CN102570284B - Realizing method and device of Raman laser source for fluoranthene fluorescence spectrum detection - Google Patents
Realizing method and device of Raman laser source for fluoranthene fluorescence spectrum detection Download PDFInfo
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- CN102570284B CN102570284B CN 201010587603 CN201010587603A CN102570284B CN 102570284 B CN102570284 B CN 102570284B CN 201010587603 CN201010587603 CN 201010587603 CN 201010587603 A CN201010587603 A CN 201010587603A CN 102570284 B CN102570284 B CN 102570284B
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Abstract
The invention discloses a realizing method and a device of a Raman laser source for fluoranthene fluorescence spectrum detection. 1064nm fundamental frequency laser generated by an Nd:YAG pulse laser passes through a twice-frequency crystal and a quadruple-frequency crystal to obtain hybrid laser with the wavelength of 1064nm, 532nm and 266nm. The hybrid laser passes through an optical filter to obtain purified 266nm quadruple-frequency laser in a linear polarization state. The 266nm quadruple-frequency laser in the linear polarization state is converted into 266nm quadruple-frequency laser in a round polarization state or an elliptical polarization state through a 1/4 wave plate. The 266nm quadruple-frequency laser in the round polarization state or the elliptical polarization state pumps a Raman tank filled with high pressure D2 after being focused by a lens for rovibronic stimulated Raman scattering to obtain (-1,1)-level rovibronic Raman scattering light with the wave length of 285.6nm, namely the laser source for fluoranthene fluorescence spectrum detection. The device has stable and reliable performance and low cost, and the Raman tank has the characteristics of long-time stable operation, no decomposition and the like.
Description
Technical field
The present invention relates to a kind of implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum, the invention still further relates to the implement device of the Raman laser source that detects for the fluoranthene fluorescence spectrum.
Background technology
Fluoranthene belongs to polycyclic aromatic hydrocarbon (polycyclic aromatic hydrocardons, PAHs) a kind of in, difficult degradation in environment, persistence are strong and have strong " three cause " effect, therefore the detection to PAHs receives much concern, and many countries are all listed it in the blacklist or gray list of priority pollutant.PAHs in the water body is mainly derived from the discharging of atmospheric sedimentation, municipal sewage and industrial wastewater, the leakage of oil etc., and these pollutants can enter surface water and underground water, cause drinking water source to be polluted.Because hydrophobicity and the anti-degradation capability of PAHs are stronger, exist PAHs concentration very low in the water environment, therefore, be a complexity and important trace analysis problem to the detection of PAHs.Fluoranthene has higher fluorescence quantum efficiency, according to this characteristic, can utilize fluorescent method that it is detected.
The fluoroscopic examination of fluoranthene needs suitable excitation source, is convenient to the detection of signal to obtain stronger fluorescence light intensity.Chinese Academy of Sciences's Anhui ray machine is used F-7000 type fluorescence spectrophotometer measurement and is obtained, and fluoranthene has two stronger fluorescence radiation zones.One of them light-emitting zone and Rayleigh scattering overlap, and the main peak of selecting complete fluorescence intensity is λ
Ex/ λ
Em=286/462nm.The wavelength that is excitation source is preferably 286nm, perhaps in its vicinity.
The easiest method of light source of obtaining this excitation wavelength is to use spectrophotometer, namely adopts the continuous spectrum light source, carries out light splitting with beam splitter such as prism or grating again, thereby obtains required wavelength light source.This method is directly easy, but the light intensity that shortcoming is to export light very a little less than, and use this method and generally need sampling, be positioned in spectrometer or the spectrophotometer and detect again, be not easy to online detection, limited its scope of application.
Tunable laser has certain wavelength tuning range, and the laser intensity of output can satisfy fully test required.But cost is high, and millions of RMB should not be popularized easily, and if adopt Dye laser of tunable, its dyestuff with carcinogenesis easily threatens to experimenter's health.
The embedded cone penetrometer of vehicle-mounted laser-fluorescence that Environmental Protection Agency USA uses detects fluoranthene content in the soil, and its excitation source adopts the pumping of Nd:YAG laser of quadruple to be filled with methane (CH
4) and the Raman pond of hydrogen gas mixture, obtain CH
4First order stokes light, wavelength is 288.4nm, as the excitation source of fluoranthene fluorescence detection.This optical source wavelength is stable, and near excitation peak 286nm, has obtained effect preferably.But shortcoming is the long-time pumping CH of Nd:YAG laser of quadruple
4, cause CH easily
4Decomposition (Chinese Academy of Sciences's Anhui related experiment that ray machine was once done also has the detail analysis report to this),
Consequently, one, the small carbon granule of generation (diameter is tens of to hundreds of microns) is attached to the two ends glass window in Raman pond, reduces the light transmittance in Raman pond; Its two, the carrying out of decomposable process causes CH in the Raman pond
4Minimizing, thereby output useful wavelength 288.4nm laser intensity reduce.
Therefore seek that wavelength is suitable, cheap, the lasing light emitter of system stability is particularly necessary.
Summary of the invention
First purpose of the present invention is to overcome the defective of prior art, provides a kind of system stability, cost is low, light intensity is big, be convenient to the implementation method of the Raman laser source that online fluoranthene fluorescence spectrum detects.
For achieving the above object, the present invention has taked following technical scheme:
A kind of implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum may further comprise the steps:
1) open the Nd:YAG pulse laser, output wavelength is the fundamental frequency ray laser of 1064nm;
2) the fundamental frequency ray laser obtains the 266nm laser of quadruple of pure linear polarization through two frequency-doubling crystals, quadruple frequency crystal and filter;
3) adjust quarter wave plate, make the 266nm laser of quadruple of linear polarization be converted into the 266nm laser of quadruple of circular polarization state or elliptical polarization through quarter wave plate;
4) the 266nm laser of quadruple with circular polarization state or elliptical polarization incides the Raman pond, produces not at the same level time the rotational raman scattering light that shakes; Adjust the prism group of Raman pond outgoing one side, not at the same level time the rotational raman scattering light that shakes is separated in the space; The window at two ends, described Raman pond is equipped with in convex lens, the Raman pond and is filled with high pressure D
2
5) utilize the diaphragm of prism group outgoing one side, select (1,1) level rotational raman scattering light that shakes, namely the laser of 285.6nm wavelength is the Raman laser source for the fluoranthene fluoroscopic examination.
Preferably, step 2) minute surface of described filter and the angle at 45 setting of the laser of incident, and described filter is high saturating to the laser of 1064nm and 532nm, and high anti-to the 266nm laser of quadruple.
Preferably, described filter is two, and the minute surface of two described filters is vertical mutually.
Preferably, described prism group is made up of 2 prisms.The effect of prism is light splitting, and polylith prismatic decomposition better effects if can shorten the volume of whole light source system, and its loss simultaneously is also bigger.Therefore, need the space size that allows according to measuring system, the combined factors such as sensitivity of subsequent probe device to consider to decide the number of prism in actual the use.If the space allows, select 2 prisms can satisfy the demands substantially; If need further reduce the volume of light-source system, then can select 3 prisms.
Preferably, the high pressure D in the described Raman pond
2Air pressure be 8-10atm.
Second purpose of the present invention is to be provided for the implement device of the Raman laser source that the fluoranthene fluorescence spectrum detects.
For achieving the above object, the present invention has taked following technical scheme:
A kind of device of realizing the Raman laser source that the fluoranthene fluorescence spectrum detects, comprise the Nd:YAG pulse laser, two frequency-doubling crystals, quadruple frequency crystal, filter, quarter wave plate, Raman pond, prism group, the diaphragm that set gradually, the window at two ends, described Raman pond is equipped with in convex lens, the Raman pond and is filled with high pressure D
2
Preferably, the minute surface of described filter and the laser of incident angle at 45 arranges, and described filter is high saturating to the laser of 1064nm and 532nm, and is high anti-to the 266nm laser of quadruple.
Preferably, described filter is two, and two described filter minute surfaces are vertical mutually.
Described quarter wave plate makes the 266nm laser of quadruple of incident be converted into circularly polarized light or elliptically polarized light by linearly polarized light.
Preferably, described prism group is made up of 2 and above prism, and its light splitting ability reaches spatially separates required 285.6nm wavelength laser and other wavelength laser, is convenient to follow-up diaphragm and selects.
Principle of the present invention is: the 1064nm fundamental frequency ray laser that the Nd:YAG pulse laser produces obtains comprising the hybrid laser of 1064nm, 532nm and 266nm wavelength behind two frequencys multiplication, quadruple frequency crystal.This hybrid laser is through filter, and the remaining 1064nm basic frequency laser of filtering and 532nm two double-frequency lasers obtain pure linear polarization 266nm laser of quadruple; The laser of quadruple of linear polarization is converted into the laser of quadruple of circular polarization state or elliptical polarization through quarter wave plate; Then, the 266nm laser of quadruple of circular polarization state or elliptical polarization focuses on pumping through lens and is filled with high pressure D
2The Raman pond, produce stimulated Raman scattering.
Its stimulated Raman scattering formula is
v
mn＝v
P+mv
V+nv
R
In the formula, v
P, v
V, v
RAnd v
MnThe wave number 1/266nm=37594cm that represents pumping laser respectively
-1, D
2Vibrating Raman frequency displacement wave number 2991cm
-1, D
2Rotary Raman frequency displacement wave number 415cm
-1With the wave number of scattered light, m, n are respectively vibrating Raman frequency displacement level time and rotary Raman frequency displacement level time, and m, n=0, and ± 1, ± 2 ....
Owing to adopted the pumping laser of circular polarization state or elliptical polarization, therefore, when the vibration stimulated Raman scattering produces, rotated stimulated Raman scattering and also be excited, thereby produce not at the same level time the commentaries on classics Raman diffused light that shakes.Get m=-1, n=1 can get (1,1) level and shake that to change the Raman diffused light wave number be v
-1,1=35014cn
-1, be converted into wavelength, i.e. 285.6nm.
Focus on pumping D
2Not at the same level inferior the shaking that produces changeed Raman diffused light and remained the 266nm laser of quadruple through prism component light, the light of mixed wavelengths is spatially separated, diaphragm of recycling selects required 285.6nm laser to see through, thereby obtains comparatively pure 285.6nm wavelength laser.The described commentaries on classics Raman 285.6nm wavelength scattered light that shakes just in time is in fluoranthene excitation peak position, therefore the lasing light emitter that it is detected as the fluoranthene fluorescence spectrum.
Compared with prior art, the present invention has following beneficial effect:
The raman laser wavelength that Raman laser source implementation method of the present invention provides just in time is in the excitation peak of fluoranthene, has improved accuracy of detection; And system stability is reliable, stable, nothing decomposition that the Raman pond works long hours; Cost is low.
Description of drawings
Fig. 1 excites-emission spectrum figure for fluoranthene;
Fig. 2 is for realizing the schematic representation of apparatus of the Raman laser source that the fluoranthene fluorescence spectrum detects;
Reference numeral: 1, Nd:YAG pulse laser; 2, two frequency-doubling crystals; 3, quadruple frequency crystal; 4, filter; 5, quarter wave plate; 6, Raman pond; 7, prism group; 8, diaphragm; 9, microcobjective; 10, optical fiber.
Embodiment
Describe the present invention in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1 is used for the implement device of the vibrating Raman lasing light emitter of fluoranthene fluorescence spectrum detection
See also Fig. 2, be the schematic diagram of the present invention for the implement device of the vibrating Raman lasing light emitter of fluoranthene fluorescence spectrum detection, comprise the Nd:YAG pulse laser 1, two frequency-doubling crystals 2, quadruple frequency crystal 3, filter 4, quarter wave plate 5, Raman pond 6, prism group 7, diaphragm 8 and object lens 9 and the optical fiber 10 that set gradually, the window at 5 two ends, described Raman pond is equipped with convex lens, the inside is filled with high pressure D
2, inner D
2Air pressure be 8-10atm.
In this embodiment, filter 4 is two, and two described filter minute surfaces are vertical mutually.The minute surface of filter and the laser of incident angle at 45 arranges, and described filter is high saturating to the laser of 1064nm and 532nm, and is high anti-to the 266nm laser of quadruple.Adjusting described quarter wave plate makes the 266nm laser of quadruple of incident be converted into circularly polarized light by linearly polarized light.The prism group is made up of 2 prisms, and its light splitting ability reaches spatially separates required 285.6nm wavelength laser and other wavelength laser, is convenient to follow-up diaphragm and selects.
Utilize the implement device of the vibrating Raman lasing light emitter that is used for the detection of fluoranthene fluorescence spectrum of embodiment 1 to be used for the detection of fluoranthene fluorescence spectrum, may further comprise the steps:
1) open Nd:YAG pulse laser 1, output wavelength is the fundamental frequency ray laser of 1064nm;
2) the fundamental frequency ray laser is through two frequency-doubling crystals 2, quadruple frequency crystal 3 and filter 4, and the laser of filtering 1064nm and 532nm wavelength obtains the 266nm laser of quadruple of pure linear polarization;
3) adjust quarter wave plate 5, make the 266nm laser of quadruple be converted into the 266nm laser of quadruple of circular polarization state or elliptical polarization through quarter wave plate 5;
The 266nm laser of quadruple of circular polarization state or elliptical polarization is incided Raman pond 6, produce not at the same level time the rotational raman scattering light that shakes; Adjust the prism group 7 of Raman pond 6 outgoing one side, not at the same level time the rotational raman scattering light that shakes is separated in the space; The window at 6 two ends, described Raman pond is equipped with in convex lens, the Raman pond 6 and is filled with high pressure D
2Inner D
2Air pressure be 8-10atm.
4) utilize the diaphragm 8 of prism group 7 outgoing one side, select (1,1) level shake rotational raman scattering light, the i.e. laser of 285.6nm wavelength.
5) laser of 285.6nm wavelength is through object lens 9 coupled into optical fibres 10, for the usefulness of fluoranthene fluorescence spectrum detection.
The present invention can be by changing the inner D in Raman pond
2Air pressure and the rotation quarter wave plate change the output intensity that wavelength is the laser of 285.6nm.
Below only be enumerating the inventive concept way of realization; protection scope of the present invention should not be regarded as the implementation method that only limits to state, protection scope of the present invention also be involved in those skilled in the art conceive according to the present invention the equivalent technologies means that can expect.
Claims (9)
1. an implementation method that is used for the Raman laser source of fluoranthene fluorescence spectrum detection is characterized in that, may further comprise the steps:
1) open the Nd:YAG pulse laser, output wavelength is the fundamental frequency ray laser of 1064nm;
2) the fundamental frequency ray laser obtains the 266nm laser of quadruple of pure linear polarization through two frequency-doubling crystals, quadruple frequency crystal and filter;
3) adjust quarter wave plate, make the 266nm laser of quadruple of linear polarization be converted into the 266nm laser of quadruple of circular polarization state or elliptical polarization through quarter wave plate;
4) the 266nm laser of quadruple with circular polarization state or elliptical polarization incides the Raman pond, produces not at the same level time the rotational raman scattering light that shakes; Adjust the prism group of Raman pond outgoing one side, not at the same level time the rotational raman scattering light that shakes is separated in the space; The window at two ends, described Raman pond is equipped with convex lens, is filled with high pressure D in the Raman pond
2
5) utilize the diaphragm of prism group outgoing one side to select (1,1) level rotational raman scattering light that shakes, namely the laser of 285.6nm wavelength is the Raman laser source for the fluoranthene fluoroscopic examination.
2. the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 1, it is characterized in that, the minute surface of filter step 2) and the laser of incident angle at 45 arranges, and described filter is high saturating to the laser of 1064nm and 532nm, and is high anti-to the 266nm laser of quadruple.
3. the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 2 is characterized in that described filter is two, and the minute surface of two described filters is vertical mutually.
4. the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 1 is characterized in that described prism group is made up of 2 prisms.
5. the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 1 is characterized in that the high pressure D in the described Raman pond
2Air pressure be 8-10atm.
6. the implement device of the implementation method of the described Raman laser source that detects for the fluoranthene fluorescence spectrum of claim 1, it is characterized in that, comprise the Nd:YAG pulse laser, two frequency-doubling crystals, quadruple frequency crystal, filter, quarter wave plate, Raman pond, prism group, the diaphragm that set gradually, the window at two ends, described Raman pond is equipped with convex lens, is filled with high pressure D in the Raman pond
2
7. the implement device of the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 6, it is characterized in that, the minute surface of described filter and the laser of incident angle at 45 arranges, and described filter is high saturating to the laser of 1064nm and 532nm, and is high anti-to the 266nm laser of quadruple.
8. the implement device of the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 7 it is characterized in that described filter is two, and two described filter minute surfaces is vertical mutually.
9. the implement device of the implementation method of the Raman laser source that detects for the fluoranthene fluorescence spectrum according to claim 6 is characterized in that described prism group is made up of 2 prisms.
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| CN106711752A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院大连化学物理研究所 | Intracavity gas Raman laser based on principle of rotational Raman |
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| CN112186494A (en) * | 2019-07-04 | 2021-01-05 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Cascade ultraviolet Raman laser |
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