CN108227057A - A kind of SERS substrates based on grating resonance and preparation method thereof - Google Patents
A kind of SERS substrates based on grating resonance and preparation method thereof Download PDFInfo
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- CN108227057A CN108227057A CN201810048528.4A CN201810048528A CN108227057A CN 108227057 A CN108227057 A CN 108227057A CN 201810048528 A CN201810048528 A CN 201810048528A CN 108227057 A CN108227057 A CN 108227057A
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- grating
- sers substrates
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1809—Diffraction gratings with pitch less than or comparable to the wavelength
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
Abstract
The invention discloses a kind of SERS substrates based on grating resonance and preparation method thereof, including substrate, the substrate surface is equipped with metal nano grating, the adhesion metal nano particle on the side wall of gratings strips, the metal nanoparticle is reacted by metal salt solution with the displacement of gratings strips side wall to be made, and separation layer is all covered in metal nano grating surface and grid trench bottom.It has higher enhancing coefficient, and consistency and favorable reproducibility, preparation process are simple.
Description
Technical field
The present invention relates to technical field of Raman spectrum, and in particular to a kind of SERS substrates and its preparation based on grating resonance
Method.
Background technology
SERS effects refer to：Molecule very close to or absorption at the surface of metal Nano structure, Raman signal intensity
It significantly increases.SERS has the advantages such as highly sensitive, highly selective and lossless detection, therefore as a kind of analysis detection means
It is widely used in every field.In terms of the research of related field mainly all focuses on the preparation of SERS substrates, application depends on
The SERS substrates of highly sensitive, low detectable limit are provided.
Due to some special effects that material has at the nanoscale, such as skin effect, small-size effect, quantum size
Effect, macro quanta tunnel effect and Dielectric confinement effect etc. so that nano material have unique optics, electricity, magnetics and
Catalytic performance and more and more paid close attention to by people, the design of device based on nano material and application become new research heat
Point.The discovery of this effect of nano-device has been largely overcoming the limitation of Raman spectrum, efficiently solves Raman
Spectrum muting sensitivity problem present in Surface Science and trace analysis.
SERS technologies can greatly enhance the Raman signal of testing molecule, can realize the trace to chemistry and biomolecule
Measure detection and identification.In SERS fields, the preparation of substrate is always one of research hotspot, because the quality of substrate is to spectrum
Signal has very important influence.After SERS phenomenons are found, new substrates continue to bring out.In recent years, period gold
Belong to nanostructured and cause extensive concern, have benefited from its uniform pattern, periodic structure often has good SERS weights
Existing property.
Existing SERS substrates substantially have two class production methods：
1）Physical deposition or chemical synthesis nanoparticle approach.It is prepared on substrate using physical methods such as sputtering, vacuum evaporation
Metal nanoparticle forms SERS active-substrate, regulates and controls nano particle scale by adjustment parameter；Or preparation presoma is molten
Liquid makes metal nanoparticle, and be deposited on substrate and to form SERS active-substrate using the method for chemical synthesis, can pass through
Solution ratio or reaction condition are adjusted, to regulate and control the scale of nano particle.The advantage of this kind of method is that production method is simple, can
To realize the making of quick, batch.Shortcoming is being unevenly distributed for nano particle, and the comparison of coherence of SERS active-substrate is poor,
The enhancing coefficient of different zones is different on i.e. same active substrate, and the enhancing coefficient between different base also has larger difference.
2）The methods of by nano-photoetching, ion etching, makes ordered nano-structure and forms SERS substrates.This method
Advantage is that the comparison of coherence of active substrate is good, and shortcoming is that manufacture craft requirement is higher.
In the prior art, it is combined using the high enhancing coefficient of metal nanoparticle with micro-nanometer ordered structure, by mutual
Coupling further improves enhancing coefficient.But the method reported at present is generally made of nano-photoetching or ion etch process
Micro-nanometer ordered structure, then the method by the physical methods or chemical synthesis nano particle such as sputtering, evaporating, in nano ordered knot
The further depositing metallic nanoparticles in structure surface, cause distribution of the metal nanoparticle on micro-nanometer ordered structure be it is random,
Although nanometer grating is coupled with nano-particle so that the enhancing coefficient of substrate increases, the consistency of substrate can not be protected
Card.
Invention content
The object of the present invention is to provide a kind of SERS substrates based on grating resonance and preparation method thereof, have higher
Enhance coefficient, consistency and favorable reproducibility, preparation method are simple for process.
SERS substrates of the present invention based on grating resonance, including substrate, the substrate surface is equipped with metal nano
Grating, the adhesion metal nano particle on the side wall of gratings strips, the metal nanoparticle pass through metal salt solution and gratings strips
The displacement reaction of side wall is made, and separation layer is all covered in metal nano grating surface and grid slot.
Further, the separation layer is silica nanometer film.
Further, the thickness of the separation layer is 5 ~ 20nm.
Further, the thickness of the metal nano grating is 10 ~ 100nm, and the spacing of grid slot is 10 ~ 500nm.
Further, the material of the metal nano grating is copper, and the material of the metal nanoparticle is silver.
A kind of preparation method of the SERS substrates based on grating resonance, it includes following steps：
1）In substrate surface deposited metal film,
2）Photoresist is coated on metallic film and carries out photoetching,
3）Side etches metal nano grating on substrate,
4）It selects metal salt solution that displacement occurs with the side wall of gratings strips to react, in the side wall reaction generation metal nano of gratings strips
Particle,
5）Photoresist is removed, the layer deposited isolating in metal nano grating surface grade grid slot obtains SERS substrates.
Further, the step 1）In metallic film for Copper thin film, step 4）In metal salt solution for silver nitrate it is molten
Liquid.
Further, a concentration of 1 ~ 100mmol/L of the silver nitrate solution.
Further, the substrate is semiconductor or glass.
Compared with prior art, the present invention it has the advantages that：
1st, metal nanoparticle of the present invention is to react to be made with the displacement of metal nano grating side wall by salting liquid so that
The position distribution of metal nanoparticle is controllable, improves the structural homogeneity of substrate, avoids existing physical deposition or chemistry
The problem of synthesizing metal nanoparticle, causing SERS substrate consistency poor；Meanwhile pass through metal nano grating and metal nano
The coupling of particle improves the enhancing coefficient of substrate.
2nd, the present invention can be effectively isolated metal and receive by adhering to separation layer in metal nano grating surface and grid slot
Rice grating and metal nanoparticle and external environment improve the stability of substrate.
3rd, preparation process flow of the present invention is simple, is manufactured convenient for mass.
Description of the drawings
Fig. 1 is the structure diagram of the substrate of the present invention.
In figure, 1-substrate, 2-metal nano grating, 3-metal nanoparticle, 4-separation layer.
Specific embodiment
It elaborates in the following with reference to the drawings and specific embodiments to the present invention.
Referring to Fig. 1, the shown SERS substrates based on grating resonance, including substrate 1,1 surface of substrate is equipped with metal
Nanometer grating 2, the adhesion metal nano particle 3 on the side wall of gratings strips, the metal nanoparticle 3 by metal salt solution with
The displacement reaction of gratings strips side wall is made, and separation layer 4 is all covered in 2 surface of metal nano grating and grid slot.
Preferably, the material of the metal nano grating 2 is copper, and the material of the metal nanoparticle 3 is silver, it is described every
Absciss layer 4 is silica nanometer film.4 upper surface of separation layer is plane, and the spacing with 2 upper surface of metal nano grating is
5~20nm.The thickness of the metal nano grating 2 is 10 ~ 100nm, the spacing between adjacent metal nanometer grating 2 for 10 ~
500nm。
Embodiment one, a kind of preparation method of the SERS substrates based on grating resonance, it includes following steps：
1）At semiconductor substrate surface one layer of Copper thin film of preparation, the stringent oxide layer of the Copper thin film surface progress, drying
Reason；
2）One layer of photoresist is coated on Copper thin film and carries out photoetching；
3）Side etches bronzing grid on substrate, and the thickness of the bronzing grid is 10nm, and the spacing of grid slot is 10nm；
4）The silver nitrate solution of 100mmol/L is selected to occur to replace at room temperature to react with bronzing grid side wall, the reaction time is
1min, then deionized water cleaning treatment is carried out, then carry out compressed nitrogen drying process；Since the top surface of gratings strips is coated with light
Photoresist, Semiconductor substrate are not reacted with salting liquid, and when being reacted into line replacement, bronzing grid are placed directly in salting liquid；
5）Photoresist is removed, silica nanometer film is deposited in copper grating surface and grid slot, silica nanometer film
Thickness is 5nm, obtains SERS substrates.
Embodiment two, a kind of preparation method of the SERS substrates based on grating resonance, it includes following steps：
1）At semiconductor substrate surface one layer of Copper thin film of preparation, the stringent oxide layer of the Copper thin film surface progress, drying
Reason；
2）One layer of photoresist is coated on Copper thin film and carries out photoetching；
3）Side etches bronzing grid on substrate, and the thickness of the bronzing grid is 100nm, and the spacing of grid slot is 500nm；
4）The silver nitrate solution of 1mmol/L is selected to occur to replace at room temperature to react with bronzing grid side wall, the reaction time is
20min, then deionized water cleaning treatment is carried out, then carry out compressed nitrogen drying process；
5）Photoresist is removed, silica nanometer film is deposited in copper grating surface and grid slot, silica nanometer film
Thickness is 20nm, obtains SERS substrates.
Embodiment three, a kind of preparation method of the SERS substrates based on grating resonance, it includes following steps：
1）At semiconductor substrate surface one layer of Copper thin film of preparation, the stringent oxide layer of the Copper thin film surface progress, drying
Reason；
2）One layer of photoresist is coated on Copper thin film and carries out photoetching；
3）Side etches bronzing grid on substrate, and the thickness of the bronzing grid is 50nm, and the spacing of grid slot is 250nm；
4）The silver nitrate solution of 50mmol/L is selected to occur to replace at room temperature to react with bronzing grid side wall, the reaction time is
10min, then deionized water cleaning treatment is carried out, then carry out compressed nitrogen drying process；
5）Photoresist is removed, silica nanometer film is deposited in copper grating surface and grid slot, silica nanometer film
Thickness is 15nm, obtains SERS substrates.
Example IV, a kind of preparation method of the SERS substrates based on grating resonance, it includes following steps：
1）At semiconductor substrate surface one layer of Copper thin film of preparation, the stringent oxide layer of the Copper thin film surface progress, drying
Reason；
2）One layer of photoresist is coated on Copper thin film and carries out photoetching；
3）Side etches bronzing grid on substrate, and the thickness of the bronzing grid is 30nm, and the spacing of grid slot is 200nm；
4）The silver nitrate solution of 25mmol/L is selected to occur to replace at room temperature to react with bronzing grid side wall, the reaction time is
8min, then deionized water cleaning treatment is carried out, then carry out compressed nitrogen drying process；
5）Photoresist is removed, silica nanometer film is deposited in copper grating surface and grid slot, silica nanometer film
Thickness is 15nm, obtains SERS substrates.
Claims (9)
1. a kind of SERS substrates based on grating resonance, it is characterised in that：Including substrate, the substrate surface is equipped with metal nano
Grating, the adhesion metal nano particle on the side wall of gratings strips, the metal nanoparticle pass through metal salt solution and gratings strips
The displacement reaction of side wall is made, and separation layer is all covered in metal nano grating surface and grid trench bottom.
2. the SERS substrates according to claim 1 based on grating resonance, it is characterised in that：The separation layer is titanium dioxide
Silicon nano thin-film.
3. the SERS substrates according to claim 1 or 2 based on grating resonance, it is characterised in that：The thickness of the separation layer
It spends for 5 ~ 20nm.
4. the SERS substrates according to claim 1 or 2 based on grating resonance, it is characterised in that：The metal nano light
The thickness of grid is 10 ~ 100nm, and the spacing of grid slot is 10 ~ 500nm.
5. the SERS substrates according to claim 1 or 2 based on grating resonance, it is characterised in that：The metal nano light
The material of grid is copper, and the material of the metal nanoparticle is silver.
6. a kind of preparation method of the SERS substrates based on grating resonance, it is characterised in that：Include the following steps：
1）In substrate surface deposited metal film,
2）Photoresist is coated on metallic film and carries out photoetching,
3）Side etches metal nano grating on substrate,
4）It selects metal salt solution that displacement occurs with the side wall of gratings strips to react, in the side wall reaction generation metal nano of gratings strips
Particle,
5）Photoresist is removed, the layer deposited isolating in metal nano grating surface and grid slot obtains SERS substrates.
7. the preparation method of the SERS substrates according to claim 6 based on grating resonance, it is characterised in that：The step
1）In metallic film for Copper thin film, step 4）In salting liquid be silver nitrate solution.
8. the preparation method of the SERS substrates according to claim 7 based on grating resonance, it is characterised in that：The nitric acid
A concentration of 1 ~ 100mmol/L of silver-colored solution.
9. the preparation method of the SERS substrates based on grating resonance described according to claim 6 or 7, it is characterised in that：It is described
Substrate is semiconductor or glass.
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| CN201810048528.4A CN108227057A (en) | 2018-01-18 | 2018-01-18 | A kind of SERS substrates based on grating resonance and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109765650A (en) * | 2019-02-28 | 2019-05-17 | 上海师范大学 | A method of the optical grating construction based on CD prepares SERS active-substrate |
| WO2020024337A1 (en) * | 2018-08-01 | 2020-02-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Grating slit waveguide composite structure-based sensor |
| CN111693502A (en) * | 2019-03-12 | 2020-09-22 | 武汉大学 | Liquid-phase Raman enhanced spectrum substrate combining cavity enhancement and surface enhancement |
| CN113092439A (en) * | 2021-03-31 | 2021-07-09 | 吉林大学重庆研究院 | Flexible ultra-smooth SERS substrate prepared by femtosecond laser processing technology, processing method and application |
| CN114829991A (en) * | 2019-12-20 | 2022-07-29 | 3M创新有限公司 | Light control film and method for manufacturing same |
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| US20130094021A1 (en) * | 2011-10-18 | 2013-04-18 | Korea Institute Of Science And Technology | Method of fabricating gold nanostructures using electroless displacement plating |
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| US20130094021A1 (en) * | 2011-10-18 | 2013-04-18 | Korea Institute Of Science And Technology | Method of fabricating gold nanostructures using electroless displacement plating |
| CN105973867A (en) * | 2016-05-06 | 2016-09-28 | 厦门大学 | Metalloid-metal composite hollow cavity array structure and preparation method thereof |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020024337A1 (en) * | 2018-08-01 | 2020-02-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Grating slit waveguide composite structure-based sensor |
| CN109765650A (en) * | 2019-02-28 | 2019-05-17 | 上海师范大学 | A method of the optical grating construction based on CD prepares SERS active-substrate |
| CN111693502A (en) * | 2019-03-12 | 2020-09-22 | 武汉大学 | Liquid-phase Raman enhanced spectrum substrate combining cavity enhancement and surface enhancement |
| CN114829991A (en) * | 2019-12-20 | 2022-07-29 | 3M创新有限公司 | Light control film and method for manufacturing same |
| CN113092439A (en) * | 2021-03-31 | 2021-07-09 | 吉林大学重庆研究院 | Flexible ultra-smooth SERS substrate prepared by femtosecond laser processing technology, processing method and application |
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Application publication date: 20180629 |