CN111077060A - Single particle detection system based on Raman and laser-induced breakdown spectroscopy integration - Google Patents
Single particle detection system based on Raman and laser-induced breakdown spectroscopy integration Download PDFInfo
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Abstract
The invention discloses a Raman and laser-induced breakdown spectroscopy integration-based single particle detection system, which comprises an objective table, an illumination unit, a microscopic imaging unit, a Raman detection unit and a laser-induced breakdown spectroscopy detection unit, wherein the objective table is provided with a plurality of scanning points; the object stage is used for placing single particles and can two-dimensionally and precisely adjust the positions of the single particles, and the microscopic imaging unit is used for acquiring images of the single particles; the Raman detection unit comprises a continuous operation laser and a first spectrometer, the continuous operation laser irradiates the surface of the single particle, excites the vibration mode of molecules contained in the single particle and generates scattered photons with the frequency different from that of the excited light, and the first spectrometer records a Raman scattering spectrum to analyze the molecular information of the single particle; the laser-induced breakdown spectroscopy detection unit comprises a pulse laser and a second spectrometer, wherein the pulse laser generates high-energy nanosecond pulses, an electric field with high intensity instantaneously ionizes particles to be detected, and plasma is generated to emit light; the second spectrometer is used for detecting plasma luminescence and analyzing the element components of the single particles to be detected.
Description
Technical Field
The invention relates to the field of single particle detection, in particular to a single particle detection system based on Raman spectrum and laser-induced breakdown spectroscopy integration.
Background
In recent years, the rapid development of the modern industrialization level of China brings negative effects such as atmospheric environmental pollution and the like while improving the living standard of people in China. The concentration of airborne particulates is often one of the important indicators of the severity of pollution. The suspended particles mainly come from a plurality of factors such as daily power generation, industrial production, automobile exhaust emission and the like, and the forming mechanism is complex. Suspended particles (suspensions having particle diameters of not more than 75 μm) have been attracting high attention from various social circles as an important pollution source, have severely polluted the atmospheric environment and affected human health, and are included as main research objects in environmental management systems.
Research results show that the suspended particles are one of the biggest factors threatening human health due to atmospheric pollution, and are caused by the accumulation of a large amount of harmful heavy metals, acidic oxides, harmful organic substances, bacteria, germs and the like on the fine particles. Suspended particles of different particle sizes and compositions can cause different degrees of harm to human health. The floating time of the suspended particles with smaller particle sizes in the air is longer, after the suspended particles directly enter the body through the mouth and the nose of a human body, bacteria and viruses attached to the particles stimulate and destroy the tracheal mucosa of a respiratory system, so that the defense capacity of the mucosa is reduced, and the particles enter lung tissues. After the respiratory system of healthy people inhales particulate matters, the particulate matters are deposited in respiratory tracts and alveoli, so that inflammation is caused in nasal cavities and bronchi, and symptoms such as cough and the like are accompanied. For people suffering from respiratory diseases, due to the destructive effect of the particles, lung infection and serious damage are caused, and obstructive lesion is generated to cause symptoms of dyspnea, chest distress and the like. The toxic and harmful substances attached to the particles can cause great damage to the cardiovascular system of a human body, increase the thickness of the blood vessel intima, influence the blood supply of heart and brain, and cause diseases such as congestive heart failure, coronary artery and the like. Besides causing damage to the respiratory system of the human body, the suspended particulate matters also cause carcinogenic effect to the human body. The results of the study indicate that suspended particles from prolonged exposure to combustion are an important environmental factor in the increased mortality of cardiopulmonary disease and lung cancer. Because the suspended particle components contain a large amount of toxic and harmful substances and have large surface area and gaps, lung tissues of a human body are in a haze environment for a long time, so that lung cells are mutated to form lung cancer. Therefore, the analysis of the single particle components is beneficial to evaluating the harm of the single particle components to human health, and can analyze the main emission source of the single particle components, thereby preventing and controlling the single particle components from the source.
Various methods have been used for chemical analysis of PM, including energy dispersive x-ray spectroscopy (EDX), gas chromatography-mass spectrometry (GC-MS), inductively coupled plasma-emission spectroscopy (ICP-OES), inductively coupled plasma-mass spectrometry (ICP-MS). Previous studies on PM chemistry have focused primarily on collective particles, but there is now an increasing interest in single particle analysis because of the high heterogeneity of composition even for co-located sampled PM. By particle identification using Scanning Electron Microscopy (SEM) and chemical analysis by EDX, multi-element analysis of individual PMs can be performed, requiring complex sample preparation procedures, expensive instruments and highly trained operators. Single particle aerosol mass spectrometers (SPMS) are a relatively common single particle detection device that can perform chemical analysis on single particles but because the energy distribution of the laser used in the device is not uniform, when particles are ionized at different locations by the laser, the differences between the same particles are large, which can lead to poor repeatability of spectrogram detection. Therefore, there is a need to develop an in situ detection technique that is reproducible.
Disclosure of Invention
The laser induced breakdown plasma spectroscopy (LIBS) technology is one of the latest technologies for substance element analysis, and has the advantages of simple structure, operation, rapid and real-time detection, no need of sample pretreatment, realization of simultaneous detection of multiple elements and the like. The Raman spectrum technology is one of the dominant technologies of the detection and analysis of the molecular structure of a substance, particularly the molecular structure of an organic molecule, and information such as the vibration, rotation and the like of a molecular chemical bond is obtained by detecting an inelastic scattering spectrum, so that the molecular structure of the substance is effectively judged. The laser-induced plasma spectroscopy technology is applied to the analysis of the types and the contents of substance elements, the laser-induced plasma spectroscopy technology is applied to the detection of a chemical bond structure of a substance molecule, and the two detection means can be separated and can also be mutually supplemented. The invention provides a single particle detection system based on Raman and laser-induced breakdown spectroscopy integration, which can realize the dual detection functions of element and molecular information of particles.
The method aims to solve the problems of harsh detection environment requirement, complex pretreatment process, slow analysis rate, poor repeatability and the like in the existing single-particle detection technology. In order to solve the technical problems, the invention provides a Raman and laser-induced breakdown spectroscopy integration-based single particle detection system, which comprises an objective table, an illumination unit, a microscopic imaging unit, a Raman detection unit and a laser-induced breakdown spectroscopy detection unit; the lighting unit comprises an LED lamp, a low-pass filter, a reflector and a condenser; the LED lamp emits illumination light, the low-pass filter filters the illumination light with longer wavelength, the reflector reflects the illumination light to the condenser lens, and the condenser lens converges the illumination light on the surface of a sample to be detected on the objective table; the microscopic imaging unit comprises a first lens, a tube lens and an industrial camera; the Raman detection unit comprises a continuous operation laser, a first dichroic mirror, a second dichroic mirror, a third dichroic mirror, a high-pass filter, a second lens and a first spectrometer; laser beams emitted by the continuous operation laser device are reflected by the first dichroic mirror, pass through the second dichroic mirror and the third dichroic mirror in sequence and are focused on the surface of the single particle on the objective table by the first lens; the back-scattered Raman photons are collected by the first lens, then sequentially pass through the third dichroic mirror, the second dichroic mirror, the first dichroic mirror and the high-pass filter, and then are focused to a slit of a first spectrometer by the second lens, and the first spectrometer records the Raman spectrum of the single particle and analyzes the molecular information in the single particle; the laser-induced breakdown spectroscopy detection unit comprises a pulse laser, an optical fiber and a second spectrometer, wherein the optical fiber is provided with a collection port; high-energy nanosecond pulses generated by the pulse laser are reflected by the third dichroic mirror and focused on the surface of the single particle on the objective table by the first lens, and the single particle is instantaneously gasified and ionized and generates plasma for luminescence; photons emitted by the plasma are coupled into the optical fiber through the collecting port and transmitted to the second spectrometer, the second spectrometer records the laser-induced breakdown spectrum of the single particle, and element information in the single particle is analyzed from the characteristic spectral line.
Furthermore, the Raman and laser-induced breakdown spectroscopy integration-based single particle detection system provided by the invention has the advantages that the wavelength range of the continuously-operated laser is 532-785nm, the line width is less than 0.1nm, and the power is more than 20 mw.
The first dichroic mirror and the second dichroic mirror are both long-pass dichroic mirrors, and the third dichroic mirror is a short-pass dichroic mirror; the first dichroic mirror is used for reflecting the laser beam output by the continuous operation laser so as to allow Raman scattered photons with longer wavelength to pass through; the second dichroic mirror is used for reflecting the light emitted by the LED lamp so as to allow photons with a wavelength range between the illumination light and the Raman excitation light to pass through; the third dichroic mirror is used for reflecting 1064nm laser light emitted by the pulse laser, so as to allow photons with the wavelength below 1064nm to transmit.
The nanosecond laser pulse width generated by the pulse laser is less than 10ns, and the pulse energy is more than 30 mJ.
The first spectrometer is a raman spectrometer with a resolution of less than 0.1 nm.
The second spectrometer is a LIBS spectrometer and is provided with an ICCD camera for detecting photons emitted by the plasma, the spectral resolution is less than 0.1nm, and the spectral measurement range at least covers the wave band of 350-785 nm.
The collection port of the optical fiber is aligned with the focal point of the first lens.
The object stage is a three-dimensional precision adjusting platform.
Compared with the prior art, the Raman and laser-induced breakdown spectroscopy integration-based single particle detection system has the beneficial effects that:
(1) the detected object does not need to be specially pretreated;
(2) the detection speed is high, and the time for detecting one single particle is 0.6s on average;
(3) can detect the molecular composition and various element compositions of the detected object at the same time.
Drawings
Fig. 1 is a schematic structural diagram of an integrated single particle detection system based on raman and laser-induced breakdown spectroscopy according to an embodiment of the present invention.
In the figure: 1-a first spectrometer, 2-a second lens, 3-a high-pass filter, 4-a first dichroic mirror, 5-a second dichroic mirror, 6-a third dichroic mirror, 7-a first lens, 8-an objective table, 9-a condenser, 10-a reflector, 11-a low-pass filter, 12-an LED lamp, 13-a second spectrometer, 14-an optical fiber, 15-a collection port, 16-a pulse laser, 17-a camera, 18-a tube lens, and 19-a continuous operation laser.
Detailed Description
The design idea of the Raman and laser-induced breakdown spectroscopy integrated single particle detection system provided by the invention is that Raman laser is used for irradiating the surface of a single particle, molecules in a substance absorb part of energy, vibration of different modes and degrees is generated, then light with lower frequency is scattered, and the light is recorded by a Raman spectrometer. Different kinds of atomic groups have unique vibration modes and frequencies, so that scattered light with specific frequencies can be generated, and the kinds of molecules forming the substances are identified according to the principle; the method comprises the steps of utilizing strongly focused nanosecond pulse laser to break down single particles to be detected to generate high-temperature and high-density plasma, recording plasma luminescence by a high-resolution LIBS spectrometer, and analyzing plasma emission spectrum to determine substance components and content of a sample.
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
In an embodiment of the present invention, an integrated single particle detection system based on raman spectroscopy and laser-induced breakdown spectroscopy is provided, as shown in fig. 1, the single particle detection system includes: the device comprises an object stage 8, an illumination unit, a microscopic imaging unit, a Raman detection unit and a laser-induced breakdown spectroscopy detection unit.
The objective table 8 is a three-dimensional precision adjusting platform, and is used for bearing a sample to be measured and precisely adjusting the position of a single particle.
The lighting unit comprises an LED lamp 12, a low-pass filter 11, a reflector 10 and a condenser 9; the LED lamp 12 emits illumination light, the low-pass filter 11 filters the illumination light with longer wavelength, the reflector 10 reflects the illumination light to enter the condenser 9, and the condenser 9 converges the illumination light on the surface of the sample to be measured on the objective table 8; the low-pass filter 11 has a cutoff wavelength of 500 nm.
The microscopic imaging unit comprises a first lens 7, a tube lens 18 and an industrial camera 17; the combination of the first lens 7 and the tube lens 18 enlarges and images the particles to be measured at the focal plane of the first lens 7 on the surface of the detector of the industrial camera 17, and the industrial camera 17 collects the images of the particles.
The Raman detection unit comprises a continuous operation laser 19, a first dichroic mirror 4, a second dichroic mirror 5, a third dichroic mirror 6, a high-pass filter 3, a second lens 2 and a first spectrometer 1; the wavelength range of the continuous operation laser 19 is 532-785nm, the line width is less than 0.1nm, and the power is more than 20 mw; the first dichroic mirror 4 is a long-pass dichroic mirror with a cut-off wavelength of 532 nm; the second dichroic mirror 5 is a long-pass dichroic mirror with a cut-off wavelength lower than the operating wavelength of the continuously operating laser 19, and the third dichroic mirror 6 is a short-pass dichroic mirror with a cut-off wavelength of 1064 nm; the first dichroic mirror 4 is used for reflecting the laser beam output by the continuous operation laser 19, so as to allow longer-wavelength Raman scattered photons to pass through; the second dichroic mirror 5 is for reflecting light emitted by the LED lamp 12, thereby allowing photons in a wavelength range falling between the illumination light and the raman excitation light to pass therethrough; the third dichroic mirror 6 is used for reflecting the 1064nm laser light emitted by the pulse laser 16, so as to allow photons with the wavelength below 1064nm to pass through; the cut-off wavelength of the high-pass filter 3 is 532nm, photons of Raman excitation laser are blocked, and Raman scattering photons with long wavelength are allowed to penetrate through the high-pass filter; the first spectrometer 1 is a raman spectrometer, and the resolution of the raman spectrometer is less than 0.1 nm.
A 532nm laser beam emitted by a continuous operation laser 19 in the Raman detection unit is reflected by a first dichroic mirror 4, sequentially passes through a second dichroic mirror 5 and a third dichroic mirror 6, and is focused on the surface of a single particle on an objective table 8 by a first lens 7; the backscattered raman photons are collected by the first lens 7, pass through the third dichroic mirror 6, the second dichroic mirror 5, the first dichroic mirror 4 and the high-pass filter 3 in sequence, are focused to the slit of the first spectrometer 1 by the second lens 2, and the first spectrometer 1 records the raman spectrum of the single particle and analyzes the molecular composition information in the single particle.
The laser induced breakdown spectroscopy detection unit comprises a pulsed laser 16, an optical fiber 14 and a second spectrometer 13, wherein the optical fiber 14 is provided with a collection port 15. The pulse laser 16 is used for generating nanosecond laser pulses to breakdown the gas to be detected to generate plasma radiation and is an excitation light source for laser-induced breakdown spectroscopy, the pulse width of the generated nanosecond laser is less than 10ns, and the pulse energy is more than 30 mJ. The repetition frequency of the laser pulse is about 10Hz, and the pulse power stability is better than 2%. . One end of the optical fiber 14 is fixed to the collection port 15, the other end of the optical fiber is connected to the second spectrometer 13, the collection port 15 is placed above the single particle on the object stage 8, and not only is the position of the single particle aligned, but also the focus of the first lens 7 is aligned, so that the plasma luminescence photons are collected and coupled into the optical fiber 14; the second spectrometer 13 is used for detecting photons radiated by the plasma, so as to analyze the material composition of the single particle to be detected; the second spectrometer 13 is a LIBS spectrometer and includes an ICCD camera for detecting photons introduced through an optical fiber; the ICCD camera records the atomic emission spectrum, and information such as the type and the content of substances contained in the single particles to be detected can be analyzed by contrasting the peak position and the height of the characteristic spectral line. The second spectrometer 13 is used to separate photons of different wavelengths of the plasma radiation and record their photo-electric signals, thereby forming an atomic emission spectrum of helium in the gas to be measured. The second spectrometer 13 is capable of not only providing a spectral resolution of 0.1nm, but also recording atomic emission spectral measurements in the 350-785nm band.
High-energy nanosecond pulses generated by the pulse laser 16 in the laser-induced breakdown spectroscopy detection unit are reflected by the third dichroic mirror 6 and focused on the surface of the single particle on the objective table 8 by the first lens 7, and the single particle is instantaneously gasified and ionized to generate plasma for luminescence; photons emitted by the plasma are coupled into the optical fiber 14 through the collection port 15 and transmitted to the second spectrometer 13, the second spectrometer 13 records the laser-induced breakdown spectrum of the single particle, and the element information in the single particle is analyzed from the characteristic spectral line.
When detecting single particles, firstly placing the single particles to be detected on the object stage 8, and adjusting the object stage 8 according to the image collected by the industrial camera 17, so that the object to be detected is positioned at the target position; starting the continuous operation laser 19, enabling continuous laser to hit the surface of the single particle, exciting the vibration mode of molecules contained in the single particle, generating scattering photons with the frequency different from that of the excited light, recording a scattering spectrum by the first spectrometer 1, identifying the types of molecules forming the substance, and closing the continuous operation laser 19; the pulse laser 16 is started to generate high-energy nanosecond pulses, the high-intensity electric field of the high-energy nanosecond pulses instantly ionizes the particles to be detected and generates plasma to emit light, and the second spectrometer 13 detects the plasma to emit light and analyzes the element components of the single particles to be detected.
In the present embodiment, the short-pass filter 11 is used in cooperation with the second dichroic mirror 5 to prevent the illumination light from entering the raman spectrum detection system.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (8)
1. A single particle detection system based on Raman and laser-induced breakdown spectroscopy integration is characterized by comprising an objective table (8), an illumination unit, a microscopic imaging unit, a Raman detection unit and a laser-induced breakdown spectroscopy detection unit;
the lighting unit comprises an LED lamp (12), a low-pass filter (11), a reflector (10) and a condenser (9); the LED lamp (12) emits illumination light, the low-pass filter (11) filters the illumination light with longer wavelength, the reflector (10) reflects the illumination light to enter the condenser (9), and the condenser (9) converges the illumination light on the surface of a sample to be detected on the objective table (8);
the microscopic imaging unit comprises a first lens (7), a tube lens (18) and an industrial camera (17);
the Raman detection unit comprises a continuous operation laser (19), a first dichroic mirror (4), a second dichroic mirror (5), a third dichroic mirror (6), a high-pass filter (3), a second lens (2) and a first spectrometer (1); laser beams emitted by a continuous operation laser (19) are reflected by a first dichroic mirror (4), pass through a second dichroic mirror (5) and a third dichroic mirror (6) in sequence and are focused on the surface of a single particle on an objective table (8) by a first lens (7); the backscattered Raman photons are collected by a first lens (7), then sequentially pass through a third dichroic mirror (6), a second dichroic mirror (5), a first dichroic mirror (4) and a high-pass filter (3), and then are focused to a slit of a first spectrometer (1) by a second lens (2), and the Raman spectrum of single particles is recorded by the first spectrometer (1) and molecular information in the single particles is analyzed;
the laser induced breakdown spectroscopy detection unit comprises a pulse laser (16), an optical fiber (14) and a second spectrometer (13); the optical fiber (14) is provided with a collection port (15); high-energy nanosecond pulses generated by the pulse laser (16) are reflected by the third dichroic mirror (6) and focused on the surface of the single particle on the objective table (8) by the first lens (7), and the single particle is instantaneously gasified and ionized to generate plasma for luminescence; photons emitted by the plasma are coupled into the optical fiber (14) through the collecting port (15) and transmitted to the second spectrometer (13), the laser-induced breakdown spectrum of the single particle is recorded by the second spectrometer (13), and element information in the single particle is analyzed from characteristic spectral lines.
2. The integrated Raman and laser induced breakdown spectroscopy-based single particle detection system according to claim 1, wherein the continuously operated laser (19) has a wavelength in the range of 532- & 785nm, a line width of less than 0.1nm, and a power of more than 20 mw.
3. The integrated single particle detection system based on raman and laser-induced breakdown spectroscopy according to claim 1, wherein the first dichroic mirror (4) and the second dichroic mirror (5) are both long-pass dichroic mirrors, and the third dichroic mirror (6) is a short-pass dichroic mirror;
the first dichroic mirror (4) is used for reflecting the laser beam output by the continuous operation laser (19) so as to allow Raman scattered photons with longer wavelength to pass through;
a second dichroic mirror (5) for reflecting light emitted by the LED lamp (12) so as to allow the transmission of photons having a wavelength range falling between the illumination light and the Raman excitation light;
the third dichroic mirror (6) is used for reflecting the 1064nm laser light emitted by the pulse laser (16) so as to allow photons with the wavelength below 1064nm to pass through.
4. The integrated Raman and laser-induced breakdown spectroscopy-based single particle detection system according to claim 1, wherein the pulsed laser (16) generates nanosecond laser pulses having a pulse width of less than 10ns and a pulse energy of greater than 30 mJ.
5. The integrated single particle detection system based on raman and laser induced breakdown spectroscopy according to claim 1, wherein the first spectrometer (1) is a raman spectrometer with a resolution of less than 0.1 nm.
6. The integrated single particle detection system based on Raman and laser-induced breakdown spectroscopy as claimed in claim 1, wherein the second spectrometer (13) is a LIBS spectrometer equipped with an ICCD camera for detecting photons emitted by the plasma, the spectral resolution is less than 0.1nm, and the spectral measurement range covers at least the 350-785nm band.
7. The integrated single particle detection system based on raman and laser induced breakdown spectroscopy according to claim 1, wherein the collection port (15) of the optical fiber (14) is aligned with the focus of the first lens (7).
8. The integrated Raman and laser-induced breakdown spectroscopy-based single particle detection system according to claim 1, wherein the stage (8) is a three-dimensional fine adjustment platform.
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