JP2009168455A - Sample stage for spectroscopic analysis, solid sample cooling device, gas sample synchronous pressure device, laser light convergence irradiation device for analysis, and analysis chamber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve spectroscopic analysis irradiating laser light for analysis to a solid sample or a gas sample. <P>SOLUTION: A sample stage for spectroscopic analysis irradiating laser light for analysis to a solid sample includes a parallel movement mechanism for moving the solid sample in parallel with a surface to be analyzed of the solid sample 1 arranged on the sample stage 111. In a solid sample cooling device for irradiating laser light for analysis to the solid sample, a coolant is jetted and supplied toward a measuring object spot which is a part of the sample. In the sample stage for spectroscopic analysis irradiating laser light for analysis to the solid sample, a plurality of analysis domains formed of a second material are arranged at intervals on a base material formed of a first material, and a thermal conductivity of the second material is higher than a thermal conductivity of the first material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a sample stage for spectroscopic analysis in which a solid sample is irradiated with a laser beam for analysis, a solid sample cooling device, and a gas sample for spectroscopic analysis in which a gas sample is irradiated with a laser beam for analysis. The present invention relates to a synchronous pressurizing device, an analytical laser beam focused irradiation device, and an analysis chamber. The present invention also relates to a spectroscopic analysis apparatus and method using them.

  As a spectroscopic analysis method using the spectroscopic characteristics of a substance, absorption spectroscopic analysis for analyzing transmitted light obtained by irradiating the sample with light; light is emitted from the sample by light irradiation, voltage application, chemical reaction, etc. And luminescence analysis for analyzing the light; scattering spectroscopic analysis (for example, Raman scattering spectroscopic analysis) for irradiating the sample with light and analyzing the obtained scattered light. In addition, time-resolved spectroscopic analysis in which these spectroscopic analyzes are performed with time is also performed. For example, it is known that the reaction process can be observed even when the reaction is extremely fast by using a pulse laser.

  An apparatus for spectroscopic analysis that irradiates light on a sample usually includes a light source; a sample stage or container on which the sample is disposed; and light emission, scattered light, and / or transmitted light obtained by irradiating the sample with light from the light source. It is comprised from the detector which detects. A light source used for spectroscopic analysis is a device that can generate infrared light, visible light, ultraviolet light, and the like, and a laser light source that generates laser light is often used.

  These spectroscopic analysis methods are used in many applications, and many studies have been made on their improvements (Patent Documents 1 to 3). One purpose of this improvement is to enhance the light (or electromagnetic waves) applied to the sample in order to analyze a diluted sample. For example, the electromagnetic waves applied to the sample can be enhanced by resonance. It has been proposed (Patent Document 1). Another object of this improvement is to provide a high time resolution, thereby enabling the phenomenon occurring in a very short time to be elucidated (Patent Document 2).

Special table 2006-501481 JP 7-76711 Special table 2006-516730

As described above, the spectroscopic analysis method is used in many applications, and many improvements have been studied. However, these improvements have not yet fully solved the following problems (1) and (2):
(1) In spectroscopic analysis in which a solid sample is irradiated with analytical laser light, the surface of the solid sample to be analyzed by the light and / or thermal energy of the analytical laser light, particularly when performing analysis over time. May be deformed and / or altered, and the original properties of the solid sample may not be measured.
(2) In spectroscopic analysis in which a gas sample is irradiated with analytical laser light, the density of the gas sample is low, so that the scattered light obtained by the irradiation of the analytical laser light, the absorption of the analytical laser light, etc. are small. In some cases, it is difficult to analyze a gas sample with sufficient accuracy.

  Therefore, the first to third aspects of the present invention solve the problem (1) related to the spectroscopic analysis of the solid sample, and the fourth to sixth aspects of the present invention solve the problem (2) related to the spectroscopic analysis of the gas sample. To do.

  The present invention is as shown in the following items (1) to (17).

  (1) A sample stage for spectroscopic analysis in which a solid sample is irradiated with a laser beam for analysis, and the solid sample is arranged in parallel to a surface to be analyzed of the solid sample arranged on the sample stage. A sample stage having a parallel motion mechanism for moving the sample.

  (2) The sample stage according to (1) above, wherein the parallel motion mechanism causes the solid sample to rotate and / or reciprocate.

  (3) A solid sample cooling device for spectroscopic analysis that irradiates an analytical laser beam to the solid sample, and jets a refrigerant toward a portion of the solid sample irradiated with the analytical laser beam. A solid sample cooling device to be supplied.

  (4) The above-mentioned (3), wherein the coolant is jetted and supplied by irradiating the vaporized laser beam obtained by dividing a part of the analytical laser beam with a liquid state. The solid sample cooling device according to Item.

  (5) A sample stage for spectroscopic analysis in which a solid sample is irradiated with a laser beam for analysis, and a plurality of layers made of a second material on a substrate made of the first material A sample stage in which the analysis regions are spaced apart and the thermal conductivity of the second material is greater than the thermal conductivity of the first material.

  (6) The sample stage according to (5), wherein the first material is a ceramic material and the second material is a metal material.

(7) Spectroscopic analysis method for transparent thermoplastic resin sheet, comprising the following steps (a) to (d):
(A) disposing the transparent thermoplastic resin sheet on the sample stage described in (5) or (6) above;
(B) One of the plurality of analysis regions of the sample stage is irradiated with the analysis laser light or other laser light through the transparent thermoplastic resin sheet, and the transparent thermoplastic resin sheet At least partially melting a portion on the analysis area;
(C) irradiating at least a partially melted portion of the transparent thermoplastic resin sheet with the laser beam for analysis to perform spectroscopic analysis of the portion; and (d) the plurality of the sample stage Repeat steps (b) and (c) for the other one of the analysis areas.

  (8) A gas sample synchronous pressurization device for spectroscopic analysis that irradiates an analysis laser beam to a gas sample, the analysis chamber holding the gas sample, and the pressurization of the gas sample in the analysis chamber A gas sample synchronous pressurizing apparatus, comprising: a pressure mechanism, an analysis laser light source that irradiates the gas sample with an analysis laser light, and a synchronization device that synchronizes the pressurization mechanism and the analysis laser light source.

  (9) The gas sample synchronous pressurizing apparatus according to (8), wherein the pressurizing mechanism pressurizes the gas sample using electromagnetic force.

  (10) A spectroscopic analysis method including irradiating a gas sample with an analytical laser beam, the method comprising applying pressure to the gas sample in synchronization with the irradiation of the analytical laser beam. .

  (11) An analytical laser beam focused irradiation device for spectroscopic analysis for irradiating a gas sample with an analytical laser beam, comprising an analytical laser light source, a first concave mirror or convex lens, and a second concave mirror The first concave mirror or the convex lens converges the analysis laser light from the analysis laser light source in the gas sample, and the second concave mirror transmits the gas sample. For analyzing and converging again at the same location in the gas sample.

  (12) A half mirror disposed between the analysis laser light source and the first concave mirror or convex lens, and the half mirror is reflected by the second concave mirror and converges again in the gas sample. The analytical laser beam focused irradiation apparatus according to (11), wherein at least a part of the analyzed laser beam is reflected and converged again at the same location in the gas sample.

  (13) An analysis chamber for spectroscopic analysis in which a gas sample is irradiated with an analysis laser beam, and holding particles that are transmissive to the analysis laser beam.

  (14) The analysis chamber according to (13), wherein the particles have a particle size of 0.01 μm to 10 μm.

  (15) A spectroscopic analysis method including irradiating a gas sample with an analysis laser beam, the method comprising adsorbing the gas sample on the surface of a particle permeable to the analysis laser beam. Spectroscopic analysis method.

  (16) A spectroscopic analyzer that irradiates a solid sample with an analytical laser beam, the sample stage according to the above item (1), (2), (5), or (6), the above (3) Or a solid sample cooling device according to item (4), or a combination thereof.

  (17) A spectroscopic analyzer for irradiating a gas sample with an analytical laser beam, the gas sample synchronous pressurizing apparatus according to (8) or (9) above, (11) or (12 above) The analytical laser beam convergence irradiation device according to item (1), the gas sample container according to item (13) or (14), or a combination thereof.

<Sample stage of the first invention>
The sample stage of the first aspect of the present invention relates to a sample stage for spectroscopic analysis in which a solid sample is irradiated with an analytical laser beam, and is parallel to the surface to be analyzed of the solid sample arranged on the sample stage. It has a parallel movement mechanism that moves the solid sample.

  According to the sample stage of the first invention, the parallel motion mechanism moves the solid sample during the analysis by moving the solid sample parallel to the analyzed surface of the solid sample placed on the sample stage. The new surface of the solid sample can be continuously analyzed while maintaining a relative distance between the surface to be analyzed of the sample and the analytical laser light source, detector, and the like. According to this, it is possible to avoid the problem caused by continuing to analyze the same part of the solid sample, that is, the problem that the part to be analyzed of the solid sample is deteriorated by the laser beam for analysis.

  In the sample stage of the first aspect of the present invention, the parallel movement mechanism can cause the solid sample to rotate and / or reciprocate. That is, for example, as shown in FIG. 1, the sample stage 111 is rotated by a motor or the like around the center of the sample stage 111, and thereby the solid sample 1 arranged on the sample stage is It can be rotated as indicated by the arrows. Further, as shown in FIG. 2, the sample stage 121 is reciprocated by a piezo element or the like, whereby the solid sample 1 arranged on the sample stage is reciprocated as indicated by arrows in the figure. Can exercise.

  Here, in FIGS. 1 and 2, FIGS. 1A and 2A are top views of the sample stage and the solid sample, and FIGS. 1B and 2B are the sample stage and It is a side view of a solid sample. It is also possible to combine a plurality of rotational motions, a plurality of reciprocating motions, and a combination of rotational motion and reciprocating motion.

<Solid Sample Cooling Device of Second Invention>
A solid sample cooling device for spectroscopic analysis that irradiates a solid sample with a laser beam for analysis, in which a solid is jetted and supplied toward a portion to which the laser beam for analysis of the solid sample is irradiated Sample cooling device.

  According to the solid sample cooling device of the second aspect of the present invention, during the analysis, the refrigerant is jetted toward the portion to be irradiated with the analysis laser light of the solid sample, that is, the measurement target portion that is a part of the solid sample. Therefore, the measurement target portion of the solid sample can be cooled by using a relatively small amount of the refrigerant. According to this, problems due to the use of a large amount of refrigerant to cool a solid sample, for example, a large amount of condensation of water vapor in the analysis atmosphere, and the pressure in the analysis chamber when performing analysis in the analysis chamber and Problems of atmospheric changes and condensation of refrigerant on the analysis window surface of the analysis chamber can be avoided.

  Changes in pressure and atmosphere in the analysis chamber may affect the analysis results by changing the properties of the sample surface, and a large amount of water vapor condensation in the analysis atmosphere and refrigerant on the analysis window surface of the analysis chamber Since the condensation of may interfere with the transmission of laser light for analysis or scattered light to be observed, it is preferable to eliminate these problems.

  In order to inject and supply the refrigerant in the solid sample cooling device of the second aspect of the present invention, a combination of a pump, a pressure vessel, and a control valve can be used. Further, in order to inject and supply a refrigerant, a laser beam, for example, a laser beam obtained by dividing a part of the laser beam for analysis is irradiated on the refrigerant in a liquid state to vaporize the refrigerant. The refrigerant can be injected by volume expansion due to vaporization. The injection of the refrigerant can be synchronized with the irradiation of the laser beam.

  For example, when the liquid refrigerant is vaporized by the laser light obtained by dividing a part of the laser beam for analysis, as shown in FIG. The liquid refrigerant container 250 for storing 251, the injection nozzle 252 for injecting the refrigerant, and the half mirror 253 for dividing a part of the laser beam for analysis. However, as described above, vaporization of the liquid refrigerant using the laser beam may be performed using a dedicated laser beam other than the analysis laser beam.

  When the solid sample cooling apparatus according to the second aspect of the present invention is used by being attached to a Raman spectroscopic analysis apparatus that irradiates an analysis laser beam to a solid sample in an analysis chamber, as shown in FIG. 3, the solid sample to be analyzed 1 is placed on the sample stage 202 in the analysis chamber 15 of the Raman spectroscopic analyzer. Here, the analysis chamber 15 has a supply port 18 and an exhaust port 19 for the atmospheric gas 17 that can be controlled by valves 18a and 19a, respectively, so that the atmosphere in the analysis chamber 15 can be set to a desired atmosphere. Has been.

  In this Raman spectroscopic analyzer having the solid sample cooling device of the second aspect of the present invention, the analysis chamber 15 is optionally filled with the atmospheric gas 17 and / or brought to the desired pressure, and then the analysis laser light source 10 is used to send the half mirror 12. The laser beam 11 for analysis is irradiated to the laser beam 11 so that the laser beam 11 for analysis is reflected by the half mirror 12 and directed toward the solid sample 1 through the analysis window 15 a of the analysis chamber 15. This analytical laser light 11 irradiates the solid sample 1, thereby providing Raman scattered light 13. The Raman scattered light 13 is detected by the scattered light detector 14 through the analysis window 15 a of the analysis chamber 15 and the half mirror 12.

  During this spectroscopic analysis, in the solid sample cooling device according to the second aspect of the present invention, the half mirror 253 divides a part of the analysis laser beam 11, and the divided portion 11 a of the analysis laser beam 11 is an injection nozzle. The liquid refrigerant 251 in the 252 is vaporized, and the refrigerant vaporized thereby is injected to the analysis target portion of the solid sample 1 as indicated by an arrow 290.

<Sample stage of the third invention>
A sample stage according to a third aspect of the present invention relates to a sample stage for spectroscopic analysis in which a solid sample is irradiated with an analytical laser beam, and is made of a second material on a substrate made of the first material. The plurality of analysis regions that are arranged are spaced apart, and the thermal conductivity of the second material is greater than the thermal conductivity of the first material.

  The sample stage of the third aspect of the present invention can be used when analyzing a thin thermoplastic resin sample that is transparent to analysis laser light or other laser light, for example, a transparent thermoplastic resin sheet.

  That is, in using the sample stage of the third aspect of the present invention, a transparent thermoplastic resin sheet is disposed on the sample stage, and the analytical laser beam is passed through one of the plurality of analysis regions through the transparent thermoplastic resin sheet. Or other laser light is irradiated. At this time, since the analysis region has a relatively large thermal conductivity, the portion of the transparent thermoplastic resin sheet on the analysis region irradiated with the laser light is at least partially melted. On the other hand, since the substrate has a relatively low thermal conductivity, the heat transfer of the substrate portion adjacent to the analysis region irradiated with the laser light is prevented, and the other portions of the transparent thermoplastic resin sheet are melted. Can be avoided.

  As described above, the transparent thermoplastic resin sheet melts on the analysis region irradiated with the laser light, thereby causing convection of the thermoplastic resin material, and overheating of the thermoplastic resin material by the analytical laser light and deterioration due thereto. Can be prevented. On the other hand, the other part of the thermoplastic resin sheet does not melt, so that the same spectroscopic analysis can be repeated in other analysis regions with the least effect of the previous thermoplastic resin material melting. That is, according to the sample stage of the third aspect of the present invention, it is possible to perform analysis at a large number of locations on the thermoplastic resin sheet with the influence of the previous analysis being minimized. Such spectroscopic analysis at a large number of locations on the thermoplastic resin sheet is preferable, for example, for analyzing uniformity of the entire thermoplastic resin sheet.

  The first and second materials for the sample stage of the third invention can be arbitrarily selected so that the thermal conductivity of the second material is larger than the thermal conductivity of the first material. In the sample stage of the third invention, the first material may be a ceramic material such as a porous ceramic material, such as silicon dioxide or quartz, and the second material may be a metallic material such as silver, copper, It may be aluminum or stainless steel.

  Specifically, the sample stage of the third aspect of the present invention may be as shown in FIG. Here, FIG. 4A is a top view of the sample stage 300, and FIG. 4B is a cross-sectional view of the sample stage 300 taken along the line B-B shown in FIG. 4A. . In the sample stage 300 shown in FIG. 4, a plurality of analysis regions 302 made of the second material are dispersed and arranged on the base material 301 made of the first material at intervals. Has been.

<Spectroscopic analysis method of the third invention>
The spectroscopic analysis method of the third aspect of the present invention is a spectroscopic analysis method for a transparent thermoplastic resin sheet, comprising the following steps (a) to (d):
(A) disposing a transparent thermoplastic resin sheet on the sample stage of the third invention;
(B) A portion on the analysis region of the transparent thermoplastic resin sheet by irradiating one of a plurality of analysis regions of the sample stage with an analysis laser beam or other laser beam through the transparent thermoplastic resin sheet. At least partially melt
(C) irradiating at least partly melted portion of the transparent thermoplastic resin sheet with laser light for analysis to perform spectroscopic analysis of this portion; and (d) among a plurality of analysis regions of the sample stage. Repeat steps (b) and (c) for the other one.

  According to the spectroscopic analysis method of the third aspect of the present invention, it is possible to perform analysis at a large number of locations on the thermoplastic resin sheet while minimizing the influence of previous analysis.

  Specifically, the spectroscopic analysis method of the third aspect of the present invention can be performed as shown in FIG. 5 for Raman spectroscopic analysis. That is, a transparent thermoplastic resin sheet 1 ′, which is a solid sample, is disposed on the sample stage 300 of the third aspect of the present invention, the analysis laser light 11 from the analysis laser light source 10 is reflected by the half mirror 12, and the transparent heat By irradiating one analysis region 302a of the plurality of analysis regions 302 of the sample stage 300 through the plastic resin sheet 1 ′, at least a portion 1′a on the analysis region of the transparent thermoplastic resin sheet 1 ′ is at least partially. Then, or simultaneously, the Raman scattered light 13 from the melted portion 1′a of the transparent thermoplastic resin sheet 1 ′ can be detected by the detector 14.

  Further, in this spectroscopic analysis method, the same processing is repeated for the other one analysis region 302b of the plurality of analysis regions 302 of the sample stage 300 and corresponding portions of the transparent thermoplastic resin sheet 1 '.

<The gas sample synchronous pressurization apparatus of 4th invention>
The gas sample synchronous pressurizing device of the fourth aspect of the present invention relates to a spectroscopic analysis device for spectroscopic analysis in which a gas sample is irradiated with an analysis laser beam, and relates to an analysis chamber for holding a gas sample, and a gas sample in the analysis chamber. A pressurizing mechanism for pressurizing, an analytical laser light source for irradiating an analytical laser beam to a gas sample, and a synchronization device for synchronizing the pressurizing mechanism and the analytical laser light source, for example, a frequency synchronous device.

  According to the gas sample synchronous pressurizing apparatus of the fourth aspect of the present invention, by synchronizing the pressurization of the gas sample with the irradiation of the laser beam for analysis for spectroscopic analysis, only the moment of performing the spectroscopic analysis is performed. The density can be increased. In order to solve the problem that analysis of a gas sample is difficult due to low density, a pressure mechanism and a sample container that can hold a high-pressure gas sample for a long time when the gas sample is always kept at high density, that is, high pressure Is required. On the other hand, increasing the density of the gas sample only at the moment of performing the spectroscopic analysis is preferable because such a pressurization mechanism and sample container are not necessary.

  In order to pressurize the gas sample in synchronization with the irradiation of the laser beam for analysis in the gas sample synchronous pressurizing apparatus of the fourth aspect of the present invention, any pressurizing mechanism can be used, for example, a pressurizing mechanism using electromagnetic force Can be used. That is, for example, when a pressurizing mechanism using electromagnetic force is used to pressurize the gas sample, as shown in FIG. 6, the pressurizing mechanism 450 includes an analysis chamber 15, an electromagnetic coil 402 around the analysis chamber 15, And a magnetic piston 403 that can pressurize the gas sample in the analysis chamber 15.

  Here, the analysis chamber 15 has an analysis window 15a that transmits light for analysis. The analysis chamber 15 also has a supply port 18 and a discharge port 19 for the gas sample 17, which can be controlled by valves 18a and 19a, respectively, so that a gas sample can be supplied into the analysis chamber 15. ing.

  When pressurizing a gas sample using the pressurizing mechanism 450, the magnetic material piston 403 is applied to the analysis chamber 15 as indicated by an arrow 490 a by providing an alternating current from the alternating current power source 410 to the electromagnetic coil 402. , And the gas sample in the analysis chamber 15 is compressed, and as shown by an arrow 490b, the magnetic piston 403 is moved with respect to the analysis chamber 15 to compress the compressed gas sample in the analysis chamber 15. The pressure can be restored. That is, when this pressurizing mechanism 450 is used, the gas sample in the analysis chamber can be compressed and released by vibrating the magnetic piston 403 at high speed as indicated by arrows 490a and 490b.

  Therefore, in this aspect of the gas sample synchronous pressurizing apparatus of the fourth aspect of the present invention, for example, the AC power supply 410 and the analysis laser light source 10 are controlled by the frequency synchronous apparatus 420 to provide an alternating current from the AC power supply 410 to the electromagnetic coil 402. Then, the gas sample in the analysis chamber 15 is pressurized with the magnetic piston 403, and the analysis laser light 11 is irradiated from the analysis laser light source 10 to the half mirror 12.

  The analysis laser light 11 irradiated from the analysis laser light source 10 is reflected by the half mirror 12 and irradiated to the gas sample in the analysis chamber 15 through the analysis window 15 a of the analysis chamber 15. The laser beam for analysis 11 irradiated on the gas sample provides Raman scattered light 13. The Raman scattered light 13 is detected by the scattered light detector 14 through the analysis window 15 a of the analysis chamber 15 and the half mirror 12.

<Spectroscopic analysis method of the fourth invention>
The spectroscopic analysis method of the fourth aspect of the present invention relates to a spectroscopic analysis method including irradiating an analytical laser beam to a gas sample, and includes pressurizing the gas sample in synchronization with the irradiation of the analytical laser beam.

  According to the spectroscopic analysis method of the fourth aspect of the present invention, there is provided a pressurizing mechanism and a sample container for holding a high-pressure gas sample for a long time by pressurizing the gas sample in synchronization with the irradiation of the laser beam for analysis. Without the need, spectroscopic analysis can be performed on a pressurized gas sample. The spectroscopic analysis method of the fourth aspect of the present invention can be performed using the gas sample synchronous pressurizing apparatus of the fourth aspect of the present invention.

<Analysis Laser Light Converging Irradiation Device of Fifth Invention>
The analytical laser beam focused irradiation device of the fifth aspect of the present invention relates to an analytical laser beam focused irradiation device for spectroscopic analysis that irradiates a gas sample with an analytical laser beam, and relates to an analytical laser light source, a first concave mirror, or It has a convex lens and a second concave mirror. Wherein the first concave mirror or convex lens focuses the analytical laser light from the analytical laser light source in the gas sample, and the second concave mirror reflects the analytical laser light transmitted through the gas sample, and Again converge at the same location in the gas sample.

  According to the analytical laser beam focused irradiation apparatus of the fifth aspect of the present invention, the analytical laser beam is focused at the same location of the gas sample and irradiated multiple times, so that the strong analytical laser beam is generated at the converged location in the gas sample. Can be obtained. Generally, in a spectroscopic analysis of a gas sample using laser light, since the density of the gas sample is small, scattered light or the like caused by the laser light is weak, and sufficient spectroscopic analysis may be difficult.

  In this regard, irradiating a gas sample with a strong laser beam for analysis as in the analytical laser beam focusing and irradiating device of the fifth aspect of the invention enhances the scattered light and the like, thereby performing spectroscopic analysis of the gas sample. Can be promoted. In order to converge the analysis laser light from the analysis laser light source, it is preferable to use a concave mirror instead of a convex lens because the absorption when the analysis laser light passes through the convex lens can be eliminated. There is.

  Further, in the analytical laser beam convergent irradiation device of the fifth aspect of the present invention, a half mirror can be arranged between the analytical laser light source and the first concave mirror or convex lens. It becomes possible to further reflect at least a part of the analysis laser beam reflected by the second concave mirror and to converge it again at the same location in the gas sample. Therefore, in this case, it becomes possible to irradiate the gas sample with a stronger laser beam for analysis.

  Specifically, the analytical laser beam convergence irradiation apparatus of the fifth aspect of the present invention may be as shown in FIGS. 7 and 8 relating to Raman spectroscopic analysis.

  In one aspect of the analytical laser beam convergent irradiation apparatus of the fifth invention shown in FIG. 7, the analytical laser beam 11 from the analytical laser light source 10 is transmitted through an optional half mirror 503, and as a Cassegrain lens, The first concave mirror 505 combined with the convex mirror 504 is converged in the gas sample in the gas sample container 506. Thereafter, the analysis laser light 11 that has passed through the gas sample is reflected by the second concave mirror 507 and converged again at the same location in the gas sample in the gas sample container 506. Thus, the Raman scattered light 13 obtained by converging and irradiating the analysis laser beam 11 on the gas sample in the gas sample container 506 can be detected by the detector 14.

  When this analytical laser beam convergence irradiation apparatus has a half mirror 503 disposed between the analytical laser light source 10 and the convex mirror 504, the analytical sample is reflected by the second concave mirror, converged, and irradiated onto the gas sample. Laser light can be reflected by concave mirror 505 and convex mirror 504 and at least partially reflected by this half mirror 503. The analysis laser light reflected by the half mirror 503 is reflected again by the convex mirror 504 and the concave mirror 505 and converged again at the same location in the gas sample in the gas sample container 506.

  In another aspect of the analytical laser beam convergent irradiation apparatus of the fifth aspect of the present invention shown in FIG. 8, the analytical laser beam 11 from the analytical laser light source 10 is transmitted by the first concave mirror 505 combined with the convex mirror 504. Except for converging instead of converging by a convex lens 555, it is the same as the embodiment of the analyzing laser beam converging irradiation apparatus of the fifth invention shown in FIG.

<Analysis chamber of the sixth invention>
An analysis chamber according to a sixth aspect of the present invention relates to an analysis chamber for spectroscopic analysis in which a gas sample is irradiated with an analysis laser beam, and holds particles that are transmissive to the analysis laser beam.

  According to the analysis chamber of the sixth aspect of the present invention, the gas sample can be physically adsorbed and / or chemically adsorbed on the surface of the particles held in the analysis chamber, and the adsorbed gas sample can be analyzed.

  In general, in a spectroscopic analysis of a gas sample using laser light, since the density of the gas sample is small, scattered light or the like caused by the laser light is weak, and spectroscopic analysis may be difficult. In this regard, as in the analysis chamber of the sixth aspect of the present invention, the gas sample is adsorbed on the surface of particles that are transparent to the laser beam for analysis so that the gas sample exists at a relatively high density. It is possible to enhance the scattered light from the gas sample, thereby facilitating spectroscopic analysis of the gas sample.

  The particles for the analysis chamber of the sixth aspect of the present invention can be made of any material that is transparent to the laser beam for analysis, such as glass or quartz. In addition, when the particles are small, the surface area of the particles is increased, thereby increasing the amount of gas sample adsorbed on the surface of the particles. Accordingly, the particles for the analysis chamber of the sixth aspect of the present invention preferably have a relatively small particle size, for example, 0.01 μm to 10 μm, and particularly 0.01 μm to 1 μm.

  Also, by reducing the temperature of the gas sample and the particles and increasing the pressure of the gas sample, the amount of gas sample adsorbed on the particles for the analysis chamber of the sixth invention can be increased. . Therefore, the analysis chamber of the sixth aspect of the present invention can also have a cooling device, for example, a flow path for circulating a refrigerant such as liquid nitrogen around the sample container, and / or a pressurizing device, for example, a pump. In addition, the analysis chamber of the sixth aspect of the present invention does not need to hold permeable particles directly, and holds such particles indirectly by holding a container containing such particles. You can also

  Specifically, the analysis chamber of the sixth aspect of the present invention may be as shown in FIG. 9 for Raman spectroscopic analysis. FIG. 9 shows a container 602 that holds glass fine particles 601 as particles that are transparent to the laser beam for analysis. In the Raman spectroscopic analysis apparatus shown in FIG. 9, the container 602 holding the particles 601 is disposed in the analysis chamber 15 of the sixth invention. Here, the analysis chamber 15 of the sixth aspect of the present invention has a supply port 18 and a discharge port 19 for the gas sample 17 that can be controlled by valves 18a and 19a, respectively. A desired atmosphere can be obtained.

  In the Raman spectroscopic analyzer shown in FIG. 9, after the analysis chamber 15 of the sixth aspect of the present invention is filled with the gas sample 17, and the inside of the analysis chamber 15 is optionally set to a desired pressure and / or temperature, the analysis laser light source 10 is used. The laser beam 11 for analysis is irradiated onto the half mirror 12, whereby the laser beam 11 for analysis is reflected by the half mirror 12 and directed toward the glass particles 601 in the gas sample container 602 through the analysis window 15 a of the analysis chamber 15. Dodge.

  The analysis laser light 11 irradiated on the glass fine particles 601 brings about Raman scattered light 13 resulting from the gas sample adsorbed on the surface of the glass fine particles 601. The Raman scattered light 13 is detected by the scattered light detector 14 through the analysis window 15 a of the analysis chamber 15 and the half mirror 12.

<Spectroscopic analysis method of the sixth invention>
A spectroscopic analysis method according to a sixth aspect of the present invention relates to a spectroscopic analysis method including irradiating a gas sample with an analytical laser beam, wherein the gas sample is adsorbed on the surface of particles that are transparent to the analytical laser beam. including.

  According to the spectroscopic analysis method of the sixth aspect of the present invention, a gas sample is physically adsorbed and / or chemically adsorbed on the surface of particles that are transparent to the laser beam for analysis, thereby increasing the density of the gas sample, thereby Spectral analysis of a gas sample can be promoted by increasing scattered light from the sample.

  In the spectroscopic analysis method of the sixth aspect of the present invention, the particles described with respect to the analysis chamber of the sixth aspect of the present invention can be used as the particles that are transparent to the analysis laser beam. In the spectroscopic analysis method of the sixth aspect of the present invention, as described with respect to the analysis chamber of the sixth aspect of the present invention, the temperature of the gas sample and / or particles, the pressure of the gas sample, etc. are adjusted to Adsorption can also be controlled. The spectroscopic analysis method of the sixth invention can be carried out using the analysis chamber of the sixth invention.

It is a figure which shows one aspect | mode of the sample stage of 1st this invention. It is a figure which shows the other aspect of the sample stage of 1st this invention. It is a figure which shows one aspect | mode of the solid sample cooling device of 2nd this invention. It is a figure which shows one aspect | mode of the sample stage of 3rd this invention. It is a figure explaining the spectroscopic analysis method of the 3rd present invention using the sample stage (shown in Drawing 4) of the 3rd present invention. It is a figure which shows one aspect | mode of the gas sample synchronous pressurization apparatus of 4th this invention. It is a figure which shows one aspect | mode of the laser beam convergence irradiation apparatus for analysis of 5th this invention. It is a figure which shows the other aspect of the laser beam convergence irradiation apparatus for analysis of 5th this invention. It is a figure which shows one aspect | mode of the analysis chamber of 6th this invention.

Explanation of symbols

1 Solid sample 1 'Solid sample (transparent thermoplastic resin sheet)
DESCRIPTION OF SYMBOLS 10 Analysis laser light source 11 Analysis laser light 12 Half mirror 13 Scattered light 14 Scattered light detector 15 Analysis chamber 15a Analysis window 17 Atmospheric gas or gas sample 18 Supply port of atmospheric gas or gas sample 19 Exhaust of atmospheric gas or gas sample Outlet 18a, 19a Valve 111, 121 Sample stage 251 Liquid refrigerant 250 Liquid refrigerant container 252 Injection nozzle 252
300 Sample stage 301 Base material made of first material 450 Pressurizing mechanism 402 Electromagnetic coil 403 Magnetic piston 420 Frequency synchronization device 504 Convex mirror 505 First concave mirror 506 Gas sample container 507 Second concave mirror 503 Half mirror 555 Convex lens 601 Glass fine particles

Claims (17)

  A spectroscopic sample stage for irradiating a solid sample with an analytical laser beam, the solid sample being moved parallel to a surface to be analyzed of the solid sample disposed on the sample stage A sample stage having a parallel motion mechanism.   The sample stage according to claim 1, wherein the parallel movement mechanism causes the solid sample to rotate and / or reciprocate.   A solid sample cooling device for spectroscopic analysis that irradiates a solid sample with an analytical laser beam, wherein a coolant is jetted and supplied toward a portion of the solid sample irradiated with the analytical laser beam. , Solid sample cooling device.   The solid sample according to claim 3, wherein the coolant is jetted and supplied by irradiating and vaporizing a laser beam obtained by dividing a part of the analysis laser beam into a liquid coolant. Cooling system.   A sample stage for spectroscopic analysis in which an analysis laser beam is irradiated onto a solid sample, and a plurality of analysis regions made of a second material on a substrate made of the first material Are arranged at intervals, and the thermal conductivity of the second material is larger than the thermal conductivity of the first material.   The sample stage according to claim 5, wherein the first material is a ceramic material and the second material is a metal material. A method for spectroscopic analysis of a transparent thermoplastic resin sheet, comprising the following steps (a) to (d):
(A) disposing the transparent thermoplastic resin sheet on the sample stage according to claim 5 or 6;
(B) One of the plurality of analysis regions of the sample stage is irradiated with the analytical laser light or other laser light through the transparent thermoplastic resin sheet, and the transparent thermoplastic resin sheet At least partially melting a portion on the analysis area;
(C) irradiating the at least partially melted portion of the transparent thermoplastic resin sheet with the laser beam for analysis to perform spectroscopic analysis of the portion; and (d) the plurality of the sample stage. Repeat steps (b) and (c) for the other one of the analysis areas.   A gas sample synchronous pressurization device for spectroscopic analysis that irradiates a gas sample with an analysis laser beam, the analysis chamber holding the gas sample, a pressurizing mechanism for pressurizing the gas sample in the analysis chamber, A gas sample synchronous pressurizing apparatus, comprising: an analysis laser light source that irradiates the gas sample with an analysis laser light; and a synchronization device that synchronizes the pressurization mechanism and the analysis laser light source.   The gas sample synchronous pressurization device according to claim 8 with which said pressurization mechanism pressurizes said gas sample using electromagnetic force.   A spectroscopic analysis method including irradiating a gas sample with an analytical laser beam, the method comprising pressurizing the gas sample in synchronization with the irradiation of the analytical laser beam.   An analytical laser beam focused irradiation device for spectroscopic analysis that irradiates a gas sample with an analytical laser beam, comprising: an analytical laser light source, a first concave mirror or convex lens, and a second concave mirror, A first concave mirror or a convex lens converges the analysis laser light from the analysis laser light source in the gas sample, and the second concave mirror reflects the analysis laser light transmitted through the gas sample. And an analytical laser beam focused irradiation apparatus for focusing again at the same location in the gas sample.   A half mirror disposed between the laser light source for analysis and the first concave mirror or convex lens, the half mirror being reflected by the second concave mirror and refocused in the gas sample; The analytical laser beam focused irradiation apparatus according to claim 11, wherein at least a part of the analytical laser beam is reflected and converged again at the same location in the gas sample.   An analysis chamber for spectroscopic analysis that irradiates a gas sample with an analysis laser beam, the analysis chamber holding particles that are transparent to the analysis laser beam.   The analysis chamber according to claim 13, wherein the particles have a particle size of 0.01 μm to 10 μm.   A spectroscopic analysis method comprising irradiating a gas sample with an analytical laser beam, the method comprising adsorbing the gas sample on the surface of a particle permeable to the analytical laser beam .   A spectroscopic analyzer that irradiates a solid sample with an analysis laser beam, the sample stage according to claim 1, 2, 5, or 6, the solid sample cooling device according to claim 3 or 4, or a A spectroscopic analyzer having a combination.   A spectroscopic analyzer that irradiates a gas sample with an analytical laser beam, the gas sample synchronous pressurizing device according to claim 8 or 9, the analytical laser beam focused irradiation device according to claim 11 or 12, A spectroscopic analyzer comprising the analysis chamber according to claim 13 or 14, or a combination thereof.

Images