WO2016082804A1 - 一种用于获取喇曼散射光谱的装置及方法 - Google Patents

一种用于获取喇曼散射光谱的装置及方法 Download PDF

Info

Publication number
WO2016082804A1
WO2016082804A1 PCT/CN2015/096451 CN2015096451W WO2016082804A1 WO 2016082804 A1 WO2016082804 A1 WO 2016082804A1 CN 2015096451 W CN2015096451 W CN 2015096451W WO 2016082804 A1 WO2016082804 A1 WO 2016082804A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
raman scattering
scattered light
spatial
raman
Prior art date
Application number
PCT/CN2015/096451
Other languages
English (en)
French (fr)
Inventor
沈嘉祺
孙文剑
Original Assignee
岛津分析技术研发（上海）有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 岛津分析技术研发（上海）有限公司 filed Critical 岛津分析技术研发（上海）有限公司
Publication of WO2016082804A1 publication Critical patent/WO2016082804A1/zh

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering

Definitions

  • the present invention relates to apparatus and methods for obtaining Raman scattering spectra for analyzing sample components.
  • the acquisition of the Raman scattering spectrum is independent of complex sample preparation and can be used for fast, non-destructive sample component analysis.
  • portable Raman spectrometers on the market, which are small in size, simple in structure, and easy to use and maintain. They use excitation wavelengths ranging from 532 nm to 1064 nm.
  • Most of the sensors used are sensor linear arrays such as charge coupled devices (CCD) and N-type metal oxide field effect transistors (NMOS).
  • the longer excitation wavelength is beneficial to reduce the fluorescence background, and the signal-to-noise ratio of Raman scattered light detection can be improved to some extent, but since the Raman scattering intensity is inversely proportional to the fourth power of the excitation wavelength,
  • the performance requirements of the detection unit used are higher (generally achieved by lowering the operating temperature and extending the detection period).
  • the spectrum detection of bands above 1100 nm generally uses indium gallium arsenide (InGaAs) photodiode arrays. At present, the manufacturing cost of such devices is much higher than that of image sensor arrays with a band below 1100 nm, which directly affects the whole machine. Production costs. Subject to the above factors, the sensitivity and spectral resolution of a typical portable Raman spectrometer are quite limited, and the cost performance is not too high.
  • the portion of the Raman scattering spectrum where the photon frequency is higher than the photon frequency of the excitation light is called the anti-stokes spectrum, and the photon frequency is lower than the photon of the excitation light.
  • the portion of the frequency (ie, the portion of the emission wavelength shorter than the excitation wavelength) is called the Stokes spectrum.
  • the former is caused by the polarization of the photons of the excitation photon by the molecules in the lower basal state. a higher base state transition occurs, the latter being caused by the polarization of the excitation photons and the transition to the lower base state.
  • the frequency shift of the spectral line with respect to the excitation spectral line is symmetrically distributed with respect to the zero point. Since the photon frequency of non-resonant fluorescence is generally lower than the photon frequency of the excitation light, detecting the anti-Stokes spectrum helps to eliminate interference from the fluorescent background. On the other hand, the number of molecules of each energy level is a Boltzmann distribution, the intensity of the anti-Stokes line is weaker than the corresponding Stokes line, and the ratio of the two decreases as the frequency shift increases. Due to the size and performance limitations, the design of a typical portable Raman spectrometer does not include the acquisition of anti-Stokes spectra.
  • the technique currently used to observe anti-Stokes Raman spectroscopy is coherent anti-Stokes Raman spectroscopy.
  • This technique directs two strong laser beams with photon frequencies ⁇ 1 , ⁇ 2 ( ⁇ 1 > ⁇ 2 ) to the sample and the frequency difference is exactly equal to the spontaneous Raman shift of the sample, thereby producing resonant molecular vibrations.
  • Simultaneously mixing with a laser beam of frequency ⁇ 3 (which may be a strong laser beam of the stated frequency ⁇ 1 ), producing an anti-Stokes spectrum of frequency ⁇ 3 + ⁇ 1 - ⁇ 2 ;
  • the relationship between the amplitude of the spectral line signal and the physical quantity (including the concentration of the sample component) is complicated, and the background noise is large. This technique is difficult to be used for the quantitative analysis of the general sample components.
  • the present invention provides an apparatus and method for obtaining Raman scattering spectra to suppress interference of fluorescence and background light commonly used in the use of a general portable Raman spectrometer to obtain a high optical signal. Noise ratio, while the cost is not too high.
  • the present invention provides an apparatus for acquiring a Raman scattering spectrum, comprising: an excitation light source for generating an excitation light beam; and an excitation light path for directing the excitation light beam to be analyzed.
  • Solid or liquid sample to produce Raman scattered light Solid or liquid sample to produce Raman scattered light; scattered light collecting optical path for collecting said Raman scattered light; detecting means comprising one or more detecting channels for receiving Raman corresponding to each detecting frequency or sub-band Scattering the optical signal and converting it into an electrical signal for analysis; connecting the scattered light collecting optical path and one or more dispersing means of the detecting means for forming a Raman scattering spectrum from the received Raman scattered light; At least one dispersing device is provided with a spatial light modulator for sequentially selecting a spatial portion corresponding to a different detecting frequency or sub-band among the Raman scattering spectra formed by the dispersing device to be sequentially guided to the detecting device for detecting, wherein Part or all of the Raman scattering spectrum is an anti-Stokes spectrum.
  • the detecting device comprises a detector and a detecting circuit;
  • the detector is a photomultiplier tube or a photodiode, and operates in a linear detection mode or a photon counting mode; in the linear detection mode, the detector outputs a current The amplitude of the signal is proportional to the luminous flux received by the detector; in the photon counting mode, the frequency of the effective signal pulse output by the detector is proportional to the luminous flux received by the detector.
  • the detecting device further includes a modulation device of the excitation beam and a corresponding detection circuit; the modulation device of the excitation beam generates a series of modulation signals, the excitation beam is modulated by the modulation signal, and the The detection circuit outputs a signal that is consistent with the frequency of the modulation signal by filtering.
  • the plurality of dispersing devices are respectively configured to form spectra of different frequency bands;
  • the scattered light collecting optical path is further provided with one or more beam splitters or one or more light guides; Raman scattered light is distributed to each of the dispersing devices through the beam splitter, or sequentially by the light guide
  • Each of the dispersing devices is directed to each of the dispersing devices to form Raman scattering spectra of different frequency bands, respectively.
  • the light guide comprises one of the following:
  • a movable micromirror array or a scanning galvanometer changing the orientation of the outgoing light by oscillating the micromirror array or the scanning galvanometer;
  • the spatial light modulator comprises one of the following:
  • a transmissive optical device the spatial light modulator directs light transmitted through the back side thereof to the detecting device;
  • the spatial light modulator directs light reflected from its surface to the detecting device.
  • the spatial light modulator is a micro mirror array
  • the micro mirror array comprises: a plurality of micro mirror units; each of the micro mirror units comprises: a micro mirror, a strip and the a pivoting, control circuit unit hinged by the micromirror; driving the micromirror of a certain micromirror unit around the pivoted pivot by the control circuit unit to control the Raman
  • Each spatial portion of the scatter spectrum is switched from the dispersing device associated with the spatial light modulator to the detecting device.
  • the spatial light modulator is a liquid crystal optical amplitude spatial modulator
  • the liquid crystal optical amplitude spatial modulator comprises: a liquid crystal mask and a polarization optical element; the liquid crystal mask comprises a plurality of spatial units; Means for changing a voltage applied to each spatial unit of the liquid crystal mask to change a polarization direction of transmitted light irradiated from the dispersing device to respective spatial units of the liquid crystal mask to cooperate with the polarizing optics
  • the component controls on/off of respective spatial portions of the Raman scattering spectrum corresponding to different detection frequencies or sub-bands from the dispersing device to the detecting device.
  • the excitation light source is a laser for generating an excitation beam having a line width of less than 0.3 nm;
  • the excitation light path includes a beam shaping element and an imaging optical system; and the beam shaping element is used to emit the laser
  • An excitation beam is shaped;
  • the imaging optical system is configured to transmit and concentrate the excitation beam onto the sample.
  • the present invention provides a method for obtaining a Raman scattering spectrum, comprising: providing an excitation light source for generating an excitation beam; and providing an excitation light path for directing the excitation beam to Analytical solid or liquid sample to produce Raman scattered light; provide scattered light to collect light a means for collecting the Raman scattered light; providing detection means including one or more detection channels for receiving Raman scattered light signals corresponding to respective detection frequencies or sub-bands and converting into electrical signals for analysis; Connecting the scattered light collecting optical path and one or more dispersing means of the detecting means for introducing the Raman scattered light collected by the scattered light collecting optical path to form a Raman scattering spectrum; wherein at least one dispersing device Configuring a spatial light modulator for selecting a spatial portion corresponding to a different detection frequency or sub-band in a Raman scattering spectrum formed by the dispersion device and sequentially guiding the detection device for detection, wherein Part or all of the Raman scattering spectrum is an anti-Stokes spectrum
  • the plurality of dispersing devices are respectively configured to form spectra of different frequency bands;
  • the scattered light collecting optical path is further provided with one or more beam splitters or one or more light guides;
  • Raman scattered light is distributed to each of the dispersing devices through the beam splitter, or is sequentially guided to each of the dispersing devices by the light guides, so that each of the dispersing devices respectively forms different frequency bands of Raman Scattering spectrum.
  • the present invention provides an apparatus and method for acquiring a Raman scattering spectrum, the apparatus comprising: an excitation light source for generating an excitation beam; and an excitation light path for directing the excitation beam to be analyzed Solid or liquid sample to produce Raman scattered light; scattered light collecting optical path for collecting said Raman scattered light; detecting means comprising one or more detecting channels for receiving Raman corresponding to each detecting frequency or sub-band Scattering the optical signal and converting it into an electrical signal for analysis; connecting the scattered light collecting optical path and one or more dispersing means of the detecting means for introducing the Raman scattering collected by the scattered light collecting optical path Light forms a Raman scattering spectrum; wherein at least one of the dispersing devices is provided with a spatial light modulator for selecting a spatial portion corresponding to a different detecting frequency or sub-band in a Raman scattering spectrum formed by the dispersing device The detection device is directed to the detection, wherein part or all of the Raman scattering spectrum is an anti-Stokes spectrum.
  • FIG. 1 is a schematic view showing the structure of an apparatus for acquiring a Raman scattering spectrum according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing the structure of an apparatus for acquiring a Raman scattering spectrum according to still another embodiment of the present invention.
  • FIG. 3 is a schematic view showing the structure of an apparatus for acquiring a Raman scattering spectrum according to still another embodiment of the present invention.
  • FIG. 4 is a schematic view showing the structure of an apparatus for acquiring a Raman scattering spectrum according to still another embodiment of the present invention.
  • FIG. 5 is a flow chart showing a method for obtaining Raman scattering spectra according to an embodiment of the present invention.
  • the present invention provides an apparatus for obtaining a Raman scattering spectrum, the apparatus comprising: an excitation light source 1 for generating an excitation beam 2, an excitation light path 3, a sample 4, for collecting scattered light 5 from the sample 4.
  • the excitation light source 1 is configured to generate an excitation beam 2, and the excitation beam is concentrated and irradiated onto the sample 4 placed in the sample region through the excitation light path 3, and the sample 4 is excited to thereby scatter;
  • the scattered light 5 generated by the sample is collected by the scattered light collecting optical path 6 and directed to the dispersing device 1i, 1j; in other embodiments, there may be only one dispersing device, and if there are more than one dispersing device,
  • the collected scattered light 5 can be distributed to the respective dispersing devices 1i, 1j, ... by the beam splitter 7 in accordance with the embodiment shown in Fig. 1, or the beam splitter 7 can be replaced by providing a light guide.
  • the collected scattered light 5 is successively directed to each of the dispersing devices for each of the dispersing devices (1i, 1j, ...) and their associated spatial light modulators (1i', 1j', ...) to form different frequency bands, respectively.
  • Raman scattering spectrum is successively directed to each of the dispersing devices for each of the dispersing devices (1i, 1j, ...) and their associated spatial light modulators (1i', 1j', ...) to form different frequency bands, respectively.
  • the spatial light modulator (1i) when the dispersing means (1i or 1j) configured with the spatial light modulator (1i' or 1j') is operated, the spatial light modulator (1i) is configured.
  • a Raman scattering spectrum is formed on 'or 1j'), some or all of which are anti-Stokes spectra, i.e., some or all of their corresponding wavelengths are shorter than the wavelength of the excitation beam.
  • Controlling the spatial light modulator (1i' or 1j') to cause the color dispersion The portions of the spectrum formed by (1i or 1j) are successively collected by the detecting means 8 for detection for obtaining a Raman scattering spectrum in the operating band of the dispersing means (1i or 1j).
  • the detecting device includes one or more detecting channels for receiving Raman scattered light signals corresponding to the respective detecting frequencies or sub-bands and converting them into electrical signals for analysis.
  • each of the dispersing devices (1i, 1j) is provided with a spatial light modulator (1i', 1j'), in other embodiments, only a part of the dispersion may be The device is configured with a spatial light modulator, and the remaining dispersion devices are not configured, and the spectrum is detected by other means, for example, the Raman scattering spectrum is directly detected by a sensor line array commonly used in current general portable Raman spectrometers.
  • the excitation light source 1 is a laser for generating an excitation beam having a line width less than 0.3 nm; the excitation light path includes a beam shaping element and an imaging optical system, and the beam shaping element is used for An excitation beam emitted by the laser is shaped; the imaging optical system is for transmitting and concentrating the excitation beam onto the sample 4.
  • the light guide for switching the guided dispersing device may include, but is not limited to: (1) a swingable micro mirror array or a scanning galvanometer, by swinging the micro mirror array or The scanning galvanometer changes the guiding of the outgoing light; (2) the rotatable platform, on which the mirror is fixed, and the guiding of the outgoing light is changed by rotating the platform. It should be noted that the foregoing several manners are only examples, and in other embodiments, other activities (such as translation) may also be implemented.
  • the operating frequency band of the dispersing device (1i, 1j) configured with the spatial light modulator is at least partially higher than the photon frequency of the excitation beam 2, and may also cover the excitation beam 2
  • the photon frequency or lower, that is, the detected spectrum contains anti-Stokes lines, and may also contain the lines of the Stokes line and the excitation beam.
  • the Raman spectrum is detected using a plurality of dispersive devices. It is advantageous to optimize the performance of the dispersive device in each frequency band.
  • the spatial light modulator may be transmissive, and the light that is transmitted from the back surface of the spatial light modulator to the detecting device 8 at this time; or may be reflective, and the light is directed to the The detection device 8 is light that is reflected from the surface of the spatial light modulator.
  • the detecting device 8 includes a detector and a detecting circuit, and the detector is a photomultiplier tube or a photodiode, and operates in a linear detecting mode or a photon counting mode; in the linear detecting mode, the current output by the detector The amplitude of the signal is proportional to the luminous flux received by the detector; in the photon counting mode, the frequency of the effective signal pulse output by the detector is proportional to the luminous flux received by the detector;
  • the detecting device further comprises a modulation device for the excitation beam and a corresponding detection circuit, the modulation device of the excitation beam generates a series of modulation signals, the excitation beam is modulated by the modulation signal, and the detection The circuit outputs a signal that is consistent with the frequency of the modulated signal by filtering.
  • Figure 2 shows an embodiment 1 of the apparatus of the invention comprising: a laser 21, a collimating shaping optical element 23, a sample zone for placing a sample 24 to be analyzed, a beam splitter 25, a collecting/collimating lens 26, a belt Resistive filter 29, scanning galvanometer 27, parabolic mirror (2i", 2j"), slit (2i"', 2j"'), concave grating (2i, 2j) for selecting the detected frequency or sub- A micromirror array (2i', 2j') of the frequency band, a collecting optical system 281, and a detector 282.
  • the micromirror array (2i', 2j') is a spatial light modulator for selecting the detected frequency or sub-band, each of the spatial units comprising a micro-mirror and a hinged to the micro-mirror a pivoting, control circuit unit, wherein the micro-mirror of a certain one of the space units is driven to wrap around the connected pivot by the control circuit unit, when the micro-mirror swings into a certain direction
  • the reflected light generated by the light irradiated to the micromirror is guided to the collecting optical system 281, and when the micromirror is swung to the other direction, the light irradiated to the micromirror is generated.
  • the reflected light is not received by the collecting optics 281, thereby controlling the on and off of the various spatial portions of the spectrum transmitted to the detector 282.
  • the detector 282 is a photomultiplier tube or a photodiode, and operates in a linear detection mode or a photon counting mode. In the linear detection mode, the amplitude of the current signal output by the detector 282 is proportional to the received luminous flux, and in the photon counting mode, the detection is performed. The frequency of the effective signal pulses output by the 282 is proportional to the received luminous flux.
  • the laser 21 produces an excitation beam having a linewidth of less than 0.3 nm, the excitation beam forming a collimated beam of relatively uniform wavefront energy distribution by the collimating shaping optical element 23, followed by partial steering by the beam splitter 25 At 90°, it is concentrated by the concentrating/collimating lens 26 onto the sample 24, and the sample 24 is thereby scattered. Part of the backscattered light of sample 24 is collected by the collecting/collimating lens 26 and forms a collimated beam that continues through the beam splitter 25 portion in the original direction, followed by a band stop filter 29 in which the wavelength is near the excitation wavelength.
  • each dispersive device consists of an inlet slit (2i"' or 2j"'), a concave grating (2i or 2j), and a micromirror array ( 2i' or 2j').
  • the concave grating functions to receive the light beam from the entrance slit of one side and form a spectral band on the other side of the micro mirror array by diffraction.
  • each spatial portion of the spectral band is successively directed to the collecting optical system 281.
  • the collecting optical system 281 collects the signal light from the micromirror array (2i' or 2j') and converges to the detector 282.
  • the operating bands of the respective dispersing devices are different, that is, the corresponding Raman scattered light bands are different, but there may be overlapping portions, and the scanning illuminating mirror 27 is used to switch the guiding of the scattered light beams to transmit the scattered light successively.
  • Each dispersive device is applied to obtain high resolution Raman spectra over a wider frequency band while eliminating the spatial resolution of the micromirror array used to limit the resolution of the acquired spectrum.
  • a typical design is to use one of the dispersive devices for analyzing the Stokes spectrum and the other for analyzing the anti-Stokes spectrum.
  • using a single detector to detect the spectrum of a certain frequency band is advantageous for obtaining higher sensitivity at a lower cost, which is advantageous for obtaining anti-Stokes.
  • the spectrum helps to eliminate interference from the fluorescent background.
  • Figure 3 shows a second embodiment of the invention comprising: a laser 31, a collimating shaping optical element 33, a sample zone for placing a sample 34 to be analyzed, a beam splitter 35, a collecting/collimating lens 36, a band stop Filter 39, scanning galvanometer 37, parabolic mirror (3i", 3j"), slit (3i"', 3j"'), plane transmission grating (3i, 3j), imaging lens (3i"" a, 3i""b,3j""a,3j””b), linear polarizing plates (3i'a, 3i'c, 3j'a, 3j'c), transmissive liquid crystals for selecting the detected frequency or sub-band An optical amplitude spatial modulator (3i'b, 3j'b), a collecting optical system 381, and a detector 382.
  • a laser 31 a collimating shaping optical element 33
  • a sample zone for placing a sample 34 to be analyzed
  • a beam splitter 35 for placing a sample 34 to be
  • the present embodiment differs from the embodiment 1 shown in Fig. 2 in the dispersion device used and the composition and operation of the spatial light modulator for selecting the detected frequency or sub-band.
  • the selected dispersing device is composed of a slit 3i"', an imaging lens (3i""a, 3i""b) and a plane transmission grating 3i, to the maximum extent.
  • the off-axis astigmatism of the dispersing device in Embodiment 1 is eliminated, which is favorable for obtaining high spectral resolution.
  • the reflective spatial light modulator is no longer suitable for selecting the detected frequency or sub-band, and switching to a linear polarizing plate.
  • the state shown in Fig. 3 is, for example, a large-scale filtering through the linear polarizing plate 3i'a in the selected dispersing device.
  • the transmissive transmissive liquid crystal optical amplitude spatial modulator 3i'b is used to control the polarization direction of each spatial portion of the transmitted light, and when a certain sub-band is selected, the 3i'b space corresponding to the strobed spectral sub-band is selected.
  • the direction of polarization of the transmitted light of the unit remains perpendicular to the plane of the paper, is substantially retained by the linearly polarizing plate 3i'c and is received by the detecting means 382, while the direction of polarization of the transmitted light of the remaining spatial elements of 3i'b is parallel to the plane of the paper, passing through the line
  • the polarizing plate 3i'c is substantially filtered out and cannot be received by the detecting means 382.
  • FIG. 4 shows a third embodiment of the present invention, comprising: a laser 41, a collimating shaping optical element 43, a sample area for placing a sample 44 to be analyzed, a beam splitter 45, a collecting/collimating lens 46, and a band stop.
  • a micromirror array (4i', 4j') for selecting a frequency or sub-band of the detected Raman scattering spectrum, a collecting optical system 481, and a detector 482.
  • the difference between this embodiment and the embodiment 1 shown in Fig. 2 lies in the composition and operation of the dispersing device used.
  • the dispersing device is composed of an entrance slit 4i"', a parabolic mirror 4ib, 4ic, a plane reflection grating 4ia, a micro mirror array 4i', a dispersing device by an entrance slit 4j"', a parabolic mirror 4jb, 4jc, a plane reflection grating 4ja, micromirror array 4j'.
  • the collected Raman scattered light is split into two parts by the beam splitter 47, a part of which continues to travel in the original direction, is concentrated by the parabolic mirror 4i" onto the entrance slit 4i"' of the dispersing device, and the other part is changed by the beam splitter reflection
  • the direction is concentrated by the parabolic mirror 4j" onto the entrance slit 4j"' of the dispersing device.
  • the role of the parabolic mirrors 4ib, 4ic is to transform the beam of the line source from the entrance slit into a collimated beam, the plane reflection grating is used to diffract the incident collimated beam, through the parabolic mirror 4ic, 4jc in the micromirror array A spectral band is formed on (4i', 4j').
  • the present invention may also provide a method for acquiring a Raman scattering spectrum, comprising:
  • Step S1 providing an excitation light source for generating an excitation beam
  • Step S2 providing an excitation light path for directing the excitation beam to a solid or liquid sample to be analyzed to generate Raman scattered light;
  • Step S3 providing a scattered light collecting optical path for collecting the Raman scattered light
  • Step S4 providing detection means including one or more detection channels for receiving corresponding detection frequencies Raman scattered light signals of rate or sub-band and converted into electrical signals for analysis;
  • Step S5 providing one or more dispersing means for connecting the scattered light collecting optical path and the detecting means for introducing the Raman scattered light collected by the scattered light collecting optical path to form a Raman scattering spectrum; At least one dispersing device is provided with a spatial light modulator for selecting a spatial portion corresponding to a different detecting frequency or sub-band in a Raman scattering spectrum formed by the dispersing device and sequentially guiding the detecting device for detecting Wherein part or all of the Raman scattering spectrum is an anti-Stokes spectrum.
  • Step S6 the excitation light source generates the excitation light beam, and the excitation light beam is guided to the sample through the excitation light path, and the sample is thereby subjected to Raman scattering;
  • Step S7 collecting the Raman scattered light generated by the sample by using the scattered light collecting optical path, and guiding the dispersion device to the dispersing device;
  • Step S8 when a certain dispersion device configured with the spatial modulator operates, forming a Raman scattering spectrum on the configured spatial light modulator, and by controlling the spatial light modulator, The portions of the spectrum formed by the dispersing device are successively collected by the detecting device for detection to obtain a Raman scattering spectrum in the operating band of the dispersing device.
  • the present invention provides an apparatus and method for acquiring a Raman scattering spectrum, the apparatus comprising: an excitation light source for generating an excitation beam; and an excitation light path for directing the excitation beam to be analyzed a solid or liquid sample to generate Raman scattered light; a scattered light collecting optical path for collecting the Raman scattered light; and detecting means for receiving a Raman scattered light signal corresponding to each detection frequency or sub-band and converting it into electricity a signal for analysis; one or more dispersing means connecting the scattered light collecting optical path and the detecting means for introducing the Raman scattered light collected by the scattered light collecting optical path to form a Raman scattering spectrum; At least one of the dispersing devices is provided with a spatial light modulator for sequentially selecting a spatial portion corresponding to a different detecting frequency or sub-band among the Raman scattering spectra formed by the dispersing device to sequentially guide the detecting device for detecting Wherein part or all of the Raman scattering spectrum is an anti-Stokes spectrum; the apparatus and

Landscapes

  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Spectrometry And Color Measurement (AREA)

Abstract

一种用于获取喇曼散射光谱的装置及方法，装置包括：产生激发光束（2）的激发光源（1）；激发光光路（3），用于将激发光束导向待分析样品（4）以产生喇曼散射光（5）；收集喇曼散射光（5）的散射光收集光路（6）；检测装置（8），用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以分析；连接散射光收集光路和检测装置的一个或多个色散装置，用于导入散射光收集光路收集的喇曼散射光形成喇曼散射光谱；至少一个色散装置配有空间光调制器，空间光调制器在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分并逐次导向检测装置检测，其中，喇曼散射光谱的部分或全部为反斯托克斯光谱。该装置可以检测反斯托克斯喇曼光谱用于样品组分定量分析。

Description

一种用于获取喇曼散射光谱的装置及方法 技术领域
本发明涉及用于获取喇曼散射光谱以分析样品组分的装置和方法。
背景技术
喇曼散射光谱(Raman scattering spectrum)的获取不依赖于复杂的样品前处理，可以用于快速、无损的样品组分分析。目前市场上已有一些便携式喇曼光谱仪，它们体积小，结构简单，使用维护方便。它们所采用的激发波长多为532nm-1064nm，所采用的传感器多为像传感器线阵，如电荷耦合器件(CCD)、N型金属氧化物场效应管(NMOS)。在近红外波段，采用较长的激发波长有利于减小荧光背景，可在一定程度上提高喇曼散射光检测的信噪比，不过由于喇曼散射强度反比于激发波长的四次方，对所用检测单元性能的要求就较高(一般通过降低工作温度和延长检测周期来实现)。另一方面，波段在1100nm以上的光谱检测一般使用铟镓砷(InGaAs)光电二极管线阵，目前这种器件的制造成本比适用波段在1100nm以下的像传感器线阵高得多，直接影响整机的生产成本。受制于上述因素，一般便携式喇曼光谱仪的灵敏度和光谱分辨率相当有限，性价比也不太高。
喇曼散射光谱中光子频率高于激发光的光子频率的部分(即发射波长长于激发波长的部分)被称作反斯托克斯光谱(anti-Stokes spectrum)，光子频率低于激发光的光子频率的部分(即发射波长短于激发波长的部分)被称作斯托克斯光谱(Stokes spectrum)，前者系由处于较低的基电子态的分子受到激发光光子的极化作用后迅即向某个较高的基电子态跃迁发生，后者系由前者所产生的处于较高的基电子态的分子受到激发光光子的极化作用后迅即向较低的基电子态跃迁发生，两者谱线相对于激发光谱线的频移关于零点对称分布。由于非共振荧光的光子频率一般低于激发光的光子频率，检测反斯托克斯光谱有助于排除荧光背景的干扰。另一方面，各能级的分子数呈玻耳兹曼分布，反斯托克斯谱线的强度弱于对应的斯托克斯谱线，且两者比值随频移增大而减小。由于受到体积大小和性能的限制，一般便携式喇曼光谱仪的设计功能不包含获取反斯托克斯光谱。
目前常用于观测反斯托克斯喇曼光谱的技术有相干反斯托克斯喇曼谱分析(coherent anti-Stokes Raman spectroscopy)。这种技术是将两束光子频率分别为ν1、 ν2(ν1>ν2)的强激光光束导向样品且其频率差恰等于样品的自发喇曼频移，从而产生共振的分子振动，同时与频率为ν3的某一激光光束(可以是所述的频率为ν1的强激光光束)混合，产生频率为ν3+ν1-ν2的反斯托克斯光谱；由于所获得的谱线信号幅值与各物理量(包括样品组分浓度)关系复杂，背景噪声大，这种技术难以用于一般的样品组分定量分析。
发明内容
鉴于以上所述现有技术的缺点，本发明提供一种用于获取喇曼散射光谱的装置及方法，以抑制一般便携式喇曼光谱仪的使用中常见的荧光和背景光的干扰，获得高光学信噪比，同时成本不致过高。
为实现上述目标及其它相关目标，本发明提供一种用于获取喇曼散射光谱的装置，包括：激发光源，用于产生激发光束；激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；散射光收集光路，用于收集所述喇曼散射光；含一个或多个检测通道的检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于根据接收的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱。
可选的，所述检测装置包括探测器和检测电路；所述探测器是光电倍增管或光电二极管，工作于线性检测模式或光子计数模式；在线性检测模式下，所述探测器输出的电流信号幅值正比于所述探测器接收的光通量；在光子计数模式下，所述探测器输出的有效信号脉冲的频度正比于所述探测器接收的光通量。
可选的，所述检测装置还包括所述激发光束的调制装置和相应的检测电路；所述激发光束的调制装置产生一串调制信号，所述激发光束通过所述调制信号调制，且所述检测电路通过滤波输出与所述调制信号频率一致的信号。
可选的，所述色散装置有多个，分别用于形成不同频段的光谱；所述散射光收集光路还设有一个或多个分束器或者设有一个或多个光导向器；所收集的喇曼散射光通过所述分束器被分配至各所述色散装置，或者通过所述光导向器被逐次 导向各个所述色散装置，以供各所述色散装置分别形成不同频段的喇曼散射光谱。
可选的，所述光导向器包括以下中的一种：
(1)可活动的微反射镜阵列或扫描振镜；通过摆动所述微反射镜阵列或所述扫描振镜改变出射光的导向；
(2)可活动的平台；所述平台上固定有反射镜，通过活动所述平台改变出射光的导向。
可选的，所述空间光调制器包括以下中的一种：
(1)透射式光学器件；所述空间光调制器将其背面透射的光导向所述检测装置；
(2)反射式光学器件；所述空间光调制器将其表面反射的光导向所述检测装置。
可选的，所述空间光调制器是微反射镜阵列，所述微反射镜阵列包括：多个微反射镜单元；每个所述微反射镜单元包括：一面微反射镜、一条与所述微反射镜相铰接的枢轴、控制电路单元；通过所述控制电路单元驱动某个所述微反射镜单元的所述微反射镜绕所连的所述枢轴摆动，以控制所述喇曼散射光谱的各个空间部分从与所述空间光调制器相配的色散装置至所述检测装置的通断。
可选的，所述空间光调制器是液晶光振幅空间调制器，所述液晶光振幅空间调制器包括：液晶掩膜与偏振光学元件；所述液晶掩膜包括多个空间单元；可调电源装置，用于改变施加在所述液晶掩膜的各个空间单元的电压来改变从所述色散装置照射到所述液晶掩膜的各个空间单元的透射光的偏振方向，以配合使用所述偏振光学元件控制对应不同检测频率或子频段的喇曼散射光谱的各个空间部分从所述色散装置至所述检测装置的通断。
可选的，所述激发光源是激光器，用于产生线宽小于0.3nm的激发光束；所述激发光光路包含光束整形元件和成像光学系统；所述光束整形元件用于对所述激光器发出的激发光束作整形；所述成像光学系统用于将所述激发光束传输并汇聚到所述样品上。
为实现上述目标及其它相关目标，本发明提供一种用于获取喇曼散射光谱的方法，包括：提供激发光源，用于产生激发光束；提供激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；提供散射光收集光 路，用于收集所述喇曼散射光；提供含一个或多个检测通道的检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；提供连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分并逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱；所述激发光源产生所述激发光束，所述激发光束通过所述激发光光路被导向所述样品，所述样品由此发生喇曼散射；用所述散射光收集光路收集所述样品所产生的喇曼散射光，并导向所述色散装置；当某个配置有所述空间调制器的所述色散装置工作时，在所配置的所述空间光调制器上形成喇曼散射光谱，通过控制该所述空间光调制器，使该所述色散装置所形成的光谱中的各部分逐次被收集到所述检测装置进行检测，用来获取在该所述色散装置工作频段内的喇曼散射光谱。
可选的，所述色散装置有多个，分别用于形成不同频段的光谱；所述散射光收集光路还设有一个或多个分束器或者设有一个或多个光导向器；所收集的喇曼散射光通过所述分束器被分配至各所述色散装置，或者通过所述光导向器被逐次导向各个所述色散装置，以供各所述色散装置分别形成不同频段的喇曼散射光谱。
如上所述，本发明提供一种用于获取喇曼散射光谱的装置及方法，所述装置包括：激发光源，用于产生激发光束；激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；散射光收集光路，用于收集所述喇曼散射光；含一个或多个检测通道的检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱。
附图说明
图1显示为本发明一实施例中用于获取喇曼散射光谱的装置的结构示意图。
图2显示为本发明又一实施例中用于获取喇曼散射光谱的装置的结构示意图。
图3显示为本发明又一实施例中用于获取喇曼散射光谱的装置的结构示意图。
图4显示为本发明又一实施例中用于获取喇曼散射光谱的装置的结构示意图。
图5显示为本发明一实施例中用于获取喇曼散射光谱的方法的流程示意图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。需说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。
如图1所示，本发明提供获取喇曼散射光谱的装置，所述装置包括：产生激发光束2的激发光源1、激发光光路3、样品4、用于收集来自样品4的散射光5的散射光收集光路6、分束器7、色散装置1i,1j,…、及检测装置8等。
具体的，所述激发光源1，用于产生激发光束2，使所述激发光束通过激发光光路3被汇聚照射到放置在样品区的样品4上，所述样品4受到激发由此发生散射；用散射光收集光路6收集所述样品所产生的散射光5，并导向所述色散装置1i,1j；在其它实施例中，色散装置可以仅有一个，若所述色散装置多于一个，则可按图1所示实施例通过分束器7将所收集的所述散射光5分配到各个色散装置1i,1j,…，或可通过提供光导向器来替代所述分束器7将所收集的所述散射光5逐次导向各个色散装置，以供各所述色散装置(1i,1j,…)和其所配的空间光调制器(1i',1j',…)分别形成不同频段的喇曼散射光谱。
在图1所示实施例中，当某个配置有空间光调制器(1i'或1j')的所述色散装置(1i或1j)工作时，在所配置的所述空间光调制器(1i'或1j')上形成喇曼散射光谱，所述光谱部分或全部是反斯托克斯光谱，即其对应波长的部分或全部比所述激发光束的波长短。控制所述空间光调制器(1i'或1j')使该所述色散装 置(1i或1j)所形成的光谱中的各部分逐次被收集到所述检测装置8进行检测，用来获取在该所述色散装置(1i或1j)工作频段内的喇曼散射光谱。检测装置含一个或多个检测通道，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析。
需说明的是，虽然在图1所示的实施例中各个色散装置(1i，1j)均配置有空间光调制器(1i'，1j')，但在其它实施例中，可以仅有一部分色散装置配置空间光调制器，其余色散装置不配置，而采用其它方式检测光谱，例如直接用目前一般便携式喇曼光谱仪中常见的像传感器线阵检测喇曼散射光谱。
在一实施例中，所述激发光源1是激光器，用于产生谱线线宽小于0.3nm的激发光束；所述激发光光路包含光束整形元件和成像光学系统，所述光束整形元件用于对所述激光器发出的激发光束作整形；所述成像光学系统用于将所述激发光束传输并汇聚到所述样品4上。
在一实施例中，所述用于切换所导向的色散装置的光导向器可以包括但不限于：(1)可摆动的微反射镜阵列或扫描振镜，通过摆动所述微反射镜阵列或所述扫描振镜改变出射光的导向；(2)可转动平台，所述平台上固定有反射镜，通过转动所述平台改变出射光的导向。需说明的是，上述几种方式仅为举例，在其它实施例中亦可通过其它活动方式(如平移)加以实现。
在一实施例中，配置有所述空间光调制器的所述色散装置(1i,1j)的工作频段，至少有一部分高于所述激发光束2的光子频率，也可以覆盖所述激发光束2的光子频率或更低的频段,即所检测的光谱包含反斯托克斯谱线，也可以同时包含斯托克斯谱线和激发光束的谱线.使用多个色散装置检测喇曼光谱，有利于在各个频段内优化所述色散装置的性能。
在一实施例中，所述空间光调制器可以是透射式，此时导向所述检测装置8的是自所述空间光调制器背面透射的光；也可以是反射式，此时导向所述检测装置8的是自所述空间光调制器表面反射的光。
进一步的，所述检测装置8包括探测器和检测电路，所述探测器是光电倍增管或光电二极管，工作于线性检测模式或光子计数模式；在线性检测模式下，所述探测器输出的电流信号幅值正比于所述探测器接收的光通量；在光子计数模式下，所述探测器输出的有效信号脉冲的频度正比于所述探测器接收的光通量；优 选的，所述检测装置还包括所述激发光束的调制装置和相应的检测电路，所述激发光束的调制装置产生一串调制信号，所述激发光束以所述调制信号调制，同时所述检测电路通过滤波输出与所述调制信号频率一致的信号。
以下给出多个具体实施例来说明本发明的装置的工作原理：
实施例1
图2示出了本发明装置的实施例1，包括：激光器21、准直整形光学元件23、用来放置待分析样品24的样品区、分束器25、聚光/准直透镜26、带阻滤光片29、扫描振镜27、抛物面反射镜(2i”,2j”)、狭缝(2i”',2j”')、凹面光栅(2i,2j)、用于选择所检测频率或子频段的微反射镜阵列(2i',2j')、集光光学系统281、及探测器282。
微反射镜阵列(2i',2j')是用于选择所检测频率或子频段的空间光调制器，它们的每个空间单元均包含一面微反射镜、一条与所述微反射镜相铰接的枢轴、控制电路单元，可通过所述控制电路单元驱动某个所述空间单元的所述微反射镜绕所连的所述枢轴摆动，当该所述微反射镜摆动到某一方向时，照射到该所述微反射镜的光所产生的反射光被导向集光光学系统281，当该所述微反射镜摆动到另一方向时，照射到该所述微反射镜的光所产生的反射光不能被集光光学系统281接收，由此控制传输到探测器282的光谱的各个空间部分的通断。
探测器282是光电倍增管或光电二极管，工作于线性检测模式或光子计数模式，在线性检测模式下，探测器282输出的电流信号幅值正比于所接收的光通量，在光子计数模式下，探测器282输出的有效信号脉冲的频度正比于所接收的光通量。
该装置的工作过程如下：激光器21产生线宽小于0.3nm的激发光束，所述激发光束通过准直整形光学元件23形成波前能量分布相对均匀的准直光束，接着通过分束器25部分转向90°，再经聚光/准直透镜26汇聚到样品24上，样品24由此发生散射。样品24的部分后向散射光被聚光/准直透镜26收集并形成准直光束，通过分束器25部分继续沿原方向行进，接着经过带阻滤光片29，其中波长在激发波长附近的成分被大幅度滤除，而在所需分析的喇曼散射波段上的成分得以最大程度的保留，用于减小杂散光对光谱分析的干扰。其后，散射光光束经扫描振镜27与抛物面反射镜(图2中为2i”)两次反射后，被汇聚到某个色散 装置的入口狭缝(图2中为2i”')。每个色散装置都由一道入口狭缝(2i”'或2j”')、一个凹面光栅(2i或2j)、一个微反射镜阵列(2i'或2j')组成。凹面光栅的作用是接收来自一侧的入口狭缝的光束，并通过衍射在另一侧的微反射镜阵列上形成光谱带。通过控制微反射镜阵列(2i'或2j')，逐次将光谱带的各个空间部分导向集光光学系统281。集光光学系统281收集自微反射镜阵列(2i'或2j')传来的信号光，汇聚到探测器282的接收面上。各个色散装置的工作波段不同，即它们所对应的喇曼散射光频段不同，不过可以存在交迭部分，通过活动扫描振镜27，切换散射光光束的导向，将散射光逐次传输到各个色散装置，以获取在较宽频段上的高分辨率喇曼光谱，同时消除所用微反射镜阵列的空间分辨率对所获取光谱的分辨率的限制。
典型的设计是将其中一个色散装置用于分析斯托克斯光谱，另一个用于分析反斯托克斯光谱。与目前一般的使用像传感器线阵获取喇曼散射光谱的装置相比，使用单个检测器检测某个频段的光谱有利于以较低的成本获得较高的灵敏度，有利于获取反斯托克斯光谱，从而有助于排除荧光背景的干扰。
实施例2
图3示出了本发明的实施例2，包括：激光器31、准直整形光学元件33、用来放置待分析样品34的样品区、分束器35、聚光/准直透镜36、带阻滤光片39、扫描振镜37、抛物面反射镜(3i”,3j”)、狭缝(3i”',3j”')、平面透射光栅(3i,3j)、成像透镜(3i””a,3i””b,3j””a,3j””b)、线偏振片(3i'a,3i'c,3j'a,3j'c)、用于选择所检测频率或子频段的透射式液晶光振幅空间调制器(3i'b,3j'b)、集光光学系统381、及探测器382。
本实施例与图2所示的实施例1的区别在于所使用的色散装置及所配的用于选择所检测频率或子频段的空间光调制器的组成和工作方式。以如图3所示的状态为例具体来说，所选通的色散装置由狭缝3i”'、成像透镜(3i””a,3i””b)及平面透射光栅3i组成，在最大程度上消除了实施例1中色散装置的离轴像散，有利于获得较高的光谱分辨率。同时，反射式空间光调制器不再适用于选择所检测频率或子频段，改用线偏振片3i'a,3i'c,3j'a,3j'c配合透射式液晶光振幅空间光调制器3i'b,3j'b，控制导向检测装置382的光谱的各个部分的通断。以如图3所示的状态为例具体来说，在所选通的色散装置中，通过线偏振片3i'a大幅度滤 除入射准直光束中偏振方向平行于纸面方向的部分，出射光束的偏振方向基本上垂直于纸面方向，经透射光栅3i衍射及透镜3i””b形成光谱带，其偏振方向基本不变，在这个前提下使用透射式透射式液晶光振幅空间调制器3i'b控制透射光的各个空间部分的偏振方向，选择检测某个子频段时，选通的光谱子频段对应的3i'b的空间单元的透射光偏振方向保持垂直于纸面，通过线偏振片3i'c基本上得以保留并被检测装置382接收，同时3i'b的其余空间单元的透射光偏振方向平行于纸面，通过线偏振片3i'c基本上被滤除而不能被检测装置382接收。
实施例3
图4示出了本发明的实施例3，包括：激光器41、准直整形光学元件43、用来放置待分析样品44的样品区、分束器45、聚光/准直透镜46、带阻滤光片49、分束器47、抛物面反射镜(4i”,4j”,4ib,4ic,4jb,4jc)、狭缝(4i”',4j”')、平面反射光栅(4ia,4ja)、用于选择所检测的喇曼散射光谱的频率或子频段的微反射镜阵列(4i',4j')、集光光学系统481、及探测器482。
本实施例与图2所示的实施例1的区别在于所使用的色散装置的组成和工作方式。色散装置由入口狭缝4i”'、抛物面反射镜4ib,4ic、平面反射光栅4ia、微反射镜阵列4i'组成，色散装置由入口狭缝4j”'、抛物面反射镜4jb,4jc、平面反射光栅4ja、微反射镜阵列4j'组成。所收集的喇曼散射光被分束器47分成两部分，一部分继续沿原方向行进，被抛物面反射镜4i”汇聚到色散装置的入口狭缝4i”'上，另一部分经分束器反射改变方向，被抛物面反射镜4j”汇聚到色散装置的入口狭缝4j”'上。抛物面反射镜4ib,4ic的作用是将来自入口狭缝的线光源的光束变成准直光束，平面反射光栅的作用是使入射准直光束衍射，经抛物面反射镜4ic,4jc在微反射镜阵列(4i',4j')上形成光谱带。
如图5所示，结合上述装置，本发明还可提供一种用于获取喇曼散射光谱的方法，包括：
步骤S1：提供激发光源，用于产生激发光束；
步骤S2：提供激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；
步骤S3：提供散射光收集光路，用于收集所述喇曼散射光；
步骤S4：提供含一个或多个检测通道的检测装置，用于接收对应各检测频 率或子频段的喇曼散射光信号并转换成电信号以供分析；
步骤S5：提供连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分并逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱。
步骤S6：所述激发光源产生所述激发光束，所述激发光束通过所述激发光光路被导向所述样品，所述样品由此发生喇曼散射；
步骤S7：用所述散射光收集光路收集所述样品所产生的喇曼散射光，并导向所述色散装置；
步骤S8：当某个配置有所述空间调制器的所述色散装置工作时，在所配置的所述空间光调制器上形成喇曼散射光谱，通过控制该所述空间光调制器，使该所述色散装置所形成的光谱中的各部分逐次被收集到所述检测装置进行检测，用来获取在该所述色散装置工作频段内的喇曼散射光谱。
综上所述，本发明提供一种用于获取喇曼散射光谱的装置及方法，所述装置包括：激发光源，用于产生激发光束；激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；散射光收集光路，用于收集所述喇曼散射光；检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱；采用本发明的装置及方法可以检测反斯托克斯喇曼光谱，用于样品组分定量分析。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利 要求所涵盖。

Claims (11)

  1. 一种用于获取喇曼散射光谱的装置，其特征在于，包括：
    激发光源，用于产生激发光束；
    激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；
    散射光收集光路，用于收集所述喇曼散射光；
    含一个或多个检测通道的检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；
    连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分并逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱。
  2. 如权利要求1所述的用于获取喇曼散射光谱的装置，其特征在于，所述检测装置包括探测器和检测电路；所述探测器是光电倍增管或光电二极管，工作于线性检测模式或光子计数模式；在线性检测模式下，所述探测器输出的电流信号幅值正比于所述探测器接收的光通量；在光子计数模式下，所述探测器输出的有效信号脉冲的频度正比于所述探测器接收的光通量。
  3. 如权利要求2所述的用于获取喇曼散射光谱的装置，其特征在于，还包括所述激发光束的调制装置和相应的检测电路，所述激发光束的调制装置产生一串调制信号，所述激发光束通过所述调制信号调制，且所述检测电路通过滤波输出与所述调制信号频率一致的信号。
  4. 如权利要求1所述的用于获取喇曼散射光谱的装置，其特征在于，所述色散装置有多个，分别用于形成不同频段的光谱；所述散射光收集光路还设有一个或多个分束器或者设有一个或多个光导向器；所收集的喇曼散射光通过所 述分束器被分配至各所述色散装置，或者通过所述光导向器被逐次导向各个所述色散装置，以供各所述色散装置分别形成不同频段的喇曼散射光谱。
  5. 如权利要求4所述的用于获取喇曼散射光谱的装置，其特征在于，所述光导向器包括以下中的一种：
    (1)可摆动的微反射镜阵列或扫描振镜；通过摆动所述微反射镜阵列或所述扫描振镜改变出射光的导向；
    (2)可活动的平台；所述平台上固定有反射镜，通过活动所述平台改变出射光的导向。
  6. 如权利要求1所述的用于获取喇曼散射光谱的装置，其特征在于，所述空间光调制器包括以下中的一种：
    (1)透射式光学器件；所述空间光调制器将其背面透射的光导向所述检测装置；
    (2)反射式光学器件；所述空间光调制器将其表面反射的光导向所述检测装置。
  7. 如权利要求6所述的用于获取喇曼散射光谱的装置，其特征在于，所述空间光调制器是微反射镜阵列，所述微反射镜阵列包括：多个微反射镜单元；
    每个所述微反射镜单元包括：一面微反射镜、一条与所述微反射镜相铰接的枢轴、控制电路单元；通过所述控制电路单元驱动某个所述微反射镜单元的所述微反射镜绕所连的所述枢轴摆动，以控制所述喇曼散射光谱的各个空间部分从与所述空间光调制器相配的色散装置至所述检测装置的通断。
  8. 如权利要求6所述的用于获取喇曼散射光谱的装置，所述空间光调制器是液晶光振幅空间调制器，所述液晶光振幅空间调制器包括：液晶掩膜与偏振光学元件；所述液晶掩膜包括多个空间单元；可调电源装置，用于改变施加在所述液晶掩膜的各个空间单元的电压来改变从所述色散装置照射到所述液晶掩膜的各个空间单元的透射光的偏振方向，以配合使用所述偏振光学元件控 制对应不同检测频率或子频段的喇曼散射光谱的各个空间部分从所述色散装置至所述检测装置的通断。
  9. 如权利要求1所述的用于获取喇曼散射光谱的装置，其特征在于，所述激发光源是激光器，用于产生谱线线宽小于0.3nm的激发光束；所述激发光光路包含光束整形元件和成像光学系统，所述光束整形元件用于对所述激光器发出的激发光束作整形；所述成像光学系统用于将所述激发光束传输并汇聚到所述样品上。
  10. 一种用于获取喇曼散射光谱的方法，其特征在于，包括：
    提供激发光源，用于产生激发光束；
    提供激发光光路，用于将所述激发光束导向待分析的固态或液态样品以产生喇曼散射光；
    提供散射光收集光路，用于收集所述喇曼散射光；
    提供含一个或多个检测通道的检测装置，用于接收对应各检测频率或子频段的喇曼散射光信号并转换成电信号以供分析；
    提供连接所述散射光收集光路和所述检测装置的一个或多个色散装置，用于导入用所述散射光收集光路所收集的所述喇曼散射光形成喇曼散射光谱；其中至少一个色散装置配置有空间光调制器，所述空间光调制器用于在所在色散装置形成的喇曼散射光谱中选择对应不同的检测频率或子频段的空间部分并逐次导向所述检测装置进行检测，其中，所述喇曼散射光谱的部分或全部为反斯托克斯光谱；
    所述激发光源产生所述激发光束，所述激发光束通过所述激发光光路被导向所述样品，所述样品由此发生喇曼散射；
    用所述散射光收集光路收集所述样品所产生的喇曼散射光，并导向所述色散装置；
    当某个配置有所述空间调制器的所述色散装置工作时，在所配置的所述空间光调制器上形成喇曼散射光谱，通过控制该所述空间光调制器，使该所述色散装置所形成的光谱中的各部分逐次被收集到所述检测装置进行检测， 用来获取在该所述色散装置工作频段内的喇曼散射光谱。
  11. 如权利要求10所述的用于获取喇曼散射光谱的方法，其特征在于，所述色散装置有多个，分别用于形成不同频段的光谱；所述散射光收集光路还设有一个或多个分束器或者设有一个或多个光导向器；所收集的喇曼散射光通过所述分束器被分配至各所述色散装置，或者通过所述光导向器被逐次导向各个所述色散装置，以供各所述色散装置分别形成不同频段的喇曼散射光谱。
PCT/CN2015/096451 2014-11-27 2015-12-04 一种用于获取喇曼散射光谱的装置及方法 WO2016082804A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410707332.3 2014-11-27
CN201410707332.3A CN105628671B (zh) 2014-11-27 2014-11-27 一种用于样品组分定量分析的装置及方法

Publications (1)

Publication Number Publication Date
WO2016082804A1 true WO2016082804A1 (zh) 2016-06-02

Family

ID=56043809

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/096451 WO2016082804A1 (zh) 2014-11-27 2015-12-04 一种用于获取喇曼散射光谱的装置及方法

Country Status (2)

Country Link
CN (1) CN105628671B (zh)
WO (1) WO2016082804A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111272732A (zh) * 2020-03-03 2020-06-12 长春长光辰英生物科学仪器有限公司 一种拉曼光谱仪及拉曼光谱拼接方法
CN113203727A (zh) * 2021-05-12 2021-08-03 华中科技大学 一种光谱测量装置和方法
CN113466179A (zh) * 2021-06-22 2021-10-01 杭州谱析光晶半导体科技有限公司 一种光学检测系统及方法
CN113983632A (zh) * 2021-11-16 2022-01-28 武汉工程大学 一种组合式空调机组净化消毒装置及方法
CN114152570A (zh) * 2021-11-26 2022-03-08 江苏师范大学 可调谐光谱滤光装置及使用方法、拉曼光谱仪
CN114402182A (zh) * 2019-03-25 2022-04-26 Mks技术(贸易用名雪域仪器) 多色散光谱仪

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109557070B (zh) * 2018-10-27 2021-03-26 西安电子科技大学 一种基于空间编码光的拉曼成像系统

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090842A2 (en) * 2009-01-21 2010-08-12 Rare Light, Inc. Raman spectroscopy devices, systems and methods using multiple discrete light sources
CN102162907A (zh) * 2011-04-15 2011-08-24 中国科学院化学研究所 一种多波长显微照明装置
CN102445273A (zh) * 2011-09-22 2012-05-09 中国科学院半导体研究所 一种用于测量低波数拉曼信号的装置
CN103196889A (zh) * 2013-04-16 2013-07-10 许春 基于微机电系统光谱分析的便携式拉曼光谱仪
CN103219638A (zh) * 2013-03-18 2013-07-24 深圳大学 一种超连续谱光源及相干反斯托克斯拉曼散射成像系统
CN105074402A (zh) * 2013-03-12 2015-11-18 赛默科技便携式分析仪器有限公司 高分辨率的基于mems的阿达玛光谱法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909132A (en) * 1974-06-11 1975-09-30 Allied Chem Spectroscopic temperature measurement
US7256885B2 (en) * 2003-01-29 2007-08-14 Yeda Research And Development Company Ltd. Coherently controlled nonlinear Raman spectroscopy and microscopy
US7782460B2 (en) * 2003-05-06 2010-08-24 Baker Hughes Incorporated Laser diode array downhole spectrometer
JP2008510982A (ja) * 2004-08-26 2008-04-10 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ 分光分析システム用の自律的な較正法
US20060262304A1 (en) * 2005-04-22 2006-11-23 Keith Carron Apparatus for automated real-time material identification
WO2011162787A1 (en) * 2010-06-22 2011-12-29 President And Fellows Of Harvard College Systems and methods providing efficient detection of back-scattered illumination in modulation transfer microscopy or micro-spectroscopy
KR101207345B1 (ko) * 2010-08-05 2012-12-05 한국표준과학연구원 자동보정 기능을 갖는 광섬유 분포 온도 센서 시스템 및 이를 이용한 온도 측정방법
WO2014143235A1 (en) * 2013-03-14 2014-09-18 Integrated Plasmonics Corporation Ambient light assisted spectroscopy
CN106908806B (zh) * 2017-03-29 2018-03-13 武汉大学 一种紫外波段准单支纯转动拉曼谱线信号探测装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090842A2 (en) * 2009-01-21 2010-08-12 Rare Light, Inc. Raman spectroscopy devices, systems and methods using multiple discrete light sources
CN102369420A (zh) * 2009-01-21 2012-03-07 莱尔照明公司 使用多个离散光源的拉曼光谱设备、系统和方法
CN102162907A (zh) * 2011-04-15 2011-08-24 中国科学院化学研究所 一种多波长显微照明装置
CN102445273A (zh) * 2011-09-22 2012-05-09 中国科学院半导体研究所 一种用于测量低波数拉曼信号的装置
CN105074402A (zh) * 2013-03-12 2015-11-18 赛默科技便携式分析仪器有限公司 高分辨率的基于mems的阿达玛光谱法
CN103219638A (zh) * 2013-03-18 2013-07-24 深圳大学 一种超连续谱光源及相干反斯托克斯拉曼散射成像系统
CN103196889A (zh) * 2013-04-16 2013-07-10 许春 基于微机电系统光谱分析的便携式拉曼光谱仪

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114402182A (zh) * 2019-03-25 2022-04-26 Mks技术(贸易用名雪域仪器) 多色散光谱仪
CN111272732A (zh) * 2020-03-03 2020-06-12 长春长光辰英生物科学仪器有限公司 一种拉曼光谱仪及拉曼光谱拼接方法
CN113203727A (zh) * 2021-05-12 2021-08-03 华中科技大学 一种光谱测量装置和方法
CN113466179A (zh) * 2021-06-22 2021-10-01 杭州谱析光晶半导体科技有限公司 一种光学检测系统及方法
CN113983632A (zh) * 2021-11-16 2022-01-28 武汉工程大学 一种组合式空调机组净化消毒装置及方法
CN114152570A (zh) * 2021-11-26 2022-03-08 江苏师范大学 可调谐光谱滤光装置及使用方法、拉曼光谱仪

Also Published As

Publication number Publication date
CN105628671B (zh) 2019-11-19
CN105628671A (zh) 2016-06-01

Similar Documents

Publication Publication Date Title
WO2016082804A1 (zh) 一种用于获取喇曼散射光谱的装置及方法
CN105424652B (zh) 用于光学检查混浊介质的内部的方法和装置
US11307092B2 (en) Swept-source Raman spectroscopy systems and methods
US7696479B2 (en) Method and apparatus for frequency-converting infrared light
US5591981A (en) Tunable excitation and/or tunable emission fluorescence imaging
US8064053B2 (en) 3-color multiplex CARS spectrometer
JP6051397B2 (ja) ラマン顕微鏡、及びラマン分光測定方法
DK2895844T3 (en) Apparatus with an arrangement of optical elements
US10794766B2 (en) Method and device for raman spectroscopy
US11041760B2 (en) Optical measurement device and optical measurement method
CN106990095A (zh) 反射式共焦cars显微光谱测试方法及装置
EP3175221B1 (en) Raster optic device for optical hyper spectral scanning
US11815462B2 (en) Broadband Raman excitation spectroscopy with structured excitation profiles
Kirchner et al. All-reflective UV-VIS-NIR transmission and fluorescence spectrometer for μm-sized samples
JP7486178B2 (ja) 分光分析装置
JP2010197359A (ja) 信号波形測定装置及び測定方法
JP5480055B2 (ja) 拡散反射測定装置
JP4397808B2 (ja) ラマン分光装置
JPH0650892A (ja) 分光光度計

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15863502

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15863502

Country of ref document: EP

Kind code of ref document: A1