CN109490279A - The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror - Google Patents

The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror Download PDF

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CN109490279A
CN109490279A CN201811355120.8A CN201811355120A CN109490279A CN 109490279 A CN109490279 A CN 109490279A CN 201811355120 A CN201811355120 A CN 201811355120A CN 109490279 A CN109490279 A CN 109490279A
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shaped
chip
spr
microtrabeculae mirror
substrate
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苑立波
韦柳夏
冯程成
杨宏艳
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Guilin University of Electronic Technology
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Guilin University of Electronic Technology
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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Abstract

The present invention is to provide a kind of rotary SPR sensorgram chips of D-shaped microtrabeculae mirror, belong to optical sensing field and material engineering field, and in particular to be the fields such as drug research and development, disease control and food safety.A kind of rotary SPR sensorgram chip of D-shaped microtrabeculae mirror is made of D-shaped microtrabeculae mirror optical base-substrate, nanoporous metal membrane, resonance enhancing film and substrate.Its modulation system are as follows: chip is fixed on rotating platform, along the central axis rotation rotating platform perpendicular to D-shaped microtrabeculae mirror optical base-substrate plane, it realizes the incidence angle for changing chip incident light, realizes and the high-resolution for the Exciting incidence degree for generating SPR phenomenon is modulated.Advantage of the invention is that; the chip have many advantages, such as at low cost, micromation, it is easy of integration, be produced on a large scale and sensor-based system chip is easily replaced; overcome the disadvantages of traditional SPR detection technique is complicated for operation, at high cost; and compared to traditional angular modulation system, the modulation system of the chip can make the measurement accuracy of SPR resonance angle improve several times.

Description

The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror
(1) technical field
The present invention is to provide a kind of rotary SPR sensorgram chips of D-shaped microtrabeculae mirror, belong to optical sensing field and material supplier Journey field, and in particular to be the fields such as drug research and development, disease control and food safety.
(2) background technique
With the improvement of living standards, the problems such as drug research and development, disease control and food safety, becomes the common concern in the whole world Focus.In recent years, optical bio sensing technology is because itself having the spies such as highly sensitive, real-time, quick, detection mode is flexible Point has been widely used in above-mentioned field, but biomolecule detection field realize only surface etc. of commercialization from Sub-resonance (Surface Plasmon Resonance, SPR) technology.There are still one for the spr sensor being commercialized currently on the market It is some insufficient, as equipment instrument is excessive, at high cost, limited, the sensor-based system that can not be identified and be detected little molecular concentration to molecule Middle replacement sensing arrangement inconvenience etc., therefore people urgently seek more commercially valuable spr sensor.
2005, State of Arizona, US found Soame Banerji of university et al. in International Periodicals Optics The article delivered on Letters is pointed out, highly sensitive survey can be realized using the sensor in the SPR double-sensing channel based on optical fiber Amount, but the SPR sensorgram device is the polymeric layer for needing to plate that thickness is strictly 100nm on the sensing unit for plated golden film, therefore Processing technology and sensing arrangement are relatively complicated.Document (Journal of Zhejiang Normal University, 1011-5051, volume 2018,41,40-45 pages) in describe a kind of Kretschmann prism-type based on SPR angle modulated molten The variation of refractive index is mapped by liquid refractive index detection system with the change of resonance angle, then through photoelectric conversion, realizes solution folding Penetrate the real-time detection of rate.But due to using prism model, causes volume big, cannot be miniaturized and large-scale production, and adopt It is direct angular modulation system, measurement accuracy is not improved.
In addition, application No. is describe a kind of prismatic angle matching surface plasma in 200910071979.0 patent Body resonance detector, has used that mirror surface is vertical with optical platform, a part on optical platform for being projected as one-dimensional ellipse Ellipsoid reflecting mirror, the center of circle of semi-cylinder prism and photodetector are respectively placed in two focuses of ellipsoid reflecting mirror.It is ellipse Face reflecting mirror follows rotating device instead of the angle machinery of photodetector in traditional detection instrument, improves detector building ring The stability in border, but the plane of incidence of semi-cylinder prism is parallel with rotatable platform, directly modulates SPR resonance by change incidence angle and swashs Angle is sent out, so that the measurement accuracy of resonance angle is not improved.Application No. is introduce a kind of stone in 201210067372.7 patent The D-type optical fiber spr sensor and preparation method thereof of black alkene film enhanced sensitivity deposits graphene film layer in silverskin layer surface to increase The sensitivity of the spr sensor.This method has certain novelty, but does not have new improvement on sensor structure, and The chip of sensing and detecting system cannot be convenient for changing.
The present invention for the above formerly technology there are the advantages of and deficiency, propose a kind of rotary SPR sensorgram of D-shaped microtrabeculae mirror Chip.On the one hand, this chip has at low cost, the easily changeable advantage in sensor-based system;On the other hand, which both has rib The advantage that mirror-type spr sensor incident angle is adjustable, and have the advantages that optical-fiber type spr sensor is miniaturized, is easy of integration, therefore Suitable for large-scale production, there is the commercial promise that can be mass-produced.And the modulation system of chip is to be fixed on chip On rotating platform, along the central axis rotation rotating platform perpendicular to D-shaped microtrabeculae mirror optical base-substrate plane, it can be achieved that changing chip The incidence angle of incident light, and realize and the high-resolution for the Exciting incidence degree for generating SPR phenomenon is modulated.
(3) summary of the invention
The purpose of the present invention is to provide a kind of D that can be used for the fields such as drug research and development, disease control and food safety The rotary SPR sensorgram chip of shape microtrabeculae mirror.
The object of the present invention is achieved like this:
The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror is enhanced by D-shaped microtrabeculae mirror optical base-substrate, nanoporous metal membrane, resonance Film and substrate composition;Preparation method are as follows: (1) prefabricated rods hot melt is drawn into D-shaped quartz or the micro- stick of glass, then uses rubbing down Technology carries out rubbing down to the side of D-shaped quartz or the micro- stick of glass, then D-shaped quartz or the micro- stick of glass are cut into suitable length, i.e., D-shaped microtrabeculae mirror optical base-substrate is made;(2) nanoporous metal membrane of suitable thickness is prepared on D-shaped microtrabeculae mirror optical base-substrate burnishing surface, Constitute SPR sensorgram structure;(3) then depositing or grow resonance in nano metal film surface enhances film, obtains sensitivity enhancing SPR sensorgram structure;(4) the SPR sensorgram structure that sensitivity enhances finally is integrated in vertical direction has the translucency of D-shaped groove good Good base center;Just constitute the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
Further, the new type of modulation mode of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror are as follows: chip is fixed on rotation Turn on platform, along the central axis rotation rotating platform perpendicular to D-shaped microtrabeculae mirror optical base-substrate plane, realizes and change chip incidence The incidence angle of light is realized and is modulated to the high-resolution for the Exciting incidence degree for generating SPR phenomenon.
Further, the material of the nanoporous metal membrane can be gold, silver.
Further, the nanoporous metal membrane with a thickness of 40nm~50nm.
Further, the material of resonance enhancing film can be graphene layer, be also possible to black phosphorus.
Further, the substrate can be glass, be also possible to organic glass.
The beneficial effects of the present invention are:
The present invention proposes a kind of D-shaped according to the demand of modern sensory field and in conjunction with the advantages of existing SPR sensorgram chip The rotary SPR sensorgram chip of microtrabeculae mirror.On the one hand, this chip has at low cost, the easily changeable advantage in sensor-based system;It is another Aspect, the chip had not only had the advantages that prism-type spr sensor incident angle was adjustable, but also had optical-fiber type spr sensor miniature Change, advantage easy of integration, therefore be suitable for large-scale production, there is the commercial promise that can be mass-produced.And the tune of chip Mode processed is that chip is fixed on rotating platform, along the central axis rotation rotation perpendicular to D-shaped microtrabeculae mirror optical base-substrate plane Turn platform, it can be achieved that changing the incidence angle of chip incident light, and realize the high score to the Exciting incidence degree for generating SPR phenomenon Resolution modulation.
(4) Detailed description of the invention
Fig. 1 is one and applies specific example lab diagram of the invention.
Fig. 2 is the structural schematic diagram of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
Fig. 3 is the longitudinal sectional view of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
Fig. 4 is the modulation system schematic diagram of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
Fig. 5 is the index path in the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
Fig. 6 is that the rotating platform for the SPR sensorgram system built by the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror horizontally rotates The graph of relation of angle and Exciting incidence degree.
Fig. 7 is the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror after Gauss light is incident, and D-shaped microtrabeculae mirror optical base-substrate excites table The graph of relation of face spot displacement and rotating platform horizontal rotation angle.
Fig. 8 is that the hot spot of D-shaped microtrabeculae mirror optical base-substrate excitating surface rotates and mobile schematic diagram with rotating platform.
Fig. 9 is the graph of relation of photodetector sensing surface spot displacement Yu rotating platform horizontal rotation angle.
Figure 10 is that the hot spot of photodetector sensing surface rotates and mobile schematic diagram with rotating platform.
Appended drawing reference in figure are as follows: 1- central wavelength is the He-Ne laser of 632.8nm, 2- Polarization Controller, the 3- present invention The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror, 31-D shape microtrabeculae mirror optical base-substrate, 32- nanoporous metal membrane, 33- resonance enhancing Film, 34- substrate, 4- rotating platform, 5- Photoelectrical detector, 6- capture card, 7- computer, 8- sensed environmental, 9-D shape microtrabeculae mirror light Learn the hot spot formed on substrate excitating surface, the moving area that hot spot is rotated with rotating platform on 10- excitating surface, 11- photoelectricity Detector sensing surface, the hot spot formed on 12- sensing surface, the turnover zone that 13- sensing surface hot spot is rotated with rotating platform Domain.
(5) specific embodiment
Below with reference to specific attached drawing, the present invention is further explained.
Disclosed by the invention is a kind of rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.As shown in Fig. 2, D-shaped microtrabeculae mirror rotates Formula SPR sensorgram chip is made of D-shaped microtrabeculae mirror optical base-substrate 31, nanoporous metal membrane 32, resonance enhancing film 33 and substrate 34.It will be pre- Stick hot melt processed is drawn into D-shaped quartz or the micro- stick of glass, is then carried out using side of the rubbing down technology to D-shaped quartz or the micro- stick of glass Rubbing down, then D-shaped quartz or the micro- stick of glass are cut into suitable length, obtain D-shaped microtrabeculae mirror optical base-substrate;In D-shaped microtrabeculae mirror The nanoporous metal membrane of suitable thickness is prepared on optical base-substrate burnishing surface, constitutes SPR sensorgram structure;Then in nano metal film surface Deposition or growth resonance enhance film, obtain the SPR sensorgram structure of sensitivity enhancing;The SPR sensorgram knot that finally sensitivity is enhanced Structure, which is integrated in vertical direction, the good base center of the translucency of D-shaped groove;It is rotary the D-shaped microtrabeculae mirror has just been prepared into SPR sensorgram chip.
The sensing arrangement of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror by D-shaped microtrabeculae mirror optical base-substrate end face and is plated in Nanoporous metal membrane on end face is constituted.Then, resonance enhancing film is deposited or grows in nano metal film surface to pass to improve the SPR Feel the sensitivity of structure.The principle generated according to SPR: after P-polarized light is incident on optical base-substrate at a certain angle, in optics Substrate end face and the interface of nanoporous metal membrane will cause evanescent waves when being totally reflected, by excitation nano metallic film surface from Surface plasma wave is generated by electronics, when surface plasma wave is identical as the frequency of evanescent waves, the two resonates, this When, energy is transferred to surface plasma wave from photon, and most of energy of incident light is absorbed by surface plasma wave, makes anti- The energy for penetrating light is sharply reduced, and can see that an absorption peak, the absorption peak are corresponding on the response curve of reflective light intensity at this time The a length of resonant wavelength λ of incident light wavespr, corresponding incidence angle is referred to as resonance angle θspr
In order to find out resonance angle θspr, mathematical description is given below.
When light beam (wave vector κ=w/c) is with θ0Angle, which is incident on nanoporous metal membrane, excites evanescent waves, and evanescent waves are in the direction x Above the wave vector parallel with surface is
W is the frequency of incident light, and c is vacuum light speed, ε0For the dielectric constant of D-shaped microtrabeculae mirror optical base-substrate.
For most metals, the real and imaginary parts of complex dielectric permittivity meet | εr|>εi> 1, then surface plasma The component of the wave vector of bulk wave in the x direction meets
ε1、ε2The respectively dielectric constant of metal and testing medium.
Know that the wave vector of evanescent waves is incidence angle θ by formula (1)0And the permittivity ε of D-shaped microtrabeculae mirror optical base-substrate0Function, It therefore can be by changing θ0And ε0To change evanescent waves κx.Change ε first0, make κxIncrease, reaches κxGreater than κsprPurpose.Change Become ε0Key to be D-shaped microtrabeculae mirror optical base-substrate use the biggish medium of refractive index.Then again by changing θ0To adjust κx, make The wave vector of evanescent waves is matched with the wave vector of surface plasma wave, and evanescent waves resonate with surface plasma wave, resonant bars Part is κxspr, the incidence angle of light wave is resonance angle θ at this timespr, have
By formula (3) it is found that resonance angle θsprIt is related with the dielectric constant of D-shaped microtrabeculae mirror optical base-substrate, metal and determinand.
The reflectivity of the rotary SPR sensorgram chip of entire D-shaped microtrabeculae mirror can be derived by fresnel formula, and then is obtained The power spectrum curve of SPR realizes the measurement of determinand.
The preparation of the rotary SPR sensorgram chip of embodiment 1:D shape microtrabeculae mirror
As shown in Figures 2 and 3, a kind of rotary SPR sensorgram chip of D-shaped microtrabeculae mirror the preparation method is as follows:
D-shaped microtrabeculae mirror optical base-substrate is prepared first: prefabricated rods hot melt being drawn into D-shaped quartz or the micro- stick of glass, is then adopted Rubbing down is carried out with side of the rubbing down technology to D-shaped quartz or the micro- stick of glass, then D-shaped quartz or the micro- stick of glass are cut into appropriate length Degree, obtains D-shaped microtrabeculae mirror optical base-substrate.
Then nanoporous metal membrane is prepared in the end face of D-shaped microtrabeculae mirror optical base-substrate, by taking golden film as an example: using sputtering method in D The end face of shape microtrabeculae mirror optical base-substrate plates the golden film that a layer thickness is 50nm or so.It can certainly be according to existing preparation side Method prepares golden film.
In order to be improved the sensitivity of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror, existed using chemical vapour deposition technique Golden film surface upper layer grows graphene layer.Graphene layer can certainly be prepared according to existing preparation method.
It finally prepares the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror: opening a vertical side at the center that substrate is organic glass To D-shaped groove, the D-shaped microtrabeculae mirror optical base-substrate for successively coating golden film and graphene layer is then integrated in preparation in groove should The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.In addition to organic glass, the base of the chip can also be made of the good glass of translucency Bottom.
The emulation testing of the rotary SPR sensorgram chip of embodiment 2:D shape microtrabeculae mirror
Fig. 6 is the rotating platform horizontal rotation angle obtained by simulation calculation and the relation curve of Exciting incidence degree Figure.In the simulation, set excitation light wave in the original incident angle on golden film surface as 72 °, with rotating platform it is horizontal just It is rotated to every 0.01 ° of variation, corresponding variation occurs for incident angle.Through emulation testing, the rotation angle of rotating platform It spends and excites the variation of angle that there is the good linearity, and every 0.01 ° of the rotation of rotating platform, resonance angle in 30 °~60 ° sections Reachable 0.001 ° of variation.Therefore, the more traditional direct angle modulated of the resonance angle measurement accuracy of the indirect angle modulation system Mode improves 10 times.
Fig. 7 is to pass through the resulting D-shaped microtrabeculae mirror optical base-substrate excitating surface spot displacement of simulation calculation and rotating platform water The graph of relation of flat rotation angle.In the emulation, the radius of D-shaped microtrabeculae mirror optical base-substrate is set as 60 μm, excitation light wave exists The original incident angle on golden film surface be 72 °, to rotate 0 ° of angle for origin, horizontally rotate rotating platform angle be 30 °~ 60°.The hot spot move mode of D-shaped microtrabeculae mirror optical base-substrate excitating surface is as shown in Figure 8.The meaning of the emulation be for D-shaped it is micro- The size design of cylindrical mirror optical base-substrate provides help.
Fig. 9 is to pass through the resulting photodetector sensing surface spot displacement of simulation calculation and rotating platform feathering angle The graph of relation of degree.Simulation parameter setting is same as above, and finds that emergent ray rotates angle with rotating platform by simulation result Variation and translate, translational movement and rotate angle relationship it is as shown in Figure 9.The hot spot of photodetector sensing surface is mobile Mode is as shown in Figure 10.The meaning of the emulation is to provide help for the selection of photodetector.
The application test of the rotary SPR sensorgram chip of embodiment 3:D shape microtrabeculae mirror
The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror being prepared into can be directly accessed sensor-based system, for testing wait try Liquid.As shown in Figure 1, the He-Ne laser 1 that central wavelength is 632.8nm generates optical signal, polarization control is input to by single mode optical fiber The control of device 2 output processed becomes P-polarized light, and P-polarized light is incident on the rotary SPR sensorgram chip 3 of D-shaped microtrabeculae mirror, and adjustment is incident The incidence angle of light is overlapped light and the radius of D-shaped microtrabeculae mirror optical base-substrate 31.It is passed with the rotary SPR of D-shaped microtrabeculae mirror is put The rotating platform 4 of sense chip 3 is horizontal positive or level reversely rotates, and corresponding variation occurs for the incident angle of incident light wave, when When incidence angle reaches a certain angle value, it is all-trans at the interface of 31 end face of D-shaped microtrabeculae mirror optical base-substrate and nanoporous metal membrane 32 The evanescent waves caused when penetrating, when identical with the frequency of the free electron generation surface plasma wave of excitation metallic film surface, two Person resonates, and the intensity of reflected light reaches minimum value at this time, and the corresponding incidence angle of the light intensity is exactly resonance angle θspr.Outgoing swashs Light enters photodetector 5, and optical signal is converted into electric signal and amplifies.Signal is acquired using capture card 6 and is transmitted to computer 7, the real-time detection to solution refractive index to be measured in environment 8 to be measured is realized by process control.Programmed control process are as follows: program control Rotating platform processed, computer real-time reception electric signal, rotating platform are rotated horizontally with every 0.01 ° of variation, and computer is certainly It is dynamic to record corresponding angle and voltage value.When rotating platform is from when turning to 60 ° for 30 °, computer analysis record data obtain one A resonance angle;Then 30 ° are turned to for 60 ° of the rotation of rotating platform opposite direction, obtains a resonance angle again.Such cycle detection, The resonance angle under different refractivity can be obtained, and then reports refractive index value according to calibration data.
Above-mentioned specific implementation is used to illustrate apparatus of the present invention, rather than limits the invention.The skill of this field Art personnel can also make improvement, these also should be regarded as in the protection scope for being no more than spirit and claims of the invention Protection scope of the present invention.

Claims (3)

1. a kind of rotary SPR sensorgram chip of D-shaped microtrabeculae mirror is enhanced by D-shaped microtrabeculae mirror optical base-substrate, nanoporous metal membrane, resonance Film and substrate composition;It is characterized by: prefabricated rods hot melt is drawn into D-shaped quartz or the micro- stick of glass by (1), rubbing down skill is then used Art carries out rubbing down to the side of D-shaped quartz or the micro- stick of glass, then D-shaped quartz or the micro- stick of glass are cut into suitable length, that is, makes Obtain D-shaped microtrabeculae mirror optical base-substrate;(2) nanoporous metal membrane of suitable thickness, structure are prepared on D-shaped microtrabeculae mirror optical base-substrate burnishing surface At SPR sensorgram structure;(3) then depositing or grow resonance in nano metal film surface enhances film, obtains the SPR of sensitivity enhancing Sensing arrangement;(4) the SPR sensorgram structure that sensitivity enhances finally is integrated in vertical direction has the translucency of D-shaped groove good Base center;Just constitute the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror.
2. a kind of new type of modulation mode of the rotary SPR sensorgram chip of D-shaped microtrabeculae mirror, it is characterised in that: by the D-shaped microtrabeculae Mirror SPR sensorgram chip is fixed on rotating platform, along the central axis rotation rotation perpendicular to D-shaped microtrabeculae mirror optical base-substrate plane Turn platform, realize the incidence angle for changing chip incident light, realizes the high-resolution to the Exciting incidence degree for generating SPR phenomenon Modulation.
3. the rotary SPR sensorgram chip of a kind of D-shaped microtrabeculae mirror according to claim 1, it is characterised in that: received in the present invention Rice metal film is prepared using gold or silver;Film with a thickness of 40nm~50nm;The material of resonance enhancing film can be graphene layer, It is also possible to black phosphorus;Substrate can be glass, be also possible to organic glass.
CN201811355120.8A 2018-09-10 2018-11-14 The rotary SPR sensorgram chip of D-shaped microtrabeculae mirror Pending CN109490279A (en)

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CN111289487A (en) * 2020-01-19 2020-06-16 中国科学院上海微系统与信息技术研究所 Graphene-based surface-enhanced Raman scattering substrate and preparation method and application thereof
CN112285065A (en) * 2020-11-26 2021-01-29 深圳瀚光科技有限公司 SPR sensor based on double elliptical reflectors and application
CN113686822A (en) * 2021-03-17 2021-11-23 广东工业大学 Sensing device, sensing system and regulation and control method based on surface plasma resonance
CN113686822B (en) * 2021-03-17 2024-04-16 广东工业大学 Sensing device, sensing system and regulation and control method based on surface plasma resonance

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