JPH0290040A - Microscope type spectrophotometer - Google Patents

Abstract

PURPOSE:To make it possible to measure spectroscopic luminous intensity at the minute part of a large specimen by using a specimen stage wherein an optical means for converting light rays for analysis into parallel light rays and an optical means for receiving the light rays and projecting the light rays on the specimen are built in. CONSTITUTION:When measurement is performed in a reflecting mode, parallel infrared rays 35 from a spectrophotometer 34 are reflected through a switching planar reflecting mirror 10, a parabolic reflecting mirror 11, elliptical reflecting mirror 32, an aperture 33 and an edge mirror 16. The infrared rays which are reflected from a specimen on a specimen stage 15 are made to pass the rear side of the edge mirror 16 and detected with an infrared-ray detector 17. When measurement is performed in a a transmitting mode, the reflecting mirror 10 is switched, and the focal point is formed on the stage 15 by passing the infrared rays 35 through a planar reflecting mirror 12, a parabolic reflecting mirror 18, planar reflecting mirrors 19 and 20 and an elliptical reflecting mirror 14. Here, the reflecting mirrors 18, 14, 19 and 20 are mounted on a boat type stage 21. Therefore, even a large specimen can be mounted on the stage 21. The spectroscopic luminous intensity at the minute part of the surface of the large specimen can be measured.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an apparatus for measuring infrared absorption spectra of extremely small parts, and in particular, it is capable of simultaneously observing the measurement site and is useful for analyzing substances in extremely small parts. The present invention relates to a microscope device for measuring infrared absorption spectra, which is suitable for accurately measuring infrared absorption spectra.

[Conventional technology]

Generally, an infrared absorption spectrum measuring device is already known and consists of an infrared light source, a monochromator for obtaining infrared a intensity for each wavelength component, an interferometer, an infrared detector, a sample chamber, etc. ing. Fourier infrared spectrophotometers using interferometers are highly sensitive for measuring infrared absorption spectra in extremely small areas. Red Microscopes (The Desig)
n, Sample Handling and Ap
-11 oation of Infrared Mio
roscopes, ASTM STD 949. Am
erican 5ociet7 for Testin
gand Materials + Ph1ladel
phia (1987), pp. 27-31, and Infrared Microscopy [Practical Spaotroacop 75ar, published by Marshall Detzker Publishing Co., Ltd.].
ies Volume 6 InfraredMicr
ospectrosoop711ted b)' Ro
bart GMesaersohmmadt MARCF
This has been done in combination with a microscopic apparatus such as that discussed in JL DliilKKFVRINC, (198B), pages 85-87.

These documents contain schematic diagrams of microscopes such as those shown in FIGS. 4 and 5. 1 in Figure 4 and IFi sample stage in Figure 5, 2.5 in Figure 4 and 2 in Figure 5 are reflective objective lenses, and 3 in the fifth factor is an ellipsoidal reflective condenser for illuminating the sample. , 4, 4 in Fig. 4 and 4.1 in Fig. 5 are apertures (holes) for limiting the measurement field of view, 5 in Fig. 5 is a reflective objective lens for condensing light, 6 and 5 in Fig. 4 are 6 in the figure is an infrared detector.

The infrared rays from the Fourier transform infrared spectrometer are 5 in FIG. 4 and 7 in FIG. 5. The infrared absorption spectrum of a sample is generally measured in either transmission or reflection mode. The infrared rays from the Fourier transform infrared spectrometer in transmission measurement mode are shown at 7K in Figure 4.5, and the infrared rays measured in reflection mode are shown at 5 in Figure 4, but are not shown in Figure 5, probably at 5K. It is thought that this is done by irradiating the reflective objective lens 2 in Figure 5 through the ellipsoidal reflector 8 in Figure 5, but the details are not described. Since the optical system of a microscope is used, no consideration is given to the size of the object to be measured. That is, the downward movement of the sample stage (1 in Figure 4.5) directs the infrared condensing mirror to the sample (2 in Figures 4 and 5), and the upward movement directs the reflection objective lens (4. Due to the limitation in 3) in Fig. 5, there is a drawback that the size of the sample that can be mounted on the sample stage is limited. In the case of spectroscopic measurement using the transmission method, the thickness of the sample that can be measured is 10 to 20 mm in infrared spectrometry.
μm, and even normal spectroscopic measurements in the visible range are several meters long, so they are not applicable because they cannot measure large samples. However, in spectroscopic measurements using the reflection method, the surface of the sample is the subject of measurement. However, in such an apparatus where the vertical movement of the sample stage is limited, a problem arises in that when measuring a large sample, it cannot be mounted on the sample stage. In addition, using various spectroscopic measurement jigs for measurement, this problem can be solved by lowering the mirror for the optical path of the infrared light to the infrared condensing mirror for the sample in Figures 4 and 5. The vertical movement of the sample stage was restricted because no consideration was taken to raise the upper VC6 of the reflective objective lens in factor 2 of 4.5. In addition, spectroscopic measurements such as infrared absorption spectroscopy are strongly affected by water vapor, carbon dioxide, etc. in the atmosphere. For this reason, it is necessary to minimize changes in the atmosphere over time in all infrared light paths. No consideration has been given to this point, and temporal changes in water vapor, carbon dioxide, etc. in the optical path cause noise in high-sensitivity measurements of extremely small areas within a sample. The purpose of the present invention is to provide an apparatus that can perform spectroscopic measurements of extremely small regions of samples of various sizes, especially large samples, with high sensitivity using the reflection method. It is necessary to increase the range of movement of the stage up and down so that even large samples can be mounted on the sample stage. To this end, the optical path of the infrared rays to the mirror was devised so that the mirror could be moved up and down together with the sample stage. This is possible by making it possible to always reproduce the focus of the infrared rays on the surface of the sample stage even if the infrared condensing mirror 1 in FIG. 5 moves up and down with the sample stage. For this purpose, the condensing mirror 5 in FIG. 5 and the reflecting mirror 9 in FIG. 5 are moved up and down simultaneously. In FIG. 5, the collector mirror 3 is an ellipsoidal reflector. The focal point 100 of this mirror is also the focal point where infrared rays from a Fourier transform infrared spectrophotometer are collected. When the condensing mirror 3 in Figure 5 is lowered to widen the width of the sample stage, the position of the focal point 100 of this mirror will also be lowered, and the infrared rays from the Fourier transform infrared spectrophotometer will be removed from the focal point. As a result, the infrared rays cannot be focused on the sample stage surface. This problem was solved by making the infrared rays shown at 7 in FIG. 5 parallel rays, and by making the infrared rays from the Fourier transform infrared spectrophotometer also parallel rays. By doing this, even if the condensing mirror 3 in FIG. 5 is lowered down, the focus of the infrared rays will always be on the sample stage surface. For this purpose, the condensing mirror 5 in Figure 5 should be a parabolic reflector, or
This is made possible by making the reflecting mirror 9 in FIG. 5 a parabolic reflecting mirror and the condensing mirror 3 in FIG. 5 an ellipsoidal reflecting mirror. That is, the reflecting mirror 9 in FIG. 5 moves on a parallel optical path,
Moreover, it is possible to make the moving axis of the reflecting mirror parallel to the optical path. The present invention was also achieved by increasing the distance between the sample stage and the reflective objective lens by vertically moving the microscope on the reflective objective lens side, which is the fifth factor. In this case as well, parallel infrared rays are created parallel to the axis of movement of the microscope, and the microscope is moved up and down along this parallel ray. By doing this, it was possible to focus the atmospheric pressure objective lens on a specific location.

Furthermore, in order to achieve the purpose of minimizing changes over time in water vapor, carbon dioxide, etc. in the atmosphere, the outside of the infrared light path is sealed as much as possible. In particular, since the infrared condensing mirror sample stage is integrated in the above-mentioned objective, the opening becomes wider. The parts that do not move are simply covered with shielding plates, and the sliding parts are covered with sliding shielding films to prevent water vapor, carbon dioxide, etc. from entering the atmosphere, and light from outside.

[Effect]

The effects of the present invention will be explained with reference to FIGS. 1, 2, and 3. 10 are two plane reflecting mirrors that receive parallel infrared rays modulated in frequency by the interferometer of the 7-Lier transform infrared spectrophotometer, and one is an optical system for the reflection (epi-illumination) measurement mode. A parabolic reflector is a mirror that directs infrared rays in the direction of the mirror. The other is an optical system in transmission measurement mode and is a mirror for directing infrared rays toward the 12 flat reflecting mirrors. These can be switched by a lever. This infrared rays are focused and irradiated onto the sample 15 by 13 reflective objective lenses and 14 ellipsoidal reflectors.

In the case of reflection measurement mode, reference numeral 16 is an edge mirror, and the infrared rays coming from the parabolic reflector 11 are reflected by this mirror toward the reflection objective lens 13, and the infrared rays from the sample pass through the back side of this edge mirror 17. This leads to an infrared detector. In the transmission measurement mode, the 16 edge mirrors are removed from the optical path for measurement.

18 is a parabolic reflector and 14 ellipsoid reflectors and 19°20
The plane reflector is mounted inside the 21 master stage.

Further, the sample stage 23 is located above the ellipsoidal reflecting mirror of the 21 matrix stages. This master stage 21 is moved up and down by a drive device 22. The infrared rays 24 reflected by 10 become infrared rays 25 which are reflected downward at right angles by 12 plane reflectors. Further, the infrared rays 26 are reflected at right angles by the 18 parabolic reflectors. Furthermore, since the infrared rays 25 are parallel rays, even if the mother stage 21 is moved up and down, the mother stage and the subsequent optical system are not affected. By doing so, it is possible to eliminate the fixed infrared irradiation condensing mirror below the sample stage, and this sample stage has the effect of being able to freely move downward.

FIG. 2 is an enlarged view of the matrix stage. The portion of this main stage that is exposed from the microscope body is closed except for the hole 124 for condensing light and irradiating the sample through nine infrared rays.

125.126Fi There are shielding membranes attached to the top and bottom of the boat-shaped stage that move up and down as the mother stage moves up and down. That is, 27 is a wire that pulls this, and a weight 28 is attached to the other end.Also, the other lower shielding film is pulled by a 2P spring, and the balance between the two is maintained. This allows the master stage to move up and down without any load, and also has the effect of preventing air or sources from entering outside the microscope.

The operation of moving the microscope body up and down will be explained with reference to FIG. In this case as well, the incident angle and reflection angle of the infrared rays to the 11 parabolic reflectors are 45 degrees, that is, the infrared rays are bent at right angles by the 11 parabolic reflectors. By keeping the incident light beam on the parabolic reflector of Mano 11 parallel to the movement axis of the vertical movement of this microscope, even if the microscope is moved up and down,
The optical system in which the infrared rays are focused by the reflective objective lens has an unchanging effect. This optical system is controlled by the vertical movement of the microscope.
) It also has the effect of preventing a significant decrease in the incidence efficiency of infrared rays into the reflective objective lens due to the change in K.

[Example 1] Example 1 of the present invention will be described below with reference to FIG. 1st
Figure (b) shows an apparatus that can measure the Fourier transform infrared absorption spectrum of a sample using two methods: transmission measurement mode and reflection measurement mode. "Switchable Plane Reflector" 0 consists of two groups of mirrors: a reflector for directing the infrared rays to a parabolic reflector for the reflection (epi-illumination) measurement mode of the Fourier transform infrared spectrophotometer and a transmissive mirror for directing the infrared rays. The measuring mode consists of a mirror for directing infrared rays to the ninth flat reflecting mirror 12, and these mirrors can be switched by a lever.

First, the optical system for reflection mode measurement will be explained based on FIG.
55 to the first focus of the ellipsoidal reflector 52 by parabolic reflection*11, this operation uses an infrared detection plate to accurately align the focus of the parabolic reflector 11 on the pre-designed optical axis.
After that, the second focus of the ellipsoidal reflector 52 is set to 7
An infrared detection plate was used to adjust the focal point of the infrared optical system. The upper half of the edge mirror 16 is a mirror and the lower half is transparent. The infrared rays coming from the ellipsoidal reflecting mirror 32 are reflected by this bowl in the direction 13 of the reflecting objective lens. Furthermore, the nine infrared rays reflected by the sample on the sample stage 15 were made to pass through the back side of this edge mirror 16 and reach the infrared detector 17.

Next, the optical system for transmission mode measurement will be explained.

One switching plane reflecting mirror is switched to direct the parallel infrared rays 555 from the spectrometer toward the plane reflecting mirror 12, and further,
The parabolic reflector 18 condenses the light to the longer focal point of the ellipsoidal reflector 14, and the shorter focus of the ellipsoidal reflector 14 is connected to the sample stage 15 using two mirrors. In addition, the parabolic reflector 18, the ellipsoid reflector 14, and the two plane reflectors are mounted on the matrix stage, and the sample stage 15 is mounted on the matrix stage. was fixed with bolts. Manoko's master stage 21 was designed so that it could be focused by a vertical movement drive device 22 in both reflection mode measurement and transmission mode measurement.

By doing the above, it became possible to freely widen the distance between the sample stage and the reflective objective lens, and even a large sample could be mounted on the sample stage. This makes it possible to measure the reflection infrared absorption spectrum of the surface of an extremely small part of a large sample, which was previously impossible.

In addition, in the case of transmission mode measurement, there are inherent limitations on the thickness of the sample that can be measured in spectroscopic measurements.6 In particular, in the case of infrared spectroscopy, the sample thickness is 20 microns or less, and the wavelength of infrared rays itself Since the distance is long, the depth of focus is deep, and if the optical system is adjusted in advance to the highest sensitivity by moving the sample stage up and down, there is little need for focusing due to differences in samples. When measuring by replacing the reflective objective lens 13 with one of a different magnification, the focal length differs depending on the reflective objective lens, and it is necessary to adjust the position of the condenser mirror for the infrared illumination light from the bottom each time. However, this was not possible with conventional equipment;
The present invention has made this possible for the first time.

[Example 2] Next, Example 2 of the present invention will be described with reference to FIG. ! 2
The figure is an enlarged view of the matrix stage and sample stage. The portion of the main stage 21 exposed from the microscope body is closed except for the hole 124 for condensing light and irradiating the sample through nine infrared rays.

Blackened stainless steel shielding films 125126 were attached above and below the master stage. A wire 27 was attached to the other end of the upper shielding film 126. Manoko's Wire 27
A weight 28 was attached to the tip. A spring 29 is attached to the other end of the lower side of the mother mold stage 21 so that it moves up and down according to the vertical movement of the mother mold stage 21. By keeping both of them in balance, the vertical movement of the mother mold stage 21 can be operated without any load. I made it possible.

As described above, it is possible to prevent air and light from entering outside the microscope, and it is now possible to measure infrared absorption spectra without the influence of noise from water vapor, carbon dioxide, etc., or external light.

[Embodiment 3] Next, Embodiment 6 of the present invention will be explained with reference to FIG. Third
The figure shows an example in which the microscope body is moved up and down. The condensed infrared rays from the Fourier transform infrared spectrophotometer are converted into υ parallel rays by the parabolic reflector 50, and the parabolic reflector 11
I made it look like someone was shooting.

The infrared rays were focused by the parabolic reflector 11 to the first focus of the ellipsoid reflector @32. The focal point of the parabolic reflector 11 was accurately adjusted on the pre-designed original axis, and then the second focus of the ellipsoidal reflector 32 was adjusted using an infrared detection plate so that it was connected to the aperture 3tI. The upper half of the edge mirror 16 is a mirror, and the lower part is intended to be transparent, and the infrared rays coming from the ellipsoidal reflecting mirror 52 are reflected in the direction of the reflective objective lens 13 by this mirror.

Furthermore, the infrared rays reflected by sample 36 are this edge! 116
It passes through the back side of the infrared detector 17 and reaches the infrared detector 17.

A parabolic reflector 30 for condensing infrared light from a Fourier transform infrared spectrophotometer was attached to a microscope mount, and the microscope could be moved up and down via a drive device 31 in a direction perpendicular to the mount. Moreover, the parabolic reflecting mirror 50 and the parabolic reflecting mirror 1
A bellows-shaped rubber cylinder 37 is used to block external air and external light.

As described above, it is now possible to create a wide space under the reflective objective lens of the microscope, and by preparing a suitable sample holder, even the smallest part of the sample can be easily captured. It has become possible to measure the infrared absorption spectrum of the surface.

〔Effect of the invention〕

According to the present invention, since the space under the reflective objective lens of the microscope can be freely enlarged, spectrophotometric measurements can be performed without any restrictions on the size of the sample to be measured. Also, even if you replace the reflective objective lens, the focal length will be ff
Since the optical system can be adjusted immediately after 1Hc, the infrared absorption spectrum of extremely small parts can be measured with simple operation and high sensitivity. This has the effect of providing a microscopic spectrophotometer.

[Brief explanation of the drawing]

Figures 1 (al and b) are diagrams showing details of a spectroscopic microscope according to the present invention. Figure 2 is a diagram showing details of a boat-shaped stage equipped with a sample stage transmitted illumination optical system according to the present invention. Figure 3 shows a device that allows the microscope body to move up and down.
FIG. FIG. 4 and FIG. 5 are diagrams for explaining a conventional example according to the present invention. Explanation of symbols 10...Switching plane reflector 11.18...Parabolic reflector 12...Flat reflector 15...Sample stage 16... ... Edge mirror 14 ... Ellipsoidal reflecting mirror 21 ... Matrix stage 22 ... Vertical movement drive device 125, 126 ... Shielding film 37・・・・・・A bellows-shaped rubber cylinder.

Claims (1)

[Scope of Claims] 1. A microscopic spectrophotometer that is composed of a spectrophotometer, a microscope, and a detector and capable of both transmission and reflection spectrometry and observation, the spectrophotometer or the light source of the spectrophotometer; and a vertically variable sample stage, the sample stage has a built-in optical means (1) for converting the analytical light beam into a parallel light beam, and an optical means (2) for receiving the light beam and irradiating it onto the sample. A microscopic spectrophotometer characterized by the use of a microscopic spectrophotometer. 2. The microscopic spectrophotometer according to claim 1, wherein parabolic reflecting mirrors are used as the optical means (1) and (2). 3. As the optical means (2), a combination of a parabolic reflecting mirror and an ellipsoidal reflecting mirror, or two mirrors on the optical path of these reflecting mirrors, or
2. The microscopic spectrophotometer according to claim 1, characterized in that a plurality of plane reflecting mirrors are used. 4. The microscopic spectrophotometer according to claim 1, wherein the optical axis of the light beam incident on the optical means (2) via the optical means (1) is parallel to the movement axis of the sample stage. 5. The microscope according to claim 1, wherein the vertically variable sample stage has a shielding film that can be moved vertically between the inside and outside of the microscope to prevent outside air and light from entering, and is shielded from areas other than the optical path. Method spectrophotometer. 6. The microscopic spectrophotometer according to claim 5, wherein the vertically variable sample stage has a shutter that can be opened and closed at an irradiation port for the sample. 7. In a microscopic spectrophotometer that is composed of a fixed sample stage, an objective lens and a detector that move up and down, and is capable of spectroscopic measurement and observation using the reflection method, the spectrophotometer or the light source of the spectrophotometer and the An epi-illumination microscope that incorporates an optical means (1) for converting the analytical light beam between the objective lens and the detector into a parallel light beam, and an optical means (3) for receiving the light beam and irradiating the sample. A microscopic spectrophotometer characterized in that these optical axes are parallel. 8. A microscopic spectrophotometer, wherein the spectrophotometer according to any one of claims 1 to 7 is a Fourier transform spectrophotometer.