CN108181296A - Optical fiber surface enhancing Raman microprobe based on surface phasmon effect and preparation method thereof - Google Patents

Optical fiber surface enhancing Raman microprobe based on surface phasmon effect and preparation method thereof Download PDF

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Publication number
CN108181296A
CN108181296A CN201810208209.5A CN201810208209A CN108181296A CN 108181296 A CN108181296 A CN 108181296A CN 201810208209 A CN201810208209 A CN 201810208209A CN 108181296 A CN108181296 A CN 108181296A
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optical fiber
metal
array
micro
phasmon effect
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CN108181296B (en
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倪海彬
葛璐
潘超
周盈
常建华
王婷婷
葛益娴
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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    • GPHYSICS
    • 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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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a kind of optical fiber surface enhancing Raman microprobes based on surface phasmon effect and preparation method thereof.The structure of the present invention is the periodical metal structure of one layer of attachment on the fiber end face of grinding.Making step includes:Spin coating PS micro-sphere arrays on substrate, partial etching and the metal-coated films at the top of PS microballoons, form hemispherical metal structure, then in its surface spin on polymers and cure, and remove substrate;By obtained film and fiber end face glue curing, PS microballoons are removed after curing completely, the geometric dimension that RIE etchings adjust metal structure makes its resonance wavelength and excitation laser consistent wavelength, only remaining metal hemispherical array at the top of optical fiber.Sample to be tested is adsorbed in metal hemispherical array surface, light source is coupled into from optical fiber one end, metal structure is irradiated from inside of optical fibre, laser generates measurable Raman signal under the action of metal structure, is exported after optical fiber is collected from the other end by spectrometer analysis.The configuration of the present invention is simple, suitable for processing.

Description

Optical fiber surface enhancing Raman microprobe and its making based on surface phasmon effect Method
Technical field
The present invention relates to a kind of optical fiber surface enhancing Raman microprobe based on surface phasmon effect and its making sides Method belongs to Optochemical sensor technical field.
Background technology
In traditional Raman spectrum spectrum analysis, for samples such as liquid, film and powder, it is special to be not required to Sample treatment can obtain satisfied spectrogram, but to some non-uniform samples or be not easy to the sample of direct sample, need Fiber Raman is popped one's head in.Through fiber Raman probe collection Raman scattering signal, signal is passed to by detector by optical fiber and obtains Raman Spectrum.Trace detection repeats detection.It is detected in local organization.Application of the optical fiber in Raman spectrum, greatly simplifies The optical system of transmission spectra method improves the measurement range of spectral instrument, especially suitable for telemetry so that online Analysis, analysis, in-vivo analysis, field monitoring, multimetering in real time etc. are possibly realized.
SERS (Surface enhanced Raman scattering) signal is that spatial orientation is unrelated, is consistent with conventional Raman signal, Therefore the angle of optical fiber can be collected by change, excitation signal and the light efficiency of collection signal is maximized, can reduce The background interference caused by fiber raman scattering.
The SERS mechanism that academic circles at present is generally accepted mainly has physics to enhance two class of mechanism and Chemical enhancement mechanism.
Physics enhancing is also known as Electromagnetic enhancement, it is believed that SERS effects derive from the enhancing of metal surface local electric field, molecule There was only physical absorption between metallic substrates almost without interaction, thus determine enhancement factor and Metal Substrate Bottom state is related, to binding molecule without selectivity.Electromagnetic enhancement model mainly has surface plasma resonance body Model, antenna Resonate submodel and mirror image field model.The specific mechanism that these model differences are embodied in respective local area electric-field enhancing has Institute is different.
Chemical enhancement mechanism thinks Molecular Adsorption in textured metal nano grain surface, nano surface particle plasma Electric charge transfer or stronger chemical action has occurred with binding molecule in body between the two, causes the polarization of metal nanoparticle Rate changes, and greatly affects or change resonance characteristics of the metal-surface nano particle as plasma, so as to cause The enhancing of Raman scattering signal.Chemical enhancement is acted on by binding molecule, molecule and plasma group key and exciting light The profound influence of the factors such as frequency, the main theory model about Chemical enhancement mechanism include bit model and electric charge transfer mould living Type.
Invention content
It is an object of the invention to overcome deficiency of the prior art, provide a kind of based on surface phasmon effect Optical fiber surface enhancing Raman microprobe and preparation method thereof, solve this technical problem of background interference in the prior art, in addition This scheme causes detection easy, and the position for being not suitable for microscopic system for tiny area can directly be visited using optical fiber Needle sampler is detected, while takes into account portability, trace detection and low-noise characteristic.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of optical fiber surface enhancing Raman microprobe based on surface phasmon effect, including optical fiber, the one of the optical fiber End is connected with metal nano waveguide array, and the other end connects light source and light spectrum detecting apparatus by coupler;The optical fiber is by light Metal nano waveguide array described in the incident light directing that source generates forms surface on the surface of the metal nano waveguide array Phasmon effect;The metal nano waveguide array is placed in sample to be tested, the molecule of adsorption sample to be tested;Institute It states incident light and irradiates the scattering light generated after the molecule of the sample to be tested by the optical fiber guiding coupler, Ran Houyou The light spectrum detecting apparatus measures Raman spectrum.
Preferably, it is hemispheric metal array that the metal nano waveguide array, which is surface, resonance wavelength with it is described The consistent wavelength of incident light.
Preferably, the material of the metal nano waveguide array is gold, silver or copper.
A kind of production method for preparing Raman microprobe as described above, includes the following steps:
A) the nanoscale microballoon of configuration PS materials and the colloid micro ball solution of deionized water mixing;
B) the colloid micro ball solution obtained in a) is added drop-wise on planar substrates, the surface for making the planar substrates is uniform Arrange PS micro-sphere arrays;
C) by b) the middle PS microballoon partial etchings prepared, then one layer of nano level metal film of array surface layer sputtering, makes PMMA photoresists are uniformly filled between PS micro-sphere arrays;Planar substrates are removed after curing to obtain film;
D) one section of optical fiber is intercepted, after described optical fiber one end is ground, the metal film of the film one side and light that will obtain in c) End face after fibre grinding is cured with glue, and film is fixed on optical fiber with this, is then just putting optical fiber, PS microballoon battle arrays Row upward, obtain device;
E) top of device in d) is subjected to reactive ion etching, makes at the top of optical fiber the only hemispherical metal of remaining separation Array is to form the optical fiber surface enhancing Raman microprobe based on surface phasmon effect.
Compared with prior art, the advantageous effect that is reached of the present invention is:
The device of the invention has metal hemispherical array, and detected sample is adsorbed in metal hemispherical array surface, Light source is coupled into from optical fiber one end, irradiates metal structure from inside of optical fibre, laser is generated under the action of metal structure and can be surveyed The Raman signal of amount;Sample is conventionally necessary to be placed in optical path, can just obtain satisfied spectrogram;And Introduce the present apparatus after, can by optical fiber will detect light from light source draw, with sample interact, and the collection through optical fiber and Transmission, flashlight is sent to monitoring system.The configuration of the present invention is simple, suitable for processing.
Description of the drawings
Fig. 1 is the schematic diagram of SERS substrate fabrications method flow of the present invention.
Fig. 2 is the schematic diagram of the production method flow of Raman microprobe of the present invention.
Fig. 3 is the structure diagram of Raman microprobe of the present invention.
Fig. 4 is the Raman spectrogram of Raman microprobe of the present invention in Fig. 3.
Reference numeral:1st, PS micro-sphere arrays;2nd, quartz substrate;3rd, metal silverskin;4th, PMMA photoresists;5th, Noa glue; 6th, multimode fibre.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating this hair Bright technical solution, and be not intended to limit the protection scope of the present invention and limit the scope of the invention.
As shown in Figure 1, being the schematic diagram of SERS substrates, including quartz substrate 2, polystyrene is provided on quartz substrate 2 (PS) nanoscale micro-sphere array, the tops of PS micro-sphere arrays 1 is also covered with metal silverskin 3, forms hemispherical metallic silver battle array Row, micro-sphere array can have certain defect.
The flow chart of the present invention is as shown in Fig. 2, PMMA photoresists 4 are uniformly filled between PS micro-sphere arrays 1, Noa Glue 5 is the surface coated in PMMA photoresists 4, is reacted after the film for removing quartz substrate 2 is transferred on optical fiber This structure can be obtained after ion etching.
Fig. 3 is a kind of schematic diagram of optical fiber surface enhancing Raman microprobe based on surface phasmon effect of the present invention, It is characterized in that PS micro-sphere arrays 1 are removed completely, while part eliminates 3 structure of metal silverskin and PMMA photoresists 5, more The end face of mode fiber 6 forms the metallic silver hemispherical array of separation.
Fig. 4 is that signal is passed to the 4ATP molecule Raman spectrum obtained after light spectrum detecting apparatus by optical fiber.
It is as follows that the present embodiment prepares the step of this device:
A) one 2.5 cun of quartz substrates are taken, respectively with acetone (purity 99.7%), alcohol (purity 99.9%), deionized water (resistivity 18.2M Ω) ultrasound (40W) is cleaned 10 minutes, is then dried up with nitrogen (purity 99.7%), then use plasma cleaning Machine handles quartz substrate 5 minutes, and by treated, quartz substrate is placed on sol evenning machine pallet, and setting 500rpm/min turns Speed, time 20s;
B) a diameter of 690nm of the colloid micro ball solution 20ml, wherein PS microballoons of configuration polystyrene (PS) microballoon, directly Diameter deviation ratio 0.2%, concentration of volume percent 0.05%, solvent are deionized water;
C) b) the middle colloid micro ball solution being configured is added drop-wise on substrate, starts sol evenning machine, uniformly revolved on the surface layer of substrate Coat PS micro-sphere arrays;
D) after the solvent of microsphere suspension liquid is evaporated completely, first PS top sections are etched, then will using magnetron sputtering coater The metal silverskin that one layer of 200nm thickness is sputtered at the top of PS microballoons forms hemispherical metal structure, then by spin coating PMMA on its surface Photoresist (administered 2.5ml/cm2), rotating speed 2500rpm/min, time 40s, spin coating three times, make PMMA glue uniformly fill out It fills between PS micro-sphere arrays;Then in 150 DEG C of front bakings 1 hour, PMMA glue and array is made to have good adhesiving effect, then Substrate is torn;
E) intercept one section of multimode fibre, 200 μm of fibre core, 220 μm of covering, by optical fiber one end it is ground after, then on PMMA One layer of Noa glue is applied, then with the silverskin gone at the top of viscous PS micro-sphere arrays of fiber perpendicular, a ultraviolet lamp is placed in its side Irradiation 10 seconds, is fully cured its bonding place, and top is PS micro-sphere arrays, there is one layer of Noa glue between silverskin and optical fiber Water;If need to be checked after precuring it is problematic, can use METHYLENE CHLORIDE into units detach, a usual night;
F) structure obtained in e) is subjected to reactive ion etching, Ar RIE etchings, portion while removing PS microballoons completely Divide removal part PMMA photoresists and metal structure, adjusting the distance between etch period, control hemispherical metallic silver makes its humorous Vibration wave is grown and excitation laser consistent wavelength makes only to be left the hemispherical metal array of separation at the top of optical fiber, so as to be formed based on table The optical fiber surface enhancing Raman microprobe of face phasmon effect.
The above is only the preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (4)

1. a kind of optical fiber surface enhancing Raman microprobe based on surface phasmon effect, which is characterized in that described including optical fiber One end of optical fiber is connected with metal nano waveguide array, and the other end connects light source and light spectrum detecting apparatus by coupler;It is described Metal nano waveguide array described in the incident light directing that optical fiber generates light source, in the surface shape of the metal nano waveguide array Into surface phasmon effect;The metal nano waveguide array is placed in sample to be tested, point of adsorption sample to be tested Son;The incident light irradiates the scattering light generated after the molecule of the sample to be tested and is oriented to the coupler by the optical fiber, so Raman spectrum is measured by the light spectrum detecting apparatus afterwards.
2. a kind of optical fiber surface enhancing Raman microprobe based on surface phasmon effect according to claim 1, special Sign is, the metal nano waveguide array is hemispherical metal array, spacing-controllable between hemispherical metal, resonance wavelength with The consistent wavelength of the incident light.
3. a kind of optical fiber surface enhancing Raman microprobe based on surface phasmon effect according to claim 1, special Sign is that the material of the metal nano waveguide array is gold, silver or copper.
4. a kind of production method for preparing Raman microprobe as described in claim 1, which is characterized in that include the following steps:
A) the nanoscale microballoon of configuration PS materials and the colloid micro ball solution of deionized water mixing;
B) the colloid micro ball solution obtained in a) is added drop-wise on planar substrates, the surface of the planar substrates is made to be evenly arranged PS Micro-sphere array;
C) by b) the middle PS microballoon partial etchings prepared, one layer of nano level metal film then is sputtered on PS micro-sphere arrays surface layer, PMMA photoresists is made uniformly to be filled between PS micro-sphere arrays;Planar substrates are removed after curing to obtain film;
D) one section of optical fiber is intercepted, after described optical fiber one end is ground, the metal film one side of the film obtained in c) is ground with optical fiber End face after mill is cured with glue, and film is fixed on optical fiber with this, obtains device;
E) film portion of device in d) is subjected to reactive ion etching, the end face of optical fiber is made only to be left the hemispherical metal of separation Array is to form the optical fiber surface enhancing Raman microprobe based on surface phasmon effect.
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CN111077120A (en) * 2018-10-19 2020-04-28 恩德莱斯和豪瑟尔分析仪表两合公司 Optical chemical sensor unit and method for determining an analyte in a measurement medium using the same
CN111650181A (en) * 2020-06-12 2020-09-11 上海大学 Detection device is preceding to optic fibre SERS
CN111708110A (en) * 2020-06-18 2020-09-25 欧菲微电子技术有限公司 Preparation method of diffuser, diffuser and camera module
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CN108896528A (en) * 2018-06-25 2018-11-27 南京信息工程大学 Online molecular detector and production method based on D-type optical fiber and nanometer annular chamber
CN108844924A (en) * 2018-07-17 2018-11-20 河南师范大学 Capillary pipe structure local surface plasma resonance biochemical sensor
CN111077120A (en) * 2018-10-19 2020-04-28 恩德莱斯和豪瑟尔分析仪表两合公司 Optical chemical sensor unit and method for determining an analyte in a measurement medium using the same
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CN110044871A (en) * 2019-04-28 2019-07-23 南京信息工程大学 The online substance qualitative detection device and production method of surface phasmon effect
CN110146482A (en) * 2019-05-13 2019-08-20 上海大学 A kind of novel near-field raman scattering detection device
CN111650181A (en) * 2020-06-12 2020-09-11 上海大学 Detection device is preceding to optic fibre SERS
CN111708110A (en) * 2020-06-18 2020-09-25 欧菲微电子技术有限公司 Preparation method of diffuser, diffuser and camera module
CN113218531A (en) * 2021-03-05 2021-08-06 广东工业大学 Optical fiber temperature sensor and preparation method thereof
CN113218531B (en) * 2021-03-05 2023-09-29 广东工业大学 Optical fiber temperature sensor and preparation method thereof

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