CN102095719A - Optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering - Google Patents

Optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering Download PDF

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Publication number
CN102095719A
CN102095719A CN 201010613143 CN201010613143A CN102095719A CN 102095719 A CN102095719 A CN 102095719A CN 201010613143 CN201010613143 CN 201010613143 CN 201010613143 A CN201010613143 A CN 201010613143A CN 102095719 A CN102095719 A CN 102095719A
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optical fiber
fiber
film
spr
optical
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常丽萍
王颖娜
刘恺
郭淑琴
李刚
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses an optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering. The system comprises a broadband light source, a P-type polaroid, a focusing convex lens, a polarization controller, an optical fiber beam splitter, an optical fiber inclined end, a surface plasma resonance (SPR) probe and an optical fiber spectrometer, wherein the P-type polaroid is positioned between the broadband light source and the focusing convex lens; the focusing convex lens optically couples the polarization broadband to the polarization controller; the polarization controller is connected with one input end of the optical fiber beam splitter, and the optical fiber spectrometer is connected with the other input end of the optical fiber beam splitter; the optical fiber inclined end is connected with one output end of the optical fiber beam splitter, and the SPR probe is connected with the other output end of the optical fiber beam splitter; the free end of the optical fiber inclined end is inclined; the SPR probe comprises an optical fiber; the end face of an exposed fiber core is provide with a first metal film, and the periphery of the exposed fiber core is provide with a second metal film; a nano-film is arranged on the surface of the second metal film; and a sensitive film is arranged on the nano-film. The system has the advantages of high universality, sensitivity and stability, and capable of realizing remote monitoring.

Description

Optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering
Technical field
The present invention relates to a kind of optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering.
Technical background
The biochemical sensitive technology is widely applied to fields such as basic life science, medical science, biochemistry, environment and food inspection, traditional biosensor technique is difficult to realize that the interactional real-time online of bioanalysis detects, as x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) etc., cost an arm and a leg, equipment is huge, experiment condition harshness (high vacuum), in addition some immunoassay technology commonly used, as fluorescence immunoassay, generally all need mark, and the test process complexity, the test duration is longer.Along with the development of measuring technology, people have higher requirement to the precision and the diversity that detect.
Summary of the invention
For overcoming the above-mentioned shortcoming of prior art, it is good to the invention provides a kind of versatility, highly sensitive, and good stability can be realized the miniature optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering of remote monitoring.
Optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering, comprise the wideband light source that sends incident light, incident light is changed into the P type polaroid of polarization broadband light, focus on convex lens, regulate the Polarization Controller of polarization broadband polarisation of light, enhancing resonance effect, fiber optic splitter prevents that light wave from reflecting to form the optical fiber beveled end of self-excitation, enter SPR probe that produces SPR spectrum in the analyzed solution and the fiber spectrometer that detects resonant wavelength;
Described P type polaroid is between described wideband light source and focusing convex lens, described focusing convex lens are coupled into the polarization broadband light in the described Polarization Controller, described Polarization Controller is connected with an input end of fiber optic splitter, described fiber spectrometer is connected with another input end of fiber optic splitter, described optical fiber beveled end is connected with an output terminal of fiber optic splitter, and described SPR probe is connected with another output terminal of described fiber optic splitter; The free end of described optical fiber beveled end is the inclined-plane;
Described SPR probe comprises the optical fiber that the head fibre core is exposed, the end face uniform deposition of exposed fibre core has first metal film as end mirror, uniform deposition one deck second metal film around the exposed fibre core, described second metallic film surface is modified with nanometer film, deposition one deck sensitive membrane on the described nanometer film.
Further, described first metal film is golden film or the silverskin of the about 300nm of thickness; Described second metal film is the golden film (Au film) of 50nm ± 0.1nm for the thickness that forms by the rf magnetron sputtering deposition; Described nanometer film is for to modify the Au nanometer film that forms by induced with laser on the Au film.
Further, described fiber optic splitter is 2 * 2 fiber optic splitters.
Further, the optical fiber of described SPR probe is general single mode fiber.
" connection " of the present invention is meant the connection at light path, for example described optical fiber polarization controller is connected with an end of described 2 * 2 fiber optic splitter input ends, promptly be interpreted as " end that is input to 2 * 2 fiber optic splitter input ends from the light signal of optical fiber polarization controller output ", also in like manner explain in other places.
Surface plasma body resonant vibration (Surface Plasmon Resonance, SPR) technology is that the evanescent wave that light produces when glass and the generation total reflection of metal interface place can cause the free electron generation surface plasma of metal surface, when the frequency of surface plasma and evanescent wave is identical with wave number, will produce surface plasma body resonant vibration (SPR), the specific inductive capacity of the main and metal film of its resonant wavelength, the concentration of solution to be measured, parameters such as refractive index are closely related, therefore under the condition of other parameter constants, there be corresponding relation between the resonant wavelength of optical fiber SPR sensor and the solution refractive index to be measured only changing solution to be measured.The SPR technology has determinand and need not purifying, sample and need not mark, dynamic process, highly sensitive, the advantage such as background interference is little, response speed is fast, detection time is short of monitoring reaction in real time, has obtained at present paying attention to widely and developing rapidly; And the surface enhanced Raman scattering effect of metal Nano structure (SERS) makes the Raman signal be adsorbed on the metal surface molecule with SERS activity compare with the Raman signal of equal number molecule in the solution to have taken place up to 10 6Huge enhancing, cause the SERS technology that surface mass is had high detection sensitivity and selectivity, can be on molecular level real-time monitored to the various materials in interface " fingerprint " information (chemical constitution and composition).
The optical fiber sensor-based system is that optical fiber technology and SPR/SERS technology are combined, the responsive part of SPR is narrowed down to optical fiber core diameter size, fibre diameter is generally below 600um, the length of SPR probe is at 5mm-25mm, very small and exquisite, and, need not the mark sample during detection, molecular structure and activity have been kept, highly sensitive, use the conduction of optical fiber simultaneously, can realize remote online detection, the testing process aspect is quick, is microminiaturized the extending naturally of requiring of technical development from now on and system.
The present invention combines surface plasma resonance (SPR) effect and optical fiber technology.The surface enhanced Raman scattering effect of SPR technology and metal Nano structure has the characteristics of high detection sensitivity, can make Raman signal obtain huge enhancing, and accuracy of detection improves; Adopt optical fiber as sensor probe, structure is small and exquisite, helps the microminiaturization of system, has overcome the influence that is subject to extraneous factors such as physical construction, light source fluctuation in the prism-type SPR structure simultaneously.
The building method of end reflection formula optical fiber probe is to get certain-length at optic fibre end, optical fiber is general single mode fiber, covering and the coat outer fibre core erode, the end face of polishing fiber, deposit layer of metal film (gold or silver) as completely reflecting mirror at optic fibre end, then sedimentary organism sensitive membrane and metal A u film on one section fibre core of this end, and on metal A u film, modify the Au nanometer film.Wideband light source is through P type polaroid with after focusing on convex lens in the coupled into optical fibres Polarization Controller, behind 2 * 2 fiber optic splitters, input to the SPR probe, in the Optical Fiber Transmission process, the light that satisfies the SPR resonant condition will be after being reflected by the metal film completely reflecting mirror, through resonance, produce SPR spectrum, the SPR spectrum of generation oppositely exports fiber spectrometer to through 2 * 2 fiber optic splitters, observes the SPR spectrum of analyte.
The present invention has highly versatile, and is highly sensitive, and stability and reproduction type are good, cheap, can realize miniature and advantage remote detection.
Description of drawings
Fig. 1 is a synoptic diagram of the present invention.
Fig. 2 is the structural representation of SPR probe.
Embodiment
With reference to accompanying drawing, further specify the present invention:
Optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering, comprise the wideband light source 1 that sends incident light, incident light is changed into the P type polaroid 2 of polarization broadband light, focus on convex lens 3, regulate the Polarization Controller 4 of polarization broadband polarisation of light, enhancing resonance effect, fiber optic splitter 5 prevents that light wave from reflecting to form the optical fiber beveled end 6 of self-excitation, enter SPR probe 8 that produces SPR spectrum in the analyzed solution and the fiber spectrometer 7 that detects resonant wavelength;
Described P type polaroid 2 is between described wideband light source 1 and focusing convex lens 3, described focusing convex lens 3 are coupled into the polarization broadband light in the described Polarization Controller 4, described Polarization Controller 4 is connected with an input end of fiber optic splitter 5, described fiber spectrometer 7 is connected with another input end of fiber optic splitter 5, described optical fiber beveled end 6 is connected with an output terminal of fiber optic splitter 5, and described SPR probe 8 is connected with another output terminal of described fiber optic splitter 5; The free end of described optical fiber beveled end 6 is the inclined-plane;
Described SPR probe 8 comprises the optical fiber 81 that the head fibre core is exposed, the end face uniform deposition of exposed fibre core 82 has first metal film 83 as end mirror, side face uniform deposition one deck second metal film 84 of exposed fibre core 82,84 finishinges of described second metal film have nanometer film 85, uniform deposition one deck sensitive membrane 86 on the described nanometer film.
Described first metal film 83 is golden film or the silverskin of the about 300nm of thickness; Described second metal film 84 is the golden film (Au film) of 50nm ± 0.1nm for the thickness that forms by the rf magnetron sputtering deposition; Described nanometer film 85 is for to modify the Au nanometer film that forms by induced with laser on the Au film.
Described fiber optic splitter 5 is 2 * 2 fiber optic splitters.
The optical fiber of described SPR probe 8 is general single mode fiber.
" connection " of the present invention is meant the connection at light path, for example described optical fiber polarization controller is connected with an end of described 2 * 2 fiber optic splitter input ends, promptly be interpreted as " end that is input to 2 * 2 fiber optic splitter input ends from the light signal of optical fiber polarization controller output ", also in like manner explain in other places.
Surface plasma body resonant vibration (Surface Plasmon Resonance, SPR) technology is that the evanescent wave that light produces when glass and the generation total reflection of metal interface place can cause the free electron generation surface plasma of metal surface, when the frequency of surface plasma and evanescent wave is identical with wave number, will produce surface plasma body resonant vibration (SPR), the specific inductive capacity of the main and metal film of its resonant wavelength, the concentration of solution to be measured, parameters such as refractive index are closely related, therefore under the condition of other parameter constants, there be corresponding relation between the resonant wavelength of optical fiber SPR sensor and the solution refractive index to be measured only changing solution to be measured.The SPR technology has determinand and need not purifying, sample and need not mark, dynamic process, highly sensitive, the advantage such as background interference is little, response speed is fast, detection time is short of monitoring reaction in real time, has obtained at present paying attention to widely and developing rapidly; And the surface enhanced Raman scattering effect of metal Nano structure (SERS) makes the Raman signal be adsorbed on the metal surface molecule with SERS activity compare with the Raman signal of equal number molecule in the solution to have taken place up to 10 6Huge enhancing, cause the SERS technology that surface mass is had high detection sensitivity and selectivity, can be on molecular level real-time monitored to the various materials in interface " fingerprint " information (chemical constitution and composition).
The optical fiber sensor-based system is that optical fiber technology and SPR/SERS technology are combined, the responsive part of SPR is narrowed down to optical fiber core diameter size, fibre diameter is generally below 600um, the length of SPR probe is at 5mm-25mm, very small and exquisite, and, need not the mark sample during detection, molecular structure and activity have been kept, highly sensitive, use the conduction of optical fiber simultaneously, can realize remote online detection, the testing process aspect is quick, is microminiaturized the extending naturally of requiring of technical development from now on and system.
The present invention combines surface plasma resonance (SPR) effect and optical fiber technology.The surface enhanced Raman scattering effect of SPR technology and metal Nano structure has the characteristics of high detection sensitivity, can make Raman signal obtain huge enhancing, and accuracy of detection improves; Adopt optical fiber as sensor probe, structure is small and exquisite, helps the microminiaturization of system, has overcome the influence that is subject to extraneous factors such as physical construction, light source fluctuation in the prism-type SPR structure simultaneously.
The building method of end reflection formula optical fiber probe is to get certain-length at optic fibre end, optical fiber is general single mode fiber, covering and the coat outer fibre core erode, the end face of polishing fiber, deposit layer of metal film (gold or silver) as completely reflecting mirror at optic fibre end, then sedimentary organism sensitive membrane and metal A u film on one section fibre core of this end, and on metal A u film, modify the Au nanometer film.Wideband light source is through P type polaroid with after focusing on convex lens in the coupled into optical fibres Polarization Controller, behind 2 * 2 fiber optic splitters, input to the SPR probe, in the Optical Fiber Transmission process, the light that satisfies the SPR resonant condition will be after being reflected by the metal film completely reflecting mirror, through resonance, produce SPR spectrum, the SPR spectrum of generation oppositely exports fiber spectrometer to through 2 * 2 fiber optic splitters, observes the SPR spectrum of analyte.
Show as described in Figure 1, the SPR probe is applied in the system of measuring the solution refractive index, use incident light to be the wideband light source of wavelength 400nm to 1000nm, after handling, P type polaroid becomes the polarization broadband light, the line focus convex lens are coupled into optical fiber polarization controller, the effect of optical fiber polarization controller is by regulating polarization, reach better resonance effect, the polarization broadband light is through 2 * 2 fiber optic splitters, export an end and connect the optical fiber beveled end, prevent that light from reflecting back the formation self-excitation, the other end is connected to the SPR probe.The SPR probe directly is inserted into detected solution, after incident light arrives the SPR probe, produce the SPR effect with the solution medium interaction, through forming reflection SPR light after the completely reflecting mirror effect of fibre core end face, reflected light enters fiber spectrometer through another input end of 2 * 2 fiber optic splitters again.Through the relation curve between output reflection light intensity after the Computer Processing and the optical wavelength.The sensing range of spectrometer is 500-900nm, and resolution is 0.5nm, can detect the resonant wavelength that changes between the 500-900nm.If change measuring accuracy and sensitivity that more high-resolution spectrometer can further improve system, can change the spectrometer in the detection system simultaneously according to actual needs.
The present invention is easy to use flexibly, only needs the SPR probe is immersed analyzed solution, can detect the fluid to be measured change of refractive in real time, stability and favorable reproducibility by measuring resonant wavelength; Utilize fiber optic conduction and computer technology combination simultaneously, can realize transmitting light signal at a distance, satisfy the application that some catastrophe risk zones are detected.Its highly versatile, characteristics such as sensitivity height make it can be widely used in fields such as chemistry, biology and environmental medicine.
The described content of this instructions embodiment only is enumerating the way of realization of inventive concept; protection scope of the present invention should not be regarded as only limiting to the concrete form that embodiment states, protection scope of the present invention also reach in those skilled in the art conceive according to the present invention the equivalent technologies means that can expect.

Claims (4)

1. based on the optical-fiber type sensor-based system of surface plasma resonance and stimulated Raman scattering, it is characterized in that: comprise the wideband light source that sends incident light, incident light is changed into the P type polaroid of polarization broadband light, focus on convex lens, regulate the Polarization Controller of polarization broadband polarisation of light, enhancing resonance effect, fiber optic splitter prevents that light wave from reflecting to form the optical fiber beveled end of self-excitation, enter SPR probe that produces SPR spectrum in the analyzed solution and the fiber spectrometer that detects resonant wavelength;
Described P type polaroid is between described wideband light source and focusing convex lens, described focusing convex lens are coupled into the polarization broadband light in the described Polarization Controller, described Polarization Controller is connected with an input end of fiber optic splitter, described fiber spectrometer is connected with another input end of fiber optic splitter, described optical fiber beveled end is connected with an output terminal of fiber optic splitter, and described SPR probe is connected with another output terminal of described fiber optic splitter; The free end of described optical fiber beveled end is the inclined-plane;
Described SPR probe comprises the optical fiber that the head fibre core is exposed, the end face uniform deposition of exposed fibre core has first metal film as end mirror, uniform deposition one deck second metal film around the exposed fibre core, described second metallic film surface is modified with nanometer film, deposition one deck sensitive membrane on the described nanometer film.
2. the optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering as claimed in claim 1 is characterized in that: described first metal film is golden film or the silverskin of the about 300nm of thickness; Described second metal film is the golden film (Au film) of 50nm ± 0.1nm for the thickness that forms by the rf magnetron sputtering deposition; Described nanometer film is for to modify the Au nanometer film that forms by induced with laser on the Au film.
3. the optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering as claimed in claim 2 is characterized in that: described fiber optic splitter is 2 * 2 fiber optic splitters.
4. the optical-fiber type sensor-based system based on surface plasma resonance and stimulated Raman scattering as claimed in claim 3 is characterized in that: the optical fiber of described SPR probe is general single mode fiber.
CN 201010613143 2010-12-30 2010-12-30 Optical fiber type sensor system based on surface plasma resonance and stimulated Raman scattering Pending CN102095719A (en)

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CN102353655A (en) * 2011-07-07 2012-02-15 天津大学 Surface plasma resonance sensor based on photonic crystal fiber
CN103900991A (en) * 2013-12-17 2014-07-02 中国计量学院 Refractive index sensor based on surface plasmon resonance
CN104155280A (en) * 2014-01-26 2014-11-19 中国科学院长春光学精密机械与物理研究所 Self-reference quantization detection method of Raman optical fiber sensor
CN105510297A (en) * 2015-12-29 2016-04-20 北京华泰诺安探测技术有限公司 Raman fluorescence spectrum testing system and optical signal collector thereof
CN106199786A (en) * 2016-08-29 2016-12-07 上海交通大学 Metal micro-nano structure and end face have the optical fiber of metal micro-nano structure
CN109444106A (en) * 2018-11-14 2019-03-08 东莞理工学院 A kind of photocatalysis in-situ monitoring system based on Surface enhanced Raman spectroscopy
CN110100171A (en) * 2017-01-16 2019-08-06 矢崎总业株式会社 Highly selective corrosion sensor system
CN110596099A (en) * 2019-09-07 2019-12-20 桂林电子科技大学 Transmission type optical fiber nanometer microscope stand based on SPR
CN112697767A (en) * 2020-12-03 2021-04-23 中国计量大学 Detection device combining Raman spectrum with SPR (surface plasmon resonance)

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CN102353655A (en) * 2011-07-07 2012-02-15 天津大学 Surface plasma resonance sensor based on photonic crystal fiber
CN103900991A (en) * 2013-12-17 2014-07-02 中国计量学院 Refractive index sensor based on surface plasmon resonance
CN104155280A (en) * 2014-01-26 2014-11-19 中国科学院长春光学精密机械与物理研究所 Self-reference quantization detection method of Raman optical fiber sensor
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CN105510297A (en) * 2015-12-29 2016-04-20 北京华泰诺安探测技术有限公司 Raman fluorescence spectrum testing system and optical signal collector thereof
CN106199786A (en) * 2016-08-29 2016-12-07 上海交通大学 Metal micro-nano structure and end face have the optical fiber of metal micro-nano structure
CN106199786B (en) * 2016-08-29 2019-05-03 上海交通大学 Metal micro-nano structure and end face have the optical fiber of metal micro-nano structure
CN110100171A (en) * 2017-01-16 2019-08-06 矢崎总业株式会社 Highly selective corrosion sensor system
CN109444106A (en) * 2018-11-14 2019-03-08 东莞理工学院 A kind of photocatalysis in-situ monitoring system based on Surface enhanced Raman spectroscopy
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CN110596099A (en) * 2019-09-07 2019-12-20 桂林电子科技大学 Transmission type optical fiber nanometer microscope stand based on SPR
CN112697767A (en) * 2020-12-03 2021-04-23 中国计量大学 Detection device combining Raman spectrum with SPR (surface plasmon resonance)

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Application publication date: 20110615