CN108593624A - Multi-wavelength metal plasma resonant structure of Selective long-range DEPT and preparation method thereof - Google Patents
Multi-wavelength metal plasma resonant structure of Selective long-range DEPT and preparation method thereof Download PDFInfo
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- 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
Abstract
Multiple light field coupling Fano resonance metal plasma resonant structures and preparation method thereof that the present invention relates to a kind of for Selective long-range DEPT, the resonant structure includes metal film, deielectric-coating and metallic hole array, the material of the wherein described deielectric-coating is optically transparent medium, and between metallic hole array and metal film.The resonant structure of the present invention can be realized simultaneously multiple multi-wavelengths resonance with the high Electromagnetic enhancement factor, and these resonance modes have that narrow linewidth, resonance peak intensity be suitable, resonant fields predominant local is in the medium characteristic of metal circular hole.These characteristics allow the structure to enhance the exciting field of target molecule simultaneously with launching site, and the selective enumeration method to target molecule is realized while the high sensitivity and pinpoint accuracy for ensureing detection.The preparation method simple process of the resonant structure, it is only necessary to traditional nano-imprint process and film vapor deposition technique, it is reproducible, convenient for application.
Description
Technical field
It is the present invention relates to a kind of plasma resonance structure and preparation method thereof, more particularly to a kind of for Selective long-range DEPT
Multiple light field coupling Fano resonance metal plasma resonant structures.
Technical background
Metal surface plasma bulk wave is a kind of physical optics phenomenon, is that light is radiated on inter metal dielectric interface and excites
The collective oscillation of metal surface electronics.Sensor and its application study in recent ten years based on metal plasma resonance principle obtain
Obtained significant progress.Due to its detection process is quick, can obtain real time data, it is easy to operate, label and need not can keep
The features such as bioactivity of molecule, metal surface plasma resonance sensor obtain in life science and pharmaceutical field extensive first
Using the research fields such as chemistry, chemical industry, material, food, environment and national defence gradually being penetrated at present, especially in immune inspection
Survey, environmental monitoring, the adsorption property at material surface and interface and electrochemical polymerization etc. are applied.Metal surface etc. from
Sub-resonance device can realize the light field near structure the Localized field enhancement of several orders of magnitude, to the enhancing of Raman signal because
Son most can reach by force 1014.Therefore the Raman scattering based on surface plasma resonance structure is to realize high sensitivity with fluorescent marker
The effective way of sensing and detection has particularly important application value in terms of hypersensitivity sensing is with detection.
Currently based on metal surface plasma resonance principle for the enhancing of Fluorescence Increasing and Raman application study mainly to
Both direction develops.First, seeking the higher Localized field enhancement factor to improve detection sensitivity.Currently used plasma is total
Structure of shaking includes mainly single metal nano particle and metal nanoparticle pair, and the resonance that Fig. 1 gives metal nanoparticle is special
Property, there are one formants for this symmetrical structure generally tool；Second is that be while detecting multiple fluorescence probes or improving Raman signal
Signal-to-noise ratio and seek multi-wavelength plasma resonance structure.Unsymmetric structure is mostly used greatly to realize being total to for multiple wavelength at present
It shakes, including the dissymmetrical structures such as ellipsoid, metal bar and polyhedron, Fig. 2 give the resonance characteristics of metal nano ellipsoid structure,
When different directions of the polarization state of exciting light along ellipsoid, the position of formant is different, but multiple formants is opposite
Position, power are not easy to adjust, and the asymmetry of structure result in light field under different resonance modes distribution it is inconsistent, be unfavorable for reality
The Selective long-range DEPT of existing target molecule.And the plasma resonance of both types all has the characteristic of ultra-wide enhanced spectrum, is total to
The peak width that shakes is about 100 nanometers, is also enhanced background signal while realizing target molecular signal enhancing.
Invention content
Goal of the invention：In order to overcome the deficiencies of the prior art, the present invention provides a kind of multiple light field for Selective long-range DEPT
Fano resonance metal plasma resonant structures are coupled, is realized on the basis of increasing sensitivity and the selectivity of target molecule is examined
It surveys, and makes the formant of excitation that there is narrow linewidth (for example, 10 nanometers) and the resonance comparable characteristic of peak intensity simultaneously.
On the other hand, the multiple light field coupling Fano that the present invention also provides above-mentioned for Selective long-range DEPT resonate metal etc. from
The preparation method of sub-resonance structure.
Technical solution：Multiple light field coupling Fano resonance metal plasmas of the present invention for Selective long-range DEPT are total
Structure of shaking includes metal film, optically transparent medium film and metallic hole array successively from below to up.
Further, the thickness of the metal film is not less than 100 nanometers, and the lower interface to eliminate the metal film excites
Surface plasma resonance and then the possibility for generating interference.
Further, the metal film is golden film or silverskin, and the optically transparent medium film is SiO2Film or MgF2Film.
Further, in the metallic hole array metal aperture a diameter of micro-nano magnitude.
Fano resonance metal plasma resonant structures are coupled provided by the present invention for the multiple light field of Selective long-range DEPT
Preparation method includes the following steps：(S1) deposited metal film and optically transparent medium film successively on an insulating substrate；(S2) pass through
The method of spin coating coats one layer of organic film on the optically transparent medium film；(S3) using the template prepared organic thin
It is imprinted on film, mould carves column symmetry structure array of discs；(S4) evaporated metal layer in column symmetry structure array of discs；
(S5) column symmetry metallic hole array is retained using organic solution cleaning removal organic film after the completion of vapor deposition.
Advantageous effect：Compared with prior art, the present invention its remarkable result is：
1, single metal hole can excite local plasmon resonance, the light field phase mutual coupling with the excitation of periodical metallic hole array
It closes, and the mirror image light field that the introducing of deielectric-coating makes metal aperture be excited with underlying metal film intercouples, Fano resonance is formed, in pole
The appearance that a variety of spatial model fields are resulted in while big raising field enhancement factor, to multiple formants occur；Meanwhile altogether
It shakes the position at peak and stiffness of coupling can be come just by adjusting the thickness of the thickness of metal circular hole, area, period and deielectric-coating
Just it is adjusted.
2, the introducing of periodical metallic hole array can be effectively compressed formant peak width while improving field enhancement factor, this
Outside, the surface plasma resonance and bottom gold of the local plasmon resonance excited around single metal hole and metallic hole array excitation
The mirror image light field of category film excitation intercouples and can form Fano resonance, further compresses formant peak width.And column symmetry pore structure
The mode distributions under different resonance modes can be made almost the same, be easy to implement the Selective long-range DEPT of target molecule.
3, by the way that different resonance modes are corresponded respectively to the multiple characteristic signals of same target molecule or multiple target molecules
Respective signal specific realizes the Selective long-range DEPT of target molecular signal.By taking Raman signal detection as an example, by by the present invention's
Three formants of metal plasma resonant structure correspond respectively to the excitation mode of target molecule and two selected Ramans are total to
It shakes pattern, enhances while the two selected Raman scattering signals can be realized on the basis of exciting light resonant check.Only
Have while the molecule for meeting the two resonance Ramans can be just identified.
4, simple in structure, simple process, it is only necessary to traditional nano-imprint process and film vapor deposition technique, it is reproducible,
Convenient for application.
Description of the drawings
Fig. 1 is the resonance characteristics figure of symmetric metal nanosphere；
Fig. 2 (a) and 2 (b) are respectively the resonance characteristics figure and optical field distribution figure of unsymmetrical metal ellipsoid structure；
Fig. 3 (a) and 3 (b) are respectively the stereogram and scanning electron microscope vertical view of the metal plasma resonant structure of the present invention；
Fig. 4 (a) to Fig. 4 (c) is respectively the metal plasma resonant structure of the present invention in different metal hole period, deielectric-coating
Resonance light spectrogram under thickness and metal pore radius；
Fig. 5 (a) is the different plasma resonance structures with metal pore structure designed for target molecule rhodamine 6G
Resonance characteristics figure；Fig. 5 (b) to Fig. 5 (d) is respectively the optical field distribution figure of corresponding three formants in Fig. 5 (a)；
Fig. 6 is to be measured in the plasma resonance structure with different structure designed for target molecule rhodamine 6G
Raman spectrogram.
Specific implementation mode
The present invention is further described below in conjunction with the accompanying drawings.
Such as Fig. 3 (a), the multiple light field coupling Fano resonance metal plasma resonance knots for Selective long-range DEPT of the invention
Structure includes metal film 1, optically transparent medium film 2 and the metallic hole array 3 sequentially formed from below to up on an insulating substrate, metal
Film 1 is golden film or silverskin, and the material of optically transparent medium film 2 is silica SiO2Or magnesium fluoride MgF2.Preferably, metal film 1
Thickness be more than 100 nanometers, with eliminate the lower interface excitating surface plasma resonance of metal film 1 so that generate interference can
Energy.In addition, in metallic hole array 3 metal aperture a diameter of micro-nano magnitude.
Correspondingly, above-mentioned metal plasma resonant structure preparation method includes the following steps：
(S1) pass through the method deposited metal film 1 of thermal evaporation and optically transparent medium film 2 on glass or quartz substrate；
(S2) one layer of organic film is coated on glass or quartz substrate by the method for spin coating；
(S3) it is imprinted on organic film using the template prepared, mould carves column symmetry structure array of discs；
(S4) evaporation metal and then in column symmetry structure array of discs；
(S5) column symmetry metallic hole array 3 is retained using organic solution cleaning removal organic film after the completion of vapor deposition.
Shown in the scanning electron microscope vertical view such as Fig. 3 (b) for the metal plasma resonant structure being prepared via above-mentioned steps.
Fig. 4 (a) to Fig. 4 (c) is shown respectively to the period of metal aperture, optically transparent medium in the resonant structure of the present invention
Film thickness and metal pore radius are adjusted obtained resonance light spectrogram.It can be seen that the metal plasma of the present invention is total
Structure of shaking can generate three surface plasma resonance peaks, thus have in Selective long-range DEPT field compared to single resonance peak structure
Apparent advantage.Meanwhile with the increase of optically transparent medium film thickness and grating constant, the formant of structure occurs respectively
Blue shift and Red Shift Phenomena, this is similar with the characteristic of periodical disk；With the increase of metal pore radius, formant occurs blue
It moves, this characteristic with periodical disk is just on the contrary, this point ensure that the simplification of sample preparation on nanoscale.Therefore,
By adjusting dielectric film thickness, thickness of metal film, Circularhole diameter size, circular hole period, can easily change pattern it
Between stiffness of coupling, to change intensity and the position of each formant.
The selective enumeration method to target molecule can be well realized in the metal plasma resonant structure of the present invention.For convenience
Comparative illustration, by 10uL a concentration of 10-5Rhodamine 6 (R6G) solution of M drips the resonant structure surface shown in structure 1 and structure 2
And be detected respectively using Raman spectrometer LabRAM HR800, excitation wavelength 784nm, focusing objective len is 50 times of object lens,
Its numerical aperture is 0.5.Wherein, structure 1 corresponds to the resonant structure of the present invention, and the wherein material of deielectric-coating is silica
SiO2, thickness is 57 nanometers；The material of metal film is silver, and thickness is 100 nanometers；The material of metallic hole array is silver, and circular hole is straight
Diameter is 220 nanometers, and thickness is 30 nanometers, and the period is 830 nanometers.Structure 2 is the resonant structure for comparison, wherein metal aperture battle array
The material of row 3 is silver, and Circularhole diameter is 220 nanometers, and thickness is 30 nanometers, and the period is 975 nanometers, and only insulate lining below array
Bottom and do not include metal film and optically transparent medium film.The resonance characteristics figure that structure 1 measures is corresponding with the line of dots in Fig. 5 (a),
The resonance characteristics figure that structure 2 measures is corresponding with the square line in Fig. 5 (a).
As shown in Fig. 5 (a) square lines, only there are one total with the wide list of wider threads for the plasma resonance structure for comparison
Shake peak, about 100 rans, and all Raman peaks of rhodamine 6 (R6G) molecule have been carried out while having been enhanced；And such as Fig. 5
(a) shown in the line of dots in, plasma resonance structure of the invention can be simultaneously in 784 nanometers, 818 nanometers and 876 nanometer waves
Length is formed about resonance, these formants have narrow linewidth (than the line width of list resonance peak structure compared to single resonance peak structure
A narrow magnitude；For example, 10 nanometers), resonance peak intensity quite, resonant fields predominant local is in characteristics such as structural perimeters.This hair
The narrow linewidth characteristic of bright plasma resonance structure is caused by multiple light field intercouples and forms Fano resonance, this three
A formant corresponds to the Raman excitation peak and two different Raman scattering peaks of rhodamine 6 (R6G) molecule respectively, when R6G points
When son falls within structure Near Circular Hole In A, two Raman scattering peaks corresponding with resonant wavelength will be enhanced, and theoretically can be improved
10000 times of Raman scattering signal corresponding with resonant wavelength.Particularly, Fig. 5 (b) is that the Localized field enhancement of 784 nano wave lengths is special
Property figure, Fig. 5 (c) is the Localized field enhancement performance plot of 818 nano wave lengths, and Fig. 5 (d) is that the Localized field enhancement of 876 nano wave lengths is special
Property figure.In addition, the plasma resonance structure of the present invention can be simultaneously to the exciting field for being detected molecule and multiple Raman scattering fields
Enhanced respectively, so as to increase target molecule and background molecular Raman scattering can discrimination, improve signal-to-noise ratio, realize
Selective Raman enhancing.
In Fig. 6 left side rhodamine 6 (R6G) Raman spectrogram in three curves of upper, middle and lower respectively with the structure on right side
1-3 is corresponded to.Wherein, the structure 1 and structure 2 on right side are identical with the structure 1 and structure 2 on right side in Fig. 5 (a) in Fig. 6, and have
There is identical parameter；The structure 3 on right side is to replace the metallic hole array of top layer in resonant structure shown in structure 1 in Fig. 6
Situation when at metal film.It can be found that the Raman peaks that structure 1 measures will be significantly stronger than the Raman of the R6G of structure 2 and structure 3
Spectrogram.In addition, Raman scattering signal corresponding with two surface plasma resonance peaks (i.e. peak in Fig. 6 corresponding to dotted line)
Other not corresponding Raman scattering signals are significantly stronger than, realize structure to R6G Raman molecular difference Raman peaks while property
Selective Raman enhancing.When containing plurality of target molecule in determinand, only the two Raman peaks obtain enhancing just simultaneously
It can determine in the determinand and contain R6G.
Claims (9)
- The metal plasma resonant structure 1. a kind of multiple light field coupling Fano for Selective long-range DEPT resonates, it is characterised in that： Include metal film (1), optically transparent medium film (2) and metallic hole array (3) successively from below to up.
- 2. metal plasma resonant structure according to claim 1, which is characterized in that the thickness of the metal film (1) is not Less than 100 nanometers.
- 3. metal plasma resonant structure according to claim 1, which is characterized in that the metal film (1) be golden film or Silverskin, the optically transparent medium film are SiO2Film or MgF2Film.
- 4. metal plasma resonant structure according to claim 1, which is characterized in that golden in the metallic hole array (3) Belong to a diameter of micro-nano magnitude in hole.
- The preparation method of metal plasma resonant structure 5. a kind of multiple light field coupling Fano for Selective long-range DEPT resonates, It is characterized in that, includes the following steps：(S1) deposited metal film (1) and optically transparent medium film (2) successively on an insulating substrate；(S2) one layer of organic film is coated on the optically transparent medium film (2) by the method for spin coating；(S3) it is imprinted on organic film using the template prepared, mould carves column symmetry structure array of discs；(S4) evaporation metal in column symmetry structure array of discs；(S5) column symmetry metallic hole array (3) is retained using organic solution cleaning removal organic film after the completion of vapor deposition.
- 6. preparation method according to claim 5, which is characterized in that the dielectric substrate is glass substrate or quartz lining Bottom.
- 7. preparation method according to claim 5, which is characterized in that the thickness of the metal film (1) is received not less than 100 Rice.
- 8. preparation method according to claim 5, which is characterized in that the metal film (1) is golden film or silverskin, the light Transparent dielectric film is SiO2Film or MgF2Film.
- 9. preparation method according to claim 5, which is characterized in that metal aperture in the column symmetry metallic hole array (3) A diameter of micro-nano magnitude.
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| CN109659387A (en) * | 2018-12-24 | 2019-04-19 | 苏州大学 | Infrared detector based on the enhancing of hydridization type plasma resonance |
| CN109921193A (en) * | 2019-03-14 | 2019-06-21 | 南京邮电大学 | Bimodal class electromagnetically induced transparent unit and method based on two kinds of coupled modes |
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| CN108593624B (en) | 2021-03-19 |
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