CN111982884A - Compact 266nm shortwave ultraviolet Raman spectrometer - Google Patents
Compact 266nm shortwave ultraviolet Raman spectrometer Download PDFInfo
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- CN111982884A CN111982884A CN202010964620.2A CN202010964620A CN111982884A CN 111982884 A CN111982884 A CN 111982884A CN 202010964620 A CN202010964620 A CN 202010964620A CN 111982884 A CN111982884 A CN 111982884A
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N2021/0106—General arrangement of respective parts
- G01N2021/0112—Apparatus in one mechanical, optical or electronic block
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/653—Coherent methods [CARS]
- G01N2021/655—Stimulated Raman
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Abstract
A compact 266nm short-wave ultraviolet Raman spectrometer comprises a light source, an external light path, a dispersion system, a receiving system and a signal acquisition system. The light source is an all-solid-state 266nm short-wave ultraviolet laser, the outer light path comprises a collimating lens, a first reflector, a dichroic mirror, a beam expanding mirror, a light filter, a relay lens, a coupling optical fiber and a shaping optical fiber bundle, the dispersion system comprises a slit, a second reflector, an off-axis parabolic reflector and a planar reflective grating, the receiving system is a back-illuminated CCD linear array detector, and the signal acquisition system is a computer. The optical fiber bundle is composed of a plurality of optical fibers, one end of the optical fiber bundle is arranged into an optical fiber array, the other end of the optical fiber bundle is arranged into a linear shape, the light flux entering the dispersion system is improved by the point-to-line optical fiber bundle, the signal to noise ratio of the system is increased, in addition, the chromatic aberration can be effectively reduced by the Raman spectrometer dispersion method based on the Littrow structure, and the resolution ratio of the spectrometer is improved.
Description
Technical Field
The invention relates to the technical field of spectral analysis, in particular to a compact 266nm short-wave ultraviolet Raman spectrometer.
Background
The Raman spectrum is a molecular vibration spectrum, the information of the molecular structure can be obtained through spectrogram analysis, and the spectral determination can be carried out on any gaseous, liquid and solid samples. The position and intensity information of characteristic peaks of different substances on the spectrogram are different. The rapid, simple, repeatable and more important qualitative and quantitative analysis without damage enables the Raman spectrum to become the fingerprint for identifying the substance, and is an important means for analyzing the structure of the organic compound.
At present, visible light or near-infrared laser is mostly adopted by a portable Raman spectrometer as an excitation light source, the Raman spectrum excitation efficiency is low, fluorescence interference is easily generated, the spectrum of a sample cannot be well presented, and information is misjudged. Short wave ultraviolet Raman effectively overcomes the defects, so that the frequency shift of an excitation light source to an ultraviolet band is widely concerned by people when a Raman spectrometer is researched.
When the Raman excitation wavelength is short-wave ultraviolet laser, the resolution of a spectrum detection system is required to reach 0.1nm, and the traditional compact dispersion spectrometer has low luminous flux, so that the sensitivity is reduced, and the detection precision is influenced. In addition, when the water solution is detected, the short-wave ultraviolet excitation light source and the Raman spectrum signal are strongly absorbed by water, and the traditional optical fiber probe is weak in collecting the Raman signal, so that the testing sensitivity is influenced.
Disclosure of Invention
The invention aims to provide a compact 266nm short-wave ultraviolet Raman spectrometer to overcome the problems in the prior art. The all-solid-state 266nm short-wave ultraviolet laser is used as a light source, so that the fluorescence interference is reduced; the beam expanding system is adopted to increase the caliber of the output laser, improve the contact surface with the aqueous solution and facilitate the detection of the liquid sample; the light flux is increased by adopting a fiber bundle shaping technology; and a grating dispersion system based on a Littrow structure is adopted to improve the spectral resolution.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a compact 266nm short-wave ultraviolet Raman spectrometer comprises a light source, an external light path, a dispersion system, a receiving system and a signal acquisition system, wherein the light source is a diode-pumped all-solid 266nm short-wave ultraviolet laser 1; outer light path includes collimating lens 2, first speculum 3, dichroic mirror 4, beam expanding mirror 5, light filter 6, relay lens 7, coupling fiber 8 and plastic fiber bundle 9, and the space precedence order of light path trend is in proper order: 266nm short-wave ultraviolet laser, collimating lens, first reflector, dichroic mirror, beam expanding lens and sample; the short wave ultraviolet laser is focused and irradiated on a sample to be detected to excite Raman scattering light, and the light path trend space sequence of the Raman scattering light is as follows: the device comprises a sample, a beam expander, a dichroic mirror, a light filter, a relay lens, a coupling optical fiber and a shaping optical fiber bundle; the dispersion system includes: the spatial trend sequence of the Raman scattering light entering the dispersion system is as follows, wherein the Raman scattering light enters the slit 10, the second reflector 11, the off-axis parabolic reflector 12 and the planar reflective grating 13: the slit, the second reflector, the off-axis parabolic reflector, the planar reflective grating and the off-axis parabolic reflector; the receiving system is a back-illuminated CCD linear array sensor 14; the signal acquisition system is a computer 15.
As a preferred technical scheme, the laser is a diode-pumped all-solid-state 266nm short-wave ultraviolet laser.
As an optimized technical scheme, Raman scattering light excited by a sample to be detected forms a circular light spot through a coupling optical fiber, the circular light spot enters the input end of a shaping optical fiber bundle through a flange at the output end of the coupling optical fiber, the circular light spot is spatially divided to form a plurality of sub light spots, each sub light spot corresponds to a small-aperture quartz ultraviolet optical fiber and correspondingly forms an optical fiber bundle, and beam shaping from a large-area circular light spot to a long light spot is realized.
As a preferred technical solution, the combination mode of the shaping optical fiber bundle is one of the following modes:
the input end is a 3 multiplied by 3 array, and the output end is a linear arrangement formed by 9 optical fibers;
the input end is a 2 x 3 x 2 array, and the output end is a linear arrangement consisting of 7 optical fibers.
As a preferred technical solution, the optical filter is a dual-sheet long-pass filter disposed in a non-parallel manner.
Preferably, the length of one field end of the shaped optical fiber bundle is consistent with the length of the slit.
The invention has the beneficial effects that:
compared with the prior art, the compact 266nm short-wave ultraviolet Raman spectrometer can directly perform Raman spectrum measurement on a liquid sample to be measured, and can be used for monitoring and analyzing in the aspects of biology, physics, chemistry and medicine.
The advantages are that:
1. the diode-pumped all-solid-state 266nm short-wave ultraviolet laser is used as an excitation light source, so that the fluorescence can be greatly reduced, the sensitivity is improved, a stronger Raman signal is excited, and the signal-to-noise ratio is improved;
2. the aperture of the output laser is increased through a beam expanding system, so that the aperture change of the emergent light beam is realized, and the detection of a liquid target sample is adapted;
3. one end of the shaping optical fiber bundle is designed into a square or round pattern, the other end of the shaping optical fiber bundle is designed into a linear pattern, a point-to-line optical fiber bundle is formed, the linear output end is highly matched with the slit end of the dispersion system, the light flux entering the dispersion system is improved, and the stray light of the system is controlled, so that the loss of Raman light is reduced, and the light transmission efficiency between an outer light path and the slit is improved;
4. the dispersion system adopts a Letto (Littrow) optical path structure design, and the off-axis parabolic reflector replaces a spherical reflector to reduce aberration and improve the resolution of the spectrometer.
Drawings
FIG. 1 is a light path structure diagram of a compact 266nm short wave UV Raman spectrometer;
FIG. 2 is a diagram of a connection structure of a large-sized ultraviolet quartz coupling fiber with a shaping fiber bundle through a flange;
fig. 3 is a diagram of an optical path structure of a dispersive raman spectrometer based on a Littrow structure.
Description of the labeling: 1. 266nm short-wave ultraviolet laser, 2, a collimating lens, 3, a first reflector, 4, a dichroic mirror, 5, a beam expanding mirror, 6, a light filter, 7, a relay lens, 8, a coupling optical fiber, 9, a shaping optical fiber bundle, 10, a slit, 11, a second reflector, 12, an off-axis parabolic reflector, 13, a plane reflective grating, 14, a back-illuminated CCD linear array sensor, 15 and a computer.
A: light source, B: outer optical path, C: dispersive system, D: receiving system, E: signal acquisition system
a: input end of coupling optical fiber, b is output end of coupling optical fiber, c: input end of a shaping fiber bundle, d: shaping optical fiber bundle output end
Detailed Description
The invention is further described with reference to the following figures and detailed description.
With reference to fig. 1, the compact 266nm short-wave ultraviolet raman spectrometer of the present invention comprises a light source a, an external optical path B, a dispersion system C, a receiving system D, and a signal acquisition system E, wherein the dispersion system is connected with the external optical path through a coupling fiber and a shaping fiber bundle. Wherein the light source is a diode-pumped all-solid-state 266nm short-wave ultraviolet laser 1; the external light path consists of a collimating lens 2, a first reflector 3, a dichroic mirror 4, a beam expander 5, an optical filter 6, a relay lens 7, a coupling optical fiber 8 and a shaping optical fiber bundle 9; the dispersion system consists of a slit 10, a second reflector 11, an off-axis parabolic reflector 12 and a planar reflective grating 13; the receiving system is a back-illuminated CCD linear array sensor 14; the signal acquisition system is a computer 15.
With reference to fig. 1, the light path of the compact 266nm short-wave uv raman spectrometer of the present invention is as follows: the 266nm short wave ultraviolet laser device excites laser to be collimated by the collimating lens, then the laser is incident to the dichroic mirror through the first reflecting mirror, and then the excited laser is focused on a sample to be measured through the beam expanding lens, simultaneously collecting Raman scattered light generated on a sample to be detected, enabling the Raman scattered light to pass through the dichroic mirror again, filtering stray light by the optical filter and enabling the stray light to enter the relay lens, enabling the Raman scattered light to pass through the coupling optical fiber with the input end at the focus of the relay lens and pass through the shaping optical fiber bundle, the output end of the optical fiber bundle is in butt joint with the slit to enter a dispersion system, the optical fiber bundle is reflected to the off-axis parabolic reflector through the second reflector to form a parallel light beam to enter a planar reflective grating, light rays with different wavelengths are emitted to the off-axis parabolic reflector according to different diffraction angles under the light splitting action of the grating, the light rays are imaged on the back-illuminated CCD linear array detector after being focused, and finally, the acquisition and analysis of signals are completed on a computer.
With reference to fig. 1, in the dispersion system C of the compact 266nm short-wave uv-raman spectrometer of the present invention, the off-axis parabolic mirror serves as both the collimating mirror and the focusing mirror, and the back-illuminated CCD line array sensor is located on the focal plane of the off-axis parabolic mirror.
With reference to fig. 2, in the compact 266nm short-wave ultraviolet raman spectrometer of the present invention, a coupling fiber is connected to a shaping fiber bundle through a flange, raman scattered light excited by a sample to be measured passes through the coupling fiber to form a circular light spot, enters an input end c of the shaping fiber bundle through the flange at an output end b of the coupling fiber, and is spatially divided to form a plurality of sub light spots, each sub light spot corresponds to one quartz ultraviolet fiber with a small aperture, and the sub light spots are arranged in a line at an output end d of the fiber bundle to form the fiber bundle, so that beam shaping from a large area circular light spot to a long light spot is completed. And aligning the linear array optical fiber bundle at the output end of the shaping optical fiber bundle to an incident slit of the spectrometer, so that Raman scattering light excited by the sample to be tested is guided into a dispersion system of the short wave ultraviolet Raman spectrometer, and the connection between the outer optical path B and the dispersion system C is completed.
With reference to fig. 2, the input end of the coupling fiber and the output end of the shaping fiber bundle in the compact 266nm short-wave ultraviolet raman spectrometer of the present invention both use SMA905 interfaces, and the input end of the coupling fiber is located at the focus of the relay lens.
Referring to fig. 3, a schematic diagram of a three-dimensional structure of a dispersion system C in a compact 266nm short-wave uv-raman spectrometer. The Raman scattering light excited by the sample to be measured is emitted by the incident slit, the incident light is reflected by the second reflecting mirror and then enters the off-axis parabolic reflecting mirror to form parallel light beams, the parallel light beams enter the dispersion element, are subjected to dispersion and splitting by the planar reflective grating, and the diffracted light beams enter the off-axis parabolic reflecting mirror again and then enter the surface of the back-illuminated CCD linear array sensor after being focused. The back-illuminated CCD linear array detector is positioned on the focal plane of the off-axis parabolic reflector.
Claims (6)
1. A compact 266nm shortwave ultraviolet Raman spectrometer is characterized in that: the system comprises a light source, an external light path, a dispersion system, a receiving system and a signal acquisition system, wherein the light source is a diode-pumped all-solid-state 266nm short-wave ultraviolet laser (1); outer light path includes collimating lens (2), first speculum (3), dichroic mirror (4), beam expanding mirror (5), light filter (6), relay lens (7), coupling optical fiber (8) and plastic optical fiber bundle (9), and the space precedence of light path trend is in proper order: 266nm short-wave ultraviolet laser, collimating lens, first reflector, dichroic mirror, beam expanding lens and sample; the short wave ultraviolet laser is focused and irradiated on a sample to be detected to excite Raman scattering light, and the light path trend space sequence of the Raman scattering light is as follows: the device comprises a sample, a beam expander, a dichroic mirror, a light filter, a relay lens, a coupling optical fiber and a shaping optical fiber bundle; the dispersion system includes: the Raman scattering light entering the dispersion system sequentially from the space direction of the slit (10), the second reflector (11), the off-axis parabolic reflector (12) and the plane reflective grating (13) is as follows: the slit, the second reflector, the off-axis parabolic reflector, the planar reflective grating and the off-axis parabolic reflector; the receiving system is a back-illuminated CCD linear array sensor (14); the signal acquisition system is a computer (15).
2. A compact 266nm short wave uv raman spectrometer according to claim 1, wherein: the laser is a diode-pumped all-solid-state 266nm short-wave ultraviolet laser.
3. A compact 266nm short wave uv raman spectrometer according to claim 1, wherein: raman scattered light excited by a sample to be detected forms a circular light spot through a coupling optical fiber, the circular light spot enters the input end of a shaping optical fiber bundle through a flange at the output end of the coupling optical fiber, the circular light spot is spatially divided to form a plurality of sub light spots, each sub light spot corresponds to a small-aperture quartz ultraviolet optical fiber and correspondingly forms an optical fiber bundle, and beam shaping from a large-area circular light spot to a long light spot is realized.
4. A compact 266nm short wave uv raman spectrometer according to claim 3, wherein said shaping fiber bundle is combined in one of the following ways:
(1) the input end is a 3 multiplied by 3 array, and the output end is a linear arrangement formed by 9 optical fibers;
(2) the input end is a 2 x 3 x 2 array, and the output end is a linear arrangement consisting of 7 optical fibers.
5. A compact 266nm short wave uv raman spectrometer according to claim 1, wherein: the optical filter is a double-sheet long-pass optical filter which is arranged in a non-parallel mode.
6. A compact 266nm short wave uv raman spectrometer according to claim 1, wherein: the length of one field end of the shaping optical fiber bundle is consistent with the length of the slit.
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Cited By (3)
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| CN113203727A (en) * | 2021-05-12 | 2021-08-03 | 华中科技大学 | Spectrum measuring device and method |
| CN115308187A (en) * | 2021-05-08 | 2022-11-08 | 上海近观科技有限责任公司 | Chip type Raman spectrometer |
| CN115452804A (en) * | 2022-11-10 | 2022-12-09 | 泉州师范学院 | Raman spectrum detection device and method for body fluid |
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