CN111929288B - SERS substrate based on surface plasmon effect - Google Patents
SERS substrate based on surface plasmon effect Download PDFInfo
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- CN111929288B CN111929288B CN202010883590.2A CN202010883590A CN111929288B CN 111929288 B CN111929288 B CN 111929288B CN 202010883590 A CN202010883590 A CN 202010883590A CN 111929288 B CN111929288 B CN 111929288B
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 title claims abstract description 21
- 230000000694 effects Effects 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 24
- 239000010931 gold Substances 0.000 description 21
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 9
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
Abstract
A SERS substrate based on surface plasmon effect is an MDM structure and comprises SiO 2 A base layer of SiO 2 A layer of Au metal film is attached to the basal layer, and a layer of SiO is arranged on the Au metal film 2 A dielectric layer of SiO 2 The dielectric layer is provided with a layer of Au top metal film. The invention utilizes SiO 2 And the Au metal film is used for manufacturing the SERS substrate based on the surface plasmon effect, so that the detection sensitivity of SERS is greatly improved.
Description
Technical Field
The invention relates to a surface plasmon effect-based SERS substrate, and belongs to the technical field of surface plasmon effect and SERS enhanced element spectrum analysis.
Background
The Raman spectrum is a scattering spectrum found by indian physicist c.v. Raman in 1928, and belongs to the molecular vibration spectrum as the infrared spectrum, and can reflect various normal vibration frequencies and related vibration levels in the molecule, so that the Raman spectrum can be used for identifying functional groups in the molecule. Raman spectroscopy is widely used as an analytical test means for the structure of a substance. At present, raman spectrum is widely applied to the fields of materials, chemical industry, petroleum, high polymer, biology, environmental protection, geology and the like. However, the raman scattering effect is a very weak process, and its intensity is typically only about 10 of the incident light -10 The raman signal is weak and almost all raman spectroscopic studies on surface adsorbates use some enhancement effect.
In 1974, fleischmann et al roughened the surface of a smooth silver electrode to obtain a high quality Raman spectrum of a monolayer of pyridine molecules adsorbed on the surface of the silver electrode for the first time. The VanDuyne and its co-workers then found, through systematic experiments and calculations, that the raman scattering signal of each pyridine molecule adsorbed on the roughened silver surface was enhanced by about 6 orders of magnitude compared to the raman scattering signal of pyridine in the solution phase, indicating that this is a surface-enhanced effect associated with roughened surfaces, known as the surface-enhanced raman scattering (SERS) effect. SERS overcomes the defect of low sensitivity of Raman spectrum, can obtain structure information which is not easily obtained by conventional Raman spectrum, and is widely used for surface research, adsorption interface surface state research, interface orientation and configuration of biological large and small molecules, conformation research, structure analysis and the like.
The sensitivity of the SERS effect is highly dependent on the substrate material. The substrate materials are quite complex and SERS substrates are generally theoretically analyzed in two ways: first, electromagnetic Enhancement Mechanisms (EM), which are mainly based on Surface Plasmon Resonance (SPR) of metal nanoparticles. Second, the chemical enhancement mechanism (CM) is based primarily on charge transfer between the substrate and the detection molecule. In the SERS enhancement effect, the electromagnetic enhancement mechanism contributes more than the chemical enhancement mechanism and dominates, so plasmon resonance around noble metal nanoparticles becomes a key issue for SERS substrate research. There are only three metals of gold, silver and copper with strong SERS effect. Recently, SERS effects, tcO, have also been found on lithium, sodium, nickel, platinum, palladium, cadmium, mercury 2 SERS effects on NiO and polymers have also been reported, but some are controversial. How to obtain a SERS substrate with ultra-high sensitivity is a hot spot of current research.
Disclosure of Invention
Based on the above, the invention utilizes SiO 2 And Au metal film to make a SERS substrate based on surface plasmon effect, when irradiated by TM polarized light, under certain condition, evanescent field generated in the structure is generated in Au/SiO 2 Excitation of conduction type surface plasmon resonance (Propagating Surface Plasmon Resonance, PSPR) in the Au composite film, and coupling of local surface plasmon resonance (Localized Surface Plasmon Resonance, LSPR) generated by the double-hole structure, so as to obtain local electromagnetic field enhancement, improve target molecule adsorptivity and further increase SERS signals.
The technical scheme of the invention is as follows:
a SERS substrate based on surface plasmon effect is an MDM structure, and the MDM structure is formed by glass/Ag/SiO 2 Au/target molecule "five phase. Comprising SiO 2 A base layer of SiO 2 A layer of Au metal film is attached to the basal layer, and a layer of SiO is arranged on the Au metal film 2 A dielectric layer of SiO 2 The dielectric layer is provided with a layer of Au top metal film.
Preferably, the Au top metal film is provided with a plurality of double round hole structures, and each double round hole structure comprises 2 round holes.
Preferably, the radius of each circular hole is 100nm, the two circular holes are intersected, the shortest distance of the intersected part is the seam distance of the double circular holes, and the seam distance is set to be 30nm.
Preferably, the double round hole structure is a periodic array, and each 600nm is a double round hole structure in a 600nm period, and the array period is 10 x 10.
Preferably, the above SiO 2 The thickness of the Au metal film attached to the substrate layer is 100nm.
Preferably, siO is adhered to the Au metal film 2 The thickness of the dielectric layer was 150nm.
Preferably, the above SiO 2 The thickness of the Au top metal layer arranged above the dielectric layer is 150nm.
The beneficial effects of the invention are as follows:
the whole structure of the invention is formed by glass/Ag/SiO 2 And the four Au layers are formed, and a periodic nano double round hole structure is etched on the uppermost gold film layer. The structure designed by the invention can effectively convert the incident light energy into the surface plasma wave energy, and the composite film SERS substrate of the etched nano double-hole ordered array is utilized to generate effective coupling of LSPR and PSPR, thereby enhancing the SERS signal to the maximum extent.
Drawings
Fig. 1 is a schematic structural view of the present invention.
FIG. 2 is a graph of the analysis results of the present invention.
Fig. 3 is a schematic view of the stitch length.
Fig. 4 is a graph of reflectance of a single layer composite structure as a function of wavelength.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
As shown in FIG. 1, a SERS substrate based on surface plasmon effect is an MDM structure and comprises SiO 2 A base layer of SiO 2 A layer of Au metal film is attached to the basal layer, and a layer of SiO is arranged on the Au metal film 2 A dielectric layer of SiO 2 The dielectric layer is provided with a layer of Au top metal film.
Preferably, the Au top metal film is provided with a plurality of double round hole structures, and each double round hole structure comprises 2 round holes.
Preferably, the radius of each circular hole is 100nm, the two circular holes are intersected, the shortest distance of the intersecting part is the seam distance of the double circular holes, the seam distance is set to be 30nm, and d is the seam distance as shown in fig. 3.
Preferably, the double round hole structure is a periodic array, and each 600nm is a double round hole structure in a 600nm period, and the array period is 10 x 10.
Preferably, the above SiO 2 The thickness of the Au metal film attached to the substrate layer is 100nm.
Preferably, siO is adhered to the Au metal film 2 The thickness of the dielectric layer was 150nm.
Preferably, the above SiO 2 The thickness of the Au top metal layer arranged above the dielectric layer is 150nm.
The basic unit structure is expanded into a periodic structure and then analyzed. FIG. 2 is a graph of analysis results. Fig. 2 (a) is a graph showing the reflectance of the entire structure as a function of wavelength for incident wavelengths of 600nm to 1200 nm. Two very distinct formants can be seen at 850.7 nm and 1045.2 nm. To further analyze the resonance modes of these two peaks, we present an electric field profile of the structure in the y-z plane at these two wavelengths. As can be seen from fig. 2 (b), when the wavelength is 850.7 and nm, localized surface plasmon resonance is corresponded; as can be seen from fig. 2 (c), when the wavelength is 1045.2 nm, the transmission type surface plasmon resonance is associated. Therefore, the designed structure can effectively convert the incident light energy into the surface plasma wave energy, and the composite film SERS substrate of the etched nano double-hole ordered array is utilized to generate effective coupling of LSPR and PSPR, so that the SERS signal is enhanced to the maximum extent.
Fig. 4 is a graph of reflectance versus wavelength for a single layer composite structure, as compared to an MDM structure. One formant can be seen at 903.6 nm. To further analyze the resonance modes of these two peaks, an electric field profile of the structure in the y-z plane at this wavelength is given. As can be seen from fig. 4 (b), when the wavelength is 903.6 and nm, localized surface plasmon resonance is associated.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (1)
1. A SERS substrate based on surface plasmon effect is characterized in that the SERS substrate is of an MDM structure and comprises SiO 2 A base layer of SiO 2 A layer of Au metal film is attached to the basal layer, and a layer of SiO is arranged on the Au metal film 2 A dielectric layer of SiO 2 A layer of Au top metal film is arranged on the dielectric layer; au/SiO 2 The method comprises the steps that/Au is combined to form a composite film, a plurality of double round hole structures are arranged on an Au top metal film, each double round hole structure comprises 2 round holes, the two round holes are intersected, the shortest distance of the intersected part is the seam distance of the double round holes, the structure converts incident light energy into surface plasma wave energy, and an effective coupling of LSPR and PSPR is generated by utilizing a composite film SERS substrate, so that an SERS signal is enhanced; the radius of each circular hole is 100nm, and the gap distance is set to be 30 nm; the double pairThe circular hole structure is a periodic array, a double circular hole structure is arranged in each 600 nm-600 nm period, and the array period is 10-10; the SiO is 2 The thickness of the Au metal film attached to the basal layer is 100 nm; siO attached to the Au metal film 2 The thickness of the dielectric layer is 150 nm; the SiO is 2 The thickness of the Au top metal layer arranged above the dielectric layer is 150nm.
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| CN202010883590.2A CN111929288B (en) | 2020-08-28 | 2020-08-28 | SERS substrate based on surface plasmon effect |
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| CN202010883590.2A CN111929288B (en) | 2020-08-28 | 2020-08-28 | SERS substrate based on surface plasmon effect |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102680453A (en) * | 2011-11-21 | 2012-09-19 | 南开大学 | Raman spectrum high electromagnetic enhancement substrate coated with gain medium and preparation |
| CN108982474A (en) * | 2018-09-07 | 2018-12-11 | 江西师范大学 | A kind of surface reinforced Raman active substrate and preparation method thereof based on the compound plasmon resonance structure of metal-dielectric |
| CN109659387A (en) * | 2018-12-24 | 2019-04-19 | 苏州大学 | Infrared detector based on the enhancing of hydridization type plasma resonance |
-
2020
- 2020-08-28 CN CN202010883590.2A patent/CN111929288B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102680453A (en) * | 2011-11-21 | 2012-09-19 | 南开大学 | Raman spectrum high electromagnetic enhancement substrate coated with gain medium and preparation |
| CN108982474A (en) * | 2018-09-07 | 2018-12-11 | 江西师范大学 | A kind of surface reinforced Raman active substrate and preparation method thereof based on the compound plasmon resonance structure of metal-dielectric |
| CN109659387A (en) * | 2018-12-24 | 2019-04-19 | 苏州大学 | Infrared detector based on the enhancing of hydridization type plasma resonance |
Non-Patent Citations (2)
| Title |
|---|
| LESUFFLEUR S等.Apex-enhanced Raman spectroscopy using double-hole arrays in a gold film.《J. Phys. Chem. C》.2007,第第111卷卷全文. * |
| 苏巍.基于纳米光子结构的光学器件设计与光传输特性的研究.《中国博士学位论文全文数据库信息科技辑》.2017,(第第6期期),正文第80-85页. * |
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