JP6784603B2 - Spectral measurement method and spectroscopic measurement device - Google Patents

Description

The present invention relates to spectroscopic measurement methods and devices, particularly Raman spectroscopic measurement methods and Raman spectroscopic devices.

Conventionally, there is known a Raman spectroscopic measurement device that specifies the composition of a substance by using the Raman scattered light generated when the substance is irradiated with laser light. Raman scattered light is generated in a unique spectrum depending on the molecular structure of the substance at the irradiation point of the laser light. For this reason, the Raman spectroscopic measurement device is provided with a light source such as a laser beam that generates Raman scattered light, a Raman spectroscope (detector), a camera for confirming the irradiation point of the laser beam, and an illumination light source for photography. There is something. For example, as in Patent Document 1.

In the microscopic Raman spectroscope described in Patent Document 1, a half mirror (semi-transparent mirror) for laser light and a half mirror for an illumination light source for photographing are arranged on the optical axis of the lens of the camera. That is, a part of the laser light reflected by the half mirror and a part of the illumination light for photography reflected by another half mirror are aligned on the optical axis connecting the camera and the lens. As a result, the micro-Raman spectroscope described in Patent Document 1 can more accurately photograph the irradiation point of the laser beam.

The technique described in Patent Document 1 is to photograph an irradiation point of a laser beam irradiated at an arbitrary position of a sample and to specify a structure of the sample at the irradiation point by spectroscopic measurement. Therefore, unless foreign matter or the like adheres to the irradiation point, or the correct answer rate for structure identification based on spectroscopic measurement is not 100%, the microscopic Raman spectroscopic device shows a structure different from the structure at the irradiation point. 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 a single irradiation point is correct. In addition, the microscopic Raman spectroscopic device can identify the structure from the spectroscopic measurement results at a plurality of irradiation points arranged in a two-dimensional plane by scanning-type spectroscopic measurement. However, the scanning microscopic Raman spectroscopic device cannot determine whether or not the determination based on the spectroscopic measurement result is correct as in the case of a single irradiation point. Further, in the scanning type microscopic Raman spectroscopic device, in addition to the long measurement time, the structure of the part other than the irradiation point can only be estimated from the surrounding spectroscopic measurement results, and the sample is composed of the same structure. It is not possible to accurately identify the area that is being used.

JP-A-2006-214899

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

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

That is, the sample is irradiated with the illumination light for photography and the illumination light for spectroscopy, and while the image of the form of the sample and the irradiation point of the illumination light for spectroscopy is acquired by the photography camera, the sample is excited by the illumination light for spectroscopy. A spectroscopic measurement method for spectroscopically measuring the light, which is an irradiation step of irradiating the sample with the illumination light for photographing and irradiating a plurality of places with the illumination light for spectroscopy, an image of the form of the sample, and the spectroscopy. An image acquisition step of acquiring images of a plurality of irradiation points of the illumination light, a spectroscopic measurement step of spectroscopically measuring the light excited from the plurality of irradiation points by the spectroscopic illumination light, and a form of the acquired sample. In the image of, an image processing step of extracting an image region composed of the same structure from the image information and dividing each extracted image region as a closed region, and spectroscopy of the spectroscopic illumination light for each of a plurality of irradiation points. The measurement result is superimposed on a plurality of irradiation points of the spectroscopic illumination light in the image in the form of the sample divided into the respective image regions, and the spectroscopy of the plurality of irradiation points of the spectroscopic illumination light in the respective image regions is performed. It is composed of a region determination step of specifying the structure of each image region based on the measurement result.

The spectroscopic measurement method is a method of determining the number of irradiation points of spectroscopic illumination light having spectral measurement results showing the same structure for a plurality of irradiation points of the spectroscopic illumination light in one image region in the region determination step. 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 irradiation step, the spectroscopic illumination light is divided into a plurality of spectroscopic illumination lights by the illumination light dividing means and simultaneously irradiated to the sample, and the image acquisition step and the spectroscopic measurement step are performed at the same time. It is to be implemented.

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

A spectroscopic measuring device that carries out the spectroscopic measurement method, wherein a spectroscopic illumination light source having a predetermined wavelength, a spectroscope, a photographing camera, an imaging illumination light source, and a total reflection mirror having pinholes formed therein. A dichroic mirror that transmits only spectroscopic illumination light having a predetermined wavelength and light having a wavelength shorter than that is provided, and the fully reflective mirror and the dichroic mirror are arranged on the optical axis of the spectroscopic illumination light. The spectroscopic illumination light from the spectroscopic illumination light source passes through the pinhole of the all-reflection mirror and irradiates the sample, and the light excited by the spectroscopic illumination light irradiated on the sample is the dichroic. The illumination light for photography reflected by the mirror and incident on the spectroscope, and the illumination light for photography from the illumination light source for photography is reflected by the all-reflection mirror and is reflected on the optical axis of the illumination light for spectroscopy. The imaging illumination light reflected from the sample is reflected by the all-reflection mirror in a state where the optical axis of the sample is aligned with the optical axis of the spectral illumination light. It is incident on the shooting camera.

The present invention has the following effects.

In the spectroscopic measurement method, the spectroscopic illumination light in the image area is irradiated by applying the spectroscopic measurement results of a plurality of points in the image area set as a range composed of one structure to the image area. The structure of the entire image area including the missing part is identified. As a result, the structure constituting the predetermined region can be specified accurately 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 inside of the image region is measured.

In the spectroscopic measurement method, one result is derived from the whole of each spectroscopic measurement result in the image region and judged, so that the structure of the entire image region can be accurately specified even if the measurement result includes an erroneous judgment. .. Thereby, the structure constituting the predetermined region can be accurately specified.

In the spectroscopic measurement method, spectroscopic illumination light is applied to a plurality of points in the image region at one time. Thereby, the structure constituting the predetermined region can be specified with high accuracy. In addition, the measurement time can be shortened as compared with the case where the measurement density is increased and the inside of the image region 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 constituting the predetermined region can be specified with high accuracy.

In the 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 measurement results are applied to the image region to illuminate the spectroscopic illumination in the image region. The structure of the entire image region including the unilluminated portion is identified. As a result, the structure constituting the predetermined region can be specified accurately and accurately. In addition, the measurement time can be shortened as compared with the case where the measurement density is increased and the inside of the image region is measured.

The schematic which shows the whole structure in one Embodiment of a Raman spectroscopic measuring apparatus. The block diagram which shows the control structure in one Embodiment of a Raman spectroscopic measuring apparatus. The figure which shows the flowchart which shows the process in one Embodiment of Raman spectroscopic measurement method. The schematic diagram which shows the irradiation mode of a laser beam in one Embodiment of a Raman spectroscopic measuring apparatus. The schematic diagram which shows the irradiation mode of the illumination light for photography and the condensing mode of the reflected light in one Embodiment of a Raman spectroscopic measuring apparatus. The schematic diagram which shows the mode of condensing Raman scattered light to a spectroscope in one Embodiment of a Raman spectroscopic measuring apparatus. (A) A diagram showing an image of a sample form taken by a camera for photographing and an image of a plurality of irradiation points of laser light in one embodiment of a Raman spectrophotometer, (b) two-dimensional of the irradiation points in FIG. 7 (a). The figure which shows the image of the state which the arrangement is reconstructed into the one-dimensional arrangement by the multi-optical fiber. (A) A diagram showing an image obtained by extracting an image region consisting of the same structure from image information in an image taken by a camera for photographing in one embodiment of a Raman spectroscopic measuring apparatus, (b) and an independent image region in FIG. 8 (a). The figure which shows the image divided as a closed area. FIG. 8B is a diagram showing an image in which the spectral measurement results are superimposed on the irradiation point in FIG. 8B, and FIG. 9B is a graph showing a graph showing the Raman spectrum of the irradiation point in the first image region of FIG. 9A.

First, the Raman spectroscopic measurement device 1 which is an embodiment of the Raman spectroscopic measurement device which is a spectroscopic measurement device for carrying out the spectroscopic measurement method will be described with reference to FIGS. 1 and 2. In the present embodiment, the Raman spectroscopic measurement device 1 will be specifically described as the spectroscopic measurement device, but the present invention is not limited to this, and a spectroscopic measurement device using various spectroscopic illumination lights such as a fluorescence spectroscopic measurement device may also be used. The same is true.

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

The laser light source 2 oscillates the laser light L1 which is the spectroscopic illumination light for generating the Raman scattered light L2. The laser light source 2 oscillates a laser beam L1 having a predetermined wavelength. In the present embodiment, 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 laser light L1 having a short wavelength.

The first lens 3 for laser light is a lens that makes the incident light parallel light. The first lens 3 for laser light is arranged so as to be 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.

The microlens array 4, which is an illumination light dividing means, divides the incident laser light L1 into a plurality of laser lights L1. In the microlens array 4, the microlenses are formed in a grid pattern. The microlens array 4 is arranged so as to be adjacent to the first lens 3 for laser light on the optical axis of the laser light L1 so that the laser light L1 from the first lens 3 for laser light is incident. The microlens array 4 is configured to divide the incident laser light L1 into a plurality of optical paths and emit the laser light L1 from the microlens array 4. In the present embodiment, the illumination light dividing means is composed of the microlens array 4, but the present invention is not limited to this, and any optical path dividing 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 arranged so as to be 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. The second lens 5 for laser light is configured to emit the laser light L1 divided into a plurality of incident optical paths from the second lens 5 for laser light so as to pass through a predetermined focusing position P.

A pinhole 6a is formed in the center of the total reflection mirror 6. The total reflection mirror 6 is arranged so as to be adjacent to the second lens 5 for laser light on the optical axis of the laser light L1 so that the laser light L1 from the second lens 5 for laser light is incident. Further, the total reflection mirror 6 is arranged so that the focusing position P of the laser light L1 divided into a plurality of optical paths transmitted through the second lens 5 for laser light and the position of the pinhole 6a coincide with each other. That is, in the total reflection mirror 6, the laser beam L1 divided into a plurality of optical paths is focused at the position of the pin hole 6a of the total reflection mirror 6 and passes through the pin hole 6a without interfering with the total reflection mirror 6. It is configured.

In the present embodiment, the total reflection mirror 6 is arranged so as to have an inclination angle of 45 degrees with respect to the optical axis of the laser beam L1. The total reflection mirror 6 is a pinhole of the total reflection mirror 6 so that the light beam 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 configured to reflect at a portion other than 6a. On the other hand, the total reflection mirror 6 directs 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 and pinhole 6a of the total reflection mirror 6. It is configured to reflect at other parts. 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, respectively, and may be arranged appropriately in terms of equipment 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 having the wavelength of the laser light L1 and the wavelength shorter than that. The dichroic mirror 7 is arranged so as to be 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 is incident. Further, the dichroic mirror 7 is arranged so as to have an inclination angle of 45 degrees with respect to the optical axis of the laser beam L1. That is, the dichroic mirror 7 is configured to reflect Raman scattered light L2 having a long wavelength 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 collects the laser beam L1. The imaging lens 8 is arranged so as to be 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 is incident. Further, in the imaging lens 8, Raman scattered light L2 generated from the irradiation point of the laser beam L1 irradiated to the sample S is incident on the sample S side of the imaging lens 8.

The Raman imaging lens 9 is a lens that collects Raman scattered light L2 and causes it to enter the Raman spectroscope 10. The Raman imaging lens 9 is arranged so as to be adjacent to the dichroic mirror 7 at a position 90 degrees with respect to the optical axis of the laser beam L1 so that the light from the dichroic mirror 7 is incident. 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 Raman scattered light L2. The Raman spectroscope 10 is composed of, 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 arranged so as to be adjacent to the Raman imaging lens 9 at a position 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. Has been done. Further, in the present embodiment, in order to cut unnecessary short wavelength light, it is preferable to have a configuration in which a long pass filter 10a is inserted between the dichroic mirror 7 and the Raman spectroscope 10.

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

The photographing imaging lens 12 is a lens that collects light on the photographing camera 13. The imaging lens 12 for photographing is arranged so as to be adjacent to the half mirror 11 at a position parallel to the optical axis of the laser beam L1 so that the light reflected by the half mirror 11 is incident. The photographing imaging lens 12 is configured to concentrate light on the photographing camera 13.

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

The photographing illumination light source 14 generates the photographing illumination light L3. The photographing illumination light source 14 is arranged adjacent to the half mirror 11 at a position 90 degrees with respect to the optical axis of the laser light L1 so as to irradiate the total reflection mirror 6 with the photographing illumination light L3. The photographing illumination light source 14 is configured to emit the 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 be substantially configured such that a CPU, ROM, RAM, HDD and the like are connected by a bus, or may be configured to be composed of 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 spectroscope 10 and can control the Raman spectroscope 10. Further, the control device 15 can acquire the spectroscopic measurement result from the Raman spectroscope 10.

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

In the Raman spectroscopy measuring device 1 configured as described above, the laser light L1 emitted from the laser light source 2 is divided into a plurality of optical paths by the microlens array 4 and the laser light L1 is applied to a plurality of locations of the sample S at a time. Is irradiated. At the same time, in the Raman spectroscopy measuring device 1, the photographing illumination light L3 from the photographing illumination light source 14 is irradiated to the sample S through 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 device 1 spectroscopically measures the Raman scattered light L2 by the Raman spectroscope 10. On the other hand, when the photographing illumination light L3 emitted from the photographing illumination light source 14 to the sample S reaches the sample S, it becomes the light reflected from the sample S (hereinafter, simply referred to as “reflected light L4”). The reflected light L4 from the sample S is reflected by the total reflection mirror 6 and the half mirror 11 and incident on the photographing camera 13. The Raman spectroscopy measuring device 1 obtains an image in the form of the sample S and an image 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 device 1 identifies the structure of the sample S from the spectroscopic measurement result, the image of the form of the sample S, and the images of the plurality of irradiation points of the laser beam L1 by the control device 15.

Next, the spectroscopic measurement method in the Raman spectroscopic measuring apparatus 1 will be described with reference to FIGS. 3 to 9.

As shown in FIG. 3, the spectroscopic measurement method includes, as step K110, an irradiation step of irradiating the sample S with the illumination light L3 for photographing and irradiating a plurality of places with the laser light L1 which is the illumination light for spectroscopy, and the step K120. An image acquisition step of acquiring an image V composed of an image of the form of the sample S and an image of a plurality of irradiation points of the laser beam L1 and a Raman light excited by the laser beam L1 from the plurality of irradiation points as the step K130. In the spectroscopic measurement step of spectroscopically measuring each of the above and the image of the form of the sample S of the acquired image V as the step K140, an image of the same structure is constructed from the image information of hue, lightness, saturation, and brightness. An image processing step of extracting an aggregate of existing pixels as an image region and dividing each extracted image region as a closed region, and as step K150, the spectroscopic measurement results of each of a plurality of irradiation points of the laser light L1 are obtained by a laser in image V. It is composed of a region determination step of superimposing an image of a plurality of irradiation points of light L1 and specifying a structure of each image region based on a spectroscopic measurement result. The spectroscopic measurement method is carried out from step K110 to step K150 in order.

As shown in FIG. 4, in the step K110 (see FIG. 3), in the Raman spectroscopic measuring apparatus 1, the laser light L1 (see the light ink portion) oscillated by the laser light source 2 is used for the laser light as the irradiation step of the laser light L1. It is incident on 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 lens 3 for laser light 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 L1 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 the long wavelength light. The laser beam L1 transmitted through the dichroic mirror 7 is incident on the imaging lens 8. The laser beam L1 is emitted from the imaging lens 8 so as to concentrate on the surface of the sample S for each optical path. The laser beam L1 irradiates a plurality of points of the sample S. As a result, the laser light L1 generates Raman scattered light L2 (see FIG. 6) having a spectrum corresponding to its molecular structure from the irradiation site of the sample S.

In this way, even if the laser light L1 is divided into a plurality of optical paths, the Raman spectroscopy measuring device 1 is focused by the second lens 5 for laser light and passes through the pinhole 6a of the total reflection mirror 6 without interfering with the laser light L1. It is configured in. Further, the Raman spectroscopic measurement device 1 is configured so 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 spectroscopy measuring device 1, the laser light L1 is not shielded by the total reflection mirror 6 and the dichroic mirror 7 arranged on the optical axis of the laser light L1. As a result, it is possible to suppress the loss that occurs before the laser beam L1 from the light source reaches the sample S.

As shown in FIG. 5, in the step K110 (see FIG. 3), the Raman spectroscopic measurement device 1 performs the photographing illumination light L3 from the photographing illumination light source 14 toward the half mirror 11 as an irradiation step of the photographing illumination light L3. 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 pin hole 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 the dichroic mirror 7 that reflects the long wavelength light along the optical axis of the laser light L1. In the imaging illumination light L3, only light in a short wavelength region passes through the dichroic mirror 7 and is incident on the imaging lens 8. The light in the short wavelength region of the photographing illumination light L3 transmitted through the dichroic mirror 7 is emitted from the imaging lens 8 so as to be focused on the surface of the sample S. Light in the short wavelength region of the imaging illumination light L3 is applied to the sample S and reflected on the surface of the sample S.

In step K120 (see FIG. 3), in the Raman spectroscopic measurement device 1, as an image acquisition step, 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 is the imaging lens 8. Is incident from the sample S side. (Hereinafter, when light is incident on the imaging lens 8 from the sample S side, it is simply referred to as “sample side lens 8”). That is, the reflected light L4 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 emitted 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 L4 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 toward the photographing camera 13 by the half mirror 11.

As shown in FIG. 7A, in the Raman spectroscopic measurement device 1, the photographing 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 an image of a plurality of irradiation points s1, s2, s3 ... S16 of the laser beam L1 are simultaneously displayed. Further, 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 spectroscopy measuring device 1, the control device 15 acquires an image V from the photographing camera 13. In this way, the Raman spectroscopic measuring device 1 can simultaneously confirm the surface state of the sample S at the plurality of irradiation points s1, s2, s3 ... S16 and the Raman spectrum of the Raman scattered light L2 (see FIG. 3). ).

With this configuration, the Raman spectroscopic measurement device 1 is configured so that the reflected light L4 from the sample S is not reflected by the dichroic mirror 7. Further, in the Raman spectroscopy measuring device 1, the reflected light L4 from the sample S is reflected by a portion other than the pinhole 6a of the total reflection mirror 6. That is, in the Raman spectroscopy measuring device 1, the reflected light L4 from the sample S is hardly obstructed by the total reflection mirror 6 and the dichroic mirror 7 arranged on the optical axis of the laser light L1. As a result, it is possible to suppress the loss that occurs before the reflected light L4 from the sample S reaches the camera. In the present embodiment, the photographing illumination light L3 from the photographing illumination light source 14 and the reflected light L4 from the sample S are configured to have the same optical axis by the half mirror 11, but the present invention is limited to this. Instead, the photographing camera 13 and the photographing illumination light source 14 may be integrally configured and the half mirror 11 may be omitted.

As shown in FIG. 6, in step K130 (see FIG. 3), in the Raman spectroscopic measurement apparatus 1, as a spectroscopic measurement step, long-wavelength Raman scattered light L2 generated from each irradiation point of the sample S is transmitted to the sample side lens 8. Be incidented. The Raman scattered light L2 composed of a plurality of optical paths is incident on and emitted from 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 L2 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 spectroscope 10.

As shown in FIG. 7B, the Raman spectroscopic measuring apparatus 1 multiplies the Raman scattered light L2 from the irradiation points s1, s2, s3 ... S16 of the laser light L1 via the Raman imaging lens 9. Light is received at the two-dimensional array portion at 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 outputs it to the diffracted lattice from the other end of the multi-optical fiber 16. The Raman scattered light L2 converted into the emitted one-dimensional array is configured to be guided to the area sensor via the diffraction grating. As a result, the Raman spectroscopic measuring device 1 can measure the Raman spectroscopic spectra of the plurality of irradiation points s1, s2, s3 ... S16 with the Raman spectroscope 10.

With this configuration, the Raman spectroscopic measurement device 1 reflects the Raman scattered light L2 composed of a plurality of optical paths generated by the laser light L1 divided into a plurality of optical paths toward the Raman spectroscope 10 by the dichroic mirror 7. Let me. That is, in the Raman spectroscopic measurement device 1, the Raman scattered light L2 composed of a plurality of generated optical paths can be incident on the Raman spectroscope 10. Therefore, in the Raman spectroscopic measurement device 1, the sample S is irradiated with the laser light L1 divided into a plurality of optical paths, and the spectroscopic measurement step of performing the spectroscopic measurement of the Raman scattered light L2 from the sample and the image V are acquired from the reflected light L4. The image acquisition step to be performed can be performed at the same time.

As shown in FIG. 8, in the step K140 (see FIG. 3), the control device 15 of the Raman spectroscopic measurement device 1 constitutes an image in the image in the form of the sample S of the acquired image V as an image processing step. The range of the same structure is specified based on the image information assigned to each unit pixel (hereinafter, simply referred to as "pixel") which is the minimum unit. In the control device 15, when at least one value arbitrarily selected among the hue, lightness, saturation, and brightness, which is image information between adjacent pixels, exceeds a specified value, the adjacent pixels are selected. It is determined that the images of different structures are formed.

The control device 15 sets boundaries for all pixels based on the determination result based on image information between adjacent pixels, and extracts an aggregate of pixels constituting an image of the same structure as an image area ( FIG. 8A). Similarly, the control device 15 extracts an aggregate of pixels constituting another image of the same structure in the image in the form of the sample S of the image V as an image region, and is an independent closed region. It 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, but the present invention is not limited to this, and the same structure is used using the image information. It suffices if the image area representing the body can be extracted.

As shown in FIG. 9A, in step K150 (see FIG. 3), the control device 15 of the Raman spectroscopic measurement device 1 is a first image which is a closed region of the same structure in image V as a region determination step. The spectroscopic measurement results of the plurality of irradiation points s1, s2, s3 ... S16 of the laser beam 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 shows the same structure among the spectroscopic measurement results of the plurality of irradiation points s1, s2, s3, s4, s5, and s6 of the laser beam L1 in the first image region Ar1 composed of the same structure. It is determined whether or not the ratio of the number of irradiation points, which is the spectral measurement result, is equal to or greater than a predetermined value, and if it is equal to or greater than the predetermined value, the structure in the first image region Ar1 is specified as the structure of the spectral measurement result. ..

The Raman spectrometer 10 (see FIG. 6) outputs the 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 Raman spectra at irradiation points s1, s2, s3, s4, s5, and s6 from the Raman spectroscope 10. Of the irradiation points s1, s2, s3, s4, s5, and s6, the waveform and peak position of the irradiation points s4 and s5 are different from the waveform and peak position of the irradiation points s1, s2, s3, and s6. This result shows that the structure at the irradiation points s1, s2, s3, and s6 (black circles in Ar1 in FIG. 9A) and the structure at the irradiation points s4 and s5 (white circles in Ar1 in FIG. 9A). It shows that it is different.

In the present embodiment, among the spectral measurement results of the six irradiation points s1, s2, s3, s4, s5, and s6 in the first image region Ar1, the four points of the irradiation points s1, s2, s3, and s6 are the same first. In the case of the spectroscopic measurement result showing the structure Sa (black circle in FIG. 9A) Ar1, the ratio of the number of irradiation points which is the spectroscopic measurement result showing the first structure Sa in the first image region Ar1 is 4/6 ≈ 0.67 = 67%. When the predetermined value is 65%, the control device 15 sets the first image region Ar1 to the first structure Sa because the ratio of the number of irradiation points, which is the spectral measurement result indicating the first structure Sa, is larger than the predetermined value. Identify as. Similarly, among the spectral measurement results of the five irradiation points s7, s8, s9, s10, and s11 in the second image region Ar2, the second structure Sb in which the four irradiation points s7, s8, s10, and s11 are the same is used. In the case of the spectroscopic measurement result shown (FIG. 9 (a) 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. 8.8 = 80%. Therefore, the control device 15 identifies the second image region Ar2 as the second structure Sb.

On the other hand, among the spectral measurement results of the five irradiation points s12, s13, s14, s15, and s16 in the third image region Ar3, the three points of the irradiation points s14, s15, and s16 show the same first structure Sa. In the case of the result (black circle in FIG. 9A Ar3), the ratio of the number of irradiation points, which is the spectroscopic measurement result showing the first structure Sa in the third image region Ar3, is 3/5 = 0.6 = It becomes 60%. Since the ratio of the number of irradiation points, which is the spectroscopic measurement result showing the first structure Sa, is less than the predetermined value of 65% in the present embodiment, the control device 15 identifies the third image region Ar3 as the first structure Sa. Can not. Therefore, the Raman spectroscopic measurement apparatus 1 re-executes the irradiation step of the laser beam L1, the image acquisition step, the spectroscopic measurement step, the image processing step, and the region determination step for the third image region Ar3. The control device 15 divides the structures of the first image region Ar1, the second image region Ar2, and the third image region Ar3 divided into closed regions of the same structure according to the above steps into the ratio of the spectral measurement results. Judge based on.

With this configuration, the Raman spectroscopic measurement device 1 acquires an image V including an image in the form of the sample S and images of a plurality of irradiation points s1, s2, s3 ... S16 of the laser beam L1. , A plurality of irradiation points s1, s2, s3 ... S16 of the laser beam L1 in the sample S can be observed. Further, the Raman spectroscopic measurement device 1 is set in the first image region Ar1, the second image region Ar2, and the third image region Ar3, which are set as a range composed of the same structure based on the image information. By superimposing the spectral measurement results of a plurality of locations on each image region, 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 beam L1. The entire structure is identified. As a result, the structures constituting the first image area Ar1, the second image area Ar2, and the third image area Ar3 can be accurately specified. Further, the measurement time can be shortened as compared with the case of measuring the first image region Ar1, the second image region Ar2, and the third image region Ar3 with a scanning microscopic Raman spectroscope.

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 beam L1 divided into a plurality of optical paths, but the present invention is not limited to this. Further, an optical path for photographing is provided at a position on the laser light source 2 side and an optical path for Raman scattered light L2 is provided at a position on the sample S side with reference to the optical path of the laser light L1, but the present invention is not limited to this. Absent. If the Raman spectroscopy measuring device 1 has a configuration in which the optical path for photography is secured by using the total reflection mirror 6 and the optical path of Raman scattered light L2 is secured by using the dichroic mirror 7 with reference to the optical path of the laser light L1. Good. The above-described embodiment only shows a typical embodiment, and can be variously modified and implemented within a range that does not deviate from the gist of one embodiment. It goes without saying that it can be carried out in various forms, and the scope of the present invention is indicated by the description of the claims, and further, the equal meaning described in the claims, and all within the scope. Including changes.

1 Spectral measuring device S Sample V image L1 Laser light L2 Raman scattered light L3 Illumination light for photography L4 Reflected light Ar1 First image area Ar2 Second image area Ar3 Third image area Sa First structure Sb Second structure

Claims (5)

Light excited by the spectroscopic illumination light while irradiating the sample with the illumination light for photography and the illumination light for spectroscopy and acquiring an image of the form of the sample and the irradiation point of the illumination light for spectroscopy by the photography camera. It is a spectroscopic measurement method that spectroscopically measures
An irradiation step of irradiating the sample with the illumination light for photographing and irradiating a plurality of places with the illumination light for spectroscopy.
An image acquisition step of acquiring an image in the form of the sample and an image of a plurality of irradiation points of the spectroscopic illumination light, and
A spectroscopic measurement step of spectroscopically measuring light excited from a plurality of irradiation points by the spectroscopic illumination light.
An image processing step of extracting an image region composed of the same structure from the image information in the acquired image in the form of the sample and dividing each extracted image region as a closed region.
The spectral measurement results for each of the plurality of irradiation points of the spectroscopic illumination light are superimposed on the plurality of irradiation points of the spectroscopic illumination light in the image in the form of the sample divided into the respective image regions, and the inside of the respective image regions. In the region determination step of specifying the structure of each image region based on the spectroscopic measurement results of a plurality of irradiation points of the spectroscopic illumination light in
A spectroscopic measurement method consisting of. In the area determination step, the ratio of the number of irradiation points of the spectral illumination light having the spectral measurement result showing the same structure to the plurality of irradiation points of the spectral illumination light in one image region is equal to or more than a predetermined value. The spectroscopic measurement method according to claim 1, wherein the structure of the image region is specified as the structure of the spectroscopic measurement result. The claim that in the irradiation step, the spectroscopic illumination light is divided into a plurality of spectroscopic illumination lights by an illumination light dividing means and the sample is simultaneously irradiated, and the image acquisition step and the spectroscopic measurement step are carried out at the same time. 1 or the spectroscopic measurement method according to claim 2. The spectroscopic measurement method according to any one of claims 1 to 3, wherein in the image processing step, the image information is composed of at least one information of hue, lightness, saturation, and brightness. A spectroscopic measurement apparatus that implements the spectroscopic measurement method according to any one of claims 1 to 4.
A spectroscopic illumination light source of a predetermined wavelength and
With a spectroscope
With a camera for shooting
Illumination light source for photography and
A total reflection mirror with pinholes and
A dichroic mirror that transmits only spectroscopic illumination light having a predetermined wavelength and light having a wavelength shorter than that is provided.
The total reflection mirror and the dichroic mirror are arranged on the optical axis of the spectroscopic illumination light.
The spectroscopic illumination light from the spectroscopic illumination light source passes through the pinhole of the total reflection mirror and irradiates the sample.
The light excited by the spectroscopic illumination light applied to the sample is reflected by the dichroic mirror and incident on the spectroscope.
The photographing illumination light from the photographing illumination light source is reflected by the total reflection mirror, and the sample is irradiated with the optical axis of the photographing illumination light aligned with the optical axis of the spectroscopic illumination light.
A spectroscopic measurement device in which the imaging illumination light reflected from the sample is reflected by the total reflection mirror in a state where the optical axis is aligned with the optical axis of the spectroscopy illumination light and is incident on the imaging camera.

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