CN110006872A - A kind of light activated SERS substrate of radial polarisation and its design method - Google Patents
A kind of light activated SERS substrate of radial polarisation and its design method Download PDFInfo
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- CN110006872A CN110006872A CN201910268863.XA CN201910268863A CN110006872A CN 110006872 A CN110006872 A CN 110006872A CN 201910268863 A CN201910268863 A CN 201910268863A CN 110006872 A CN110006872 A CN 110006872A
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- gold nanorods
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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
Abstract
The invention belongs to the element spectrum analysis technical field of surface phasmon effect, discloses a kind of light activated SERS substrate of radial polarisation and its design method, the substrate include SiO2Basal layer, the SiO2Graphene oxide film layer is provided on basal layer, multiple double gold nanorods groups are provided on the graphene oxide film layer, each double gold nanorods groups include 2 gold nanorods, one of gold nanorods horizontal arrangement, one vertical arrangement, and erect the gold nanorods of straight arranged gold nanorods bottom face horizontal arrangement.The present invention can greatly increase the enhancement factor of SERS substrate, can be widely applied to SERS detection field.
Description
Technical field
The invention belongs to the element spectrum analysis technical fields of surface phasmon effect, and in particular to a kind of radial direction
Polarize light activated gold nanorods graphene oxide high-performance SERS substrate and its design method.
Background technique
Surface enhanced Raman scattering technology (SERS), it is a kind of quick, lossless, non-contact, highly sensitive detection skill
Art receives people in recent years and widely pays close attention to, therefore how obtaining one, there is the SERS substrate of hypersensitivity to become
Instantly the hot spot studied.SERS substrate is sufficiently complex, to SERS substrate progress theory analysis generally in terms of two: first, electricity
Magnetic enhances mechanism (EM), is based primarily upon the surface plasma body resonant vibration (SPR) of metal nanoparticle.Second, Chemical enhancement machine
It makes (CM), mainly based on the electric charge transfer between substrate and detection molecules.In SERS enhancement effect, electromagnetic enhancement mechanism
It is more than the contribution of chemical enhanced mechanism, and occupy an leading position, so the plasma resonance around noble metal nano particles becomes
The key content of SERS substrate research.
Researchers mainly obtain high performance SERS effect by changing SERS base material and structure design at present.
Excitaton source is commonly linearly polarized light, ignores influence of the polarization characteristic of incident light to SERS performance.Ling in 2010 et al. is ground
The relationship of graphene and raman spectrum strength is studied carefully, and it was found that graphene has biggish specific surface area, and macromolecular is examined
Surveying substance has stronger adsorption capacity, has a certain impact to SERS effect.Graphene oxide is shown under excited by visible light
SERS effect out based on CM theory.GO has oxygen-containing functional group abundant, can enhance absorption of the SERS substrate to organic molecule,
Suitable for some highly sensitive detections for being difficult to be adsorbed on the organic molecule of metal SERS substrate surface.It is different from passing as one kind
The SERS material based on EM theory of system, GO, which is introduced into metal SERS substrate, can further improve SERS performance.2012, grandson
Big waves et al. restores silver ion precursor solution using femtosecond direct writing technology in year, has prepared the micron that Nano silver piece is gathered into
Floral structure, SERS enhancement factor is up to 108.The raising of substrate SERS performance depends on your gold of electromagnetic enhancement mechanism
Belong to " hot spot " existing between material plasma bulk effect and noble metal nano particles and makes the generation that interacts between them
Stronger SERS effect.In order to further increase SERS effect, researchers combine two kinds of enhancing mechanism.It is 2014, yellow
Organic dyestuff crystal violet detects using redox graphene/silver nano-grain (rGO/AgNPs) composite substrate in luicd and elegant seminar
(CV), rGO/AgNPs composite substrate is due to that can adsorb more detection molecules comprising redox graphene, so that between them
Electric charge transfer occurs, plasma resonance can be generated between silver nano-grain under the excitation of incident light, SERS electromagnetism is caused to increase
By force.The composite substrate for enhancing mechanism in conjunction with two kinds can reach 10 to the concentration monitor of CV-8M, SERS enhancement factor be 2.3 ×
104.2014, Xu Ying realized the position of gold nanorods using the three-dimensional precision positioning of femtosecond laser processing and process control
With shape can design and assembly, and gold nanorods are used for micro-fluidic chip Raman detection, have obtained preferable reinforcing effect.
With the fast development of laser technology, axially symmetry polarization light beam causes to grind due to its unique axially symmetry polarization distribution
Study carefully personnel's concern, and is combined with SERS technology, but up to the present, the report of the SERS substrate under the excitation of different polarization light
Also seldom.In order to further increase the detection sensitivity of SERS technology, it is desirable to provide a kind of with higher SERS enhancement factor
The light activated SERS substrate of radial polarisation.
Summary of the invention
The present invention overcomes the shortcomings of the prior art, technical problem to be solved are as follows: provides a kind of radial polarisation light
The SERS substrate of excitation, to improve the detection sensitivity of SERS.
In order to solve the above-mentioned technical problem, a kind of the technical solution adopted by the present invention are as follows: light activated SERS of radial polarisation
Substrate, including SiO2Basal layer, the SiO2Graphene oxide film layer, the graphene oxide film are provided on basal layer
Gold nanorods are provided on layer, the radial polarisation light is by perpendicular to the SiO2It is incident on SERS substrate in the direction of basal layer.
Multiple double gold nanorods groups are provided on the graphene oxide film layer, each double gold nanorods groups include 2
Gold nanorods, one of gold nanorods horizontal arrangement, a vertical arrangement, and erect straight arranged gold nanorods bottom face
The gold nanorods of the horizontal arrangement.
The SiO2Basal layer with a thickness of 20nm, the length of gold nanorods is 114nm, radius 13nm, the radial direction
The wavelength of polarised light is 785nm, and in double gold nanorods groups, the distance of two gold nanorods is 2nm.
The embodiment of the invention also provides a kind of design methods of the light activated SERS substrate of radial polarisation, including following step
It is rapid:
S1, the structure that SERS substrate is set in FDTD solution software comprising SiO2Basal layer is located at SiO2Substrate
Graphene oxide film layer on layer and the gold nanorods on graphene oxide film layer, while the substrate is set by entering
Direction is penetrated perpendicular to the SiO2The radial polarisation light in the direction of basal layer excites；
S2, the primary condition for determining emulation, the thickness of fixed SiO2 basal layer and graphene oxide film layer, the length of gold nanorods
Degree and radius；
S3, the quantity for successively changing gold nanorods, the spacing between arrangement mode and gold nanorods utilize FDTD
Solution software calculate SERS substrate electric-field intensity distribution, according to electric-field intensity distribution calculate SERS substrate enhancing because
Son；
S4, from step S3, filter out the biggish structure of enhancement factor as preferred SERS substrate.
In the step S3, the quantity of gold nanorods is 2 ~ 4, the arrangement mode of gold nanorods include it is horizontally arranged, erect
In line column, and horizontal vertical composite bar column.
Swashed compared with the prior art, the invention has the following beneficial effects: the invention proposes one kind based on radial vector light
The novel height of gold nanorods-graphene oxide film (Au Nanocone Arrays-GO, AuNRAs-GO) composite construction of hair
The design method of performance SERS substrate, by FDTD solution, theoretically simulation analysis radial polarisation light excites lower oxygen
The thickness of graphite alkene, influence of the spacing of the quantity of gold nanorods, arrangement mode and more gold nanorods for SERS performance,
It finally obtains a SERS enhancement factor and is up to 9 × 109SERS composite substrate so that biology, environment, food safety etc. lead
Domain is widely used.
Detailed description of the invention
Fig. 1 is the light activated gold nanorods graphene oxide high-performance of radial polarisation of one kind provided in an embodiment of the present invention
The structural schematic diagram of SERS substrate；
Fig. 2 is that the radial polarisation light of same intensity and linearly polarized light excite single gold nanorods SiO2When/GO/AuNRs composite substrate
Electric-field intensity distribution figure, left figure is radial polarisation light in figure, and right figure indicates linearly polarized light；
Fig. 3 is that the radial polarisation light of same intensity excites double gold nanorods, three gold nanorods and four gold nanorods closely to arrange
SiO2/ GO/AuNRs composite substrate electric-field intensity distribution；
Fig. 4 is the arrangement schematic diagram of double gold nanorods relative positions, and wherein Fig. 4 a indicates end face to end face, and Fig. 4 b expression lies low flat
Row, Fig. 4 c indicate that end face vertical centering point, Fig. 4 d indicate vertical parallel, and Fig. 4 e indicates end face base vertical；
Fig. 5 is that double gold nanorods are in corresponding electric field strength when the arrangement mode in Fig. 4 in SiO2/GO/AuNRs composite substrate
Distribution.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiment is a part of the embodiments of the present invention, without
It is whole embodiments；Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a kind of design methods of the light activated SERS substrate of radial polarisation, including following step
It is rapid:
S1, the structure that SERS substrate is set in FDTD solution software comprising SiO2Basal layer is located at SiO2Substrate
Graphene oxide film layer on layer and the gold nanorods on graphene oxide film layer, while the substrate is set by entering
Direction is penetrated perpendicular to the SiO2The radial polarisation light in the direction of basal layer excites；As shown in Figure 1, being the structure of the SERS substrate
Schematic diagram.
S2, the primary condition for determining emulation, the thickness of fixed SiO2 basal layer and graphene oxide film layer, gold nanorods
Length and radius.
In the present embodiment, SiO2It is 20nm as substrate thickness, graphene oxide GO film is located at centre, gold nanorods
Draw ratio has an impact to SERS effect, we select length for 114nm here, and to be attached to GO thin for the gold nanorods that radius is 13nm
The upper surface of film, ambient enviroment are full of air (n=1), and the physics of boundary is reduced by perfect domination set (PMLs) envelope
Reflection, entire substrate are that 785nm incident light is excited by the wavelength propagated along Z-direction.
S3, the quantity for successively changing gold nanorods, the spacing between arrangement mode and gold nanorods utilize FDTD
Solution software calculate SERS substrate electric-field intensity distribution, according to electric-field intensity distribution calculate SERS substrate enhancing because
Son.
Wherein, the quantity of gold nanorods can be 2 ~ 4, and the arrangement mode of gold nanorods includes being horizontally arranged, and put vertically
It sets, horizontal and vertical compound placement.The distance between nanometer gold bar is 1 ~ 5nm.
As shown in Fig. 2, the radial polarisation light and linearly polarized light for same intensity excite single gold nanorods SiO2/GO/AuNRs
Electric-field intensity distribution figure when composite substrate, left figure is radial polarisation light excitation in figure, and right figure indicates linearly polarized light excitation.From Fig. 2
In as can be seen that radial polarisation light is when exciting the GO/AuNRs composite substrate, single gold nanorods enhancement factor is up to 108, and line
Under polarised light excitation, enhancement factor is only 3.6 × 102.Radial polarisation light excites GO/AuNRs composite substrate, and SERS can be enhanced
Performance.In the present embodiment, the incident direction of light is set as Z-direction, the plane where SERS substrate is set as X/Y plane.
Wherein, SERS enhancement factor is usedEFTo indicate:
(1)；
WhereinE iIt is the electric field of incident light source,E 0It is the summation of the electric field at the macromolecular substances being detected.
Generally during FDTD is emulated, the electric field of incident light sourceE i=1, therefore SERS enhancement factor is approximately:
(2).
As shown in figure 3, under the excitation for the radial polarisation light being in vertical distribution with SERS substrate, and gap is 1nm's
The distribution map of the electric field of double gold nanorods, three gold nanorods and four gold nanorods.FDTD simulated electric field distribution results are shown, wherein erecting
The electric field strength for the double gold nanorods being directly distributed is 103.5, the electric field strength of three gold nanorods is 103.3, the electricity of four gold nanorods
Field intensity is 103.2, it can be found that the electric field strength of double gold nanorods is slightly larger than three gold nanorods and four gold nanorods, illustrate more
There are gaps can generate " hot spot " between root gold stick, has certain contribution to SERS effect, but its reinforcing effect is unobvious, only
106。
As shown in figure 4, for several schematic diagrames of double gold nanorods relative position arrangements, the arrangement of double gold nanorods in figure
Mode include it is horizontally arranged, be vertically arranged and horizontal vertical composite bar column.Wherein, such as Fig. 4 a, 4b, shown in 4c, horizontally arranged point
Not Bao Kuo two nanometer gold bar end faces to the arranged in a straight line of end face, three kinds of vertical arrangement to center of arranged in parallel and end face
Arrangement mode, in these three arrangement modes, nanometer gold bar and SERS substrate are relatively parallel；As shown in figure 4d, vertical arrangement refers to
It is relatively parallel between two nanometer gold bars but vertical with SERS substrate；As shown in fig 4e, horizontal vertical composite bar column refer to,
In a gold nanorods horizontal arrangement, a vertical arrangement, and erect horizontal row described in the face of straight arranged gold nanorods bottom
The gold nanorods of cloth.
As shown in figure 5, under 5 kinds of arrangement modes in Fig. 4, electric field when radial polarisation light excites SERS substrate
Distribution schematic diagram, wherein the spacing of double nano gold stick is 2nm, from Fig. 5 e as can be seen that when double gold nanorods are in horizontal vertical
When meeting arrangement mode, enhancement factor is up to 9 × 109, that is to say, that this arrangement mode has higher enhancement factor.
S4, from step S3, filter out the biggish structure of enhancement factor as preferred SERS substrate.
From fig. 5, it can be seen that the embodiment of the present invention is by more design method, it is reachable that screening has obtained a kind of enhancement factor
9×109SERS substrate, therefore, the embodiment of the invention also discloses a kind radial polarisation light excitation SERS substrate, packet
Include SiO2Basal layer, the SiO2It is provided with graphene oxide film layer on basal layer, is arranged on the graphene oxide film layer
There are gold nanorods, the radial polarisation light is by perpendicular to the SiO2It is incident on SERS substrate in the direction of basal layer.
Specifically, multiple double gold nanorods groups are provided on the graphene oxide film layer, each double gold nanorods groups
Including 2 gold nanorods, one of gold nanorods horizontal arrangement, a vertical arrangement, and erect straight arranged gold nanorods
The gold nanorods of horizontal arrangement described in the face of bottom.
Specifically, the SiO2Basal layer with a thickness of 20nm, the length of gold nanorods is 114nm, radius 13nm, institute
The wavelength of radial polarisation light is stated as 785nm, in double gold nanorods groups, the distance of two gold nanorods is 2nm.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (5)
1. a kind of light activated SERS substrate of radial polarisation, which is characterized in that including SiO2Basal layer, the SiO2On basal layer
Be provided with graphene oxide film layer, be provided with gold nanorods on the graphene oxide film layer, the radial polarisation light by
Perpendicular to the SiO2It is incident on SERS substrate in the direction of basal layer.
2. the light activated SERS substrate of a kind of radial polarisation according to claim 1, which is characterized in that the graphite oxide
Multiple double gold nanorods groups are provided in alkene film layer, each double gold nanorods groups include 2 gold nanorods, one of Jenner
Rice stick horizontal arrangement, a vertical arrangement, and erect the gold nano of horizontal arrangement described in the face of straight arranged gold nanorods bottom
Stick.
3. the light activated SERS substrate of a kind of radial polarisation according to claim 2, which is characterized in that the SiO2Substrate
Layer with a thickness of 20nm, the length of gold nanorods is 114nm, and radius 13nm, the wavelength of the radial polarisation light is 785nm,
In double gold nanorods groups, the distance of two gold nanorods is 2nm.
4. a kind of design method of the light activated SERS substrate of radial polarisation, which comprises the following steps:
S1, the structure that SERS substrate is set in FDTD solution software comprising SiO2Basal layer is located at SiO2Basal layer
On graphene oxide film layer and the gold nanorods on graphene oxide film layer, while the substrate is set by incidence
Direction is perpendicular to the SiO2The radial polarisation light in the direction of basal layer excites；
S2, the primary condition for determining emulation, the thickness of fixed SiO2 basal layer and graphene oxide film layer, the length of gold nanorods
Degree and radius；
S3, the quantity for successively changing gold nanorods, the spacing between arrangement mode and gold nanorods utilize FDTD
Solution software calculate SERS substrate electric-field intensity distribution, according to electric-field intensity distribution calculate SERS substrate enhancing because
Son；
S4, from step S3, filter out the biggish structure of enhancement factor as preferred SERS substrate.
5. a kind of design method of the light activated SERS substrate of radial polarisation according to claim 4, which is characterized in that institute
State in step S3, the quantity of gold nanorods is 2 ~ 4, the arrangement mode of gold nanorods include it is horizontally arranged, be vertically arranged, and
Horizontal vertical composite bar column.
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| CN110412668A (en) * | 2019-08-07 | 2019-11-05 | 太原理工大学 | A kind of structure and its application generating multiple surface lattice resonance |
| CN111912829A (en) * | 2020-08-28 | 2020-11-10 | 河海大学常州校区 | Surface plasmon effect-based SERS substrate design method |
| WO2021129267A1 (en) * | 2019-12-27 | 2021-07-01 | 深圳大学 | Tip-enhanced raman spectroscope microscopic imaging device |
| CN113866099A (en) * | 2021-09-29 | 2021-12-31 | 太原理工大学 | Graphene biosensor system based on gold nanorod signal amplification |
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