CN104986724B - A kind of fexible film surface micronano structure and application thereof - Google Patents
A kind of fexible film surface micronano structure and application thereof Download PDFInfo
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- CN104986724B CN104986724B CN201510307201.0A CN201510307201A CN104986724B CN 104986724 B CN104986724 B CN 104986724B CN 201510307201 A CN201510307201 A CN 201510307201A CN 104986724 B CN104986724 B CN 104986724B
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Abstract
The invention discloses a kind of fexible film surface micronano structure. This fexible film surface micronano structure is to be prepared by following methods: the particle diameter deviation microsphere less than 3% is dispersed in acid solution surface as microsphere template, then watering polymer solution and form fexible film, described polymer solution is made up of organic high molecular polymer and non-polar organic solvent; Fexible film removes, after solidifying, the microsphere adhered on surface, obtains fexible film surface micronano structure. The preparation technology of fexible film surface micronano structure of the present invention is simple, does not need depositing them at other substrate surfaces, eliminates the machining equipment of complexity; Can preparing high-quality, large-area micro nano structure, micro nano structure is uniform, fine and close, complete. The invention also discloses the application of described fexible film surface micronano structure, can be used for preparing surface enhanced Raman substrate, the surface enhanced Raman substrate obtained is highly sensitive, signal conformance good, application is convenient.
Description
Technical field
The invention belongs to micro-nano manufacture field, particularly to a kind of fexible film surface micronano structure and application thereof.
Background technology
Current era is the epoch being principal character with opto-electronic information technology, owing to regularly arranged micro-nano array structure has the feature of micro-nano structure device, so being widely used in the field such as photonic crystal, surface plasma Raman enhancing test, super-hydrophobic interface, pressure transducer, nanocomposite optical device. Presently, there are multiple method for preparing micro-nano array structure, such as photoetching corrosion, micromachined etc. Although these method controllabilitys are better, but equipment investment is much more expensive, and process is complicated, and preparation cost is high, thus limiting business promotion and the application of micro-nano array structure.
In recent years, along with the development of self-assembling technique, it is possible to low cost prepare large area rule micro-nano array structure. This method utilizes the self assembly of uniform particle diameter microsphere at substrate surface formation template or mask, uses the technology such as transfer printing or ion etching to make regularly arranged array structure in substrate or the former substrate of transfer printing. But these methods are required for depositing them at a kind of substrate surface, add operation sequence, and the quality of forming film being easily caused self-assembly microspheres declines, it is impossible to prepare the large-area micro nano structure array of high-quality.
Such as, the preparation method that application for a patent for invention CN103512875 discloses a kind of surface enhanced raman spectroscopy composite substrate, method polystyrene microsphere mask plate of prepared monolayer alignment on silicon chip initially with liquid level self assembly, then vacuum coating equipment is utilized, polystyrene microsphere mask plate is first deposited with Cr nanometer film, it is deposited with Ag nanometer film again, is subsequently placed in chloroform and dissolves removes polystyrene microsphere, washing;Finally by adopting the single-layer graphene that grow on Copper Foil of CVD technology to transfer on the silver nanoparticle array prepared by polystyrene microsphere template method, after being incubated 30min at 50 DEG C, form the substrate of composite surface enhancing Raman spectrum. The method needs to deposit to polystyrene microsphere silicon wafer-based basal surface, not only increases operation sequence, and the quality of forming film being easily caused self-assembly microspheres declines, and then reduce the detection sensitivity of surface enhanced Raman substrate.
Summary of the invention
It is an object of the invention to overcome above-mentioned deficiency existing in prior art, it is provided that a kind of fexible film surface micronano structure. This fexible film surface micronano structure is prepared by following methods: the microsphere suspension liquid of uniform particle sizes is dispersed in acid solution surface as microsphere template, then on microsphere template, build the mixed solution of organic high molecular polymer and non-polar organic solvent composition, fexible film is formed after dry solidification, remove the microsphere of fexible film surface adhesion, obtain fexible film surface micronano structure. The inventive method technique is simple, does not need depositing them on hard substrate surfaces such as silicon chips, eliminates the machining equipment of complexity; Technique is easily controlled, and can prepare high-quality, large-area micro nano structure, and the micro nano structure obtained is uniform, fine and close, complete; Can need arbitrarily to adjust the size of micro nano structure according to application simultaneously.
Another object of the present invention is to provide the application of described fexible film surface micronano structure. This fexible film surface micronano structure can be used for preparing surface enhanced Raman substrate, before deposition gold silver nanoparticle, fexible film surface micronano structure is carried out surface hydrophilic process and surface silanization processes, can at the gold silver nanoparticle of fexible film surface deposit sufficient levels, and gold silver nanoparticle is evenly distributed, make the surface enhanced Raman substrate detection sensitivity finally given high.
In order to realize foregoing invention purpose, the invention provides techniques below scheme:
Fexible film surface micronano structure of the present invention, is prepared by following methods:
(1) preparation of microsphere template
Being distributed in acid solution by microsphere suspension liquid, add surfactant, the surface tension by surfactant forms the microsphere template arranging densification on acid solution surface; The standard deviation < 3% of described microspherulite diameter;
(2) preparation of fexible film
Polymer solution is built on the microsphere template described in step (1); After the polymer solution dry solidification on microsphere template, obtaining surface adhesion has the fexible film of microsphere; Described polymer solution is made up of organic high molecular polymer and non-polar organic solvent;
(3) preparation of fexible film surface micronano structure
The fexible film that step (2) described surface adhesion has microsphere takes out from acid solution surface, and soaking and washing in abluent removes the microsphere of surface adhesion, namely obtains fexible film surface micronano structure.
In the method for the invention, the microsphere of uniform particle sizes is added dropwise in acid solution, microsphere swims in solution surface by buoyancy, add surfactant, surface tension by surfactant, microsphere forms the monolayer microsphere template that arrangement is uniform, fine and close on acid solution surface, as next step template. Then organic high molecular polymer is dissolved in non-polar solven and forms polymer solution, build on the monolayer microsphere template swimming in acid solution surface. Non-polar organic solvent can increase the organic high molecular polymer mobility on microsphere template surface, it is simple to organic high molecular polymer is sprawled; Non-polar organic solvent be easy to volatilization, until non-polar organic solvent volatilize after, organic high molecular polymer natural drying, solidification, film forming, obtain being stained with the fexible film of microsphere. The fexible film being stained with microsphere is taken off from acid solution surface, put into after abluent soaks the microsphere that removing sticks to fexible film surface, namely can leave uniform, fine and close, complete micro-nano sunk structure on fexible film surface, obtain fexible film surface micronano structure.
Preferably, described microsphere suspension liquid be microsphere be dispersed in water or ethanol formed suspension.Preferably, in described microsphere suspension liquid, the mass percent of microsphere is 1��5%.
Preferably, described microsphere is silicon dioxide microsphere, carborundum microsphere, polystyrene microsphere or aluminium sesquioxide microsphere. Described microsphere has uniform particle diameter, when it is as template, can make the hole micro nano structure that uniform pore diameter is retained on fexible film surface, the degree of depth is consistent.
Preferably, the particle diameter of described microsphere is 0.01��10 ��m. When microspherulite diameter is less than 10nm, microsphere is susceptible on acid solution surface reunite, it is impossible to form the microsphere template that arrangement is uniform, fine and close; When microspherulite diameter is more than 10 ��m, microsphere can cannot be made to float on acid solution surface due to surface tension deficiency, thus microsphere template cannot be formed as. It is further preferred that the particle diameter of described microsphere is 0.2��1 ��m.
In order to make fexible film surface micronano structure size uniform, in the present invention, it is desirable to the standard deviation of microspherulite diameter controls in 3% scope. The best preferably, the uniform particle diameter of described microsphere.
Preferably, described acid solution is sulphuric acid, nitric acid or hydrochloric acid.
Preferably, in described acid solution, hydrionic concentration is 0.001��10mol/L. Applicant finds through test of many times, and when hydrogen ion concentration is less than 0.001mol/L, microsphere will be suspended in acid solution, it is impossible to floats on acid solution surface; When hydrogen ion concentration is more than 10mol/L, the organic high molecular polymer of follow-up cast can be corroded, it is impossible to form the fexible film with consistent appearance micro nano structure. It is further preferred that hydrionic concentration is 0.01��1mol/L in described acid solution.
Preferably, described surfactant is dodecyl sodium sulfate or sodium lauryl sulphate. Dodecyl sodium sulfate is anionic surfactant, and relative to nonionic surfactant polyvinylpyrrolidone and cationic surface active agent cetab, dodecyl sodium sulfate will not be subject to H in acid solution+Impact, it is possible to make microsphere can more be closely spaced together into high-quality microsphere template, and then be not easy to make microsphere template crack in follow-up polymer solution casting process.
Preferably, described organic high molecular polymer is polydimethylsiloxane or polymethyl methacrylate. Preferably, described organic high molecular polymer is polydimethylsiloxane to the best.
Preferably, described non-polar organic solvent is normal hexane, hexamethylene or benzene. After described non-polar organic solvent mixes with organic high molecular polymer, the mobility of organic high molecular polymer can be improved, reduce its density, increase the immiscible property of organic high molecular polymer and acid solution, make organic high molecular polymer can be uniformly distributed in microsphere template surface under the premise not destroying microsphere template.
Preferably, in described polymer solution, the mol ratio of organic high molecular polymer and non-polar organic solvent is 1:0.1��1000. When mol ratio is less than 1:1000, can cause that non-polar organic solvent is wasted when forming the thin film of adequate thickness; When mol ratio is more than 1:0.1, polymer solution flow is poor, it is impossible to form fexible film in uniform thickness. It is further preferred that organic high molecular polymer is 1:1��100 with the mol ratio of non-polar organic solvent in described polymer solution.
Preferably, described abluent is dimethylformamide, benzene,toluene,xylene or Fluohydric acid.. Adopt above-mentioned abluent, not only can easily remove the microsphere of organic high molecular polymer film surface, organic high molecular polymer thin film itself will not be destroyed simultaneously, make organic high molecular polymer film surface form uniform, fine and close, complete micro-nano sunk structure.
The application of fexible film surface micronano structure of the present invention, is be used for preparing surface enhanced Raman substrate by the fexible film surface micronano structure obtained, specifically includes following steps:
A. surface hydrophilic processes
Fexible film surface micronano structure is cleaned for several times, is then soaked in the mixed solution of concentrated sulphuric acid and hydrogen peroxide composition and carries out surface hydrophilic process, take out, clean for several times;
B. surface silanization processes
Being soaked in the organic solution of silane coupler by the fexible film surface micronano structure processed through step A surface hydrophilic and carry out surface silanization process, reaction is cleaned successively with second alcohol and water after terminating; The organic solution of described silane coupler is made up of silane coupler and alcohols solvent, and in the organic solution of described silane coupler, the percentage by volume of silane coupler is 1��4%; Described silane coupler is 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane or N-[3-(trimethoxy is silica-based) propyl group] ethylenediamine;
C. surface depositing gold nanoparticles
The fexible film surface micronano structure crossed through step B surface silanization treatment is soaked in golden nanometer particle colloidal sol, takes out;
D. surface deposition Nano silver grain
The fexible film surface micronano structure processed through step C is dipped in Nano silver grain precursor solution, takes out, obtain surface enhanced Raman substrate.
The present invention adopts the mixed solution of concentrated sulphuric acid and hydrogen peroxide that fexible film is carried out surface treatment, and by the Oxidation of concentrated sulphuric acid Yu hydrogen peroxide, a large amount of hydrophilic hydroxy group on fexible film surface connects, to reach the effect of hydrophilic treated. Preferably, in above-mentioned application, in described step A mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 3��5:1. Applicant finds through test of many times, and in mixed solution, the deposition of follow-up silanization performance process and gold, silver nanoparticle is played the effect of key by the volume ratio of concentrated sulphuric acid and hydrogen peroxide. When the volume ratio of concentrated sulphuric acid and hydrogen peroxide is less than 3:1, solution can be caused overheated or the danger such as blast; When the volume ratio of concentrated sulphuric acid and hydrogen peroxide is more than 5:1, do not reach desired hydrophilic treatment effect. Preferably, the mass percent of described concentrated sulphuric acid is 90��98%, and the mass percent of described hydrogen peroxide is 20��40%; Preferably, the time that described surface hydrophilic processes is 0.5��5min, and the temperature that surface hydrophilic processes is 5��80 DEG C. Less than 0.5min between when treated, treatment temperature is less than 5 DEG C, it is impossible to connect abundant hydrophilic group on fexible film surface; More than 5min between when treated, treatment temperature is higher than 80 DEG C, and fexible film surface can by concentrated sulphuric acid and hydrogen peroxide excessive corrosion.
After surface hydrophilic processes, hydrophilic group hydroxyl can react with silane coupler, thus at the flexible substrates finishing last layer silane coupled agent molecule with amino or sulfydryl.
Preferably, in surface silanization processing procedure, described alcohols solvent is methanol, ethanol, ethylene glycol. Preferably, in above-mentioned application, the time that in described step B, surface silanization processes is 0.5��10h, and temperature is 1��100 DEG C. Less than 0.5h between when treated, treatment temperature is less than 1 DEG C, it is impossible to connect enough amino or sulfydryl on fexible film surface; More than 10h between when treated, treatment temperature is higher than 100 DEG C, can cause silane coupler degeneration thus affecting the silanization on fexible film surface.
After above-mentioned surface hydrophilic processes and surface silanization processes, utilize the silane coupler can better at fexible film surface micronano structure finishing last layer golden nanometer particle, and then modify last layer Nano silver grain better, gold silver nanoparticle deposition is sufficient, and be evenly distributed, significantly improve the detection sensitivity of gained surface enhanced Raman substrate.Preferably, in described step C, the preparation method of golden nanometer particle colloidal sol is: in the aqueous solution of chloraurate being heated to backflow, maintains and adds sodium citrate under stirring, and namely natural cooling after reaction 5min obtains the golden nanometer particle colloidal sol of aqueous phase. Preferably, in described golden nanometer particle colloidal sol, the concentration of golden nanometer particle is 0.5��2mmol/L. Preferably, the particle diameter of described golden nanometer particle is 2��100nm. Preferably, the temperature of described golden nanometer particle colloidal sol is 1��99 DEG C, and described soak time is 5��14h. When soak time is less than 5h, it is impossible to the golden nanometer particle of depositing sufficient amount; When soak time is more than 14h, can cause that golden nanometer particle is reunited thus affecting the deposition of follow-up nanometer silver; When solution temperature is less than 1 DEG C, golden nanometer particle activity reduces, it is impossible to the golden nanometer particle of depositing sufficient amount; When solution temperature is higher than 99 DEG C, can cause that golden nanometer particle is reunited affects follow-up Nano silver deposition.
After fexible film surface micronano structure modifies upper golden nanometer particle, immersing in Nano silver grain precursor solution, in-situ reducing generates nanometer silver. Preferably, described Nano silver grain precursor solution is that 0.03��0.07:0.4��0.8:8��12 are made by silver nitrate, reducing agent and deionized water according to weight ratio; Described reducing agent is trisodium citrate or sodium borohydride. Preferably, in described step D, the temperature of Nano silver grain precursor solution is 1��99 DEG C, and soak time is 30��80min. When soak time is less than 30min, it is impossible to generate enough nanometer silvers; When soak time is more than 80min, can cause that nanometer silver is reunited and precipitate; When solution temperature is less than 1 DEG C, it is impossible to generate enough nanometer silvers; When solution temperature is higher than 99 DEG C, can cause that Nano silver grain precursor solution goes bad.
Compared with prior art, the beneficial effects of the present invention is:
(1) fexible film surface micronano structure of the present invention is prepared by simple technique, does not need, by the depositing them surface in hard substrate such as silicon chips, to eliminate the machining equipment of complexity.
(2) fexible film surface micronano structure of the present invention is easier to control, high-quality, large-area micro nano structure can be prepared, the micro nano structure obtained is uniform, fine and close, complete, simultaneously can according to application needs, by arbitrarily adjusting microspherulite diameter to obtain various sizes of micro nano structure, it is suitable for large-scale production.
(3) fexible film surface micronano structure of the present invention, after the physical or chemical treatment of routine techniques, can be widely applied to the multiple fields such as opto-electronic conversion, Surface Science.
(4) it is applied to prepare surface enhanced Raman substrate by fexible film surface micronano structure of the present invention, before deposition gold silver nanoparticle, first carry out surface hydrophilic process and surface silanization process, can at the gold silver nanoparticle of fexible film surface deposit sufficient levels, and gold silver nanoparticle is evenly distributed, and then significantly improve the detection sensitivity of surface enhanced Raman substrate, 1 �� 10 can be reached-9Mol/L, solves because gold silver nanoparticle deposition is little in prior art, particle skewness and problem that the surface enhanced Raman substrate detection sensitivity that causes reduces.
Accompanying drawing explanation
Fig. 1 is the process schematic that the present invention prepares fexible film surface micronano structure.
Fig. 2 is the SEM figure of the fexible film surface micronano structure of embodiment 1 preparation.
Fig. 3 is that the surface enhanced Raman substrate of embodiment 1 preparation is for detecting trace dyestuff Nai Er blue light spectrogram.
Fig. 4 is that the surface enhanced Raman substrate of embodiment 2 preparation is for detecting trace dyestuff Nai Er blue light spectrogram.
Fig. 5 is that the surface enhanced Raman substrate of embodiment 3 preparation is for detecting trace dyestuff Nai Er blue light spectrogram.
Fig. 6 is that the surface enhanced Raman substrate of embodiment 4 preparation is for detecting trace dyestuff Nai Er blue light spectrogram.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail. But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to the scope of the present invention.
Embodiment 1
(1) preparation of microsphere template
Polystyrene (PS) microsphere suspension liquid of 2ml (being purchased from AlfaAesar company, suspension is the suspension that PS microsphere is distributed in deionized water to be formed, and the mass percent of suspension is 4%) is dropwise added drop-wise to 20mlH+Concentration is in the sulphuric acid of 0.1mol/L, adds the sodium dodecyl sulfate aqueous solution that 1ml concentration is 0.5wt%, and by the surface tension of surfactant sodium dodecyl base sodium sulfonate, microsphere forms the monolayer microsphere template that arrangement is uniform, fine and close on sulphuric acid surface; The particle diameter of described PS microsphere is about 500nm (standard deviation < 3%).
(2) preparation of the fexible film of microsphere it is stained with
4ml polydimethylsiloxane (PDMS) is dissolved in 20ml normal hexane, stirring and evenly mixing, obtain polymer solution; Polymer solution is built on the monolayer microsphere template described in step (1), utilize the mobility of polymer solution self to make it automatically sprawl; After the polymer solution natural air drying on monolayer microsphere template surface solidifies, obtain being stained with the fexible film of microsphere.
(3) preparation of fexible film surface micronano structure
The fexible film being stained with microsphere described in step (2) is taken out from sulphuric acid surface, put into soaking and washing in 30ml dimethylformamide (DMF), remove the microsphere on fexible film surface, take out, namely obtain fexible film surface micronano structure.
Fig. 2 is scanning electron microscope (SEM) figure of fexible film surface micronano structure. As shown in Figure 2, the micro nano structure that the present embodiment is prepared on PDMS fexible film surface is uniform, fine and close, complete, and size is about 400nm.
The fexible film surface micronano structure prepared by the present embodiment is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, employing deionized water clean fexible film surface micronano structure 5 times, remove the organic solvent of residual; Being then immersed in the concentrated sulphuric acid of 98% and the hydrogen peroxide mixed solution of 30% and process 3min, the temperature of mixed solution is 30 DEG C, and in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 3:1; Taking-up deionized water cleans 5 times;
B, the fexible film surface micronano structure crossed through processing of step A being placed in the organic solution of 40ml silane coupler reaction 200min, the organic solution temperature of described silane coupler is 50 DEG C; The organic solution of described silane coupler is made up of 3-aminopropyl trimethoxysilane and ethanol, and in the organic solution of described silane coupler, the percentage by volume of 3-aminopropyl trimethoxysilane is 1%; Reaction uses ethanol purge thin film 5 times after terminating, and then cleans thin film 5 times with water, modifies last layer 3-aminopropyl trimethoxysilane molecule at film surface;
C, the fexible film surface micronano structure processed through step B is immersed in 600min in 20ml golden nanometer particle colloidal sol, utilizes the bonding action of golden nanometer particle and silane to modify one layer of golden nanometer particle at film surface;In described golden nanometer particle colloidal sol, the particle diameter of golden nanometer particle is 30nm, and the concentration of golden nanometer particle is 1mmol/L; The temperature of described golden nanometer particle colloidal sol is 30 DEG C. The preparation method of described golden nanometer particle colloidal sol is: in the aqueous solution of chloraurate being heated to backflow, maintains and adds sodium citrate under stirring, and namely natural cooling after reaction 5min obtains the golden nanometer particle colloidal sol of aqueous phase.
D, take 0.05g silver nitrate, 0.5g sodium citrate is dissolved in 10ml deionized water, obtains Nano silver grain precursor solution; The fexible film surface micronano structure processed through step C is transferred in the Nano silver grain precursor solution of 25 DEG C, react 40min, generate nanometer silver at film surface, obtain surface enhanced Raman substrate.
Taking 5 �� L concentration is 1 �� 10-9Nai Erlan (NileBlueA) the water-soluble drop of mol/L is in prepared surface enhanced Raman substrate surface, treat that solution is dried, it is placed under 50 �� microscope objective, with 633nm laser, Nai Erlan is remained position to be irradiated, laser irradiation time is 2s, detects that surface-enhanced Raman signals is as shown in Figure 3. Showing that described surface enhanced Raman substrate signal conformance is good, detection sensitivity is high, can reach 1 �� 10-9mol/L��
Embodiment 2
(1) preparation of monolayer microsphere template
3ml silicon dioxide microsphere suspension (being purchased from Sigma, suspension is distributed in ethanol by silicon dioxide microsphere and makes) is dropwise added drop-wise to 30mlH+Concentration is in the nitric acid of 1mol/L, adds the sodium dodecyl sulfate aqueous solution that 1ml concentration is 0.5wt%, and by the surface tension of surfactant sodium dodecyl base sodium sulfonate, microsphere forms the monolayer microsphere template that arrangement is uniform, fine and close on nitric acid surface; Described silicon dioxide microsphere particle diameter is about 300nm (standard deviation < 3%).
(2) preparation of the fexible film of microsphere it is stained with
5ml polymethyl methacrylate (PMMA) is dissolved in 15ml hexamethylene, stirring and evenly mixing, obtain polymer solution; Polymer solution is built on the monolayer microsphere template described in step (1), utilize the mobility of polymer solution to make it automatically sprawl; After the polymer solution natural air drying on monolayer microsphere template surface solidifies, obtain being stained with the fexible film of microsphere;
(3) preparation of fexible film surface micronano structure
The fexible film being stained with microsphere described in step (2) is taken out from nitric acid surface, puts into soaking and washing in 50ml benzene, remove the microsphere on fexible film surface, take out, namely obtain fexible film surface micronano structure.
Detecting through SEM, the fexible film surface micronano structure described in the present embodiment is uniform, fine and close, complete, and size is about 200nm.
The fexible film surface micronano structure prepared by the present embodiment is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, employing deionized water clean fexible film surface micronano structure 7 times, remove the organic solvent of residual; Being then immersed in the concentrated sulphuric acid of 95% and the hydrogen peroxide mixed solution of 40% and process 1min, the temperature of mixed solution is 40 DEG C, and in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 4:1; Taking-up deionized water cleans 7 times;
B, being placed in the organic solution of 40ml silane coupler reaction 5h by crossing fexible film surface micronano structure through processing of step A, the organic solution temperature of described silane coupler is 20 DEG C; The organic solution of described silane coupler is made up of N-[3-(trimethoxy is silica-based) propyl group] ethylenediamine and methanol, and in the organic solution of described silane coupler, the percentage by volume of N-[3-(trimethoxy is silica-based) propyl group] ethylenediamine is 4%;Modifying one layer of N-[3-(trimethoxy is silica-based) propyl group] ethylenediamine molecule at film surface, reaction cleans thin film 7 times successively with second alcohol and water after terminating;
C, the fexible film surface micronano structure processed through step B is immersed in 6h in 20ml golden nanometer particle colloidal sol, utilizes the bonding action of golden nanometer particle and silane coupler to modify one layer of golden nanometer particle at film surface; In described golden nanometer particle colloidal sol, the particle diameter of golden nanometer particle is 80nm, and the concentration of golden nanometer particle is 0.5mmol/L; The temperature of described golden nanometer particle colloidal sol is 25 DEG C. The preparation method of described golden nanometer particle colloidal sol is: in the aqueous solution of chloraurate being heated to backflow, and under maintenance stirring, natural cooling after addition reducing agent reaction 5min, namely obtains the golden nanometer particle colloidal sol of aqueous phase.
D, take 0.03g silver nitrate, 0.4g sodium citrate is dissolved in 8ml deionized water, obtains Nano silver grain precursor solution; The fexible film surface micronano structure processed through step C is transferred in the Nano silver grain precursor solution of room temperature, react 70min, generate nanometer silver at film surface, obtain surface enhanced Raman substrate.
Taking 5 �� L concentration is 1 �� 10-9Nai Erlan (NileBlueA) the water-soluble drop of mol/L is in prepared surface enhanced Raman substrate surface, treat that solution is dried, it is placed under 50 �� microscope objective, with 633nm laser, Nai Erlan is remained position to be irradiated, laser irradiation time is 2s, detects that surface-enhanced Raman signals is as shown in Figure 4. Indicating that described surface enhanced Raman substrate signal conformance is good, detection sensitivity is high, can reach 1 �� 10-9mol/L��
Embodiment 3
(1) preparation of monolayer microsphere template
2ml aluminium sesquioxide microsphere suspension liquid (being purchased from AlfaAesar company, suspension is scattered in deionized water by aluminium sesquioxide microsphere and is formed) is dropwise added drop-wise to 40mlH+Concentration is in the hydrochloric acid of 5mol/L, adds the lauryl sodium sulfate aqueous solution that 2ml concentration is 0.5wt%, and by the surface tension of surfactant, microsphere forms, at salt acid surfaces, the monolayer microsphere template that arrangement is uniform, fine and close; Described aluminium sesquioxide microspherulite diameter is about 750nm (standard deviation < 3%);
(2) preparation of the fexible film of microsphere it is stained with
5ml polymethyl methacrylate (PMMA) is dissolved in 30ml benzene, stirring and evenly mixing, obtain polymer solution; Polymer solution is built on the monolayer microsphere template described in step (1), utilize the mobility of polymer solution to make it automatically sprawl; After the polymer solution natural air drying on monolayer microsphere template surface solidifies, obtain being stained with the fexible film of microsphere;
(3) preparation of fexible film surface micronano structure
The fexible film being stained with microsphere described in step (2) is taken out from salt acid surfaces, puts into soaking and washing in 60ml toluene, remove the microsphere on fexible film surface, take out, obtain fexible film surface micronano structure.
Detecting through SEM, fexible film surface micronano structure prepared by the present embodiment is uniform, fine and close, complete, and size is about 600nm.
The fexible film surface micronano structure prepared by the present embodiment is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, employing deionized water clean fexible film surface micronano structure 4 times, remove the organic solvent of residual; Being then immersed in the concentrated sulphuric acid of 90% and the hydrogen peroxide mixed solution of 20% and process 2min, the temperature of mixed solution is 80 DEG C, and in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 5:1;Taking-up deionized water cleans 4 times;
B, being placed in the organic solution of 40ml silane coupler reaction 10h by crossing fexible film surface micronano structure through processing of step A, the organic solution temperature of described silane coupler is 5 DEG C; The organic solution of described silane coupler is made up of 3-aminopropyl trimethoxysilane and methanol, and in the organic solution of described silane coupler, the percentage by volume of 3-aminopropyl trimethoxysilane is 3%; Reaction uses ethanol purge thin film 4 times after terminating, and cleans thin film 4 times with water, modifies one layer of 3-aminopropyl trimethoxysilane molecule at film surface;
C, the fexible film surface micronano structure processed through step B is immersed in 7h in 20ml golden nanometer particle colloidal sol, utilizes the bonding action of golden nanometer particle and silane to modify one layer of golden nanometer particle at film surface; In described golden nanometer particle colloidal sol, the particle diameter of golden nanometer particle is 50nm, and the concentration of golden nanometer particle is 2mmol/L; The temperature of described golden nanometer particle colloidal sol is 20 DEG C. The preparation method of described golden nanometer particle colloidal sol is: in the aqueous solution of chloraurate being heated to backflow, maintains and adds sodium citrate under stirring, and namely natural cooling after reaction 5min obtains the golden nanometer particle colloidal sol of aqueous phase.
D, take 0.07g silver nitrate, 0.8g sodium citrate is dissolved in 12ml deionized water, obtains Nano silver grain precursor solution; The fexible film surface micronano structure processed through step C is transferred in 25 DEG C of Nano silver grain precursor solutions, react 30min, generate nanometer silver at film surface, obtain surface enhanced Raman substrate.
Taking 5 �� L concentration is 1 �� 10-9Nai Erlan (NileBlueA) the water-soluble drop of mol/L is in prepared surface enhanced Raman substrate surface, treat that solution is dried, it is placed under 50 �� microscope objective, with 633nm laser, Nai Erlan is remained position to be irradiated, laser irradiation time is 2s, detects that surface-enhanced Raman signals is as shown in Figure 5. Indicating that described surface enhanced Raman substrate signal conformance is good, detection sensitivity is high, can reach 1 �� 10-9mol/L��
Embodiment 4
(1) preparation of monolayer microsphere template
2ml carborundum microsphere suspension liquid (being purchased from Sigma, suspension is scattered in ethanol by carborundum microsphere and is formed) is dropwise added drop-wise to 40mlH+Concentration is in the nitric acid of 0.5mol/L, adds in the sodium dodecyl sulfate aqueous solution that 3ml concentration is 0.5wt%, and by the surface tension of surfactant, microsphere forms the monolayer microsphere template that arrangement is uniform, fine and close on nitric acid surface; The particle diameter of described carborundum microsphere is about 1000nm (standard deviation < 3%).
(2) preparation of the fexible film of microsphere it is stained with
6ml polydimethylsiloxane (PDMS) is dissolved in 20ml normal hexane, stirring and evenly mixing, obtain polymer solution; Polymer solution is built on the monolayer microsphere template described in step (1), utilize the mobility of polymer solution to make it automatically sprawl; After the polymer solution natural air drying on monolayer microsphere template surface solidifies, obtain being stained with the fexible film of microsphere;
(3) preparation of fexible film surface micronano structure
The fexible film being stained with microsphere described in step (2) is taken out from aqueous solution of nitric acid surface, puts into soaking and washing in 30ml Fluohydric acid., remove the microsphere of organic high molecular polymer film surface, take out, namely obtain fexible film surface micronano structure.
Detecting through SEM, fexible film surface micronano structure prepared by the present embodiment is uniform, fine and close, complete, is of a size of about 800nm.
The fexible film surface micronano structure prepared by the present embodiment is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, employing deionized water clean fexible film surface micronano structure 4 times, remove the organic solvent of residual; Being then immersed in the concentrated sulphuric acid of 90% and the hydrogen peroxide mixed solution of 20% and process 2min, the temperature of mixed solution is 80 DEG C, and in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 3:1; Taking-up deionized water cleans 4 times;
B, being placed in the organic solution of 40ml silane coupler reaction 1h by crossing fexible film surface micronano structure through processing of step A, the organic solution temperature of described silane coupler is 80 DEG C; The organic solution of described silane coupler is made up of 3-mercaptopropyi trimethoxy silane and ethylene glycol, and in the organic solution of described silane coupler, the percentage by volume of 3-mercaptopropyi trimethoxy silane is 3%; Reaction uses ethanol purge thin film 4 times after terminating, and cleans 4 times with water, modifies one layer of 3-mercaptopropyi trimethoxy silane molecule at film surface;
C, the fexible film surface micronano structure processed through step B is immersed in 8h in 20ml golden nanometer particle colloidal sol, utilizes the bonding action of golden nanometer particle and silane to modify one layer of golden nanometer particle at film surface; In described golden nanometer particle colloidal sol, the particle diameter of golden nanometer particle is 10nm, and the concentration of golden nanometer particle is 1.5mmol/L; The temperature of described golden nanometer particle colloidal sol is 30 DEG C. The preparation method of described golden nanometer particle colloidal sol is: in the aqueous solution of chloraurate being heated to backflow, maintains and adds sodium citrate under stirring, and namely natural cooling after reaction 5min obtains the golden nanometer particle colloidal sol of aqueous phase.
D, take 0.04g silver nitrate, 0.7g sodium citrate is dissolved in 10ml deionized water, obtains Nano silver grain precursor solution; The fexible film surface micronano structure processed through step C is transferred in the Nano silver grain precursor solution of room temperature, react 30min, generate nanometer silver at film surface, obtain surface enhanced Raman substrate.
Taking 5 �� L concentration is 1 �� 10-9Nai Erlan (NileBlueA) the water-soluble drop of mol/L is in prepared surface enhanced Raman substrate surface, treat that solution is dried, it is placed under 50 �� microscope objective, with 633nm laser, Nai Erlan is remained position to be irradiated, laser irradiation time is 2s, detects that surface-enhanced Raman signals is as shown in Figure 6. Indicating that described surface enhanced Raman substrate signal conformance is good, detection sensitivity is high, can reach 1 �� 10-9mol/L��
Comparative example 1
Fexible film surface micronano structure embodiment 1 prepared is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, fexible film surface micronano structure embodiment 1 prepared are placed in the organic solution of 40ml silane coupler and react 200min, and the organic solution temperature of described silane coupler is 50 DEG C; The organic solution of described silane coupler is made up of r-aminopropyltriethoxywerene werene and ethanol, and in the organic solution of described silane coupler, the percentage by volume of r-aminopropyltriethoxywerene werene is 1%; Modifying one layer of r-aminopropyltriethoxywerene werene molecule at film surface, reaction cleans thin film 5 times successively with second alcohol and water after terminating;
B, the fexible film surface micronano structure crossed through processing of step A is immersed in 600min in 20ml golden nanometer particle colloidal sol, utilizes the bonding action of golden nanometer particle and silane to modify one layer of golden nanometer particle at film surface; In described golden nanometer particle colloidal sol, the particle diameter of golden nanometer particle is 30nm, and the concentration of golden nanometer particle is 1mmol/L;The temperature of described golden nanometer particle colloidal sol is 30 DEG C. The preparation method of described golden nanometer particle colloidal sol is:.
C, take 0.05g silver nitrate, 0.5g sodium citrate is dissolved in 10ml deionized water, obtains Nano silver grain precursor solution; The fexible film surface micronano structure processed through step B is transferred in the Nano silver grain precursor solution of room temperature, react 40min, generate nanometer silver at film surface, obtain surface enhanced Raman substrate.
Adopt the method described in embodiment 1 that this surface enhanced Raman substrate is used for Raman detection. The nanometer silver deposited due to this sample is sparse discontinuous, causes that signal conformance is poor, and detection sensitivity is low, only reaches 5 �� 10-7mol/L��
This comparative example shows, surface hydrophilic processing procedure of the present invention can affect follow-up surface silanization processing procedure, thus affecting the gold silver nanoparticle deposition on fexible film surface, and then significantly reducing the detection sensitivity of surface enhanced Raman substrate, signal conformance is poor.
Comparative example 2
Fexible film surface micronano structure embodiment 1 prepared is used for preparing surface enhanced Raman substrate, and concrete grammar is as follows:
A, employing deionized water clean fexible film surface micronano structure 5 times, remove the organic solvent of residual; Being then immersed in the concentrated sulphuric acid of 98% and the hydrogen peroxide mixed solution of 30% and process 3min, the temperature of mixed solution is 30 DEG C, and in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 6:1; Taking-up deionized water cleans 5 times;
Step B��D, with embodiment 1, obtains surface enhanced Raman substrate.
Adopt the method described in embodiment 1 that this surface enhanced Raman substrate is used for Raman detection. Due to this sample surfaces nanometer silver skewness, causing that signal conformance is poor, detection sensitivity is low, only reaches 1 �� 10-7mol/L��
This comparative example shows, in hydrophilic treated process, in described mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is more than 5:1, can significantly reduce the detection sensitivity of surface enhanced Raman substrate, and signal conformance is poor.
Claims (10)
1. a fexible film surface micronano structure, it is characterised in that it is prepared by following methods:
(1) preparation of microsphere template
Being distributed in acid solution by microsphere suspension liquid dropping, add surfactant, the tension force by surfactant forms the microsphere template arranging densification, the standard deviation < 3% of described microspherulite diameter on acid solution surface;
(2) preparation of fexible film
Polymer solution is built on the microsphere template described in step (1); After the polymer solution dry solidification on microsphere template, obtaining surface adhesion has the fexible film of microsphere; Described polymer solution is made up of organic high molecular polymer and non-polar organic solvent;
(3) preparation of fexible film surface micronano structure
The fexible film that step (2) described surface adhesion has microsphere takes out from acid solution surface, and soaking and washing in abluent removes the microsphere of surface adhesion, obtains fexible film surface micronano structure.
2. fexible film surface micronano structure according to claim 1, it is characterised in that: described microsphere is silicon dioxide microsphere, carborundum microsphere, polystyrene microsphere or aluminium sesquioxide microsphere; The particle diameter of described microsphere is 0.01 ~ 10 ��m; In described microsphere suspension liquid, the mass percent of microsphere is 1 ~ 5%.
3. fexible film surface micronano structure according to claim 1, it is characterised in that: described acid solution is sulphuric acid, nitric acid or hydrochloric acid; In described acid solution, hydrionic concentration is 0.001 ~ 10mol/L;Described surfactant is dodecyl sodium sulfate or sodium lauryl sulphate.
4. fexible film surface micronano structure according to claim 1, it is characterised in that: described microspherulite diameter is homogeneous.
5. the fexible film surface micronano structure described in claim 1, it is characterised in that: described organic high molecular polymer is polydimethylsiloxane or polymethyl methacrylate; Described non-polar organic solvent is normal hexane, hexamethylene or benzene; Described polymer solution is that 1:0.1 ~ 1000 form by organic high molecular polymer and non-polar organic solvent according to volume ratio.
6. the application of a fexible film surface micronano structure as claimed in claim 1, it is characterised in that: described fexible film surface micronano structure can be used for preparing surface enhanced Raman substrate, comprises the following steps:
A. surface hydrophilic processes
Fexible film surface micronano structure is cleaned for several times, is then soaked in the mixed solution of concentrated sulphuric acid and hydrogen peroxide composition and carries out surface hydrophilic process, take out and clean for several times;
B. surface silanization processes
Being soaked in the organic solution of silane coupler by the fexible film surface micronano structure processed through step A surface hydrophilic and carry out surface silanization process, reaction is cleaned successively with second alcohol and water after terminating; The organic solution of described silane coupler is made up of silane coupler and alcohols solvent, and in the organic solution of described silane coupler, the percentage by volume of silane coupler is 1 ~ 4%; Described silane coupler is 3-aminopropyl trimethoxy silicon
Alkane, 3-aminopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, 3-Mercaptopropyltriethoxysilane or N-[3-(trimethoxy is silica-based) propyl group] ethylenediamine;
C. surface depositing gold nanoparticles
The fexible film surface micronano structure crossed through step B surface silanization treatment is dipped in golden nanometer particle colloidal sol, takes out;
D. surface deposition Nano silver grain
The fexible film surface micronano structure processed through step C is dipped in Nano silver grain precursor solution, takes out, obtain surface enhanced Raman substrate; Described Nano silver grain precursor solution is made up of silver nitrate, reducing agent and deionized water; Described reducing agent is trisodium citrate or sodium borohydride.
7. application according to claim 6, it is characterised in that: in described step A mixed solution, the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 3 ~ 5:1; The time that described surface hydrophilic processes is 0.5 ~ 5min, and the temperature that surface hydrophilic processes is 5 ~ 80 DEG C.
8. application according to claim 6, it is characterised in that: the time that in described step B, surface silanization processes is 0.5 ~ 10h.
9. application according to claim 6, it is characterised in that: in described step C golden nanometer particle colloidal sol, the concentration of golden nanometer particle is 0.5 ~ 2mmol/L; The particle diameter of described golden nanometer particle is 2 ~ 100nm; Described soak time is 5 ~ 14h.
10. application according to claim 6, it is characterised in that: in described step D, soak time is 30 ~ 80min; Described Nano silver grain precursor solution is that 0.03 ~ 0.07:0.4 ~ 0.8:8 ~ 12 are made by silver nitrate, reducing agent and deionized water according to weight ratio.
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