CN108896533A - A kind of surface enhanced Raman scattering substrate and preparation method thereof - Google Patents
A kind of surface enhanced Raman scattering substrate and preparation method thereof Download PDFInfo
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- CN108896533A CN108896533A CN201810886368.0A CN201810886368A CN108896533A CN 108896533 A CN108896533 A CN 108896533A CN 201810886368 A CN201810886368 A CN 201810886368A CN 108896533 A CN108896533 A CN 108896533A
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- substrate
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- strip groove
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a kind of surface enhanced Raman scattering substrates and preparation method thereof, multiple micro-nano strip grooves (210) of parallel arrangement are formed including metal substrate (21) and on the metallic substrate, and, silver nano-grain is uniformly distributed in micro-nano strip groove (210), particle is structurally gathered in micro-nano strip groove in conjunction with the micro-nano strip groove, enhance electric field strength, and then enhances Raman scattering intensities.Compared with prior art, a kind of surface enhanced Raman scattering substrate and preparation method thereof of the invention, realizing has stronger Raman signal enhancing characteristic and high sensory characteristic；It is easy to make, it is reproducible.
Description
Technical field
The present invention relates to Surface enhanced Raman scattering technical field more particularly to a kind of underlying structure and its production sides
Method.
Background technique
Surface enhanced Raman scattering (surface enhanced raman scattering, SERS) refers to when some points
When son is adsorbed on certain coarse metal (such as gold, silver or copper etc.) surfaces, their Raman scattering signal intensity can increase
Add 104~106Times or so.
The multiple that can Surface enhanced Raman scattering signal occur and enhance, all absorption with testing molecule in metal surface
Form it is related.Therefore, the roughness of substrate surface is most important.Enhancing substrate in the related technology has：Metal electrode activity
Substrate, metal-sol active substrate, metal island film activity substrate, chemical etching and chemical deposition active substrate, bimetallic receive
Rice grain active substrate and offset printing and ordered fabrication active substrate.Most of above-mentioned substrate is formed by chemical method
's.But poor repeatability, area are small, it is difficult to control roughness, process is complicated, at high cost.It is therefore desirable to develop one kind
New surface enhanced Raman scattering substrate, the purpose of enhancing big with area, repeatable.
Summary of the invention
In order to solve the Related Technical Issues such as the poor repeatability of substrate, process in the prior art be complicated and at high cost,
The present invention proposes a kind of substrate and preparation method thereof of Surface enhanced Raman scattering, generates propagation using micro-nano metal slot structure
SPP (surface plasmons, Surface Plasmons Polaritons), to the gap between metallic particles and substrate
In electric field can further enhance, to substantially increase the reinforcing effect of Raman signal.
A kind of surface enhanced Raman scattering substrate of the invention, the underlying structure include metal substrate (21) and in metal
Multiple micro-nano strip grooves (210) of parallel arrangement are formed on substrate, also, are uniformly distributed Yin Na in micro-nano strip groove (210)
Particle is structurally gathered in micro-nano strip groove by rice grain in conjunction with the micro-nano strip groove, enhances electric field strength, and then enhance
Raman scattering intensities.
Optionally, the metal substrate (21) is golden substrate.
Optionally, the silver nano-grain is nanosphere, and the diameter of the nanosphere is 30nm~50nm.
Optionally, the width of the micro-nano strip groove (210) is 3 μm, micro-nano strip groove described in adjacent any two it
Between spacing be 8 μm.
A kind of production method of surface enhanced Raman scattering substrate of the invention, this approach includes the following steps：
Step 1, the micro-nano strip groove for forming parallel arrangement on the metallic substrate；
Step 2 forms equally distributed silver nano-grain in the micro-nano strip groove.
The step 2 is further comprising the steps of：
Silver nano-grain deionized water solution is added in micro-nano strip groove；
The deionized water in the silver nano-grain deionized water solution is removed, to be formed in the micro-nano strip groove
Equally distributed silver nano-grain.
The metal substrate is golden substrate.
The micro-nano strip groove for forming parallel arrangement on the metallic substrate of the step 1, specifically includes following processing：
Golden substrate first is cleaned with dehydrated alcohol and deionized water, is then placed in the examination equipped with analytically pure ethanol solution
It in pipe and is put into sonic oscillation machine and carries out sonic oscillation 20 minutes, take out；
Again with analytically pure washes of absolute alcohol, deionized water cleaning, with being dried with nitrogen golden substrate surface；
With plasma dryer, drying time is 30 seconds, obtains the clean golden substrate in surface；
With afm scan gold substrate surface；
Then tapping-mode is used using atomic force microscope, etching operation is carried out on golden substrate surface；
Silver nanoparticle solution is added dropwise in the etched features structure of golden substrate surface later, after natural evaporation, until
Reach diffusion into the surface effect.
The preparation of the silver nanoparticle solution includes the following steps：
Taking 20 μ L silver nano-grain concentration is the silver nanoparticle solution of 0.02mg/mL, is uniformly mixed with 200 μ L deionized waters
It closes, obtains the mixed solution of 10 times of dilution, concentration is 2 × 10-3M, wherein
Compared with prior art, a kind of surface enhanced Raman scattering substrate and preparation method thereof of the invention, realizes tool
There is stronger Raman signal enhancing characteristic, there is high sensitivity, be easy to make, it is reproducible.
Appended drawing reference
Fig. 1 is a kind of structural schematic diagram of surface enhanced Raman scattering substrate of the embodiment of the present invention；
Fig. 2 is a kind of graphic structure schematic diagram that micro-nano bar shaped is groove etched of the embodiment of the present invention；2a, top view, 2b, edge
The schematic diagram of the section structure of hatching A-A '；
Fig. 3 is a kind of surface enhanced Raman scattering substrate and preparation method thereof of the embodiment of the present invention；
Appended drawing reference：
21, metal substrate, 210, micro-nano strip groove.
Specific embodiment
The embodiment of the present invention is described in further detail with reference to the accompanying drawings and examples.
Raman enhancement method based on physical mechanism is Electromagnetic enhancement.When illumination is mapped to coarse metal surface, meeting
Excitating surface generates plasma, and the plasma of metal surface can be coupled with the electric field of the light of excitation, in particle and slot
Between gap (gap) in generate very strong LGSP (local gap surface plasma, Localized Gap Surface
Plasmons), to enhance Raman scattering, enhance Raman signal intensity.
As shown in Figure 1, being a kind of surface enhanced Raman scattering substrate structural schematic diagram of the embodiment of the present invention.The knot of substrate
Structure includes the metal substrate 21 with micro-nano strip groove 210, and silver nano-grain is evenly distributed in micro-nano strip groove 210.
Optionally, the metal substrate is golden substrate.Gold can inspire the nanometer material of surface phasmon as one kind
Material has each opposite sex of unique optics, the rough surface of golden substrate after adsorbing metal particle, between being formed between metallic particles
Gap generates " hot spot ", then in conjunction with the bar shaped slot structure of etching, may be implemented have stronger Raman signal enhancing characteristic and pole
Highly sensitive characteristic.
As shown in Fig. 2, forming the micro-nano strip groove 210 of multiple parallel arrangements in metal substrate 21, wherein micro-nano bar shaped
The width of slot 210 is the size of micron or Nano grade.Optionally, the width of micro-nano strip groove 210 is 3um, arbitrary neighborhood two
Spacing between a micro-nano strip groove is 8um.
As shown in figure 3, a kind of production method of the enhancing Raman scattering substrate provided for the present embodiment one, this method are specific
Include the following steps：
Step 110, the multiple micro-nano strip grooves for forming parallel arrangement on the metallic substrate；
Step 120 forms equally distributed silver nano-grain in the micro-nano strip groove.
Optionally, the step of forming multiple micro-nano strip grooves of parallel arrangement on the metallic substrate, including：
The multiple of the parallel arrangement are etched in metal substrate 21 described using atomic force microscope lithographic technique
Micro-nano strip groove 210.
Optionally, described the step of forming equally distributed silver nano-grain in the micro-nano strip groove, includes：
Silver nano-grain deionized water solution is added in the micro-nano strip groove 210；
The deionized water in the silver nano-grain deionized water solution is removed, with the shape in the micro-nano strip groove 210
At equally distributed silver nano-grain.
In another embodiment by taking the metal substrate is golden substrate as an example：
Firstly, choosing one piece of clean golden substrate, size can be that length and width is respectively 20mm.Etching golden substrate
Before, golden substrate first is cleaned with dehydrated alcohol and deionized water, is then placed in the test tube equipped with analytically pure ethanol solution
And be put into sonic oscillation machine and carry out sonic oscillation, it can be 20 minutes；It takes out, it is clear with analytically pure dehydrated alcohol again
It washes, deionized water cleaning, with being dried with nitrogen surface；With plasma dryer, drying time can be 30 seconds, and it is clean to obtain surface
Golden substrate；With afm scan gold substrate surface.Then operation is performed etching using atomic force microscope.Using light
Rapping formula, performs etching.Silver nanoparticle solution is added dropwise in surface again later.Due to the distribution density and configuration of metal nanoparticle
Solution concentration it is related.Dilution ratio can be designed according to actual demand.And the practical ruler of metal nanoparticle diameter
It is very little to be equipped with according to specific requirement to choose.The silver nanoparticle for the deposition being evenly distributed is realized in the slot of etching structure
Grain, in conjunction with slot structure, particle can be preferably gathered in slot, enhanced electric field strength, and then enhance Raman scattering intensities, obtained
Surface enhanced Raman substrate big to area, being evenly distributed.
As shown in Fig. 2, being a kind of graphic structure schematic diagram that micro-nano bar shaped is groove etched of the embodiment of the present invention, select parallel
Bar shaped slot structure, the width of strip groove can be 3um, and interval can be 8um.
Silver nanoparticle solution is prepared, silver nano-grain (solubility can be 0.02mg/mL) can take 20 μ L silver nanoparticles
Grain solution is uniformly mixed with 200 μ L deionized waters, obtains the mixed solution of 10 times of dilution.The golden film in etched features structure is added dropwise
On, after natural evaporation, observe diffusion into the surface situation.
A kind of substrate of Surface enhanced Raman scattering of the present embodiment, the substrate is by any surface in above-described embodiment
Enhance the production method production of Raman scattering substrate.
It above are only the preferred embodiment and institute's application technology principle of the embodiment of the present invention.Specific implementation described herein
Example embodiment for explaining only the invention, rather than the restriction to the embodiment of the present invention.It will be appreciated by those skilled in the art that of the invention
Embodiment is not limited to specific embodiment described here, be able to carry out for a person skilled in the art it is various it is apparent variation,
The protection scope readjusted and substituted without departing from the embodiment of the present invention.Therefore, although by above embodiments to this hair
Bright embodiment is described in further detail, but the embodiment of the present invention is not limited only to above embodiments, is not departing from this
It can also include more other equivalent embodiments in the case that inventive embodiments are conceived, and the range of the embodiment of the present invention is by institute
Attached scope of the claims determines.
Claims (9)
1. a kind of surface enhanced Raman scattering substrate, which is characterized in that the underlying structure includes metal substrate (21) and in gold
Belong to the multiple micro-nano strip grooves (210) for forming parallel arrangement on substrate, also, is uniformly distributed silver in micro-nano strip groove (210)
Particle is structurally gathered in micro-nano strip groove by nano particle in conjunction with the micro-nano strip groove, enhances electric field strength, Jin Erzeng
Strong Raman scattering intensities.
2. a kind of surface enhanced Raman scattering substrate as described in claim 1, which is characterized in that optional, the metal liner
Bottom (21) is golden substrate.
3. a kind of surface enhanced Raman scattering substrate as described in claim 1, which is characterized in that optional, the silver nanoparticle
Particle is nanosphere, and the diameter of the nanosphere is 30nm~50nm.
4. a kind of surface enhanced Raman scattering substrate as described in claim 1, which is characterized in that optional, the micro-nano item
The width of shape slot (210) is 3 μm, and the spacing between micro-nano strip groove described in adjacent any two is 8 μm.
5. a kind of production method of surface enhanced Raman scattering substrate, which is characterized in that this approach includes the following steps：
Step (1), the micro-nano strip groove for forming parallel arrangement on the metallic substrate；
Step (2) forms equally distributed silver nano-grain in the micro-nano strip groove.
6. a kind of production method of surface enhanced Raman scattering substrate as claimed in claim 5, which is characterized in that the step
(2) further comprising the steps of：
Silver nano-grain deionized water solution is added in micro-nano strip groove；
The deionized water in the silver nano-grain deionized water solution is removed, to be formed in the micro-nano strip groove uniform
The silver nano-grain of distribution.
7. a kind of production method of surface enhanced Raman scattering substrate as claimed in claim 5, which is characterized in that it is optional,
The metal substrate is golden substrate.
8. a kind of production method of surface enhanced Raman scattering substrate as claimed in claim 7, which is characterized in that the step
(1) the micro-nano strip groove for forming parallel arrangement on the metallic substrate, specifically includes following processing：
Golden substrate first is cleaned with dehydrated alcohol and deionized water, is then placed in the test tube equipped with analytically pure ethanol solution
And be put into sonic oscillation machine and carry out sonic oscillation 20 minutes, it takes out；
Again with analytically pure washes of absolute alcohol, deionized water cleaning, with being dried with nitrogen golden substrate surface；
With plasma dryer, drying time is 30 seconds, obtains the clean golden substrate in surface；
With afm scan gold substrate surface；
Then tapping-mode is used using atomic force microscope, etching operation is carried out on golden substrate surface；
Silver nanoparticle solution is added dropwise in the etched features structure of golden substrate surface later, after natural evaporation, until reaching
Diffusion into the surface effect.
9. a kind of production method of surface enhanced Raman scattering substrate as claimed in claim 8, which is characterized in that the silver is received
The preparation of rice grain solution includes the following steps：
Taking 20 μ L silver nano-grain concentration is the silver nanoparticle solution of 0.02mg/mL, is uniformly mixed with 200 μ L deionized waters,
The mixed solution of 10 times of dilution is obtained, concentration is 2 × 10-3M, wherein
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109694035A (en) * | 2019-02-25 | 2019-04-30 | 北京理工大学 | A method of preparing composite nanostructure |
| CN110412015A (en) * | 2019-06-23 | 2019-11-05 | 南京理工大学 | A kind of high sensitivity microwave molecular spectrum instrument |
| CN111678907A (en) * | 2020-06-17 | 2020-09-18 | 华中农业大学 | Module for Raman detection and preparation method thereof |
| CN112775434A (en) * | 2020-12-24 | 2021-05-11 | 江苏理工学院 | Preparation method and application of nano star-chain-shaped nano structure array |
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| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN101776603A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Enhancement method for raman scattering by using artificial metal micro-nano structure |
| CN101799420A (en) * | 2010-03-10 | 2010-08-11 | 中国科学院光电技术研究所 | Metal micro-nano structure for improving Raman scattering of molecule |
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Patent Citations (3)
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| CN101776604A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Production method of basement for enhancing raman scattering of molecule |
| CN101776603A (en) * | 2010-01-26 | 2010-07-14 | 中国科学院光电技术研究所 | Enhancement method for raman scattering by using artificial metal micro-nano structure |
| CN101799420A (en) * | 2010-03-10 | 2010-08-11 | 中国科学院光电技术研究所 | Metal micro-nano structure for improving Raman scattering of molecule |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694035A (en) * | 2019-02-25 | 2019-04-30 | 北京理工大学 | A method of preparing composite nanostructure |
| CN110412015A (en) * | 2019-06-23 | 2019-11-05 | 南京理工大学 | A kind of high sensitivity microwave molecular spectrum instrument |
| CN111678907A (en) * | 2020-06-17 | 2020-09-18 | 华中农业大学 | Module for Raman detection and preparation method thereof |
| CN112775434A (en) * | 2020-12-24 | 2021-05-11 | 江苏理工学院 | Preparation method and application of nano star-chain-shaped nano structure array |
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