CN106442401B - A kind of detection device and detection method of combination Raman spectrum and near infrared spectrum - Google Patents
A kind of detection device and detection method of combination Raman spectrum and near infrared spectrum Download PDFInfo
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Abstract
The invention discloses the detection device and detection method of a kind of combination Raman spectrum and near infrared spectrum, this device includes laser (1), beam splitter (2), mechanical face mirror switching device, plane mirror (13), focused acquisition lens (4), Raman spectrometer coupled lens (5), Raman spectrometer (6), half-reflection and half-transmission beam splitter (17), near-infrared light source (8), near infrared spectrometer coupled lens (9), near infrared spectrometer (10).When mechanical face mirror switching device is in the first switching state, plane mirror (13) is located in the optical path of the laser beam of beam splitter (2) reflection, when in the second switching state, the laser beam of beam splitter (2) reflection is directly inputted into focused acquisition lens (4).Present invention combination Raman spectrum detects in conjunction near infrared spectrum, realizes that Raman spectrometer and near infrared spectrometer share a detecting head, realizes the acquisition time of raman spectral signal and near infrared light spectrum signal.
Description
Technical Field
The invention relates to the technical field of Raman signal processing, in particular to a detection device and a detection method combining Raman spectrum and near infrared spectrum.
Background
Raman spectroscopy (Raman spectroscopy) is a scattering spectrum. The Raman spectroscopy is an analysis method for analyzing scattering spectra with different incident light frequencies to obtain information on molecular vibration and rotation based on Raman scattering effect found by indian scientists c.v. Raman (Raman), and is applied to molecular structure research. The raman spectroscopy technology is rapidly developed and widely applied in the field of non-invasive detection due to the advantages of sensitivity, rapidity, convenient operation and the like.
When light is irradiated to a medium, a part of the light is scattered except for absorption, reflection and transmission of the medium, and the scattering includes elastic scattering and inelastic scattering. The scattered light that is elastically scattered is of the same component as the wavelength of the excitation light, and the scattered light that is inelastically scattered has components longer and shorter than the wavelength of the excitation light, and is collectively referred to as the raman effect. The scattered light can be classified into three categories by frequency: the first, caused by some scattering center (molecules or dust particles), has a wave number variation of less than 10-5cm－1Or substantially constant, such scattering is known as mie scattering; second, scattering from interaction of the incident wavefield with elastic waves in the medium, with wave number variations of about 0.1cm－1Known as Brillouin scattering; the two types of scattering are generally difficult to distinguish and are collectively called rayleigh scattering; third, the wave number variation is greater than 1cm－1The scattering of (2) corresponding to the transition range between molecular rotation, vibrational energy level and electronic energy level is called Raman scattering.
Near Infrared Spectroscopy (NIRS) analysis technology is used for predicting the content and the performance of unknown sample components by utilizing the mathematical relationship established between the Near Infrared characteristic absorption peak of a sample and the content and the performance of the sample components. Although the double or combined frequency absorption intensity of the near infrared spectrum is about 1 to 3 orders of magnitude lower than the fundamental peak intensity compared to the mid infrared, there is a linear relationship between the absorption band intensities and the analyte concentration over a larger dynamic range of absorption since these weak absorption bands do not show marginal interference at the MIR absorption band. The near infrared spectrum analysis technology is also an efficient and rapid modern analysis technology, comprehensively utilizes the latest research results of a plurality of subjects such as computer technology, spectrum technology, chemometrics and the like, is increasingly widely applied in a plurality of fields with unique advantages, and is gradually and generally accepted by the public. In recent years, due to the development of computers and chemometrics software, especially the intensive research and wide application of chemometrics, the near infrared spectroscopy technology has become the most rapidly developing and most attractive spectroscopy technology. In the short decade or so, the near infrared spectroscopy has rapidly developed into a very competitive analysis technique.
Essentially, the near infrared spectrum is an absorption spectrum and the raman spectrum is an inelastic scattering spectrum, both of which characterize the structure of a substance molecule. However, for some substances, the raman spectrum signal is sensitive to laser heat, or is very weak, or has a strong fluorescence signal when being excited by laser, so that the raman signal is submerged in the fluorescence signal and cannot be acquired. Similarly, part of the near infrared absorption signals of the substances are weak, and the Raman signals are strong. In the prior art, a realization scheme for performing time-sharing acquisition on Raman spectrum signals and near infrared spectrum signals by using the same probe does not exist.
Disclosure of Invention
The invention provides a detection device and a detection method combining Raman spectrum and near infrared spectrum, aiming at solving the problem that the prior art can not provide a realization scheme for performing time-sharing acquisition of Raman spectrum signals and near infrared spectrum signals by using the same detection head.
The invention provides a detection device combining a Raman spectrum and a near infrared spectrum, which comprises a laser, a beam splitter, a mechanical mirror switching device, a plane reflector, a focusing collection lens, a Raman spectrometer coupling lens, a Raman spectrometer, a semi-reflecting and semi-transmitting beam splitter, a near infrared light source, a near infrared spectrometer coupling lens and a near infrared spectrometer, wherein the laser is arranged on the plane reflector;
the laser is used for outputting parallel monochromatic laser beams;
the beam splitter is arranged on a laser beam output optical path output by the laser in a manner of forming a preset angle with a laser beam output by the laser;
the plane mirror is positioned on the light path of the laser beam reflected by the beam splitter and forms a preset angle with the laser beam reflected by the beam splitter when the mechanical mirror switching device is in a first switching state, the plane mirror is used for reflecting the light beam transmitted by the semi-reflective and semi-transparent beam splitter onto the focusing and collecting lens and is also used for reflecting the light beam collimated by the focusing and collecting lens onto the semi-reflective and semi-transparent beam splitter; when the mechanical mirror switching device is in a second switching state, the laser beam reflected by the beam splitter is directly input to the focusing and collecting lens;
the focusing and collecting lens is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter, and the focal point of the focusing and collecting lens corresponds to the position where the sample is placed;
the semi-reflecting and semi-transmitting beam splitter is arranged in parallel with the plane reflector on the mechanical mirror switching device in the first switching state, and is used for transmitting light beams emitted by the near-infrared light source and reflecting light beams reflected back from the plane reflector;
the Raman spectrometer coupling lens is arranged on one side of the beam splitter in a mode of being perpendicular to a sample reflected light beam transmitted by the beam splitter and is used for coupling the light beam into a slit or an optical fiber of the Raman spectrometer;
and the coupling lens of the near-infrared spectrometer is used for coupling the light beam reflected by the semi-reflecting and semi-transmitting beam splitter to the near-infrared spectrometer.
The detection device combining the Raman spectrum and the near infrared spectrum also has the following characteristics:
the Raman channel optical filter is arranged between the beam splitter and the coupling lens of the Raman spectrometer; and the near-infrared channel optical filter is arranged between the semi-reflecting and semi-transmitting beam splitter and the coupling lens of the near-infrared spectrometer.
The detection device combining the Raman spectrum and the near infrared spectrum also has the following characteristics:
the preset angle is 45 degrees.
The invention also provides a detection device combining the Raman spectrum and the near infrared spectrum, which comprises a laser, a beam splitter, a mechanical mirror switching device, a first plane mirror, a focusing collection lens, a Raman spectrometer coupling lens, a Raman spectrometer, a second plane mirror, a near infrared light source, a near infrared spectrometer coupling lens and a near infrared spectrometer;
the laser is used for outputting parallel monochromatic laser beams;
the beam splitter is arranged on an output light path of the laser beam output by the laser in a manner of forming a preset angle with the laser beam output by the laser;
one end of the mechanical mirror switching device is provided with a first plane mirror, the other end of the mechanical mirror switching device is vacant, when the mechanical mirror switching device is in a first switching state, the first plane mirror is positioned on a light path of a laser beam reflected by the beam splitter and forms a preset angle with the laser beam reflected by the beam splitter, and the first plane mirror is used for reflecting the beam collimated by the focusing and collecting lens to the second plane mirror; when the mechanical mirror switching device is in a second switching state, the laser beam reflected by the beam splitter is directly input to the focusing and collecting lens;
the focusing and collecting lens is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter, and the focal point of the focusing and collecting lens corresponds to the position where the sample is placed;
the second plane mirror is arranged in parallel with the first plane mirror on the mechanical mirror switching device in the first switching state and is used for reflecting the light beam reflected by the first plane mirror to the coupling lens of the near-infrared spectrometer;
the Raman spectrometer coupling lens is arranged on one side of the beam splitter in a mode of being perpendicular to a sample reflected light beam transmitted by the beam splitter and is used for coupling the light beam into a slit or an optical fiber of the Raman spectrometer;
the near-infrared spectrometer coupling lens is used for coupling the light beam reflected by the second plane mirror to the near-infrared spectrometer;
the near-infrared light source is arranged outside the focus of the focusing collection lens and used for emitting light beams to the focus of the focusing collection lens.
The invention also provides a detection method using the detection device combining the Raman spectrum and the near infrared spectrum, which comprises the following steps:
placing a sample at a focal point of the focused collection lens;
when Raman spectrum signal acquisition is needed, the near-infrared light source is turned off, the mechanical mirror switching device is controlled to be in a second switching state, the laser is turned on, and Raman spectrum signal acquisition is carried out;
when near infrared spectrum signal acquisition is needed, the laser is turned off, the mechanical mirror switching device is controlled to be in a first switching state, the near infrared light source is turned on, and near infrared spectrum signal acquisition is conducted.
The invention also provides a detection device combining the Raman spectrum and the near infrared spectrum, which comprises a laser, a beam splitter, a first mechanical mirror switching device, a first plane reflector, a focusing collection lens, a Raman spectrometer coupling lens, a Raman spectrometer, a second mechanical mirror switching device, a second plane reflector, a semi-reflecting and semi-transparent mirror, a near infrared light source, a near infrared spectrometer coupling lens and a near infrared spectrometer;
the laser is used for outputting parallel monochromatic laser beams;
the beam splitter is arranged on an output light path of the laser beam output by the laser in a manner of forming a preset angle with the laser beam output by the laser;
one end of the first mechanical mirror switching device is provided with the first plane mirror, the other end of the first mechanical mirror switching device is vacant, and when the mechanical mirror switching device is in a first switching state, the first plane mirror is positioned on a light path of a laser beam reflected by the beam splitter and forms a preset angle with the laser beam reflected by the beam splitter;
one end of the second mechanical mirror switching device is provided with the second planar reflector, and the other end of the second mechanical mirror switching device is provided with a semi-reflecting and semi-transmitting mirror; when the second mechanical mirror switching device is in a first switching state and the first mechanical mirror switching device is in the first switching state, the first planar reflector is located between the near-infrared light source and the second planar reflector, and the second planar reflector is arranged in parallel with the first planar reflector and used for reflecting the laser beam reflected by the first planar reflector to the focusing and collecting lens;
when the first mechanical mirror switching device is in a second switching state and the second mechanical mirror switching device is in the second switching state, the semi-reflective semi-transparent mirror on the second mechanical mirror switching device receives the light beam emitted by the near-infrared light source, reflects the light beam to the focusing collection lens, and is further used for transmitting the light beam of the sample transmitted by the focusing collection lens to the coupling lens of the near-infrared spectrometer;
the near-infrared spectrometer coupling lens is used for coupling the light beam reflected by the semi-reflecting and semi-transmitting beam splitter to the near-infrared spectrometer;
the Raman spectrometer coupling lens is used for coupling the light beam of the sample transmitted by the beam splitter to the Raman spectrometer.
The detection device combining the Raman spectrum and the near infrared spectrum also has the following characteristics: the Raman channel optical filter is arranged between the beam splitter and the coupling lens of the Raman spectrometer; and the near-infrared channel optical filter is arranged on an input optical path of the coupling lens of the near-infrared spectrometer.
The detection method using the detection device combining the Raman spectrum and the near infrared spectrum comprises the following steps:
placing a sample at a focal point of the focused collection lens;
when Raman spectrum signal acquisition is needed, the near-infrared light source is turned off, the first mechanical mirror switching device is controlled to be in a first switching state, the second mechanical mirror switching device is controlled to be in the first switching state, the laser is turned on, and Raman spectrum signal acquisition is conducted;
when near infrared spectrum signal acquisition is needed, the laser is turned off, the first mechanical mirror switching device is controlled to be in the second switching state, the second mechanical mirror switching device is controlled to be in the second switching state, the near infrared light source is turned on, and near infrared spectrum signal acquisition is conducted.
The invention also provides a detection device combining the Raman spectrum and the near infrared spectrum, which comprises a laser, a beam splitter, a first plane mirror, a focusing acquisition lens, a Raman spectrometer coupling lens, a Raman spectrometer, a mechanical mirror switching device, a second plane mirror, a near infrared light source, a near infrared spectrometer coupling lens and a near infrared spectrometer;
the laser is used for outputting parallel monochromatic laser beams;
the beam splitter is arranged on an output light path of the laser beam output by the laser in a manner of forming a preset angle with the laser beam output by the laser;
the first plane mirror is positioned on the light path of the laser beam reflected by the beam splitter and forms a preset angle with the laser beam reflected by the beam splitter;
one end of the mechanical mirror switching device is provided with the second plane mirror, and the other end of the mechanical mirror switching device is vacant; when the mechanical mirror switching device is in a first switching state, the second plane mirror is arranged in parallel with the first plane mirror and is used for reflecting the laser beam reflected by the first plane mirror to the focusing and collecting lens;
the near infrared light source is arranged outside the focus of the focusing collection lens and is used for emitting light beams to the focus of the focusing collection lens;
when the mechanical mirror switching device is in a second switching state, the light beam transmitted by the focusing and collecting lens is directly input to the coupling lens of the near-infrared spectrometer;
the near-infrared spectrometer coupling lens is used for coupling the light beam received from the focusing collection lens to the near-infrared spectrometer;
the Raman spectrometer coupling lens is used for coupling the light beam of the sample transmitted by the beam splitter to the Raman spectrometer.
The detection method also has the following characteristics:
placing a sample at a focal point of the focused collection lens;
when Raman spectrum signal acquisition is needed, the near-infrared light source is turned off, the mechanical mirror switching device is controlled to be in a first switching state, the laser is turned on, and Raman spectrum signal acquisition is carried out;
and when near infrared spectrum signal acquisition is required, the laser is turned off, the mechanical mirror switching device is controlled to be in a second switching state, and the near infrared light source is turned on to acquire near infrared spectrum signals.
Aiming at the defects of single detection technologies of a Raman spectrometer and a near infrared spectrometer, the Raman spectrometer and the near infrared spectrometer are mutually complementary, and detection is carried out by combining Raman spectrum and near infrared spectrum, so that the Raman spectrometer and the near infrared spectrometer share one detection head, and time-sharing acquisition of Raman spectrum signals and near infrared spectrum signals is realized.
Drawings
FIG. 1 is a block diagram of a detection device incorporating a Raman spectroscopy detection device and a near infrared spectroscopy detection device according to an embodiment;
FIG. 2 is a structural view of a detecting unit of the detecting unit combining Raman spectroscopy and near infrared spectroscopy according to the second embodiment;
FIG. 3 is a structural diagram of a detecting unit incorporating the Raman spectrum and the near infrared spectrum detecting unit according to the third embodiment;
FIG. 4 is a block diagram of a detecting unit incorporating the Raman spectrum and the near infrared spectrum according to the fourth embodiment.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, 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 with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
Example one
FIG. 1 is a block diagram of a detection device incorporating a Raman spectroscopy detection device and a near infrared spectroscopy detection device according to an embodiment. The device comprises: the device comprises a laser 1, a beam splitter 2, a mechanical mirror switching device, a plane mirror 13, a focusing collection lens 4, a Raman spectrometer coupling lens 5, a Raman spectrometer 6, a semi-reflective and semi-transparent beam splitter 17, a near-infrared light source 8, a near-infrared spectrometer coupling lens 9 and a near-infrared spectrometer 10.
The laser 1 is used for outputting parallel monochromatic laser beams;
the beam splitter 2 is arranged on a laser beam output optical path output by the laser 1 in a manner of forming a preset angle (for example, 45 degrees) with a laser beam output by the laser 1;
one end of the mechanical mirror switching device is provided with a plane reflector 13, and the other end of the mechanical mirror switching device is vacant. The mechanical mirror switching device can adopt an electromagnetic type or a mechanical rotating target wheel type. When the mechanical mirror switching device is in the first switching state, the plane reflector 13 is positioned on the light path of the laser beam reflected by the beam splitter 2 and forms a preset angle with the laser beam reflected by the beam splitter 2, and the plane reflector 13 is used for reflecting the beam transmitted by the semi-reflective and semi-transparent beam splitter 17 to the focusing and collecting lens 4 and reflecting the beam collimated by the focusing and collecting lens 4 to the semi-reflective and semi-transparent beam splitter 17; when the mechanical mirror switching device is in the second switching state, the laser beam reflected by the beam splitter 2 is directly input to the focusing and collecting lens 4.
The focusing and collecting lens 4 is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter 2, is used for converging the laser beam and the near-infrared illumination light source to a focus, and is also used for collimating Raman scattering signals and near-infrared reflection signals of a sample, and the focus of the focusing and collecting lens 4 corresponds to a sample placing position.
The half-reflecting and half-transmitting beam splitter 17 is arranged in parallel with the plane mirror on the mechanical mirror switching device in the first switching state, and is used for transmitting the light beam emitted by the near-infrared light source 8 and reflecting the light beam reflected back from the plane mirror.
The raman spectrometer coupling lens 5 is arranged on one side of the beam splitter 2 in a manner perpendicular to the sample reflected beam transmitted by the beam splitter 2 for coupling the beam into the slit or optical fiber of the raman spectrometer 6.
And the near-infrared spectrometer coupling lens 9 is used for coupling the light beam reflected by the semi-reflecting and semi-transmitting beam splitter 17 to the near-infrared spectrometer 10.
Wherein,
when the laser 1 in the device outputs parallel monochromatic laser beams, the monochromatic laser beams can be directly output in space, or output after being output through optical fiber in a collimating way, if the monochromaticity of the laser cannot meet the requirement, the energy of a side lobe peak is overlarge, and a laser purifying optical filter can be added in front of the laser 1.
The beam splitter 2 is a dichroic beam splitter, and is configured to reflect the laser beam and transmit the optical signal fed back by the sample.
The near infrared light source 8 adopts coaxial illumination, and the compression divergence angle is collimated by a certain collimating optical system.
The device also comprises a Raman channel optical filter arranged between the beam splitter 2 and the Raman spectrometer coupling lens 5 and used for filtering Rayleigh scattered light; and the near-infrared channel filter is arranged between the semi-reflecting and semi-transmitting beam splitter 17 and the coupling lens 9 of the near-infrared spectrometer.
The detection method using the detection device in the first embodiment comprises the following steps:
step 1, the sample is placed at the focus of the focus collection lens 4.
And 2, when Raman spectrum signal acquisition is required, closing the near-infrared light source 8, controlling the mechanical mirror switching device to be in a second switching state, and turning on the laser 1 to acquire the Raman spectrum signal.
And 3, when near infrared spectrum signal acquisition is required, turning off the laser 1, controlling the mechanical mirror switching device to be in a first switching state, turning on the near infrared light source 8, and acquiring the near infrared spectrum signal.
Wherein,
in step 2, when raman spectrum signal acquisition is required, the near-infrared light source 8 is turned off, the mechanical mirror switching device is controlled to be in a second switching state, namely, a hollow end of the mechanical mirror switching device is arranged at the position of the original plane reflector 13, a raman spectrum channel is gated at the moment, the laser 1 is turned on, laser emitted by the laser 1 is reflected to the focusing collection lens 4 through the beam splitter 2, the focusing collection lens 4 collects laser beams to a focus position where a sample is placed, optical signals reflected by the sample are collimated through the focusing collection lens 4 and then are directly input to the raman spectrometer coupling lens 5 or input to the raman spectrometer coupling lens 5 through a raman channel optical filter, and the optical signals are coupled to the raman spectrometer 6 through the raman spectrometer coupling lens 5.
In step 3, when near infrared spectrum signal acquisition is needed, the laser 1 is closed, the mechanical mirror switching device is controlled to be in a first switching state, the plane mirror 13 is arranged between the beam splitter 2 and the focusing collection lens 4, the near-infrared light source 8 is turned on, the semi-reflecting and semi-transmitting beam splitter 17 transmits light beams emitted by the near-infrared light source 8 and reflects the light beams to the focusing collection lens 4 through the plane mirror 13, the focusing collection lens 4 converges laser light beams to a focal point where a sample is placed, light signals reflected by the sample are collimated through the focusing collection lens 4 and then input to the plane mirror 13, are reflected to the semi-reflecting and semi-transmitting beam splitter 17 through the plane mirror 13, are input to the near-infrared spectrometer coupling lens 9 directly or through a near-infrared channel optical filter after being reflected by the semi-reflecting and semi-transmitting beam splitter 17, and light beams reflected by the near-infrared spectrometer coupling lens 9 are coupled to the near-infrared spectrometer 10.
Example two
The difference between the second embodiment and the first embodiment is that the near-infrared light source 8 adopts a paraxial illumination mode, the near-infrared light source 8 directly irradiates the sample, a single near-infrared lamp light source can be used, and a plurality of light sources can be symmetrically and annularly arranged on the side of the focusing and collecting lens 4. In the second embodiment, a semi-reflecting and semi-transmitting beam splitter is not needed.
Fig. 2 is a structural diagram of a detection device combining a raman spectrum and a near infrared spectrum according to a second embodiment, where the detection device includes a laser 1, a beam splitter 2, a mechanical mirror switching device, a first plane mirror 23, a focusing collection lens 4, a raman spectrometer coupling lens 5, a raman spectrometer 6, a second plane mirror 27, a near infrared light source 8, a near infrared spectrometer coupling lens 9, and a near infrared spectrometer 10;
the laser 1 is used for outputting parallel monochromatic laser beams;
the beam splitter 2 is arranged on an output light path of the laser beam output by the laser 1 in a manner of forming a preset angle (for example, 45 degrees) with the laser beam output by the laser 1;
one end of the mechanical mirror switching device is provided with a first plane reflector 23, the other end of the mechanical mirror switching device is vacant, when the mechanical mirror switching device is in a first switching state, the first plane reflector 23 is positioned on a light path of a laser beam reflected by the beam splitter 2 and forms a preset angle with the laser beam reflected by the beam splitter 2, the first plane reflector 23 is used for reflecting the beam collimated by the focusing collection lens 4 to a second plane reflector 27, and when the mechanical mirror switching device is in a second switching state, the laser beam reflected by the beam splitter 2 is directly input to the focusing collection lens 4;
the focusing and collecting lens 4 is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter 2, and the focal point of the focusing and collecting lens 2 corresponds to the position where the sample is placed;
the second plane mirror 27 is arranged in parallel with the first plane mirror 23 on the mechanical mirror switching device in the first switching state, and is used for reflecting the light beam reflected by the first plane mirror 23 to the coupling lens 9 of the near-infrared spectrometer;
the Raman spectrometer coupling lens 5 is arranged on one side of the beam splitter 2 in a mode of being perpendicular to the sample reflected light beam transmitted by the beam splitter 2 and is used for coupling the light beam into a slit or an optical fiber of the Raman spectrometer 6;
the near-infrared spectrometer coupling lens 9 is used for coupling the light beam reflected by the second plane mirror 27 to the near-infrared spectrometer 10;
the near-infrared light source 8 is arranged outside the focal point of the focusing collection lens 4 and is used for emitting light beams to the focal point of the focusing collection lens 4.
The device also comprises a Raman channel optical filter arranged between the beam splitter 2 and the Raman spectrometer coupling lens 5; and the near infrared channel filter is arranged between the second plane reflecting mirror 27 and the coupling lens 9 of the near infrared spectrometer.
The detection method of the detection device using the detection device combining the raman spectrum and the near infrared spectrum in the second embodiment is the same as that in the first embodiment.
Wherein,
in step 2, when raman spectrum signal acquisition is required, the near-infrared light source 8 is turned off, the mechanical mirror switching device is controlled to be in a second switching state, namely, a hollow end of the mechanical mirror switching device is arranged at the position of the first plane reflecting mirror 23, a raman spectrum channel is gated at the moment, the laser 1 is turned on, laser emitted by the laser 1 is reflected to the focusing collecting lens 4 through the beam splitter 2, the focusing collecting lens 4 collects laser beams to a focus position where a sample is placed, optical signals reflected by the sample are collimated through the focusing collecting lens 4 and then are directly input to the raman spectrometer coupling lens 5 or input to the raman spectrometer coupling lens 5 through a raman channel optical filter, and the optical signals are coupled to the raman spectrometer 6 through the raman spectrometer coupling lens 5.
In step 3, when near infrared spectrum signal acquisition is required, the laser 1 is turned off, the mechanical mirror switching device is controlled to be in a first switching state, that is, the first plane mirror 23 is arranged between the beam splitter 2 and the focusing collection lens 4, the near infrared light source 8 is turned on to directly irradiate a sample, an optical signal reflected by the sample is collimated by the focusing collection lens 4 and then input to the first plane mirror 23, is reflected to the second plane mirror 27 by the first plane mirror 23, is reflected by the second plane mirror 27 and then input to the near infrared spectrometer coupling lens 9 directly or through a near infrared channel optical filter, and a light beam reflected by the near infrared spectrometer coupling lens 9 is coupled to the near infrared spectrometer 10.
EXAMPLE III
The third embodiment is different from the first and second embodiments in that the positions of the near-infrared channel and the raman channel are exchanged, the near-infrared channel is a through channel, the raman channel is a turning gating channel, and two mechanical mirror switching devices are arranged in the scheme.
Fig. 3 is a structural diagram of a detection apparatus combining a raman spectrum and a near infrared spectrum in the third embodiment, where the apparatus includes a laser 1, a beam splitter 2, a first mechanical mirror switching device, a first plane mirror 33, a focus collection lens 4, a raman spectrometer coupling lens 5, a raman spectrometer 6, a second mechanical mirror switching device, a second plane mirror 37, a semi-reflective and semi-transparent mirror, a near infrared light source 8, a near infrared spectrometer coupling lens 9, and a near infrared spectrometer 10.
The laser 1 is arranged to output a parallel monochromatic laser beam.
The beam splitter 2 is disposed on an output optical path of the laser beam output from the laser 1 at a predetermined angle (for example, 45 degrees) with respect to the laser beam output from the laser 1.
One end of the first mechanical mirror switching device is provided with a first plane mirror 33, the other end of the first mechanical mirror switching device is vacant, and when the mechanical mirror switching device is in the first switching state, the first plane mirror 33 is positioned on the light path of the laser beam reflected by the beam splitter 2 and forms a preset angle with the laser beam reflected by the beam splitter 2.
One end of the second mechanical mirror switching device is provided with a second plane reflector 37, and the other end is provided with a semi-reflecting and semi-transmitting mirror; when the second mechanical mirror switching device is in the first switching state and the first mechanical mirror switching device is in the first switching state, the first plane mirror 33 is located between the near-infrared light source 8 and the second plane mirror 37, and the second plane mirror 37 is arranged in parallel with the first plane mirror 33 and is used for reflecting the laser beam reflected by the first plane mirror 33 to the focusing and collecting lens 4.
When the first mechanical mirror switching device is in the second switching state and the second mechanical mirror switching device is in the second switching state, the semi-reflective semi-transparent mirror on the second mechanical mirror switching device receives the light beam emitted by the near-infrared light source 8, reflects the light beam to the focusing and collecting lens 4, and is further used for transmitting the light beam of the sample transmitted by the focusing and collecting lens 4 to the coupling lens 9 of the near-infrared spectrometer.
The near-infrared spectrometer coupling lens 9 is used for coupling the light beam transmitted by the half-reflecting and half-transmitting mirror to the near-infrared spectrometer 10.
The raman spectrometer coupling lens 5 is used to couple the beam of the sample transmitted by the beam splitter 2 to the raman spectrometer 6.
The device also comprises a Raman channel optical filter arranged between the beam splitter 2 and the Raman spectrometer coupling lens 5; and the near-infrared channel optical filter is arranged on an input optical path of the coupling lens 9 of the near-infrared spectrometer.
The detection method using the detection device in the third embodiment includes:
step 1, placing a sample at a focus of a focusing collection lens 4;
step 2, when Raman spectrum signal acquisition is needed, the near-infrared light source 8 is turned off, the first mechanical mirror switching device is controlled to be in the first switching state, the second mechanical mirror switching device is controlled to be in the first switching state, the laser 1 is turned on, and Raman spectrum signal acquisition is conducted;
and 3, when near infrared spectrum signal acquisition is required, turning off the laser 1, controlling the first mechanical mirror switching device to be in the second switching state, controlling the second mechanical mirror switching device to be in the second switching state, turning on the near infrared light source 8, and performing near infrared spectrum signal acquisition.
Specifically, the method comprises the following steps:
in step 2, when raman spectrum signal acquisition is required, the near-infrared light source 8 is turned off, the first mechanical mirror switching device is controlled to be in a first switching state (i.e. a first reflecting mirror state), the second mechanical mirror switching device is controlled to be in a first switching state (i.e. a second reflecting mirror state), the laser 1 is turned on, laser light emitted by the laser 1 is reflected to the first plane reflecting mirror 33 through the beam splitter 2, reflected to the second plane reflecting mirror 37 through the first plane reflecting mirror 33 and reflected to the focus collecting lens 4 through the second plane reflecting mirror 37, the focus collecting lens 4 collects laser beams to a focus point where a sample is placed, light signals reflected by the sample are collimated through the focus collecting lens 4, input to the second plane reflecting mirror 37, reflected to the first plane reflecting mirror 33 through the second plane reflecting mirror 37 and reflected to the beam splitter 2 through the first plane reflecting mirror 33, The light is transmitted by the beam splitter 2, is directly input to a Raman spectrometer coupling lens 5 or is input through a Raman channel filter, and is coupled to a Raman spectrometer 6 through the Raman spectrometer coupling lens 5.
In step 3, when near infrared spectrum signal acquisition is needed, the laser 1 is turned off, the first mechanical mirror switching device is controlled to be in a second switching state (namely, an idle state), the second mechanical mirror switching device is controlled to be in a second switching state (namely, a semi-reflective semi-transparent mirror state), the near infrared light source 8 is turned on, light beams of the infrared light source 8 directly irradiate the semi-reflective semi-transparent mirror, the semi-reflective semi-transparent mirror reflects the light beams to the focusing acquisition lens 4, the focusing acquisition lens 4 converges the near infrared light beams to a focus position where a sample is placed, light signals reflected by the sample are collimated by the focusing acquisition lens 4 and then input to the semi-reflective semi-transparent mirror, and after being transmitted by the semi-reflective semi-transparent mirror, the light beam is directly input to the near-infrared spectrometer coupling lens 9 or is input to the near-infrared spectrometer coupling lens 9 through a near-infrared channel filter, and the light beam reflected by the near-infrared spectrometer coupling lens 9 is coupled to the near-infrared spectrometer 10.
Example four
The fourth embodiment is different from the third embodiment in that a paraxial illumination mode is adopted for the infrared light source 8. When the two mechanical mirror switching devices are switched to a mirror state, the Raman channel is gated, and when the two mechanical mirror switching devices are switched to a vacant state, the near infrared channel is gated.
Fig. 4 is a structural diagram of a detection apparatus combining a raman spectrum and a near infrared spectrum according to a fourth embodiment, where the apparatus includes a laser 1, a beam splitter 2, a first plane mirror 43, a focusing and collecting lens 4, a raman spectrometer coupling lens 5, a raman spectrometer 6, a mechanical mirror switching device, a second plane mirror 47, a near infrared light source 8, a near infrared spectrometer coupling lens 9, and a near infrared spectrometer 10.
The laser 1 is used for outputting parallel monochromatic laser beams;
the beam splitter 2 is disposed on an output optical path of the laser beam output from the laser 1 at a predetermined angle (for example, 45 degrees) with respect to the laser beam output from the laser 1.
The first plane mirror 43 is located on the light path of the laser beam reflected by the beam splitter 2 and forms a predetermined angle with the laser beam reflected by the beam splitter 2.
One end of the mechanical mirror switching device is provided with a second plane mirror 47, and the other end of the mechanical mirror switching device is vacant; when the mechanical mirror switching device is in the first switching state and the first mechanical mirror switching device is in the first switching state, the second plane mirror 47 is disposed parallel to the first plane mirror 43 and is used for reflecting the laser beam reflected by the first plane mirror 43 to the focus collecting lens 4.
The near-infrared light source 8 is arranged outside the focal point of the focusing collection lens 4 and is used for emitting light beams to the focal point of the focusing collection lens 4.
When the mechanical mirror switching device is in the second switching state, the light beam transmitted by the focusing and collecting lens 4 is directly input to the coupling lens 9 of the near-infrared spectrometer.
The near-infrared spectrometer coupling lens 9 is used for coupling the light beam reflected by the semi-reflecting and semi-transmitting beam splitter to the near-infrared spectrometer 10.
The raman spectrometer coupling lens 5 is used to couple the beam of the sample transmitted by the beam splitter 2 to the raman spectrometer 6.
The device also comprises a Raman channel optical filter arranged between the beam splitter 2 and the Raman spectrometer coupling lens 5; and the near-infrared channel optical filter is arranged on an input optical path of the coupling lens 9 of the near-infrared spectrometer.
The detection method using the detection device in the fourth embodiment includes:
step 1, placing a sample at a focus of a focusing collection lens 4;
step 2, when Raman spectrum signal acquisition is needed, the near-infrared light source 8 is turned off, the mechanical mirror switching device is controlled to be in a first switching state, the laser 1 is turned on, and Raman spectrum signal acquisition is carried out;
and 3, when near infrared spectrum signal acquisition is required, turning off the laser 1, controlling the mechanical mirror switching device to be in a second switching state, turning on the near infrared light source 8, and acquiring the near infrared spectrum signal.
Specifically, the method comprises the following steps:
in step 2, when raman spectrum signal acquisition is required, the near-infrared light source 8 is turned off, the mechanical mirror switching device is controlled to be in a first switching state (namely, a second reflecting mirror state), the laser 1 is turned on, laser light emitted by the laser 1 is reflected to a first plane reflecting mirror 43 through a beam splitter 2, reflected to a second plane reflecting mirror 47 through the first plane reflecting mirror 43 and reflected to a focusing collecting lens 4 through the second plane reflecting mirror 47, the focusing collecting lens 4 collects laser beams to a focal point where a sample is placed, an optical signal reflected by the sample is collimated through the focusing collecting lens 4, input to the second plane reflecting mirror 47, reflected to the first plane reflecting mirror 43 through the second plane reflecting mirror 47, reflected to the beam splitter 2 through the first plane reflecting mirror 43, transmitted through the beam splitter 2, and input to the raman spectrometer coupling lens 5 directly or through a channel filter, coupled to a raman spectrometer 6 by a raman spectrometer coupling lens 5.
In step 3, when near infrared spectrum signal acquisition is required, the laser 1 is turned off, the mechanical mirror switching device is controlled to be in a second switching state (namely, an idle state), the near infrared light source 8 is turned on, light beams of the infrared light source 8 are directly irradiated to the focusing collection lens 4, the focusing collection lens 4 converges the near infrared light beams to a focus position where a sample is placed, light signals reflected by the sample are collimated by the focusing collection lens 4 and then are directly input to the near infrared spectrometer coupling lens 9 or are input to the near infrared spectrometer coupling lens 9 through a near infrared channel optical filter, and light beams reflected by the near infrared spectrometer coupling lens 9 are coupled to the near infrared spectrometer 10.
The near-infrared light source used in the present invention is typically a near-infrared broad spectrum light source such as a near-infrared tungsten light source.
Aiming at the defects of single detection technologies of a Raman spectrometer and a near infrared spectrometer, the Raman spectrometer and the near infrared spectrometer are mutually complementary, and detection is carried out by combining Raman spectrum and near infrared spectrum, so that the Raman spectrometer and the near infrared spectrometer share one detection head, and time-sharing acquisition of Raman spectrum signals and near infrared spectrum signals is realized.
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (8)
1. A detection device combining a Raman spectrum and a near infrared spectrum is characterized by comprising a laser (1), a beam splitter (2), a mechanical mirror switching device, a plane reflector (13), a focusing and collecting lens (4), a Raman spectrometer coupling lens (5), a Raman spectrometer (6), a semi-reflecting and semi-transmitting beam splitter (17), a near infrared light source (8), a near infrared spectrometer coupling lens (9) and a near infrared spectrometer (10);
the laser (1) is used for outputting parallel monochromatic laser beams;
the beam splitter (2) is arranged on a laser beam output optical path output by the laser (1) in a manner of forming a preset angle with a laser beam output by the laser (1);
the plane mirror (13) is arranged at one end of the mechanical mirror switching device, the other end of the mechanical mirror switching device is arranged in a vacant position, when the mechanical mirror switching device is in a first switching state, the plane mirror (13) is located on a light path of a laser beam reflected by the beam splitter (2) and forms a preset angle with the laser beam reflected by the beam splitter (2), the plane mirror (13) is used for reflecting a beam transmitted by the semi-reflective and semi-transparent beam splitter (17) to the focusing and collecting lens (4) and is also used for reflecting the beam collimated by the focusing and collecting lens (4) to the semi-reflective and semi-transparent beam splitter (17); when the mechanical mirror switching device is in a second switching state, the laser beam reflected by the beam splitter (2) is directly input to the focusing and collecting lens (4);
the focusing and collecting lens (4) is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter (2), and the focus of the focusing and collecting lens (4) corresponds to a sample placing position;
the half-reflecting and half-transmitting beam splitter (17) is arranged in parallel with the plane reflector (13) on the mechanical mirror switching device in the first switching state, and is used for transmitting the light beam emitted by the near-infrared light source (8) and reflecting the light beam reflected back from the plane reflector (13);
the Raman spectrometer coupling lens (5) is arranged on one side of the beam splitter (2) in a mode of being perpendicular to a sample reflected light beam transmitted by the beam splitter (2) and is used for coupling the light beam into a slit or an optical fiber of the Raman spectrometer (6);
and the near-infrared spectrometer coupling lens (9) is used for coupling the light beam reflected by the semi-reflecting and semi-transmitting beam splitter (17) to the near-infrared spectrometer (10).
2. The combined raman and near infrared spectroscopy detection device of claim 1, further comprising a raman channel filter disposed between the beam splitter (2) and the raman spectrometer coupling lens (5); and the near-infrared channel optical filter is arranged between the semi-reflecting and semi-transmitting beam splitter (17) and the coupling lens (9) of the near-infrared spectrometer.
3. The combined raman and near infrared spectroscopy detection device of claim 1, wherein the predetermined angle is 45 degrees.
4. A detection device combining a Raman spectrum and a near infrared spectrum is characterized by comprising a laser (1), a beam splitter (2), a mechanical mirror switching device, a first plane reflector (23), a focusing and collecting lens (4), a Raman spectrometer coupling lens (5), a Raman spectrometer (6), a second plane reflector (27), a near infrared light source (8), a near infrared spectrometer coupling lens (9) and a near infrared spectrometer (10);
the laser (1) is used for outputting parallel monochromatic laser beams;
the beam splitter (2) is arranged on an output light path of the laser beam output by the laser (1) in a manner of forming a preset angle with the laser beam output by the laser (1);
one end of the mechanical mirror switching device is provided with a first plane reflector (23), the other end of the mechanical mirror switching device is vacant, when the mechanical mirror switching device is in a first switching state, the first plane reflector (23) is positioned on a light path of a laser beam reflected by the beam splitter (2) and forms a preset angle with the laser beam reflected by the beam splitter (2), and the first plane reflector (23) is used for reflecting the beam collimated by the focusing and collecting lens (4) to the second plane reflector (27); when the mechanical mirror switching device is in a second switching state, the laser beam reflected by the beam splitter (2) is directly input to the focusing and collecting lens (4);
the focusing and collecting lens (4) is arranged in a mode of being perpendicular to the laser beam reflected by the beam splitter (2), and the focus of the focusing and collecting lens (4) corresponds to a sample placing position;
the second plane mirror (27) is arranged in parallel with the first plane mirror (23) on the mechanical mirror switching device in the first switching state and is used for reflecting the light beam reflected by the first plane mirror (23) to the near-infrared spectrometer coupling lens (9);
the Raman spectrometer coupling lens (5) is arranged on one side of the beam splitter (2) in a mode of being perpendicular to a sample reflected light beam transmitted by the beam splitter (2) and is used for coupling the light beam into a slit or an optical fiber of the Raman spectrometer (6);
the near infrared spectrometer coupling lens (9) is used for coupling the light beam reflected by the second plane mirror (27) to the near infrared spectrometer (10);
the near-infrared light source (8) is arranged on the outer side of the focus of the focusing collection lens (4) and used for emitting light beams to the focus of the focusing collection lens (4).
5. A detection method using the detection apparatus combining raman spectroscopy and near infrared spectroscopy of claim 1, 2, 3 or 4, characterized by comprising:
-placing the sample at the focus of the focusing collection lens (4);
when Raman spectrum signal acquisition is needed, the near-infrared light source (8) is closed, the mechanical mirror switching device is controlled to be in a second switching state, the laser (1) is opened, and Raman spectrum signal acquisition is conducted;
when near infrared spectrum signal acquisition is needed, the laser (1) is closed, the mechanical mirror switching device is controlled to be in a first switching state, the near infrared light source (8) is opened, and near infrared spectrum signal acquisition is conducted.
6. A detection device combining Raman spectrum and near infrared spectrum is characterized by comprising a laser (1), a beam splitter (2), a first mechanical mirror switching device, a first plane reflector (33), a focusing collection lens (4), a Raman spectrometer coupling lens (5), a Raman spectrometer (6), a second mechanical mirror switching device, a second plane reflector (37), a semi-reflecting and semi-transparent mirror, a near infrared light source (8), a near infrared spectrometer coupling lens (9) and a near infrared spectrometer (10);
the laser (1) is used for outputting parallel monochromatic laser beams;
the beam splitter (2) is arranged on an output light path of the laser beam output by the laser (1) in a manner of forming a preset angle with the laser beam output by the laser (1);
one end of the first mechanical mirror switching device is provided with the first plane reflector (33), the other end of the first mechanical mirror switching device is vacant, and when the mechanical mirror switching device is in a first switching state, the first plane reflector (33) is positioned on a light path of a laser beam reflected by the beam splitter (2) and forms a preset angle with the laser beam reflected by the beam splitter (2);
one end of the second mechanical mirror switching device is provided with the second plane reflector (37), and the other end of the second mechanical mirror switching device is provided with a semi-reflecting and semi-transmitting mirror; when the second mechanical mirror switching device is in a first switching state and the first mechanical mirror switching device is in the first switching state, the first plane mirror (33) is located between the near-infrared light source (8) and the second plane mirror (37), and the second plane mirror (37) is arranged in parallel with the first plane mirror (33) and is used for reflecting the laser beam reflected by the first plane mirror (33) to the focusing and collecting lens (4);
when the first mechanical mirror switching device is in a second switching state and the second mechanical mirror switching device is in the second switching state, a semi-reflective semi-transparent mirror on the second mechanical mirror switching device receives a light beam emitted by the near-infrared light source (8), reflects the light beam to the focusing and collecting lens (4), and is further used for transmitting the light beam of the sample transmitted by the focusing and collecting lens (4) to the coupling lens (9) of the near-infrared spectrometer;
the near-infrared spectrometer coupling lens (9) is used for coupling the light beam transmitted by the semi-reflecting and semi-transmitting mirror to the near-infrared spectrometer (10);
the Raman spectrometer coupling lens (5) is used for coupling the light beam of the sample transmitted by the beam splitter (2) to the Raman spectrometer (6).
7. The combined Raman and near infrared detection apparatus of claim 6, further comprising a Raman channel filter disposed between the beam splitter (2) and the Raman spectrometer coupling lens (5); and the near-infrared channel optical filter is arranged on an input optical path of the coupling lens (9) of the near-infrared spectrometer.
8. A detection method using the detection apparatus combining Raman spectroscopy and near-infrared spectroscopy according to claim 6 or 7, comprising:
-placing the sample at the focus of the focusing collection lens (4);
when Raman spectrum signal acquisition is needed, the near-infrared light source (8) is turned off, the first mechanical mirror switching device is controlled to be in a first switching state, the second mechanical mirror switching device is controlled to be in the first switching state, the laser (1) is turned on, and Raman spectrum signal acquisition is conducted;
when near infrared spectrum signal acquisition is needed, the laser (1) is closed, the first mechanical mirror switching device is controlled to be in the second switching state, the second mechanical mirror switching device is controlled to be in the second switching state, and the near infrared light source (8) is opened to acquire near infrared spectrum signals.
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| CN109827946B (en) * | 2019-02-28 | 2021-08-03 | 华北水利水电大学 | Soil component in-situ analysis system and method |
| CN110146483B (en) * | 2019-05-17 | 2020-06-30 | 中国科学院力学研究所 | Spectrum online detection device and method |
| CN111562249A (en) * | 2020-05-25 | 2020-08-21 | 重庆冠雁科技有限公司 | Two-in-one probe capable of simultaneously detecting Raman spectrum and near infrared spectrum |
| CN111579544A (en) * | 2020-05-25 | 2020-08-25 | 重庆冠雁科技有限公司 | Method capable of simultaneously measuring visible near infrared spectrum and Raman spectrum of substance |
| CN111474164B (en) * | 2020-06-01 | 2024-07-30 | 广州贝拓科学技术有限公司 | Microscopic laser Raman spectrometer and working method thereof |
| EP4397962A1 (en) * | 2021-08-31 | 2024-07-10 | Shimadzu Corporation | Raman-infrared spectroscopic analysis multifunction machine, and measuring method employing raman spectroscopy and infrared spectroscopy |
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