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CN104422680A - Raman signal acquisition device - Google Patents

Raman signal acquisition device Download PDF

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CN104422680A
CN104422680A CN201310392047.2A CN201310392047A CN104422680A CN 104422680 A CN104422680 A CN 104422680A CN 201310392047 A CN201310392047 A CN 201310392047A CN 104422680 A CN104422680 A CN 104422680A
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objective lens
filter
raman signal
raman
acquisition device
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李�灿
黄保坤
冯兆池
李光亚
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种拉曼信号采集装置,可以高效的采集样品被激发出的拉曼信号,同时具有将激光聚焦到样品,滤除杂散光和瑞利线等干扰信号的功能,并且具有体积小、传输效率高等优点。与激光器、光谱仪联用可以组成拉曼光谱仪,采用紫外光学元件,与紫外激光器,紫外光谱仪联用可以组成紫外拉曼光谱仪。The invention relates to a Raman signal acquisition device, which can efficiently collect Raman signals excited by samples, and at the same time has the functions of focusing laser light on the sample, filtering out interference signals such as stray light and Rayleigh lines, and has a small volume , High transmission efficiency and so on. Combined with lasers and spectrometers, it can form a Raman spectrometer. Using ultraviolet optical components, combined with ultraviolet lasers and ultraviolet spectrometers, can form an ultraviolet Raman spectrometer.

Description

一种拉曼信号采集装置A Raman signal acquisition device

技术领域technical field

本发明涉及一种拉曼信号采集装置,可以高效的采集样品被激发出的拉曼信号,同时具有将激光聚焦到样品,滤除杂散光和瑞利线等干扰信号的功能。与激光器、光谱仪联用可以组成拉曼光谱仪,采用紫外光学元件,与紫外激光器,紫外光谱仪联用可以组成紫外拉曼光谱仪。The invention relates to a Raman signal acquisition device, which can efficiently collect Raman signals excited by samples, and has the functions of focusing laser light on samples and filtering out interference signals such as stray light and Rayleigh lines. Combined with lasers and spectrometers, it can form a Raman spectrometer. Using ultraviolet optical components, combined with ultraviolet lasers and ultraviolet spectrometers, can form an ultraviolet Raman spectrometer.

背景技术Background technique

拉曼光谱被称为分子指纹谱,可以对样品进行快速、准确的分析。拉曼光谱应用广泛,可以应用于检测食品,安检,文检材料,矿物,环境,化学,材料,生物等领域。样品种类包括固体、粉末、液体、气体、界面、胶体等多种形态。当前,拉曼光谱的重要性逐渐被大家认识,其应用也越来越广泛。Raman spectroscopy, known as molecular fingerprinting, allows fast and accurate analysis of samples. Raman spectroscopy is widely used in the detection of food, security inspection, document inspection materials, minerals, environment, chemistry, materials, biology and other fields. Sample types include solid, powder, liquid, gas, interface, colloid and other forms. At present, the importance of Raman spectroscopy is gradually being recognized by everyone, and its application is becoming more and more extensive.

拉曼光谱的原理是:一个光子与一个分子发生相互作用,如果分子吸收光子的能量从振动或者转动状态的低能级跃迁到高能级,那么根据能量守恒定律,光子损失的能量和分子的振动或者转动的能级跃迁需要的能量相等,光子损失能量后振动频率发生变化,通过拉曼光谱仪记录光子频率发生的变化规律,即为拉曼光谱。The principle of Raman spectroscopy is: a photon interacts with a molecule. If the energy of the molecule absorbing the photon transitions from a low energy level in a vibration or rotational state to a high energy level, then according to the law of energy conservation, the energy lost by the photon and the vibration or vibration of the molecule The energy required for the energy level transition of the rotation is equal, and the vibration frequency changes after the photon loses energy. The change law of the photon frequency is recorded by the Raman spectrometer, which is the Raman spectrum.

拉曼散射现象发生的几率很低,108个光子与样品分子发生作用,最多只有一个光子能形成拉曼散射,因此拉曼信号采集装置要具有收集拉曼信号效率高,降低其他未发生拉曼散射光子的影响,并且实现拉曼信号的高效率传输等功能。The probability of Raman scattering phenomenon is very low. 10 8 photons interact with sample molecules, and at most only one photon can form Raman scattering. Raman scattered photons, and realize the high-efficiency transmission of Raman signals and other functions.

目前市场上有三种类型的拉曼光谱仪:一种是三光栅拉曼光谱仪(专利号98113710.5),使用透镜或者反射椭球镜采集拉曼信号,前两级光栅采用相加或者相减模式滤除瑞利散射等产生的杂散光的干扰,适用于深紫外,紫外,可见,近红外等多种波段的激发光源,尤其在紫外区采用反射椭球镜(专利号98113709.1)收集拉曼信号,可以提高采集效率,消除色差的影响。但是三光栅拉曼光谱仪也具有体积大,拉曼信号传输效率低,调试和维护困难等缺点。第二种是实验室用的共聚焦拉曼光谱仪,采用显微镜采集拉曼信号,用滤光片滤除杂散光的干扰,具有体积小,采集和传输效率高等优点,但是采集用的显微镜体积较大,成本高,且采集系统和滤光系统是独立的结构,使用中必须与特定厂家的光谱仪配套购买,无法根据用户自己的需要搭建拉曼光谱仪。第三种是光纤拉曼光谱仪,采用光纤来收集拉曼信号,采用拉曼滤光片滤除杂散光,具有体积小,便于携带,可远程测量等优点。但是光纤传输效率低,不适用于紫外波段,无法实现共聚焦功能。There are currently three types of Raman spectrometers on the market: one is a three-grating Raman spectrometer (patent No. 98113710.5), which uses a lens or a reflective ellipsoid to collect Raman signals, and the first two gratings are filtered by addition or subtraction The interference of stray light caused by Rayleigh scattering is suitable for excitation light sources in various bands such as deep ultraviolet, ultraviolet, visible, and near-infrared. Especially in the ultraviolet region, a reflective ellipsoid mirror (patent No. 98113709.1) is used to collect Raman signals, which can Improve collection efficiency and eliminate the influence of chromatic aberration. However, the three-grating Raman spectrometer also has the disadvantages of large volume, low Raman signal transmission efficiency, and difficulty in debugging and maintenance. The second is the confocal Raman spectrometer used in the laboratory. It uses a microscope to collect Raman signals and filters out the interference of stray light. It has the advantages of small size, high collection and transmission efficiency, but the volume of the microscope used for collection is relatively large. Large, high cost, and the acquisition system and filter system are independent structures, which must be purchased together with spectrometers from specific manufacturers during use, and it is impossible to build Raman spectrometers according to the needs of users. The third is the fiber optic Raman spectrometer, which uses optical fiber to collect Raman signals, and uses Raman filters to filter out stray light. It has the advantages of small size, portability, and remote measurement. However, the optical fiber transmission efficiency is low, it is not suitable for the ultraviolet band, and the confocal function cannot be realized.

发明内容Contents of the invention

本发明提供一种拉曼信号采集装置,包括二端开口的中空筒状容器,于筒状容器的二个开口端分别设有物镜、聚焦透镜,物镜和聚焦透镜同光轴设置,于物镜和聚焦透镜间的筒状容器内设有滤光片;于筒状容器的侧壁面上开设有通孔,作为入光孔,激发光源发出的激发光通过入光孔进入筒状容器内,经设有于筒状容器内的反射镜反射至滤光片表面,再由滤光片反射至物镜,由物镜聚焦到待测样品上,由待测样品散射的拉曼信号、瑞利信号和反射的激发光均经过物镜收集和滤光片滤光,反射的光和散射的瑞利信号被滤除,拉曼信号透过滤光片到达聚焦透镜聚焦。The invention provides a Raman signal acquisition device, which comprises a hollow cylindrical container with two openings, and an objective lens and a focusing lens are respectively arranged at the two opening ends of the cylindrical container, and the objective lens and the focusing lens are arranged on the same optical axis, and the objective lens and the focusing lens are arranged on the same optical axis. A filter is provided in the cylindrical container between the focusing lenses; a through hole is opened on the side wall of the cylindrical container as a light entrance hole, and the excitation light emitted by the excitation light source enters the cylindrical container through the light entrance hole. The reflection mirror in the cylindrical container is reflected to the surface of the filter, and then reflected by the filter to the objective lens, which is focused on the sample to be measured by the objective lens, and the Raman signal and Rayleigh signal scattered by the sample to be measured and the reflected The excitation light is collected by the objective lens and filtered by the filter, the reflected light and the scattered Rayleigh signal are filtered out, and the Raman signal passes through the filter and reaches the focusing lens for focusing.

技术方案:滤光片的几何中心处于物镜和聚焦透镜的光轴;滤光片的光轴与物镜和聚焦透镜的光轴间的夹角小于10度;反射镜将激发光反射到滤光片的中心,且反射镜不在物镜和聚焦透镜的光轴上,不影响物镜和滤光片之间光的传输;滤光片将反射镜反射来的激发光沿物镜的光轴反射到物镜;于拉曼信号采集装置上聚焦透镜一侧的外部设有光谱仪,聚焦透镜将拉曼信号聚焦到光谱仪的入光孔中;可在滤光片和聚焦透镜之间增加设置有第二滤光片来优化瑞利信号和反射光的滤除效果,滤光片光轴角度与聚焦透镜的光轴夹角小于10度。Technical solution: the geometric center of the optical filter is on the optical axis of the objective lens and the focusing lens; the angle between the optical axis of the optical filter and the optical axis of the objective lens and the focusing lens is less than 10 degrees; the mirror reflects the excitation light to the optical filter center, and the mirror is not on the optical axis of the objective lens and the focusing lens, and does not affect the transmission of light between the objective lens and the optical filter; the optical filter reflects the excitation light reflected by the mirror to the objective lens along the optical axis of the objective lens; A spectrometer is arranged on one side of the focusing lens on the Raman signal acquisition device, and the focusing lens focuses the Raman signal into the light entrance hole of the spectrometer; a second filter can be added between the filter and the focusing lens to Optimize the filtering effect of Rayleigh signal and reflected light, the angle between the optical axis of the filter and the optical axis of the focusing lens is less than 10 degrees.

有益效果:本发明,一种拉曼信号采集装置,可以高效的采集样品被激发出的拉曼信号,同时具有将激光聚焦到样品,滤除杂散光和瑞利线等干扰信号的功能。采用背散射式采集拉曼信号,采集效率高;滤光片既具有反射镜的作用,又有滤除杂散光的作用,减少了光学元件的使用,提高了通光效率。主要部件固定中空筒状容器,体积小,重量轻,结构稳固,方便与光谱仪进行耦合。适用于固定激发波长的拉曼光谱测试,包括紫外,可见,近红外波段的拉曼光谱的测试。Beneficial effects: the present invention provides a Raman signal collection device, which can efficiently collect Raman signals excited by samples, and has the functions of focusing laser light on samples and filtering out interference signals such as stray light and Rayleigh lines. The backscattering method is used to collect Raman signals, and the collection efficiency is high; the filter not only has the function of a reflector, but also filters out stray light, which reduces the use of optical components and improves the light transmission efficiency. The main part is a fixed hollow cylindrical container, which is small in size, light in weight, and stable in structure, which is convenient for coupling with the spectrometer. It is suitable for Raman spectrum testing with fixed excitation wavelength, including Raman spectrum testing in ultraviolet, visible, and near-infrared bands.

附图说明Description of drawings

下面结合附图和实施例对本发明进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

图1是本发明的结构原理图。Fig. 1 is a schematic diagram of the structure of the present invention.

图2是本发明的具体应用实例:金刚石的拉曼光谱图。Fig. 2 is a specific application example of the present invention: a Raman spectrum diagram of diamond.

图中1.入光孔,2.小反射镜,3.滤光片,4.物镜,5.聚焦透镜,6.装置外壳,7.样品。In the figure 1. light entrance hole, 2. small mirror, 3. optical filter, 4. objective lens, 5. focusing lens, 6. device housing, 7. sample.

具体实施方式Detailed ways

在图1中,一种拉曼信号采集装置,包括二端开口的中空筒状容器6,于筒状容器6的二个开口端分别设有物镜4、聚焦透镜5,物镜4和聚焦透镜5同光轴设置,于物镜4和聚焦透镜5间的筒状容器内设有滤光片3;In Fig. 1, a kind of Raman signal collecting device comprises the hollow cylindrical container 6 of two end openings, and two open ends of cylindrical container 6 are respectively provided with objective lens 4, focusing lens 5, objective lens 4 and focusing lens 5 It is arranged on the same optical axis, and an optical filter 3 is arranged in the cylindrical container between the objective lens 4 and the focusing lens 5;

于筒状容器6的侧壁面上开设有通孔,作为入光孔1(处于物镜4和滤光片3之间),激发光源发出的激发光通过入光孔1进入筒状容器6内,经设有于筒状容器6内的反射镜2(处于物镜4和滤光片3之间)反射至滤光片3表面,再由滤光片3反射至物镜4,由物镜4聚焦到待测样品7上,由待测样品7散射的拉曼信号、瑞利信号和反射的激发光均经过物镜4收集和滤光片3滤光,反射的光和散射的瑞利信号被滤除,拉曼信号透过滤光片3到达聚焦透镜5聚焦。A through hole is opened on the side wall of the cylindrical container 6 as the light entrance hole 1 (between the objective lens 4 and the optical filter 3), and the excitation light emitted by the excitation light source enters the cylindrical container 6 through the light entrance hole 1, It is reflected to the surface of the filter 3 through the reflector 2 (between the objective lens 4 and the filter 3) provided in the cylindrical container 6, and then reflected to the objective lens 4 by the filter 3, and then focused by the objective lens 4 to the surface of the optical filter 3. On the test sample 7, the Raman signal, the Rayleigh signal and the reflected excitation light scattered by the test sample 7 are all collected by the objective lens 4 and filtered by the filter 3, and the reflected light and the scattered Rayleigh signal are filtered out, The Raman signal passes through the optical filter 3 and reaches the focusing lens 5 for focusing.

滤光片3的几何中心处于物镜4和聚焦透镜5的光轴;The geometric center of the optical filter 3 is on the optical axis of the objective lens 4 and the focusing lens 5;

滤光片3的光轴与物镜4和聚焦透镜5的光轴间的夹角小于10度,滤光片3反射激发光的效率大于90%,滤除干扰信号的效率大约99.99%,拉曼信号透过率大于80%;The angle between the optical axis of the optical filter 3 and the optical axis of the objective lens 4 and the focusing lens 5 is less than 10 degrees, the efficiency of the optical filter 3 to reflect the excitation light is greater than 90%, and the efficiency of filtering out the interference signal is about 99.99%. Raman Signal transmittance greater than 80%;

反射镜2将激发光反射到滤光片3的中心,且反射镜不在物镜4和聚焦透镜5的光轴上,不影响物镜4和滤光片3之间光的传输。The mirror 2 reflects the excitation light to the center of the optical filter 3 , and the mirror is not on the optical axis of the objective lens 4 and the focusing lens 5 , and does not affect the light transmission between the objective lens 4 and the optical filter 3 .

滤光片3将反射镜2反射来的激发光沿物镜4的光轴反射到物镜4,使物镜4的使用达到共光轴效果。The optical filter 3 reflects the excitation light reflected by the mirror 2 to the objective lens 4 along the optical axis of the objective lens 4, so that the use of the objective lens 4 achieves a common optical axis effect.

于拉曼信号采集装置上聚焦透镜5一侧的外部(即远离中空筒状容器5-6的一侧)设有光谱仪,聚焦透镜5将拉曼信号聚焦到光谱仪的入光孔中。A spectrometer is arranged on the outside of the focusing lens 5 on the Raman signal collection device (that is, the side away from the hollow cylindrical container 5-6), and the focusing lens 5 focuses the Raman signal into the light entrance hole of the spectrometer.

可在滤光片3和聚焦透镜5之间增加设置有第二滤光片来优化瑞利信号和反射光的滤除效果,滤光片光轴角度与聚焦透镜5的光轴夹角小于10度。A second optical filter can be added between the optical filter 3 and the focusing lens 5 to optimize the filtering effect of the Rayleigh signal and reflected light, and the angle between the optical axis of the optical filter and the optical axis of the focusing lens 5 is less than 10° Spend.

在图2所示实施例中,记录金刚石的拉曼谱,激发光源为355纳米固体激光器,图中横坐标为拉曼频移,实验条件为:激发波长,355纳米固体激光器。In the embodiment shown in Figure 2, the Raman spectrum of diamond is recorded, the excitation light source is a 355nm solid-state laser, the abscissa in the figure is the Raman frequency shift, and the experimental conditions are: excitation wavelength, 355nm solid-state laser.

Claims (7)

1.一种拉曼信号采集装置,包括二端开口的中空筒状容器(6),其特征在于:于筒状容器(6)的二个开口端分别设有物镜(4)、聚焦透镜(5),物镜(4)和聚焦透镜(5)同光轴设置,于物镜(4)和聚焦透镜(5)间的筒状容器(6)内设有滤光片(3);1. A Raman signal acquisition device, comprising a hollow cylindrical container (6) with two open ends, characterized in that: two open ends of the cylindrical container (6) are respectively provided with an objective lens (4), a focusing lens ( 5), the objective lens (4) and the focusing lens (5) are arranged on the same optical axis, and a filter (3) is arranged in the cylindrical container (6) between the objective lens (4) and the focusing lens (5); 于筒状容器(6)的侧壁面上开设有通孔,作为入光孔(1),激发光源发出的激发光通过入光孔(1)进入筒状容器(6)内,经设有于筒状容器(6)内的反射镜(2)反射至滤光片(3)表面,再由滤光片(3)反射至物镜(4),由物镜(4)聚焦到待测样品(7)上,由待测样品(7)散射的拉曼信号、瑞利信号和反射的激发光均经过物镜(4)收集和滤光片(3)滤光,反射的光和散射的瑞利信号被滤除,拉曼信号透过滤光片(3)到达聚焦透镜(5)聚焦。A through hole is opened on the side wall of the cylindrical container (6) as the light entrance hole (1). The excitation light emitted by the excitation light source enters the cylindrical container (6) through the light entrance hole (1), and passes through the The reflection mirror (2) in the cylindrical container (6) is reflected to the surface of the optical filter (3), and then reflected by the optical filter (3) to the objective lens (4), and the objective lens (4) focuses on the sample to be tested (7 ), the Raman signal, Rayleigh signal and reflected excitation light scattered by the sample to be measured (7) are collected by the objective lens (4) and filtered by the filter (3), and the reflected light and scattered Rayleigh signal After being filtered out, the Raman signal passes through the filter (3) and reaches the focusing lens (5) for focusing. 2.根据权利要求1所述的拉曼信号采集装置,其特征是:滤光片(3)的几何中心处于物镜(4)和聚焦透镜(5)的光轴。2. The Raman signal acquisition device according to claim 1, characterized in that: the geometric center of the optical filter (3) is on the optical axis of the objective lens (4) and the focusing lens (5). 3.根据权利要求1或2所述的拉曼信号采集装置,其特征是:滤光片(3)的光轴与物镜(4)和聚焦透镜(5)的光轴间的夹角小于10度。3. The Raman signal acquisition device according to claim 1 or 2, characterized in that: the angle between the optical axis of the optical filter (3) and the optical axis of the objective lens (4) and the focusing lens (5) is less than 10 Spend. 4.根据权利要求1所述的拉曼信号采集装置,其特征是:反射镜(2)将激光反射到滤光片(3)的中心,且反射镜(2)不在物镜(4)和聚焦透镜(5)的光轴上,不影响物镜(4)和滤光片(3)之间光的传输。4. The Raman signal acquisition device according to claim 1, characterized in that: the mirror (2) reflects the laser light to the center of the filter (3), and the mirror (2) is not between the objective lens (4) and the focusing The optical axis of the lens (5) does not affect the transmission of light between the objective lens (4) and the optical filter (3). 5.根据权利要求1所述的拉曼信号采集装置,其特征是:所述的滤光片(3)将反射镜(2)反射来的激发光沿物镜(4)的光轴反射到物镜(4)。5. The Raman signal acquisition device according to claim 1, characterized in that: the filter (3) reflects the excitation light reflected by the mirror (2) to the objective lens along the optical axis of the objective lens (4) (4). 6.根据权利要求1所述的拉曼信号采集装置,其特征是:于拉曼信号采集装置上聚焦透镜(5)一侧的外部设有光谱仪,聚焦透镜(5)将拉曼信号聚焦到光谱仪的入光孔中。6. The Raman signal acquisition device according to claim 1, characterized in that: a spectrometer is arranged outside one side of the focusing lens (5) on the Raman signal acquisition device, and the focusing lens (5) focuses the Raman signal to in the light entrance of the spectrometer. 7.根据权利要求1所述的拉曼信号采集装置,其特征是:可在滤光片(3)和聚焦透镜(5)之间增加设置有第二滤光片来优化瑞利信号和反射光的滤除效果,滤光片光轴角度与聚焦透镜(5)的光轴夹角小于10度。7. The Raman signal acquisition device according to claim 1, characterized in that: a second filter can be added between the filter (3) and the focusing lens (5) to optimize the Rayleigh signal and reflection For the filtering effect of light, the included angle between the optical axis angle of the optical filter and the optical axis of the focusing lens (5) is less than 10 degrees.
CN201310392047.2A 2013-09-02 2013-09-02 Raman signal acquisition device Pending CN104422680A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107449767A (en) * 2016-06-01 2017-12-08 中国科学院大连化学物理研究所 A kind of ultraviolet Raman fiber optic probe
CN109580494A (en) * 2018-11-21 2019-04-05 深圳达闼科技控股有限公司 A kind of detection method, relevant apparatus and storage medium
CN111426677A (en) * 2020-04-29 2020-07-17 中国工程物理研究院核物理与化学研究所 Raman spectrum multi-site excitation structure and gas analysis method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107449767A (en) * 2016-06-01 2017-12-08 中国科学院大连化学物理研究所 A kind of ultraviolet Raman fiber optic probe
CN109580494A (en) * 2018-11-21 2019-04-05 深圳达闼科技控股有限公司 A kind of detection method, relevant apparatus and storage medium
CN109580494B (en) * 2018-11-21 2021-09-28 深圳达闼科技控股有限公司 Detection method, related device and storage medium
CN111426677A (en) * 2020-04-29 2020-07-17 中国工程物理研究院核物理与化学研究所 Raman spectrum multi-site excitation structure and gas analysis method
CN111426677B (en) * 2020-04-29 2023-09-19 中国工程物理研究院核物理与化学研究所 Raman spectrum multi-site excitation structure and gas analysis method

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