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, and another part is the strip-type structure, and its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the ordered structure that conductive polymer sub-surface and polymer barrier layer distribute alternately.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this structural substrates, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 3h with 300mv, obtain the ordered structure that Nano silver grain and polymer barrier layer distribute alternately, by immersing in the acetone 3 times, each 5min, remove polymer barrier layer MRI-7030, and dry up with high pure nitrogen, just obtained and the surface of silicon nitride formwork structure complementation is a ordered structure between Nano silver grain and quartz or glassy phase, with shown in Figure 4 similar.

Embodiment 7

Monocrystalline silicon is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min, after drying up with high pure nitrogen, utilize power, the processing 3min of the body of oxygen plasma with 200mW, make the surface form the silica residual bond, with the method for self-assembled monolayer with alkyl silane reagent (Octadecyltrimethoxysilane, tech., 90%, Sigma～aldrich.inc) is mixed with 2 μ g/ml toluene solutions, insert monocrystalline silicon in solution, after soaking assembling 1h, take out with toluene ultrasonic cleaning 2 times each 2min.Form the self-assembled monolayer monocrystal silicon substrate.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this substrate, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.With the constant voltage deposition 2h of 400mv, obtain and the different structure in blank surface, as shown in figure 10.Its particle diameter is compared than the structure of the blank surface deposition of ITO, and the surface coverage of particle is higher, and the particle diameter selectivity is higher, and particle diameter has only 20～30nm, and the particle diameter of its particle is about 200～400nm on blank substrate, as shown in Fig. 4 D.

Embodiment 8

Utilize vapour deposition process in vacuum desiccator in the vial Dropwise 5 μ l target silylating reagent (as silicon fluoride reagent (Heptadecafluoro-1,1.2,2-tetrahydradecyl) triethoxysilane, C ₁₆H ₁₉F ₁₇O ₃Si, ABCR GmbH﹠amp; Co.KG), monocrystalline silicon is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min, after drying up with high pure nitrogen, utilize power, the processing 3min of the body of oxygen plasma with 200mW, make the surface form the silica residual bond, be fixed on the specimen holder in the vacuum desiccator, make the vacuum in the vacuum desiccator remain on 0.012Mpa then, behind the 15min, take out sample, with deionized water ultrasonic cleaning two to three times, each 5min, dry up with nitrogen then, form the silicon base of modifying target silylating reagent monofilm.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this substrate, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.With the constant voltage deposition 2h of 400mv, obtain and the different structure in blank surface, similar with the result of embodiment 7 gained.

Embodiment 9

2000, amphipathic organic molecules such as discoveries such as Gleiche M two palmitic acid phosphatid ylcholine DPPC lift fast in low pressure (3.0mN/m) with the L-B technology under the condition of (1000 μ m/s) can performance period controlled groove array structure (GLEICHE M, CHI L F, FUCHS H.Nanoscopic channel lattices withcontrolled anisotropic wetting, Nature, 2000,403:173-175).

We carry membrane technology with L-B and lift two palmitic acid phosphatid ylcholines (DPPC 〉=99%, Sigma Aldrich) on silicon base.

The preparation parameter of LB film: V ₀=20 μ l, C ₁=1mg/ml, CHCl ₃Solution, t ₁=15min,

S ₁＝15cm ²/min，P＝2.5mN/m，t ₂＝5min，S ₂＝10mm/min

Realize constructing of ribbon structure, shown in Figure 13 (A), on ribbon structure, carry out electro-deposition, obtained the structure of orderly argent nano particle equally.Shown in Figure 13 (B), the particle diameter of its Nano silver grain is 80～100nm.

Embodiment 10

S ₁＝15cm ²/min，P＝2.5mN/m，t ₂＝5min，S ₂＝10mm/min

Realize constructing of ribbon structure, the gold, silver of the about 10nm of vacuum evaporation or aluminum metal on ribbon structure are further modified the surface of film, improve its electric conductivity, obtain orderly metallic array.Its pattern is similar to embodiment 9, but compares with embodiment 9 and since evaporation layer of metal, its electric conductivity promotes, bigger than embodiment 9, particle diameter is about 160nm～190nm.The pattern that obtains and Figure 13 (B) are similar.

Embodiment 11

Thermal plastic polymer MRI-7030 (Micro Resist company takes a morsel, Germany) be spun on the ITO surface of handling well, spin coating thickness is about 300nm, processing method is that ITO is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min are after drying up with high pure nitrogen, utilize power, the processing 3min of the body of oxygen plasma, make the ITO surface active with 200mW.Utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the template of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the conductive surface of ITO and the ordered structure that polymer barrier layer distributes alternately.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is auxiliary electrode with ITO, adds the chlorauric acid solution (HAuCl of the 0.10mol/l of 20 μ l ₄4H ₂O, Beijing chemical industry one factory) as electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 2h with 500mv, obtain the ordered structure that golden nanometer particle and polymer barrier layer distribute alternately, by immersing in the acetone 3 times, each 5min, remove polymer barrier layer MRI-7030, and dry up with high pure nitrogen, the surface that has just obtained with the complementation of silicon nitride formwork structure is the alternate ordered structure of golden nanometer particle and ITO, as shown in figure 11.

Embodiment 12

Thermal plastic polymer MRI-7030 (Micro Resist company takes a morsel, Germany) be spun on the monocrystalline silicon surface of handling well, spin coating thickness is about 300nm, processing method is that monocrystalline silicon is cut into 2cm * 2cm size, use acetone successively, ethanol and high purity water ultrasonic cleaning 5min dry up with high pure nitrogen.Utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the masterplate of silicon nitride material, its structure is divided into two parts, a part is the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m) (part is for concave point formation structure to construct out the ordered structure of macromolecule and formwork structure complementation, its size range is that the size of concave point is 800nm * 800nm～10 μ m * 10 μ m, spacing is 800nm～10 μ m, another part is the strip-type structure, its live width and distance between centers of tracks are 800nm～10 μ m), promptly utilize the method for nano impression to construct micro-structural at substrate surface, whole process is as shown in Figure 3.Utilize oxygen plasma treatment to remove each bar interband and interlattice polymer barrier layer, expose the surface of monocrystalline and the ordered structure that polymer barrier layer distributes alternately.

Utilize vapour deposition process Dropwise 5 μ l target silylating reagent in the vial in vacuum desiccator, to handle that impression is handled well and etching processing obtains exposing the surface of monocrystalline and ordered structure substrate that polymer barrier layer distributes alternately and is fixed on the specimen holder in the vacuum desiccator, make the vacuum in the vacuum desiccator remain on 0.012Mpa then, behind the 25min, take out sample, with deionized water ultrasonic cleaning 3 times, each 5min dries up with nitrogen then.With acetone or chloroform ultrasonic cleaning 3 times, each 3min washes away high molecular barrier layer, obtains orderly single-layer membrane structure.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this monofilm, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 20 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.With the constant voltage deposition 1h of 300mv, obtain the structure of orderly Nano silver grain, as shown in figure 12.

Embodiment 13

Utilizing the method for photoetching, is the BP212 type ultraviolet eurymeric photoresist that Beijing Inst. of Chemical Reagent produces with photoresist, viscosity (25 ℃): (37 ± 2) * 10 ^-3PaS.The thickness of our photoresist layer all is controlled at about 2 μ m among the present invention, and photoresist spin coating condition is: 3000 commentaries on classics/S, Rotate 180 S; Adopt the method for spin coating the plus or minus photoresist film to be spun on base materials such as plasma treated quartz, glass, ito glass, metal, silicon chip or metal, the substrate of conducting high polymers thing.

Chromium dioxide (its structure is that live width and distance between centers of tracks are the ribbon structure of the 5 μ m) ordered structure of constructing with the method that adopts the deep ultraviolet etching is a baffle plate, the substrate of the photoresist that spin coating is good places under the baffle plate, (light source is the high-pressure sodium lamp of 1000 ± 200W under ultraviolet light, emission wavelength is at 390 ± 20nm) exposure 200s, behind corresponding developer solution wash-out, obtain the structure with the baffle plate complementation, thereby construct out the substrate of structure.

Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is working electrode with this structure, is auxiliary electrode with ITO, and the liquor argenti nitratis ophthalmicus that adds the 0.05mol/l of 40 μ l is an electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.With the constant voltage deposition 3h of 300mv, obtain the micrometer structure of orderly Nano silver grain, thereby large tracts of land is constructed orderly micro-nano metal structure effectively.

Embodiment 14

The monofilm that utilizes example 7 and example 8 to obtain, utilize AFM (Nanosope IIIa, DigitalInstrument Co., Santa Babara, CA) contact mode, use conductive pinpoint,, make monofilm carry out selective oxidation applying the voltage of 8v between monofilm and the needle point, part through the making alive oxidation, be oxidized to carboxyl functional group,, obtain the ordered structure that orderly carboxylic acid functional and target silane functional distribute alternately by programming and location translation, shown in Figure 14 (B), carry out electro-deposition on this structure, the pattern and the Figure 13 (B) that can obtain orderly metal structure are similar, but the particle diameter of Nano silver grain has only 30～80nm.

Utilize the burnt Raman spectrometer system1000 of Britain Renishaw copolymerization, measure, behind the surface absorption 4-mercaptopyridine of the orderly Nano silver grain of this structure, the Raman enhanced spectrum, the reflection Raman is enhanced propertied, and its enhancer is about 10 ³(as shown in figure 15),

Embodiment 15

On the ITO surface of handling well (processing method is that ITO is cut into 2cm * 2cm size, uses acetone successively, ethanol and high purity water ultrasonic cleaning 5min, after drying up with high pure nitrogen, utilize the body of oxygen plasma with the power of 200mW, handle 3min, make the ITO surface active.) carry out electro-deposition in the designed electrolytic cell voluntarily at us, be working electrode with this structure, be auxiliary electrode with Pt, the Prussian blue aqueous solution that adds the 0.05mol/l of 20 μ l is electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 3h with 300mv obtains good Prussian blue film.Also can under the pattern of singly sweeping cyclic voltammetry scan, carry out electrochemical reaction on common electrochemical workstation, be electrolyte with the Prussian blue aqueous solution, also can obtain Prussian blue film.Prussian blue film and derivative thereof have good electrochemical reversibility, the stability of height, and easy advantage such as preparation, thereby have good application prospects at aspects such as electrochemical catalysis, electrochemical analysis, electric colour developing, secondary cells.

Embodiment 16

In embodiment 15,, the ITO surface of no any structure is working electrode if being changed to the ordered structure substrate that we utilize barrier material that the technology of nano impression or photoetching, electron beam lithography constructs and ITO surface to distribute alternately.Carrying out electro-deposition in the designed electrolytic cell voluntarily at us, is auxiliary electrode with ITO, and the Prussian blue aqueous solution that adds the 0.05mol/l of 20 μ l is electrolyte.The thickness of plastic splint is 0.1mm, and silver strip thickness is 100 ± 5 μ m, thereby two interelectrode distances are 0.3mm.Constant voltage deposition 3h with 300mv obtains Prussian blue ordered structure, and atomic force picture and Figure 12 are similar.We can also obtain the orderly structure of other dye molecules by this method.

Embodiment 17

By method of the present invention, be electrolyte (small, 2006,2,1068-1074 with the dna fragmentation of golden nanometer particle modified; J.Mater.Chem.2004,14,3488-3494), utilize nano impression, or photoetching, the constructed micro-structural substrate of electron beam lithography is a working electrode, with platinum or other conductive substrates is auxiliary electrode, is reference with the silver strip, carries out electrochemical reaction with 5v, behind the 1h, after immersing organic solvent (as alcohols, acetone, acetonitrile etc., this patent adopts acetone solvent) 2s rapidly, remove high molecular barrier layer, just obtain the DNA ordered structure array of modified, obtain the oldered array of biomolecule.

Claims

1. adopt barrier layer polymer to construct the method that metal ordered structure surface strengthens the Raman substrate, comprise the steps:

B, by photoetching, electron beam lithography or nano-imprinting method, go out the orderly nano/micron structure that barrier layer polymer and conductive substrates distribute alternately at the surface construction of conductive substrates; The thickness of the barrier layer polymer that photoetching method is constructed is 1～4 μ m, and the thickness of the barrier layer polymer that electron beam lithography or nano-imprinting method are constructed is 200～500nm, and the nano/micron structure is 100nm～25 μ m;

C, in electrolytic cell with the conductive substrates of the above-mentioned steps preparation electrode of working, do auxiliary electrode with another conductive substrates, in voltage swing 0.1～20v, time is that the constant voltage mode of 0.1～12h or size of current are 0.1～5A, time to be to carry out electrochemical deposition under the constant current mode of 0.1～12h, thereby realizes the orderly structures of metal nanoparticles array that barrier layer polymer and metal nanoparticle distribute alternately on working electrode;

D, the working electrode that above-mentioned steps is obtained are immersed in and carry out wash-out in the organic solvent to remove barrier layer polymer, after repeating 3～4 times, utilize high purity nitrogen to dry up, finally obtain conductive substrates and metal nanoparticle metal ordered structure surface alternately and strengthen the Raman substrate.

2. adopt different functional groups to construct the method that orderly metal structure surface strengthens the Raman substrate, comprise the steps:

C, in electrolytic cell with the conductive substrates of the above-mentioned steps preparation electrode of working, do auxiliary electrode with another conductive substrates, in voltage swing 0.1～20v, time is that the constant voltage mode of 0.1～12h or size of current are 0.1～5A, time to be to carry out electrochemical deposition under the constant current mode of 0.1～12h, thereby forms the structures of metal nanoparticles array on working electrode;

D, utilize high purity nitrogen to dry up conductive substrates, finally obtain metal ordered structure surface and strengthen the Raman substrate as working electrode.

3. metal ordered structure surface as claimed in claim 1 or 2 strengthens the construction method of substrate, and it is characterized in that: substrate is ito glass, monocrystalline silicon piece, n-silicon, P-silicon, gold, silver, platinum, copper, cobalt, nickel, aluminium, cadmium, zinc oxide, aluminium oxide, chromium oxide, titanium oxide, zirconia, quartz, glass, mica sheet, silica, calcirm-fluoride, ruby, dimethyl silicone polymer, polyurethane, polyvinyl chloride, PETG, polystyrene, polyethylene, polypropylene, polyaniline or polypyrrole.

4. employing barrier layer polymer as claimed in claim 1 is constructed the method that metal ordered structure surface strengthens the Raman substrate, and it is characterized in that: the step of nano-imprinting method is

A. make with the method for photoetching or electron beam lithography and have micron rigid template of sub-micron micro-structural, be impressed into this rigid template in the substrate on spin on polymers barrier layer;

B. 10～the 70Bar that keep-ups pressure, heating keeps 2～30min under the condition that is higher than 30～100 ℃ of barrier polymers glass transition temperatures, and molten polymer is flowed in the groove of rigid template;

C. reduce temperature to the polymer glass conversion temperature, rigid template is peeled off;

D. remove polymer residue layer in the polymer barrier layer groove with plasma etching again, thereby in substrate, obtain the polymer nano/micrometer structure surface with the rigid template complementary structure.

5. employing barrier layer polymer as claimed in claim 4 is constructed the method that metal ordered structure surface strengthens the Raman substrate, it is characterized in that: the barrier layer is polymethyl methacrylate, polystyrene, polyurethane, polyethylene, polypropylene, polyvinyl chloride, dibutene, polyvinyl alcohol, polystyrene butadiene copolymer, poly-MEH-PPV, BEH-PPV to styrene polyoxyethylene alkene copolymer, ABS resin, polyphenylene ethylene class, BuEH-PPV or poly-PPP to the benzene class.

6. metal ordered structure surface as claimed in claim 1 or 2 strengthens the construction method of substrate, it is characterized in that: between working electrode and auxiliary electrode, plastic sandwich is arranged, make reference electrode with simple substance silver, construct airtight micro reaction pool, the volume of electrolyte is at 10～500 μ l.

7. metal ordered structure surface as claimed in claim 6 strengthens the construction method of substrate, it is characterized in that: electrolyte is the soluble-salt solution of gold, copper, cobalt, nickel, platinum, silver, cadmium, indium or germanium.

Any one described metal ordered structure surface of claim 1-7 construction method of strengthening substrate biomolecule or dye molecule electrophoresis, ordered structure is constructed and thin film electroplating and wash-out aspect application.

9. any one described metal ordered structure surface of claim 1-7 construction method of strengthening substrate is at preparation metal oldered array, metal sensor, Raman substrate preparation and based on the application in the Raman detection.