CN110260974A - Microscopic Raman detecting devices - Google Patents

Microscopic Raman detecting devices Download PDF

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Publication number
CN110260974A
CN110260974A CN201910639345.4A CN201910639345A CN110260974A CN 110260974 A CN110260974 A CN 110260974A CN 201910639345 A CN201910639345 A CN 201910639345A CN 110260974 A CN110260974 A CN 110260974A
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CN
China
Prior art keywords
optical filter
laser
switching device
optical
sample
Prior art date
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Pending
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CN201910639345.4A
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Chinese (zh)
Inventor
仇巍
常颖
亢一澜
曲传咏
张茜
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Tianjin University
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Tianjin University
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Priority to CN201910639345.4A priority Critical patent/CN110260974A/en
Publication of CN110260974A publication Critical patent/CN110260974A/en
Pending legal-status Critical Current

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    • 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
    • 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
    • G01J3/28Investigating the spectrum
    • G01J3/2823Imaging spectrometer
    • 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
    • G01J3/28Investigating the spectrum
    • G01J3/44Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • 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

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The present invention relates to optical-mechanical technical field more particularly to a kind of microscopic Raman detecting devices.The equipment includes: export agency, the first optical filter, switching device, the second optical filter and introducing mechanism;The laser signal that laser is launched is irradiated on the first optical filter by export agency, the laser signal that first optical filter can launch laser is reflected into sample upper surface, the reflection signal that sample surfaces are inspired enters in introducing mechanism after the first optical filter, switching device and the second optical filter, and is imported into spectrograph by introducing mechanism and carry out Raman analysis;Observation device is located above switching device, switching device receives the illumination light that observation device issues, the illumination light that first optical filter can reflect switching device is reflected into the surface of sample, by sample surface reflection illumination light through the first optical filter, be reflected into observation device by switching device.To solve Raman probe described in background technique.

Description

Microscopic Raman detecting devices
Technical field
The present invention relates to optical-mechanical technical fields, in particular to a kind of microscopic Raman detecting devices.
Background technique
It is well known that micro Raman spectra measuring technique is that the micro scale experiment to grow up in recent years measures new skill Art.The technology can pass through acquisition Raman scattering signal and analyze chemical component, crystal phase and stress that its spectrum obtains material Or the information such as strain, it is widely used in the experimental analysis of numerous areas.Micro Raman spectra system is mature business Melt the spectral measurement system of hair and application.These systems usually can have excellent spectrographic detection performance, such as high spatial point Resolution, Gao Laman signal-to-noise ratio etc., have taken in the application study in the fields such as analytical chemistry, cell biology, materials physics Obtain a series of success achievements.
On this basis, it is contemplated that these systems often structure fix, accurate and environmental requirement it is high, it is difficult to be same as engineering Scene and with the spectrographic detection under environmental load.Some producers and scholar successfully have developed a variety of contacts or contactless Raman detection probe, freedom degree and flexibility ratio with higher, to realize complex environment, scene or material and organization internal Raman detection.However, existing Raman probe does not often have micro- real-time observing capacity, and usually poor sensitivity, light Spectral resolution and spatial resolution are all very low, are unable to satisfy suitable to spatial discrimination, spectrally resolved and sensitivity and environmental load Higher forward position experimental study is required to property.
Summary of the invention
The purpose of the present invention is to provide a kind of microscopic Raman detecting devices, are visited with solving Raman existing in the prior art Head does not often have micro- real-time observing capacity, and usually poor sensitivity, the spectral resolution technology low with spatial resolution Problem.
The embodiment of the present invention is achieved in that
One kind be used for microscopic Raman detecting devices, comprising: export agency and successively every the first optical filter of setting, switching dress It sets, the second optical filter and introducing mechanism;
First optical filter is equipped with sample to be tested, the side of first optical filter far from the side of the switching device Equipped with laser, the export agency is located between the laser and first optical filter, the side of the switching device Equipped with observation device, the laser signal that the laser is launched is irradiated to first optical filter by the export agency On, the laser signal that first optical filter can launch laser is reflected into the sample upper surface, the sample table The reflection signal that face is inspired enters the importing machine after first optical filter, switching device and the second optical filter In structure, and it is imported into the spectrograph by the introducing mechanism and carries out Raman analysis;
The observation device is located above the switching device, and the switching device receives the photograph that the observation device issues The illumination light that the switching device reflects can be reflected into the surface of the sample by Mingguang City, first optical filter, be passed through The illumination light of the surface reflection of sample is reflected into the observation device through first optical filter, by the switching device In.
It further, further include microcobjective camera lens, the microcobjective camera lens is located at the sample and first filter Between mating plate.
Further, the optical axis of second optical filter, switching device, the first optical filter and microcobjective camera lens is same On straight line.
Further, first optical filter is two-color laser spectroscope.
Further, second optical filter is Raman optical filter.
Further, the export agency includes the first optical fiber and the first fiber coupler, and the introducing mechanism includes the Two optical fiber and the second fiber coupler;
First optical fiber and first fiber coupler be sequentially arranged at the laser and first optical filter it Between, second optical fiber and second fiber coupler are located between second optical filter and the spectrograph, described to swash The laser signal that light device is launched enters in first optical fiber, and first fiber coupler is emitted to described first and filters On piece, on the laser reflection to the sample for launched the laser by first optical filter, the second optical fiber coupling Clutch and second optical fiber receive the reflection signal that the sample surfaces are inspired and filter, and by the sample surfaces quilt It inspires and the reflection signal filtered is imported into the spectrograph.
Further, the switching device is to intervene/withdraw from changeable reflecting mirror, half-reflecting half mirror or polarization spectro Mirror.
A kind of microscopic Raman detecting devices provided by the invention, by export agency, introducing mechanism, switching device, the first filter Mating plate, the second optical filter, the laser and spectrograph form signal optical path, and what laser was launched in the signal optical path swashs Optical signal acts on the sample surfaces, and the reflection signal that the sample surfaces are inspired, which enters, carries out Raman in spectrograph Analysis, forms observation optical path by switching device, the first optical filter and observation device.Using above-mentioned scheme, observation optical path is main For realizing the function of sample surfaces white-light illuminating and microexamination, it is equivalent to a complete optical microscope system.Compared to Traditional optical microscopy, signal optical path are mainly used for realizing excitation and the collecting function of Raman signal, incident laser and most The Raman scattering signal being collected into eventually is all to be carried out importing by means of export agency and introducing mechanism and derived, therefore its space Position is very flexible, unrestricted;Often do not have micro- real-time observation to solve Raman probe existing in the prior art Ability, and usually poor sensitivity, the spectral resolution technical problem low with spatial resolution.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the structural schematic diagram of microscopic Raman detecting devices provided in an embodiment of the present invention.
In figure: 100- switching device;The first optical filter of 200-;300- microcobjective camera lens;The second optical filter of 400-; 500- introducing mechanism;600- laser;700- spectrograph;800- observation device;900- sample.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.The present invention being usually described and illustrated herein in the accompanying drawings is implemented The component of example can be arranged and be designed with a variety of different configurations.
Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects It encloses.
It should also be noted that similar label and letter indicate similar terms in following attached drawing, therefore, once a certain Xiang Yi It is defined in a attached drawing, does not then need that it is further defined and explained in subsequent attached drawing.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical", The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, or be somebody's turn to do Invention product using when the orientation or positional relationship usually put, be merely for convenience of description of the present invention and simplification of the description, without It is that the device of indication or suggestion meaning or element must have a particular orientation, be constructed and operated in a specific orientation, therefore not It can be interpreted as limitation of the present invention.In addition, term " first ", " second ", " third " etc. are only used for distinguishing description, and cannot manage Solution is indication or suggestion relative importance.
In addition, the terms such as term "horizontal", "vertical", " pendency " are not offered as requiring component abswolute level or pendency, and It is that can be slightly tilted.It is not to indicate the structure if "horizontal" only refers to that its direction is more horizontal with respect to for "vertical" It has to fully horizontally, but can be slightly tilted.
In the description of the present invention, it is also necessary to which explanation is unless specifically defined or limited otherwise, term " setting ", " installation ", " connected ", " connection " shall be understood in a broad sense, for example, it may be fixedly connected, may be a detachable connection or one Connect to body;It can be mechanical connection, be also possible to be electrically connected;It can be directly connected, it can also be indirect by intermediary It is connected, can be the connection inside two elements.For the ordinary skill in the art, on being understood with concrete condition State the concrete meaning of term in the present invention.
With reference to the accompanying drawing, it elaborates to some embodiments of the present invention.In the absence of conflict, following Feature in embodiment and embodiment can be combined with each other.
A kind of be used for microscopic Raman detecting devices as shown in Figure 1, provided by the invention, comprising: export agency and successively every The first optical filter 200, switching device 100, the second optical filter 400 and the introducing mechanism 500 being arranged;
First optical filter 200 is equipped with sample to be tested 900, first filter far from the side of the switching device 100 The side of mating plate 200 is equipped with laser 600, the export agency be located at the laser 600 and first optical filter 200 it Between, the side of the switching device 100 is equipped with observation device 800, described in the laser signal process that the laser 600 is launched Export agency is irradiated on first optical filter 200, and what first optical filter 200 can launch laser 600 swashs Optical signal is reflected into 900 upper surface of sample, and the reflection signal that 900 surface of sample is inspired is by first filter It is entered in the introducing mechanism 500 after mating plate 200, switching device 100 and the second optical filter 400, and by the introducing mechanism 500 imported into the spectrograph 700 and carry out Raman analysis;
The observation device 800 is located at 100 top of switching device, and the switching device 100 receives the observation dress The illumination light of 800 sendings is set, the illumination light that the switching device 100 reflects can be reflected by first optical filter 200 The surface of the sample 900, by sample 900 surface reflection the illumination light through first optical filter 200, by described Switching device 100 is reflected into the observation device 800.
It further, further include microcobjective camera lens 300, the microcobjective camera lens 300 is located at the sample 900 and institute It states between the first optical filter 200.
Further, second optical filter 400, switching device 100, the first optical filter 200 and microcobjective camera lens 300 Optical axis on the same line.
Further, the first optical filter 200 is two-color laser spectroscope.Two-color laser spectroscope is a kind of beam splitter, Wavelength can be made to reflect lower than the light of special value, and the light higher than the numerical value is allowed to penetrate.
Further, second optical filter 400 is Raman optical filter.Used herein is Edge optical filter, this is one Kind long wave leads to (high pass) optical filter, it can be absorbed light of the wavelength lower than some special value and wavelength is allowed to be greater than the numerical value Light passes through.For filtering out through the Rayleigh scattering and anti-Stokes scattering signal under being remained after two-color laser spectroscope, obtain The Raman signal of " pure ".
Wherein, observation device 800 includes lighting source and image acquisition device.
Wherein, the first optical filter 200 and switching device 100 are symmetrical arranged, and the first optical filter 200 is to close to microcobjective The inclination of 300 one end of camera lens.
In the present embodiment, filtered by export agency, introducing mechanism 500, switching device 100, the first optical filter 200, second Piece 400, the laser 600 and spectrograph 700 form signal optical path, and excitation signal is emitted by laser 600, by exporting machine Structure outgoing after the reflection of the first optical filter 200, and focuses on 900 surface of sample by microcobjective camera lens 300;900 table of sample The scattering envelope that face is inspired includes reflected light signal, Rayleigh scattering signal (identical as laser wavelength of incidence), Stokes and draws Graceful signal (wavelength is less than incident laser) and anti-Stokes Raman signal (wavelength is greater than incident laser), by microcobjective mirror First 300 collect, and eliminate most of reflected light, Rayleigh scattering and anti-Stokes by the transmission of the first optical filter 200 and draw Graceful signal and after retaining most Stokes Raman signals, filters out remaining reflected light, Rayleigh using the second filter Scattering and anti-Stokes scattering signal, only Stokes Raman signal are able to by and are finally imported by introducing mechanism 500 Raman signal analysis is carried out into spectrograph 700, and sight is formed by switching device 100, the first optical filter 200 and observation device 800 Optical path is examined, the illumination light that the lighting source in observation device 800 issues, through the reflection of switching device 100, through the first optical filter 200 and 900 surface of sample is focused on by microcobjective camera lens 300;Illumination light is after 900 surface reflection of sample, by micro- object Lens head 300 is collected, and is successively reflected by the first optical filter 200, switching device 100, is finally entered 800 formation figure of observation device Picture realizes the observation to 900 surface of sample.Compared to traditional optical microscopy, signal optical path is mainly used for realizing Raman letter Number excitation and collecting function, incident laser and the Raman scattering signal being finally collected into all be by means of export agency and to lead Enter mechanism 500 import and derived, therefore its spatial position is very flexible, unrestricted;To solve to deposit in the prior art Raman probe often do not have micro- real-time observing capacity, and usually poor sensitivity, spectral resolution and spatial discrimination The low technical problem of rate.
On the basis of the above embodiments, further, the export agency includes the first optical fiber and the first fiber coupling Device, the introducing mechanism 500 include the second optical fiber and the second fiber coupler;
First optical fiber and first fiber coupler are sequentially arranged at the laser 600 and first optical filter Between 200, second optical fiber and second fiber coupler are located at second optical filter 400 and the spectrograph 700 Between, the laser signal that the laser 600 is launched enters in first optical fiber, the first fiber coupler transmitting Onto first optical filter 200, the laser reflection for being gone out the Laser emission by first optical filter 200 is to the sample On 900, second fiber coupler and second optical fiber receive the reflection that 900 surface of sample is inspired and filters Signal, and 900 surface of sample is inspired and the reflection signal filtered is imported into the spectrograph 700.
In the present embodiment, due to setting for the first optical fiber, the first fiber coupler, the second optical fiber and the second fiber coupler It sets, laser signal and filtered excitation signal can be made efficiently to pass in and out, so as to save space.
On the basis of the above embodiments, further, the switching device 100 is to intervene/withdraw from changeable reflection Mirror, half-reflecting half mirror or polarization spectroscope.
In the present embodiment, when switching device 100 is using intervening/withdrawing from changeable reflecting mirror, then by intervening and withdrawing from The switching of reflecting mirror realization observation optical path and signal optical path.If, can be automatic using half-reflecting half mirror or polarization spectroscope It is divided and realizes automatically the switching of the two.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of microscopic Raman detecting devices characterized by comprising export agency and successively spaced first optical filtering Piece, switching device, the second optical filter and introducing mechanism;
First optical filter is equipped with sample to be tested far from the side of the switching device, and the side of first optical filter is equipped with Laser, the export agency are located between the laser and first optical filter, and the side of the switching device is equipped with Observation device, the laser signal that the laser is launched are irradiated on first optical filter by the export agency, institute The laser signal that laser can be launched by stating the first optical filter is reflected into the sample upper surface, and the sample surfaces are swashed The reflection signal of sending enters in the introducing mechanism after first optical filter, switching device and the second optical filter, And it is imported into spectrograph by the introducing mechanism and carries out Raman analysis;
The observation device is located above the switching device, and the switching device receives the illumination that the observation device issues Light, the illumination light that the switching device reflects can be reflected into the surface of the sample by first optical filter, by sample The illumination light of the surface reflection of product is reflected into the observation device through first optical filter by the switching device.
2. microscopic Raman detecting devices according to claim 1, which is characterized in that it further include microcobjective camera lens, it is described Microcobjective camera lens is located between the sample and first optical filter.
3. microscopic Raman detecting devices according to claim 2, which is characterized in that second optical filter, switching device, The optical axis of first optical filter and microcobjective camera lens is on the same line.
4. microscopic Raman detecting devices according to claim 1, which is characterized in that first optical filter is two-color laser Spectroscope.
5. microscopic Raman detecting devices according to claim 1, which is characterized in that second optical filter is Raman optical filtering Piece.
6. microscopic Raman detecting devices according to claim 1, which is characterized in that the export agency includes the first optical fiber With the first fiber coupler, the introducing mechanism includes the second optical fiber and the second fiber coupler;
First optical fiber and first fiber coupler are sequentially arranged between the laser and first optical filter, institute It states the second optical fiber and second fiber coupler is located between second optical filter and the spectrograph, the laser hair The laser signal of injection enters in first optical fiber, and first fiber coupler is emitted on first optical filter, On the laser reflection to the sample for launched the laser by first optical filter, second fiber coupler and Second optical fiber receives the reflection signal that the sample surfaces are inspired and filter, and the sample surfaces are inspired And the reflection signal filtered is imported into the spectrograph.
7. microscopic Raman detecting devices according to claim 1, which is characterized in that the switching device is to intervene/withdraw from Changeable reflecting mirror, half-reflecting half mirror or polarization spectroscope.
CN201910639345.4A 2019-07-15 2019-07-15 Microscopic Raman detecting devices Pending CN110260974A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116392729A (en) * 2023-05-29 2023-07-07 广州市五合医疗器械有限公司 Laser therapeutic instrument

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050248759A1 (en) * 2004-04-30 2005-11-10 Peidong Wang Method and apparatus for conducting Raman spectroscopy
CN102507002A (en) * 2011-11-09 2012-06-20 厦门大学 Optical fiber microprobe of tip-enhanced Raman spectrometer
CN103033497A (en) * 2012-12-25 2013-04-10 吉林大学 Microfluidic chip analyzer applying raman spectrum for detection
CN103743720A (en) * 2014-01-20 2014-04-23 厦门大学 Confocal microscopic Raman spectrometer with angle resolution capacity
CN105758838A (en) * 2016-04-11 2016-07-13 北京大学 Method and device for detecting and selecting laser-induce enhanced Raman spectrum in liquid
CN108717057A (en) * 2018-05-31 2018-10-30 中央民族大学 A kind of portable surface enhancing Raman spectrometer and its measurement method
CN209910826U (en) * 2019-07-15 2020-01-07 天津大学 micro-Raman detection device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050248759A1 (en) * 2004-04-30 2005-11-10 Peidong Wang Method and apparatus for conducting Raman spectroscopy
CN102507002A (en) * 2011-11-09 2012-06-20 厦门大学 Optical fiber microprobe of tip-enhanced Raman spectrometer
CN103033497A (en) * 2012-12-25 2013-04-10 吉林大学 Microfluidic chip analyzer applying raman spectrum for detection
CN103743720A (en) * 2014-01-20 2014-04-23 厦门大学 Confocal microscopic Raman spectrometer with angle resolution capacity
CN105758838A (en) * 2016-04-11 2016-07-13 北京大学 Method and device for detecting and selecting laser-induce enhanced Raman spectrum in liquid
CN108717057A (en) * 2018-05-31 2018-10-30 中央民族大学 A kind of portable surface enhancing Raman spectrometer and its measurement method
CN209910826U (en) * 2019-07-15 2020-01-07 天津大学 micro-Raman detection device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116392729A (en) * 2023-05-29 2023-07-07 广州市五合医疗器械有限公司 Laser therapeutic instrument

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