WO2021007782A1 - Cavity ring-down spectrometer system - Google Patents

Cavity ring-down spectrometer system Download PDF

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Publication number
WO2021007782A1
WO2021007782A1 PCT/CN2019/096200 CN2019096200W WO2021007782A1 WO 2021007782 A1 WO2021007782 A1 WO 2021007782A1 CN 2019096200 W CN2019096200 W CN 2019096200W WO 2021007782 A1 WO2021007782 A1 WO 2021007782A1
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WIPO (PCT)
Prior art keywords
ring
cavity
beam splitter
output
optical
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PCT/CN2019/096200
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French (fr)
Chinese (zh)
Inventor
冯伟
张艳辉
张晨宁
冯亚春
尹铎
刘笑
Original Assignee
深圳先进技术研究院
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Application filed by 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Priority to PCT/CN2019/096200 priority Critical patent/WO2021007782A1/en
Publication of WO2021007782A1 publication Critical patent/WO2021007782A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/10—Arrangements of light sources specially adapted for spectrometry or colorimetry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/42—Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • G01J3/433—Modulation spectrometry; Derivative spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry

Definitions

  • This application belongs to the field of scientific research equipment manufacturing, and in particular relates to an optical cavity ring-down spectrometer system.
  • gas concentration detection there are many methods for gas concentration detection, including acoustic sensors, sensors based on traditional absorption spectroscopy, Raman spectroscopy sensors, mass spectrometry sensors, nuclear magnetic resonance sensors, and electrical sensors. Although these existing sensors play an important role in gas detection, they generally have the characteristics of low sensitivity and complicated operation, so their application in the detection of trace gas concentration has obvious limitations.
  • Cavity Ringdown Spectroscopy (CRDS) technology is an absorption spectroscopy technology that achieves high-sensitivity spectral detection by measuring the optical loss caused by sample scattering and absorption in an optical cavity.
  • CRDS technology can obtain high sensitivity; in addition, CRDS
  • the direct measurement parameter of the technology is not the absolute intensity change of the light intensity after the laser passes through the substance to be measured, but the exponential decay rate of the light intensity. Therefore, the CRDS technology is not sensitive to the fluctuation of the light source intensity.
  • the purpose of this application is to provide an optical cavity ring-down spectrometer system to improve the sensitivity of spectrum measurement.
  • the first aspect of the present application provides an optical cavity ring-down spectrometer system.
  • the system includes: a continuous laser, a first optical beam splitter coupled with the continuous laser, and an acousto-optic coupled with the first optical beam splitter.
  • a modulator and a wavelength meter a second optical beam splitter coupled with the acousto-optic modulator, a third optical beam splitter coupled with the second optical beam splitter, and a third optical beam splitter coupled with the third optical beam splitter
  • the ring-down cavity and the computer coupled with the ring-down cavity, the wavelength meter and the continuous laser, the inner two ends of the ring-down cavity are respectively provided with a first mirror and a second mirror, and the output end of the ring-down cavity Set up a piezoelectric ceramic tube, the piezoelectric ceramic tube is connected to the computer via a photoelectric conversion device;
  • the continuous laser is used to generate continuous laser light pumped by a solid laser and output to the first optical beam splitter;
  • the first light beam splitter is used to split the continuous laser light generated by the continuous laser into a first beam and a second beam through refraction and reflection, the first beam is output to the acousto-optic modulator, and the first beam Output two light beams to the wavelength meter;
  • the acousto-optic modulator is configured to modulate the light from the first light beam and output it to the second light beam splitter under the modulation of the acoustic signal;
  • the second light beam splitter is used to output the dimmed light beam splitter to the third light beam splitter through a lens
  • the third light beam splitter is used to output the dimmed light output by the lens to the ring-down cavity after being refracted;
  • the ring-down cavity is used for ring-down the dimmed light input by the third light beam splitter under the action of the first mirror and the second mirror, and then output to the photoelectric conversion device;
  • the photoelectric conversion device is used to convert the ring-down light signal output by the ring-down cavity into an electrical signal, the electrical signal is output to the acousto-optic modulator one way, and the other is output to the computer;
  • the piezoelectric ceramic tube is used to vibrate at a preset frequency under the action of a function generator, so that the longitudinal mode of the ring-down cavity can match the dimmed frequency input by the third light beam splitter .
  • a constant temperature gas channel is provided in the ring down cavity for inputting constant temperature gas into the ring down cavity and outputting from the ring down cavity.
  • the wavelength meter is used to monitor the wavelength of the continuous laser light generated by the continuous laser, and the monitoring signal generated thereby is output to the computer.
  • the computer is used to control the continuous laser to scan the laser frequency one by one to perform measurement under the action of the electrical signal output by the photoelectric conversion device and the monitoring signal.
  • the continuous laser is a continuous ring cavity Ti:Sapphire laser.
  • the nominal reflectivity of the first reflector and the second reflector is 99.995%, and the radius of curvature is 1 m.
  • the preset frequency is 100 Hz.
  • the cavity length of the ring-down cavity is 1.25 m.
  • system further includes a solid-state laser for pumping the continuous laser.
  • the output wavelength of the solid-state laser is 532 nanometers.
  • the continuous laser is coupled with the first optical beam splitter
  • the first optical beam splitter is coupled with the acousto-optic modulator and the wavelength meter
  • the ring-down cavity the wavelength meter and the continuous laser are coupled with the computer.
  • the laser control successive individual scans to measure the laser frequency, and therefore, can be highly accurate continuous wavelength scanning, spectral measurements to a 10 -
  • the 4 cm -1 level significantly improves the sensitivity of spectrum measurement.
  • FIG. 1 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by an embodiment of the present application
  • FIG. 2 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application.
  • FIG. 3 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application.
  • FIG. 4 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application.
  • Fig. 1 is a schematic diagram of the structure of an optical cavity ring-down spectrometer system provided by an embodiment of the present application. The detailed description is as follows:
  • the optical cavity ring-down spectrometer system illustrated in FIG. 1 includes a continuous laser 101, a first optical beam splitter 102 coupled with the continuous laser 101, an acousto-optic modulator 103 coupled with the first optical beam splitter 102, and a wavelength meter 104,
  • the second optical beam splitter 105 coupled with the acousto-optic modulator 103
  • the third optical beam splitter 106 coupled with the second optical beam splitter 105
  • the ring-down cavity 107 coupled with the third optical beam splitter 106
  • the ring-down cavity 107, the wavelength meter 104 and the computer 108 coupled with the continuous laser 101, the inner two ends of the ring-down cavity 107 are provided with a first mirror 109 and a second mirror 110 respectively, and the output end of the ring-down cavity 107 is set with piezoelectric ceramics Tube 111, piezoelectric ceramic tube 111 is connected to computer 108 via photoelectric conversion device 112, where:
  • the continuous laser 101 is used to generate continuous laser light pumped by the solid laser and output to the first optical beam splitter 102;
  • the first beam splitter 102 is used to split the continuous laser light generated by the continuous laser 101 into a first beam and a second beam by refraction and reflection, that is, the continuous laser light generated by the continuous laser 101 is refracted to obtain the first beam, that is, the continuous laser 101
  • the generated continuous laser light is reflected to obtain a second beam, the first beam is output to the acousto-optic modulator 103, and the second beam is output to the wavelength meter 104;
  • the acousto-optic modulator 103 is used to modulate the first light beam and output the dimmed light to the second light beam splitter 105 under the modulation of the acoustic signal;
  • the second light beam splitter 105 is used to output the dimmed light to the third light beam splitter 106 through the lens after being dimmed and reflected;
  • the third light beam splitter 106 is used to output the dimmed light output by the lens to the ring-down cavity 107 after being refracted;
  • the ring down cavity 107 is used to ring down the dimmed light input by the third light beam splitter 106 under the action of the first mirror 109 and the second mirror 110 and output to the photoelectric conversion device 112;
  • the photoelectric conversion device 112 is used to convert the ring-down light signal output by the ring-down cavity 107 into an electrical signal, the electrical signal is output to the acousto-optic modulator 103 and the other is output to the computer 108;
  • the piezoelectric ceramic tube 111 is used to vibrate at a preset frequency under the action of the function generator, so that the longitudinal mode of the ring-down cavity 107 can match the dimmed frequency input by the third light beam splitter 106.
  • the ring-down chamber 107 is provided with a constant temperature gas channel, as shown in the black circle in Figure 2.
  • the constant-temperature gas channel is used to input constant-temperature gas into the ring-down cavity 107 and output from the ring-down cavity 107.
  • the direction indicated by the arrow represents Direction of entry and exit of thermostatic gas.
  • the wavelength meter 104 is used to monitor the wavelength of the continuous laser light generated by the continuous laser 101, and the monitoring signal generated thereby is output to the computer 108.
  • the computer 108 is used to control the continuous laser 101 to scan the laser frequency one by one under the action of the electrical signal output by the photoelectric conversion device 112 and the monitoring signal output by the wavelength meter 104, where the continuous laser 101 is a continuous ring cavity Ti:Sapphire laser.
  • the nominal reflectivity of the first reflector 109 and the second reflector 110 may be 99.995%, and the radius of curvature may be 1 meter.
  • the preset frequency is 100 Hz.
  • the cavity length of the ring-down cavity 107 is 1.2 meters.
  • the optical cavity ring-down spectrometer system also includes a solid-state laser. As shown in FIG. 3, the solid-state laser is used to pump the continuous laser 101.
  • the output wavelength of the solid-state laser may be 532 nanometers.
  • the continuous laser is coupled with the first optical beam splitter, the first optical beam splitter is coupled with the acousto-optic modulator and the wavelength meter.
  • the ring-down cavity, wavelength meter and The continuous laser is coupled with the computer.
  • the computer controls the continuous laser to scan to the laser frequency one by one under the action of the electrical signal output by the photoelectric conversion device and the monitoring signal output by the wavelength meter. Therefore, high-precision continuous wavelength scanning can be realized.
  • the accuracy of the spectrum measurement can reach the level of 10 -4 cm -1 , which significantly improves the sensitivity of the spectrum measurement compared with the prior art.
  • Fig. 4 shows a schematic structural diagram of an optical cavity ring-down spectrometer system according to another embodiment of the present application, which will be described in detail below:
  • the continuous laser 101 can be the 899-21 continuous ring-cavity Ti:Sapphire laser produced by the American Coherent Company. It is pumped by a solid-state laser (Verdi-18) with an output wavelength of 532 nanometers and can cover the spectral range of 700 to 1000 nanometers. When 101 is working, its wavelength is monitored by a wavelength meter 104, such as a WA-1500 wavelength meter. After the laser light output by the continuous laser 101 passes through the acousto-optic modulator 103, it passes through the second beam splitter 105 and the third beam splitter 106 in turn, and then passes through the fiber coupler, the fiber, the fiber coupler and the two lenses in turn After the coupling, it is sent to the ring-down cavity 107.
  • a wavelength meter 104 such as a WA-1500 wavelength meter.
  • the cavity length of the ring-down cavity 107 can be set to 1.25 meters, the nominal reflectivity of the first mirror 109 and the second mirror 110 at both ends can be 99.995%, the radius of curvature is up to 1 meter, and the output of the ring-down cavity 107
  • the end cavity mirror uses the piezoelectric ceramic tube 111 to vibrate at a frequency of 100 Hz, so that the longitudinal mode of the ring-down cavity 107 can match the frequency of the incident laser.
  • the light output from the ring-down cavity 107 is received by a photoelectric conversion device 112, such as a silicon diode detector, and divided into two electrical signals. One electrical signal passes through a potential comparator.
  • the trigger source After the threshold voltage is exceeded, the trigger source generates a trigger signal to control the sound
  • the optical modulator 103 turns off the laser input from the first beam splitter 102; the other electrical signal, that is, the detector signal, is sent to the data acquisition card of the computer 108 for data collection, the ring-down signal is recorded, and then controlled after about 1 millisecond
  • the acousto-optic modulator 103 turns on the laser light input from the first optical beam splitter 102 again.
  • Each ring-down curve recorded by the computer 108 is quickly fitted with a single exponential function by the online computer 108, and the ring-down time data and the corresponding fitting error are obtained and stored. The results of multiple ring-downs are averaged to obtain the average ring-down time.
  • the computer 108 After that, the computer 108 generates a scanning signal to control the continuous laser 101 to scan to the next laser frequency for measurement.
  • the wavelength of the laser output from the continuous laser 101 is monitored by the wavelength meter 104 and a highly stable etalon.
  • the computer 108 Through the control of the computer 108, high-precision continuous wavelength scanning can be realized.
  • the optical cavity ring-down spectrometer system illustrated in FIG. 4 The accuracy of spectral measurement can reach the level of 10 -4 cm -1 .
  • a channel for pre-passing the constant temperature gas through the ring-down cavity 107 is designed so that the ring-down cavity 107 maintains a constant temperature.

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Abstract

A cavity ring-down spectrometer system, for use in improving the sensitivity of spectrum measurement. The system comprises: a continuous laser, a first beam splitter coupled to the continuous laser, an acousto-optic modulator and a wavemeter coupled to the first beam splitter, a second beam splitter coupled to the acousto-optic modulator, a third beam splitter coupled to the second beam splitter, a ring-down cavity coupled to the third beam splitter, and a computer coupled to the ring-down cavity, the wavemeter, and the continuous laser; a first reflector and a second reflector are respectively arranged at two ends inside the ring-down cavity, a piezoelectric ceramic tube is arranged at an output end of the ring-down cavity, and the piezoelectric ceramic tube is connected to the computer by means of a photoelectric conversion device. The technical solution of the present application can achieve high-precision continuous wavelength scanning, and the spectrum measurement precision can reach the level of 10-4 cm-1. Compared with the prior art, the sensitivity of spectrum measurement is significantly improved.

Description

一种光腔衰荡光谱仪系统Optical cavity ring-down spectrometer system 技术领域Technical field
本申请属于科研设备制造领域，尤其涉及一种光腔衰荡光谱仪系统。This application belongs to the field of scientific research equipment manufacturing, and in particular relates to an optical cavity ring-down spectrometer system.
背景技术Background technique
目前，气体浓度检测的方法有很多种，包括声学传感器、基于传统吸收光谱的传感器、拉曼光谱传感器、质谱传感器、核磁共振传感器以及电学传感器等。现有的这些传感器虽然对于气体的探测发挥了重要作用，但普遍存在灵敏度偏低以及操作复杂等特点，因而应用在痕量气体浓度检测上有明显的局限性。At present, there are many methods for gas concentration detection, including acoustic sensors, sensors based on traditional absorption spectroscopy, Raman spectroscopy sensors, mass spectrometry sensors, nuclear magnetic resonance sensors, and electrical sensors. Although these existing sensors play an important role in gas detection, they generally have the characteristics of low sensitivity and complicated operation, so their application in the detection of trace gas concentration has obvious limitations.
腔衰荡光谱（Cavity Ringdown Spectroscopy，CRDS）技术是一种通过测量光学腔内由样品散射和吸收引起的光损耗而实现高灵敏度光谱检测的吸收光谱技术。它除了传统光谱技术所具有的分析、检测能力外，还具有独特的优势：由于激光在光学腔内往返次数多，吸收光程长度很长，所以CRDS技术能够获得很高的灵敏度；另外，CRDS技术的直接测量参数不是激光通过待测物质后的光强绝对强度变化，而是光强指数衰减速率，因此，CRDS技术对光源强度起伏不敏感。Cavity Ringdown Spectroscopy (CRDS) technology is an absorption spectroscopy technology that achieves high-sensitivity spectral detection by measuring the optical loss caused by sample scattering and absorption in an optical cavity. In addition to the analysis and detection capabilities of traditional spectroscopy technology, it also has unique advantages: due to the large number of round-trips in the optical cavity and long absorption path length, CRDS technology can obtain high sensitivity; in addition, CRDS The direct measurement parameter of the technology is not the absolute intensity change of the light intensity after the laser passes through the substance to be measured, but the exponential decay rate of the light intensity. Therefore, the CRDS technology is not sensitive to the fluctuation of the light source intensity.
早期的腔内衰荡光谱大多采用脉冲激光作为光源，但由于激光线宽较大，在激光衰荡的过程中会出现多纵模同时与光腔耦合的情况，如此激光的衰荡曲线便成为多个指数衰减相叠加的结果，此时作拟合得到的样品气体吸收系数存在较大的偏差（约１％水平），从而降低了检测的灵敏度。Early intracavity ring-down spectroscopy mostly used pulsed lasers as the light source. However, due to the large laser line width, multiple longitudinal modes would be coupled to the optical cavity at the same time during the laser ring-down process, so the laser ring-down curve became As a result of the superposition of multiple exponential attenuations, the sample gas absorption coefficient obtained by fitting at this time has a large deviation (about 1% level), which reduces the detection sensitivity.
技术问题technical problem
本申请的目的在于提供一种光腔衰荡光谱仪系统，以提高光谱测量的灵敏度。The purpose of this application is to provide an optical cavity ring-down spectrometer system to improve the sensitivity of spectrum measurement.
技术解决方案Technical solutions
本申请第一方面提供一种光腔衰荡光谱仪系统，所述系统包括：连续激光器、与所述连续激光器耦合的第一光分束镜、与所述第一光分束镜耦合的声光调制器和波长计、与所述声光调制器耦合的第二光分束镜、与所述第二光分束镜耦合的第三光分束镜、与所述第三光分束镜耦合的衰荡腔以及与所述衰荡腔、波长计和连续激光器耦合的计算机，所述衰荡腔的内部两端分别设置第一反射镜和第二反射镜，所述衰荡腔的输出端设置压电陶瓷管，所述压电陶瓷管经光电转换装置与所述计算机连接；The first aspect of the present application provides an optical cavity ring-down spectrometer system. The system includes: a continuous laser, a first optical beam splitter coupled with the continuous laser, and an acousto-optic coupled with the first optical beam splitter. A modulator and a wavelength meter, a second optical beam splitter coupled with the acousto-optic modulator, a third optical beam splitter coupled with the second optical beam splitter, and a third optical beam splitter coupled with the third optical beam splitter The ring-down cavity and the computer coupled with the ring-down cavity, the wavelength meter and the continuous laser, the inner two ends of the ring-down cavity are respectively provided with a first mirror and a second mirror, and the output end of the ring-down cavity Set up a piezoelectric ceramic tube, the piezoelectric ceramic tube is connected to the computer via a photoelectric conversion device;
所述连续激光器，用于在固体激光器的泵浦下产生连续激光后输出至所述第一光分束镜；The continuous laser is used to generate continuous laser light pumped by a solid laser and output to the first optical beam splitter;
所述第一光分束镜，用于将所述连续激光器产生的连续激光经折射和反射分成第一光束和第二光束，所述第一光束输出至所述声光调制器，所述第二光束输出至所述波长计；The first light beam splitter is used to split the continuous laser light generated by the continuous laser into a first beam and a second beam through refraction and reflection, the first beam is output to the acousto-optic modulator, and the first beam Output two light beams to the wavelength meter;
所述声光调制器，用于在声信号的调制下，将来自所述第一光束调制后得到已调光输出至所述第二光分束镜；The acousto-optic modulator is configured to modulate the light from the first light beam and output it to the second light beam splitter under the modulation of the acoustic signal;
所述第二光分束镜，用于将所述已调光反射后经透镜输出至所述第三光分束镜；The second light beam splitter is used to output the dimmed light beam splitter to the third light beam splitter through a lens;
所述第三光分束镜，用于将所述透镜输出的已调光经折射后输出至所述衰荡腔；The third light beam splitter is used to output the dimmed light output by the lens to the ring-down cavity after being refracted;
所述衰荡腔，用于在所述第一反射镜和第二反射镜的作用下，对所述第三光分束镜输入的已调光进行衰荡后输出至所述光电转换装置；The ring-down cavity is used for ring-down the dimmed light input by the third light beam splitter under the action of the first mirror and the second mirror, and then output to the photoelectric conversion device;
所述光电转换装置，用于将所述衰荡腔输出的衰荡光信号转换为电信号，所述电信号一路输出至所述声光调制器，另一路输出至所述计算机；The photoelectric conversion device is used to convert the ring-down light signal output by the ring-down cavity into an electrical signal, the electrical signal is output to the acousto-optic modulator one way, and the other is output to the computer;
所述压电陶瓷管，用于在函数发生器的作用下以预设频率振动，使所述衰荡腔的纵模能与所述第三光分束镜输入的已调光的频率相匹配。The piezoelectric ceramic tube is used to vibrate at a preset frequency under the action of a function generator, so that the longitudinal mode of the ring-down cavity can match the dimmed frequency input by the third light beam splitter .
进一步地，衰荡腔设置一恒温气体通道，用于向所述衰荡腔输入恒温气体并从所述衰荡腔输出。Further, a constant temperature gas channel is provided in the ring down cavity for inputting constant temperature gas into the ring down cavity and outputting from the ring down cavity.
进一步地，所述波长计用于对所述连续激光器产生的连续激光的波长进行监测，由此产生的监测信号输出至所述计算机。Further, the wavelength meter is used to monitor the wavelength of the continuous laser light generated by the continuous laser, and the monitoring signal generated thereby is output to the computer.
进一步地，所述计算机用于在所述光电转换装置输出的电信号和所述监测信号的作用下，控制所述连续激光器逐个扫描到激光频率处进行测量。Further, the computer is used to control the continuous laser to scan the laser frequency one by one to perform measurement under the action of the electrical signal output by the photoelectric conversion device and the monitoring signal.
进一步地，所述连续激光器为连续环形腔钛宝石激光器。Further, the continuous laser is a continuous ring cavity Ti:Sapphire laser.
进一步地，所述第一反射镜和第二反射镜的标称反射率为99.995%，曲率半径为1m。Further, the nominal reflectivity of the first reflector and the second reflector is 99.995%, and the radius of curvature is 1 m.
进一步地，所述预设频率为100赫兹。Further, the preset frequency is 100 Hz.
进一步地，所述衰荡腔的腔体长为1.25m。Further, the cavity length of the ring-down cavity is 1.25 m.
进一步地，所述系统还包括固体激光器，用于对所述连续激光器进行泵浦。Further, the system further includes a solid-state laser for pumping the continuous laser.
进一步地，所述固体激光器的输出波长为532纳米。Further, the output wavelength of the solid-state laser is 532 nanometers.
有益效果Beneficial effect
从上述本申请技术方案可知，由于连续激光器与第一光分束镜耦合，第一光分束镜与声光调制器和波长计耦合，衰荡腔、波长计和连续激光器与计算机耦合，计算机在光电转换装置输出的电信号和波长计输出的监测信号的作用下，控制连续激光器逐个扫描到激光频率处进行测量，因此，可实现高精度的连续波长扫描，其光谱测量精度可达到10 -4cm -1的水平，与现有技术相比，显著提高了光谱测量的灵敏度。 It can be seen from the above technical solution of the present application that because the continuous laser is coupled with the first optical beam splitter, the first optical beam splitter is coupled with the acousto-optic modulator and the wavelength meter, and the ring-down cavity, the wavelength meter and the continuous laser are coupled with the computer. under the influence of the electrical signal and monitoring the output of the wavemeter outputs of the photoelectric conversion means, the laser control successive individual scans to measure the laser frequency, and therefore, can be highly accurate continuous wavelength scanning, spectral measurements to a 10 - Compared with the prior art, the 4 cm -1 level significantly improves the sensitivity of spectrum measurement.
附图说明Description of the drawings
图1是本申请实施例提供的光腔衰荡光谱仪系统的结构示意图；1 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by an embodiment of the present application;
图2是本申请另一实施例提供的光腔衰荡光谱仪系统的结构示意图；2 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application;
图3是本申请另一实施例提供的光腔衰荡光谱仪系统的结构示意图；3 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application;
图4是本申请另一实施例提供的光腔衰荡光谱仪系统的结构示意图。4 is a schematic structural diagram of an optical cavity ring-down spectrometer system provided by another embodiment of the present application.
本发明的实施方式Embodiments of the invention
为了使本申请的目的、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。In order to make the purpose, technical solutions, and beneficial effects of this application clearer, the following further describes this application in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the application, and are not used to limit the application.
以下描述中，为了说明而不是为了限定，提出了诸如特定系统结构、技术之类的具体细节，以便透彻理解本申请实施例。然而，本领域的技术人员应当清楚，在没有这些具体细节的其它实施例中也可以实现本申请。在其它情况中，省略对众所周知的系统、装置、电路以及方法的详细说明，以免不必要的细节妨碍本申请的描述。In the following description, for the purpose of illustration rather than limitation, specific details such as a specific system structure and technology are proposed for a thorough understanding of the embodiments of the present application. However, it should be clear to those skilled in the art that the present application can also be implemented in other embodiments without these specific details. In other cases, detailed descriptions of well-known systems, devices, circuits, and methods are omitted to avoid unnecessary details from obstructing the description of this application.
附图1是本申请实施例提供的光腔衰荡光谱仪系统结构示意图，详细说明如下：Fig. 1 is a schematic diagram of the structure of an optical cavity ring-down spectrometer system provided by an embodiment of the present application. The detailed description is as follows:
附图1示例的光腔衰荡光谱仪系统包括连续激光器101、与连续激光器101耦合的第一光分束镜102、与第一光分束镜102耦合的声光调制器103和波长计104、与声光调制器103耦合的第二光分束镜105、与第二光分束镜105耦合的第三光分束镜106、与第三光分束镜106耦合的衰荡腔107以及与衰荡腔107、波长计104和连续激光器101耦合的计算机108，衰荡腔107的内部两端分别设置第一反射镜109和第二反射镜110，衰荡腔107的输出端设置压电陶瓷管111，压电陶瓷管111经光电转换装置112与计算机108连接，其中：The optical cavity ring-down spectrometer system illustrated in FIG. 1 includes a continuous laser 101, a first optical beam splitter 102 coupled with the continuous laser 101, an acousto-optic modulator 103 coupled with the first optical beam splitter 102, and a wavelength meter 104, The second optical beam splitter 105 coupled with the acousto-optic modulator 103, the third optical beam splitter 106 coupled with the second optical beam splitter 105, the ring-down cavity 107 coupled with the third optical beam splitter 106, and the The ring-down cavity 107, the wavelength meter 104 and the computer 108 coupled with the continuous laser 101, the inner two ends of the ring-down cavity 107 are provided with a first mirror 109 and a second mirror 110 respectively, and the output end of the ring-down cavity 107 is set with piezoelectric ceramics Tube 111, piezoelectric ceramic tube 111 is connected to computer 108 via photoelectric conversion device 112, where:
连续激光器101，用于在固体激光器的泵浦下产生连续激光后输出至第一光分束镜102；The continuous laser 101 is used to generate continuous laser light pumped by the solid laser and output to the first optical beam splitter 102;
第一光分束镜102，用于将连续激光器101产生的连续激光经折射和反射分成第一光束和第二光束，即将连续激光器101产生的连续激光经折射得到第一光束，即将连续激光器101产生的连续激光经反射得到第二光束，第一光束输出至声光调制器103，第二光束输出至波长计104；The first beam splitter 102 is used to split the continuous laser light generated by the continuous laser 101 into a first beam and a second beam by refraction and reflection, that is, the continuous laser light generated by the continuous laser 101 is refracted to obtain the first beam, that is, the continuous laser 101 The generated continuous laser light is reflected to obtain a second beam, the first beam is output to the acousto-optic modulator 103, and the second beam is output to the wavelength meter 104;
声光调制器103，用于在声信号的调制下，将来自第一光束调制后得到已调光输出至第二光分束镜105；The acousto-optic modulator 103 is used to modulate the first light beam and output the dimmed light to the second light beam splitter 105 under the modulation of the acoustic signal;
第二光分束镜，105用于将已调光反射后经透镜输出至第三光分束镜106；The second light beam splitter 105 is used to output the dimmed light to the third light beam splitter 106 through the lens after being dimmed and reflected;
第三光分束镜106，用于将透镜输出的已调光经折射后输出至衰荡腔107；The third light beam splitter 106 is used to output the dimmed light output by the lens to the ring-down cavity 107 after being refracted;
衰荡腔107，用于在第一反射镜109和第二反射镜110的作用下，对第三光分束镜106输入的已调光进行衰荡后输出至光电转换装置112；The ring down cavity 107 is used to ring down the dimmed light input by the third light beam splitter 106 under the action of the first mirror 109 and the second mirror 110 and output to the photoelectric conversion device 112;
光电转换装置112，用于将衰荡腔107输出的衰荡光信号转换为电信号，该电信号一路输出至声光调制器103，另一路输出至计算机108；The photoelectric conversion device 112 is used to convert the ring-down light signal output by the ring-down cavity 107 into an electrical signal, the electrical signal is output to the acousto-optic modulator 103 and the other is output to the computer 108;
压电陶瓷管111，用于在函数发生器的作用下以预设频率振动，使衰荡腔107的纵模能与第三光分束镜106输入的已调光的频率相匹配。The piezoelectric ceramic tube 111 is used to vibrate at a preset frequency under the action of the function generator, so that the longitudinal mode of the ring-down cavity 107 can match the dimmed frequency input by the third light beam splitter 106.
进一步地，衰荡腔107设置一恒温气体通道，如附图2所示的黑色圆圈部分，恒温气体通道用于向衰荡腔107输入恒温气体并从衰荡腔107输出，箭头所指方向代表恒温气体的进出方向。Further, the ring-down chamber 107 is provided with a constant temperature gas channel, as shown in the black circle in Figure 2. The constant-temperature gas channel is used to input constant-temperature gas into the ring-down cavity 107 and output from the ring-down cavity 107. The direction indicated by the arrow represents Direction of entry and exit of thermostatic gas.
进一步地，波长计104用于对连续激光器101产生的连续激光的波长进行监测，由此产生的监测信号输出至计算机108。Further, the wavelength meter 104 is used to monitor the wavelength of the continuous laser light generated by the continuous laser 101, and the monitoring signal generated thereby is output to the computer 108.
进一步地，计算机108用于在光电转换装置112输出的电信号和波长计104输出的监测信号的作用下，控制连续激光器101逐个扫描到激光频率处进行测量，其中，连续激光器101为连续环形腔钛宝石激光器。Further, the computer 108 is used to control the continuous laser 101 to scan the laser frequency one by one under the action of the electrical signal output by the photoelectric conversion device 112 and the monitoring signal output by the wavelength meter 104, where the continuous laser 101 is a continuous ring cavity Ti:Sapphire laser.
进一步地，第一反射镜109和第二反射镜110的标称反射率可以是99.995%，曲率半径可以是1米。Further, the nominal reflectivity of the first reflector 109 and the second reflector 110 may be 99.995%, and the radius of curvature may be 1 meter.
进一步地，预设频率为100赫兹。Further, the preset frequency is 100 Hz.
进一步地，衰荡腔107的腔体长为1.2米。Further, the cavity length of the ring-down cavity 107 is 1.2 meters.
进一步地，光腔衰荡光谱仪系统还包括固体激光器，如附图3所示，固体激光器用于对连续激光器101进行泵浦。Further, the optical cavity ring-down spectrometer system also includes a solid-state laser. As shown in FIG. 3, the solid-state laser is used to pump the continuous laser 101.
进一步地，固体激光器的输出波长可以是532纳米。Further, the output wavelength of the solid-state laser may be 532 nanometers.
从附图1示例的光腔衰荡光谱仪系统可知，由于连续激光器与第一光分束镜耦合，第一光分束镜与声光调制器和波长计耦合，述衰荡腔、波长计和连续激光器与计算机耦合，计算机在光电转换装置输出的电信号和波长计输出的监测信号的作用下，控制连续激光器逐个扫描到激光频率处进行测量，因此，可实现高精度的连续波长扫描，其光谱测量精度可达到10 -4cm -1的水平，与现有技术相比，显著提高了光谱测量的灵敏度。 As can be seen from the optical cavity ring-down spectrometer system illustrated in Figure 1, because the continuous laser is coupled with the first optical beam splitter, the first optical beam splitter is coupled with the acousto-optic modulator and the wavelength meter. The ring-down cavity, wavelength meter and The continuous laser is coupled with the computer. The computer controls the continuous laser to scan to the laser frequency one by one under the action of the electrical signal output by the photoelectric conversion device and the monitoring signal output by the wavelength meter. Therefore, high-precision continuous wavelength scanning can be realized. The accuracy of the spectrum measurement can reach the level of 10 -4 cm -1 , which significantly improves the sensitivity of the spectrum measurement compared with the prior art.
附图4给出了本申请另一实施例的光腔衰荡光谱仪系统结构示意图，以下进行详细说明：Fig. 4 shows a schematic structural diagram of an optical cavity ring-down spectrometer system according to another embodiment of the present application, which will be described in detail below:
连续激光器101可以是美国相干公司生产的899-21型连续环形腔钛宝石激光器，由输出波长为532纳米的固体激光器（Verdi-18）泵浦，可覆盖700至1000纳米的光谱范围，连续激光器101工作时，其波长由波长计104，例如一台WA-1500型波长计监测。连续激光器101输出的激光经过声光调制器103后，依次经过第二光分束镜105和第三光分束镜106的折射，再依次通过光纤耦合器、光纤、光纤耦合器以及两个透镜的耦合后送入衰荡腔107。衰荡腔107的腔体长度可以设置为1.25米，其两端的第一反射镜109和第二反射镜110的标称反射率可以是99.995%，曲率半径达1米，衰荡腔107的输出端腔镜利用压电陶瓷管111以100赫兹的频率振动，使衰荡腔107的纵模能与入射激光的频率相匹配。衰荡腔107输出的光通过光电转换装置112，例如硅二极管探测器接收后分为两路电信号，一路电信号通过一个电位比较器，超过设定阈值电压后，触发源产生触发信号控制声光调制器103关断来自第一光分束镜102输入的激光；另一路电信号即探测器信号被送往计算机108的数据采集卡进行数据采集，记录衰荡信号，约１毫秒后再控制声光调制器103重新打开来自第一光分束镜102输入的激光。计算机108记录的每个衰荡曲线被在线的计算机108迅速进行单指数函数拟合，得到衰荡时间数据及其相应的拟合误差并被存储下来。多次衰荡的结果被平均后得到平均的衰荡时间，其后，计算机108再产生一个扫描信号，控制连续激光器101扫描到下一个激光频率处进行测量。连续激光器101输出的激光的波长由波长计104和高稳定的标准具进行监测，通过计算机108的控制，可实现高精度的连续波长扫描，实验表明，附图4示例的光腔衰荡光谱仪系统的光谱测量精度可达到10 -4cm -1水平。 The continuous laser 101 can be the 899-21 continuous ring-cavity Ti:Sapphire laser produced by the American Coherent Company. It is pumped by a solid-state laser (Verdi-18) with an output wavelength of 532 nanometers and can cover the spectral range of 700 to 1000 nanometers. When 101 is working, its wavelength is monitored by a wavelength meter 104, such as a WA-1500 wavelength meter. After the laser light output by the continuous laser 101 passes through the acousto-optic modulator 103, it passes through the second beam splitter 105 and the third beam splitter 106 in turn, and then passes through the fiber coupler, the fiber, the fiber coupler and the two lenses in turn After the coupling, it is sent to the ring-down cavity 107. The cavity length of the ring-down cavity 107 can be set to 1.25 meters, the nominal reflectivity of the first mirror 109 and the second mirror 110 at both ends can be 99.995%, the radius of curvature is up to 1 meter, and the output of the ring-down cavity 107 The end cavity mirror uses the piezoelectric ceramic tube 111 to vibrate at a frequency of 100 Hz, so that the longitudinal mode of the ring-down cavity 107 can match the frequency of the incident laser. The light output from the ring-down cavity 107 is received by a photoelectric conversion device 112, such as a silicon diode detector, and divided into two electrical signals. One electrical signal passes through a potential comparator. After the threshold voltage is exceeded, the trigger source generates a trigger signal to control the sound The optical modulator 103 turns off the laser input from the first beam splitter 102; the other electrical signal, that is, the detector signal, is sent to the data acquisition card of the computer 108 for data collection, the ring-down signal is recorded, and then controlled after about 1 millisecond The acousto-optic modulator 103 turns on the laser light input from the first optical beam splitter 102 again. Each ring-down curve recorded by the computer 108 is quickly fitted with a single exponential function by the online computer 108, and the ring-down time data and the corresponding fitting error are obtained and stored. The results of multiple ring-downs are averaged to obtain the average ring-down time. After that, the computer 108 generates a scanning signal to control the continuous laser 101 to scan to the next laser frequency for measurement. The wavelength of the laser output from the continuous laser 101 is monitored by the wavelength meter 104 and a highly stable etalon. Through the control of the computer 108, high-precision continuous wavelength scanning can be realized. Experiments show that the optical cavity ring-down spectrometer system illustrated in FIG. 4 The accuracy of spectral measurement can reach the level of 10 -4 cm -1 .
需要说明的是，由于环境温度波动时，测得的衰荡时间可能会随着测量时间的增加存在明显的漂移，因此，在上述示例的光腔衰荡光谱仪系统中，为改善环境温度变化对光腔衰荡光谱仪系统检测灵敏度的影响，设计了使恒温气体预通过衰荡腔107的通道，从而使得衰荡腔107中保持恒温。It should be noted that when the ambient temperature fluctuates, the measured ring-down time may drift significantly with the increase of the measurement time. Therefore, in the optical cavity ring-down spectrometer system in the above example, in order to improve the environmental temperature change Due to the influence of the detection sensitivity of the optical cavity ring-down spectrometer system, a channel for pre-passing the constant temperature gas through the ring-down cavity 107 is designed so that the ring-down cavity 107 maintains a constant temperature.
以上实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围，均应包含在本申请的保护范围之内。The above embodiments are only used to illustrate the technical solutions of the application, but not to limit them; although the application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still compare the previous embodiments. The recorded technical solutions are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the application, and shall be included in the application Within the scope of protection.

Claims (10)

  1. 一种光腔衰荡光谱仪系统，其特征在于，所述系统包括连续激光器、与所述连续激光器耦合的第一光分束镜、与所述第一光分束镜耦合的声光调制器和波长计、与所述声光调制器耦合的第二光分束镜、与所述第二光分束镜耦合的第三光分束镜、与所述第三光分束镜耦合的衰荡腔以及与所述衰荡腔、波长计和连续激光器耦合的计算机，所述衰荡腔的内部两端分别设置第一反射镜和第二反射镜，所述衰荡腔的输出端设置压电陶瓷管，所述压电陶瓷管经光电转换装置与所述计算机连接；An optical cavity ring-down spectrometer system, characterized in that the system comprises a continuous laser, a first optical beam splitter coupled with the continuous laser, an acousto-optic modulator coupled with the first optical beam splitter, and Wavelength meter, second optical beam splitter coupled with said acousto-optic modulator, third optical beam splitter coupled with said second optical beam splitter, ring-down coupled with said third optical beam splitter Cavity and a computer coupled with the ring-down cavity, wavelength meter and continuous laser, the inner two ends of the ring-down cavity are respectively provided with a first mirror and a second mirror, and the output end of the ring-down cavity is provided with a piezoelectric A ceramic tube, the piezoelectric ceramic tube is connected to the computer via a photoelectric conversion device;
    所述连续激光器，用于在固体激光器的泵浦下产生连续激光后输出至所述第一光分束镜；The continuous laser is used to generate continuous laser light pumped by a solid laser and output to the first optical beam splitter;
    所述第一光分束镜，用于将所述连续激光器产生的连续激光经折射和反射分成第一光束和第二光束，所述第一光束输出至所述声光调制器，所述第二光束输出至所述波长计；The first light beam splitter is used to split the continuous laser light generated by the continuous laser into a first beam and a second beam through refraction and reflection, the first beam is output to the acousto-optic modulator, and the first beam Output two light beams to the wavelength meter;
    所述声光调制器，用于在声信号的调制下，将来自所述第一光束调制后得到已调光输出至所述第二光分束镜；The acousto-optic modulator is configured to modulate the light from the first light beam and output it to the second light beam splitter under the modulation of the acoustic signal;
    所述第二光分束镜，用于将所述已调光反射后经透镜输出至所述第三光分束镜；The second light beam splitter is used to output the dimmed light beam splitter to the third light beam splitter through a lens;
    所述第三光分束镜，用于将所述透镜输出的已调光经折射后输出至所述衰荡腔；The third light beam splitter is used to output the dimmed light output by the lens to the ring-down cavity after being refracted;
    所述衰荡腔，用于在所述第一反射镜和第二反射镜的作用下，对所述第三光分束镜输入的已调光进行衰荡后输出至所述光电转换装置；The ring-down cavity is used for ring-down the dimmed light input by the third light beam splitter under the action of the first mirror and the second mirror, and then output to the photoelectric conversion device;
    所述光电转换装置，用于将所述衰荡腔输出的衰荡光信号转换为电信号，所述电信号一路输出至所述声光调制器，另一路输出至所述计算机；The photoelectric conversion device is used to convert the ring-down light signal output by the ring-down cavity into an electrical signal, the electrical signal is output to the acousto-optic modulator one way, and the other is output to the computer;
    所述压电陶瓷管，用于在函数发生器的作用下以预设频率振动，使所述衰荡腔的纵模能与所述第三光分束镜输入的已调光的频率相匹配。The piezoelectric ceramic tube is used to vibrate at a preset frequency under the action of a function generator, so that the longitudinal mode of the ring-down cavity can match the dimmed frequency input by the third light beam splitter .
  2. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，衰荡腔设置一恒温气体通道，用于向所述衰荡腔输入恒温气体并从所述衰荡腔输出。4. The optical cavity ring-down spectrometer system of claim 1, wherein the ring-down cavity is provided with a constant temperature gas channel for inputting constant-temperature gas into the ring-down cavity and outputting from the ring-down cavity.
  3. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，所述波长计用于对所述连续激光器产生的连续激光的波长进行监测，由此产生的监测信号输出至所述计算机。3. The optical cavity ring-down spectrometer system of claim 1, wherein the wavelength meter is used to monitor the wavelength of the continuous laser light generated by the continuous laser, and the monitoring signal generated thereby is output to the computer.
  4. 如权利要求3所述的光腔衰荡光谱仪系统，其特征在于，所述计算机用于在所述光电转换装置输出的电信号和所述监测信号的作用下，控制所述连续激光器逐个扫描到激光频率处进行测量。The optical cavity ring-down spectrometer system of claim 3, wherein the computer is used to control the continuous laser to scan one by one under the action of the electrical signal output by the photoelectric conversion device and the monitoring signal Measure at the laser frequency.
  5. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，所述连续激光器为连续环形腔钛宝石激光器。The optical cavity ring-down spectrometer system of claim 1, wherein the continuous laser is a continuous ring cavity Ti:Sapphire laser.
  6. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，所述第一反射镜和第二反射镜的标称反射率为99.995%，曲率半径为1米。The optical cavity ring-down spectrometer system of claim 1, wherein the nominal reflectivity of the first reflector and the second reflector is 99.995%, and the radius of curvature is 1 meter.
  7. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，所述预设频率为100赫兹。3. The optical cavity ring-down spectrometer system of claim 1, wherein the preset frequency is 100 Hz.
  8. 如权利要求1所述的光腔衰荡光谱仪系统，其特征在于，所述衰荡腔的腔体长为1.25米。The optical cavity ring-down spectrometer system of claim 1, wherein the cavity length of the ring-down cavity is 1.25 meters.
  9. 如权利要求1至8任意一项所述的光腔衰荡光谱仪系统，其特征在于，所述系统还包括固体激光器，用于对所述连续激光器进行泵浦。8. The optical cavity ring-down spectrometer system according to any one of claims 1 to 8, wherein the system further comprises a solid-state laser for pumping the continuous laser.
  10. 如权利要求9所述的光腔衰荡光谱仪系统，其特征在于，所述固体激光器的输出波长为532纳米。9. The optical cavity ring-down spectrometer system of claim 9, wherein the output wavelength of the solid-state laser is 532 nanometers.
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