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CN104316506B - Raman probe and Raman signal detection system and method capable of focusing automatically - Google Patents

Raman probe and Raman signal detection system and method capable of focusing automatically Download PDF

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CN104316506B
CN104316506B CN201410541693.5A CN201410541693A CN104316506B CN 104316506 B CN104316506 B CN 104316506B CN 201410541693 A CN201410541693 A CN 201410541693A CN 104316506 B CN104316506 B CN 104316506B
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CN104316506A (en
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黄梅珍
孙振华
季芸
余镇岗
汪洋
宋彪
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Shanghai Jiao Tong University
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Abstract

本发明提供了一种拉曼探头和可自动对焦的拉曼信号探测系统以及方法,所述系统包括拉曼探头、数控位移样品台、控制器;拉曼探头安装于数控位移样品台上,拉曼探头与数控位移样品台可相对移动,拉曼探头的信号输出侧设有光强探测单元;光强探测单元的输出端连接至控制器,控制器根据光强探测单元输出信号比较判断样品是否在焦点处,如果不在焦点处,发出指令控制数控位移样品台作相应的位移,如此反复多次,直至样品调节在拉曼探头焦距处或设定的精度范围内。本发明能够精确对焦,使拉曼信号最大化且稳定;对比于现有商品化的增加固定距离套筒的探头,本发明可对表面粗糙不平的样品进行直接检测,而不需要样品前处理。

The invention provides a Raman probe and a Raman signal detection system and method capable of autofocusing. The system includes a Raman probe, a numerically controlled displacement sample stage, and a controller; the Raman probe is installed on a numerically controlled displacement sample stage, and the The Raman probe and the CNC displacement sample stage can move relatively, and the signal output side of the Raman probe is equipped with a light intensity detection unit; the output end of the light intensity detection unit is connected to the controller, and the controller judges whether the sample is At the focal point, if it is not at the focal point, an instruction is issued to control the CNC displacement sample stage to make a corresponding displacement, and this is repeated several times until the sample is adjusted at the focal length of the Raman probe or within the set accuracy range. The invention can focus precisely, and maximize and stabilize the Raman signal; compared with the existing commercial probe with a fixed-distance sleeve, the invention can directly detect samples with rough and uneven surfaces without sample pretreatment.

Description

拉曼探头和可自动对焦的拉曼信号探测系统以及方法Raman probe and autofocusable Raman signal detection system and method

技术领域technical field

本发明涉及光学机械、仪器学领域,具体地,涉及一种拉曼探头,以及在激光拉曼光谱测量或拉曼光谱仪中使用的可自动对焦的拉曼信号探测系统与方法。The present invention relates to the field of optical machinery and instrumentation, in particular to a Raman probe, and an autofocusable Raman signal detection system and method used in laser Raman spectrum measurement or Raman spectrometer.

背景技术Background technique

便携式拉曼光谱仪具有体积小、速度快、现场化等优点,在药品、食品安全、安检等领域具有广阔的应用前景。便携式拉曼光谱仪一般由小型半导体激光器、拉曼光纤探头、光谱仪及计算机系统构成。其中,拉曼探头的功能主要有两方面,一方面将激光高效传导并聚焦于待检测样品,另一方面高效收集和过滤拉曼散射信号并将其传导至光谱仪。The portable Raman spectrometer has the advantages of small size, fast speed, and on-site operation, and has broad application prospects in the fields of medicine, food safety, and security inspection. A portable Raman spectrometer generally consists of a small semiconductor laser, a Raman fiber probe, a spectrometer and a computer system. Among them, the function of the Raman probe mainly has two aspects. On the one hand, it efficiently transmits and focuses the laser light on the sample to be detected, and on the other hand, it efficiently collects and filters Raman scattering signals and transmits them to the spectrometer.

拉曼光谱的激发效率与激光线宽以及能量密度等有关。为了获得较强的拉曼信号,需要将激光精确地对准聚焦于被测样品以获得较高的激光能量密度。因此,在大型拉曼测量系统中都配置了显微聚焦系统,操作人员借助显微图像进行人工对焦。目前,商品化便携式拉曼光谱仪系统因体积限制一般不含显微聚焦系统,而拉曼光纤探头仅能通过手动调节的方式对焦,操作麻烦,无法精确对焦,导致拉曼强度减弱,信号不稳定等等。The excitation efficiency of Raman spectroscopy is related to the laser linewidth and energy density. In order to obtain a strong Raman signal, the laser needs to be precisely aligned and focused on the sample to obtain a high laser energy density. Therefore, a micro-focusing system is configured in large-scale Raman measurement systems, and operators use microscopic images to manually focus. At present, the commercialized portable Raman spectrometer system generally does not contain a microscopic focusing system due to volume limitations, and the Raman fiber optic probe can only focus through manual adjustment, which is cumbersome to operate and unable to focus accurately, resulting in weakened Raman intensity and unstable signals wait.

商品化的一种定距离探头通过在探头前加装固定长度套筒来固定测量距离从而确保聚焦的新型探头。这种探头在一定程度上简化了对焦操作过程,但使用这种探头进行测量时,套筒必须与样品进行接触,如果样品表面不平整,将不能精确聚焦。A commercially available fixed-distance probe is a new type of probe that fixes the measurement distance by installing a fixed-length sleeve in front of the probe to ensure focus. This probe simplifies the focusing operation process to a certain extent, but when using this probe for measurement, the sleeve must be in contact with the sample, and if the sample surface is uneven, it will not be able to focus accurately.

发明内容Contents of the invention

针对现有技术中的缺陷,本发明的目的是提供一种能够精确自动对焦使收集到的拉曼信号最大化的拉曼探头、可自动对焦的拉曼信号探测系统以及方法。In view of the defects in the prior art, the object of the present invention is to provide a Raman probe capable of precise autofocus to maximize the collected Raman signal, a Raman signal detection system and method capable of autofocus.

根据本发明的一个方面,提供一种拉曼探头,所述拉曼探头包括第一透镜、第一滤光片、反射镜、第四透镜、第二滤光片、第三滤光片、第四滤光片、第二透镜、光强探测单元;其中:激光从光纤传导进入拉曼探头后,由第一透镜将其变成平行光,然后经过第一滤光片对光谱进行纯化处理,再依次经过与平行光呈45°设置的反射镜反射、第二滤光片反射来改变光束路径,最后由第四透镜将激光聚焦于被测样品;被测样品被激光激发后发生拉曼散射,散射光和反射光反方向进入拉曼探头由第四透镜收集,其中的拉曼散射光透过由第二滤光片及第四滤光片构成的镜片组,再经由第二透镜会聚耦合进入光纤,非拉曼信号光由第二滤光片及第四滤光片构成的镜片组所阻挡抑制(反射或吸收),因此不能到达第二透镜,其中被样品反射回来的激光由第三滤光片反射,进入光强探测单元;According to one aspect of the present invention, a Raman probe is provided, the Raman probe includes a first lens, a first filter, a mirror, a fourth lens, a second filter, a third filter, a first Four optical filters, second lens, and light intensity detection unit; among them: after the laser is transmitted from the optical fiber into the Raman probe, it is transformed into parallel light by the first lens, and then the spectrum is purified by the first optical filter. Then the beam path is changed through the reflection of the mirror set at 45° to the parallel light and the reflection of the second filter, and finally the fourth lens focuses the laser light on the sample to be measured; Raman scattering occurs after the sample to be measured is excited by the laser , the scattered light and reflected light enter the Raman probe in the opposite direction and are collected by the fourth lens. The Raman scattered light passes through the lens group composed of the second filter and the fourth filter, and then converges and couples through the second lens. Entering the optical fiber, the non-Raman signal light is blocked and suppressed (reflected or absorbed) by the lens group composed of the second filter and the fourth filter, so it cannot reach the second lens, and the laser light reflected back by the sample is transmitted by the third lens. The filter is reflected and enters the light intensity detection unit;

所述光强探测单元包括:第三透镜、小孔以及光电转换器件,所述小孔处于第三透镜的焦点处;第三滤光片反射的激光经第三透镜聚焦,会聚后再经过小孔,通过小孔照射在光电转换器件上,被光电探测器件接收探测。The light intensity detection unit includes: a third lens, a small hole and a photoelectric conversion device, the small hole is at the focal point of the third lens; the laser light reflected by the third filter is focused by the third lens, converged and then passes through the small Holes, illuminated on the photoelectric conversion device through the small hole, are received and detected by the photodetector device.

优选地,在所述第二滤光片之后以及所述第四滤光片之前设置第三滤光片,此时,被样品反射回来的激光一部分由第二滤光片反射,另一部分由第三滤光片反射,第三滤光片反射的激光进入光强探测单元;第二滤光片透射的拉曼光再经由所述第四滤光片、第二透镜会聚耦合进入光纤。Preferably, a third optical filter is provided after the second optical filter and before the fourth optical filter, at this time, part of the laser light reflected back by the sample is reflected by the second optical filter, and the other part is reflected by the second optical filter. The laser light reflected by the third optical filter enters the light intensity detection unit; the Raman light transmitted by the second optical filter is converged and coupled into the optical fiber through the fourth optical filter and the second lens.

优选地,所述第二滤光片和第三滤光片为二色镜,与光路成45°夹角设置,且所述第二滤光片和第三滤光片不平行,两者对激光反射而对拉曼散射光透射。Preferably, the second optical filter and the third optical filter are dichroic mirrors, which are arranged at an angle of 45° to the optical path, and the second optical filter and the third optical filter are not parallel to each other. Laser light is reflected and Raman scattered light is transmitted.

优选地,所述反射镜、第二滤光片、第三滤光片,均与光路成45°角;所述第一滤光片、第四滤光片则与光路成90°。Preferably, the reflector, the second filter and the third filter all form an angle of 45° with the optical path; the first filter and the fourth filter form an angle of 90° with the optical path.

上述拉曼探头,当被测样品不在所述拉曼探头的焦点处时,激光将通过光路会聚于小孔的前方或后方处,仅小部分光能通过小孔,样品离焦点越远,能通过小孔的反射光越少;仅当激光光斑正好聚焦于物体上时,反射的激光的光斑将通过光路会聚于小孔,几乎全部的反射光能将通过小孔,光电转换器件接收到的光强信号最大。由于小孔的空间选择性,在对焦状态下,大部分能量能够通过小孔,此时光电转换器件得到光强最大。这样就将一个对焦的测距问题转化为一个光学上量化的光强测量问题。For the above-mentioned Raman probe, when the sample to be measured is not at the focus of the Raman probe, the laser light will converge at the front or rear of the small hole through the optical path, and only a small part of the light energy will pass through the small hole. The farther the sample is from the focus, the energy The less reflected light passes through the small hole; only when the laser spot is just focused on the object, the reflected laser spot will converge on the small hole through the optical path, and almost all the reflected light energy will pass through the small hole, and the photoelectric conversion device receives The light intensity signal is maximum. Due to the spatial selectivity of the small holes, most of the energy can pass through the small holes in the focusing state, and the photoelectric conversion device can obtain the maximum light intensity at this time. In this way, a focused ranging problem is transformed into an optically quantified light intensity measurement problem.

根据本发明的第二方面,提供一种上述拉曼探头组成的可自动对焦的拉曼信号探测系统,包括拉曼探头、数控位移样品台、控制器;所述拉曼探头安装于数控位移样品台上,拉曼探头与数控位移样品台可相对移动,所述拉曼探头的信号输出侧设有光强探测单元;所述光强探测单元的输出端连接至控制器,控制器根据所述光强探测单元输出信号比较判断样品是否在焦点处,如果不在焦点处,发出指令控制数控位移样品台作相应的位移,如此反复多次,直至样品调节在拉曼探头焦距处或设定的精度范围内。According to the second aspect of the present invention, there is provided an auto-focusing Raman signal detection system composed of the above-mentioned Raman probe, including a Raman probe, a numerically controlled displacement sample stage, and a controller; the Raman probe is installed on a numerically controlled displacement sample On the stage, the Raman probe and the numerical control displacement sample stage can move relatively, and the signal output side of the Raman probe is provided with a light intensity detection unit; the output end of the light intensity detection unit is connected to the controller, and the controller according to the The output signal of the light intensity detection unit compares and judges whether the sample is at the focal point. If it is not at the focal point, an instruction is issued to control the numerical control displacement sample stage to make corresponding displacements, and this is repeated many times until the sample is adjusted at the focal length of the Raman probe or the set accuracy within range.

根据本发明的第三方面,提供一种可自动对焦的拉曼信号探测方法,所述方法步骤如下:According to a third aspect of the present invention, there is provided an autofocusable Raman signal detection method, the method steps are as follows:

a)将待测样品置于数控位移样品台上;a) Place the sample to be tested on the numerical control displacement sample stage;

b)将拉曼探头置于数控位移样品台上方大于拉曼探头焦距处;b) Place the Raman probe above the digitally controlled displacement sample stage at a place greater than the focal length of the Raman probe;

c)打开激光器输出一激光,经光纤进入拉曼探头,由第一透镜将其变成平行光,然后经过第一滤光片对光谱进行纯化处理,再依次经过反射镜反射、第二滤光片反射来改变光束路径,最后由第四透镜将激光聚焦于被测样品;c) Turn on the laser to output a laser, enter the Raman probe through the optical fiber, turn it into parallel light by the first lens, then purify the spectrum through the first filter, and then pass through the reflection of the mirror and the second filter in turn The laser beam is reflected to change the beam path, and finally the fourth lens focuses the laser light on the sample to be measured;

d)被测样品被激光激发后发生拉曼散射,散射光和反射光反方向进入拉曼探头由第四透镜收集,其中的拉曼散射光透过由第二滤光片及第四滤光片构成的镜片组,再经由第二透镜会聚耦合进入光纤;非拉曼信号光由第二滤光片及第四滤光片构成的镜片组所阻挡抑制,因此不能到达第二透镜,其中被样品反射回来的激光由第三滤光片反射后进入光强探测单元;d) Raman scattering occurs after the measured sample is excited by the laser, the scattered light and reflected light enter the Raman probe in the opposite direction and are collected by the fourth lens, and the Raman scattered light passes through the second filter and the fourth filter The lens group composed of the second optical filter and the fourth optical filter is blocked and suppressed by the lens group composed of the second optical filter and the fourth optical filter, so the non-Raman signal light cannot reach the second lens, where it is The laser light reflected by the sample enters the light intensity detection unit after being reflected by the third filter;

e)光强探测单元将信号输出到控制器,经控制器控制数控位移样品台移动,直至收集到的信号最大,完成对焦。e) The light intensity detection unit outputs the signal to the controller, and the controller controls the movement of the digitally controlled displacement sample stage until the collected signal reaches the maximum and the focusing is completed.

与现有技术相比,本发明具有如下的有益效果:Compared with the prior art, the present invention has the following beneficial effects:

本发明中的技术创新避免了人为手动操作,能够精确对焦,使拉曼信号最大化且稳定;对比于现有商品化的增加固定距离套筒的探头,本发明技术可对表面粗糙不平的样品进行直接检测,而不需要样品前处理。The technical innovation in the present invention avoids manual operation, can focus accurately, and maximizes and stabilizes the Raman signal; compared with the existing commercial probe with a fixed distance sleeve, the technology of the present invention can be used for samples with rough and uneven surfaces Perform direct detection without sample preparation.

附图说明Description of drawings

通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:Other characteristics, objects and advantages of the present invention will become more apparent by reading the detailed description of non-limiting embodiments made with reference to the following drawings:

图1为本发明一实施例具有自动对焦功能的拉曼探测装置的结构示意图;Fig. 1 is a schematic structural diagram of a Raman detection device with autofocus function according to an embodiment of the present invention;

图2为本发明一实施例中光强探测单元的结构示意图;Fig. 2 is a schematic structural diagram of a light intensity detection unit in an embodiment of the present invention;

图3为本发明一实施例中位移调节装置调节流程图;Fig. 3 is an adjustment flowchart of the displacement adjustment device in an embodiment of the present invention;

图4为小孔取100微米情况下探头焦平面与样品之间的距离与光强关系曲线;Figure 4 is the distance and light intensity relationship curve between the focal plane of the probe and the sample when the small hole is 100 microns;

图中:100为拉曼探头,200为数控位移样品台,300为控制器;1为光纤,2为第一透镜,3为第一滤光片,4为反射镜,5为第四透镜,6为第二滤光片,7为第三滤光片,8为第四滤光片,9为第二透镜,10为光强探测单元,11为样品,12为样品台,13为控制器,14为第三透镜,15为小孔,16为光电探测器件。In the figure: 100 is the Raman probe, 200 is the digital control displacement sample stage, 300 is the controller; 1 is the optical fiber, 2 is the first lens, 3 is the first filter, 4 is the mirror, 5 is the fourth lens, 6 is the second filter, 7 is the third filter, 8 is the fourth filter, 9 is the second lens, 10 is the light intensity detection unit, 11 is the sample, 12 is the sample stage, 13 is the controller , 14 is the third lens, 15 is the small hole, and 16 is the photodetection device.

具体实施方式detailed description

下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

如图1所示,为本发明具有自动对焦功能的拉曼探测装置一实施例的结构示意图,包括拉曼探头100,数控位移样品台200,控制器300;所述拉曼探头100安装于数控位移样品台200上,拉曼探头100与数控位移样品台200可相对移动。As shown in Figure 1, it is a schematic structural view of an embodiment of a Raman detection device with autofocus function in the present invention, including a Raman probe 100, a numerically controlled displacement sample stage 200, and a controller 300; the Raman probe 100 is installed on a numerically controlled On the shifting sample stage 200, the Raman probe 100 and the numerical control shifting sample stage 200 can move relatively.

本实施例中,所述拉曼探头100包括第一透镜2、第一滤光片3、反射镜4、第四透镜5、第二滤光片6、第三滤光片7、第四滤光片8、第二透镜9、光强探测单元10;所述光强探测单元10包括:第三透镜14、小孔15以及光电转换器件16。In this embodiment, the Raman probe 100 includes a first lens 2, a first filter 3, a mirror 4, a fourth lens 5, a second filter 6, a third filter 7, a fourth filter A light sheet 8 , a second lens 9 , and a light intensity detection unit 10 ; the light intensity detection unit 10 includes: a third lens 14 , a small hole 15 and a photoelectric conversion device 16 .

图中:由第一透镜2、第一滤光片3、反射镜4、第二滤光片6、作为激光聚焦用的第四透镜5构成的传导激光组件一,由作为拉曼光收集用的第四透镜5、第二滤光片6、第三滤光片7、第四滤光片8、第二透镜9构成的传导拉曼光及抑制杂散光组件二,由作为激光准直用的第四透镜5、第二滤光片6、第三滤光片7、光强探测单元10构成的激光自动测距对焦组件三。组件一、组件二和组件三构成拉曼探头100,所述拉曼探头100安装于数控位移样品台200上。Among the figure: the first lens 2, the first optical filter 3, the reflection mirror 4, the second optical filter 6, and the fourth lens 5 used for laser focusing are used as the transmission laser assembly one, which is used as the Raman light collection The fourth lens 5, the second optical filter 6, the third optical filter 7, the fourth optical filter 8, and the second lens 9 are used to transmit Raman light and suppress stray light components 2, which are used as laser collimation The fourth lens 5, the second optical filter 6, the third optical filter 7, and the light intensity detection unit 10 constitute the laser automatic ranging focusing assembly three. Component one, component two and component three constitute a Raman probe 100 , and the Raman probe 100 is installed on a digitally controlled displacement sample stage 200 .

沿着光纤1输出光的方向依次设置第一透镜2、第一滤光片3和反射镜4,第一透镜2、第一滤光片3与光路垂直,反射镜4与光路成45度,沿着反射镜4反射光的方向45度设置第二滤光片6,第二滤光片6与反射镜4平行设置,在第二滤光片6的反射光路上垂直设置第四透镜5,反向沿着第四透镜5和第二滤光片6的光路方向依次设置第三滤光片7、第四滤光片8和第二透镜9,第二透镜9的另一侧设置光纤。第三滤光片7与光路成45度设置,第四滤光片8和第二透镜9与光路垂直,沿着第三滤光片7的反射光路一侧依次设置第三透镜14、小孔15以及光电转换器件16,第三透镜14、小孔15以及光电转换器件16构成光强探测单元10。The first lens 2, the first optical filter 3 and the reflector 4 are sequentially arranged along the direction of the output light of the optical fiber 1, the first lens 2, the first optical filter 3 are perpendicular to the optical path, and the reflector 4 is at 45 degrees to the optical path. The second optical filter 6 is arranged at 45 degrees along the direction of the reflected light of the reflector 4, the second optical filter 6 is arranged in parallel with the reflector 4, and the fourth lens 5 is vertically arranged on the reflected light path of the second optical filter 6, The third optical filter 7 , the fourth optical filter 8 and the second lens 9 are sequentially arranged along the optical path direction of the fourth lens 5 and the second optical filter 6 , and an optical fiber is arranged on the other side of the second lens 9 . The third optical filter 7 is arranged at 45 degrees with the optical path, the fourth optical filter 8 and the second lens 9 are perpendicular to the optical path, and the third lens 14 and the small hole are arranged successively along one side of the reflection optical path of the third optical filter 7 15 and the photoelectric conversion device 16 , the third lens 14 , the pinhole 15 and the photoelectric conversion device 16 constitute the light intensity detection unit 10 .

激光从光纤1传导进入拉曼探头100后,由第一透镜2将其变成平行光,然后经过第一滤光片3对光谱进行纯化处理,再依次经过与平行光呈45°设置的反射镜4反射、第二滤光片6反射来改变光束路径,最后由第四透镜5将激光聚焦于被测样品,此处第四透镜5起到激光聚焦的作用;被测样品11被激光激发后发生拉曼散射,散射光和反射光反方向进入拉曼探头100由第四透镜5收集,其中的拉曼散射光透过由第二滤光片6、第三滤光片7及第四滤光片8构成的镜片组,再经由与光路垂直的第二透镜9会聚耦合进入光纤;非拉曼信号光由第二和第三滤光片6和7及第四滤光片8构成的镜片组所阻挡抑制(反射或吸收),因此不能到达第二透镜9,其中被样品反射回来的激光一部分由第二滤光片6反射,另一部分由第三滤光片7反射,第三滤光片7反射的激光进入光强探测单元10。After the laser light is transmitted from the optical fiber 1 into the Raman probe 100, it is converted into parallel light by the first lens 2, and then the spectrum is purified by the first filter 3, and then it is reflected at 45° to the parallel light in turn. Mirror 4 reflection, second filter 6 reflection to change the beam path, and finally the fourth lens 5 focuses the laser on the sample under test, where the fourth lens 5 plays the role of laser focus; the sample under test 11 is excited by the laser After that, Raman scattering occurs, and the scattered light and reflected light enter the Raman probe 100 in the opposite direction and are collected by the fourth lens 5, and the Raman scattered light is transmitted through the second filter 6, the third filter 7 and the fourth filter. The lens group formed by the optical filter 8 is converged and coupled into the optical fiber through the second lens 9 perpendicular to the optical path; the non-Raman signal light is formed by the second and third optical filters 6 and 7 and the fourth optical filter 8 The suppression (reflection or absorption) is blocked by the lens group, so it cannot reach the second lens 9, wherein part of the laser light reflected by the sample is reflected by the second filter 6, and the other part is reflected by the third filter 7, and the third filter The laser light reflected by the light sheet 7 enters the light intensity detection unit 10 .

光强探测单元10的信号经前置处理、放大、AD转换后送至控制器300,控制器300根据信号比较判断样品是否在焦点处,如果不在焦点处,发出指令控制数控位移样品台200作相应的位移,如此反复多次,直至样品调节在探头焦距处或设定的精度范围内。同时,数控位移样品台200还可以进行另外两维的调节,以使探头工作在一个固定平面上。The signal from the light intensity detection unit 10 is sent to the controller 300 after pre-processing, amplification, and AD conversion. The controller 300 judges whether the sample is at the focus according to the signal comparison. The corresponding displacement is repeated many times until the sample is adjusted at the focal length of the probe or within the set accuracy range. At the same time, the digitally controlled displacement sample stage 200 can also be adjusted in another two dimensions, so that the probe can work on a fixed plane.

如图2所示,所述光强探测单元10包括与第四透镜5相同焦距的第三透镜14、小孔15以及光电转换器件16。该光强探测单元10用以探测收集光路的光强,并将信号输入控制器300,由控制器300调节数控位移样品台200,直至光强最大。具体地,传导拉曼光及抑制杂散光组件的激光先经过一个与第四透镜5焦距一样的第三透镜14会聚后再经过小孔15,最后被光电探测器件16接收探测。所述光电转换器件16可以采用光电池,光电二极管,CCD,PSD或其他光强探测器件。如附图4所示,第四透镜5、第二滤光片6和第三滤光片7、第三透镜14将第四透镜5焦面图像成像于其共轭面上及小孔14上;由于小孔的空间选择性,在对焦状态下,大部分能量能够通过小孔14,此时光电探测器件16得到光强最大。这样就将一个对焦的测距问题转化为一个光学上量化的光强测量问题。As shown in FIG. 2 , the light intensity detection unit 10 includes a third lens 14 having the same focal length as the fourth lens 5 , a small hole 15 and a photoelectric conversion device 16 . The light intensity detection unit 10 is used to detect the light intensity of the collecting light path, and input the signal to the controller 300, and the controller 300 adjusts the digitally controlled displacement sample stage 200 until the light intensity reaches the maximum. Specifically, the laser light of the Raman light-transmitting and stray-light suppressing components is converged by a third lens 14 having the same focal length as the fourth lens 5 , then passes through the pinhole 15 , and is finally received and detected by the photodetection device 16 . The photoelectric conversion device 16 can be a photocell, a photodiode, a CCD, a PSD or other light intensity detection devices. As shown in Figure 4, the fourth lens 5, the second optical filter 6 and the third optical filter 7, and the third lens 14 image the focal plane image of the fourth lens 5 on its conjugate plane and the small hole 14 ; Due to the spatial selectivity of the small hole, in the focusing state, most of the energy can pass through the small hole 14, and the photodetector device 16 obtains the maximum light intensity at this time. In this way, a focused ranging problem is transformed into an optically quantified light intensity measurement problem.

在一优选实施方式中,第二滤光片6和第三滤光片7为45°二色镜,设置要求为在与光路成45°夹角,作用为对激光反射,而对拉曼散射光透射。第四滤光片8为抑制瑞利散射光的长波通部件,设置要求为与光路成垂直关系。即反射镜4、第二滤光片6和第三滤光片7,需要与光路成45°角;而对于第一滤光片3、第四滤光片8则需要与光路成90°。第二滤光片6反射的激光是杂散光,不被利用。In a preferred embodiment, the second optical filter 6 and the third optical filter 7 are 45 ° dichroic mirrors, which are required to be set at an angle of 45 ° with the optical path, so as to reflect the laser light and not to Raman scattering light transmission. The fourth optical filter 8 is a long-wave pass component that suppresses Rayleigh scattered light, and is required to be arranged perpendicular to the optical path. That is, the mirror 4, the second filter 6 and the third filter 7 need to form an angle of 45° with the optical path; while the first filter 3 and the fourth filter 8 need to form an angle of 90° with the optical path. The laser light reflected by the second filter 6 is stray light, which is not utilized.

本发明中,为了使结构更加紧凑、减少部件、降低成本,第二透镜5同时作为组件一中的激光聚焦透镜、组件二中的拉曼光收集透镜、组件三中的激光准直透镜,即同一个透镜,由于光路的可逆性,该透镜对于正方向和反方向通过它的不同类型的光所起的作用并不相同,从功能上区分为聚焦激光、收集拉曼光和准直激光。具体如图1所示部件5。第四透镜5可以与光路垂直设置,也可以其他设置方式。In the present invention, in order to make the structure more compact, reduce components, and reduce costs, the second lens 5 simultaneously serves as the laser focusing lens in component one, the Raman light collection lens in component two, and the laser collimating lens in component three, namely The same lens, due to the reversibility of the optical path, has different effects on different types of light passing through it in the forward and reverse directions, and is functionally divided into focusing laser, collecting Raman light and collimating laser. Part 5 is specifically shown in FIG. 1 . The fourth lens 5 can be arranged perpendicular to the optical path, or in other ways.

本发明所述具有自动对焦功能拉曼探测装置不限于上述形式,还包括其他结构形式。The Raman detection device with auto-focus function in the present invention is not limited to the above forms, but also includes other structural forms.

以图1所示实施例为例,光强探测单元10具体工作为:Taking the embodiment shown in Figure 1 as an example, the specific work of the light intensity detection unit 10 is as follows:

a)经光路准直聚焦的激光作用于被测样品上;a) The laser collimated and focused through the optical path acts on the sample to be tested;

b)经物体反射后的激光,经第四透镜5进行拉曼收集,透过45度放置的第二滤光片6,并在第三滤光片7上部分反射,反射光经第三透镜14聚焦,通过小孔15照射在光电转换器件16上;所述第三透镜14与第四透镜5焦距一致;所述小孔15处于第三透镜14的焦点处;b) The laser light reflected by the object is collected by Raman through the fourth lens 5, passes through the second filter 6 placed at 45 degrees, and is partially reflected on the third filter 7, and the reflected light passes through the third lens 14 focusing, and irradiating on the photoelectric conversion device 16 through the small hole 15; the third lens 14 has the same focal length as the fourth lens 5; the small hole 15 is at the focal point of the third lens 14;

c)当被测样品不在探头焦点处时,反射的激光将通过光路会聚于小孔15的前方或后方处,仅小部分光能通过小孔15,样品离焦点越远,能通过小孔的反射光越少;仅当激光光斑正好聚焦于物体上时(此时光斑最小,即处于对焦状态),反射的激光的光斑将通过光路会聚于小孔15,几乎全部的反射光能将通过小孔15,探测器接收到的光强信号最大。c) When the sample to be measured is not at the focal point of the probe, the reflected laser light will converge at the front or rear of the small hole 15 through the optical path, and only a small part of the light can pass through the small hole 15. The farther the sample is from the focus, the more light can pass through the small hole. The less reflected light; only when the laser spot is just focused on the object (at this time, the spot is the smallest, that is, in the focused state), the reflected laser spot will converge on the small hole 15 through the optical path, and almost all of the reflected light energy will pass through the small hole 15. Hole 15, the light intensity signal received by the detector is the largest.

在本发明另一优选实施方式中,所述数控位移样品台200中设有位移调节装置和样品台12,该位移调节装置是一种可在三维移动的精确调整装置,尤其是指能在三维移动的步进电机控制或压电陶瓷控制的三维移动装置。由于探头与样品存在相对运动,可将探头固定,样品作三维移动,也可以反过来将样品固定,探头作三维运动,或者也可以采取探头作一维运动与样品作二维运动相结合的方式,样品在与探头输出光束垂直的平面作二维相对移动的情况特别适合于需要对多个位置进行扫描检测的情形,例如当拉曼与薄层色谱等技术进行联用时,需要对展开在薄层板上多个位置样品进行拉曼光谱测量。In another preferred embodiment of the present invention, the numerically controlled displacement sample stage 200 is provided with a displacement adjustment device and the sample stage 12. The displacement adjustment device is a precise adjustment device that can move in three dimensions, especially a three-dimensional movement. Three-dimensional mobile devices controlled by moving stepper motors or piezoelectric ceramics. Due to the relative motion between the probe and the sample, the probe can be fixed, and the sample can move in three dimensions, or the sample can be fixed in turn, and the probe can move in three dimensions, or a combination of one-dimensional movement of the probe and two-dimensional movement of the sample can be adopted. , the sample moves two-dimensionally relative to the plane perpendicular to the output beam of the probe, which is especially suitable for the situation where multiple positions need to be scanned and detected. For example, when Raman is combined with thin-layer chromatography, it is necessary to analyze Samples at multiple positions on the laminate were measured by Raman spectroscopy.

本发明上述实施例中的可自动对焦的拉曼信号探测系统,所述位移调节装置可与拉曼探头100以及样品台12固定连接,拉曼探头100可以与样品台12相对移动。In the Raman signal detection system capable of autofocusing in the above embodiments of the present invention, the displacement adjustment device can be fixedly connected to the Raman probe 100 and the sample stage 12 , and the Raman probe 100 can move relative to the sample stage 12 .

基于图1所示的探头和上述的探测装置,其采用的可自动对焦的拉曼信号探测方法,步骤如下:Based on the probe shown in Figure 1 and the above-mentioned detection device, the auto-focusing Raman signal detection method adopted, the steps are as follows:

a)将待测样品11置于数控位移样品台上;a) placing the sample 11 to be tested on the numerically controlled displacement sample stage;

b)将探头置于数控位移样品台上方大于探头焦距约3-5mm处;b) Place the probe above the CNC displacement sample stage at a place about 3-5mm larger than the focal length of the probe;

c)打开激光器输出一激光,经光纤进入拉曼探头,由第一透镜2将其变成平行光,然后经过第一滤光片3对光谱进行纯化处理,再依次经过反射镜4反射、第二滤光片6反射来改变光束路径,最后由第四透镜5将激光聚焦于被测样品;c) Turn on the laser to output a laser, enter the Raman probe through the optical fiber, and turn it into parallel light by the first lens 2, then pass through the first filter 3 to purify the spectrum, and then reflect by the mirror 4 in turn, and the second The second filter 6 is reflected to change the beam path, and finally the fourth lens 5 focuses the laser light on the sample to be tested;

d)被测样品11被激光激发后发生拉曼散射,散射光和反射光反方向进入拉曼探头由第四透镜5收集,其中的拉曼散射光透过由第二滤光片6和第三滤光片7及第四滤光片8构成的镜片组,再经由第二透镜9会聚耦合进入光纤;非拉曼信号光由第二和第三滤光片6和7及第四滤光片8构成的镜片组所阻挡抑制(反射或吸收),因此不能到达第二透镜9,其中被样品反射回来的激光一部分由第二滤光片6反射,另一部分由第三滤光片7反射,第三滤光片7反射的激光进入光强探测单元10;d) Raman scattering occurs after the measured sample 11 is excited by the laser, and the scattered light and reflected light enter the Raman probe in the opposite direction and are collected by the fourth lens 5, and the Raman scattered light is transmitted through the second filter 6 and the second filter. The lens group composed of three optical filters 7 and the fourth optical filter 8 is converged and coupled into the optical fiber through the second lens 9; the non-Raman signal light is transmitted by the second and third optical filters 6 and 7 and the fourth optical filter The lens group formed by the sheet 8 blocks suppression (reflection or absorption), so it cannot reach the second lens 9, wherein part of the laser light reflected by the sample is reflected by the second filter 6, and the other part is reflected by the third filter 7 , the laser light reflected by the third filter 7 enters the light intensity detection unit 10;

e)光强探测单元10将信号输出到控制器,经控制器控制数控位移样品台移动,直至收集到的信号最大,完成对焦。e) The light intensity detection unit 10 outputs the signal to the controller, and the controller controls the movement of the digitally controlled displacement sample stage until the collected signal reaches the maximum, and the focusing is completed.

上述实施例中,控制器采用计算机实现,光电转换器件16的信号经放大电路、AD转换进入计算机,计算机通过运算控制位移调节装置移动(比如机控制位移调节装置在竖直方向推进等),直至收集到的信号最大,此时完成对焦。In the above-described embodiment, the controller is implemented by a computer, and the signal of the photoelectric conversion device 16 enters the computer through the amplifying circuit and AD conversion, and the computer controls the movement of the displacement adjustment device through calculation (for example, the computer controls the displacement adjustment device to advance in the vertical direction, etc.), until The collected signal is the largest, and the focus is completed at this time.

在本发明一优选实施方式中,上述探测装置中涉及的位移调节装置进行位移调整时按照以下步骤,如图3所示:In a preferred embodiment of the present invention, the displacement adjustment device involved in the above detection device performs displacement adjustment according to the following steps, as shown in Figure 3:

a)拉曼探头位于样品台外焦点距离外3-5mm处,初始光强信号为x0a) The Raman probe is located 3-5mm away from the focus distance outside the sample stage, and the initial light intensity signal is x 0 ;

b)控制位移调节装置每向下移动一个步距,测量此时光强信号为xib) Control the displacement adjustment device to move down by one step, and measure the light intensity signal at this time as x i ;

c)当相邻两次光强信号差值xi-xi-1大于0时,继续控制位移调节装置移动,直至xi-xi-1小于0,位移控制器控制反向移动;c) When the difference between two adjacent light intensity signals x i -x i-1 is greater than 0, continue to control the movement of the displacement adjustment device until x i -x i-1 is less than 0, and the displacement controller controls the reverse movement;

d)根据实际对焦精度,可控制步骤c)过程中xi-xi-1小于0时缩小步进值,并反复多次,直至光强差小于设定的最小值esp。d) According to the actual focus accuracy, the step c) can be controlled to reduce the step value when x i -x i-1 is less than 0, and repeat it several times until the light intensity difference is less than the set minimum value esp.

图4为小孔15取100微米情况下拉曼探头100焦平面与样品11之间的距离与光强的关系。由光强与拉曼探头100距离关系可知,本发明可实现焦点附近10微米以内的精确控制,小孔15更小则精确度更高。FIG. 4 shows the relationship between the distance between the focal plane of the Raman probe 100 and the sample 11 and the light intensity when the aperture 15 is 100 microns. From the relationship between the light intensity and the distance of the Raman probe 100, it can be seen that the present invention can achieve precise control within 10 microns near the focal point, and the smaller the aperture 15, the higher the precision.

以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art may make various changes or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims (6)

1. a kind of Raman probe, it is characterised in that the Raman probe include the first lens, the first optical filter, speculum, the 4th Lens, the second optical filter, the 3rd optical filter, the 4th optical filter, the second lens, light intensity detection unit;Wherein:Laser is passed from optical fiber Lead into after Raman probe, by the first lens directional light is become, then spectrum is carried out at purifying through the first optical filter Reason, then sequentially pass through speculum reflection, the reflection of the second optical filter changing beam path, finally by the 4th lens by Laser Focusing In sample;There is Raman scattering after laser excitation in sample, scattered light and reflected light opposite direction enter Raman probe Collected by the 4th lens, the lens set that Raman scattering light transmission therein is made up of the second optical filter and the 4th optical filter, then Jing Assembled by the second lens and be coupled into optical fiber, the lens set institute that non-Raman signal light is made up of the second optical filter and the 4th optical filter Stop and suppress, therefore the second lens can not be reached, wherein the laser reflected by sample is reflected by the 3rd optical filter, into light Strong probe unit;
The light intensity detection unit includes:3rd lens, aperture and electrooptical device, the aperture is in the 3rd lens Focal point;The lens focus of laser Jing the 3rd of the 3rd optical filter reflection, photoelectricity is radiated at after convergence through aperture by aperture again On switching device, the device that is photoelectrically converted receives detection;
3rd optical filter is set after second optical filter and before the 4th optical filter, now, is reflected by sample The laser part returned is reflected by the second optical filter, and another part is reflected by the 3rd optical filter, and what the 3rd optical filter reflected swashs Light enters light intensity detection unit;The Raman light of the second filter transmission assembles coupling via the 4th optical filter, the second lens again Conjunction enters optical fiber;
Second optical filter and the 3rd optical filter are 45 ° of dichroic mirrors, are arranged with light path angle at 45 °, and described second filters Piece and the 3rd optical filter are not parallel, and both are highly transmissive to Raman diffused light to laser high reflection;
The speculum, the second optical filter, the 3rd optical filter, with light path angle at 45 °;First optical filter, the 4th filter Piece is then in 90 ° with light path, and the 4th optical filter is the logical part of long wave for suppressing Rayleigh scattering light.
2. Raman probe according to claim 1, it is characterised in that when sample is not in the focus of the Raman probe During place, laser will be converged at the front or behind of aperture by light path, and only fraction luminous energy by aperture, get over by sample focal point Far, the reflected light that can pass through aperture is fewer;Only when laser facula is just focused on object, the hot spot of the laser of reflection will be logical Cross light path and converge at aperture, most reflection luminous energy will be by aperture, and the light intensity signal that electrooptical device is received is most Greatly.
3. it is a kind of comprising Raman probe described in any one of claim 1-2 can auto-focusing Raman signal detection system, its It is characterised by, the system includes Raman probe, numerical control displacement sample stage, controller;The Raman probe is installed on numerical control position Move on sample stage, Raman probe and numerical control displacement sample stage can relative movement, the signal output side of the Raman probe is provided with light Strong probe unit;The output end of the light intensity detection unit is connected to controller, and controller is defeated according to the light intensity detection unit Whether go out signal multilevel iudge sample in focal point, if not in focal point, sending instruction control numerical control displacement sample stage and making phase The displacement answered, it is so repeated multiple times, until sample is adjusted at Raman probe focal length or in the accuracy rating of setting.
4. it is according to claim 3 can auto-focusing Raman signal detection system, it is characterised in that the numerical control displacement Displacement adjustment device and sample stage are provided with sample stage, the displacement adjustment device is a kind of accurate adjustment dress that can be moved in three-dimensional Put, the displacement adjustment device is fixedly connected with Raman probe and sample stage, Raman probe can be with sample stage relative movement.
5. Raman probe described in a kind of any one of employing claim 1-2 can auto-focusing Raman signal detection method, its It is characterised by that methods described step is as follows:
A) testing sample is placed on numerical control displacement sample stage;
B) Raman probe is placed in into numerical control displacement sample stage top more than at Raman probe focal length;
C) open laser instrument and export a laser, Jing optical fiber enters Raman probe, by the first lens directional light, Ran Houjing are become Crossing the first optical filter carries out purification process to spectrum, then sequentially passes through speculum reflection, the reflection of the second optical filter changing light beam Path, finally by the 4th lens by Laser Focusing in sample;
D) there is Raman scattering after laser excitation in sample, and scattered light and reflected light opposite direction enter Raman probe by the 4th Lens are collected, the lens set that Raman scattering light transmission therein is made up of the second optical filter and the 4th optical filter, then via second Lens are assembled and are coupled into optical fiber;Non- Raman signal light stops suppression by the lens set that the second optical filter and the 4th optical filter are constituted System, therefore the second lens can not be reached, wherein visiting into light intensity after the laser reflected by sample is reflected by the 3rd optical filter Survey unit;
E) light intensity detection unit outputs a signal to controller, via controller control numerical control displacement sample stage movement, until collecting The signal for arriving is maximum, completes focusing.
6. it is according to claim 5 can auto-focusing Raman signal detection method, it is characterised in that the controller control Numerical control displacement sample stage movement processed, the numerical control displacement sample stage is provided with displacement adjustment device and sample stage, and the displacement is adjusted According to following steps when device carries out adjustment of displacement:
A) Raman probe is located at the outer 3-5mm of the outer focal length of sample stage, and initial beam intensity signal is x0
B) command displacement adjusting means moves down a step pitch, and now light intensity signal is x for measurementi
C) when adjacent light intensity signal difference x twicei-xi-1During more than 0, continue the movement of command displacement adjusting means, until xi-xi-1 Less than 0, displacement controller control reverse movement;
D) according to actual focusing precision, can control x during step c)i-xi-1Step value is reduced during less than 0, and it is repeated multiple times, directly To light intensity difference less than minimum of a value esp for setting.
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