CN103776812A - Preparation method of surface enhanced Raman substrate (SERS) - Google Patents
Preparation method of surface enhanced Raman substrate (SERS) Download PDFInfo
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- CN103776812A CN103776812A CN201210394955.0A CN201210394955A CN103776812A CN 103776812 A CN103776812 A CN 103776812A CN 201210394955 A CN201210394955 A CN 201210394955A CN 103776812 A CN103776812 A CN 103776812A
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Abstract
The invention discloses a preparation method of surface enhanced Raman substrate (SERS). The preparation method comprises the following steps: step a, forming a surface enhanced Raman substrate (SERS) on a surface enhanced layer formed by attaching nano silver particles on a basic layer; step b, preserving the surface enhanced Raman substrate (SERS) formed in the step a in the protection of inert gas. Because the nano silver particle substrate is preserved in the protection of nitrogen gas, the surface will not be oxidized after a long period, thus the substrate, which has been preserved for a long time, still has a very good enhancing effect when the substrate is applied to an SERS substrate. The SERS has ultrahigh analysis sensitivity, is suitable for the detection of ultra-trace samples, has the advantages of simple preparation, short production time, low cost, and suitability for batch production, and provides conditions for promoting the SERS technology to be used in the fields of national security, environmental supervision, food safety, medical treatment and public health, and the like.
Description
Technical field
The present invention relates to Molecular Spectral Analysis detection field, be specifically related to a kind of substrate for Surface enhanced raman spectroscopy and preparation method thereof.
Background technology
Illumination is mapped to elastic scattering and inelastic scattering occurs on material, the scattered light of elastic scattering is the composition identical with excitation wavelength, inelastically scattered scattered light has the composition long and shorter than excitation light wave, is referred to as Ramam effect, and the spectrum obtaining is referred to as Raman spectrum.Raman spectrum belongs to molecular vibration spectrum, is the fingerprint of material molecule, and the Raman spectrometer of making according to Ramam effect can be for accurate qualitative discriminating sample.The analytical approach of Raman spectrum does not generally need sample to carry out pre-treatment, and easy and simple to handle in analytic process, and minute is short, is a kind of analytical technology that can simultaneously carry out to sample quantitative and qualitative analysis, has application prospect very widely.But it is lower that its shortcoming is sensitivity.
Surface enhanced raman spectroscopy (SERS) is a kind of high sensitivity spectral analysis technique growing up along with Nano-technology Development in the nineties in 20th century.The same with Raman spectrum, SERS can be for accurate qualitative discriminating sample.SERS has the sensitivity for analysis of superelevation, and more common Raman analysis sensitivity improves an about 6-10 order of magnitude, can analyze the little unimolecule that arrives, and arrives greatly the research object of cellular level.In prior art, SERS detects generally three kinds of modes: 1. in sample solution, add nano material, and induced nano particle assembles to form SERS focus; 2. in SERS substrate, directly drip sample solution, allow it sprawl, to be dried and to analyze; 3. SERS auroral poles is inserted to sample solution collection signal etc.
In prior art, in the mode of making the more use growing nano silver particle of the suprabasil enhancement layer of SERS, cost and the comprehensive sexual valence of enhancing effect are higher.But can produce oxide film on Nano Silver surface after the long-term preservation of the substrate of the nano-Ag particles of having grown, and its surface nature of nano-Ag particles after oxidized changes, make SERS substrate strengthen effect decay comparatively obvious, generally about two days, do not reach the enhancing effect of expectation; Cause the waste of silver metal and base material.
Therefore, need to improve the preparation process of SERS substrate, SERS substrate is carried out long-time preservation and is still had good enhancing effect, thereby make substrate there is the sensitivity for analysis of superelevation, be applicable to the detection of ultratrace sample, and make simple, with short production cycle, cost is low, be suitable for batch production, save nano-Ag particles, thereby cost-saving, for further promoting SERS technology at Homeland Security, environmental monitoring, the fields such as food security and health care are more widely used provides condition.
Summary of the invention
In view of this, the object of this invention is to provide a kind of preparation method of surface enhanced Raman substrate, SERS substrate is carried out long-time preservation and is still had good enhancing effect, thereby make substrate there is the sensitivity for analysis of superelevation, be applicable to the detection of ultratrace sample, and make simple, with short production cycle, cost is low, be suitable for batch production, save nano-Ag particles, thereby cost-saving, for further promoting SERS technology at Homeland Security, environmental monitoring, the fields such as food security and health care are more widely used provides condition.
The preparation method of surface enhanced Raman substrate of the present invention, comprises the following steps:
A. form surface enhanced Raman substrate at basal layer surface attachment nano-Ag particles surface accumulation layer;
B. the surface enhanced Raman substrate forming in step a is placed in inert gas and is preserved.
Further, in step a, first form super-drainage structure on basal layer surface, described nano-Ag particles surface accumulation layer is attached to super-drainage structure surface;
Further, the surperficial roughness that described basal layer is used to form super-drainage structure is equivalent to 180 to 5000 object abrasive paper for metallograph surfacenesses;
Further, described basal layer is level and smooth groove type structure, and described super-drainage structure is positioned at level and smooth groove inside surface;
Further, described inert gas is nitrogen;
Further, in step c, nano-Ag particles surface accumulation layer forming process comprises the following steps:
I. basal layer is placed in to liquid adhesive and soaks after 10-40 minute and take out;
II. clean by secondary deionized water, and be placed in the mixed liquid of silver nano material water and soak 60-180 minute;
III. after repeating step I and II 2-8 time with washed with de-ionized water and dry up;
IV. 80-160 ℃ of dry 30-80 minute in blanket of nitrogen or vacuum.
Beneficial effect of the present invention: the preparation method of surface enhanced Raman substrate of the present invention, the mode that the substrate of nano-Ag particles adopts inert gas shielding to preserve, after guaranteeing long period preservation, its surface is not oxidized, make substrate carry out long-time preservation and still there is good enhancing effect for SERS substrate, make substrate there is the sensitivity for analysis of superelevation, be applicable to the detection of ultratrace sample, and make simple, with short production cycle, cost is low, be suitable for batch production, save nano-Ag particles, thereby cost-saving, for further promoting SERS technology at Homeland Security, environmental monitoring, the field such as food security and health care is more widely used provides condition.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is underlying structure schematic diagram of the present invention.
Embodiment
The preparation method of the surface enhanced Raman substrate of the present embodiment, comprises the following steps:
A. form surface enhanced Raman substrate at basal layer 1 surface attachment nano-Ag particles surface accumulation layer 3; Basal layer is the basal layer that is used to form substrate, and basal layer 1 can adopt any disclosed basal layer of the prior art, comprises organic material etc.;
B. the surface enhanced Raman substrate forming in step a is placed in inert gas and is preserved.
Certainly,, in the time carrying out step a, need to carry out necessary cleaning to basal layer 1, to guarantee adhesion effect.
In the present embodiment, in step a, first form super-drainage structure 2 on basal layer 1 surface, described nano-Ag particles surface accumulation layer 3 is attached to super-drainage structure surface; Can be that direct surface processing formation can also be to increase super-hydrophobic film; Adopt super-drainage structure, aqueous solution class sample is formed approximate spherical, increase and be exposed to airborne surface area, not only make solvent be easy to volatilization, realize and purifying; And that comparatively concentrates is positioned at bottom, and composition in sample is concentrated, and is beneficial to the detection degree of accuracy improving trace and ultratrace composition; The enhancement effect of super-drainage structure and nanometer Ag is better; Outermost self-assembled nanometer material layer outside surface also can be modified with for separating of enrichment and identification sample self assembly molecule film; When making, make it have separation and concentration and interior reference function concurrently, form the SERS substrate of supporting high sensitivity and high reliability.
In the present embodiment, the surperficial roughness that described basal layer 1 is used to form super-drainage structure 2 is equivalent to 180 to 5000 object abrasive paper for metallograph surfacenesses; There is good bond strength, and can self form super-drainage structure, save manufacturing cost and save manufacturing process; In the present embodiment, adopt ground glass or abrasive paper for metallograph; Can avoid adopting in prior art etching to form, also just avoid the said structure of prior art need to be in solid basis material surface etching and basis of formation layer, growth matrix thereafter, has cost high, and fabrication cycle is long, is difficult to adapt to the shortcoming of producing in batches; And solid basic substance is harder and crisp, be easy to damage, when use, do not have according to environmental baseline and adapt to the feature in orientation etc. shortcoming.
Adopt and on ground glass or abrasive paper for metallograph, directly form super-drainage structure, need on basal layer, not form etching surface, the substrate forming has fabulous enhancing effect and the sensitivity for analysis of superelevation equally, be applicable to the detection of ultratrace sample, the most outstanding is, the making of SERS substrate is simple, with short production cycle, cost is lower, be applicable to mass production, owing to not thering is etching surface, in application, can not strengthen and analytic process forms and disturbs Raman, this is that the SERS substrate preparation method institute of prior art is inaccessiable.
Fig. 1 is underlying structure schematic diagram of the present invention, as shown in the figure: in the present embodiment, described basal layer 1 is level and smooth groove type structure, and described super-drainage structure 2 is positioned at level and smooth groove inside surface; When use, detected sample utilizes Action of Gravity Field to be located immediately at bottom minimum point, has the effect of automatic location, increases work efficiency.
In the present embodiment, described inert gas is nitrogen, and cost is low, easily obtains.
In the present embodiment, in step a, nano-Ag particles surface accumulation layer forming process comprises the following steps:
I. basal layer is placed in to liquid adhesive and soaks after 10-40 minute and take out; The present embodiment adopts 20 minutes, in the present embodiment, also soaks 10 minutes and soak experiment in 40 minutes, and acquired results there is no significant difference; Bonding agent adopts two mercaptan, any one in the hydrolysate of sulfydryl and amino silane, and the present embodiment adopts the hydrolysate of amino silane;
II. clean by secondary deionized water, and be placed in the mixed liquid of silver nano material water and soak 60-180 minute; The present embodiment adopts 100 minutes, in the present embodiment, also soaks 60 minutes and soak experiment in 80 minutes, and acquired results there is no significant difference; In the present embodiment, the mixed liquid of silver nano material water refers to the mixed liquid of water that the silver-colored nano particle of the rear reduction of liquor argenti nitratis ophthalmicus adding citric acid trisodium reaction forms in this solution;
III. after repeating step I and II 2-8 time with washed with de-ionized water and dry up; The present embodiment repeating step I and II 6 times;
IV. 80-160 ℃ of dry 30-80 minute in blanket of nitrogen or vacuum; The present embodiment adopts under nitrogen atmosphere and be dried 30 minutes under 110 ℃ of condition, in the present embodiment, also carries out under 80 ℃ of conditions, being dried 80 minutes and being dried 30 minutes under 160 ℃ of conditions, and acquired results there is no significant difference; Dry time and temperature can according to oven dry situation complement each other length and height.
Can be shown that by said structure and preparation method the surfaceness outbalance of the matte surface of basal layer adopts the surfaceness that is similar to 3000 order abrasive paper for metallograph for optimum, the too high or too low deleterious that all can make.This is because the too high or too low number that all can make SERS focus reduces.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (6)
1. a preparation method for surface enhanced Raman substrate, is characterized in that: comprise the following steps:
A. form surface enhanced Raman substrate at basal layer surface attachment nano-Ag particles surface accumulation layer;
B. the surface enhanced Raman substrate forming in step a is placed in inert gas and is preserved.
2. the preparation method of surface enhanced Raman substrate according to claim 1, is characterized in that: in step a, first form super-drainage structure on basal layer surface, described nano-Ag particles surface accumulation layer is attached to super-drainage structure surface.
3. the preparation method of surface enhanced Raman substrate according to claim 2, is characterized in that: the surperficial roughness that described basal layer is used to form super-drainage structure is equivalent to 180 to 5000 object abrasive paper for metallograph surfacenesses.
4. according to the preparation method of the surface enhanced Raman substrate described in the arbitrary claim of claims 1 to 3, it is characterized in that: described basal layer is level and smooth groove type structure, and described super-drainage structure is positioned at level and smooth groove inside surface.
5. the preparation method who requires described surface enhanced Raman substrate according to claim 4, is characterized in that: described inert gas is nitrogen.
6. the preparation method of surface enhanced Raman substrate according to claim 5, is characterized in that: in step c, nano-Ag particles surface accumulation layer forming process comprises the following steps:
I. basal layer is placed in to liquid adhesive and soaks after 10-40 minute and take out;
II. clean by secondary deionized water, and be placed in the mixed liquid of silver nano material water and soak 60-180 minute;
III. after repeating step I and II 2-8 time with washed with de-ionized water and dry up;
IV. 80-160 ℃ of dry 30-80 minute in blanket of nitrogen or vacuum.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210394955.0A CN103776812A (en) | 2012-10-17 | 2012-10-17 | Preparation method of surface enhanced Raman substrate (SERS) |
| PCT/CN2013/084136 WO2014044228A1 (en) | 2012-09-24 | 2013-09-24 | Surface-enhanced raman substrate, preparation method, raman spectrometer, detection method, and fine-tuning device |
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| CN201210394955.0A CN103776812A (en) | 2012-10-17 | 2012-10-17 | Preparation method of surface enhanced Raman substrate (SERS) |
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| CN105973866A (en) * | 2016-05-05 | 2016-09-28 | 吉林大学 | Method for producing low-friction super hydrophobic surface enhanced Raman substrate by using micro-nano particle coating layer |
| CN107576648A (en) * | 2017-09-14 | 2018-01-12 | 电子科技大学 | A kind of preparation method of Raman enhancing substrate |
| CN108318471A (en) * | 2017-12-26 | 2018-07-24 | 中国科学院合肥物质科学研究院 | The magnetic test paper and its preparation, application method of detection nitrite anions based on SERS |
| CN108645832A (en) * | 2018-03-22 | 2018-10-12 | 苏州天际创新纳米技术有限公司 | A kind of SERS chips and its preparation method and application |
| CN108872192A (en) * | 2018-01-30 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | SERS unit and SERS system |
| CN108872185A (en) * | 2018-03-22 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | A kind of preparation method of SERS chip |
| CN109467043A (en) * | 2018-11-14 | 2019-03-15 | 重庆大学 | A kind of SERS substrate of integrated micro-concave mirror and preparation method thereof |
| WO2019179006A1 (en) * | 2018-03-22 | 2019-09-26 | 苏州天际创新纳米技术有限公司 | Method for preparing, saving and loading sers chip |
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Cited By (12)
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| CN105973866A (en) * | 2016-05-05 | 2016-09-28 | 吉林大学 | Method for producing low-friction super hydrophobic surface enhanced Raman substrate by using micro-nano particle coating layer |
| CN105973866B (en) * | 2016-05-05 | 2018-07-27 | 吉林大学 | A method of preparing low friction super hydrophobic surface using micro-and nano-particles coating enhances Raman substrate |
| CN107576648A (en) * | 2017-09-14 | 2018-01-12 | 电子科技大学 | A kind of preparation method of Raman enhancing substrate |
| CN108318471A (en) * | 2017-12-26 | 2018-07-24 | 中国科学院合肥物质科学研究院 | The magnetic test paper and its preparation, application method of detection nitrite anions based on SERS |
| CN108872192A (en) * | 2018-01-30 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | SERS unit and SERS system |
| CN108872192B (en) * | 2018-01-30 | 2024-01-12 | 苏州纳微生命科技有限公司 | SERS unit and SERS system |
| CN108645832A (en) * | 2018-03-22 | 2018-10-12 | 苏州天际创新纳米技术有限公司 | A kind of SERS chips and its preparation method and application |
| CN108872185A (en) * | 2018-03-22 | 2018-11-23 | 苏州天际创新纳米技术有限公司 | A kind of preparation method of SERS chip |
| WO2019179006A1 (en) * | 2018-03-22 | 2019-09-26 | 苏州天际创新纳米技术有限公司 | Method for preparing, saving and loading sers chip |
| CN108645832B (en) * | 2018-03-22 | 2021-07-27 | 苏州英菲尼纳米科技有限公司 | SERS chip and preparation method and application thereof |
| CN109467043A (en) * | 2018-11-14 | 2019-03-15 | 重庆大学 | A kind of SERS substrate of integrated micro-concave mirror and preparation method thereof |
| CN109467043B (en) * | 2018-11-14 | 2023-11-14 | 重庆大学 | SERS substrate integrated with micro concave mirror and preparation method thereof |
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Application publication date: 20140507 |