CN117647510A - Fluorescent microcavity device based on whispering gallery mode and preparation method and application thereof - Google Patents

Fluorescent microcavity device based on whispering gallery mode and preparation method and application thereof Download PDF

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CN117647510A
CN117647510A CN202311553300.8A CN202311553300A CN117647510A CN 117647510 A CN117647510 A CN 117647510A CN 202311553300 A CN202311553300 A CN 202311553300A CN 117647510 A CN117647510 A CN 117647510A
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fluorescent
wgm
cavity
microcavity
optical fiber
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王梦宇
雷进杰
谢成峰
谭庆贵
张巍巍
郭状
魏斌
柴明钢
杜丽军
陈进
万生鹏
史久林
何兴道
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Jiangxi Tuomai Technology Co ltd
Nanchang Hangkong University
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Jiangxi Tuomai Technology Co ltd
Nanchang Hangkong University
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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
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02Details
    • G01J3/0205Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/12Generating the spectrum; Monochromators
    • 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
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6402Atomic fluorescence; Laser induced fluorescence
    • 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
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N2021/6463Optics
    • G01N2021/6469Cavity, e.g. ellipsoid

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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention relates to the technical field of optics, and discloses a fluorescent microcavity device based on whispering gallery modes, which comprises a fluorescent material and a polymer cavity, wherein the fluorescent material is dispersed in a polymer WGM microcavity; the fluorescent material is selected from any one of rhodamine B, LDS722 and DCM. The polymer cavity material is selected from any one of polydimethylsiloxane, SU-8 and ultraviolet curing adhesive NOA 61. Besides the advantages of the common microcavity, the WGM fluorescent micro-bottle cavity provided by the invention also has the advantage of being capable of directionally selecting a spectrum by changing the axial profile and the cut-off point, so that a spectrum with a lower mode, sparsity and easy identification is obtained. In addition, WGM fluorescent micro-bottle chambers form a series of closely spaced axial modes due to their highly oblong shape degenerating their azimuthal modes, such that light within the micro-cavity continually shuttles between the turning points of the bottle neck cavity resulting in enhanced regions at the turning points.

Description

Fluorescent microcavity device based on whispering gallery mode and preparation method and application thereof
Technical Field
The invention relates to the technical field of optics, in particular to a fluorescent microcavity device based on a whispering gallery mode, and a preparation method and application thereof.
Background
The whispering gallery mode optical microcavity, WGM (Whispering gallery mode) microcavity for short, is named because it supports whispering gallery modes. The light transmitted in a WGM microcavity exists in the form of a traveling wave, with a very high quality factor (Q) value and a very small mode volume (V). The WGM microcavity not only can easily obtain high energy density in the cavity, but also has excellent performance due to the ultrahigh Q value characteristic, so that the WGM microcavity structure has wide application prospect in the fields of high-precision sensing measurement, optoelectronic devices and high-sensitivity detection. In recent years, researchers have developed and studied WGM microcavities of many different structures and materials. By combining different structures and materials, the requirements of scientific research and practical application are met. The WGM microcavity has the characteristics of high Q value, small volume, easy integration and the like, and is suitable for lasers with different wavelengths such as ultraviolet light, visible light, infrared light and the like in a transmission window of microcavity materials. Along with the continuous improvement of micro-processing technology, the research of echo wall microcavities with more varieties and higher quality factors is also continuously broken through, so that the application technology of the microcavities is further improved.
Fluorescence is a photoluminescence cold-emission phenomenon. When a certain normal temperature substance is irradiated with incident light of a certain wavelength, the light energy is absorbed and enters an excited state, and the excited state is immediately de-excited and emits outgoing light longer than the wavelength of the incident light. In general, the light emission phenomenon immediately disappears upon stopping the incident light. Fluorescent materials have the advantages of high emission intensity, small emission peak width, high quantum yield, wide emission spectrum and the like, so that the application and development trend of the fluorescent materials are receiving more and more attention. Fluorescent materials have become central materials in the fields of excitation fluorescence detection, biomedical imaging and the like, and in recent years, great development has been made in aspects of biosensing, medical diagnosis, treatment and the like due to the existence of fluorescent effects. In addition, fluorescence detection techniques based on a variety of physicochemical parameters have also attracted widespread interest. The core principle of the fluorescence sensor is to acquire the carried environmental parameter information from the fluorescence spectrum of the substance. The use of fluorescence for chemical and temperature sensing has been relatively mature to date [ Journal ofEnvironmental Sciences,103,228-240], and new developments continue.
Since some of the characteristics of the WGM microcavity are affected by the input light, the characteristics of the fluorescence are also affected by the input light. By combining the WGM microcavity with fluorescence, the method has the advantages of the characteristics and fluorescence of the WGM microcavity, so that the application of the WGM microcavity is better optimized, and the research value of fluorescence is widened. However, there are few reports of WGM microcavity studies based on fluorescent materials, and there are few references to the preparation and processing of whispering gallery mode-based fluorescent microcavities. The main reason is that both the fluorescent material and the WGM microcavity are affected by the input light, and if the two are combined, more optimal materials, structures and manufacturing methods need to be selected to avoid not degrading the characteristics of the two and not affecting each other. WGM microcavities can reduce the loss of light coupled into optical microcavities due to their extremely high quality factor, and combining fluorescent materials to make the resulting WGM microcavities is a good choice for studying fluorescence spectra and sensing applications. In addition, the WGM microcavity based on the fluorescent material has the advantages of simple preparation process, low preparation cost, obvious fluorescence spectrum excitation phenomenon and the like, and has great research prospect in the application research of label-free biomolecule detection. The invention adopts the space optical system to excite the resonance mode of the fluorescent microcavity, and is simple, convenient and easy to operate. Because it does not need to use a coupling mode to excite the whispering gallery mode of the microcavity, detection of the unlabeled biomolecules is facilitated more than the coupling mode. By combining whispering gallery mode micro-bottle cavities with fluorescence [ Laser & Photonics Reviews,12 (6), 1800078], the bottle cavities can be studied in three dimensions and have a wider range than the two-dimensional mode characteristics of the ball cavities, and the whispering gallery mode micro-bottle cavities are designed to achieve a higher quality factor than the microsphere cavities, which means that light waves can be stored and propagated in the cavities for a longer time, thereby achieving higher sensitivity and lower detection thresholds. In addition, the whispering gallery mode micro-vial chambers are more sensitive to minor changes than the microsphere chambers due to higher quality factors and more localized modes, such as weak adsorption effects in microbiological, molecular or biological assays. Besides the advantages of the common microcavity, the WGM fluorescent microcavity also has the advantage of directionally selecting a spectrum by changing the axial profile and the cut-off point, so that a spectrum with a lower mode, sparsity and easy identification is obtained. In addition, WGM fluorescent micro-bottle chambers form a series of closely spaced axial modes due to their highly oblong shape degenerating their azimuthal modes, such that light within the micro-cavity continually shuttles between the turning points of the bottle neck cavity resulting in enhanced regions at the turning points. And the FSR of the WGM fluorescent micro-bottle cavity is smaller than that of other micro-cavities with the equatorial WGM mode structure with the same size, so that the micro-bottle cavity can be better applied to precise sensing. The fluorescent optical characteristic and the whispering gallery mode characteristic which are shown after the WGM fluorescent micro-bottle cavity is excited are very sensitive to weak changes in the environment, so that the novel micro-cavity can detect physical quantity and chemical quantity with high precision. Since the WGM fluorescent micro-vial chamber limits fluorescence to a very narrow chamber volume, the sensitivity of detection is greatly improved.
Disclosure of Invention
In order to solve the technical problems in the background technology, the invention provides a fluorescent microcavity device based on a whispering gallery mode, and a preparation method and application thereof.
The invention is realized by adopting the following technical scheme:
a whispering gallery mode-based fluorescent microcavity device comprising a fluorescent material and a polymer cavity, the fluorescent material being dispersed within a polymer WGM microcavity;
preferably, the fluorescent material is selected from any one of rhodamine B, LDS and DCM.
Preferably, the polymer cavity material is selected from any one of polydimethylsiloxane, SU-8 and ultraviolet curing adhesive NOA 61.
The invention provides a method for manufacturing a fluorescent microcavity device based on a whispering gallery mode, which comprises the following steps of
Step 1, fully dissolving a fluorescent material fully dissolved in an ethanol solution with a polymer cavity material in a ratio of 3:7 under the stirring of a digital display constant temperature magnetic stirrer to obtain the fluorescent cavity material
Step 2, stripping the cladding of the standard optical fiber to expose the fiber core, and wiping the fiber core by using wet gauze and dry gauze dipped with alcohol in sequence;
step 3, placing the clean optical fiber with the exposed fiber core obtained in the step 2 in an optical fiber melting cone-drawing machine controlled by an upper computer, fixing the clean optical fiber through a vacuum pump, setting proper H2 and O2 flow parameters, igniting flame, drawing 10000 mu m to prepare a conical optical fiber, and cutting the conical optical fiber from the middle to prepare a semi-conical optical fiber;
step 4, dipping a small amount of the fluorescent cavity material prepared in the step 1 by a syringe, slightly scraping the dipped fluorescent cavity material on the semi-conical optical fiber prepared in the step 3 by adopting a blade coating method, standing for 3 minutes vertically, then observing fusion condition of the fluorescent material and the cavity material and cavity forming condition under a CCD microscope after the fluorescent cavity material is vertically and anticlockwise rotated for 5 minutes under the connection of a development board controlled by an upper computer, and preparing the WGM fluorescent microcavity with viscosity;
and 5, air-drying the WGM fluorescent microcavity with the viscosity obtained in the step 4 in an electrothermal blowing drying box, and air-drying the WGM fluorescent microcavity for 24 hours at 60 ℃ to obtain a dry and firm WGM fluorescent microcavity.
The performance detection method of the WGM fluorescent micro-bottle cavity device (WGM is interpreted as Whispering gallery mode) provided by the invention comprises the following steps:
the excitation performance of a WGM fluorescent micro-bottle cavity is researched by building a space light path, and a 405nm blue-violet laser is used as a laser light source of the whole system in a light path system;
after the laser beam passes through the iris diaphragm to adjust the numerical aperture to eliminate stray light, focusing is carried out through a convex lens, the position of the WGM fluorescent micro-bottle cavity is adjusted and controlled through a high-precision three-dimensional translation stage with a piezoelectric driver, the positions of the laser beam and the cavity are monitored in real time through CCD microscopes in the side face and the top end, and the WGM fluorescent micro-bottle cavity is arranged at the focus of the laser beam;
after the WGM fluorescent micro-bottle cavity is excited by laser light energy, obvious fluorescence phenomenon appears, and because the excitation spectrum range of rhodamine B fluorescent material is 550-750 nm wave band, a light filter is arranged at the fluorescence spectrum receiving end to filter stray light outside 550-750 nm;
the optical fiber probe is adjusted to a proper angle so that the optical fiber probe can receive visible light signals emitted by the WGM fluorescent micro-bottle cavity, the other end of the optical fiber probe is connected with the spectrometer through an optical fiber, the spectrometer is connected with the computer through a data line, and finally, the required fluorescent micro-bottle cavity excitation spectrum signals are observed and collected from the computer.
The invention also provides application of the fluorescent microcavity device, and detection and analysis of the binding of biomolecules are realized through the change of resonance frequency.
Compared with the prior art, the invention has the beneficial effects that:
the special structure of the WGM fluorescent microcavity provided by the invention makes the WGM fluorescent microcavity very sensitive to small changes, so that high-precision and multi-parameter detection, such as detection of microorganisms, biochemical molecules, gas and the like, can be realized. The optimization can be further adjusted according to different detection targets, such as changing the types of fluorescent materials or the shape and the size of the microcavities, so as to realize simultaneous detection of multiple parameters. Even can realize miniaturization and integration through the optical device integration technology, thereby greatly reducing the device volume and manufacturing cost, and facilitating the mobile detection. Therefore, the WGM fluorescent microcavity has the advantages of high sensitivity, high precision detection capability, simple preparation, capability of performing multiparameter detection, integration and the like, and has wide application prospects in the fields of biomedicine, environmental monitoring, chemical analysis and the like;
the present invention can use WGM fluorescent microcavities for biosensing by specifically capturing and detecting biomolecules with fluorescent signals provided by fluorescent materials. Because of the special structure and advantages of WGM fluorescent microcavities, it can be made into high-sensitivity temperature, pressure and humidity sensors for environmental monitoring. According to the characteristic that the high quality factor of the WGM fluorescent microcavity is highly sensitive to small changes of an optical field, the WGM fluorescent microcavity can be applied to detecting weak optical interference effects, small optical scattering phenomena and other photonic sensing.
Besides the advantages of the common microcavity, the WGM fluorescent micro-bottle cavity provided by the invention also has the advantage of being capable of directionally selecting a spectrum by changing the axial profile and the cut-off point, so that a spectrum with a lower mode, sparsity and easy identification is obtained. In addition, WGM fluorescent micro-bottle chambers form a series of closely spaced axial modes due to their highly oblong shape degenerating their azimuthal modes, such that light within the micro-cavity continually shuttles between the turning points of the bottle neck cavity resulting in enhanced regions at the turning points. And the FSR of the WGM fluorescent micro-bottle cavity is smaller than that of other micro-cavities with the equatorial WGM mode structure with the same size, so that the micro-bottle cavity can be better applied to precise sensing. The fluorescent optical characteristic and the whispering gallery mode characteristic which are shown after the WGM fluorescent micro-bottle cavity is excited are very sensitive to weak changes in the environment, so that the novel micro-cavity can detect physical quantity and chemical quantity with high precision. Since the WGM fluorescent micro-vial chamber limits fluorescence to a very narrow chamber volume, the sensitivity of detection is greatly improved.
Based on the invention, fluorescence can be flexibly combined with the WGM microcavity to prepare different WGM fluorescence microcavities. In the selection of the fluorescent material, rhodamine B, LDS722, DCM, and the like can be selected. The cavity structure can also be made into structures such as a double-bottle cavity, a ball cavity, a hemispherical cavity and the like. The preparation method can flexibly prepare, simplify the preparation and processing modes, and have low manufacturing cost, thereby better meeting different application requirements.
Drawings
Fig. 1 is a schematic diagram of a fluorescent microcavity fluorescent cavity material configuration based on whispering gallery modes.
Fig. 2 is a schematic diagram of the preparation of a fluorescent micro-bottle cavity based on whispering gallery mode.
FIG. 3 is a pictorial view of a fabricated WGM fluorescent micro-vial chamber, (a) a cascaded WGM fluorescent micro-vial chamber, (b) a single WGM fluorescent micro-vial chamber.
FIG. 4 is a schematic cross-sectional view of a WGM fluorescent micro-vial chamber.
FIG. 5 is a model of a fluorescent micro-vial chamber label-free biomolecular sensor.
FIG. 6 is a diagram of a fluorescent micro-vial chamber WGM resonance excitation system.
FIG. 7 is a fluorescence spectrum excitation spectrum plot of a WGM fluorescent micro-vial chamber.
Fig. 8 (a) is a schematic diagram of a Whispering Gallery Mode (WGM) optical resonance in a fluorescent micro-vial cavity, wherein binding of a biomolecule to the micro-cavity surface increases the WGM path length, fig. 8 (b) is a schematic diagram of a shift in resonance frequency when the biomolecule is detected, and fig. 8 (c) is a schematic diagram of the biomolecule bound to the fluorescent micro-vial cavity surface being polarized within the evanescent field of the WGM, such that the energy required for the polarization of the biomolecule results in a shift in resonance frequency.
Fig. 9 is a graph of resonance intensities of OM and IM.
FIG. 10 is a graph of RWS as a function of RI and increase in biomolecule size.
Main symbol description:
reference numerals in the drawings: 1-rhodamine B, 2-ethanol solution, 3-digital display constant temperature magnetic stirrer, 4-rhodamine B ethanol solution, 5-ultraviolet curing glue NOA61, 6-fluorescent cavity material, 7-stripped optical fiber cladding, 8-gauze wiping, 9-oxyhydrogen flame stretching, 10-upper computer, 11-middle cutting, 12-semi-conical optical fiber, 13-surface tension forming process, 14-development plate, 15-CCD microscope, 16-electric heating blast drying box, 17-405nm blue-violet laser, 18-iris diaphragm, 19-convex lens, 20-three-dimensional translation stage, 21-optical filter, 22-optical fiber probe, 23-visible light wave band spectrometer and 24-fluorescent microcavity.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein it is to be understood that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
In order to solve the problem that the WGM microcavity and fluorescence are better combined, so that the characteristics of the WGM microcavity and the fluorescence are not eliminated after the combination, and the WGM microcavity and the fluorescence are simultaneously provided, and the WGM microcavity is applied to label-free biomolecule detection, we design a WGM fluorescence microcavity prepared by processing a fluorescent material and a polymer cavity material under a certain condition. According to the whispering gallery mode-based fluorescent microcavity device and the manufacturing method thereof, different fluorescent materials can be flexibly selected to prepare different WGM fluorescent microcavity structures, and the WGM fluorescent microcavities with different performances are prepared by controlling the proportion of the fluorescent materials to the cavity materials and the difference of auxiliary materials and instrument parameters in the preparation process so as to better meet the application requirements of different optical sensing.
In order to achieve the above purpose, the invention adopts the technical proposal that
The invention provides a fluorescent microcavity device based on a whispering gallery mode; it includes the preparation of a fluorescent material dispersed within a polymeric WGM microcavity and a polymeric cavity material.
According to an embodiment of the invention, the fluorescent material is selected from any one of rhodamine B, LDS, DCM.
According to an embodiment of the invention, the polymeric cavity material is selected from any one of polydimethylsiloxane, SU-8, ultraviolet curing glue NOA 61.
According to an embodiment of the present invention, the fluorescent material is required to be sufficiently uniformly dissolved in 50ml of ethanol solution.
The method for manufacturing the fluorescent microcavity device based on the whispering gallery mode is used for manufacturing the fluorescent microcavity device based on the WGM mode, and comprises the following operation steps of:
step 1, fully dissolving a fluorescent material fully dissolved in an ethanol solution with a polymer cavity material in a ratio of 3:7 under the stirring of a digital display constant temperature magnetic stirrer to obtain a fluorescent cavity material 6;
step 2, stripping the cladding of the standard optical fiber to expose the fiber core, and wiping the fiber core by using wet gauze and dry gauze dipped with alcohol in sequence;
step 3, placing the clean optical fiber with the exposed fiber core obtained in the step 2 in an optical fiber melting cone-drawing machine controlled by an upper computer, fixing the clean optical fiber through a vacuum pump, setting proper H2 and O2 flow parameters, igniting flame, drawing 10000 mu m to prepare a conical optical fiber, and cutting the conical optical fiber from the middle to prepare a semi-conical optical fiber;
and 4, dipping a small amount of the fluorescent cavity material prepared in the step 1 by using a syringe, slightly scraping the fluorescent cavity material on the semi-conical optical fiber prepared in the step 3 by using a scraping method, and standing vertically for 3 minutes. Then, after the fluorescent material and the cavity material are vertically and anticlockwise rotated for 5 minutes under the connection of a development board controlled by an upper computer, the fusion condition and the cavity forming condition of the fluorescent material and the cavity material are observed under a CCD microscope, and a WGM fluorescent microcavity with viscosity is prepared;
step 5, air-drying in an electrothermal blowing drying box, putting and fixing the WGM fluorescent microcavity with the viscosity prepared in the step 4 in the electrothermal blowing drying box, and air-drying at 60 ℃ for 24 hours to prepare a dry and firm WGM fluorescent microcavity:
example 3:
the invention provides a performance detection method of a fluorescent microcavity device based on a whispering gallery mode, which comprises the following steps:
the excitation performance of a WGM fluorescent micro-bottle cavity is researched by building a space light path, and a 405nm blue-violet laser is used as a laser light source of the whole system in a light path system;
after the laser beam passes through the iris diaphragm to adjust the numerical aperture to eliminate stray light, focusing is carried out through a convex lens, the position of the WGM fluorescent micro-bottle cavity is adjusted and controlled through a high-precision three-dimensional translation stage with a piezoelectric driver, the positions of the laser beam and the cavity are monitored in real time through CCD microscopes in the side face and the top end, and the WGM fluorescent micro-bottle cavity is arranged at the focus of the laser beam;
after the WGM fluorescent micro-bottle cavity is excited by laser light energy, obvious fluorescence phenomenon appears, and because the excitation spectrum range of rhodamine B fluorescent material is 550-750 nm wave band, a light filter is arranged at the fluorescence spectrum receiving end to filter stray light outside 550-750 nm;
the optical fiber probe is adjusted to a proper angle so that the optical fiber probe can receive visible light signals emitted by the WGM fluorescent micro-bottle cavity, the other end of the optical fiber probe is connected with the spectrometer through an optical fiber, the spectrometer is connected with the computer through a data line, and finally, the required fluorescent micro-bottle cavity excitation spectrum signals are observed and collected from the computer
Example 4:
the application of the fluorescent microcavity device proposed in the present embodiment detects and analyzes the binding of biomolecules through the change of the resonance frequency.
In the present system, biomolecules are tightly attached to microcavity surfaces. After attachment of the biomolecules, the Resonant Wavelength Shift (RWS) of the microcavities was 0.141nm and 0.040nm, respectively. The results indicate that RWS of OM (external mode) is greater than IM (internal mode). In this case, the RWS of OM is more suitable for detecting biomolecules. Our structure provides additional degrees of freedom compared to conventional microsphere or microbubble cavities to achieve higher detection sensitivity and thus greater flexibility in sensitivity.
In order to describe the process of attaching biomolecules to microcavities, numerical studies were performed on the Attachment Distance (AD) of biomolecules in the number range of 0 to 500nm in FIG. 9. The distribution exhibits a decreasing exponential function in that the evanescent field strength exhibits a decreasing exponential function in the surrounding medium. When the biomolecules were tightly attached to the surface, the induced RWS was 0.163nm. RWS of OM is less than 0.001nm when AD becomes 500 nm. Exponential decay suggests that AD from nanoparticle to microcavity has a significant impact on RWS.
OM in figure 10 reveals RI (refractive index) and size effects of biomolecules. Wherein RWS increases rapidly when RI of the biomolecule increases from n=1 to n=1.4, and it rises slowly from n=1.4 to n=1.6 when d=200 nm. Further, RWS rises linearly with increasing d, n=1.4. RWS reaches 0.1645nm if a single biomolecule with refractive index n=1.45 and diameter d=200 nm is attached to the microcavity. For biomolecules with RI in the range of 1.35-1.60, the sensor can maintain high sensitivity.
The biomolecules are tightly attached to the microcavity surface. The WGM microcavity detects the binding of the analyte biomolecule by a change in resonance frequency. WGMs exhibit considerable sensitivity to such perturbations because the optical field is confined near the surface where the evanescent field interacts strongly with the surrounding medium. After attachment of the biomolecules, the resonant wavelength of the microcavities shifts. Binding of the biomolecules will shift the WGM resonance frequency by a very small amount. The shift to longer resonant wavelengths occurs because the bound biomolecules will effectively "pull" part of the optical field outside the microcavity, increasing the round trip path length by 2pi Δl. An increase in path length will produce a shift (Δω) to lower frequencies.
Once the biomolecules bind to the surface where the evanescent field strength E (r) is high, the molecules will be polarized at the optical frequency ω. The total induced dipole moment P is calculated as p=α ex E, wherein alpha ex Is the hyperpolarity of the biomolecule. The energy required to polarize the molecule and induce this dipole moment is 1/2 alpha ex |E(r 0 )| 2 Wherein E (r 0 ) Is a biomolecule binding site r 0 The electric field strength at that location.
By first order perturbation theory, the frequency shift can be estimated by comparing the energy required for polarization of the biomolecules with the total electromagnetic energy stored in the undisturbed resonator:where ε is the dielectric constant of the medium. Equations reflect the biosensing principle, allowing quantification of the frequency shift of any optical resonator in response to molecular or nanoparticle binding events.
To solve the fractional frequency shift Δω/ω predicted by the equation, a large Q factor is required. In practice, the resonant wavelength shift Δλ, i.e. Δλ/λ= - Δω/ω, is monitored. Detection limits, i.e. minimum detectable wavelength shift Deltalambda min Not only the line width delta lambda FWHM . Only Deltalambda FWHM An offset of a portion of the scale factor F may be sensed, thus Δλ min /λ=F*Δλ FWHM λ=f/Q, where F is typically 1/50-1/100, determined by a noise source (e.g., thermal refraction noise).
Importantly, the magnitude of the wavelength shift Δλ itself is related to the die volume V given by the denominator in the equation mode Inversely proportional. For WGMs in microcavities, it is:the size (die volume) of the optical microcavity is reduced, thereby improving the sensitivity. For microcavities, the optimal coupling diameter can be calculated because the radiation loss limits the Q-factor of very small microcavities as the diameter approaches the wavelength of the confining light.
Besides the advantages of the common microcavity, the WGM fluorescent microcavity also has the advantage of directionally selecting a spectrum by changing the axial profile and the cut-off point, so that a spectrum with a lower mode, sparsity and easy identification is obtained. In addition, WGM fluorescent micro-bottle chambers form a series of closely spaced axial modes due to their highly oblong shape degenerating their azimuthal modes, such that light within the micro-cavity continually shuttles between the turning points of the bottle neck cavity resulting in enhanced regions at the turning points. And the FSR of the WGM fluorescent micro-bottle cavity is smaller than that of other micro-cavities with the equatorial WGM mode structure with the same size, so that the micro-bottle cavity can be better applied to precise sensing. The fluorescent optical characteristic and the whispering gallery mode characteristic which are shown after the WGM fluorescent micro-bottle cavity is excited are very sensitive to weak changes in the environment, so that the novel micro-cavity can detect physical quantity and chemical quantity with high precision. Since the WGM fluorescent micro-vial chamber limits fluorescence to a very narrow chamber volume, the sensitivity of detection is greatly improved.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.

Claims (6)

1. A whispering gallery mode based fluorescent microcavity device comprising a fluorescent material and a polymer cavity, wherein the fluorescent material is dispersed within a polymer WGM microcavity.
2. The whispering gallery mode based fluorescent microcavity device of claim 1, wherein the fluorescent material is selected from any one of rhodamine B, LDS722, DCM.
3. The whispering gallery mode based fluorescent microcavity device of claim 1, wherein the polymeric cavity material is selected from any one of polydimethylsiloxane, SU-8, ultraviolet cured glue NOA 61.
4. A method of manufacturing a whispering gallery mode based fluorescent microcavity device as claimed in any one of claims 1-3, comprising the steps of:
step 1, fully dissolving a fluorescent material fully dissolved in an ethanol solution with a polymer cavity material in a ratio of 3:7 under the stirring of a digital display constant temperature magnetic stirrer to obtain the fluorescent cavity material;
step 2, stripping the cladding of the standard optical fiber to expose the fiber core, and wiping the fiber core by using wet gauze and dry gauze dipped with alcohol in sequence;
step 3, placing the clean optical fiber with the exposed fiber core obtained in the step 2 in an optical fiber melting cone-drawing machine controlled by an upper computer, fixing the clean optical fiber through a vacuum pump, setting proper H2 and O2 flow parameters, igniting flame, drawing 10000 mu m to prepare a conical optical fiber, and cutting the conical optical fiber from the middle to prepare a semi-conical optical fiber;
step 4, dipping a small amount of the fluorescent cavity material prepared in the step 1 by a syringe, slightly scraping the dipped fluorescent cavity material on the semi-conical optical fiber prepared in the step 3 by adopting a blade coating method, standing for 3 minutes vertically, then observing fusion condition of the fluorescent material and the cavity material and cavity forming condition under a CCD microscope after the fluorescent cavity material is vertically and anticlockwise rotated for 5 minutes under the connection of a development board controlled by an upper computer, and preparing the WGM fluorescent microcavity with viscosity;
and 5, air-drying the WGM fluorescent microcavity with the viscosity obtained in the step 4 in an electrothermal blowing drying box, and air-drying the WGM fluorescent microcavity for 24 hours at 60 ℃ to obtain a dry and firm WGM fluorescent microcavity.
The performance detection method of the WGM fluorescent micro-bottle cavity device is characterized by comprising the following steps:
the excitation performance of a WGM fluorescent micro-bottle cavity is researched by building a space light path, and a 405nm blue-violet laser is used as a laser light source of the whole system in a light path system;
after the laser beam passes through the iris diaphragm to adjust the numerical aperture to eliminate stray light, focusing is carried out through a convex lens, the position of the WGM fluorescent micro-bottle cavity is adjusted and controlled through a high-precision three-dimensional translation stage with a piezoelectric driver, the positions of the laser beam and the cavity are monitored in real time through CCD microscopes in the side face and the top end, and the WGM fluorescent micro-bottle cavity is arranged at the focus of the laser beam;
after the WGM fluorescent micro-bottle cavity is excited by laser light energy, obvious fluorescence phenomenon appears, and because the excitation spectrum range of rhodamine B fluorescent material is 550-750 nm wave band, a light filter is arranged at the fluorescence spectrum receiving end to filter stray light outside 550-750 nm;
the optical fiber probe is adjusted to a proper angle so that the optical fiber probe can receive visible light signals emitted by the WGM fluorescent micro-bottle cavity, the other end of the optical fiber probe is connected with the spectrometer through an optical fiber, the spectrometer is connected with the computer through a data line, and finally, the required fluorescent micro-bottle cavity excitation spectrum signals are observed and collected from the computer.
6. The use of a fluorescent microcavity device according to claim 1, wherein the binding of the analyte biomolecules is detected by a change in the resonance frequency.
CN202311553300.8A 2023-11-21 2023-11-21 Fluorescent microcavity device based on whispering gallery mode and preparation method and application thereof Pending CN117647510A (en)

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