JP2007303912A - Photothermal conversion measuring device, and sample storage vessel used for device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve accuracy of photothermal conversion measurement by heightening irradiation efficiency of excitation light to a sample with a simple and inexpensive constitution. <P>SOLUTION: When generating a photothermal effect by allowing the excitation light to enter the sample S, an excitation light reflector 56 is provided in a sample storage vessel 50 for storing the sample S. The excitation light reflector 56 encloses a sample storing space from the outside, reflects the excitation light to be scattered from the sample storing space, and allows the excitation light to re-enter the space. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photothermal conversion measurement technique used for analysis of substances contained in various samples.

  Conventionally, as a means for performing analysis of substances contained in various samples, photothermal conversion measurement using a photothermal effect, that is, an effect that an irradiation site absorbs the excitation light and generates heat when the sample is irradiated with excitation light. Are known.

For example, Patent Document 1 below discloses a liquid sample that is irradiated with excitation light to cause the photothermal effect, and the calorific value thereof is measured by an optical measuring device. This measuring apparatus transmits measurement light different from the excitation light to the liquid sample and measures the amount of heat generated by the photothermal effect from the change in the refractive index of the measurement light. Here, the refractive index is obtained from the phase change of the measurement light, and the phase change is measured by optical interferometry.
JP 2004-301520 A

  In the photothermal conversion measuring apparatus, in order to increase the measurement accuracy, it is important to improve the photothermal effect by the excitation light. As a means for this, it is conceivable to enhance the excitation light. In this case, the optical system for irradiating the excitation light is large and expensive.

  In view of such circumstances, an object of the present invention is to provide a technique capable of measuring the improvement in measurement accuracy by increasing the irradiation efficiency of excitation light on a sample with a simple and low-cost configuration.

  As a means for solving the above-mentioned problems, the present invention provides a sample container used in a photothermal conversion measuring apparatus that measures the amount of heat generated by the sample by the excitation light incident on the sample and the photothermal effect thereof. A container body that encloses a sample storage space for receiving the excitation light, and has an entrance for allowing the excitation light to enter the sample storage space, and the excitation light in the sample storage space. And an excitation light reflector that reflects excitation light arriving from the sample storage space toward the sample storage space.

  The present invention also relates to a photothermal conversion measuring device for measuring the calorific value of the sample due to the photothermal effect of the excitation light incident on the sample, the sample container being accommodated in the sample accommodating space of the sample container. An excitation light incident optical system that makes the excitation light incident on the sample to be received from the entrance of the sample container, and the measurement light different from the excitation light is transmitted through the sample, and the phase of the transmitted measurement light And a measuring device for measuring the change.

  According to the above configuration, of the excitation light that enters the sample storage space of the sample container, the light that is to be scattered outside the sample storage space is the excitation light reflector that surrounds the sample storage space. Since the light is reflected and re-entered in the sample storage space, the irradiation efficiency of the excitation light on the sample stored in the sample storage space is increased. Therefore, the photothermal effect of the sample by the excitation light can be enhanced without particularly increasing the excitation light.

  Here, the excitation light reflector may cover only a part of the sample storage space in the optical axis direction of the excitation light in the sample storage space. The irradiation efficiency of the excitation light is further increased.

  It is preferable that the excitation light reflector is on an inner surface of the container body surrounding the sample accommodation space. Alternatively, at least a part of the container body that faces the sample storage space is a transparent body that transmits the excitation light, and the excitation is provided on the opposite side of the sample storage space with the transparent body interposed therebetween. It may be a sample container in which the light reflector is located. In the latter, direct contact between the excitation light reflector and the sample in the sample storage space is prevented. Therefore, inconvenience due to the contact, for example, deterioration of the excitation light reflector and influence on the characteristics of the sample can be avoided. Further, even when the inner diameter of the container body surrounding the sample storage space is very small and it is difficult to arrange the excitation light reflector on the inner surface of the container body, the excitation light reflection by the excitation light reflector is not possible. It becomes possible.

  Furthermore, the container body includes an inner container that includes the translucent body and surrounds the sample storage space, and an outer container that is positioned outside the inner container, and the inner container is detachable inside the outer container. If the excitation light reflector is provided on the surface of the inner container facing the translucent body among the inner surfaces of the outer container, the outer container remains installed and the outer container is installed. The sample can be exchanged simply by inserting and removing the inner container with respect to the container. Therefore, it is possible to efficiently perform measurement on a plurality of types of samples.

  In the present invention, the shape of the sample storage space can be set as appropriate. Of these, the shape in which the sample storage space extends in a direction parallel to the optical axis direction of the excitation light incident on the space is particularly preferable. If the excitation light and the measurement light are incident on the sample in the sample storage space coaxially in the direction along the longitudinal direction of the sample storage space using this sample storage device, the volume of the container body is particularly increased. Without this, the optical path lengths of the excitation light and the measurement light in the sample can be extended, thereby further improving the measurement accuracy.

  As described above, according to the present invention, the excitation light to be scattered outward from the sample storage space is reflected by the excitation light reflector and re-entered into the sample storage space. With the configuration, there is an effect that it is possible to measure the improvement of the photothermal effect and hence the measurement accuracy by increasing the irradiation efficiency of the excitation light to the sample.

  A preferred embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 shows an example of a photothermal conversion measuring apparatus according to the first embodiment of the present invention. This apparatus includes an excitation light incident optical system (hereinafter simply referred to as “excitation system”) 10, a measurement system (measurement apparatus) 20, and a sample container 40. A sample container 50 shown in FIG. 2 or the like is set in the sample container 40, and a target sample S such as an aqueous dye solution or ethanol is set in the container 50.

  The excitation system 10 is for entering excitation light into the sample storage unit 40, and includes an excitation light source 12, a spectroscopic mechanism 14, a modulation mechanism 16, and a light guide unit 18. As the excitation light source 12, for example, a xenon lamp that outputs white light is suitable. The light emitted from the excitation light source 12 is dispersed by the spectroscopic mechanism 14 and periodically modulated by the modulation mechanism 16 to become excitation light suitable for measurement. When the excitation light is irradiated onto the sample in the sample storage unit 40 through the light guide unit (for example, a collimating mechanism or a light guide) 18, the sample absorbs the excitation light and generates heat. The refractive index of the sample changes.

  The measurement system 20 irradiates the sample S with measurement light for measuring the refractive index of the sample, and measures the refractive index from the measurement light. In this embodiment, the measurement system 20 includes a measurement light source 22 and necessary optical systems, a photodetector 36, and a signal processing device 38.

  The measurement light source 22 is composed of a He—Ne laser generator with an output of 1 mW, for example, and the light irradiated from the measurement light source 22 is adjusted in polarization plane by a λ / 2 wavelength plate 23 as shown in FIG. After being received, the light is divided into two by the polarization beam splitter 24, which are polarized light L1 and L2 orthogonal to each other.

  The polarized light L1 is used as reference light. After being subjected to optical frequency shift (frequency conversion) by the acousto-optic modulator 25A, the polarized light L1 is reflected by the mirror 26A and input to the polarization beam splitter 28. The polarized light L2 is used as measurement light. After being subjected to optical frequency shift (frequency conversion) by the acousto-optic modulator 25B, the polarized light L2 is reflected by the mirror 26B and input to the polarizing beam splitter 28. The light is combined with the polarized light L 1 by the splitter 28.

  The frequency difference fb between the two polarized lights L1 and L2 orthogonal to each other is preferably about 30 MHz, for example.

  The polarized light L1 passes through the deflecting beam splitter 30 as it is and is reflected by the mirror 34 by 180 °, thereby returning to the polarizing beam splitter 30. At this time, a quarter wavelength plate 33 is interposed between the polarization beam splitter 30 and the mirror 34, and the polarized light L1 passes back and forth through the quarter wavelength plate 33. The polarization plane rotates 90 °. Accordingly, the polarized light L1 that has returned to the polarizing beam splitter 30 is reflected by 90 ° on the side opposite to the sample container 40. This polarized light L 1 is input to the photodetector 36 through the polarizing plate 35.

  On the other hand, the polarized light L2 is reflected by 90 ° toward the sample container 40 by the polarization beam splitter 30 and guided to the sample container 40 through the quarter-wave plate 32. As will be described later, the polarized light L2 is incident on the sample, is further reflected by 180 °, and returns to the polarizing beam splitter 30 through the quarter-wave plate 32. Since the polarization plane of the polarized light L2 is rotated by 90 ° due to the reciprocal transmission of the quarter-wave plate 32, the polarized light splitter 30 is transmitted through the polarized beam splitter 30 as it is and merged with the polarized light L2. To the plate 35 and the photodetector 36.

  In the polarizing plate 35, the polarizations L1 and L2 interfere with each other as reference light and measurement light, and the light intensity of the interference light is converted into an electric signal (detection signal) by the photodetector 36. The signal processing device 38 calculates a phase change of the polarized light L2 (measurement light) based on the detection signal. Thereby, the measurement of the phase change by the optical interferometry is achieved.

  Here, the interference light intensity S1 is expressed by the following equation (1).

S1 = C1 + C2 · cos (2π · fb · t + φ) (1)
In the equation, C1 and C2 are constants determined by the transmittance of the optical system such as the polarizing beam splitter and the sample S, φ is a phase difference due to the optical path length difference between the polarized lights L1 and L2, and fb is a frequency of the two polarized lights L1 and L2. It is a difference. From this equation (1), the change in the phase difference φ can be obtained from the change in the interference light intensity S1 (the difference between when the excitation light is not irradiated or when the light intensity is low and when the light intensity is high). I understand. The signal processing device 38 calculates the change in the phase difference φ based on the equation (1).

  Note that when the intensity of the excitation light Le is periodically intensity-modulated at a frequency f by, for example, chopper rotation, the refractive index of the sample S also changes at the frequency f, and the optical path length of the measurement light L2 is also the frequency f. (The optical path length of the reference light L1 is constant), and the phase difference φ also changes with the frequency f. Therefore, if the change in the phase difference φ is measured (calculated) with respect to the component of the frequency f (the same period component as the intensity modulation period of the excitation signal), the influence of noise having no component of the frequency f is removed. Only the refractive index change of S can be measured. This measurement improves the S / N ratio of the measurement of the phase difference φ.

  When a laser diode or LED is used for the excitation light source 12, the modulation can be performed by controlling the power source of the excitation light source 12 with an electric circuit.

  Next, the configuration of the sample container 40 will be described with reference to FIG. The sample container 40 includes a condenser lens 42, a dichroic mirror 44, and a sample container 50 according to the present invention.

  The condensing lens 42 condenses the excitation light Le introduced from the excitation system 10 and enters the sample S accommodated in the sample container 50. The dichroic mirror 44 is located between the condenser lens 42 and the sample container 50 and transmits the excitation light Le collected by the condenser lens 42 as it is. On the other hand, the dichroic mirror 44 reflects the polarized light L2 (hereinafter referred to as “measurement light L2”) introduced from the measurement system 20 in a direction orthogonal to the excitation light Le by 90 °, thereby exciting the excitation light Le. And enters the sample S coaxially.

  The excitation light Le introduced from the excitation system 10 may be irradiated to the condenser lens 42 as it is as shown in FIG. 2A, or a reflector 46 as shown in FIG. The light may be guided to the condenser lens 42 by reflection. In the latter case, if a diffraction grating is used for the reflector 46, the excitation light Le can be split simultaneously.

  Next, a specific structure of the sample container 50 will be described with reference to FIG.

  The sample container 50 has a cylindrical peripheral wall 54 and a bottom wall 52 that closes one opening of the peripheral wall 54, and a sample storage space for storing the sample S is formed inside the peripheral wall 54. Has been. That is, the peripheral wall 54 and the bottom wall 52 constitute a container body surrounding the sample storage space. The sample storage space is opened to the side opposite to the bottom wall 52 (right side in the figure), and the opening serves as the entrance 55 for the excitation light Le and the measurement light L2.

  In this embodiment, the sample storage space has a cylindrical shape extending in a direction parallel to the central axis of the peripheral wall 54. And the sample container 50 is installed with the attitude | position in which the longitudinal direction of this sample accommodation space corresponds with the optical axis direction of the said excitation light Le and the said measurement light L2.

  The installation posture of the sample container 50 is not particularly limited. In the posture in which the opening (incident port 55) faces sideward or downward as shown in the figure, the incident port may be closed with a lid made of a translucent material so that the sample S does not flow out of the sample storage space. . On the other hand, the lid may be omitted when the incident port faces upward.

  As a characteristic of the sample container 50 shown in the figure, a thin-film excitation light reflector 56 is formed on the inner peripheral surface of the peripheral wall 54 and the inner side surface (bottom surface) of the bottom wall 54 surrounding the sample storage space. . The excitation light reflector 56 only needs to reflect the excitation light Le coming from within the sample storage space toward the sample storage space (that is, inside the sample container), and the specific material is not limited. . Preferable examples include a thin film made of aluminum or gold, a dielectric multilayer film, and other films made of a material having a low refractive index.

  The excitation light reflector 56 only needs to be formed on at least the inner peripheral surface of the peripheral wall 54. However, if the excitation light reflector 56 is also formed on the inner surface of the bottom wall 54 as shown in the figure and reflects the measurement light L2, the measurement light L2 reciprocates in the sample storage space. Since it passes through the sample S, its actual optical path length is about twice the axial length of the peripheral wall 54. Therefore, it is possible to earn a large optical path length while keeping the volume of the sample container 50 small.

  Next, the operation of this photothermal conversion measuring device will be described.

  First, the excitation light Le emitted from the excitation system 10 to the sample container 40 is collected by the condenser lens 42 and is incident into the sample accommodation space from the entrance 55 of the sample container 50. The sample S accommodated in the accommodation space is transmitted. At this time, the predetermined contained material of the sample S absorbs the excitation light Le and generates heat (photothermal effect). Therefore, this calorific value changes according to the content of the contained substance in the sample S.

  Moreover, of the excitation light Le, the light that is to be scattered out of the sample accommodation space is reflected inward by the excitation light reflector 56 surrounding the sample accommodation space, and reentered into the sample accommodation space. The Therefore, the irradiation efficiency of the excitation light Le with respect to the sample S in the sample accommodation space is increased. That is, the photothermal effect of the sample by the excitation light can be enhanced without particularly increasing the excitation light.

  On the other hand, the measurement light L2 introduced from the measurement light 20 into the sample storage unit 40 is reflected by 90 ° by the dichroic mirror 44, and is incident on the sample reception space coaxially with the excitation light Le from the incident port 55. Is done. At this time, since the refractive index in the sample S changes according to the amount of heat generated by the photothermal effect, and the phase difference φ changes according to the refractive index, the measurement system 20 according to the amount of heat generated. The intensity of the interference light between the measurement light L2 returning to the reference light L1 in the measurement system 20 changes. By measuring the interference light intensity with the measurement system 20, a change in the refractive index of the measurement light L2 caused by a temperature change of the sample S is obtained. As a result, the amount (concentration) of the substance contained in the sample Can be analyzed.

  In this apparatus, the fact that the excitation efficiency of the excitation light Le to the sample S is increased by the presence of the excitation light reflector 56 means that the photothermal effect by the specific substance in the sample S is increased correspondingly. It leads to improvement of accuracy (sensitivity). Further, as shown in FIG. 3, in the apparatus in which the measurement light L2 is incident on the sample receiving space coaxially with the excitation light Le, the sample receiving space is parallel to the optical axis direction of both the light Le and L2. In the case of having a shape extending in the direction, the optical path length of the measurement light L2 in the sample S is effectively increased without significantly increasing the overall size of the sample container 50, and the measurement sensitivity by the measurement light L2 is increased. It can be further increased.

  Here, the arrangement region of the excitation light reflector 56 can be set as appropriate. For example, the excitation light reflector 56 may cover only a part of the sample storage space in the optical axis direction of the excitation light Le. Specifically, it may be intermittently arranged in the same direction, or may be provided only in a region near the entrance or only in a region on the back side of the sample storage space. However, if the excitation light reflector 56 covers the entire area of the sample storage space as shown in the drawing, the irradiation efficiency of the excitation light can be further increased.

  Further, the excitation light reflector 56 is not necessarily limited to being on the inner side surface of the container body. For example, at least a part of the portion of the container body that faces the sample storage space is a transparent body that transmits the excitation light, and the excitation is provided on the opposite side of the sample storage space with the transparent body interposed therebetween. A light reflector may be located. In the case of the sample container having such a configuration, the excitation light reflector and the sample in the sample storage space are prevented from coming into direct contact with each other. Therefore, inconvenience due to the contact, such as deterioration of the excitation light reflector, etc. The inconvenience can be avoided.

  An example thereof is shown in FIG. 4 as a second embodiment. In the sample container 50 shown in the figure, the bottom wall 52 and the peripheral wall 54 constitute an outer container, and an excitation light reflector 56 is provided on the inner surface thereof in the same manner as in the first embodiment. An inner container 58 is provided that is inserted inside the outer container.

  The inner container 58 is made of a translucent material (particularly a material having a high ultraviolet light transmission property) such as quartz or PDMS (polydimethyl siloxane), and is detachably inserted into the outer container with almost no gap. It has an external shape. That is, it has an outer surface shape that is substantially the same as the surface shape of the excitation light reflector 56. In other words, the excitation light reflector 56 is provided on the surface of the inner surface of the outer container that faces the inner container 58.

  The inner container 58 has a shape surrounding a sample storage space that is slightly smaller than the inner space of the outer container, and has a shape having an incident port 55 for allowing the excitation light Le to enter the sample storage space. is doing. That is, the outer container has a shape that is slightly smaller, and is inserted into the outer container in a posture that opens in the same direction as the outer container (opens on the excitation light incident side).

  Also in the sample container 50, the sample S is stored in the sample storage space surrounded by the inner container 58, and the excitation light Le and the measurement light L2 are incident on the sample storage space from the incident port 55. The photothermal conversion measurement similar to that in the first embodiment can be performed. In addition, the excitation light Le incident on the sample accommodation space is scattered from the same space to the outside, and passes through the inner container 58 made of the translucent material. Since the light is reflected and again enters the sample accommodation space, the incident efficiency of the excitation light can be increased as in the first embodiment.

  Furthermore, in this sample container 50, the incident efficiency of the excitation light Le can be increased while preventing the excitation light reflector 56 and the sample S from coming into direct contact.

  Further, when exchanging the sample S, it is only necessary to attach and detach the inner container 58, and the outer container and the excitation light reflector 56 can be repeatedly used as they are. Therefore, it is possible to efficiently perform measurement on a plurality of types of samples. The inner container 58 may be a commercially available relatively inexpensive transparent cell.

  In the sample container according to the present invention, the container body may surround a plurality of sample storage spaces. Moreover, a part of the container body may have a light guide function. An example thereof is shown in FIGS. 5A and 5B as a third embodiment.

  The container body of the sample container 60 shown in the figure is composed of a main body plate 62, a pair of left and right prisms 63 and 64, and a lid plate 65.

  On the upper surface of the main body plate 62, a plurality of sample storage space forming grooves 62a are formed. Each of the grooves 62a has, for example, a square or rectangular cross-sectional shape, extends from the left end to the right end of the main body plate 62, and these grooves 62a are parallel to each other in the front-rear direction (in FIG. Direction). Then, the cover plate 65 is overlaid on the main body plate 62 so as to cover these grooves 62a from above.

  Further, the inner surface of each groove 62a and the lower surface of the cover plate 65 are coated with an excitation light reflector 66, respectively, and the excitation light reflector 66 allows the sample storage space corresponding to each groove 62 to be orthogonal to the axial direction. It is arranged to surround from the direction to do.

  The prisms 63 and 64 have the main body plate 62 and the cover plate so as to block the left and right ends of the sample storage space corresponding to the grooves 62a (that is, the sample storage space surrounded by the main body plate 62 and the cover plate 65). It is joined to the left and right end faces of 65. Specifically, each of the prisms 63 and 64 has an isosceles triangular cross section, and a height (horizontal plane) corresponding to one of the equilateral sides is flush with the upper surface of the lid plate 65. At a position, a surface (vertical surface) corresponding to the other equal side is joined to the end surfaces of the plates 62 and 65.

  Further, in each of the prisms 63 and 64, the slope corresponding to the hypotenuse of the isosceles triangle is coated with the measurement light reflecting films 63a and 64a, respectively. These measurement light reflection films 63a and 64a transmit the excitation light Le and reflect only the measurement light L2. For example, a dielectric multilayer film is suitable. As the dielectric multilayer film, for example, when the measurement light L2 is a He—Ne laser, a metal oxide multilayer film is suitable.

  The sample container 60 has a posture in which the axial direction of each sample storage space is parallel to the optical axis of the excitation light Le from the excitation system 10 and the prism 64 faces the excitation system 10 side. The sample storage unit 40 is installed. Further, the measurement system 20 makes the measurement light L2 incident on the upper surface of the prism 63 with respect to the sample container 60. Then, the measurement light L2 is reflected by the measurement light reflecting film 63a of the prism 63, so that the measurement light L2 enters the sample storage spaces along the axial direction (longitudinal direction) and exits from the sample storage spaces. The incident position of the measurement light L2 is set so that the measurement light L2 is reflected by the measurement light reflection film 64a of the prism 64 and returned to the measurement system 20.

  Also in this configuration, the excitation light Le introduced from the excitation system 10 into the sample storage unit 40 is collected by the condenser lens 42 and is incident on the sample S in each sample storage space through the prism 64. Cause a photothermal effect. Of the excitation light Le, light that is to be scattered out of the sample accommodation spaces is reflected by an excitation light reflector 66 formed on the surfaces of the main body plate 62 and the cover plate 65. That is, it is re-entered into the sample storage space.

  On the other hand, the measurement light L2 incident on the upper surface of the prism 63 from the measurement system 20 is reflected by the measurement light reflecting film 63a of the prism 63 and is incident on the sample storage spaces. After coming off, it is reflected upward by the measurement light reflector 64 a of the prism 64 and returned to the measurement system 20.

  According to this configuration, the photothermal conversion measurement of a plurality of samples S can be performed simultaneously with a single sample container 60. Further, since the sample container 60 itself has light guide means (prisms 63 and 64) for guiding the measurement light into the sample accommodating space, the configuration of the optical system around the sample container 60 can be simplified. .

  Further, as shown in FIG. 6 as the fourth embodiment, the vertical surface of the prism 64 of the sample container 60 according to the third embodiment (that is, the surface facing the main body plate 62 and the cover plate 65). In the case of the coating with the measurement light reflecting film 62b, the measurement light L2 passing through the sample accommodation space is reflected by the measurement light reflection film 62b and retransmits through the sample accommodation space. Doubles the optical path length in the accommodation space.

  A fifth embodiment is shown in FIG. The sample container shown here uses a transparent and elongated glass tube (for example, a capillary glass tube) 68, and its inner space is used as a sample storage space. However, the glass tube 68 has a shape whose inner diameter is minute compared to the axial length (for example, the axial length is 1 to 2 m and the inner diameter is 0.1 to 0.2 mm). It is difficult to coat the inner surface with an excitation light reflector (for example, film formation by vapor deposition). Therefore, in this embodiment, the outer peripheral surface of the glass tube 68 is mirror-coated so that the excitation light reflector 66 is formed on the outer peripheral surface.

  Also in this capillary glass tube 68, the excitation light and the measurement light are coaxially incident on the sample S accommodated in the inner space along the axial direction of the glass tube 68, so that the photothermal conversion measurement with high accuracy is performed. Is done efficiently. That is, the light that reaches the excitation light reflector 66 from the inner space through the tube body out of the excitation light is reflected by the reflector 66 toward the inner space (that is, re-entered in the same space). Incident efficiency of excitation light is increased. In addition, the optical path length of the measurement light in the inner space can be increased while avoiding an increase in the size of the entire sample container.

  In the sample container 50 shown in FIG. 3, the bottom wall 52 and the peripheral wall 54 are made of quartz, and the surface thereof is coated with an aluminum thin film corresponding to the excitation light reflector 56. The axial length Z of the peripheral wall 54 is 1.5 cm (therefore, the optical path length of the measuring light is 3 cm), and the inner diameter (that is, the diameter of the sample storage space) is 5 mm.

  An aqueous dye solution is placed as sample S in the sample storage space. Excitation light emitted from an LED or mercury lamp is incident on the sample S, and measurement light composed of a He—Ne—laser (wavelength 633 mm) is incident coaxially with the excitation light.

It is a whole lineblock diagram of a photothermal conversion measuring device concerning a 1st embodiment of the present invention. (A) and (b) are figures which show the example of the sample accommodating part in the said photothermal conversion measuring apparatus. It is sectional drawing of the sample container installed in the said sample accommodating part. It is sectional drawing of the sample container which concerns on the 2nd Embodiment of this invention. (A) is a partial top view of the sample container which concerns on the 3rd Embodiment of this invention, (b) is the 4B-4B sectional view taken on the line of (a). It is sectional drawing of the sample container which concerns on the 4th Embodiment of this invention. It is sectional drawing of the sample container which concerns on the 5th Embodiment of this invention.

Explanation of symbols

L1 polarized light (reference light)
L2 polarized light (excitation light)
Le Excitation light S Sample 10 Excitation system 20 Measurement system 40 Sample container 50 Sample container 52 Bottom wall (container)
54 Perimeter wall (container)
55 Entrance 56 Excitation light reflector 58 Inner container 60 Sample container 62 Main plate (container)
63 Prism (container)
64 Prism (container)
65 Lid (container)
66 Excitation light reflector 68 Capillary glass tube (container)

Claims (8)

A sample container used in a photothermal conversion measurement device that measures the amount of heat generated by the sample by the excitation light incident on the sample and the photothermal effect thereof,
A container body that encloses a sample storage space for storing the sample and has an entrance for allowing the excitation light to enter the sample storage space;
An excitation light reflector that surrounds the sample storage space from a direction substantially orthogonal to the optical axis direction of the excitation light in the sample storage space and reflects the excitation light coming from the sample storage space toward the sample storage space; A sample container. The sample container of claim 1,
The sample container is characterized in that the excitation light reflector covers the entire area of the sample storage space in the optical axis direction of the excitation light in the sample storage space. The sample container according to claim 1 or 2,
The sample container is characterized in that the excitation light reflector is on an inner surface of the container body surrounding the sample housing space. The sample container according to claim 1 or 2,
At least a part of the container body that faces the sample storage space is a transparent body that transmits the excitation light, and the excitation light is reflected on a side opposite to the sample storage space with the transparent body interposed therebetween. A sample container in which a body is located. The sample container of claim 4,
The container body includes an inner container that includes the translucent body and surrounds the sample storage space, and an outer container positioned outside the inner container, and the inner container is detachably inserted into the outer container. The sample container is characterized in that the excitation light reflector is provided on a surface of the inner side surface of the outer side container facing the translucent body. In the sample container according to any one of claims 1 to 5,
The sample container is characterized in that the sample storage space has a shape extending in a direction parallel to the optical axis direction of the excitation light entering the same space. A photothermal conversion measuring device for measuring the calorific value of the sample due to the photothermal effect when excitation light is incident on the sample,
The sample container according to any one of claims 1 to 6, which accommodates the sample;
An excitation light incident optical system that makes the excitation light incident on the sample accommodated in the sample accommodating space of the sample container from the incident port of the sample container;
A photothermal conversion measurement apparatus comprising: a measurement apparatus that transmits measurement light different from the excitation light to the sample and measures a phase change of the transmitted measurement light. A photothermal conversion measuring device for measuring the calorific value of the sample due to the photothermal effect when excitation light is incident on the sample,
The sample container according to claim 6, which accommodates the sample;
An excitation light incident optical system that makes the excitation light incident on the sample accommodated in the sample accommodating space of the sample container from the incident port of the sample container;
A measurement device that transmits measurement light different from the excitation light to the sample and measures a phase change of the transmitted measurement light; and
The excitation light incidence optical system and the measurement device are characterized in that the excitation light and the measurement light are incident on the sample in the sample accommodation space coaxially in a direction along the longitudinal direction of the sample accommodation space. Photothermal conversion measuring device.

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