CN217112030U - Picosecond time resolution laser Raman spectrum measuring device - Google Patents
Picosecond time resolution laser Raman spectrum measuring device Download PDFInfo
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- CN217112030U CN217112030U CN202123248249.9U CN202123248249U CN217112030U CN 217112030 U CN217112030 U CN 217112030U CN 202123248249 U CN202123248249 U CN 202123248249U CN 217112030 U CN217112030 U CN 217112030U
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Abstract
The utility model relates to a Raman spectrum measuring device, in particular to a picosecond time resolution laser Raman spectrum measuring device, which solves the technical problems of low time resolution and high cost of the existing time resolution Raman spectrum detection; the picosecond time resolution laser Raman spectrum measuring device comprises a laser, a first light beam adjusting module, a second light beam adjusting module, an encoding module and an acquisition module; the first light beam adjusting module adjusts emergent light of the laser and then emits the adjusted emergent light to a sample to be detected; the second light beam adjusting module is used for receiving scattered light of the sample to be detected; the encoding module comprises a grating spectrometer, a first collimating mirror, a galvanometer unit, a multi-slit encoding template and a de-dispersion device which are sequentially arranged along an emergent light path of the second light beam adjusting module; the grating spectrometer is used for splitting scattered light emitted by a sample to be detected and emitting a spectral band; the cost of Raman spectrum testing is reduced, and the time resolution is improved.
Description
Technical Field
The utility model relates to a raman spectroscopy measuring device, concretely relates to picosecond time resolution laser raman spectroscopy measuring device.
Background
Laser raman spectroscopy is a powerful tool for detecting molecular characteristic information, and has been widely applied in the fields of chemical production, biomedicine, environmental protection, food safety and the like. However, for many samples, the laser excitation can generate a strong fluorescence signal, and in some cases, the intensity of the fluorescence signal may even be several orders of magnitude higher than that of the raman spectrum, which may cause the weak raman spectrum to be submerged in the fluorescence background, especially in the aspects of biomedicine, food illegal additive detection, pesticide detection, etc., the fluorescence phenomenon is particularly prominent, and in order to obtain a high-quality raman spectrum, a certain inhibition measure must be taken for fluorescence.
In recent years, researchers have proposed some novel laser raman spectroscopy techniques to eliminate or reduce fluorescence; for example, in a shift-frequency excitation Raman spectroscopy (SERDS), two lasers with similar wavelengths are used to excite a sample to be measured respectively to obtain two original Raman spectra, and the two original Raman spectra are subtracted to obtain a difference spectrum; because the fluorescence signal hardly changes with the change of the excitation wavelength, and the Raman spectrum moves closely following the change of the excitation wavelength, the fluorescence spectrum signal in the difference spectrum is almost completely eliminated, and the Raman spectrum can be reserved, and the Raman spectrum without the fluorescence background can be accurately reconstructed by a mathematical method. The SERDS technology has high requirements on stability and consistency in the test process, and if the test conditions of different wavelengths are slightly different, a foreign peak which does not belong to a sample to be tested may be generated in the reconstruction process; in addition, the use of ultraviolet laser (with wavelength less than 300nm) or infrared laser (with wavelength more than 800nm) as an excitation source can also reduce the fluorescence background to some extent, but has selectivity for the sample to be detected, and may not be applicable to some biological samples to be detected and cultural relic products.
Generally, the fluorescence life of a sample to be detected is in the range of hundreds of picoseconds (ps) to tens of nanoseconds (ns), the generation and duration of a Raman spectrum are in the ps magnitude, a short-pulse picosecond laser is used as a light source, a proper gating time window is set, the Raman spectrum and a fluorescence signal can be separately and respectively measured, a long-life fluorescence photon signal is removed in the data processing process, and the signal-to-noise ratio of the Raman spectrum can be effectively improved. At present, the existing time-resolved Raman spectrum mostly adopts an ICCD, an ICMOS and other surface detectors to realize Raman spectrum imaging detection, the cost is high, the time resolution is low, and only ns magnitude can be reached; the adoption of the SPAD array can realize picosecond time resolution Raman detection, but the time resolution of the SPAD array is low, and the cost is high.
SUMMERY OF THE UTILITY MODEL
The utility model aims at solving current time resolution raman spectroscopy and surveying, time resolution is low and with high costs technical problem, and provides a picosecond time resolution laser raman spectroscopy measuring device, realizes reducing the cost of raman spectroscopy test to improve time resolution.
For solving the technical problem, the utility model discloses the technical scheme who adopts does:
a picosecond time resolution laser Raman spectrum measuring device is characterized in that: the device comprises a laser, a first light beam adjusting module, a second light beam adjusting module, a coding module and an acquisition module;
the first light beam adjusting module adjusts emergent light of the laser and then emits the adjusted emergent light to a sample to be detected;
the second light beam adjusting module is used for receiving scattered light of the sample to be detected;
the coding module comprises a grating spectrometer, a first collimating mirror, a galvanometer unit, a multi-slit coding template and a dispersing device which are sequentially arranged along the emergent light path of the second light beam adjusting module;
the grating spectrometer is used for splitting scattered light emitted by a sample to be detected and emitting a spectral band;
the galvanometer unit is used for enabling the spectral band emitted by the grating spectrometer to be incident on the multi-slit coding template;
the multi-slit coding template is used for coding the spectral band emitted by the galvanometer unit;
the dispersion eliminating device is used for restoring the spectral band coded by the multi-slit coding template into composite light; the acquisition module comprises a single-point detector, a synchronous control unit and a control computer which are connected in sequence;
the single-point detector is positioned on an emergent light path of the dispersion eliminating device;
the single-point detector is used for converting the composite light restored by the de-dispersion device into an electric signal and transmitting the electric signal to the synchronous control unit;
the synchronous control unit is used for synchronously acquiring a laser pulse signal of the laser and an electric signal converted by the single-point detector and transmitting the electric signal into the control computer;
the control computer is used for decoding the laser pulse signals and the electric signals transmitted by the synchronous control unit.
Furthermore, the first light beam adjusting module comprises a first reflecting mirror, a second reflecting mirror, a beam expander, a third reflecting mirror and a fourth reflecting mirror which are sequentially arranged along the emergent light path of the laser;
the beam expander is used for intensively injecting the light beam reflected by the second reflector to the third reflector; the sample to be detected is positioned in an emergent light path of the fourth reflector;
the second beam conditioning module comprises a Cassegrain unit;
the Cassegrain unit is arranged on a scattering light path of the sample to be detected and is used for collecting scattering light of the sample to be detected.
Further, the cassegrain unit comprises a concave mirror and a convex mirror which are sequentially arranged along the scattering light path of the sample to be detected.
Furthermore, the first light beam adjusting module comprises a second collimating lens, a first focusing lens and a beam splitter which are sequentially arranged along the emergent light path of the laser;
the beam splitter is used for transmitting emergent light of the first focusing mirror to a sample to be detected and reflecting scattered light of the sample to be detected;
the second light beam adjusting module comprises a filter, a first reflector and a second focusing mirror which are sequentially arranged along the reflected light of the beam splitter;
the filter is used for filtering Rayleigh scattered light generated by the sample to be measured.
Further, the laser light source is monochromatic laser; the galvanometer unit consists of a galvanometer X and a galvanometer Y; the multi-slit coding template is a Hadamard transform light modulation coding template and consists of a plurality of light-transmitting or light-tight grooves at intervals, and the width of each groove is 5-200 mu m.
Compared with the prior art, the utility model discloses technical scheme's beneficial effect is:
1. the utility model relates to a picosecond time resolution laser raman spectrum measuring device adopts mirror unit, many slits coding template, decoloration ware, single-point detector, synchronous control unit and control computer, effectively filters the fluorescence noise among the raman spectrum, improves raman spectrum's SNR, makes picosecond time resolution laser raman spectrum measuring device's structure complexity lower, can realize picosecond time resolution raman spectrum, has low cost, the advantage of small volume.
2. The utility model relates to a picosecond time resolution laser raman spectrum detection device, through first speculum, second speculum, beam expander, third speculum, fourth speculum and cassegrain unit, make picosecond time resolution laser raman spectrum measurement device's detection distance can reach more than 10m, be applied to explosive detection and dangerous operation environment, can realize picosecond time resolution laser raman spectrum long-range detection, guarantee personnel and equipment safety in safe distance.
3. The utility model relates to a picosecond time resolution laser raman spectrum micro-measuring device adopts light second collimating mirror, first focusing mirror, beam splitter, filter, first speculum and second focusing mirror, makes picosecond time resolution laser raman spectrum measuring device's detection distance below 20cm, and the observable particle diameter is applied to medicine, drug detection and historical relic research at the sample that awaits measuring of mu m level.
Drawings
Fig. 1 is a schematic structural diagram of a first embodiment of the present invention;
fig. 2 is a schematic structural diagram of a second embodiment of the present invention;
fig. 3 is a schematic structural diagram of a 16-channel multi-slit coding template according to the first and second embodiments of the present invention;
fig. 4 is a schematic structural diagram of a galvanometer unit in a first embodiment and a second embodiment of the present invention;
the reference signs are:
1-a laser power supply, 2-a laser, 3-a first reflector, 4-a second reflector, 5-a beam expander, 6-a third reflector, 7-a fourth reflector, 8-a sample to be tested, 9-a convex mirror, 10-a concave mirror, 11-a grating spectrometer, 12-a first collimating mirror, 13-a vibrating mirror X, 14-a vibrating mirror Y, 15-a multi-slit coding template, 16-an anti-dispersion device, 17-a single-point detector, 18-a synchronous control unit, 19-a control computer, 20-a first focusing mirror, 21-a beam splitter, 22-a filter, 23-a second focusing mirror and 24-a second collimating mirror.
Detailed Description
The technical solutions of the present invention will be described more clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Example one
As shown in fig. 1, a picosecond time-resolved laser raman spectroscopy measurement apparatus includes a laser 2, a first beam adjustment module, a second beam adjustment module, a coding module, and an acquisition module;
the laser 2 and the synchronous control unit 18 are respectively and electrically connected with the laser power supply 1, and the emergent light of the laser 2 is adjusted and then is incident to the sample 8 to be measured by the first light beam adjusting module; the first light beam adjusting module is sequentially provided with a first reflector 3, a second reflector 4, a beam expander 5, a third reflector 6 and a fourth reflector 7 along the emergent light path of the laser 2; the beam expander 5 is used for intensively incidence the light beam reflected by the second reflector 4 to the third reflector 6; the sample 8 to be detected is positioned in the emergent light path of the fourth reflector 7;
the second light beam adjusting module is used for receiving scattered light of the sample 8 to be detected; the second light beam adjusting module is provided with a Cassegrain unit; the cassegrain unit is arranged on a scattering light path of the sample to be detected 8, and the cassegrain unit is sequentially provided with a concave mirror 10 and a convex mirror 9 along the scattering light path of the sample to be detected 8; for collecting scattered light from the sample 8 to be measured.
The encoding module is sequentially provided with a grating spectrometer 11, a first collimating mirror 12, a galvanometer unit, a multi-slit encoding template 15 and a dispersing device 16 along the emergent light path of the second light beam adjusting module; the grating spectrometer 11 is used for splitting scattered light emitted by the sample 8 to be measured and emitting a spectral band; the galvanometer unit is used for enabling the spectral band emitted by the grating spectrometer 11 to be incident on the multi-slit coding template 15; the multi-slit coding template 15 is used for coding the spectral band emitted by the galvanometer unit; the de-dispersion device 16 is used for reducing the spectral band coded by the multi-slit coding template 15 into composite light; the acquisition module is provided with a single-point detector 17, a synchronous control unit 18 and a control computer 19 which are connected in sequence; the single-point detector 17 is positioned on an emergent light path of the dispersion eliminating device 16; the single-point detector 17 is used for converting the composite light restored by the de-dispersion device 16 into an electrical signal and transmitting the electrical signal to the synchronous control unit 18; the synchronous control unit 18 is used for synchronously acquiring a laser pulse signal of the laser 2 and an electric signal converted by the single-point detector 17 and transmitting the electric signal into the control computer 19; the control computer 19 is used for decoding the laser pulse signal and the electric signal which are transmitted by the synchronous control unit 18.
Wherein, the light source of the laser 2 is monochromatic laser; as shown in fig. 4, the galvanometer unit is composed of a galvanometer X13 and a galvanometer Y14; the multi-slit coding module 15 plate is a coding template modulated by Hadamard transform light and consists of a plurality of light-transmitting or light-tight grooves at intervals, and the width of each groove is 5-200 mu m.
The working principle of the above embodiment is as follows:
the time-resolved Raman spectroscopy technology is that the fluorescence life of a sample 8 to be detected is in the range of hundreds of picoseconds (ps) to tens of nanoseconds (ns), the generation and duration of a Raman spectrum are in the magnitude of ps, a short-pulse picosecond laser 2 is used as a light source, a proper gating time window is set, the Raman spectrum and a fluorescence signal can be separated and respectively measured, a long-life fluorescence photon signal is removed in the data processing process, and the signal-to-noise ratio of the Raman spectrum can be effectively improved.
The utility model uses 532nm picosecond pulse laser 2 as excitation light source, after the detection laser is emitted through the laser 2, the detection laser is emitted to the beam expander 5 through the first reflector 3 and the second reflector 4, the laser facula is optimized to be proper in size, and the optimized light beam is emitted to the surface of the sample 8 to be measured through the third reflector 6 and the fourth reflector 7; the distance from the sample to be measured 8 to the fourth reflecting mirror 7 is 10m, and the concave mirror 10 and the convex mirror 9 of the cassegrain unit are controlled by the stepping motor to enable the cassegrain unit to be focused on the surface of the sample to be measured 8; scattered light on the surface of a sample 8 to be detected is collected by a Cassegrain unit and then is split by a grating spectrometer 11, a spectral band after splitting is incident to a mirror vibrating unit through a collimating mirror, the spectral band is mapped onto a multi-slit coding template 15 through the mirror vibrating unit controlled by a servo motor, the spectral band is coupled to a single-point detector 17 through a focusing mirror of a de-chromatic device 16 after being coded by the template, the single-point detector 17 converts composite light generated by the de-chromatic device 16 into an electric signal, the electric signal of the single-point detector 17 is compared with a laser pulse signal through a synchronous control unit 18, proper gating time is set, and data after a fluorescence signal is filtered are transmitted to a control computer 19.
The temporal light intensity signal can be converted into a spatial light intensity signal using a single point detector 17. However, the energy corresponding to a single wavelength is very weak, and the noise of the detector is relatively large, which inevitably results in a large measurement error if the energy at the single wavelength is detected. If different spectra are combined and detected in a certain mode, the signal-to-noise ratio of the measurement result can be greatly improved. The combined measurement of different wavelengths is achieved with a multi-slit encoded template 15. The radiation of multiple channels reaches the detector at the same time, so that the measurement signal is far larger than the noise signal, thereby improving the signal-to-noise ratio of the spectrometer system. As shown in fig. 3, the multi-slit code template 15 is composed of a plurality of light-transmitting or light-opaque recyclable notches, each notch has a width of 0.1mm, the light-transmitting notch is marked as 1, and the light-opaque notch is marked as 0.
When the multi-slit coding template 15 works, a vibration mirror unit is utilized to map a spectral band onto the multi-slit coding template 15, the vibration mirror unit controls projection to sequentially pass through different slits on the multi-slit coding template 15, and finally a single-point detector 17 collects composite light generated by a chromatic dispersion elimination device 16 and converts the composite light into an electric signal which is transmitted to a synchronous control unit 18; the control computer 19 decodes the laser pulse signal and the electric signal transmitted by the synchronous control unit 18 to obtain the raman spectrum.
Example two
As shown in fig. 2, the present embodiment is different from the first embodiment in that the first beam adjusting module includes a second collimating mirror 24, a first focusing mirror 20 and a beam splitter 21, which are sequentially arranged along the exit optical path of the laser 2; the beam splitter 21 is configured to transmit the emergent light of the first focusing mirror 20 to the sample 8 to be measured, and reflect the scattered light of the sample 8 to be measured;
the second light beam adjusting module comprises a filter 22, a first reflector 3 and a second focusing mirror 23 which are arranged in sequence along the reflected light of the beam splitter 21; the filter 22 is used for filtering rayleigh scattered light generated by the sample 8 to be measured.
The difference between the present embodiment and the first embodiment of the picosecond time-resolved laser raman spectroscopy measurement method is that,
the step 3 specifically comprises the following steps: the first light beam adjusting module adjusts and transmits a laser pulse signal emitted by the laser 2 to a sample 8 to be measured;
the monochromatic laser emitted by the laser 2 is incident to the beam splitter 21 through the second collimating lens 24 and the first focusing lens 20, and the beam splitter 21 transmits the emergent light of the first focusing lens 20 and reflects the emergent light to the filter 22;
the step 4 specifically comprises the following steps: the second light beam adjusting module receives scattered light of the sample 8 to be detected;
the filter 22 filters rayleigh scattered light generated by the sample 8 to be measured, and then the rayleigh scattered light enters the grating spectrometer 11 through the first reflecting mirror 3 and the second focusing mirror 23.
The remaining devices and methods of the second embodiment are the same as those of the first embodiment.
The working principle of the above embodiment is as follows:
the utility model uses 532nm picosecond pulse laser 2 as excitation light source, the detection laser is emitted through the laser 22 and then is focused to the surface of the sample 8 to be measured after passing through the second collimating lens 24, the first focusing lens 20 and the beam splitter 21, and the beam splitter 21 makes the detection distance of the picosecond time resolution laser Raman spectrum measuring device below 20 cm; the scattered light on the surface of the sample 8 to be measured is reflected by the beam splitter 21 and then filtered by the filter 22 to remove the rayleigh scattered light, after passing through the second focusing mirror 23, the spectrum band is coupled to the grating spectrometer 11, the spectrum band obtained by the light splitting of the grating spectrometer 11 is collimated by the second collimating mirror 24, and then is mapped onto the multi-slit coding template 15 by the vibrating mirror unit, after the spectrum band is coded by the multi-slit coding template 15, then coupled to a single-point detector 17 through a focusing lens of the achromatic device 16, the single-point detector 17 converts the composite light generated by the achromatic device 16 into an electric signal, the electrical signal of the single point detector 17 is compared with the laser pulse signal by a synchronization control unit 18, and setting proper gate control time, transmitting the data after filtering the fluorescence signal into a control computer 19, and decoding the laser pulse signal and the electric signal transmitted by the synchronous control unit 18 by the control computer 19 to obtain the Raman spectrum signal of the sample 8 to be detected for microscopic detection.
Claims (5)
1. The utility model provides a picosecond time resolution laser raman spectroscopy measuring device which characterized in that: the device comprises a laser (2), a first light beam adjusting module, a second light beam adjusting module, a coding module and an acquisition module;
the first light beam adjusting module adjusts emergent light of the laser (2) and then emits the adjusted emergent light to a sample (8) to be measured;
the second light beam adjusting module is used for receiving scattered light of a sample (8) to be detected;
the encoding module comprises a grating spectrometer (11), a first collimating mirror (12), a galvanometer unit, a multi-slit encoding template (15) and a decoloration device (16) which are sequentially arranged along an emergent light path of the second light beam adjusting module;
the grating spectrometer (11) is used for splitting scattered light emitted by the sample (8) to be detected and emitting a spectral band;
the galvanometer unit is used for enabling the spectral band emitted by the grating spectrometer (11) to be incident on the multi-slit coding template (15);
the multi-slit coding template (15) is used for coding the spectral band emitted by the galvanometer unit;
the de-dispersion device (16) is used for reducing the spectral band coded by the multi-slit coding template (15) into composite light; the acquisition module comprises a single-point detector (17), a synchronous control unit (18) and a control computer (19) which are connected in sequence;
the single-point detector (17) is positioned on an emergent light path of the dispersion eliminating device (16);
the single-point detector (17) is used for converting the composite light restored by the de-dispersion device (16) into an electric signal and transmitting the electric signal to the synchronous control unit (18);
the synchronous control unit (18) is used for synchronously acquiring a laser pulse signal of the laser (2) and an electric signal converted by the single-point detector (17) and transmitting the electric signal to the control computer (19);
the control computer (19) is used for decoding the laser pulse signals and the electric signals transmitted by the synchronous control unit (18).
2. The picosecond time-resolved laser raman spectroscopy apparatus of claim 1, wherein:
the first light beam adjusting module comprises a first reflector (3), a second reflector (4), a beam expander (5), a third reflector (6) and a fourth reflector (7) which are sequentially arranged along the emergent light path of the laser (2);
the beam expander (5) is used for intensively enabling the light beam reflected by the second reflector (4) to enter the third reflector (6); the sample (8) to be detected is positioned in an emergent light path of the fourth reflector (7);
the second beam conditioning module comprises a Cassegrain unit;
the Cassegrain unit is arranged on a scattering light path of the sample (8) to be detected and is used for collecting scattering light of the sample (8) to be detected.
3. The picosecond time-resolved laser raman spectroscopy apparatus of claim 2, wherein: the Cassegrain unit comprises a concave mirror (10) and a convex mirror (9) which are sequentially arranged along a scattering light path of a sample (8) to be detected.
4. The picosecond time-resolved laser raman spectroscopy apparatus of claim 1, wherein:
the first light beam adjusting module comprises a second collimating lens (24), a first focusing lens (20) and a beam splitter (21) which are sequentially arranged along an emergent light path of the laser (2);
the beam splitter (21) is used for transmitting emergent light of the first focusing mirror (20) to a sample (8) to be detected and reflecting scattered light of the sample (8) to be detected;
the second light beam adjusting module comprises a filter plate (22), a first reflecting mirror (3) and a second focusing mirror (23) which are sequentially arranged along the reflected light of the beam splitter (21);
the filter (22) is used for filtering Rayleigh scattered light generated by the sample (8) to be measured.
5. The picosecond time-resolved laser raman spectroscopy apparatus of any one of claims 1 to 4, wherein: the light source of the laser (2) is monochromatic laser;
the galvanometer unit consists of a galvanometer X (13) and a galvanometer Y (14);
the multi-slit coding template (15) is a Hadamard transform light modulation coding template and consists of a plurality of light-transmitting or light-tight grooves at intervals, and the width of each groove is 5-200 mu m.
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