CN104316507B - Raman signal detection system and method - Google Patents

Raman signal detection system and method Download PDF

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Publication number
CN104316507B
CN104316507B CN201410542095.XA CN201410542095A CN104316507B CN 104316507 B CN104316507 B CN 104316507B CN 201410542095 A CN201410542095 A CN 201410542095A CN 104316507 B CN104316507 B CN 104316507B
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optical filter
lens
raman
light
laser
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CN104316507A (en
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黄梅珍
汪洋
孙振华
余镇岗
刘天元
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention provides a kind of Raman signal detection system and method, the system includes Raman probe, numerical control displacement sample stage, controller;The Raman probe is installed on numerical control displacement sample stage, and Raman probe can be relatively moved with numerical control displacement sample stage, and the signal output side of the Raman probe is provided with light intensity detection unit;The output end of the light intensity detection unit is connected to controller, and controller driving numerical control displacement sample stage changes measurement distance, judges whether measurement distance is optimal according to the change of the light intensity detection element output signal.The Raman probe includes the first lens, the first optical filter, the second optical filter, the 4th lens, the 3rd optical filter, the 4th optical filter, the second lens, light intensity detection unit.The present invention can maximize the Raman signal that measures and stably, the invention is particularly suited to solid sample measurement.The uneven sample of rough surface is directly detected, without sample pre-treatments.

Description

Raman signal detection system and method
Technical field
The present invention relates to optical-mechanical, instrument field, in particular it relates to which one kind can adjust measurement distance to optimal shape The Raman probe of state, and the Raman signal detection system used in laser Raman spectroscopy measurement or Raman spectrometer and side Method.
Background technology
Portable Raman spectrometer has the advantages that small volume, speed is fast, scene, in medicine, food security, safety check etc. Field has broad application prospects.Portable Raman spectrometer is general by small semiconductor laser, Raman fiber optic probe, light Spectrometer and computer system are constituted.Wherein, the function of Raman probe mainly has two aspects, on the one hand efficiently conducts laser and gathers On the other hand Jiao efficiently collect and filter Raman scattering signal in detected sample and conducted to spectrometer.
The launching efficiency of Raman spectrum is relevant with laser linewidth and energy density etc..In order to obtain stronger Raman letter Number, it is necessary to which laser is accurately aligned with focusing on sample to obtain higher laser energy density.Therefore, in large-scale Raman Micro- focusing system is all configured with measuring system, operating personnel are manually focused by micro-image.At present, commercialization is just Formula Raman spectroscopy system is taken because volumetric constraint is typically free of micro- focusing system, and Raman fiber optic probe is only capable of by adjusting manually The mode of section is focused, troublesome poeration, it is impossible to exact focus, causes raman scattering intensity to weaken, jitter etc..
Commercialization a kind of fixed range probe by installed additional before probe regular length sleeve come fixation measuring distance from And ensure the new detector of suitable distance.This probe simplifies focus operation process to a certain extent, but using this When probe is measured, sleeve must be contacted with sample, if sample surfaces out-of-flatness, it is impossible to vernier focusing.
The content of the invention
For defect of the prior art, can automatically adjust measurement distance it is an object of the invention to provide one kind makes collection The maximized Raman probe of Raman signal, Raman signal detection system and the method arrived.
According to an aspect of the present invention there is provided a kind of Raman probe, the Raman probe includes the first lens, the first filter Mating plate, the second optical filter, the 4th lens, the 3rd optical filter, the 4th optical filter, the second lens, light intensity detection unit;Wherein:Swash Light enters after Raman probe from fiber optic conduction, is become directional light by the first lens, then by the first optical filter to spectrum Carry out purification process, then by the second filter transmission, finally by the 4th lens by Laser Focusing in sample;Sample Raman scattering is occurred after laser excitation, scattered light and reflected light opposite direction are collected into Raman probe by the 4th lens, wherein Raman diffused light pass through the lens set that is made up of the second optical filter and the 4th optical filter, then assemble and be coupled into via the second lens Enter optical fiber, the lens set that non-Raman signal light is made up of the second optical filter and the 4th optical filter stops suppression, therefore can not arrive Up to the second lens, wherein the laser reflected by sample is by the low reflection of the second optical filter, the 3rd optical filter is highly transmissive, into light Strong probe unit;
The light intensity detection unit includes:3rd lens, aperture and electrooptical device, it is saturating that the aperture is in the 3rd The focal point of mirror;The laser of 3rd filter transmission is radiated at through small holes by aperture again through the 3rd lens focus after convergence On electrooptical device, received and detect by photoelectric detector.
Preferably, second optical filter, the 3rd optical filter be arranged in parallel and at 45 ° with light path, and described the two the Three optical filters are 45 ° of dichroic mirrors, and the effect of second, third optical filter is highly transmissive laser and high reflection Raman light.
According to the second aspect of the invention there is provided second of Raman probe, the Raman probe includes the first lens, first Optical filter, the second optical filter, the 4th lens, the 3rd optical filter, the 4th optical filter, the second lens, light intensity detection unit;Wherein: Laser enters after Raman probe from fiber optic conduction, is become directional light by the first lens, then by the first optical filter to light Spectrum carries out purification process, then sequentially pass through with directional light in 45 ° of settings the reflection of the second optical filters, last will be swashed by the 4th lens Light focuses on sample;Raman scattering is occurred after laser excitation for sample, and scattered light and reflected light opposite direction, which enter, draws It is graceful probe by the 4th lens collect, Raman diffused light therein pass through the second optical filter, by the 3rd optical filter reflect, by with light The 4th vertical optical filter of road, then assembled via the second lens and be coupled into optical fiber, non-Raman signal light by the 3rd optical filter and The lens set that 4th optical filter is constituted stops suppression, therefore can not reach the second lens, wherein by swashing that sample is reflected Light is by the second filter transmission and the 3rd filter transmission, into light intensity detection unit;
The light intensity detection unit includes:3rd lens, aperture and electrooptical device, it is saturating that the aperture is in the 3rd The focal point of mirror;The laser of 3rd filter transmission is radiated at through small holes by aperture again through the 3rd lens focus after convergence On electrooptical device, received and detect by photoelectric detector.
Second optical filter, the 3rd optical filter be arranged in parallel and at 45 ° with light path, second optical filter and Three optical filters be 45 ° of dichroic mirrors, the second optical filter reflection laser and transmission Raman light, the 3rd filter transmission laser and reflect drawing Graceful light.
Above-mentioned Raman probe, when sample is not in the focal point of the Raman probe, laser will be assembled by light path At the front or behind of aperture, only fraction luminous energy is by aperture, and sample focal point is more remote, can be got over by the reflected light of aperture It is few;Only when laser facula is just focused on object, the hot spot of the laser of reflection will converge at aperture, Ji Huquan by light path The reflection luminous energy in portion will be by aperture, and the light intensity signal that electrooptical device is received is maximum.Due to the spatial selectivity of aperture, Under focusing state, most of energy can be by aperture, and now to obtain light intensity maximum for electrooptical device.
Measurement distance is automatically adjusted to most there is provided a kind of above-mentioned Raman probe composition according to the third aspect of the invention we The Raman signal detection system of good state, including Raman probe, numerical control displacement sample stage, controller;The Raman probe is installed In on numerical control displacement sample stage, Raman probe can be relatively moved with numerical control displacement sample stage, the signal output of the Raman probe Side is provided with light intensity detection unit;The output end of the light intensity detection unit is connected to controller, controller driving numerical control displacement sample Sample platform changes measurement distance, judges whether measurement distance is optimal according to the change of the light intensity detection element output signal.
According to the fourth aspect of the invention there is provided a kind of Raman signal detection method, methods described step is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, become directional light by the first lens, so Purification process is carried out to spectrum by the first optical filter afterwards, then by the second filter transmission, finally by the 4th lens by laser Focus on sample;
D) Raman scattering occurred after laser excitation for sample, scattered light and reflected light opposite direction enter Raman probe by 4th lens are collected, and Raman diffused light therein passes through the lens set that is made up of the 3rd optical filter and the 4th optical filter, then via Second lens are assembled and are coupled into optical fiber;The lens set that non-Raman signal light is made up of the 3rd optical filter and the 4th optical filter is hindered Gear suppresses, therefore can not reach the second lens, wherein the laser reflected by sample enters light after the 3rd filter transmission Strong probe unit;
E) light intensity detection unit outputs a signal to controller, and via controller control numerical control displacement sample stage is moved, until The signal being collected into is maximum, completes focusing.
According to the fifth aspect of the invention there is provided another measurement distance that automatically adjusts to the Raman signal of optimum state Detection method, methods described step is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, become directional light by the first lens, so Purification process is carried out to spectrum by the first optical filter afterwards, then by the reflection of the second optical filter, finally by the 4th lens by laser Focus on sample;
D) Raman scattering occurred after laser excitation for sample, scattered light and reflected light opposite direction enter Raman probe by 4th lens are collected, and Raman diffused light therein is made up of the second filter transmission through the 3rd optical filter and the 4th optical filter Lens set, then it is coupled into optical fiber via the convergence of the second lens;Non- Raman signal light is by the 3rd optical filter and the 4th optical filter structure Into lens set stop suppression, therefore the second lens can not be reached, wherein the laser reflected by sample is filtered by second Piece low transmission again through the 3rd optical filter it is highly transmissive after enter light intensity detection unit;
E) light intensity detection unit outputs a signal to controller, and via controller control numerical control displacement sample stage is moved, until The signal being collected into is maximum.
Compared with prior art, the present invention has following beneficial effect:
Technological innovation in the present invention avoids manually operated, can automatically adjust measurement distance to optimum state, Make Raman signal maximize and stably;In contrast to the probe of existing commercial increase fixed range sleeve, the technology of the present invention can The uneven sample of rough surface is directly detected, without sample pre-treatments.
Brief description of the drawings
By reading the detailed description made with reference to the following drawings to non-limiting example, further feature of the invention, Objects and advantages will become more apparent upon:
Fig. 1 can automatically adjust measurement distance for one embodiment of the invention and show to the structure of the Raman detection device of optimum state It is intended to;
Fig. 2 is that another embodiment of the present invention can automatically adjust measurement distance to the structure of the Raman detection device of optimum state Schematic diagram;
Fig. 3 is displacement adjustment device regulation flow process figure in one embodiment of the invention;
Fig. 4 is the distance between Raman probe and sample and the Raman signal intensity and the relation curve of light intensity that measure;
In figure:100 be Raman probe, and 200 be numerical control displacement sample stage, and 300 be controller;1 is optical fiber, and 2 be first saturating Mirror, 3 be the first optical filter, and 5 be the 4th lens, and 6 ', 6 " be the second optical filter, and 7 ', 7 " be the 3rd optical filter, and 8 filter for the 4th Piece, 9 be the second lens, and 10 be light intensity detection unit, and 11 be sample, and 12 be sample stage, and 13 be controller, and 14 be the 3rd lens, 15 be aperture, and 16 be photoelectric detector.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
As shown in figure 1, in a preferred embodiment of the invention, measurement distance can be automatically adjusted to the Raman of optimum state Detection device includes Raman probe 100, numerical control displacement sample stage 200, controller 300;The Raman probe 100 is installed on numerical control On displacement sample stage 200, Raman probe 100 can be relatively moved with numerical control displacement sample stage 200.
Wherein described Raman probe 100 includes the first lens, the first optical filter, the second optical filter, the 4th lens, the 3rd Optical filter, the 4th optical filter, the second lens, light intensity detection unit.
In figure:By the first lens 2, the first optical filter 3, the second optical filter 6 ', the structure of the 4th lens 5 as Laser Focusing Into conduction laser module one, by being used as the 4th lens 5 of Raman light collection, the second optical filter 6 ', the 3rd optical filter 7 ', Conduction Raman light and suppress spuious optical assembly two that four optical filters 8, the second lens 9 are constituted, by being used as the 4th of laser alignment The laser automatic measuring that lens 5, the second optical filter 6 ', the 3rd optical filter 7 ', light intensity detection unit 10 are constituted is away from focusing component three.Group Part one, component two and component three constitute Raman probe 100, and the Raman probe 100 is installed on numerical control displacement sample stage 200.
The first lens 2, the first optical filter 3, the second optical filter 6 ' and the 4th are set gradually along the direction of the output light of optical fiber 1 Lens 5, the first lens 2, the first optical filter 3, the 4th lens 5 are vertical with light path, and the second optical filter 6 ' and light path are into 45 degree, by sample Product 11 scatter or reflect after light opposite direction after the 4th lens 5, reflected by the second optical filter 6 ', it is anti-along the second optical filter 6 ' Penetrate optical path direction and the 3rd optical filter 7 ', light intensity detection unit 10 be set, the 3rd optical filter 7 ' be arranged in parallel with the second optical filter 6 ', The 4th optical filter 8 and the second lens 9 are set gradually along the 3rd optical filter 7 ' reflection light direction, the opposite side of the second lens 9 is set Put optical fiber.4th optical filter 8 and the second lens 9 are vertical with light path, are set successively along the transmitted light path side of the 3rd optical filter 7 ' The 3rd lens 14, aperture 15 and electrooptical device 16 are put, the 3rd lens 14, aperture 15 and electrooptical device 16 are constituted Light intensity detection unit 10.
Laser output shown in Fig. 1 is placed in left channel, and laser enters after Raman probe 100 from the conduction of optical fiber 1, by the One lens 2 are become directional light, then carry out purification process to spectrum by the first optical filter 3, through the second optical filter 6 ' thoroughly Penetrate, finally by the 4th lens 5 by Laser Focusing in sample;After laser excitation Raman scattering is occurred for sample 11, is dissipated Penetrate light and reflected light opposite direction is collected into Raman probe 100 by the 4th lens 5, Raman diffused light therein is through the second optical filter 6 ' reflections and the reflection of the 3rd optical filter 7 ', are coupled into through the 4th vertical optical filter 8 of light path, then via the convergence of the second lens 9 Enter optical fiber, the lens set that non-Raman signal light is made up of the 3rd optical filter 7 ' and the 4th optical filter 8 stops suppression, therefore can not The second lens 9 are reached, wherein the laser reflected by sample is transmitted by the 3rd optical filter 7 ', into light intensity detection unit 10;
The light intensity detection unit 10 includes:3rd lens 14, aperture 15 and electrooptical device 16, the aperture 15 Focal point in the 3rd lens 14;The laser of 3rd optical filter 7 ' transmission is focused on through the 3rd lens 14, again through too small after convergence Hole 15, is radiated on electrooptical device 16 by aperture 15, and detection is received by photoelectric detector 16.
The signal of light intensity detection unit 10 delivers to controller 300, controller 300 after preposition processing, amplification, AD conversion It is believed that whether number multilevel iudge sample is in focal point, if not in focal point, sending instruction control numerical control displacement sample stage 200 and making Corresponding displacement, it is so repeated multiple times, until sample regulation is at probe focal length or in the accuracy rating of setting.Meanwhile, numerical control Displacement sample stage 200 can also carry out the regulation of other bidimensional, so that probe is operated on a fixed pan.
As shown in Fig. 2 in second of embodiment of the invention, Raman probe includes the first lens, the first optical filter, the Two optical filters, the 4th lens, the 3rd optical filter, the 4th optical filter, the second lens, light intensity detection unit;Laser output is vertical In left channel, different mounting conditions are applicable to.The first lens 2, first are set gradually along the direction of the output light of optical fiber 1 Optical filter 3, the second optical filter 6 ", the first lens 2, the first optical filter 3 are vertical with light path, and the second optical filter 6 " and light path are into 45 Degree, along the second optical filter 6 " reflected light path direction set the 4th lens 5, by sample 11 scatter or reflect after light opposite direction warp Cross after the 4th lens 5, transmitted by the second optical filter 6 ", set gradually the 3rd optical filter 7 " along transmitted light path direction and light intensity is visited Unit 10 is surveyed, the 3rd optical filter 7 " be arranged in parallel with the second optical filter 6 ", set successively along the 3rd optical filter 7 " reflection light direction Put the 4th optical filter 8 and the second lens 9, the opposite sides of the second lens 9 sets optical fiber, the 4th optical filter 8 and the second lens 9 with Light path is vertical.The 3rd lens 14, aperture 15 and opto-electronic conversion are set gradually along the transmitted light path side of the 3rd optical filter 7 " Device 16, the 3rd lens 14, aperture 15 and electrooptical device 16 constitute light intensity detection unit 10.
Laser enters after Raman probe 100 from the conduction of optical fiber 1, and directional light is become by the first lens 2, then by the One optical filter 3 carries out purification process to spectrum, then by with directional light in 45 ° of settings the reflection of the second optical filters 6 ", it is last by 4th lens 5 are by Laser Focusing in sample;Raman scattering, scattered light and reflection are occurred after laser excitation for sample 11 Light opposite direction is collected into Raman probe 100 by the 4th lens 5, and Raman diffused light therein passes through the second optical filter 6 ", by the Three optical filters 7 " reflect, by fourth optical filter 8 vertical with light path, then are coupled into optical fiber via the convergence of the second lens 9, non- The lens set that Raman signal light is made up of the 3rd optical filter 7 " and the 4th optical filter 8 stops suppression, therefore can not reach second Lens 9, wherein the laser reflected by sample is transmitted by the transmission of the second optical filter 6 " and the 3rd optical filter 7 ", are visited into light intensity Survey unit 10.
It should be noted that in order to reach second, third optical filter used in foregoing function and purpose, Fig. 1,2 Spectral characteristic is otherwise varied, and optical filter 6 ', 7 ' shown in Fig. 1 reflects Raman light for transmission laser;Optical filter 6 " shown in Fig. 2 reflects Laser and transmission Raman light, the transmission laser of optical filter 7 " and reflect Raman light.
In order that structure is compacter, reduce part, reduce cost, the second lens 5 are used as the laser in component one simultaneously The laser collimator lens in Raman light collecting lens, component three in condenser lens, component two, i.e., same lens, due to light The invertibity on road, the role of the different types of light that the lens pass through it for positive direction and opposite direction is simultaneously differed, from Functionally divide into focusing laser, collect Raman light and collimation laser.Specific part 5 as shown in Figure 1.4th lens 5 can be with Light path is vertically arranged, can also other set-up modes.
As shown in figure 1, the light intensity detection unit 10 includes the 3rd lens 14, the aperture with the identical focal length of the 4th lens 5 15 and electrooptical device 16.The light intensity detection unit 10 collects the light intensity of light path to detect, and inputs a signal into control Device 300, numerical control displacement sample stage 200 is adjusted by controller 300, until light intensity is maximum.Specifically, conduction Raman light and suppression are miscellaneous The laser of astigmatism component is first passed through after the 3rd lens 14 as the focal length of the 4th lens 5 are assembled again through small holes 15, most Detection is received by photoelectric detector 16 afterwards.The electrooptical device 16 can use photocell, photodiode, PSD, CCD or other light intensity detection devices.As shown in Figure 1, the 4th lens 5, the second optical filter 6 and the 3rd optical filter 7, the 3rd lens 14 image in the focal plane image of the 4th lens 5 in its conjugate planes and on aperture 14;Due to the spatial selectivity of aperture, to coke-like Under state, most of energy can be by aperture 14, and now to obtain light intensity maximum for photoelectric detector 16.
The principle of light intensity detection unit described in above-described embodiment 10 is identical, by taking embodiment illustrated in fig. 1 as an example, light intensity detection The specific works of unit 10 are:
A) laser action focused on through beam path alignment is on sample;
B) laser after being reflected through object, Raman collection is carried out through the 4th lens 5, through the second optical filter of 45 degree of placements 6 ', and partly reflected on the 3rd optical filter 7 ', reflected light is focused on through the 3rd lens 14, and opto-electronic conversion is radiated at by aperture 15 On device 16;3rd lens 14 are consistent with the focal length of the 4th lens 5;The aperture 15 is in the focal point of the 3rd lens 14;
C) when sample is not at probe focus, the laser of reflection by converged at by light path aperture 15 front or At rear, only fraction luminous energy is by aperture 15, and sample focal point is more remote, can be fewer by the reflected light of aperture;Only work as laser When hot spot is just focused on object (now hot spot is minimum, i.e., in focusing state), the hot spot of the laser of reflection will pass through light Road converges at aperture 15, and most reflection luminous energy will be by aperture 15, and the light intensity signal that detector is received is maximum.
Light intensity detection unit 10 in embodiment illustrated in fig. 2 is realized essentially identical with above-mentioned, no longer describes in detail herein.
In another preferred embodiment of the invention, in the numerical control displacement sample stage 200 provided with displacement adjustment device and Sample stage 12, the displacement adjustment device is a kind of precise adjusting device that can be moved in three-dimensional, and referring in particular to can be mobile in three-dimensional Step motor control or piezoelectric ceramics control three-dimensional moving device.Because probe and sample have relative motion, it will can visit Head is fixed, and sample makees three-dimensional mobile, in turn can also fix sample, probe makees three-dimensional motion, or can also take spy Head makees the mode that motion in one dimension is combined with sample as two dimensional motion, and sample makees two dimension in the plane vertical with probe output beam The situation of relative movement is particularly suitable for the situation for needing to be scanned multiple positions detection, such as when Raman and thin-layer chromatography , it is necessary to carry out raman spectroscopy measurement to being deployed in multiple position samples on lamellae when being combined etc. technology.
In the above embodiment of the present invention can auto-focusing Raman signal detection system, the displacement adjustment device can be with Raman probe 100 and sample stage 12 are fixedly connected, and Raman probe 100 can be relatively moved with sample stage 12.
In further embodiment of the present invention, based on detection device shown in Fig. 1, what it was used automatically adjusts measurement Distance arrives the Raman signal detection method of optimum state, and step is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, become directional light by the first lens, so Purification process is carried out to spectrum by the first optical filter afterwards, then by the second filter transmission, finally by the 4th lens by laser Focus on sample;
D) Raman scattering occurred after laser excitation for sample, scattered light and reflected light opposite direction enter Raman probe by 4th lens are collected, and Raman diffused light therein passes through the lens set that is made up of the 3rd optical filter and the 4th optical filter, then via Second lens are assembled and are coupled into optical fiber;The lens set that non-Raman signal light is made up of the 3rd optical filter and the 4th optical filter is hindered Gear suppresses, therefore can not reach the second lens, wherein the laser reflected by sample enters light after the 3rd filter transmission Strong probe unit;
E) light intensity detection unit outputs a signal to controller, and via controller control numerical control displacement sample stage is moved, until The signal being collected into is maximum.
Similar, based on the detection device shown in Fig. 2, what it was used automatically adjusts measurement distance to the Raman of optimum state Signal detection method, is comprised the following steps that:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, become directional light by the first lens, so Purification process is carried out to spectrum by the first optical filter afterwards, then by the reflection of the second optical filter, finally by the 4th lens by laser Focus on sample;
D) Raman scattering occurred after laser excitation for sample, scattered light and reflected light opposite direction enter Raman probe by 4th lens are collected, and Raman diffused light therein is made up of the second filter transmission through the 3rd optical filter and the 4th optical filter Lens set, then it is coupled into optical fiber via the convergence of the second lens;Non- Raman signal light is by the 3rd optical filter and the 4th optical filter structure Into lens set stop suppression, therefore the second lens can not be reached, wherein the laser reflected by sample is filtered by second Piece low transmission again through the 3rd optical filter it is highly transmissive after enter light intensity detection unit;
E) light intensity detection unit outputs a signal to controller, and via controller control numerical control displacement sample stage is moved, until The signal being collected into is maximum.
In above-described embodiment, controller is realized using computer, and the amplified circuit of signal, the AD of electrooptical device 16 turn Swap-in enters computer, and (such as machine command displacement adjusting means is vertical by the movement of operation control displacement adjustment device for computer Direction propulsion etc.), until the signal being collected into is maximum, now complete focusing.
In a preferred embodiment of the invention, the displacement adjustment device being related in above-mentioned detection device carries out adjustment of displacement When according to following steps, as shown in Figure 3:
A) Raman probe is located at the outer 3-5mm of the outer focal length of sample stage, and initial beam intensity signal is x0
B) command displacement adjusting means often moves down a step pitch, and now light intensity signal is x for measurementi
C) as the adjacent difference of light intensity signal twice xi-xi-1During more than 0, continue the movement of command displacement adjusting means, until xi- xi-1Less than 0, displacement controller control reverse movement;
D) according to actual precision of focusing, it can control x during step c)i-xi-1Step value is reduced during less than 0, and it is repeatedly many It is secondary, until light intensity difference is less than the minimum value esp of setting.
Fig. 4 is the experimental result using apparatus of the present invention:The distance between Raman probe 100 and sample 11 and the drawing measured The relation of graceful signal intensity and light intensity.As seen from the figure, light intensity occur the distance and position exactly Raman signal maximum of extreme value away from Off normal and put.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (8)

1. a kind of Raman probe, it is characterised in that including the first lens, the first optical filter, the second optical filter, the 4th lens, Three optical filters, the 4th optical filter, the second lens, light intensity detection unit;Wherein:Laser enters after Raman probe from fiber optic conduction, Become directional light by the first lens, purification process is then carried out to spectrum by the first optical filter, it is saturating through the second optical filter Penetrate, finally by the 4th lens by Laser Focusing in sample;Raman scattering, scattered light are occurred after laser excitation for sample Collected with reflected light opposite direction into Raman probe by the 4th lens, Raman diffused light therein is through the second optical filter reflection and the Three optical filters reflect, through fourth optical filter vertical with light path, then are coupled into optical fiber, non-Raman via the convergence of the second lens The lens set that flashlight is made up of the 3rd optical filter and the 4th optical filter stops suppression, therefore can not reach the second lens, its The middle laser reflected by sample is by the 3rd filter transmission, into light intensity detection unit;
The light intensity detection unit includes:3rd lens, aperture and electrooptical device, the aperture are in the 3rd lens Focal point;The laser of 3rd optical filter reflection is radiated at photoelectricity through small holes by aperture again through the 3rd lens focus after convergence On switching device, the device that is photoelectrically converted receives detection;
Second optical filter, the 3rd optical filter are dichroic mirror, be arranged in parallel and at 45 ° with light path, the second optical filter, the 3rd filter The highly transmissive laser of mating plate and high reflection Raman light.
2. a kind of Raman probe, it is characterised in that including the first lens, the first optical filter, the second optical filter, the 4th lens, Three optical filters, the 4th optical filter, the second lens, light intensity detection unit;Wherein:Laser enters after Raman probe from fiber optic conduction, Become directional light by the first lens, purification process then is carried out to spectrum by the first optical filter, then sequentially pass through and light Road in 45 ° of settings the reflection of the second optical filters, it is last by the 4th lens by Laser Focusing in sample;Sample is by laser Raman scattering occurs after exciting, scattered light and reflected light opposite direction are collected into Raman probe by the 4th lens, Raman therein Scattered light passes through the second optical filter, is reflected by the 3rd optical filter, by fourth optical filter vertical with light path, then saturating via second Mirror is assembled and is coupled into optical fiber, and the lens set that non-Raman signal light is made up of the 3rd optical filter and the 4th optical filter stops suppression System, therefore the second lens can not be reached, wherein the laser reflected by sample is by the second filter transmission and the 3rd optical filter Transmission, into light intensity detection unit;
The light intensity detection unit includes:3rd lens, aperture and electrooptical device, the aperture are in the 3rd lens Focal point;The laser of 3rd filter transmission is radiated at photoelectricity through small holes by aperture again through the 3rd lens focus after convergence On switching device, the device that is photoelectrically converted receives detection;
Second optical filter, the 3rd optical filter are dichroic mirror, be arranged in parallel and at 45 ° with light path, the second optical filter high reflection Laser and highly transmissive Raman light, the 3rd highly transmissive laser of optical filter and high reflection Raman light.
3. the Raman probe according to claim any one of 1-2, it is characterised in that when sample is not visited in the Raman During the focal point of head, laser will be converged at the front or behind of aperture by light path, and only fraction luminous energy passes through aperture, sample Focal point is more remote, can be fewer by the reflected light of aperture;Only when laser facula is just focused on object, the laser of reflection Hot spot will converge at aperture by light path, and most reflection luminous energy will be by aperture, the light that electrooptical device is received Strong signal is maximum.
4. a kind of Raman signal detection system for including any one of the claim 1-3 Raman probe, it is characterised in that described System includes Raman probe, numerical control displacement sample stage, controller;The Raman probe is installed on numerical control displacement sample stage, is drawn Graceful probe can be relatively moved with numerical control displacement sample stage, and the signal output side of the Raman probe is provided with light intensity detection unit;Institute The output end for stating light intensity detection unit is connected to controller, and controller driving numerical control displacement sample stage changes measurement distance, according to The change of the light intensity detection element output signal judges whether measurement distance is optimal.
5. Raman signal detection system according to claim 4, it is characterised in that be provided with the numerical control displacement sample stage Displacement adjustment device and sample stage, the displacement adjustment device are a kind of precise adjusting device that can be moved in three-dimensional, the displacement Adjusting means is fixedly connected with Raman probe and sample stage, and Raman probe can be relatively moved with sample stage.
6. a kind of Raman signal detection method of Raman probe described in use claim 1, it is characterised in that methods described step It is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, directional light, Ran Houjing are become by the first lens Cross the first optical filter and purification process is carried out to spectrum, then by the second filter transmission, finally by the 4th lens by Laser Focusing In sample;
D) Raman scattering is occurred after laser excitation for sample, and scattered light and reflected light opposite direction enter Raman probe by the 4th Lens are collected, and Raman diffused light therein is reflected by the second optical filter, the eyeglass constituted through the 3rd optical filter and the 4th optical filter Group, then it is coupled into optical fiber via the convergence of the second lens;What non-Raman signal light was made up of the 3rd optical filter and the 4th optical filter Lens set stops suppression, therefore can not reach the second lens, wherein the laser reflected by sample is low by the second optical filter Reflection again through the 3rd optical filter it is highly transmissive after enter light intensity detection unit;
E) light intensity detection unit outputs a signal to controller, via controller control numerical control displacement sample stage movement, until collecting The signal arrived is maximum.
7. a kind of Raman signal detection method of Raman probe described in use claim 2, it is characterised in that methods described step It is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in above numerical control displacement sample stage and be more than at Raman probe focal length;
C) open laser and export a laser, enter Raman probe through optical fiber, directional light, Ran Houjing are become by the first lens Cross the first optical filter and purification process is carried out to spectrum, then by the reflection of the second optical filter, finally by the 4th lens by Laser Focusing In sample;
D) Raman scattering is occurred after laser excitation for sample, and scattered light and reflected light opposite direction enter Raman probe by the 4th Lens are collected, and Raman diffused light therein is by the second filter transmission, the eyeglass constituted through the 3rd optical filter and the 4th optical filter Group, then it is coupled into optical fiber via the convergence of the second lens;What non-Raman signal light was made up of the 3rd optical filter and the 4th optical filter Lens set stops suppression, therefore can not reach the second lens, wherein the laser reflected by sample is low by the second optical filter Transmission again through the 3rd optical filter it is highly transmissive after enter light intensity detection unit;
Light intensity detection unit outputs a signal to controller, via controller control numerical control displacement sample stage movement, until being collected into Signal it is maximum.
8. the Raman signal detection method according to claim 6 or 7, it is characterised in that the controller control numerical control position Sample stage movement is moved, the numerical control displacement sample stage is provided with displacement adjustment device and sample stage, and the displacement adjustment device is carried out According to following steps during adjustment of displacement:
A) Raman probe is located at the outer 3-5mm of the outer focal length of sample stage, and initial beam intensity signal is x0
B) command displacement adjusting means moves down a step pitch, and now light intensity signal is x for measurementi
C) as the adjacent difference of light intensity signal twice xi-xi-1During more than 0, continue the movement of command displacement adjusting means, until xi-xi-1 Less than 0, displacement controller control reverse movement;
D) according to actual precision of focusing, it can control x during step c)i-xi-1Step value is reduced during less than 0, and it is repeated multiple times, directly It is less than the minimum value esp of setting to light intensity difference.
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