CN101776604A - Method for manufacturing substrate for enhancing molecular Raman scattering - Google Patents
Method for manufacturing substrate for enhancing molecular Raman scattering Download PDFInfo
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- CN101776604A CN101776604A CN201010101588A CN201010101588A CN101776604A CN 101776604 A CN101776604 A CN 101776604A CN 201010101588 A CN201010101588 A CN 201010101588A CN 201010101588 A CN201010101588 A CN 201010101588A CN 101776604 A CN101776604 A CN 101776604A
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Abstract
A method for preparing a substrate for enhancing molecular Raman scattering comprises (1) selecting substrate material, cleaning, and performing hydrophilic treatment; (2) manufacturing a micro-nano structure layer on the surface of a substrate; (3) metallizing the micro-nano structure layer to obtain a substrate attached with a nano metal structure; (4) modifying the surface of the substrate obtained in the step (3) to obtain a surface decoration layer, wherein the surface modification is a behavior of preparing a gas-sensitive interface, or a molecular biological film, or an adsorption film, or a surface activation material according to the properties of molecules to be detected so as to improve the capability of enriching the molecules to be detected on the substrate and activate the substrate; (5) adding molecules to be detected to the substrate with the surface modification layer; (6) changing the external medium environment around the substrate to improve the Raman scattering enhancement effect of the molecules to be detected; the environment of the external medium surrounding the substrate comprises surrounding environment materials, or excitation light wavelength, or optical field distribution, or magnetic field distribution. The invention can be used for high-sensitivity detection, and meanwhile, the substrate has the advantages of controllability, consistency, repeatability, stability and the like.
Description
Technical field
The invention belongs to the micro-nano technical field, relate to a kind of substrate that strengthens Raman scattering of molecule, the particularly a kind of local surfaces plasma resonance effect of metal Nano structure and finishing mechanism utilized realizes efficient, the high stability substrate that the molecule Raman strengthens.
Background technology
Raman scattering (RS) is a kind of scattering phenomenon of light, is photon and testing molecule interaction when monochromatic incident light, and inelastic collision takes place, and between photon and the molecule energy exchange takes place, and photon changes the scattering that direction of motion and frequency took place.Raman spectrum (RS) is called as the dactylogram of molecule, the characteristics of this spectrum are narrow, the abundant information of bands of a spectrum, be applied to sensing technology, have the specificity height, need not that sample is prepared, can be provided fast, can repeat, the advantage of undamaged qualitative and quantitative analysis.But a little less than the Raman scattering very, Raman spectrum is applied to Detection Techniques and has the high specific while, and sensitivity is very low.Can scattering is strengthened be the key of RS Detection Techniques practicability.
Fleischman in 1974 observes the Raman diffused light spectral intensity that is attached to textured metal micro-nano structure surface molecular and can increase substantially, and is called as Surface enhanced raman spectroscopy (Surface-enhanced Raman Scattering is called for short SERS).Primary Study shows that this is a kind of special optical enhancement effect with surface selectivity, and the Raman signal that can will be adsorbed on the metal Nano structure surface molecular strengthens several magnitude singularly.The report that adopts nano metal colloidal sol to improve Raman scattering of molecule is also arranged.But at present these two kinds of methods exist all that enhancer is low, shortcoming such as repeatability and poor stability.Experiment and theoretical research show that the surrounding environment of SERS phenomenon and testing molecule is closely related, and having at the bottom of the SERS active group of high enhancing ability, high stability is one of key factor of utilizing the enlarge-effect realization high sensitivity detection of SERS.Making Raman scattering of molecule enhancing in the substrate, is that the Raman scattering efficient of molecule is improved on the one hand, is to make testing molecule at utmost accumulate in substrate surface on the other hand.Research to the Raman scattering enhancement effect at present only rests on the primary stage, and the mechanism of generation effect is also indeterminate.
Summary of the invention
The problem to be solved in the present invention is: overcome existing textured metal structural substrates, it is low that nano metal colloidal sol improves testing molecule Raman scattering efficient, detection sensitivity is low, the shortcoming of repeatability and poor stability, a kind of substrate fabrication method that strengthens Raman scattering of molecule is provided, this substrate utilizes metal micro-nanostructure local plasmon resonance body enhancement effect, adopt finishing coat, improve the external agency environment, improve substrate enrichment testing molecule quantity simultaneously and strengthened testing molecule Raman scattering efficient, realize the efficient of testing molecule Raman scattering, the high sensitivity detection demand is satisfied in maximization output.
The technical solution adopted for the present invention to solve the technical problems is: a kind of substrate fabrication method that strengthens Raman scattering of molecule, and described substrate is made up of the decorative layer and external agency environment four parts on substrate, metal micro-nanostructure layer, surface, and it is produced as follows:
(1) select for use backing material, clean and do hydrophilic treatment;
(2) produce the micro-nano structure layer at substrate surface;
(3), obtain to be attached with the substrate of metal Nano structure layer with the metallization of micro-nano structure layer;
(4) substrate surface that step (3) is obtained is modified, obtain surface decoration layer, described finishing is according to molecular property to be detected, preparation air-sensitive interface or molecular biosciences film or adsorption film or surface active material are with ability that improves substrate enrichment testing molecule and the behavior that substrate is activated;
(5) to the additional testing molecule of the substrate that has finishing coat;
(6) change substrate peripheral outer media environment, to improve testing molecule Raman scattering enhancement effect; Described substrate peripheral outer media environment comprises surrounding environment material or excitation wavelength or optical field distribution or Distribution of Magnetic Field.
Backing material in the described step (1) is glass or quartzy or silicon or germanium.
Produce the micro-nano structure layer at substrate surface by nanosphere self assembly or nano-photoetching or nano impression in the described step (2).
The characteristic dimension of micro-nano structure layer is from 20nm～900nm in the described step (2), and the cycle, thickness was from 10nm～500nm from 40nm～8 μ m.
Metallization micro-nano structure layer in the described step (3), metallization material are gold or silver or silver back gold or gold back silver earlier earlier.
The arrangement mode of metal Nano structure is triangle or quadrilateral or hexagon or annular in the described step (3).
Described step (5) feeds or drips or the mode of coating or injection is attached to testing molecule the substrate that has finishing coat.
Testing molecule in the described step (5) is probe gas molecule or solid molecule or fluid molecule.
The advantage that the present invention is compared with prior art had is: the present invention improves Raman scattering of molecule by improving substrate to the accumulation ability of testing molecule and Raman scattering two aspects that improve molecule in the substrate, make full use of the enlarge-effect of SERS, can realize high sensitivity detection; The present invention simultaneously has controllability, can guarantee consistance, repeatability, the stability of same batch or different batches substrate, guarantee that this method is used for the repeated and stable of Detection Techniques, solved the key technical problem that Raman spectrum is surveyed, can be widely used in the gas trace and survey or fields such as high sensitivity solid, solution detection.
Description of drawings
Fig. 1 is a kind of structural representation that strengthens the substrate of Raman scattering of molecule of the present invention;
Fig. 2 is a Raman scattering of molecule synoptic diagram in the embodiment of the invention 1;
Fig. 3 realizes the synoptic diagram that Raman scattering strengthens after utilizing the plasma enhancement effect of metal micro-nanostructure in the embodiment of the invention 1;
Fig. 4 does not carry out under the situation of finishing substrate in the embodiment of the invention 2, and substrate is to the enrichment condition synoptic diagram of molecule;
Fig. 5 is that substrate is to the enrichment condition synoptic diagram of molecule after in the embodiment of the invention 3 substrate being carried out finishing;
Among the figure: 1, base substrate, 2, metal micro-nanostructure, 3, finishing coat, 4, testing molecule, 5, Raman scattering, 6, incident laser, 7, free electron, 8, the plasma density ripple, 9, the Raman scattering after strengthening.
Embodiment
Fig. 1 is a kind of structural representation that strengthens the substrate of Raman scattering of molecule of the present invention.Substrate is made up of the decorative layer and external agency environment four parts on substrate, metal micro-nanostructure layer, surface.Wherein 1 is base substrate, and 2 is metal micro-nanostructure, and 3 is finishing coat.
In TNT gas trace was surveyed, method for making of the present invention was:
(1) selecting K9 glass for use is base substrate, the washing lotion of putting into concentration 90%～98% concentrated sulphuric acid and oxydol H 2SO4: 30%H2O22～be made at 4: 1 is heated to 80 ℃～120 ℃ and soaked 30～60 minutes, to remove impurity, flushing repeatedly then, put into the solution NH3 that ammoniacal liquor, hydrogen peroxide and water are made into again: H2O2: H2O/1: ultrasonic Treatment was 20～60 minutes in 1: 5, take out substrate again and wash usefulness repeatedly, preserve, in order to using;
(2) design the triangle metal nanostructured that hexagon is arranged, structural metallic materials is a gold, characteristic dimension 100nm, and cycle 500nm, thickness 10nm, the plasma resonance frequency of this structure is about 420nm.Adopt the method for nano impression on base substrate 1, to produce metal micro-nanostructure 2;
(3) method by gold evaporation metallizes micro-nano structure, obtains to be attached with the substrate of nm of gold structure;
(4) substrate surface is modified, and formation can be carried out the decorative layer of selective adsorption to the TNT vapour molecule.Concrete approach is as follows: with certain herbaceous plants with big flowers mercaptan (CH3 (CH2) 9SH of substrate at concentration 1mM, soaked 24 hours 1-DT), by-HS group 1-DT will be at the individual layer of the metal surface of substrate self assembly formation ordered arrangement, this individual layer will effectively adsorb TNT, and with the confinement of TNT molecule in electromagnetic field enhancing scope.Micro-concentrations 1mg/ml cetomacrogol 1000 chloroformic solution (PEG100) is covered the substrate surface film forming, and at 80 ℃ of oven dry 1h, allow solvent evaporates remove, formation can be carried out the gas sensing layer of selective adsorption to the TNT vapour molecule;
(5) additional testing molecule places vacuum environment with this substrate, feeds gas to be measured, and gas molecule is enriched in the decorative layer 3 of substrate surface;
(6) introduce the incident laser 6 irradiation substrate surfaces that wavelength is 442nm, free electron 7 in the laser excitation metal nanoparticle, local surfaces plasma resonance phenomenon (LSPR) takes place in substrate, produce plasma density ripple 8, gas molecule to be measured 4 Raman scatterings that are in the field intensity are strengthened greatly, shown among the figure 9.Adopt spectrometer to survey.
In sucrose solution is surveyed, realize the making of substrate by following steps
(1) to select silicon for use be substrate, clean and do hydrophilic treatment.
(2) produce triangle at substrate surface by the nanosphere self assembly and distribute characteristic dimension 50nm, the nanostructured of cycle 300nm.
(3) method of passing through magnetron sputtering is with nanostructured metalization, and first sputter last layer argent changes target sputter last layer metallic gold then, obtains to be attached with 50nm gold, the substrate of the nanometer metal structure of the double-level-metal of the thick silver of 20nm.
(4) if this substrate directly is positioned in the solution to be measured, survey, substrate to the suction-operated of testing molecule as shown in Figure 4.This substrate surface is added one deck molecular biosciences film 3, and activate: with octane mercaptan (1-octanethiol, 1-OT) and the 11-Mercaptoundecanoic acid (11-MUA) that contains sulfydryl in ethanol, prepare the solution of 1mM, 3: 1 by volume ratio is made into activating reagent, substrate is dipped in the activated solution 4 ℃ hatched 18 hours, make the reactive group of carboxyl on the band of metal surface, increase accumulation ability, as shown in Figure 5 testing molecule.
(5) substrate is placed solution to be measured, and then change its refractive index, to improve testing molecule Raman scattering enhancement effect by improving the electric-field intensity distribution in the solution or improving solution concentration.
In charcoal is surveyed apart from viral powder, realize the making of substrate by following steps
(1) to select germanium for use be backing material, clean and do hydrophilic treatment;
(2) adopt nano impression to produce characteristic dimension 800nm at substrate surface, cycles 3 μ m, the nanostructured layers that quadrilateral is arranged;
(3) with the metallization of micro-nano structure layer, first sputter last layer metallic gold is changed target sputter last layer argent then, obtains to be attached with 300nm gold, the substrate of the nanometer metal structure of the double-level-metal of the thick silver of 100nm;
(4) substrate surface that step (3) is obtained is modified, and obtains surface decoration layer, and the preparation adsorption film improves the ability of substrate enrichment testing molecule, and substrate is activated;
(5) adopt the method for coating to the additional testing molecule of the substrate that has finishing coat;
(6) distribution of light intensity of enhancing substrate peripheral outer media environment distributes, to improve testing molecule Raman scattering enhancement effect.
Embodiment 4
In viral solution is surveyed, realize the making of substrate by following steps
(1) select for use melt quartzy for backing material, clean and do hydrophilic treatment;
(2) utilize nanoimprinting technology to produce the micro-nano structure layer at substrate surface, the micro-nano structure layer is arranged characteristic dimension 20nm, the structure of cycle 40nm for annular.
(3) with the metallization of micro-nano structure layer, obtain to be attached with the substrate of metal Nano structure layer, structural thickness is 50nm;
(4) substrate surface that step (3) is obtained is modified, and obtains the molecular biosciences film, with ability that improves substrate enrichment testing molecule and the behavior that substrate is activated;
(5) to the additional testing molecule of the substrate that has finishing coat;
(6) change substrate peripheral outer media environment, substrate is placed nitrogen chamber (it promptly is a kind of method that changes substrate peripheral outer media environment that substrate is placed nitrogen chamber), improve testing molecule Raman scattering enhancement effect.
In the toxin detection of gas, realize the making of substrate by following steps
(1) to select zinc selenide for use be backing material, clean and do hydrophilic treatment;
(2) adopt nanoimprinting technology to produce the micro-nano structure layer that hexagon is arranged at substrate surface, characteristic dimension is 900nm, and the cycle is 8 μ m;
(3) method that adopts chemical silvering obtains to be attached with the substrate of metal Nano structure layer with the metallization of micro-nano structure layer, and structural thickness is 500nm;
(4) the substrate preparation adsorption film that step (3) is obtained is with ability that improves substrate enrichment testing molecule and the behavior that substrate is activated;
(5) to the additional testing molecule of the substrate that has finishing coat;
(6) improve substrate peripheral outer magnetic field distribution, to improve testing molecule Raman scattering enhancement effect.
In a word, the present invention is according to the difference of detected object, and by selecting the substrate of different materials, the optimal design underlying structure makes Raman scattering of molecule obtain maximum the enhancing; By substrate surface is modified, change simultaneously the external agency environment, realize testing molecule farthest enrichment in substrate. Can be used for high sensitivity detection, simultaneously this substrate has controllability, uniformity, repeatability, stable advantages of higher.
Claims (8)
1. substrate fabrication method that strengthens Raman scattering of molecule is characterized in that: described substrate is made up of the decorative layer and external agency environment four parts on substrate, metal micro-nanostructure layer, surface, and it is produced as follows:
(1) select for use backing material, clean and do hydrophilic treatment;
(2) produce the micro-nano structure layer at substrate surface;
(3), obtain to be attached with the substrate of metal Nano structure layer with the metallization of micro-nano structure layer;
(4) substrate surface that step (3) is obtained is modified, obtain surface decoration layer, described finishing is according to molecular property to be detected, preparation air-sensitive interface or molecular biosciences film or adsorption film or surface active material are with ability that improves substrate enrichment testing molecule and the behavior that substrate is activated;
(5) to the additional testing molecule of the substrate that has finishing coat;
(6) change substrate peripheral outer media environment, to improve testing molecule Raman scattering enhancement effect; Described substrate peripheral outer media environment comprises surrounding environment material or excitation wavelength or optical field distribution or Distribution of Magnetic Field.
2. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: the backing material in the described step (1) is glass or quartzy or silicon or germanium.
3. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: produce the micro-nano structure layer at substrate surface by nanosphere self assembly or nano-photoetching or nano impression in the described step (2).
4. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: the characteristic dimension of micro-nano structure layer is from 20nm～900nm in the described step (2), and the cycle, thickness was from 10nm～500nm from 40nm～8 μ m.
5. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: the metallization material in the described step (3) in the metal Nano structure layer is gold or silver or silver back gold or gold back silver earlier earlier.
6. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: the arrangement mode of metal Nano structure is triangle or quadrilateral or hexagon or annular in the described step (3).
7. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: described step (5) adopts the mode that feeds or drip or apply or inject testing molecule to be attached to the substrate that has finishing coat.
8. a kind of substrate fabrication method that strengthens Raman scattering of molecule according to claim 1 is characterized in that: the testing molecule in the described step (5) is probe gas molecule or solid molecule or fluid molecule.
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| CN101566570A (en) * | 2009-05-27 | 2009-10-28 | 东南大学 | Orderly controllable surface-reinforced Raman scattering active substrate and preparation method thereof |
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