CN105092560A - Device and method for detecting signal intensity of frequency-shift excitation raman spectrum based on tunable laser - Google Patents

Device and method for detecting signal intensity of frequency-shift excitation raman spectrum based on tunable laser Download PDF

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CN105092560A
CN105092560A CN201510582530.6A CN201510582530A CN105092560A CN 105092560 A CN105092560 A CN 105092560A CN 201510582530 A CN201510582530 A CN 201510582530A CN 105092560 A CN105092560 A CN 105092560A
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赵晓荣
娄秀涛
哈斯乌力吉
巴德欣
吕志伟
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Harbin Institute of Technology Shenzhen
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Abstract

一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置及方法,涉及拉曼光谱的信号强度检测技术领域。它为了解决移频激发装置结构复杂,实时性差及无法探测宽谱物质,根据差分拉曼光谱信号反演原始拉曼光谱信号的过程计算量大,而且会引入误差的问题。光栅控制器控制光栅的偏摆和俯仰姿态,通过改变光栅的偏摆角度来改变半导体激光器的出射波长,通过控制光束耦合至激发光纤的效率来调节激发光功率的大小,对获得的初始差分拉曼光谱信号积分并归一化,得到归一化的差分拉曼光谱信号,均匀提取N个数据点并取绝对值求和,得到拉曼光谱信号强度值。本发明可用于获得拉曼光谱的信号强度。

A signal intensity detection device and method based on tunable laser frequency shift excitation Raman spectroscopy, relating to the technical field of signal intensity detection of Raman spectroscopy. In order to solve the problem of complex structure of the frequency-shifting excitation device, poor real-time performance and inability to detect broad-spectrum substances, the process of inverting the original Raman spectrum signal from the differential Raman spectrum signal is computationally intensive and will introduce errors. The grating controller controls the yaw and pitch attitude of the grating, changes the output wavelength of the semiconductor laser by changing the yaw angle of the grating, and adjusts the excitation light power by controlling the coupling efficiency of the beam to the excitation fiber. The Mann spectrum signal is integrated and normalized to obtain a normalized differential Raman spectrum signal, and N data points are uniformly extracted and summed by absolute values to obtain the Raman spectrum signal intensity value. The present invention can be used to obtain the signal intensity of Raman spectrum.

Description

一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置及方法A signal intensity detection device and method based on tunable laser frequency shift excitation Raman spectroscopy

技术领域technical field

本发明涉及拉曼光谱的信号强度检测技术领域。The invention relates to the technical field of Raman spectrum signal intensity detection.

背景技术Background technique

拉曼光谱是一种检测速度快、无需预处理、对被测物质无损伤且能够完整地反应分子内部结构信息等显著优势的检测技术,被广泛地应用于食品安全、化学分析和材料分析等领域。但是在大多数拉曼检测过程中会伴随着荧光信号的产生,弱荧光信号会严重干扰对弱拉曼信号的识别,强荧光信号甚至会淹没拉曼信号,所以在拉曼检测过程中去除荧光干扰能够非常有效地提高检测效率。Raman spectroscopy is a detection technology with significant advantages such as fast detection speed, no need for pretreatment, no damage to the measured substance, and the ability to completely reflect the internal structure information of the molecule. It is widely used in food safety, chemical analysis and material analysis, etc. field. However, most Raman detection processes will be accompanied by the generation of fluorescent signals. Weak fluorescent signals will seriously interfere with the identification of weak Raman signals, and strong fluorescent signals will even drown out Raman signals. Interference can be very effective in improving detection efficiency.

目前被广泛采用的有效的抑制荧光的方法主要有荧光猝灭法、时间分辨法、数值处理法和移频激发法。荧光猝灭法是通过在待测样品中加入特定荧光猝灭剂或增加样品的曝光时间来降低荧光产率,此方法只能针对少数特定样品且测量过程引入的额外条件给测量结果带来很大不确定性。时间分辨法利用了拉曼光寿命远远小于荧光寿命的特性,通过采用超短脉冲光或高频调制光源在时域将二者分开,但基于此方法构建的拉曼系统由于需要采用高速响应器件而大幅提高了成本。数值处理法利用拉曼信号和荧光信号的不同频谱特性,通过傅立叶变换和曲线拟合等方式从荧光背景中提取微弱的拉曼信号,但该方法受软件算法的影响较大,测量结果一致性差。At present, the effective methods of suppressing fluorescence widely used mainly include fluorescence quenching method, time-resolved method, numerical processing method and frequency-shift excitation method. The fluorescence quenching method is to reduce the fluorescence yield by adding a specific fluorescence quencher to the sample to be tested or increasing the exposure time of the sample. This method can only be used for a small number of specific samples, and the additional conditions introduced in the measurement process bring great impact on the measurement results. big uncertainty. The time-resolved method takes advantage of the fact that the Raman light lifetime is much shorter than the fluorescence lifetime, and separates the two in the time domain by using ultrashort pulse light or high-frequency modulation light source. However, the Raman system built based on this method needs to adopt high-speed response Devices significantly increase the cost. The numerical processing method uses the different spectral characteristics of the Raman signal and the fluorescent signal, and extracts the weak Raman signal from the fluorescent background through Fourier transform and curve fitting. However, this method is greatly affected by the software algorithm, and the consistency of the measurement results is poor. .

移频激发法是基于荧光与激发波长不相关的特性,在相同的收集条件下,当用两束波长具有微小差别的激光激发样品时,获得的两个光谱中荧光信号几乎不发生改变,而所有的拉曼信号都会产生微小偏移。将两次收集的信号相减即可以获得去除荧光干扰的差分拉曼光谱信号,再反演出原始拉曼光谱信号,进而实现对待测样品的分析,反演原始拉曼光谱信号的过程计算量大,而且会引入误差。移频激发法能够实现的关键是要确保有至少两个稳定的、具有不同波长的激发光。已有的技术中,大多是采用两个不同波长输出的激光器,激光器的波长需要做高精度的电流控制和温度控制来确保激光波长输出的稳定性,使用多支激光器不利于系统集成,且增加了成本。另一种广为采用的技术是采用单支波长可调的激光器,通过调节激光的工作温度、电流或通过外腔反馈来实现激发波长的改变,这种技术的优势是只使用一个激光源减小了系统体积、降低了成本。但是电流调节实现的波长改变通常只能达到0.5nm,不能满足具有宽谱物质的探测;温度调节波长速度慢,稳定调节1nm所需时间大于30s,导致整个系统实时性差;外腔反馈调节对于机械装置精密度等级要求高,且需要严格的温度控制确保波长稳定输出,大大提高了系统的复杂度和成本。The frequency-shift excitation method is based on the fact that fluorescence is independent of the excitation wavelength. Under the same collection conditions, when the sample is excited by two laser beams with slightly different wavelengths, the fluorescence signals in the two spectra obtained hardly change, while All Raman signals are slightly shifted. Subtract the two collected signals to obtain the differential Raman spectrum signal that removes the fluorescence interference, and then invert the original Raman spectrum signal, and then realize the analysis of the sample to be tested. The process of inverting the original Raman spectrum signal is computationally intensive. , and will introduce errors. The key to the realization of the frequency-shift excitation method is to ensure that there are at least two stable excitation lights with different wavelengths. In the existing technologies, most of them use two lasers with different wavelength output. The wavelength of the laser needs to be controlled by high-precision current and temperature to ensure the stability of the laser wavelength output. Using multiple lasers is not conducive to system integration and increases costs. Another widely used technology is to use a single wavelength-tunable laser to change the excitation wavelength by adjusting the operating temperature and current of the laser or through external cavity feedback. The advantage of this technology is that only one laser source is used to reduce the The system volume is small and the cost is reduced. However, the wavelength change achieved by current adjustment can usually only reach 0.5nm, which cannot meet the detection of substances with a wide spectrum; the temperature adjustment wavelength speed is slow, and the time required for stable adjustment of 1nm is more than 30s, resulting in poor real-time performance of the entire system; The precision level of the device is high, and strict temperature control is required to ensure stable wavelength output, which greatly increases the complexity and cost of the system.

发明内容Contents of the invention

本发明是为了解决移频激发装置结构复杂,实时性差及无法探测宽谱物质,根据差分拉曼光谱信号反演原始拉曼光谱信号的方法计算量大,而且会引入误差的问题,从而提供一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置及方法。The present invention aims to solve the problems of complex structure of the frequency-shift excitation device, poor real-time performance and inability to detect broad-spectrum substances. The method of reversing the original Raman spectrum signal based on the differential Raman spectrum signal has a large amount of calculation and will introduce errors, thereby providing a A signal intensity detection device and method based on tunable laser frequency shift excitation Raman spectroscopy.

本发明所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置,包括电流驱动器、半导体激光器、光栅、光栅控制器、反射镜、带通滤光片、第一凸透镜、激发光纤、第二凸透镜、样品容器、高通滤光片、耦合透镜组、收集光纤、光谱仪和光谱分析模块;A signal strength detection device based on a frequency-shifted excitation Raman spectrum of a tunable laser according to the present invention includes a current driver, a semiconductor laser, a grating, a grating controller, a mirror, a band-pass filter, a first convex lens, Excitation fiber, second convex lens, sample container, high-pass filter, coupling lens group, collection fiber, spectrometer and spectrum analysis module;

电流驱动器的控制信号输出端连接半导体激光器的控制信号输入端,半导体激光器发出的准直光束入射至光栅,光栅固定在光栅控制器上,经光栅衍射后的第零级光束入射至反射镜,反射镜反射后的光束入射至带通滤光片,带通滤光片出射的光束入射至第一凸透镜,第一凸透镜将光束汇聚并耦合进激发光纤的一端,从激发光纤的另一端出射的光束入射至第二凸透镜,第二凸透镜将光束汇聚至样品容器,样品容器中样品的拉曼散射光经高通滤光片后入射至耦合透镜组,耦合透镜组将光束汇聚到收集光纤的一端,收集光纤的另一端连接光谱仪的光学接口,光谱仪的信号输出端连接光谱分析模块的信号输入端。The control signal output terminal of the current driver is connected to the control signal input terminal of the semiconductor laser. The collimated beam emitted by the semiconductor laser is incident on the grating, and the grating is fixed on the grating controller. The zeroth order beam diffracted by the grating is incident on the mirror and reflected The light beam reflected by the mirror enters the band-pass filter, and the light beam exiting the band-pass filter enters the first convex lens. Incident to the second convex lens, the second convex lens converges the light beam to the sample container, and the Raman scattered light of the sample in the sample container enters the coupling lens group after passing through the high-pass filter, and the coupling lens group converges the light beam to one end of the collection fiber, collecting The other end of the optical fiber is connected to the optical interface of the spectrometer, and the signal output end of the spectrometer is connected to the signal input end of the spectrum analysis module.

上述经光栅衍射后的第零级光束的光功率大于100mW,线宽小于0.5nm,波长调谐范围大于10nm。The optical power of the zero-order light beam diffracted by the grating is greater than 100mW, the line width is less than 0.5nm, and the wavelength tuning range is greater than 10nm.

上述第一凸透镜和激发光纤的距离范围为(f1-5mm)~(f1+5mm),f1为第一凸透镜的焦距。The range of the distance between the first convex lens and the exciting optical fiber is (f 1 -5 mm) to (f 1 +5 mm), where f 1 is the focal length of the first convex lens.

上述半导体激光器发出的光束入射至光栅的入射角θ的范围为:10°<θ<80°,且θ与半导体激光器的输出波长λ和光栅的空间结构周期d满足关系式:λ=2dsinθ。The incident angle θ of the light beam emitted by the above-mentioned semiconductor laser incident on the grating is in the range of: 10°<θ<80°, and θ, the output wavelength λ of the semiconductor laser and the spatial structure period d of the grating satisfy the relationship: λ=2dsinθ.

上述光栅摆偏角度变化量其中△λ为待测物质拉曼光谱线宽。The above grating swing angle variation Where Δλ is the Raman spectrum linewidth of the substance to be measured.

上述经光栅衍射后的第零级光束的光功率的范围为100mW~300mW。The optical power of the zeroth-order light beam diffracted by the grating is in the range of 100 mW to 300 mW.

基于上述检测装置的检测方法,包括拉曼光谱的信号强度采集过程和分析过程:The detection method based on the above-mentioned detection device includes the signal intensity acquisition process and analysis process of Raman spectroscopy:

拉曼光谱的信号强度采集过程包括以下步骤:The signal intensity acquisition process of Raman spectroscopy includes the following steps:

步骤一一,将待测样品放置在样品容器中,开启电流驱动器,波长为λ1的激光照射在样品上;Step 11, the sample to be tested is placed in the sample container, the current driver is turned on, and the laser with a wavelength of λ1 is irradiated on the sample;

步骤一二,光谱仪采集初始光谱并输送至光谱分析模块,光谱分析模块对接收到的光谱做初步分析,判定光谱的时间稳定度和荧光背景水平;Steps 1 and 2, the spectrometer collects the initial spectrum and sends it to the spectrum analysis module, and the spectrum analysis module conducts a preliminary analysis of the received spectrum to determine the time stability and fluorescence background level of the spectrum;

步骤一三,根据步骤一二中的光谱时间稳定度和荧光背景水平,判断激光功率是否合适即既不破坏样品分子结构,所激发的荧光又不会造成光谱仪的光探测单元饱和,如果判断结果为是,则执行步骤一四,如果判断结果为否,则调整第一凸透镜与激发光纤的入射端面间的距离,并返回步骤一二;Step 13, according to the spectral time stability and fluorescence background level in step 12, judge whether the laser power is appropriate, that is, neither destroy the molecular structure of the sample, nor cause the light detection unit of the spectrometer to be saturated by the excited fluorescence. If yes, then execute step 14, if the judgment result is no, then adjust the distance between the first convex lens and the incident end face of the excitation fiber, and return to step 12;

步骤一四,光谱分析模块采集记录激发波长为λ1时的光谱信号强度R1; Step 14, the spectral analysis module collects and records the spectral signal intensity R1 when the excitation wavelength is λ1 ;

步骤一五,通过光栅反馈控制器调整光栅的偏摆角度,使激发波长为λ2,光谱分析模块采集记录激发波长为λ2时的光谱信号强度R2Step 15, adjust the deflection angle of the grating through the grating feedback controller so that the excitation wavelength is λ 2 , and the spectral analysis module collects and records the spectral signal intensity R 2 when the excitation wavelength is λ 2 ;

拉曼光谱的信号强度分析过程包括以下步骤:The signal intensity analysis process of Raman spectroscopy includes the following steps:

步骤二一,将光谱分析模块采集记录的两个不同激发波长下的光谱信号强度R1和R2做差,获得初始差分拉曼光谱信号强度D0,D0=R2-R1Step 21, making a difference between the spectral signal intensities R 1 and R 2 at two different excitation wavelengths collected and recorded by the spectral analysis module to obtain the initial differential Raman spectral signal intensity D 0 , D 0 =R 2 −R 1 ;

步骤二二,获取初始差分拉曼光谱信号强度D0中强度最大的差分信号的中心波数分别对光谱信号强度R1和R2的波数范围内做积分,分别获得表征激发光功率的值I1和I2Step 22, obtain the central wavenumber of the differential signal with the highest intensity in the initial differential Raman spectrum signal intensity D 0 Respectively for the spectral signal intensities R1 and R2 at Integrate within the range of wavenumbers to obtain the values I 1 and I 2 representing the excitation light power respectively;

步骤二三,对光谱信号强度R1和R2分别进行功率归一化,然后将二者做差获得归一化的差分拉曼光谱信号强度D,D=R2/I2-R1/I1Step two and three, perform power normalization on the spectral signal intensities R 1 and R 2 respectively, and then make a difference between the two to obtain a normalized differential Raman spectral signal intensity D, D=R 2 /I 2 -R 1 / I 1 ;

步骤二四,在范围内均匀提取归一化的差分拉曼光谱信号强度共计N个数据点,为待测物质拉曼光谱线宽,i=1~N,N为大于1的整数;Step two and four, in Extract normalized differential Raman spectrum signal intensity uniformly over the range A total of N data points, is the Raman spectrum linewidth of the substance to be measured, i=1~N, N is an integer greater than 1;

步骤二五,对范围内提取的N个数据点分逐点取绝对值求和,获得拉曼光谱信号强度值A, Step two five, yes The N data points extracted in the range are summed point by point to obtain the Raman spectrum signal intensity value A,

本发明所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置,利用单支、无温控、无需精密机械装置且波长可调谐的激光器并结合本发明所述的光谱信号强度分析方法实现强荧光物质的拉曼信号强度的检测装置和方法。用一个波长可调谐激光器可以使整个移频激发系统结构变得更加简化和紧凑,有利于系统的小型化和便携化。利用了外腔半导体激光器输出波长主要依赖于光栅反馈角、对工作温度变化不敏感的物理特性,以及当激发光波长差值大于待测物质拉曼光谱线宽情况下差分光谱信号幅值与波长差无关的光谱特性,结合本发明所述的光谱分析方法,激光器无需温控,实时性好,能够保证测量的准确度,降低了系统复杂度,缩减了系统体积和成本,提高了系统集成度和稳定性,通过改变光栅反馈角调节激光器输出波长,波长调谐范围大,可实现宽谱物质的探测。激发光功率大小的调节是通过控制自由光耦合至激发光纤的效率来实现,而非传统技术中通过改变激光注入电流来改变输出功率,这样能够确保不改变激发光的输出光谱特性,实现纯粹的光功率调整。本发明的装置与现有商品化的小型光谱仪具有很好的兼容性,易于被应用构建新型拉曼光谱检测系统。A signal intensity detection device based on tunable laser frequency shift excitation Raman spectroscopy according to the present invention uses a single, no temperature control, no precision mechanical device and tunable wavelength laser combined with the spectrum described in the present invention The signal intensity analysis method realizes the detection device and method of the Raman signal intensity of a strong fluorescent substance. Using a wavelength tunable laser can make the structure of the whole frequency shift excitation system more simplified and compact, which is beneficial to the miniaturization and portability of the system. The output wavelength of the external cavity semiconductor laser is mainly dependent on the grating feedback angle, the physical characteristics of insensitivity to operating temperature changes, and the amplitude and wavelength of the differential spectral signal when the wavelength difference of the excitation light is greater than the Raman spectrum linewidth of the substance to be measured. Difference-independent spectral characteristics, combined with the spectral analysis method described in the present invention, the laser does not need temperature control, has good real-time performance, can ensure the accuracy of measurement, reduces system complexity, reduces system volume and cost, and improves system integration. And stability, the output wavelength of the laser is adjusted by changing the grating feedback angle, the wavelength tuning range is large, and the detection of wide-spectrum substances can be realized. The adjustment of the excitation light power is realized by controlling the coupling efficiency of the free light to the excitation fiber, instead of changing the output power by changing the laser injection current in the traditional technology, which can ensure that the output spectral characteristics of the excitation light do not change, and achieve pure Optical power adjustment. The device of the invention has good compatibility with the existing commercial small-scale spectrometer, and is easy to be applied to build a new Raman spectrum detection system.

本发明所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测方法,对获得的初始差分拉曼光谱信号积分并归一化,得到归一化的差分拉曼光谱信号,均匀提取N个数据点并取绝对值求和,得到拉曼光谱信号强度值,进而实现对待测样品的分析。不必反演原始拉曼光谱信号,就能实现对待测样品的分析,计算量小,计算结果准确。A signal intensity detection method based on frequency-shifted excitation Raman spectroscopy of tunable lasers according to the present invention integrates and normalizes the obtained initial differential Raman spectral signals to obtain normalized differential Raman spectral signals, Evenly extract N data points and take the absolute value summation to obtain the Raman spectrum signal intensity value, and then realize the analysis of the sample to be tested. The analysis of the sample to be tested can be realized without inverting the original Raman spectrum signal, the calculation amount is small, and the calculation result is accurate.

附图说明Description of drawings

图1是具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置的结构示意图。FIG. 1 is a schematic structural diagram of a signal intensity detection device based on frequency-shifted excitation Raman spectroscopy of a tunable laser according to the first embodiment.

图2是具体实施方式七中的杀菌剂三环唑的工业原药在两种不同波长激发下获取的归一化的拉曼光谱图。Fig. 2 is the normalized Raman spectrum obtained under the excitation of two different wavelengths of the industrial technical material of the fungicide tricyclazole in Embodiment 7.

图3是具体实施方式七中的杀菌剂三环唑的工业原药的归一化的差分拉曼光谱图。Fig. 3 is the normalized differential Raman spectrum of the industrial technical material of the fungicide tricyclazole in Embodiment 7.

具体实施方式Detailed ways

具体实施方式一:结合图1具体说明本实施方式,本实施方式所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置,包括电流驱动器1、半导体激光器2、光栅3、光栅控制器4、反射镜5、带通滤光片6、第一凸透镜7、激发光纤8、第二凸透镜9、样品容器10、高通滤光片11、耦合透镜组12、收集光纤13、光谱仪14和光谱分析模块15;Specific Embodiment 1: This embodiment is specifically described in conjunction with FIG. 1. A signal strength detection device based on frequency-shifted excitation Raman spectroscopy of a tunable laser described in this embodiment includes a current driver 1, a semiconductor laser 2, and a grating 3. , grating controller 4, mirror 5, bandpass filter 6, first convex lens 7, excitation fiber 8, second convex lens 9, sample container 10, high-pass filter 11, coupling lens group 12, collection fiber 13, Spectrometer 14 and spectral analysis module 15;

电流驱动器1的控制信号输出端连接半导体激光器2的控制信号输入端,半导体激光器2发出的准直光束入射至光栅3,光栅3固定在光栅控制器4上,经光栅3衍射后的第零级光束入射至反射镜5,反射镜5反射后的光束入射至带通滤光片6,带通滤光片6出射的光束入射至第一凸透镜7,第一凸透镜7将光束汇聚并耦合进激发光纤8的一端,从激发光纤8的另一端出射的光束入射至第二凸透镜9,第二凸透镜9将光束汇聚至样品容器10,样品容器10中样品的拉曼散射光经高通滤光片11后入射至耦合透镜组12,耦合透镜组12将光束汇聚到收集光纤13的一端,收集光纤13的另一端连接光谱仪14的光学接口,光谱仪14的信号输出端连接光谱分析模块15的信号输入端。The control signal output terminal of the current driver 1 is connected to the control signal input terminal of the semiconductor laser 2, the collimated beam emitted by the semiconductor laser 2 is incident on the grating 3, and the grating 3 is fixed on the grating controller 4, and the zeroth order after diffraction by the grating 3 The light beam is incident on the reflector 5, the light beam reflected by the reflector 5 is incident on the bandpass filter 6, the light beam emitted by the bandpass filter 6 is incident on the first convex lens 7, and the first convex lens 7 converges the light beam and couples it into the excitation One end of the optical fiber 8, the light beam emitted from the other end of the excitation optical fiber 8 enters the second convex lens 9, the second convex lens 9 converges the light beam to the sample container 10, and the Raman scattered light of the sample in the sample container 10 passes through the high-pass filter 11 After incident to the coupling lens group 12, the coupling lens group 12 converges the light beam to one end of the collection fiber 13, the other end of the collection fiber 13 is connected to the optical interface of the spectrometer 14, and the signal output end of the spectrometer 14 is connected to the signal input end of the spectrum analysis module 15 .

电流驱动器1的控制信号输出端连接半导体激光器2的控制信号输入端,为半导体激光器2提供电流激励,为半导体激光器2芯片中的增益介质提供能量,使其出射最佳输出功率。半导体激光器2发射的激光由其自带的准直镜准直后入射至光栅3,光栅3安装在光栅控制器4上。由光栅控制器4控制光栅3的偏摆和俯仰姿态到特定位置,能将光栅3衍射的第一级光束反馈给半导体激光器2的谐振腔,从而实现纵模选择和线宽压缩的作用,通过改变光栅3的偏摆角度来改变半导体激光器2的出射波长。光栅3的偏摆角度θ与半导体激光器2输出波长λ和光栅3的空间结构周期d之间满足的关系由光栅方程决定:λ=2dsinθ。光栅3衍射后的第零级光束入射至反射镜5,反射镜5与光栅安装在同一底座上,可确保激光光束的传播方向不因光栅3偏摆角度的调整而发生改变。经反射镜5反射后的光束入射至带通滤光片6,带通滤光片6只允许激光波长附近10nm左右波长范围的光通过,其他波段的透过率小于千分之一,有效抑制半导体激光器2的自发辐射荧光对测量的干扰。透过带通滤光片6的光束入射至第一凸透镜7,经第一凸透镜7汇聚耦合进激发光纤8的一端,再从激发光纤8另一端出射后入射至第二凸透镜9,经过第二凸透镜9汇聚后的光束入射至样品容器10。样品容器可以容纳固态物质也可容纳液态物质,可实现固液两种形态物质的检测。样品容器10中样品的拉曼散射光经高通滤光片11后入射至耦合透镜组12,高通滤光片11为截止型滤光片,小于激发波长的光的透过率小于千分之一,可进一步抑制半导体激光器2的自发辐射荧光及其他背景光对测量的干扰。样品散射光由耦合透镜组12汇聚后入射至收集光纤13的一端,收集光纤13的另一端连接至光谱仪14的光学接口,光谱仪14的信号输出端连接至光谱分析模块15的信号输入端。光谱仪14为市面常见的微型光栅光谱仪。The control signal output terminal of the current driver 1 is connected to the control signal input terminal of the semiconductor laser 2 to provide current excitation for the semiconductor laser 2 and energy for the gain medium in the semiconductor laser 2 chip to make it emit optimal output power. The laser light emitted by the semiconductor laser 2 is collimated by its own collimating mirror and then incident on the grating 3 , which is installed on the grating controller 4 . The yaw and pitch attitude of the grating 3 is controlled by the grating controller 4 to a specific position, and the first-order light beam diffracted by the grating 3 can be fed back to the resonator of the semiconductor laser 2, thereby realizing the functions of longitudinal mode selection and line width compression, through Changing the deflection angle of the grating 3 changes the emission wavelength of the semiconductor laser 2 . The satisfying relationship between the deflection angle θ of the grating 3 and the output wavelength λ of the semiconductor laser 2 and the period d of the spatial structure of the grating 3 is determined by the grating equation: λ=2dsinθ. The zero-order light beam diffracted by the grating 3 is incident on the reflector 5, and the reflector 5 and the grating are installed on the same base to ensure that the propagation direction of the laser beam does not change due to the adjustment of the deflection angle of the grating 3. The light beam reflected by the mirror 5 enters the band-pass filter 6, which only allows the light in the wavelength range of about 10nm near the laser wavelength to pass through, and the transmittance of other bands is less than one thousandth, effectively suppressing Interference of the measurement by the spontaneous emission fluorescence of the semiconductor laser 2. The light beam passing through the band-pass filter 6 is incident on the first convex lens 7, converged and coupled into one end of the excitation fiber 8 through the first convex lens 7, and then emerges from the other end of the excitation fiber 8 and enters the second convex lens 9, passes through the second The light beam converged by the convex lens 9 enters the sample container 10 . The sample container can accommodate both solid and liquid substances, which can realize the detection of substances in both solid and liquid forms. The Raman scattered light of the sample in the sample container 10 enters the coupling lens group 12 after passing through the high-pass filter 11. The high-pass filter 11 is a cut-off filter, and the transmittance of light smaller than the excitation wavelength is less than one thousandth. , can further suppress the interference of the spontaneous emission fluorescence of the semiconductor laser 2 and other background light on the measurement. The scattered light from the sample is converged by the coupling lens group 12 and then incident on one end of the collection fiber 13, the other end of the collection fiber 13 is connected to the optical interface of the spectrometer 14, and the signal output end of the spectrometer 14 is connected to the signal input end of the spectrum analysis module 15. The spectrometer 14 is a miniature grating spectrometer common in the market.

具体实施方式二:本实施方式是对具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置作进一步说明,本实施方式中,经光栅3衍射后的第零级光束的光功率大于100mW,线宽小于0.5nm,波长调谐范围大于10nm。Specific embodiment 2: This embodiment is a further description of the signal strength detection device based on the frequency-shifted excitation Raman spectrum of the tunable laser described in the specific embodiment 1. In this embodiment, the grating 3 diffracted The optical power of the zeroth order beam is greater than 100mW, the line width is less than 0.5nm, and the wavelength tuning range is greater than 10nm.

现有技术中通过电流调节实现的波长改变通常只能达到0.5nm,而本实施方式的波长调谐范围大于10nm,可实现宽谱物质的探测。In the prior art, the wavelength change achieved by current regulation can only reach 0.5 nm, but the wavelength tuning range of this embodiment is greater than 10 nm, which can realize the detection of broadband substances.

具体实施方式三:本实施方式是对具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置作进一步说明,本实施方式中,第一凸透镜7和激发光纤8的距离范围为(f1-5mm)~(f1+5mm),f1为第一凸透镜7的焦距。Specific Embodiment 3: This embodiment is a further description of the signal strength detection device based on the frequency-shifted excitation Raman spectrum of the tunable laser described in the specific embodiment 1. In this embodiment, the first convex lens 7 and the excitation The distance range of the optical fiber 8 is (f 1 −5 mm)˜(f 1 +5 mm), and f 1 is the focal length of the first convex lens 7 .

第一凸透镜7和激发光纤8的距离在(f1-5mm)~(f1+5mm)范围内时光束才能耦合进激发光纤8,当距离超过此范围时几乎没有光束耦合进光纤。When the distance between the first convex lens 7 and the excitation fiber 8 is within the range of (f 1 -5mm) to (f 1 +5mm), the light beam can be coupled into the excitation fiber 8, and when the distance exceeds this range, almost no light beam is coupled into the fiber.

具体实施方式四:本实施方式是对具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置作进一步说明,本实施方式中,半导体激光器2发出的光束入射至光栅3的入射角θ的范围为:10°<θ<80°,且θ与半导体激光器2的输出波长λ和光栅3的空间结构周期d满足关系式:λ=2dsinθ。Embodiment 4: This embodiment is a further description of the signal strength detection device based on the frequency-shifted excitation Raman spectrum of the tunable laser described in Embodiment 1. In this embodiment, the light beam emitted by the semiconductor laser 2 The range of the incident angle θ to the grating 3 is: 10°<θ<80°, and θ and the output wavelength λ of the semiconductor laser 2 and the spatial structure period d of the grating 3 satisfy the relationship: λ=2dsinθ.

具体实施方式五:本实施方式是对具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置作进一步说明,本实施方式中,光栅3摆偏角度变化量其中△λ为待测物质拉曼光谱线宽。Embodiment 5: This embodiment is a further description of the signal strength detection device based on the frequency-shifted excitation Raman spectrum of the tunable laser described in Embodiment 1. In this embodiment, the swing angle of the grating 3 changes quantity Where Δλ is the Raman spectrum linewidth of the substance to be measured.

具体实施方式六:本实施方式是对具体实施方式二所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置作进一步说明,本实施方式中,经光栅3衍射后的第零级光束的光功率的范围为100mW~300mW。Embodiment 6: This embodiment is a further description of the signal strength detection device based on the frequency-shifted excitation Raman spectrum of the tunable laser described in Embodiment 2. In this embodiment, the grating 3 diffracted The optical power of the zeroth order light beam ranges from 100mW to 300mW.

具体实施方式七:结合图2和图3具体说明本实施方式,本实施方式是基于具体实施方式一所述的一种基于可调谐激光的移频激发拉曼光谱的信号强度检测装置的检测方法,包括拉曼光谱的信号强度采集过程和分析过程:Specific Embodiment 7: This embodiment is described in detail in conjunction with Fig. 2 and Fig. 3. This embodiment is based on the detection method of a signal strength detection device based on frequency-shifted excitation Raman spectroscopy of a tunable laser described in Embodiment 1. , including the signal intensity acquisition process and analysis process of Raman spectroscopy:

拉曼光谱的信号强度采集过程包括以下步骤:The signal intensity acquisition process of Raman spectroscopy includes the following steps:

步骤一一,将待测样品放置在样品容器10中,开启电流驱动器1,波长为λ1的激光照射在样品上;Step 11, the sample to be tested is placed in the sample container 10, the current driver 1 is turned on, and the laser with a wavelength of λ1 is irradiated on the sample;

步骤一二,光谱仪14采集初始光谱并输送至光谱分析模块15,光谱分析模块15对接收到的光谱做初步分析,判定光谱的时间稳定度和荧光背景水平;Steps one and two, the spectrometer 14 collects the initial spectrum and sends it to the spectrum analysis module 15, and the spectrum analysis module 15 performs a preliminary analysis on the received spectrum to determine the temporal stability and fluorescence background level of the spectrum;

步骤一三,根据步骤一二中的光谱时间稳定度和荧光背景水平,判断激光功率是否合适即既不破坏样品分子结构,所激发的荧光又不会造成光谱仪14的光探测单元饱和,如果判断结果为是,则执行步骤一四,如果判断结果为否,则调整第一凸透镜7与激发光纤8的入射端面间的距离,并返回步骤一二;Step 13, according to the spectral time stability and fluorescence background level in step 12, judge whether the laser power is appropriate, that is, neither destroy the molecular structure of the sample, and the excited fluorescence will not cause the light detection unit of the spectrometer 14 to saturate, if judged If the result is yes, then perform step 14, if the judgment result is no, then adjust the distance between the first convex lens 7 and the incident end face of the excitation fiber 8, and return to step 12;

步骤一四,光谱分析模块15采集记录激发波长为λ1时的光谱信号强度R1In step 14, the spectral analysis module 15 collects and records the spectral signal intensity R 1 when the excitation wavelength is λ 1 ;

步骤一五,通过光栅反馈控制器4调整光栅3的偏摆角度,使激发波长为λ2,光谱分析模块15采集记录激发波长为λ2时的光谱信号强度R2Step 15, adjust the deflection angle of the grating 3 through the grating feedback controller 4, so that the excitation wavelength is λ 2 , and the spectral analysis module 15 collects and records the spectral signal intensity R 2 when the excitation wavelength is λ 2 ;

拉曼光谱的信号强度分析过程包括以下步骤:The signal intensity analysis process of Raman spectroscopy includes the following steps:

步骤二一,将光谱分析模块15采集记录的两个不同激发波长下的光谱信号强度R1和R2做差,获得初始差分拉曼光谱信号强度D0,D0=R2-R1Step 21, making a difference between the spectral signal intensities R 1 and R 2 at two different excitation wavelengths collected and recorded by the spectral analysis module 15 to obtain the initial differential Raman spectral signal intensity D 0 , D 0 =R 2 −R 1 ;

步骤二二,获取初始差分拉曼光谱信号强度D0中强度最大的差分信号的中心波数分别对光谱信号强度R1和R2的波数范围内做积分,分别获得表征激发光功率的值I1和I2Step 22, obtain the central wavenumber of the differential signal with the highest intensity in the initial differential Raman spectrum signal intensity D 0 Respectively for the spectral signal intensities R1 and R2 at Integrate within the range of wavenumbers to obtain the values I 1 and I 2 representing the excitation light power respectively;

步骤二三,对光谱信号强度R1和R2分别进行功率归一化,然后将二者做差获得归一化的差分拉曼光谱信号强度D,D=R2/I2-R1/I1Step two and three, perform power normalization on the spectral signal intensities R 1 and R 2 respectively, and then make a difference between the two to obtain a normalized differential Raman spectral signal intensity D, D=R 2 /I 2 -R 1 / I 1 ;

步骤二四,在范围内均匀提取归一化的差分拉曼光谱信号强度共计N个数据点,为待测物质拉曼光谱线宽,i=1~N,N为大于1的整数;Step two and four, in Extract normalized differential Raman spectrum signal intensity uniformly over the range A total of N data points, is the Raman spectrum linewidth of the substance to be measured, i=1~N, N is an integer greater than 1;

步骤二五,对范围内提取的N个数据点分逐点取绝对值求和,获得拉曼光谱信号强度值A, Step two five, yes The N data points extracted in the range are summed point by point to obtain the Raman spectrum signal intensity value A,

拉曼光谱信号强度表征待测样品的浓度,拉曼光谱信号强度可用于对待测物浓度实施定量分析。光谱分析模块15的拉曼光谱分析方法基于两点:1)半导体激光器2的输出波长主要依赖于光栅3的偏摆角度,而对工作温度变化不敏感;2)当激发光波长差值大于待测物质拉曼光谱线宽情况下,差分光谱信号幅值与波长差无关。因此,只要保证激发光波长差值大于待测物质拉曼光谱线宽,即使激光波长有nm级别的浮动,在光谱分析模块15中的新型拉曼光谱分析方法的保证下,对半导体激光器2也无需实施温度控制。图2为杀菌剂三环唑的工业原药在两种不同波长激发下获取的归一化的拉曼光谱图,可见在两种波长下归一化的拉曼光谱图几乎重合,将两种波长下光谱信号强度作差,得到归一化的差分拉曼光谱图,如图3所示。The Raman spectrum signal intensity represents the concentration of the sample to be tested, and the Raman spectrum signal intensity can be used for quantitative analysis of the concentration of the sample to be tested. The Raman spectral analysis method of the spectral analysis module 15 is based on two points: 1) the output wavelength of the semiconductor laser 2 mainly depends on the deflection angle of the grating 3, and is insensitive to changes in the operating temperature; 2) when the wavelength difference of the excitation light is greater than the In the case of the Raman spectrum linewidth of the measured substance, the amplitude of the differential spectral signal has nothing to do with the wavelength difference. Therefore, as long as the wavelength difference of the excitation light is guaranteed to be greater than the Raman spectrum linewidth of the substance to be measured, even if the laser wavelength fluctuates at the nm level, under the guarantee of the novel Raman spectrum analysis method in the spectrum analysis module 15, the semiconductor laser 2 is also No temperature control is required. Figure 2 is the normalized Raman spectrum obtained under the excitation of two different wavelengths for the industrial technical fungicide tricyclazole. It can be seen that the normalized Raman spectra of the two wavelengths almost overlap, and the two The spectral signal intensities at different wavelengths are subtracted to obtain a normalized differential Raman spectrum, as shown in FIG. 3 .

Claims (7)

1. the shift frequency based on tunable laser excites the signal strength detection device of Raman spectrum, it is characterized in that, it comprises current driver (1), semiconductor laser (2), grating (3), grid controller (4), catoptron (5), bandpass filter (6), first convex lens (7), excitation fiber (8), second convex lens (9), sampling receptacle (10), high-pass filter (11), coupled lens group (12), collect optical fiber (13), spectrometer (14) and spectral analysis module (15),
The control signal output terminal of current driver (1) connects the control signal input end of semiconductor laser (2), the collimated light beam that semiconductor laser (2) sends is incident to grating (3), grating (3) is fixed on grid controller (4), zero order beam after grating (3) diffraction is incident to catoptron (5), light beam after catoptron (5) reflection is incident to bandpass filter (6), the light beam of bandpass filter (6) outgoing is incident to the first convex lens (7), first convex lens (7) are by beams converge and be coupled into one end of excitation fiber (8), the second convex lens (9) are incident to from the light beam of the other end outgoing of excitation fiber (8), second convex lens (9) by beams converge to sampling receptacle (10), in sampling receptacle (10), the Raman diffused light of sample is incident to coupled lens group (12) after high-pass filter (11), coupled lens group (12) is by beams converge one end to collection optical fiber (13), the other end collecting optical fiber (13) connects the optical interface of spectrometer (14), the signal output part of spectrometer (14) connects the signal input part of spectral analysis module (15).
2. a kind of shift frequency based on tunable laser according to claim 1 excites the signal strength detection device of Raman spectrum, it is characterized in that, the luminous power of described zero order beam after grating (3) diffraction is greater than 100mW, live width is less than 0.5nm, and wavelength tuning range is greater than 10nm.
3. a kind of shift frequency based on tunable laser according to claim 1 excites the signal strength detection device of Raman spectrum, it is characterized in that, the distance range of described first convex lens (7) and excitation fiber (8) is (f 1-5mm) ~ (f 1+ 5mm), f 1it is the focal length of the first convex lens (7).
4. a kind of shift frequency based on tunable laser according to claim 1 excites the signal strength detection device of Raman spectrum, it is characterized in that, the scope that the light beam that semiconductor laser (2) sends is incident to the incidence angle θ of grating (3) is: 10 ° of < θ <80 °, and the space structure cycle d of the output wavelength λ of θ and semiconductor laser (2) and grating (3) meets relational expression: λ=2dsin θ.
5. a kind of shift frequency based on tunable laser according to claim 1 excites the signal strength detection device of Raman spectrum, it is characterized in that, grating (3) pendulum inclination angle variable quantity wherein △ λ is test substance Raman spectrum live width.
6. a kind of shift frequency based on tunable laser according to claim 2 excites the signal strength detection device of Raman spectrum, it is characterized in that, the scope of the luminous power of the zero order beam after grating (3) diffraction is 100mW ~ 300mW.
7. excite the detection method of the signal strength detection device of Raman spectrum based on a kind of shift frequency based on tunable laser according to claim 1, it is characterized in that, comprise signal intensity gatherer process and the analytic process of Raman spectrum:
The signal intensity gatherer process of Raman spectrum comprises the following steps:
One by one, be placed on by testing sample in sampling receptacle (10), firing current driver (1), wavelength is λ to step 1laser be radiated on sample;
Step one two, spectrometer (14) gathers initial spectrum and is delivered to spectral analysis module (15), spectral analysis module (15) does initial analysis to the spectrum received, and judges time degree of stability and the fluorescence background level of spectrum;
Step one three, according to the spectral temporal degree of stability in step one two and fluorescence background level, judge that whether laser power is suitable and namely neither destroy sample molecule structure, the fluorescence excited can not cause again the photo detecting unit of spectrometer (14) saturated, if judged result is yes, then perform step one four, if judged result is no, distance between the incident end face then adjusting the first convex lens (7) and excitation fiber (8), and return step one two;
Step one four, spectral analysis module (15) acquisition and recording excitation wavelength is λ 1time spectral signal intensity R 1;
The step First Five-Year Plan, by the deflection angle of grating feedback controller (4) adjustment grating (3), excitation wavelength is made to be λ 2, spectral analysis module (15) acquisition and recording excitation wavelength is λ 2time spectral signal intensity R 2;
The signal strength analysis process of Raman spectrum comprises the following steps:
Step 2 one, by the spectral signal intensity R under two different excitation wavelengths of spectral analysis module (15) acquisition and recording 1and R 2do difference, obtain initial differential raman spectral signal intensity D 0, D 0=R 2-R 1;
Step 2 two, obtains initial differential raman spectral signal intensity D 0the center wave number of the differential signal that middle intensity is maximum respectively to spectral signal intensity R 1and R 2? wave-number range in do integration, obtain respectively and characterize the value I of excitation light power 1and I 2;
Step 2 three, to spectral signal intensity R 1and R 2carry out power normalization respectively, then the two is done difference and obtain normalized difference raman spectral signal intensity D, D=R 2/ I 2-R 1/ I 1;
Step 2 four, evenly normalized difference raman spectral signal intensity is extracted in scope amount to N number of data point, for test substance Raman spectrum live width, i=1 ~ N, N be greater than 1 integer;
Step 2 five is right the N number of data point extracted in scope divides pointwise to take absolute value summation, acquisition raman spectral signal intensity level A,
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