JP2018109568A - Spectrometry method and spectrometry device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spectrometry method and a spectrometry device capable of quickly, precisely, and accurately identifying a structure for composing a predetermined area.SOLUTION: A spectrometry method comprises: an irradiation process for applying photographing illumination light L3 to a sample S and applying laser beams L1, namely irradiation light for spectroscopy, to a plurality of places; an image acquiring process for acquiring an image V comprising a form of the sample S and a plurality of irradiation points of the laser beams L1; a spectrometry process for performing spectrometry of light excited by the laser beams L1; an image processing process for extracting a first image area Ar1 or the like as an image area composed of an identical structure from image information and dividing each extracted area as a closed area in the image V of the sample S; and an area determination process for overlapping a spectrometry result to an irradiation point of the laser beams L1 in the image of the sample S divided into respective image areas, and for identifying structures of the respective image areas based on the spectrometry results of a plurality of irradiation points of the laser beams L1 within the respective image areas.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a spectroscopic measurement method and a spectroscopic measurement device, and more particularly to a Raman spectroscopic measurement method and a Raman spectroscopic device.

  2. Description of the Related Art Conventionally, there has been known a Raman spectroscopic measurement apparatus that specifies the configuration of a substance using Raman scattered light generated when the substance is irradiated with laser light. The Raman scattered light is generated with a unique spectrum according to the molecular structure of the substance at the irradiation point of the laser beam. For this reason, the Raman spectroscopic measurement apparatus includes a light source such as a laser beam for generating Raman scattered light, a camera for confirming an irradiation point of the laser beam in addition to a Raman spectroscope (detector), and an illumination light source for photographing. There is something. For example, it is like patent document 1.

  In the microscopic Raman spectroscopic device described in Patent Document 1, a laser beam half mirror (translucent mirror) and a photographing illumination light source half mirror are arranged on the optical axis of a camera lens. In other words, a part of the laser light reflected by the half mirror and a part of the illumination light for photographing reflected by another half mirror are made to coincide on the optical axis connecting the camera and the lens. Thereby, the micro Raman spectroscopic device described in Patent Literature 1 can more accurately capture the irradiation point of the laser beam.

  The technique described in Patent Document 1 captures an irradiation point of a laser beam irradiated to an arbitrary position of a sample and specifies a structure of the sample at the irradiation point by spectroscopic measurement. For this reason, the micro Raman spectroscopic device shows a structure different from the structure at the irradiation point unless foreign matter or the like is attached to the irradiation point or unless the accuracy rate of structure identification based on the spectroscopic measurement is 100%. Spectroscopic measurement results may be obtained. However, the microscopic Raman spectroscopic device cannot determine whether or not the determination of the structure based on the spectroscopic measurement result of the single irradiation point is correct. Further, the microscopic Raman spectroscopic device can specify the structure from the spectroscopic measurement results at a plurality of irradiation points arranged in a two-dimensional plane by scanning spectroscopic measurement. However, the scanning microscopic Raman spectroscopic device cannot determine whether the determination based on the spectroscopic measurement result is correct as in the case of a single irradiation point. Furthermore, in the scanning micro-Raman spectrometer, in addition to the long measurement time, the structure other than the irradiation point can only be estimated from the surrounding spectroscopic measurement results, and the sample is composed of the same structure. The specified area cannot be accurately identified.

JP 2006-214899 A

  An object of the present invention is to provide a spectroscopic measurement method and a spectroscopic measurement apparatus that can accurately and accurately specify a structure constituting a predetermined region in a short time.

  The problem to be solved by the present invention is as described above. Next, means for solving the problem will be described.

  That is, the sample illumination light and the spectral illumination light are irradiated onto the sample, and the sample is excited by the spectral illumination light while the image of the sample and the irradiation point of the spectral illumination light are acquired by the photographing camera. A method of irradiating the sample with the photographing illumination light and irradiating the spectroscopic illumination light to a plurality of locations, an image of the form of the sample, and the spectroscopy An image acquisition step for acquiring images of a plurality of irradiation points of illumination light for light, a spectroscopic measurement step for spectroscopically measuring light excited from a plurality of irradiation points by the illumination light for spectroscopy, and a form of the acquired sample An image processing step of extracting an image region composed of the same structure from the image information, dividing each extracted image region as a closed region, and spectral for each of a plurality of irradiation points of the spectral illumination light The measurement results are Based on the spectral measurement results of the plurality of irradiation points of the spectroscopic illumination light in each image region, superimposed on the plurality of irradiation points of the spectroscopic illumination light in the image in the form of the sample divided into image regions An area determination step for specifying the structure of each image area.

  In the spectroscopic measurement method, in the region determination step, the number of irradiation points of spectroscopic illumination light having spectroscopic measurement results indicating the same structure with respect to a plurality of irradiation points of the spectroscopic illumination light in one image region is calculated. When the ratio is equal to or greater than a predetermined value, the structure of the image region is specified as the structure of the spectroscopic measurement result.

  In the spectroscopic measurement method, in the irradiating step, the spectroscopic illumination light is divided into a plurality of spectroscopic illumination lights by an illumination light splitting unit and simultaneously irradiated onto the sample, and the image acquisition step and the spectroscopic measurement step are performed simultaneously. To be implemented.

  In the spectroscopic measurement method, in the image processing step, the image information includes at least one information of hue, brightness, saturation, and luminance.

  A spectroscopic measurement apparatus that performs the spectroscopic measurement method, a spectroscopic illumination light source having a predetermined wavelength, a spectroscope, a photographing camera, a photographing illumination light source, a total reflection mirror in which a pinhole is formed, A dichroic mirror that transmits only the spectroscopic illumination light having a predetermined wavelength and light having a shorter wavelength than the spectroscopic illumination light, and the total reflection mirror and the dichroic mirror are disposed on an optical axis of the spectroscopic illumination light. The spectral illumination light from the spectral illumination light source passes through the pinhole of the total reflection mirror and is irradiated on the sample, and the light excited by the spectral illumination light irradiated on the sample is the dichroic The imaging illumination light reflected from the mirror and incident on the spectroscope, and the imaging illumination light from the imaging illumination light source is reflected by the total reflection mirror and is applied to the optical axis of the spectral illumination light. Illumination light for photographing reflected on the sample with the optical axis aligned and reflected from the sample is reflected on the total reflection mirror with the optical axis aligned with the optical axis of the spectroscopic illumination light. Incident on the photographing camera.

  The present invention has the following effects.

  In the spectroscopic measurement method, the spectroscopic illumination light in the image region is irradiated by applying the spectroscopic measurement results at a plurality of locations in the image region set as a range composed of one structure to the image region. A structure of the entire image region including the missing part is specified. As a result, the structure constituting the predetermined region can be accurately identified in a short time. In addition, the measurement time can be shortened as compared with the case where the measurement density is increased and the image area is measured.

  In the spectroscopic measurement method, one result is determined from all the spectroscopic measurement results in the image area, so that the structure of the entire image area can be accurately specified even if the measurement result includes an erroneous determination. . Thereby, the structure which comprises a predetermined area | region can be pinpointed correctly.

  In the spectroscopic measurement method, the spectroscopic illumination light is irradiated to a plurality of locations in the image area at a time. Thereby, the structure which comprises a predetermined area | region can be pinpointed accurately. In addition, the measurement time can be shortened as compared with the case where the measurement density is increased and the image area is measured.

  In the spectroscopic measurement method, an image in the form of a sample is appropriately divided into image regions according to the form. Thereby, the structure which comprises a predetermined area | region can be pinpointed accurately.

  In a spectroscopic measurement device, a plurality of spectroscopic illumination lights are irradiated at once while maintaining the output without being affected by the optical system, and the spectroscopic illumination is applied to the image area by applying the spectroscopic measurement result to the image area. A structure of the entire image region including a portion not irradiated with light is specified. Thereby, the structure which comprises a predetermined area | region can be pinpointed accurately and correctly. In addition, the measurement time can be shortened as compared with the case where the measurement density is increased and the image area is measured.

Schematic which shows the whole structure in one Embodiment of a Raman spectrometer. The block diagram which shows the control structure in one Embodiment of a Raman spectroscopy measuring apparatus. The figure showing the flowchart which shows the process in one Embodiment of a Raman spectroscopy measurement method. Schematic which shows the irradiation aspect of the laser beam in one Embodiment of a Raman spectrometer. Schematic which shows the irradiation aspect of the illumination light for imaging | photography in one Embodiment of a Raman spectrometer, and the aspect of condensing the reflected light. Schematic which shows the aspect of condensing the Raman scattered light to the spectrometer in one Embodiment of a Raman spectrometer. (A) The figure which shows the image of the form of the sample by the camera for imaging | photography in one Embodiment of a Raman spectroscopy measuring apparatus, and the image of the several irradiation point of a laser beam, (b) Two-dimensional of the irradiation point in Fig.7 (a) The figure which shows the image of the state by which the arrangement | sequence was reconfigure | reconstructed into the one-dimensional arrangement | sequence with the multi optical fiber. (A) The figure which shows the image which extracted the image area | region which consists of the same structure from image information in the image by the camera for imaging | photography in one Embodiment of a Raman spectrometry apparatus, (b) The image area | region in Fig.8 (a) is made independent. The figure which shows the image divided | segmented as a closed area. The figure which shows the image which piled up the spectral measurement result on the irradiation point in FIG.8 (b), (b) The figure which shows the graph showing the Raman spectrum of the irradiation point in the 1st image area | region of Fig.9 (a).

  First, a Raman spectroscopic measurement apparatus 1 which is an embodiment of a Raman spectroscopic measurement apparatus which is a spectroscopic measurement apparatus that performs a spectroscopic measurement method will be described with reference to FIGS. 1 and 2. In the present embodiment, the Raman spectroscopic measurement apparatus 1 will be specifically described as the spectroscopic measurement apparatus. However, the present invention is not limited to this, and the spectroscopic measurement apparatus using various spectroscopic illumination lights, such as a fluorescence spectroscopic measurement apparatus, may be used. It is the same.

  As shown in FIG. 1, the Raman spectroscopic measurement apparatus 1 detects Raman scattered light L2 generated from the sample S by irradiating the sample S with laser light L1 as spectroscopic illumination light. The Raman spectroscopic measurement apparatus 1 includes a laser light source 2, a laser light first lens 3, a laser light second lens 5, a total reflection mirror 6, a dichroic mirror 7, an imaging lens 8, a Raman imaging lens 9, and a Raman spectroscopy. The apparatus 10 includes a half mirror 11, a photographing imaging lens 12, a photographing camera 13, a photographing illumination light source 14, and a control device 15.

  The laser light source 2 oscillates laser light L1 which is spectroscopic illumination light for generating Raman scattered light L2. The laser light source 2 oscillates laser light L1 having a predetermined wavelength. In the present embodiment, it is assumed that the laser light source 2 oscillates a short wavelength (400 nm to 600 nm) laser light L1. In the present embodiment, the medium of the laser light source 2 may be any medium that oscillates the short-wavelength laser light L1.

  The first lens 3 for laser light is a lens that converts incident light into parallel light. The first laser light lens 3 is disposed adjacent to the laser light source 2 on the optical axis of the laser light L1 so that the laser light L1 from the laser light source 2 is incident thereon.

  The microlens array 4 serving as illumination light dividing means divides the incident laser light L1 into a plurality of laser lights L1. In the microlens array 4, microlenses are formed in a lattice shape. The microlens array 4 is disposed on the optical axis of the laser light L1 so as to be adjacent to the first laser light lens 3 so that the laser light L1 from the first laser light lens 3 is incident thereon. The microlens array 4 is configured to divide the incident laser light L1 into a plurality of optical paths and emit the laser light from the microlens array 4. In the present embodiment, the illumination light splitting means is composed of the microlens array 4, but the invention is not limited to this, and any optical path splitting optical system such as a diffractive optical element or a multi-optical fiber may be used.

  The second lens 5 for laser light is a lens that focuses the incident laser light L1. The second lens 5 for laser light is disposed adjacent to the microlens array 4 on the optical axis of the laser light L1 so that the laser light L1 from the microlens array 4 is incident thereon. The second lens 5 for laser light is configured to emit from the second lens 5 for laser light so that the laser light L1 divided into a plurality of incident optical paths passes through a predetermined focusing position P.

  The total reflection mirror 6 has a pinhole 6a at the center. The total reflection mirror 6 is disposed on the optical axis of the laser light L1 so as to be adjacent to the second laser light lens 5 so that the laser light L1 from the second laser light lens 5 is incident thereon. The total reflection mirror 6 is arranged so that the converging position P of the laser light L1 divided into a plurality of optical paths transmitted through the second laser light lens 5 coincides with the position of the pinhole 6a. That is, the total reflection mirror 6 causes the laser light L1 divided into a plurality of optical paths to converge at the position of the pinhole 6a of the total reflection mirror 6 and pass through the pinhole 6a without interfering with the total reflection mirror 6. It is configured.

  In the present embodiment, the total reflection mirror 6 is disposed so as to have an inclination angle of 45 degrees with respect to the optical axis of the laser light L1. The total reflection mirror 6 is a pinhole of the total reflection mirror 6 so that the light emitted from the direction of 90 degrees with respect to the optical axis of the laser light L1 toward the total reflection mirror 6 coincides with the optical axis of the laser light L1. It is comprised so that it may reflect in parts other than 6a. On the other hand, the total reflection mirror 6 emits a light beam emitted from the optical axis direction of the laser light L1 toward the total reflection mirror 6 in a direction of 90 degrees with respect to the optical axis of the laser light L1. It is comprised so that it may reflect in parts other than. In the present embodiment, the arrangement angles of the total reflection mirror 6, the dichroic mirror 7, and the half mirror 11 are not limited to 45 degrees, but may be an arrangement suitable for the device configuration.

  The dichroic mirror 7 which is a wavelength selection half mirror selectively transmits only light having a predetermined wavelength. In the present embodiment, the dichroic mirror 7 is configured to selectively transmit only the light of the laser beam L1 and the shorter wavelength. The dichroic mirror 7 is disposed adjacent to the total reflection mirror 6 on the optical axis of the laser light L1 so that the laser light L1 that has passed through the pinhole 6a of the total reflection mirror 6 enters. Further, the dichroic mirror 7 is disposed so as to have an inclination angle of 45 degrees with respect to the optical axis of the laser light L1. In other words, the dichroic mirror 7 is configured to reflect the long-wavelength Raman scattered light L2 in a direction of 90 degrees with respect to the optical axis of the laser light L1.

  The imaging lens 8 is a lens that condenses the laser light L1. The imaging lens 8 is disposed adjacent to the dichroic mirror 7 on the optical axis of the laser light L1 so that the laser light L1 from the dichroic mirror 7 enters. Further, the imaging lens 8 receives Raman scattered light L2 generated from the irradiation point of the laser light L1 applied to the sample S from the sample S side of the imaging lens 8.

  The Raman imaging lens 9 is a lens that collects the Raman scattered light L <b> 2 and enters the Raman spectrometer 10. The Raman imaging lens 9 is disposed adjacent to the dichroic mirror 7 at a position of 90 degrees with respect to the optical axis of the laser light L1 so that light from the dichroic mirror 7 enters. That is, the Raman imaging lens 9 is arranged so that the Raman scattered light L2 reflected by the dichroic mirror 7 in the direction of 90 degrees with respect to the optical axis of the laser light L1 is incident.

  The Raman spectroscope 10 detects a Raman spectrum from the Raman scattered light L2. The Raman spectroscope 10 includes, for example, a multi optical fiber, a diffraction grating, an area sensor and a lens, a mirror, and the like. The Raman spectroscope 10 is disposed adjacent to the Raman imaging lens 9 at a position of 90 degrees with respect to the optical axis of the laser light L1 so that the Raman scattered light L2 from the Raman imaging lens 9 is incident thereon. Has been. Further, in the present embodiment, it is preferable to adopt a configuration in which a long pass filter 10 a is inserted between the dichroic mirror 7 and the Raman spectrometer 10 in order to cut unnecessary short wavelength light.

  The half mirror 11 transmits a part of light and reflects a part thereof. The half mirror 11 is disposed adjacent to the total reflection mirror 6 at a position of 90 degrees with respect to the optical axis of the laser beam L1 so that the light reflected by the total reflection mirror 6 is incident. The half mirror 11 is arranged so as to have an inclination angle of 45 degrees with respect to the optical axis of the laser light L1. That is, the half mirror 11 reflects light in a direction parallel to the optical axis of the laser light L1.

  The imaging imaging lens 12 is a lens that collects light on the imaging camera 13. The imaging imaging lens 12 is disposed adjacent to the half mirror 11 at a position parallel to the optical axis of the laser light L1 so that the light reflected by the half mirror 11 enters. The imaging imaging lens 12 is configured to focus on the imaging camera 13.

  The imaging camera 13 captures an image in the form of the sample S and an image of the irradiation point of the laser light L1. The photographing camera 13 is composed of a CMOS camera or the like. The photographing camera 13 is disposed adjacent to the photographing imaging lens 12 at a position parallel to the optical axis of the laser beam L1 so that light from the photographing imaging lens 12 is incident. The photographing camera 13 can visually recognize the irradiation point of the laser light L1 and the surface state of the sample S.

  The photographing illumination light source 14 generates photographing illumination light L3. The photographing illumination light source 14 is arranged adjacent to the half mirror 11 at a position of 90 degrees with respect to the optical axis of the laser light L1 so that the total reflection mirror 6 is irradiated with the photographing illumination light L3. The photographing illumination light source 14 is configured to emit photographing illumination light L3 toward the total reflection mirror 6 via the photographing illumination light lens 14a and the half mirror 11.

  As shown in FIG. 2, the control device 15 controls the Raman spectroscopic measurement device 1. The control device 15 may actually be configured such that a CPU, ROM, RAM, HDD, or the like is connected by a bus, or may be configured by a one-chip LSI or the like. The control device 15 stores various programs and data for controlling the Raman spectroscopic measurement device 1.

  The control device 15 is connected to the laser light source 2 and the photographing illumination light source 14 and can control the laser light source 2 and the photographing illumination light source 14.

  The control device 15 is connected to the Raman spectrometer 10 and can control the Raman spectrometer 10. In addition, the control device 15 can acquire the spectroscopic measurement result from the Raman spectrometer 10.

  The control device 15 is connected to the photographing camera 13 and can control the photographing camera 13. Further, the control device 15 can acquire an image taken from the photographing camera 13.

  The Raman spectroscopic measurement apparatus 1 configured in this way has the laser light L1 applied to a plurality of locations of the sample S at a time in a state where the laser light L1 emitted from the laser light source 2 is divided into a plurality of optical paths by the microlens array 4. Is irradiated. In addition, the Raman spectroscopic measurement apparatus 1 irradiates the sample S with the photographic illumination light L <b> 3 from the photographic illumination light source 14 via the total reflection mirror 6. The Raman scattered light L2 generated from the sample S by the irradiation of the laser light L1 is incident on the Raman spectroscope 10 by the dichroic mirror 7. The Raman spectroscopic measurement apparatus 1 spectroscopically measures the Raman scattered light L2 with the Raman spectroscope 10. On the other hand, the imaging illumination light L3 irradiated to the sample S from the imaging illumination light source 14 becomes light reflected from the sample S (hereinafter simply referred to as “reflected light L4”) when reaching the sample S. The reflected light L 4 from the sample S is reflected by the total reflection mirror 6 and the half mirror 11 and enters the photographing camera 13. The Raman spectroscopic measurement apparatus 1 obtains an image in the form of the sample S and images of a plurality of irradiation points of the laser light L1 from the reflected light L4 by the photographing camera 13. The Raman spectroscopic measurement apparatus 1 specifies the structure of the sample S from the spectroscopic measurement result, the image in the form of the sample S, and the images of the plurality of irradiation points of the laser light L1 by the control device 15.

  Next, a spectroscopic measurement method in the Raman spectroscopic measurement apparatus 1 will be described with reference to FIGS.

  As shown in FIG. 3, in the spectroscopic measurement method, as a process K110, an irradiation process in which the sample S is irradiated with the imaging illumination light L3 and the laser light L1 that is the spectral illumination light is irradiated to a plurality of locations, and a process K120. As an image acquisition process for acquiring an image V composed of an image in the form of the sample S and images of a plurality of irradiation points of the laser light L1, and as a process K130, Raman light excited from the plurality of irradiation points by the laser light L1. In the image of the sample S form of the acquired image V, an image of the same structure is formed from the hue, brightness, saturation, and luminance that are image information as the spectroscopic measurement step for spectroscopic measurement and the step K140. An image processing step of extracting an aggregate of existing pixels as an image region and dividing each of the extracted image regions as a closed region, and a step K150 for each of a plurality of irradiation points of the laser light L1 Measurement results superposed on the image of a plurality of irradiation points of the laser beam L1 in the image V a, and a, a region determining step of identifying the structure of the image regions based on the spectral measurements. The spectroscopic measurement method is performed from step K110 to step K150 in order.

  As shown in FIG. 4, in the process K110 (see FIG. 3), the Raman spectroscopic measurement apparatus 1 uses the laser light L1 oscillated by the laser light source 2 as the laser light L1 irradiation process. The light enters the first lens 3. The laser light L1 is emitted from the first lens 3 for laser light as parallel light from a point light source at infinity. The laser light L1 emitted from the first laser light lens 3 is incident on the microlens array 4. The laser light L1 is divided into a plurality of optical paths and emitted from the microlens array 4. The laser light L1 divided into a plurality of optical paths emitted from the microlens array 4 is incident on the second lens 5 for laser light.

  The laser light L1 composed of a plurality of optical paths is emitted from the second lens 5 for laser light so as to be focused at the position of the pinhole 6a of the total reflection mirror 6. The laser light L1 emitted from the second lens 5 for laser light passes through the pinhole 6a without interfering with the total reflection mirror 6. The laser beam L 1 that has passed through the total reflection mirror 6 is incident on the dichroic mirror 7. The laser light L1 which is short wavelength light is transmitted without being reflected by the dichroic mirror 7 which reflects long wavelength light. The laser beam L 1 that has passed through the dichroic mirror 7 is incident on the imaging lens 8. The laser light L1 is emitted from the imaging lens 8 so as to be condensed on the surface of the sample S for each optical path. The laser beam L1 is irradiated to a plurality of locations on the sample S. Thereby, the laser beam L1 generates Raman scattered light L2 (see FIG. 6) having a spectrum corresponding to the molecular structure from the irradiated portion of the sample S.

  As described above, the Raman spectroscopic measurement apparatus 1 is focused by the second laser light lens 5 and passes through the pinhole 6a of the total reflection mirror 6 without interference even when the laser light L1 is divided into a plurality of optical paths. It is configured. Further, the Raman spectroscopic measurement apparatus 1 is configured such that a part of the laser light L1 is not reflected by the dichroic mirror 7 that reflects the Raman scattered light L2. That is, in the Raman spectroscopic measurement apparatus 1, the laser beam L1 is not shielded by the total reflection mirror 6 and the dichroic mirror 7 arranged on the optical axis of the laser beam L1. Thereby, it is possible to suppress a loss that occurs before the laser light L1 from the light source reaches the sample S.

  As shown in FIG. 5, in step K110 (see FIG. 3), the Raman spectroscopic measurement device 1 shoots the illumination light L3 for photographing from the illumination light source 14 for photographing toward the half mirror 11 as an irradiation step of the illumination light L3 for photographing. Is emitted. A part of the photographing illumination light L3 passes through the half mirror 11 and is emitted toward the total reflection mirror 6. The photographing illumination light L3 emitted toward the total reflection mirror 6 is reflected by a portion other than the pinhole 6a of the total reflection mirror 6 so as to coincide with the optical axis of the laser light L1. The photographing illumination light L3 reflected by the total reflection mirror 6 is incident on a dichroic mirror 7 that reflects long wavelength light along the optical axis of the laser light L1. Only the light in the short wavelength region of the photographic illumination light L <b> 3 passes through the dichroic mirror 7 and enters the imaging lens 8. The light in the short wavelength region of the illuminating illumination light L3 transmitted through the dichroic mirror 7 is emitted from the imaging lens 8 so as to be condensed on the surface of the sample S. Light in the short wavelength region of the imaging illumination light L3 is irradiated on the sample S and reflected by the surface of the sample S.

  In the process K120 (see FIG. 3), the Raman spectroscopic measurement apparatus 1 uses the reflected light L4 from the sample S of the laser light L1 and the light in the short wavelength region of the imaging illumination light L3 as the image acquisition process. From the sample S side. (Hereinafter, when light enters the imaging lens 8 from the sample S side, it is simply referred to as “sample-side lens 8”). That is, the reflected light L 4 from the sample S is incident on the sample side lens 8. The reflected light L4 from the sample S is emitted from the sample side lens 8 as light from a point light source at infinity. The reflected light L4 from the sample S emitted from the sample side lens 8 is incident on the dichroic mirror 7 that reflects long wavelength light. The reflected light L4 from the sample S, which is light in the short wavelength region, passes through the dichroic mirror 7. That is, the reflected light L 4 from the sample S is emitted toward the total reflection mirror 6. The reflected light L4 from the sample S emitted toward the total reflection mirror 6 is reflected toward the half mirror 11 by the total reflection mirror 6. A part of the reflected light L4 from the sample S is reflected by the half mirror 11 toward the photographing camera 13.

  As shown in FIG. 7A, in the Raman spectroscopic measurement apparatus 1, the imaging camera 13 (see FIG. 4) generates an image V from the reflected light L4. In the image V, an image in the form of the sample S and images of a plurality of irradiation points s1, s2, s3,... S16 of the laser light L1 are displayed at the same time. Furthermore, in the image V, a portion of the first structure Sa and a portion of the second structure Sb (light ink portion) of the sample S are displayed. In the Raman spectroscopic measurement device 1, the control device 15 acquires the image V from the photographing camera 13. As described above, the Raman spectrometer 1 can simultaneously confirm the surface state of the sample S and the Raman spectrum of the Raman scattered light L2 at a plurality of irradiation points s1, s2, s3,... S16 (see FIG. 3). ).

  With this configuration, the Raman spectroscopic measurement apparatus 1 is configured such that the reflected light L4 from the sample S is not reflected by the dichroic mirror 7. In the Raman spectroscopic measurement apparatus 1, the reflected light L <b> 4 from the sample S is reflected by a portion other than the pinhole 6 a of the total reflection mirror 6. That is, in the Raman spectroscopic measurement apparatus 1, the reflected light L4 from the sample S is hardly inhibited by the total reflection mirror 6 and the dichroic mirror 7 arranged on the optical axis of the laser light L1. Thereby, it is possible to suppress a loss that occurs before the reflected light L4 from the sample S reaches the camera. In the present embodiment, the illumination light L3 for imaging from the illumination light source for imaging 14 and the reflected light L4 from the sample S are configured to have the same optical axis by the half mirror 11, but this is not limitative. Instead of this, a configuration in which the shooting camera 13 and the shooting illumination light source 14 are integrally configured and the half mirror 11 is omitted may be employed.

  As shown in FIG. 6, in step K130 (see FIG. 3), the Raman spectroscopic measurement apparatus 1 performs, as a spectroscopic measurement step, long-wavelength Raman scattered light L <b> 2 generated from the irradiated portion of the sample S to the sample-side lens 8. Incident. The Raman scattered light L2 composed of a plurality of optical paths enters and exits the sample side lens 8. The Raman scattered light L2 emitted from the sample side lens 8 is incident on the dichroic mirror 7. The long-wavelength Raman scattered light L2 is reflected by the dichroic mirror 7 that reflects the long-wavelength light. That is, the Raman scattered light L <b> 2 composed of a plurality of optical paths is incident on the Raman imaging lens 9 by the dichroic mirror 7. The Raman scattered light L2 is emitted from the Raman imaging lens 9 so as to form an image on the incident surface of the Raman spectrometer 10.

  As shown in FIG. 7 (b), the Raman spectroscopic measurement apparatus 1 uses the Raman imaging light 9 to multi-scatter the Raman scattered light L2 from the irradiation points s1, s2, s3,... S16 of the laser light L1. Light is received by a two-dimensional array portion which is one end of the optical fiber 16. The Raman spectroscopic measurement device 1 converts the two-dimensional array received at one end of the multi-optical fiber 16 into a one-dimensional array, and emits it from the other end of the multi-optical fiber 16 to the diffraction grating. The emitted Raman scattered light L2 converted into a one-dimensional array is guided to the area sensor via the diffraction grating. Thereby, the Raman spectroscopic measurement apparatus 1 can measure the Raman spectroscopic spectrum of the plurality of irradiation points s1, s2, s3,.

  With this configuration, the Raman spectroscopic measurement apparatus 1 reflects the Raman scattered light L2 including a plurality of optical paths generated by the laser light L1 divided into the plurality of optical paths toward the Raman spectroscope 10 by the dichroic mirror 7. Let That is, in the Raman spectrometer 1, the Raman scattered light L <b> 2 composed of a plurality of generated optical paths can be incident on the Raman spectrometer 10. Accordingly, the Raman spectroscopic measurement apparatus 1 acquires the image V from the reflected light L4 and the spectroscopic measurement process in which the sample S is irradiated with the laser light L1 divided into a plurality of optical paths and the Raman scattered light L2 from the sample is measured. The image acquisition process to be performed can be performed simultaneously.

  As shown in FIG. 8, in the process K140 (see FIG. 3), the control device 15 of the Raman spectroscopic measurement apparatus 1 constructs an image in the image of the sample S in the acquired image V as an image processing process. A range of the same structure is specified based on image information assigned to each unit pixel (hereinafter simply referred to as “pixel”) which is the smallest unit. When at least one value arbitrarily selected from hue, brightness, saturation, and luminance, which are image information, between adjacent pixels exceeds a specified value, the control device 15 determines that the adjacent pixels are It is determined that images of different structures are formed.

  The control device 15 sets a boundary based on the determination result based on the image information between adjacent pixels in all the pixels, and extracts an aggregate of pixels constituting an image of the same structure as an image region ( FIG. 8 (a)). Similarly, the control device 15 extracts a group of pixels constituting an image of another identical structure as an image area from the image of the sample S in the image V, and is an independent closed area. The image is divided into a first image area Ar1, a second image area Ar2, and a third image area Ar3 (FIG. 8B). In the present embodiment, the boundary of the image area is determined based on whether or not the image information between adjacent pixels exceeds a specified value. However, the present invention is not limited to this, and the same structure is used using the image information. It suffices if an image area representing the body can be extracted.

  As shown in FIG. 9A, in step K150 (see FIG. 3), the controller 15 of the Raman spectroscopic measurement apparatus 1 performs the region determination step in which the first image that is a closed region of the same structure in the image V is displayed. The spectral measurement results of the plurality of irradiation points s1, s2, s3,... S16 of the laser light L1 are superimposed on the image in the form of the sample S divided into the region Ar1, the second image region Ar2, and the third image region Ar3. The control device 15 indicates the same structure among the spectroscopic measurement results of the plurality of irradiation points s1, s2, s3, s4, s5, and s6 of the laser light L1 in the first image region Ar1 having the same structure. It is determined whether or not the ratio of the number of irradiation points that is the spectroscopic measurement result is equal to or greater than a predetermined value. If the ratio is equal to or greater than the predetermined value, the structure in the first image region Ar1 is specified as the structure of the spectroscopic measurement result. .

The Raman spectroscope 10 (see FIG. 6) outputs a Raman spectrum of the Raman scattered light L2 at the irradiation points s1, s2, s3... S16 (see FIG. 7).
As shown in FIG. 9B, the control device 15 acquires the Raman spectra of the irradiation points s 1, s 2, s 3, s 4, s 5, and s 6 from the Raman spectrometer 10. Of the irradiation points s1, s2, s3, s4, s5, and s6, the waveforms and peak positions of the irradiation points s4, s5 are different from the waveforms and peak positions of the irradiation points s1, s2, s3, and s6. As a result, the structure at the irradiation points s1, s2, s3, and s6 (FIG. 9A, black circles in Ar1) and the structure at the irradiation points s4, s5 (FIG. 9A, white circles in Ar1) are obtained. It shows different things.

  In the present embodiment, four points of the irradiation points s1, s2, s3, and s6 are the same among the six measurement points s1, s2, s3, s4, s5, and s6 in the first image area Ar1. In the case of a spectroscopic measurement result indicating the structure Sa (black circle in FIG. 9A), the ratio of the number of irradiation points that is the spectroscopic measurement result indicating the first structure Sa in the first image region Ar1 is: 4 / 6≈0.67 = 67%. When the predetermined value is 65%, since the ratio of the number of irradiation points, which is the spectroscopic measurement result indicating the first structure Sa, is larger than the predetermined value, the control device 15 defines the first image area Ar1 as the first structure Sa. To be identified. Similarly, among the five measurement points s7, s8, s9, s10, and s11 in the second image area Ar2, the four points of the irradiation points s7, s8, s10, and s11 have the same second structure Sb. In the case of the spectroscopic measurement result shown in FIG. 9A (black circle in Ar2), the ratio of the number of irradiation points, which is the spectroscopic measurement result showing the second structure Sb in the second image region Ar2, is 4/5 = 0. .8 = 80%. Therefore, the control device 15 specifies the second image region Ar2 as the second structure Sb.

  On the other hand, among the spectroscopic measurement results of the five irradiation points s12, s13, s14, s15, and s16 in the third image area Ar3, the three measurement points of the irradiation points s14, s15, and s16 indicate the same first structure Sa. In the case of the result (FIG. 9A, black circle in Ar3), the ratio of the number of irradiation points, which is the spectroscopic measurement result indicating the first structure Sa in the third image region Ar3, is 3/5 = 0.6 = 60%. The control device 15 specifies the third image region Ar3 as the first structure Sa because the ratio of the number of irradiation points, which is the spectroscopic measurement result indicating the first structure Sa, is less than the predetermined value 65% in the present embodiment. Can not. Accordingly, the Raman spectroscopic measurement apparatus 1 performs again the irradiation process of the laser beam L1, the image acquisition process, the spectroscopic measurement process, the image processing process, and the area determination process for the third image area Ar3. The control device 15 converts the structure of the first image region Ar1, the second image region Ar2, and the third image region Ar3 divided into the closed regions of the same structure along the above steps into the ratio of the spectroscopic measurement result. Judgment based on.

  With this configuration, the Raman spectroscopic measurement apparatus 1 acquires an image V including an image in the form of the sample S and images of the plurality of irradiation points s1, s2, s3,... S16 of the laser light L1. A plurality of irradiation points s1, s2, s3,... S16 of the laser light L1 on the sample S can be observed. Further, the Raman spectroscopic measurement apparatus 1 is configured to set each of the first image area Ar1, the second image area Ar2, and the third image area Ar3 that are set as ranges constituted by the same structure based on the image information. Each image region including a portion in the first image region Ar1, the second image region Ar2, and the third image region Ar3 that is not irradiated with the laser light L1 by superimposing a plurality of spectral measurement results on each image region. The entire structure is specified. Thereby, the structure which comprises 1st image area | region Ar1, 2nd image area | region Ar2, and 3rd image area | region Ar3 can be pinpointed accurately. In addition, the measurement time can be shortened compared with the case where the first image area Ar1, the second image area Ar2, and the third image area Ar3 are measured with a scanning microscopic Raman spectroscopic apparatus.

  As described above, the Raman spectroscopic measurement apparatus 1 which is an embodiment of the Raman spectroscopic measurement apparatus is configured to irradiate the sample S with the laser light L1 divided into a plurality of optical paths, but is not limited thereto. Further, on the basis of the optical path of the laser light L1, a photographing optical path is provided at a position on the laser light source 2 side, and an optical path of Raman scattered light L2 is provided at a position on the sample S side. However, the present invention is not limited to this. Absent. The Raman spectroscopic measurement device 1 has a configuration in which an optical path for photographing is secured using the total reflection mirror 6 and an optical path of the Raman scattered light L2 is secured using the dichroic mirror 7 with the optical path of the laser light L1 as a reference. Good. The above-described embodiments are merely representative, and various modifications can be made without departing from the scope of one embodiment. It goes without saying that the present invention can be embodied in various forms, and the scope of the present invention is indicated by the description of the scope of claims, and the equivalent meanings of the scope of claims, and all the scopes within the scope of the claims. Includes changes.

DESCRIPTION OF SYMBOLS 1 Spectrometer S Sample V Image L1 Laser light L2 Raman scattered light L3 Imaging illumination light L4 Reflected light Ar1 1st image area Ar2 2nd image area Ar3 3rd image area Sa 1st structure Sb 2nd structure

Claims (5)

Light that is excited by the spectroscopic illumination light while irradiating the sample with illumination light for spectroscopy and spectroscopic illumination light, and obtaining an image of the form of the sample and the point of irradiation of the spectroscopic illumination light with a photographing camera A spectroscopic measurement method for spectroscopically measuring
Irradiating the sample with the imaging illumination light and irradiating the spectroscopic illumination light to a plurality of locations; and
An image acquisition step of acquiring an image in the form of the sample and images of a plurality of irradiation points of the spectroscopic illumination light;
A spectroscopic measurement step of spectroscopically measuring light excited from a plurality of irradiation points by the spectroscopic illumination light;
In the acquired image in the form of the sample, an image processing step of extracting an image region composed of the same structure from image information and dividing each extracted image region as a closed region;
Spectral measurement results for each of a plurality of irradiation points of the spectroscopic illumination light are superimposed on the plurality of irradiation points of the spectroscopic illumination light in an image in the form of the sample divided into the image regions, A region determination step of identifying the structure of each image region based on the spectral measurement results of a plurality of irradiation points of the spectral illumination light in
A spectroscopic measurement method comprising:   In the region determination step, a ratio of the number of irradiation points of the spectral illumination light having a spectroscopic measurement result indicating the same structure with respect to a plurality of irradiation points of the spectral illumination light in one image region is a predetermined value or more In this case, the spectroscopic measurement method according to claim 1, wherein the structure of the image region is specified as the spectroscopic measurement structure.   In the irradiation step, the spectroscopic illumination light is divided into a plurality of spectroscopic illumination lights by an illumination light splitting unit and simultaneously irradiated onto the sample, and the image acquisition step and the spectroscopic measurement step are performed simultaneously. The spectroscopic measurement method according to claim 1 or 2.   The spectroscopic measurement method according to any one of claims 1 to 3, wherein, in the image processing step, the image information includes at least one information of hue, brightness, saturation, and luminance. A spectroscopic measurement apparatus for performing the spectroscopic measurement method according to any one of claims 1 to 4,
A spectral illumination light source of a predetermined wavelength;
A spectroscope,
A camera for shooting,
An illumination light source for photographing;
A total reflection mirror in which a pinhole is formed;
A dichroic mirror that transmits only the spectral illumination light having the predetermined wavelength and light having a shorter wavelength than that,
The total reflection mirror and the dichroic mirror are disposed on an optical axis of the spectroscopic illumination light;
The spectroscopic illumination light from the spectroscopic illumination light source is irradiated to the sample through the pinhole of the total reflection mirror,
Light excited by the spectroscopic illumination light applied to the sample is reflected by the dichroic mirror and incident on the spectroscope,
Illumination light for photographing from the illumination light source for photographing is reflected on the total reflection mirror and irradiated on the sample in a state in which the optical axis of the illumination light for photographing coincides with the optical axis of the illumination light for spectroscopy,
A spectroscopic measurement apparatus in which imaging illumination light reflected from the sample is reflected by the total reflection mirror and incident on the imaging camera in a state where the optical axis thereof coincides with the optical axis of the spectroscopy illumination light.

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