CN103994973A - Raman spectrum detection head and detection method - Google Patents
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Abstract
本发明提供一种拉曼光谱检测头和检测方法,包括:遮光罩,遮光罩包括狭缝和检测镜,狭缝用于令拉曼散射光出射至样品,并令样品表面产生的信号光射入,检测镜用于出射信号光;遮光罩内还包括:激光线光源,用于发射线状激光;过滤滤光片,用于过滤线状激光中的瑞利散射光,剩余拉曼散射光;分束滤光片,用于将拉曼散射光反射至扫描镜,并令扫描镜反射回的信号光通过检测镜出射;扫描镜,扫描镜通过往复振动的方式反射经过分束滤光片反射的拉曼散射光,以获取均匀的线状拉曼散射光,使其通过狭缝出射至样品表面,并将经狭缝射入的样品表面产生的拉曼检测的信号光反射至分束滤光片。本发明能够对样品进行快速移动检测和信号采集。
The invention provides a Raman spectrum detection head and a detection method, including: a light shield, the light shield includes a slit and a detection mirror, the slit is used to let the Raman scattered light emit to the sample, and let the signal light generated on the surface of the sample emit In, the detection mirror is used to emit signal light; the hood also includes: laser line light source, used to emit linear laser light; filter filter, used to filter Rayleigh scattered light in the linear laser, and the remaining Raman scattered light ; The beam splitting filter is used to reflect the Raman scattered light to the scanning mirror, and the signal light reflected back by the scanning mirror is emitted through the detection mirror; the scanning mirror, the scanning mirror is reflected through the beam splitting filter by reciprocating vibration Reflected Raman scattered light, in order to obtain uniform linear Raman scattered light, make it exit to the sample surface through the slit, and reflect the signal light of Raman detection generated by the sample surface incident through the slit to the beam splitter filter. The invention can perform fast moving detection and signal collection on samples.
Description
技术领域technical field
本发明涉及光学检测领域,尤其涉及一种拉曼光谱检测头和检测方法。The invention relates to the field of optical detection, in particular to a Raman spectrum detection head and a detection method.
背景技术Background technique
拉曼散射是光通过介质时由于入射光与分子运动相互作用而引起的频率发生变化的散射,拉曼光谱经常用来表征分子的结构特征,也被称为分子的“指纹谱”。拉曼光谱技术分析手段主要有傅里叶变换、高温、共振、表面增强、共焦显微、固体光声等技术。拉曼光谱在许多领域有着广泛的应用,尤其是其可以提供快速、简单、无损、可重复的定性定量分析技术,无需繁琐的前处理步骤,避免了对样品的破坏,实现了筛查速度的快速化。当然拉曼技术也存在一些不足,如谱峰易重叠,易受仪器参数等因素的影响,当测定具有荧光性的物质时,会产生荧光干扰,拉曼效应太弱,约为入射光强的10-6倍。虽然纳米技术的快速发展为拉曼光谱检测提供了新的方向,但是借助于纳米技术来增强拉曼信号较弱的限制还有待于深入的研究。Raman scattering is the scattering of frequency changes caused by the interaction between incident light and molecular motion when light passes through a medium. Raman spectroscopy is often used to characterize the structural characteristics of molecules, also known as the "fingerprint" of molecules. The analysis methods of Raman spectroscopy mainly include techniques such as Fourier transform, high temperature, resonance, surface enhancement, confocal microscopy, and solid-state photoacoustics. Raman spectroscopy has a wide range of applications in many fields, especially it can provide fast, simple, non-destructive, repeatable qualitative and quantitative analysis techniques, without cumbersome pretreatment steps, avoiding damage to samples, and achieving screening speed Speed up. Of course, Raman technology also has some shortcomings, such as the peaks are easy to overlap, and it is easy to be affected by factors such as instrument parameters. When measuring fluorescent substances, there will be fluorescence interference, and the Raman effect is too weak, about 10-6 times. Although the rapid development of nanotechnology provides a new direction for Raman spectroscopy detection, the limitation of using nanotechnology to enhance the weak Raman signal remains to be further studied.
在现有技术中,只能利用拉曼技术进行点光谱检测,由于拉曼信号比较微弱,且荧光背景信号比较强,因此虽然拉曼光谱对于物质的化学键识别具有很大的优势,但是往往由于检测限不能达到标准方法,即气相光谱及液相光谱测定的最低含量检测限,导致在定量分析上还存在明显的不足和劣势。并且,拉曼光谱的检测装置较为复杂,对光路要求较高,且不便于移动,对拉曼检测的实际应用造成了一定的阻碍。In the prior art, Raman technology can only be used for point spectrum detection. Since the Raman signal is relatively weak and the fluorescence background signal is relatively strong, although Raman spectroscopy has great advantages in identifying the chemical bonds of substances, it is often due to The detection limit cannot reach the standard method, that is, the minimum content detection limit determined by gas spectrometry and liquid spectrometry, resulting in obvious deficiencies and disadvantages in quantitative analysis. Moreover, the detection device of Raman spectroscopy is relatively complicated, has high requirements on the optical path, and is not easy to move, which has caused certain obstacles to the practical application of Raman detection.
发明内容Contents of the invention
(一)要解决的技术问题(1) Technical problems to be solved
本发明提供拉曼光谱检测头和检测方法,以解决现有技术中拉曼技术只能进行点光谱检测,且检测装置不便于移动的技术问题。The invention provides a Raman spectrum detection head and a detection method to solve the technical problem in the prior art that the Raman technology can only perform point spectrum detection and the detection device is not easy to move.
(二)技术方案(2) Technical solutions
为解决上述技术问题,本发明提供一种拉曼光谱检测头,包括:遮光罩,所述遮光罩包括狭缝和检测镜,所述狭缝用于令拉曼散射光出射至样品,并令所述样品表面产生的信号光射入,所述检测镜用于出射所述信号光;In order to solve the above technical problems, the present invention provides a Raman spectroscopy detection head, comprising: a shading cover, the shading cover includes a slit and a detection mirror, the slit is used to let the Raman scattered light exit to the sample, and make the The signal light generated on the surface of the sample is incident, and the detection mirror is used to emit the signal light;
所述遮光罩内还包括:The hood also includes:
激光线光源,用于发射线状激光;Laser line light source, used to emit line laser;
过滤滤光片,用于过滤所述线状激光中的瑞利散射光,剩余拉曼散射光;filter filter, used to filter the Rayleigh scattered light in the linear laser, and the remaining Raman scattered light;
分束滤光片,用于将经过所述过滤滤光片的拉曼散射光反射至扫描镜,并令扫描镜反射回的信号光通过所述检测镜出射;A beam splitting filter, used to reflect the Raman scattered light passing through the filter filter to the scanning mirror, and make the signal light reflected back by the scanning mirror exit through the detection mirror;
扫描镜,所述扫描镜通过往复振动的方式反射经过所述分束滤光片反射的拉曼散射光,以获取均匀的线状拉曼散射光,使其通过所述狭缝出射至样品表面,并将经狭缝射入的样品表面产生的拉曼检测的信号光反射至所述分束滤光片。A scanning mirror, the scanning mirror reflects the Raman scattered light reflected by the beam splitting filter by reciprocating vibration, so as to obtain uniform linear Raman scattered light, which is emitted to the sample surface through the slit , and reflect the Raman detection signal light generated on the sample surface incident through the slit to the beam splitting filter.
进一步地,所述激光线光源和所述过滤滤光片之间还包括:Further, between the laser line light source and the filter filter also includes:
准直透镜,用于将所述激光线光源发射的线状激光准直汇聚为均匀的平行光。The collimating lens is used for collimating and converging the linear laser light emitted by the laser line light source into uniform parallel light.
进一步地,所述激光线光源为:Further, the laser line light source is:
785nm激光线光源,最大输出功率5w,最大输出1mm×20cm长的激光线。785nm laser line light source, maximum output power 5w, maximum output 1mm×20cm long laser line.
进一步地,further,
所述激光线光源包括多个排成一排的激光点光源。The laser line light source includes a plurality of laser point light sources arranged in a row.
进一步地,further,
所述激光线光源中包括9个排成一排的激光点光源。The laser line light source includes 9 laser point light sources arranged in a row.
进一步地,further,
所述激光线光源、准直透镜、过滤滤光片和分束滤光片依次分布在一条直线上;The laser line light source, collimating lens, filtering filter and beam splitting filter are sequentially distributed on a straight line;
所述扫描镜、分束滤光片和检测镜依次分布在与所述直线垂直的另一条直线上;The scanning mirror, the beam splitting filter and the detecting mirror are sequentially distributed on another straight line perpendicular to the straight line;
所述扫描镜和分束滤光片相互平行,分别与这两条直线成45度夹角。The scanning mirror and the beam splitting filter are parallel to each other and form an angle of 45 degrees with the two straight lines respectively.
进一步地,所述遮光罩还包括:Further, the hood also includes:
提手,用于移动和携带所述检测头。Handle for moving and carrying the detection head.
另一方面,本发明还提供一种拉曼光谱检测方法,利用如上任一项所述的拉曼光谱检测头进行拉曼光谱检测,包括:On the other hand, the present invention also provides a Raman spectrum detection method, using the Raman spectrum detection head as described in any one of the above to perform Raman spectrum detection, including:
通过激光线光源发射线状激光;Emit a linear laser through a laser line light source;
利用过滤滤光片过滤所述线状激光中的瑞利散射光,剩余拉曼散射光;Using a filter filter to filter the Rayleigh scattered light in the linear laser, and the remaining Raman scattered light;
将过滤后的拉曼散射光利用分束滤光片反射至扫描镜;The filtered Raman scattered light is reflected to the scanning mirror by a beam splitting filter;
利用扫描镜通过往复振动的方式反射所述拉曼散射光,得到均匀的线状拉曼散射光,将均匀的线状拉曼散射光通过遮光罩的狭缝出射至样品表面;Using the scanning mirror to reflect the Raman scattered light by reciprocating vibration to obtain uniform linear Raman scattered light, and emit the uniform linear Raman scattered light to the sample surface through the slit of the light shield;
令均匀的线状拉曼散射光照射在样品表面产生的拉曼检测的信号光通过狭缝入射至扫描镜,利用扫描镜反射所述信号光经分束滤光片后通过遮光罩上的检测镜出射。Let the uniform linear Raman scattered light irradiate on the surface of the sample, and the signal light of Raman detection generated by the Raman detection enters the scanning mirror through the slit, and the signal light is reflected by the scanning mirror, passes through the beam splitting filter, and then passes through the detection on the light shield. mirror out.
(三)有益效果(3) Beneficial effects
可见,在本发明提供的拉曼光谱检测头和检测方法中,将激光线光源、过滤滤光片、分束滤光片和扫描镜集成于拉曼光谱检测头的遮光罩中,提供了一种便携式的集成拉曼光谱检测头,能够对样品进行快速移动检测和信号采集。并且,本发明通过线状激光对样品进行检测,解决了现有技术的拉曼检测技术中只能进行点光谱检测的技术问题,具有很高的应用价值。It can be seen that in the Raman spectrum detection head and detection method provided by the present invention, the laser line light source, filter filter, beam splitting filter and scanning mirror are integrated in the hood of the Raman spectrum detection head, providing a A portable, integrated Raman spectroscopy detection head that enables rapid mobile detection and signal acquisition of samples. Moreover, the present invention detects the sample by using a linear laser, which solves the technical problem that only point spectrum detection can be performed in the prior art Raman detection technology, and has high application value.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention. Those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1是本发明实施例拉曼光谱检测头的基本结构示意图;1 is a schematic diagram of the basic structure of a Raman spectrum detection head according to an embodiment of the present invention;
图2是本发明实施例拉曼光谱检测头的一个优选结构示意图;2 is a schematic diagram of a preferred structure of a Raman spectrum detection head according to an embodiment of the present invention;
图3是本发明实施例拉曼光谱检测方法的基本流程示意图。Fig. 3 is a schematic flow chart of a Raman spectroscopy detection method according to an embodiment of the present invention.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
本发明实施例首先提供一种拉曼光谱检测头,参见图1,包括:遮光罩1,遮光罩1包括狭缝2和检测镜3,狭缝2用于令拉曼散射光出射至样品4,并令样品4表面产生的信号光射入,检测镜3用于出射信号光;The embodiment of the present invention firstly provides a Raman spectrum detection head, referring to FIG. 1 , including: a light shield 1, the light shield 1 includes a slit 2 and a detection mirror 3, and the slit 2 is used to let the Raman scattered light exit to the sample 4 , and the signal light generated on the surface of the sample 4 is incident, and the detection mirror 3 is used to emit the signal light;
遮光罩1内还包括:The hood 1 also includes:
激光线光源5,用于发射线状激光;Laser line light source 5, used to emit line laser;
过滤滤光片6,用于过滤线状激光中的瑞利散射光,剩余拉曼散射光;filter filter 6, used to filter the Rayleigh scattered light in the linear laser, and the remaining Raman scattered light;
分束滤光片7,用于将经过过滤滤光片6的拉曼散射光反射至扫描镜8,并令扫描镜8反射回的信号光通过检测镜3出射;The beam splitting filter 7 is used to reflect the Raman scattered light passing through the filter filter 6 to the scanning mirror 8, and make the signal light reflected by the scanning mirror 8 exit through the detection mirror 3;
扫描镜8,扫描镜8通过往复振动的方式反射经过分束滤光片7反射的拉曼散射光,以获取均匀的线状拉曼散射光,使其通过狭缝2出射至样品4表面,并将经狭缝2射入的样品4表面产生的拉曼检测的信号光反射至分束滤光片7。The scanning mirror 8, the scanning mirror 8 reflects the Raman scattered light reflected by the beam splitting filter 7 by reciprocating vibration, so as to obtain uniform linear Raman scattered light, so that it is emitted to the surface of the sample 4 through the slit 2, And reflect the Raman detection signal light generated on the surface of the sample 4 incident through the slit 2 to the beam splitting filter 7 .
为了获得更加均匀的线状激光,优选地,激光线光源5和过滤滤光片6之间还可以包括:准直透镜9,见图2,用于将激光线光源5发射的线状激光准直汇聚为均匀的平行光。In order to obtain a more uniform linear laser, preferably, between the laser line light source 5 and the filter filter 6, a collimating lens 9, as shown in FIG. Converge straight into a uniform parallel light.
优选地,激光线光源5可以为:785nm激光线光源,其最大输出功率为5w,激光输出1mm(MAX)×20cm长的激光线。Preferably, the laser line light source 5 can be: a 785nm laser line light source with a maximum output power of 5w, and the laser outputs a laser line with a length of 1mm (MAX)×20cm.
优选地,激光线光源5可以通过多个排成一排的激光点光源来激发汇聚成线光源,其中,激光点光源的个数可以为9个。Preferably, the laser line light source 5 can be excited and converged into a line light source by a plurality of laser point light sources arranged in a row, wherein the number of laser point light sources can be nine.
优选地,如图2所示,激光线光源5、准直透镜9、过滤滤光片6和分束滤光片7可以依次分布在一条直线上;而扫描镜8、分束滤光片7和检测镜3可以依次分布在与上述直线垂直的另一条直线上;其中扫描镜8和分束滤光片7相互平行,分别与这两条直线成45度夹角。并且,由于扫描镜8反射的拉曼散射光需要通过狭缝2出射到样品4上,样品4表面的信号光也需要通过狭缝2入射到扫描镜8上,因此,扫描镜8、狭缝2和样品4也依次分布在一条直线上,扫描镜8以与直线呈45度角为中心进行循环往复振动。Preferably, as shown in Figure 2, the laser line light source 5, the collimating lens 9, the filter filter 6 and the beam splitting filter 7 can be distributed on a straight line in turn; and the scanning mirror 8, the beam splitting filter 7 And the detection mirror 3 can be distributed in turn on another straight line perpendicular to the above straight line; wherein the scanning mirror 8 and the beam splitting filter 7 are parallel to each other and form an angle of 45 degrees with the two straight lines respectively. Moreover, since the Raman scattered light reflected by the scanning mirror 8 needs to exit on the sample 4 through the slit 2, the signal light on the surface of the sample 4 also needs to be incident on the scanning mirror 8 through the slit 2. Therefore, the scanning mirror 8, the slit 2 and sample 4 are also sequentially distributed on a straight line, and the scanning mirror 8 vibrates cyclically around a 45-degree angle with the straight line.
为了使得本发明实施例中的拉曼光谱检测头便于携带和移动,优选地,遮光罩1上还可以包括提手,以便针对不同场合的样品利用集成式的拉曼光谱检测头进行快速移动检测和信号采集。In order to make the Raman spectrum detection head in the embodiment of the present invention easy to carry and move, preferably, the light shield 1 can also include a handle, so that the integrated Raman spectrum detection head can be used for fast mobile detection of samples in different occasions and signal acquisition.
其中,本发明实施例中的拉曼光谱检测头在检测样品时,可以将样品4置于二维平移样品台上,从而通过在二维方向移动样品4对其整个表面进行二维激光线扫描,以获取整个样品表面的图谱信息,得到更加全面精确的拉曼光谱检测数据。Wherein, when the Raman spectroscopy detection head in the embodiment of the present invention detects a sample, the sample 4 can be placed on a two-dimensional translational sample stage, so as to perform two-dimensional laser line scanning on the entire surface of the sample 4 by moving the sample 4 in the two-dimensional direction , to obtain the spectrum information of the entire sample surface, and obtain more comprehensive and accurate Raman spectrum detection data.
本发明实施例还提供一种拉曼光谱检测方法,利用本发明实施例中的拉曼光谱检测头进行拉曼光谱检测,如图3,具体步骤包括:The embodiment of the present invention also provides a Raman spectrum detection method, using the Raman spectrum detection head in the embodiment of the present invention to perform Raman spectrum detection, as shown in Figure 3, the specific steps include:
步骤301:通过激光线光源发射线状激光;Step 301: emit a linear laser through a laser line light source;
步骤302:利用过滤滤光片过滤所述线状激光中的瑞利散射光,剩余拉曼散射光;Step 302: Using a filter filter to filter the Rayleigh scattered light in the linear laser, leaving the remaining Raman scattered light;
步骤303:将过滤后的拉曼散射光利用分束滤光片反射至扫描镜;Step 303: Reflect the filtered Raman scattered light to the scanning mirror by using a beam splitting filter;
步骤304:利用扫描镜通过往复振动的方式反射所述拉曼散射光,得到均匀的线状拉曼散射光,将均匀的线状拉曼散射光通过遮光罩的狭缝出射至样品表面;Step 304: using the scanning mirror to reflect the Raman scattered light by reciprocating vibration to obtain uniform linear Raman scattered light, and emit the uniform linear Raman scattered light to the sample surface through the slit of the light shield;
步骤305:令均匀的线状拉曼散射光照射在样品表面产生的拉曼检测的信号光通过狭缝入射至扫描镜,利用扫描镜反射所述信号光经分束滤光片后通过遮光罩上的检测镜出射。Step 305: irradiating the uniform linear Raman scattered light on the surface of the sample, the signal light of Raman detection generated by the Raman detection is incident on the scanning mirror through the slit, and the signal light is reflected by the scanning mirror, passes through the beam splitting filter, and then passes through the hood The detection mirror on the exit.
可见,本发明实施例至少具有如下有益效果:It can be seen that the embodiments of the present invention have at least the following beneficial effects:
在本发明实施例提供的拉曼光谱检测头和检测方法中,将激光线光源、过滤滤光片、分束滤光片和扫描镜集成于拉曼光谱检测头的遮光罩中,提供了一种便携式的集成拉曼光谱检测头,能够对样品进行快速移动检测和信号采集。并且,本发明实施例通过线状激光对样品进行检测,解决了现有技术的拉曼检测技术中只能进行点光谱检测的技术问题,具有很高的应用价值。In the Raman spectroscopy detection head and detection method provided in the embodiments of the present invention, the laser line light source, filter filter, beam splitting filter and scanning mirror are integrated in the hood of the Raman spectroscopy detection head, providing a A portable, integrated Raman spectroscopy detection head that enables rapid mobile detection and signal acquisition of samples. Moreover, the embodiment of the present invention detects the sample by using a linear laser, which solves the technical problem that only point spectrum detection can be performed in the prior art Raman detection technology, and has high application value.
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still be Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.
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