JPH0968465A - Infrared microscope - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a diffusion reflection spectrum and a highly sensitive emission spectrum from a single sample. SOLUTION: A Cassegrain objective lens 8 included in a lens cylinder is shared in a diffusion reflection measuring system and an emission measuring system, and a diffusion reflection measuring mirror 19 is provided in a light path leading to a diffusion reflection measuring sensor 21, and an emission measuring mirror 23 is set in another light path leading to an emission measuring sensor 25.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared microscope capable of switching between a diffuse reflectance measurement system and a luminescence measurement system.

[0002]

2. Description of the Related Art Conventionally, as a method for measuring an infrared absorption spectrum of a substance adhered to or adsorbed on the surface of a catalyst for oxidizing an exhaust gas of an automobile, for example, a diffuse reflection accessory of an FTIR device is used, There are two ways to use the microscope objective, these are:
The sample is finely pulverized and heated to activate it, and is measured through an optical system for diffuse reflection.
In either case, the same diffuse reflection spectrum can be obtained.

[0003]

Although the diffuse reflection spectrum obtained as described above is similar to the transmission absorption spectrum, it is easily affected by the state, shape, and diffusivity of the sample surface, and only the diffuse reflection spectrum is obtained. It was difficult to perform high-precision surface analysis with.

In order to make up for such difficulties, a method of combining another surface state analysis method, luminescence measurement method, has been proposed. In the conventional luminescence measurement method, infrared light emitted from a heated sample is used. High sensitivity could not be obtained because the light was collected by the concave mirror and introduced into the interferometer.

The present invention has been made in view of such circumstances.
It is an object of the present invention to provide an infrared microscope capable of obtaining a highly sensitive emission spectrum together with a diffuse reflection spectrum from the same sample.

[0006]

The present invention comprises means for solving the above-mentioned problems as follows. That is, in the infrared microscope in which the diffuse reflection measurement system and the emission measurement system can be switched and selected, and the diffuse reflection spectrum and the emission spectrum of the same sample can be obtained, the first optical path from the light source to the interferometer A second optical path from the interferometer to a sample storage container with a heating device, a third optical path from the sample storage container to a relay optical system via a Cassegrain objective mirror, and the second optical path from the relay optical system To the sensor, and a fifth optical path branching from the middle of the fourth optical path to the sensor for measuring diffuse reflection, and a confluence point of the fourth optical path and the second optical path via the interferometer. A sixth optical path leading to a measuring sensor, a diffuse reflection measuring mirror is provided at a branch point of the fourth optical path to the fifth optical path, and a luminescence measuring mirror is provided at a confluence point of the fourth optical path and the second optical path. Is provided It is characterized by a door.

[0007]

When measuring the diffuse reflection spectrum, a diffuse reflection measuring mirror is provided at the branch point of the fourth optical path to the fifth optical path, while the emission measuring mirror is provided at the confluence of the fourth optical path and the second optical path. Do not set.

The light from the light source passes through the first optical path, the interferometer, and then the second optical path to irradiate the sample heated and activated in the sample storage container.

The light reflected by the sample reaches the relay optical system via the third optical path, is further diffuse-reflected by the diffuse reflection measuring mirror via the fourth optical path, and is then diffuse-reflected via the fifth optical path. It is incident on the measuring sensor, and the diffuse reflection spectrum is detected.

On the other hand, when measuring the emission spectrum,
The diffuse reflection measuring mirror provided at the branch point of the fourth optical path to the fifth optical path is removed, while the luminescence measuring mirror is provided at the confluence of the fourth optical path and the second optical path.

In this case, the infrared light emitted from the sample heated in the sample container reaches the relay optical system via the third optical path, passes through the fourth optical path, and is then reflected by the luminescence measuring mirror. Then, the emission spectrum is detected by the emission measurement sensor through the interferometer.

Switching between the above-mentioned two measuring systems can be easily and reliably performed by, for example, an extremely simple operation of attaching and detaching the diffuse reflection measuring mirror and the luminescence measuring mirror, and by a switching mechanism for switching between the two mirrors. It can also be done reliably. In addition, high sensitivity can be obtained by collecting infrared light from the sample with the Cassegrain objective mirror also at the time of luminescence measurement.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of an infrared microscope of the present invention will be described in detail below with reference to the drawings. FIG. 1 shows a configuration of a main part incorporated in a microscopic infrared FTIR apparatus. Reference numeral 1 is an infrared light source (light source), 2 is a concave mirror, 3 is an interferometer including a beam splitter, a fixed mirror, a movable mirror, and the like. Is a first optical path from the infrared light source 1 through the concave mirror 2 to the interferometer 3, 5 is a plane mirror, 6 is a concave mirror, 7 is an edge mirror for diffuse reflection, 8 is a Cassegrain objective mirror, 9 is a sample container,
10 is a sample such as a catalyst, 11 is a heating device, 12 is the interferometer 3 to the sample container 9 (more appropriately, the sample 1
It is the second optical path leading to 0).

Reference numeral 13 is a mask, 14 is a plane mirror, 15 is an inverse telescope (relay optical system) for obtaining parallel light, 16 is a third optical path from the sample container 9 to the inverse telescope 15, and 17
Is a plane mirror, and 18 is a fourth telescope which merges from the reverse telescope 15 through the plane mirror 17 into the second optical path 12 between the interferometer 3 and the plane mirror 5.
An optical path 19 is a diffuse reflection measuring mirror detachably provided at a branch point B between the plane mirror 17 and the confluence J of the second optical path 12 in the fourth optical path 18, 20 is a concave mirror, 21
Is a diffuse reflection measurement sensor, 22 is a fifth optical path from the diffuse reflection measurement mirror 19 to the diffuse reflection measurement sensor 21, and is the above-mentioned first optical path 4, second optical path 12, third optical path 16,
The fourth optical path 18 and the fifth optical path 22 form a diffuse reflection measurement optical path.

On the other hand, the fourth optical path 18 in the second optical path 12
A luminescence measuring mirror 23 is detachably provided at a confluence point J with the luminescence measuring mirror 23, and the light reflected by the luminescence measuring mirror 23 passes through the interferometer 3 and is condensed by the concave mirror 24. The third optical path 1
6, the sixth optical path 26 from the fourth optical path 18 and the luminescence measuring mirror 23 to the luminescence measuring sensor 25 via the interferometer 3 and the concave mirror 24 constitutes a luminescence measuring optical path.

From the Cassegrain objective mirror 8 to the plane mirror 14 described above.
The part up to is forming a microscopic optical system included in the lens barrel, and switching between the above-mentioned two measurement systems should be performed very easily and reliably by attaching and detaching the diffuse reflection measurement mirror 19 and the luminescence measurement mirror 23. You can It is also possible to visually observe the sample 10 from the observation mode optical path 31 by removing the above-mentioned plane mirror 14 and irradiating the sample 10 with light from a visible light source (not shown).
In this case, the visible light source may be arranged in the second optical path 12 between the concave mirror 6 and the diffuse reflection edge mirror 7. The two mirrors 19 and 23 may be configured to be switchable by using a switching mechanism instead of being detachable.

When measuring the diffuse reflection spectrum, a diffuse reflection measuring mirror 19 is provided at the branch point B in the fourth optical path 18 to the fifth optical path 22, while the fourth optical path 18 and the second optical path 18 are provided.
The luminescent measurement mirror 23 is not provided at the confluence J with the optical path 12.

The light from the light source 1 passes through the first optical path 4 and then the interferometer 3, and then passes through the second optical path 12 to irradiate the heated and activated sample 10 in the sample storage container 9. To be done.

The light reflected by the sample 10 passes through the third optical path 1
6 to the reverse telescope 15 and further to the fourth optical path 18
After being diffused and reflected by the diffuse reflection measuring mirror 19 via, the light is incident on the diffuse reflection measuring sensor 21 via the fifth optical path 22, and the diffuse reflection spectrum is detected.

On the other hand, when measuring the emission spectrum,
While removing the diffuse reflection measurement mirror 19 provided at the branch point B to the fifth optical path 22 in the fourth optical path 18, the emission measurement mirror 2 is provided at the confluence J of the fourth optical path 18 and the second optical path 12.
3 is provided.

In this case, the infrared light emitted from the sample 10 heated in the sample storage container 9 is emitted from the third optical path 16
To the reverse telescope 15 via the fourth optical path 18, and after being reflected by the emission measurement mirror 23, the interferometer 3
After that, the emission spectrum is detected by the emission measuring sensor 25.

The emission spectrum detected in this manner has a highly sensitive Cassegrain objective mirror 8 provided in the lens barrel.
Since it can be obtained by using, the light collection efficiency is much higher than that of the conventional device using the concave mirror, and the high correlation with the diffuse reflection spectrum is obtained. Therefore, it is possible to obtain reliable and powerful spectrum information by comparing and examining the two spectra. Further, the emission spectrum of the sample 10 has good correlation with the normal transmission absorption spectrum, and valuable information on the state change of the sample 10 depending on the heating temperature can be obtained.

Further, by utilizing the characteristics of the microscopic infrared FTIR device, it becomes possible to analyze the microscopic portion. That is, since the mask 13 provided in the lens barrel can focus light only on a minute portion, it is possible to measure a sample such as a spherical surface or a concave surface, and the surface shape of the detectable sample is enlarged. Became.

It is needless to say that the sample 10 is not limited to the catalyst and can be applied to various other organic compounds, or the sample is sliced into thin layers and subjected to layer analysis such as adsorption and permeation. (Depth analysis) can also be performed. In this case, the sliced sample may be placed on a moving stage (not shown), and the Cassegrain objective mirror 8 may be sequentially focused along the cut surface to detect the sample.

[0025]

As described above, according to the infrared microscope of the present invention, the Cassegrain objective mirror included in the lens barrel is shared by the diffuse reflectance measuring system and the luminescence measuring system, and the diffuse reflectance measuring sensor is used. Since the diffuse reflection measurement mirror is provided in the optical path leading to and the emission measurement mirror is provided in the optical path reaching the emission measurement sensor, the emission spectrum can be measured with high sensitivity, and the emission spectrum is In addition to obtaining a spectrum that correlates well with the transmission absorption spectrum, the state change due to the heating temperature of the sample can also be obtained as information, and powerful information can be obtained by comparing and examining the diffuse reflection spectrum and the emission spectrum. it can.

[Brief description of drawings]

FIG. 1 is a drawing showing a main configuration in an embodiment of an infrared microscope of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Light source, 3 ... Interferometer, 4 ... 1st optical path, 8 ... Cassegrain objective, 9 ... Sample storage container, 12 ... 2nd optical path, 15
... relay optical system, 16 ... third optical path, 18 ... fourth optical path, 1
9 ... Diffuse reflection measurement mirror, 21 ... Diffuse reflection measurement sensor, 22 ... Fifth optical path, 23 ... Luminescence measurement mirror, 25 ...
Luminescence measuring sensor, 26 ... Sixth optical path, B ... Branch point, J ...
Confluence.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Fumio Nakagawa 2 Higashimachi, Kichijoin Miya, Minami-ku, Kyoto-shi, Kyoto Prefecture Horiba Manufacturing Co., Ltd. (72) Tsukasa Satake 2 Higashi-cho, Kichijoin Miya, Minami-ku, Kyoto, Kyoto Horiba Manufacturing Co., Ltd. (72) Inventor Kazuyuki Ikemoto 2 Higashi-cho, Kichijoin-miya, Minami-ku, Kyoto-shi, Kyoto (72) Inventor Naohisa Oyama 14 Iwatani, Shimohakaku-cho, Nishio-shi, Aichi Japan Motor Co., Ltd. Part Research Institute (72) Inventor Ogata Ippei 14 Iwatani, Shimohakaku-cho, Nishio-shi, Aichi Japan Auto Parts Research Institute (72) Inventor Atsuhiro Sumiya 14 Iwatani, Shimohakaku-cho, Nishio-shi Aichi Japan Automobile Co., Ltd. Inside the Parts Research Institute

Claims (1)

[Claims] 1. An infrared microscope in which a diffuse reflection measurement system and a luminescence measurement system can be switched and selected so that a diffuse reflection spectrum and a luminescence spectrum of the same sample can be obtained. One optical path, a second optical path from the interferometer to the sample storage container with a heating device, a third optical path from the sample storage container to the relay optical system via the Cassegrain objective, and from the relay optical system A fourth optical path reaching the second optical path, a fifth optical path branching from the middle of the fourth optical path to the diffuse reflection measurement sensor, and a confluence point of the fourth optical path and the second optical path through the interferometer. And a sixth optical path leading to a light emission measuring sensor, and a diffuse reflection measuring mirror is provided at a branch point of the fourth optical path to the fifth optical path, and light is emitted at a confluence point of the fourth optical path and the second optical path. Don't set up a measuring mirror An infrared microscope characterized by the following.