CN104568897A - Raman spectrum enhancement device, raman spectrum enhancement system and raman spectrum enhancement method based on external resonant cavity technology - Google Patents
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Abstract
本发明揭示了一种基于腔外谐振腔技术的拉曼光谱增强装置、系统及方法，所述装置包括激光器、激光传输光纤、激发晶体、透反镜、倍频晶体以及谐振腔；所述激光器为拉曼检测提供激光光源，激光器通过激光传输光纤连接激发晶体，激发晶体产生特定波长的激光；所述透反镜经过镀膜处理，只允许特定频率光通过，全反射其他波长的光；倍频晶体用于改变激光的频率；所述谐振腔用于保证改变频率后的激光能实现全反射。本发明克服了在线拉曼光谱在检测较低组分物质时，拉曼效应弱造成的谱图不全不准确的影响，保证了拉曼光谱仪对在线复杂多组分物质得到有效分析检测。
The present invention discloses a Raman spectrum enhancement device, system and method based on extracavity resonant cavity technology. The device includes a laser, a laser transmission fiber, an excitation crystal, a mirror, a frequency doubling crystal and a resonant cavity; the laser Provide a laser light source for Raman detection. The laser is connected to the excitation crystal through a laser transmission fiber, and the excitation crystal generates laser light of a specific wavelength; the mirror is coated to only allow light of a specific frequency to pass through, and totally reflect light of other wavelengths; frequency doubling The crystal is used to change the frequency of the laser; the resonant cavity is used to ensure that the frequency-changed laser can achieve total reflection. The invention overcomes the influence of incomplete and inaccurate spectrograms caused by weak Raman effect when the online Raman spectrum detects lower component substances, and ensures that the Raman spectrometer can effectively analyze and detect online complex multi-component substances.
Description
技术领域technical field
本发明属于光电技术领域，涉及一种拉曼光谱增强装置，尤其涉及一种基于腔外谐振腔技术的拉曼光谱增强装置；同时，本发明还涉及一种基于腔外谐振腔技术的拉曼光谱增强系统及增强方法。本发明用于拉曼光谱仪实时在线监测气体、液体或气液混合物质组分时的拉曼光谱效应的增强，从而实现在线拉曼光谱在检测较低组分物质时，准确的进行定性定量分析。The invention belongs to the field of photoelectric technology, and relates to a Raman spectrum enhancement device, in particular to a Raman spectrum enhancement device based on extracavity resonator technology; at the same time, the invention also relates to a Raman spectrum enhancement device based on extracavity resonator technology Spectrum enhancement system and enhancement method. The invention is used to enhance the Raman spectrum effect when the Raman spectrometer is used for real-time online monitoring of gas, liquid or gas-liquid mixed substance components, so as to realize accurate qualitative and quantitative analysis of the online Raman spectrum when detecting lower component substances .
背景技术Background technique
拉曼散射是指光通过介质时由于入射光与分子运动相互作用而引起光的频率变化，1928年由印度物理学家钱德拉塞卡拉·拉曼发现。拉曼光谱分析技术是一种以拉曼散射效应为基础的非接触式光谱分析技术，它能对物质的成分和结构进行定性、定量分析。拉曼光谱测量速度快，应用拉曼光谱分析可以做到原位实时测量，有利于过程控制的实时在线监测。从1928年到1940年，拉曼光谱一直是研究中的热点，但由于拉曼效应太弱，人们无法检测研究较弱的拉曼散射信号，在测定时要求样品体积足够大、无色、无尘埃、无荧光等。这些缺点很大程度上制约了拉曼光谱的进一步研究及实际应用，因此随着40年代红外光谱技术的进步和商业化，拉曼光谱的地位受到了极大的削弱。由于拉曼散射光太微弱，科学家几十年来很难将拉曼散射付诸于实践。自1960年出现激光后，由于激光具有单色性好、能量集中、输出功率大等特点、尤其是光谱辐射密度高、激光源体积小、重量轻、易自动化操作等优点，故而很快将激光用于拉曼光谱仪的激发光源，从而使拉曼光谱获得了新的起点。采用激光作为单色光源，将样品分子激发到某一虚态，随后受激分子跃迁到一个与基态不同的振动能级，此时，散射辐射的频率将与入射频率不同。这种频率变化与基态和终态的振动能级差相当。这种“非弹性散射”光就称之为拉曼散射。拉曼光谱的优点在于它的快速，准确，测量时通常不破坏样品(固体、半固体、液体或气体)，样品制备简单甚至不需样品制备。Raman scattering refers to the frequency change of light caused by the interaction between incident light and molecular motion when light passes through a medium. It was discovered by Indian physicist Chandrasekara Raman in 1928. Raman spectroscopic analysis technology is a non-contact spectroscopic analysis technology based on Raman scattering effect, which can perform qualitative and quantitative analysis on the composition and structure of substances. The measurement speed of Raman spectroscopy is fast, and the application of Raman spectroscopy analysis can achieve in-situ real-time measurement, which is conducive to real-time online monitoring of process control. From 1928 to 1940, Raman spectroscopy has always been a hot spot in research, but because the Raman effect is too weak, people cannot detect and study the weaker Raman scattering signal, and the sample volume is required to be large enough, colorless, and colorless. Dust, no fluorescence, etc. These shortcomings have largely restricted the further research and practical application of Raman spectroscopy. Therefore, with the advancement and commercialization of infrared spectroscopy in the 1940s, the status of Raman spectroscopy has been greatly weakened. Because Raman scattered light is too weak, it has been difficult for scientists to put Raman scattering into practice for decades. Since the appearance of laser in 1960, due to the characteristics of good monochromaticity, concentrated energy, and large output power, especially the advantages of high spectral radiation density, small volume of laser source, light weight, and easy automatic operation, lasers will soon be used The excitation light source used for Raman spectrometer, so that Raman spectroscopy has obtained a new starting point. The laser is used as a monochromatic light source to excite the sample molecules to a virtual state, and then the excited molecules transition to a vibration level different from the ground state. At this time, the frequency of the scattered radiation will be different from the incident frequency. This frequency change is comparable to the difference in vibrational energy levels between the ground state and the final state. This "inelastically scattered" light is called Raman scattering. The advantages of Raman spectroscopy are that it is fast, accurate, usually does not destroy the sample (solid, semi-solid, liquid or gas) during measurement, and sample preparation is simple or even requires no sample preparation.
现在的拉曼光谱检测完全可以进行直接针对产品的具体指标进行直接反馈控制。在现场实际拉曼光谱定性定量分析中，拉曼谱图信号的准确获取是整个拉曼光谱分析流程中的关键，只有信号的准确可靠，才能谈论它的定性、定量准确度。现场监测在物料低浓度、微量时，其拉曼效应不强，相对拉曼信号比较微弱,从而导致在进行在线拉曼监测时的准确性降低，而恰恰这些微量的物质组分含量是在线检测中最需要检测的物质。The current Raman spectroscopy detection can completely carry out direct feedback control directly for the specific indicators of the product. In the actual qualitative and quantitative analysis of Raman spectroscopy on site, the accurate acquisition of Raman spectroscopy signals is the key to the entire Raman spectroscopy analysis process. Only when the signals are accurate and reliable can we talk about its qualitative and quantitative accuracy. When the on-site monitoring is low in concentration and trace amount of material, the Raman effect is not strong, and the relative Raman signal is relatively weak, which leads to a decrease in the accuracy of online Raman monitoring, and it is precisely the content of these trace material components that are detected online substances most in need of detection.
有鉴于此，如何解决低浓度、微量物质检测这一拉曼光谱监测在流程工业中应用的瓶颈问题，是目前在线拉曼光谱仪应用的棘手问题，也是必须解决的问题。本发明装置就是基于谐振腔全反射原理，结合腔外倍频技术，增强拉曼效应，提供高质量的拉曼信号，使拉曼对于低浓度物质检测更加准确，将对流程工业的未来产生深远的影响。In view of this, how to solve the bottleneck problem of Raman spectroscopy monitoring in the process industry, which is the detection of low-concentration and trace substances, is a thorny problem in the application of online Raman spectroscopy, and it must also be solved. The device of the present invention is based on the principle of total reflection of the resonant cavity, combined with extra-cavity frequency doubling technology, enhances the Raman effect, provides high-quality Raman signals, and makes Raman more accurate for low-concentration substance detection, which will have a profound impact on the future of the process industry Impact.
发明内容Contents of the invention
本发明所要解决的技术问题是：提供一种基于腔外谐振腔技术的拉曼光谱增强装置，可提供高质量的拉曼信号，使拉曼光谱对于低浓度物质检测更加准确，将对流程工业的未来产生深远的影响。The technical problem to be solved by the present invention is to provide a Raman spectrum enhancement device based on extracavity resonant cavity technology, which can provide high-quality Raman signals and make Raman spectrum more accurate for detection of low-concentration substances, which will be beneficial to the process industry have a profound impact on the future.
同时，本发明提供一种基于腔外谐振腔技术的拉曼光谱增强系统，可提供高质量的拉曼信号，使拉曼光谱对于低浓度物质检测更加准确，将对流程工业的未来产生深远的影响。At the same time, the present invention provides a Raman spectrum enhancement system based on extracavity resonant cavity technology, which can provide high-quality Raman signals and make Raman spectroscopy more accurate for detection of low-concentration substances, which will have far-reaching implications for the future of the process industry Influence.
此外，本发明还提供一种基于腔外谐振腔技术的拉曼光谱增强方法，可提供高质量的拉曼信号，使拉曼光谱对于低浓度物质检测更加准确，将对流程工业的未来产生深远的影响。In addition, the present invention also provides a Raman spectrum enhancement method based on extracavity resonant cavity technology, which can provide high-quality Raman signals and make Raman spectroscopy more accurate for detection of low-concentration substances, which will have a profound impact on the future of the process industry Impact.
为解决上述技术问题，本发明采用如下技术方案：In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:
一种基于腔外谐振腔技术的拉曼光谱增强装置，用于液体、气体、及气液混合物质在进行在线拉曼光谱检测时拉曼信号的增强；A Raman spectrum enhancement device based on extracavity resonant cavity technology, which is used to enhance Raman signals during online Raman spectrum detection of liquids, gases, and gas-liquid mixtures;
所述装置包括激光器、激光传输光纤、激发晶体、透反镜、倍频晶体以及谐振腔；The device includes a laser, a laser transmission fiber, an excitation crystal, a mirror, a frequency doubling crystal and a resonant cavity;
所述激光器为拉曼检测提供激光光源，激光器通过激光传输光纤连接激发晶体，激发晶体产生特定波长的激光；The laser provides a laser light source for Raman detection, the laser is connected to the excitation crystal through a laser transmission fiber, and the excitation crystal generates laser light of a specific wavelength;
所述透反镜经过镀膜处理，只允许特定频率光通过，全反射其他波长的光；倍频晶体用于改变激光的频率；所述谐振腔用于保证改变频率后的激光能实现全反射。The mirror is coated to only allow light of a specific frequency to pass through, and totally reflect light of other wavelengths; the frequency doubling crystal is used to change the frequency of the laser; the resonant cavity is used to ensure that the laser after changing the frequency can achieve total reflection.
作为本发明的一种优选方案，所述谐振腔包括两面互相平行的反射镜，两个反射镜之间放置工作物质，构成这种谐振腔的两个全反镜为透反镜；当特定波长的激光进入谐振腔后，在腔内进行无限次数的反射，激光器发射的激光和谐振腔内进行全反射增强的两个光的频率不同。As a preferred solution of the present invention, the resonant cavity includes two reflecting mirrors parallel to each other, and the working substance is placed between the two reflecting mirrors. After the laser light enters the resonant cavity, it is reflected for an infinite number of times in the cavity. The frequency of the laser emitted by the laser and the two lights enhanced by total reflection in the resonant cavity are different.
作为本发明的一种优选方案，所述透反镜、倍频晶体以及谐振腔内的全反射镜集成在一个镀膜晶体上，该镀膜晶体能透射过特定频率的激光，通过倍频技术改变特设的激光频率，并且全反射倍频后的特定频率的激光。As a preferred solution of the present invention, the mirror, the frequency doubling crystal and the total reflection mirror in the resonant cavity are integrated on a coated crystal. The laser frequency is set, and the laser of a specific frequency after frequency doubling is totally reflected.
作为本发明的一种优选方案，所述装置使用腔外倍频技术；激光器发射的某波长的激光，照射相应的激发晶体，通过只允许透过特定波长激光的透反镜，进入到倍频晶体；所述倍频晶体通过镀膜技术，使透过它的一定频率的光通过它之后频率增加；使用的是二倍倍频晶体，即使原来的激光频率增加为原来的两倍，波长减短为原来的二分之一。As a preferred solution of the present invention, the device uses extracavity frequency doubling technology; the laser of a certain wavelength emitted by the laser irradiates the corresponding excitation crystal, and enters the frequency doubling process through a mirror that only allows the laser of a specific wavelength to pass through. Crystal; the frequency-doubling crystal uses coating technology to increase the frequency of light of a certain frequency passing through it; it uses a double-frequency crystal, even if the original laser frequency is doubled, and the wavelength is shortened One-half of the original.
作为本发明的一种优选方案，波长改变后的激光在谐振腔内进行增强，通过腔内全反射镜可使激光波长达到几乎无损失全反射加强。As a preferred solution of the present invention, the wavelength-changed laser is enhanced in the resonant cavity, and the laser wavelength can be strengthened by total reflection with almost no loss through the total reflection mirror in the cavity.
一种基于腔外谐振腔技术的拉曼光谱增强系统，其特征在于，所述系统包括：所述的拉曼光谱增强装置、拉曼检测器、第二光纤、拉曼光谱仪；A Raman spectrum enhancement system based on extracavity resonator technology, characterized in that the system includes: the Raman spectrum enhancement device, a Raman detector, a second optical fiber, and a Raman spectrometer;
所述拉曼光谱增强装置的谐振腔内设置所述拉曼检测器，拉曼信号通过第二光纤传导至拉曼光谱仪进行光谱分析。The Raman detector is arranged in the resonant cavity of the Raman spectrum enhancement device, and the Raman signal is transmitted to the Raman spectrometer through the second optical fiber for spectral analysis.
作为本发明的一种优选方案，原发射激光频率改变后，在谐振腔经过全反射，于谐振腔的腔体内经过多次反复振荡增强，同时增大了与样品的接触面积，从而增强了样品的拉曼散射信号，由位于谐振腔一侧的所述拉曼检测器收集增强信号后通过第二光纤传输到拉曼光谱仪，获得增强的拉曼光谱谱图。As a preferred solution of the present invention, after the frequency of the original emitted laser is changed, it undergoes total reflection in the resonant cavity, and undergoes multiple repeated oscillations in the cavity of the resonant cavity. At the same time, the contact area with the sample is increased, thereby strengthening the sample. The Raman scattering signal is collected by the Raman detector located on one side of the resonant cavity and then transmitted to the Raman spectrometer through the second optical fiber to obtain an enhanced Raman spectrum.
一种上述拉曼光谱增强装置的增强方法，所述方法包括：A method for enhancing the above-mentioned Raman spectroscopy enhancement device, the method comprising:
将激光器发射的激光照射激发晶体，产生特定波长的激光，到达只允许特定频率光通过的透反镜，过滤掉有激光产生过程中可能出现的杂散光；选取的透反镜与激发晶体激发的波长相同，这样，进入倍频晶体后，激光频率发生成倍数的改变；The laser emitted by the laser is irradiated to excite the crystal to generate laser light of a specific wavelength, which reaches the mirror that only allows light of a specific frequency to pass through, and filters out the stray light that may appear during the laser generation process; the selected mirror and the excitation crystal excite The wavelength is the same, so that after entering the frequency doubling crystal, the laser frequency changes exponentially;
改变频率后的激光在谐振腔内，进行全反射增强激光效应；由于在激光进入谐振腔时设置了倍频晶体，在谐振腔内进行全反射的激光不会再透过前面的透反镜损失掉；The laser after changing the frequency is totally reflected in the resonator to enhance the laser effect; since the frequency doubling crystal is set when the laser enters the resonator, the laser that is totally reflected in the resonator will not be lost through the front mirror Lose;
激光器发射的激光和谐振腔内进行全反射增强的光的频率不同，在腔内进行多次全反射增强的激光多次直接照射在待检测的待测物料上，此时进行拉曼信号收集，获得增强后的物料拉曼检测谱图。The frequency of the laser emitted by the laser is different from that of the light enhanced by total reflection in the resonant cavity. The laser beam enhanced by total reflection multiple times in the cavity is directly irradiated on the material to be tested for multiple times. At this time, the Raman signal is collected. Obtain the enhanced Raman detection spectrum of the material.
本发明的有益效果在于：本发明提出的基于腔外谐振腔技术的拉曼光谱增强装置、系统及方法，实现了实时在线监测气体、液体或气液混合物质组分时的拉曼光谱信号的增强，通过对激光器发射的特定波长激光的波长改变，以及使用Fabry-Perot谐振腔使激光进行多次全反射，达到激光的增强和增大接触面积的目的，克服了在线拉曼光谱在检测较低组分物质时，拉曼效应弱造成的谱图不全不准确的影响，保证了拉曼光谱仪对在线复杂多组分物质得到有效分析检测。The beneficial effect of the present invention is that: the Raman spectrum enhancement device, system and method based on the extra-cavity resonant cavity technology proposed by the present invention realizes the real-time on-line monitoring of the Raman spectrum signal of the gas, liquid or gas-liquid mixture components. Enhancement, by changing the wavelength of the specific wavelength laser emitted by the laser, and using the Fabry-Perot resonator to make the laser perform multiple total reflections, the purpose of laser enhancement and increase of the contact area is achieved, which overcomes the difficulty of online Raman spectroscopy in detection. In the case of low-component substances, the incomplete and inaccurate spectrum caused by the weak Raman effect ensures that the Raman spectrometer can effectively analyze and detect online complex multi-component substances.
附图说明Description of drawings
图1为本发明拉曼光谱增强系统的原理示意图。Fig. 1 is a schematic diagram of the principle of the Raman spectrum enhancement system of the present invention.
图2为本发明装置的谐振腔内部结构示意图。Fig. 2 is a schematic diagram of the internal structure of the resonant cavity of the device of the present invention.
具体实施方式Detailed ways
下面结合附图详细说明本发明的优选实施例。Preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings.
实施例一Embodiment one
本发明揭示了一种基于腔外谐振腔技术的拉曼光谱增强装置及系统，本发明装置可应用于拉曼光谱仪实时在线监测气体、液体或气液混合物质组分时的拉曼光谱信号的增强，从而实现在线拉曼光谱在检测较低组分物质时，能够进行准确的定性定量分析。由于光谱在线检测现场比较复杂、恶劣，在线拉曼光谱检测通过光纤传导的范围在150m内为较佳状态，所以本发明的校正装置随在线拉曼检测器主体装置一起被安放在分析小屋内，同时本发明装置的结构体积较小、使用较方便。The invention discloses a Raman spectrum enhancement device and system based on extracavity resonant cavity technology. The device of the invention can be applied to Raman spectrometer real-time online monitoring of Raman spectrum signals of gas, liquid or gas-liquid mixture components Enhanced, so that online Raman spectroscopy can perform accurate qualitative and quantitative analysis when detecting lower component substances. Since the on-line spectrum detection site is relatively complex and harsh, the range of online Raman spectrum detection through optical fiber transmission is the best state within 150m, so the correction device of the present invention is placed in the analysis cabin together with the main device of the on-line Raman detector. Simultaneously, the device of the present invention has a smaller structural volume and is more convenient to use.
以下结合较佳实施例，对依据本发明提供的具体实施方式、特征及其功效，详细说明后，为了简单清楚地目的，下文恰当的省略了公知技术的描述以免那些不必要的细节影响对本技术方案的描述。In the following, in conjunction with the preferred embodiments, the specific implementation, features and effects provided by the present invention are described in detail. For the purpose of simplicity and clarity, the description of known technologies is appropriately omitted below to avoid those unnecessary details from affecting the technology. A description of the scheme.
请参阅图1，在本实施例中，选取波长为808nm的激光作为激光器1，为后续拉曼检测提供激发光源，激光变频及增强部分包括：激光传导光纤2，激发产生1064nm波长激光的激发晶体3，允许特定频率激光通过的透反镜6、7，改变激光频率的倍频晶体4，以及保证改变频率后的激光可以实现全反射的Fabry-Perot谐振腔5；Fabry-Perot谐振腔5腔内充满了待检测物料，腔体内设有拉曼检测器8，拉曼信号通过光纤9传导至拉曼光谱仪10进行光谱分析。Please refer to Fig. 1, in this embodiment, the laser with a wavelength of 808nm is selected as the laser 1 to provide an excitation light source for subsequent Raman detection. The laser frequency conversion and enhancement part includes: a laser conduction fiber 2, which excites an excitation crystal that generates a laser with a wavelength of 1064nm 3. Mirrors 6 and 7 that allow specific frequency lasers to pass through, frequency doubling crystals 4 that change the laser frequency, and Fabry-Perot resonators 5 that ensure total reflection of the laser after changing the frequency; Fabry-Perot resonators 5 cavities The cavity is filled with materials to be detected, and a Raman detector 8 is installed in the cavity, and the Raman signal is transmitted to the Raman spectrometer 10 through the optical fiber 9 for spectral analysis.
如图2，图2揭示了上述谐振腔的内部结构示意图，本发明中选用的允许特定频率激光通过的透反镜6、7，改变激光频率的倍频晶体4，以及保证改变频率后的激光可以实现全反射的Fabry-Perot谐振腔5，在实际应用中，可以集成在一个镀膜晶体11上，镀膜晶体11的特征在于可以透射过特定频率的激光，通过倍频技术改变特设的激光频率，并且全反射倍频后的特定频率的激光。As shown in Fig. 2, Fig. 2 discloses the internal structure diagram of the above-mentioned resonant cavity, the mirrors 6 and 7 that allow specific frequency lasers to pass through, the frequency doubling crystal 4 that changes the laser frequency, and the laser that guarantees the frequency change. The Fabry-Perot resonant cavity 5 that can realize total reflection can be integrated on a coated crystal 11 in practical applications. The feature of the coated crystal 11 is that it can transmit laser light of a specific frequency, and change the ad hoc laser frequency through frequency doubling technology , and totally reflect the laser of a specific frequency after frequency doubling.
对于特定激光频率的改变，将激光器1发射的808nm的激光，通过光纤2进行传导，到达激发晶体3产生1064nm的激光，然后通过只允许特定波长1064nm通过的透反镜6，所以进入倍频晶体4前的激光波长为1064nm。特定波长为1064nm的激光通过倍频晶体4后将改变其原来的波长，波长的改变在于倍频晶体的选定，选用两倍倍频晶体，1064nm的激光转化为原来波长的一半即为532nm。For the change of the specific laser frequency, the 808nm laser emitted by the laser 1 is transmitted through the optical fiber 2, reaches the excitation crystal 3 to generate 1064nm laser, and then passes through the mirror 6 that only allows a specific wavelength of 1064nm to pass through, so it enters the frequency doubling crystal The laser wavelength before 4 is 1064nm. The laser with a specific wavelength of 1064nm will change its original wavelength after passing through the frequency doubling crystal 4. The change of the wavelength lies in the selection of the frequency doubling crystal. If the double frequency doubling crystal is selected, the 1064nm laser will be converted into half of the original wavelength to be 532nm.
对于特定激光增强，改变频率后的激光在Fabry-Perot谐振腔5内，进行全反射，反复震荡增强，。由于我们在激光进入Fabry-Perot谐振腔时设置了倍频晶体4，在腔内进行全反射的激光不会透过前面的透反镜损失掉。在腔内进行多次全反射增强的激光多次直接照射在待检测的待测物料上，产生拉曼光，并由放置在腔内的拉曼效应检测器8进行拉曼信号采集，获得增强后的物料拉曼检测信号，通过光纤9传至拉曼光谱成像系统，最后获得增强后的检测物料拉曼谱图。For specific laser enhancement, the frequency-changed laser undergoes total reflection in the Fabry-Perot resonator 5, and is repeatedly oscillated for enhancement. Since we set up a frequency doubling crystal 4 when the laser light enters the Fabry-Perot resonant cavity, the laser light that undergoes total reflection in the cavity will not be lost through the front mirror. The laser that has undergone multiple total reflection enhancements in the cavity is directly irradiated on the material to be tested multiple times to generate Raman light, and the Raman signal is collected by the Raman effect detector 8 placed in the cavity to obtain enhanced The final Raman detection signal of the material is transmitted to the Raman spectrum imaging system through the optical fiber 9, and finally the enhanced Raman spectrum of the detection material is obtained.
以上介绍了本发明基于腔外谐振腔技术的拉曼光谱增强装置及系统，本发明在揭示上述装置及系统的同时，还揭示一种上述拉曼光谱增强装置的增强方法，所述方法包括：将激光器发射的激光照射激发晶体，产生特定波长的激光，到达只允许特定频率光通过的透反镜，过滤掉所有激光产生过程中可能出现的杂散光；选取的透反镜与激发晶体激发的波长相同，这样，进入倍频晶体后，激光频率发生成倍数的改变。改变频率后的激光在谐振腔内，进行全反射增强激光效应；由于在激光进入谐振腔时设置了倍频晶体，在谐振腔内进行全反射的激光不会再透过前面的透反镜损失掉。激光器发射的激光和谐振腔内进行全反射增强的光的频率不同，在腔内进行多次全反射增强的激光多次直接照射在待检测的待测物料上，此时进行拉曼信号收集，获得增强后的物料拉曼检测谱图。The Raman spectrum enhancement device and system based on the extracavity resonant cavity technology of the present invention have been introduced above. While disclosing the above-mentioned device and system, the present invention also discloses a method for enhancing the above-mentioned Raman spectrum enhancement device. The method includes: The laser emitted by the laser is irradiated to excite the crystal to generate laser light of a specific wavelength, which reaches the mirror that only allows light of a specific frequency to pass through, and filters out all stray light that may appear during the laser generation process; the selected mirror and the excitation crystal excite The wavelength is the same, so after entering the frequency doubling crystal, the laser frequency changes exponentially. The laser after changing the frequency is totally reflected in the resonator to enhance the laser effect; since the frequency doubling crystal is set when the laser enters the resonator, the laser that is totally reflected in the resonator will not be lost through the front mirror Lose. The frequency of the laser emitted by the laser is different from that of the light enhanced by total reflection in the resonant cavity. The laser beam enhanced by total reflection multiple times in the cavity is directly irradiated on the material to be tested for multiple times. At this time, the Raman signal is collected. Obtain the enhanced Raman detection spectrum of the material.
综上所述，本发明提出的基于腔外谐振腔技术的拉曼光谱增强装置、系统及方法，实现了实时在线监测气体、液体或气液混合物质组分时的拉曼光谱信号的增强，通过对激光器发射的特定波长激光的波长改变，以及使用Fabry-Perot谐振腔使激光进行多次全反射，达到激光的增强和增大接触面积的目的，克服了在线拉曼光谱在检测较低组分物质时，拉曼效应弱造成的谱图不全不准确的影响，保证了拉曼光谱仪对在线复杂多组分物质得到有效分析检测。In summary, the Raman spectrum enhancement device, system and method based on the extracavity resonant cavity technology proposed by the present invention realizes the enhancement of Raman spectrum signals when real-time online monitoring of gas, liquid or gas-liquid mixture components, By changing the wavelength of the specific wavelength laser emitted by the laser, and using the Fabry-Perot resonator to make the laser perform multiple total reflections, the purpose of enhancing the laser and increasing the contact area is achieved, which overcomes the problem of online Raman spectroscopy in the detection of lower groups. When separating substances, the incomplete and inaccurate spectrum caused by the weak Raman effect ensures that the Raman spectrometer can effectively analyze and detect online complex multi-component substances.
这里本发明的描述和应用是说明性的，并非想将本发明的范围限制在上述实施例中。这里所披露的实施例的变形和改变是可能的，对于那些本领域的普通技术人员来说实施例的替换和等效的各种部件是公知的。本领域技术人员应该清楚的是，在不脱离本发明的精神或本质特征的情况下，本发明可以以其它形式、结构、布置、比例，以及用其它组件、材料和部件来实现。在不脱离本发明范围和精神的情况下，可以对这里所披露的实施例进行其它变形和改变。The description and application of the invention herein is illustrative and is not intended to limit the scope of the invention to the above-described embodiments. Variations and changes to the embodiments disclosed herein are possible, and substitutions and equivalents for various components of the embodiments are known to those of ordinary skill in the art. It should be clear to those skilled in the art that the present invention can be realized in other forms, structures, arrangements, proportions, and with other components, materials and components without departing from the spirit or essential characteristics of the present invention. Other modifications and changes may be made to the embodiments disclosed herein without departing from the scope and spirit of the invention.
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