JP4708139B2 - Photodetector - Google Patents

Description

  The present invention relates to a photodetecting device including an integrating sphere for observing light to be measured generated by irradiating a sample with excitation light, and a sample holder removably attached to the integrating sphere, and a cell in the sample holder. The present invention relates to a jig for a sample holder for attaching the.

An integrating sphere is used to measure the intensity of the light to be measured when the light to be measured is generated radially. The integrating sphere is coated with a high diffuse reflection powder on the inner wall of the spherical body, and when the light to be measured is generated radially, the diffuse diffuse reflection is performed by the high diffuse reflection powder. The diffusely reflected light is incident on the photodetector, the output signal thereof is guided to the optical intensity meter, and the intensity of the light to be measured emitted can be measured. Such integrating spheres are disclosed in the following Patent Documents 1 to 3.
Japanese Patent No. 2517102 Japanese Patent No. 2811565 Japanese Patent Publication No.54-35114

  The integrating spheres disclosed in Patent Documents 1 to 3 are for measuring a light to be measured from a solution placed in a cell by arranging a reaction tube called a cell therein. By the way, in the conventional integrating sphere as exemplified in Patent Documents 1 to 3, when the light to be measured is measured for the solution placed in the cell, the intensity of the light to be measured may not always be measured accurately.

  Therefore, in the present invention, there are provided a photodetection device for more accurately measuring the light to be measured from the sample accommodated in the cell, and a sample holder jig for attaching the cell to the sample holder used in the photodetection device. The purpose is to provide.

  The inventors of the present invention have repeatedly studied the cause of the fact that the intensity of the light to be measured cannot be measured accurately in the conventional integrating sphere. When the sample accommodated in the cell is irradiated with excitation light, light to be measured is generated from the sample. This generated light to be measured generally includes at least one component of the reflected component of the excitation light and the component generated from the sample that has absorbed the excitation light (for example, if any one of the components is filtered, Consisting of the other component). Then, the excitation light is introduced into the integrating sphere to irradiate the sample, and measured light generated in response to the irradiation returns to a hole provided in the integrating sphere for excitation light incidence under certain conditions. I found out. The present invention has been made based on this finding.

A light detection apparatus according to the present invention is a light detection apparatus including an integrating sphere for observing light to be measured generated by irradiating a sample with excitation light and a sample holder that is detachably attached to the integrating sphere. The integrating sphere has an excitation light introduction hole for introducing excitation light and a sample introduction hole for introducing a cell held by the sample holder. The cell is formed in the prismatic part and the prismatic part. The sample holder is locked to the sample introduction hole, the holding unit for holding the branch of the cell for containing the sample, and the excitation light is incident on the cell. For placing the cells in a state where the prisms are angled around the branch pipe so that the incident surface and the exit surface parallel to the incident surface are inclined from the plane perpendicular to the optical axis of the excitation light. And positioning means.

  According to the present invention, the sample holder that can be arranged with the incident surface of the cell in which the sample is accommodated inclined with respect to the optical axis of the excitation light is detachably attached to the integrating sphere. On the other hand, the cell can be held at an angle corresponding to the shape of the cell. Accordingly, it is possible to set so that measured light generated by irradiating the sample with excitation light does not return to the excitation light introduction hole.

  In the present invention, it is also preferable that the holding portion has a gripping portion for gripping the cell, and the gripping portion has a buffer member in a portion in contact with the cell. Since the gripping portion having the buffer member in the portion in contact with the cell holds the cell, it can be held without damaging the cell.

  In the present invention, it is also preferable that the positioning means is a locking portion for locking the sample holder to the integrating sphere. As a positioning means for positioning the cell such that a locking portion such as a positioning pin for locking the sample holder to the integrating sphere tilts the incident surface when the excitation light is incident on the cell from a plane perpendicular to the optical axis of the excitation light Since it functions, the sample holder can be easily attached and detached.

  The jig for a sample holder according to the present invention includes a cell introduced into an integrating sphere for observing light to be measured generated by irradiating a sample with excitation light, and a sample introducing hole provided in the integrating sphere. A jig for a sample holder for adjusting a relative positional relationship between a detachably mounted sample holder for holding a cell, and a main body extending along the cell, and formed on the main body. A holder holding portion for holding the sample holder, and an angle forming means that is formed in the main body portion and directs an incident surface when excitation light is incident on the cell in a predetermined direction with respect to the sample holder. Features.

  According to the present invention, it is possible to arrange a cell oriented in a predetermined direction with respect to a sample holder while holding the sample holder. If the cell is held by the sample holder in this arrangement state, the cell can be held in a predetermined positional relationship with respect to the sample holder. Therefore, the sample holder holding the cell can be attached to the integrating sphere, and the incident surface of the cell can be held at a predetermined angle with respect to the optical axis of the excitation light.

  In the present invention, it is also preferable that the angling means is a hole having a shape substantially the same as the cross-sectional shape of the cell, formed in the cell holding portion that extends so as to intersect the main body portion. Since the cell is oriented with a hole having substantially the same shape as the cross-sectional shape of the cell, it can be oriented easily and accurately.

  In the present invention, it is also preferable that the angling means is a mark provided at a predetermined position where the cell is seen. Since the mark is provided at the position where the cell is seen, the angle of the cell with respect to the sample holder can be adjusted and held in accordance with the mark.

  In the present invention, it is also preferable to provide height adjusting means for matching the position of the optical axis of the excitation light in the integrating sphere with the incident position of the excitation light in the cell. Since the position of the optical axis of the excitation light and the incident position of the cell can be held together, it is possible to accurately irradiate the sample accommodated in the cell with the excitation light.

  The light detection device according to the present invention is a light detection device including an integrating sphere for observing light to be measured generated by irradiating a sample with excitation light, and a sample holder that is detachably attached to the integrating sphere. The integrating sphere includes an excitation light introduction hole for introducing excitation light, a first sample introduction hole for introducing the first sample holder, and a second sample introduction hole for introducing the second sample holder. The first sample holder includes a holding unit for holding a cell for containing the sample, and a first locking unit for locking the first sample holder to the integrating sphere, The two-sample holder includes a sample stage for placing the sample and a second locking portion for locking the second sample holder to the integrating sphere, and the first sample introduction hole is an excitation light introduction hole And the position where the second sample introduction hole is formed as both poles. A on the meridian, is formed in a position that is substantially equidistant from the poles, characterized in that.

  According to the present invention, the first sample holder and the second sample holder are provided, and the first sample introduction hole is provided between the excitation light introduction hole and the second sample introduction hole. The first sample holder can be disposed between the two sample holders. Accordingly, the first sample holder can be arranged with the second sample holder attached to the integrating sphere, and the light to be measured by the sample held by the first sample holder can be observed. Further, the second sample holder can be arranged with the first sample holder attached to the integrating sphere, and the light to be measured by the sample held by the second sample holder can be observed.

  In the present invention, the first locking portion has positioning means for arranging the cell so that the incident surface when the excitation light is incident on the cell is inclined from the plane perpendicular to the optical axis of the excitation light. Is also preferable. Since the cells are arranged so as to be inclined from the plane perpendicular to the optical axis of the excitation light, it is possible to suppress the excitation light from returning to the excitation light introduction hole.

  In the present invention, the mounting surface on which the sample is mounted is formed on the sample stage so as to be inclined from a surface perpendicular to the optical axis of the excitation light, and the second locking portion has the mounting surface. It is also preferable that the second sample holder is locked to the integrating sphere so that the second sample holder is oriented in a predetermined direction within the integrating sphere. Since the mounting surface is formed so as to be inclined from the surface perpendicular to the optical axis of the excitation light, it is possible to suppress the excitation light from returning to the excitation light introduction hole.

  Moreover, in this invention, it is also preferable that the site | part exposed to the inside of the integrating sphere in at least one of a 1st sample holder and a 2nd sample holder becomes a diffuse reflection surface. Since the part exposed to the integrating sphere of the first sample holder and the second sample holder is covered with the diffuse reflector, one sample holder is attached with the first sample holder and the second sample holder attached to the integrating sphere. When observing the sample held by the lens, the portion of the other sample holder covered with the diffuse reflector can function as a part of the inner wall of the integrating sphere.

  In the present invention, it is also preferable that the integrating sphere is attached to an L-shaped gantry having two mounting surfaces. Since the integrating sphere is attached to the L-shaped gantry, the angle at which the integrating sphere is held can be changed by 90 degrees, and the integrating sphere can be placed vertically and horizontally. Therefore, for example, when the second sample holder is used, it can be placed vertically, and when the first sample holder is used, it can be placed horizontally.

  According to the present invention, it is possible to set so that measured light generated by irradiating a sample with excitation light does not return to the excitation light introduction hole. Therefore, the light to be measured of the sample accommodated in the cell can be measured more accurately.

  The knowledge of the present invention can be easily understood by considering the following detailed description with reference to the accompanying drawings shown for illustration only. Subsequently, embodiments of the present invention will be described with reference to the accompanying drawings. Where possible, the same parts are denoted by the same reference numerals, and redundant description is omitted.

  A photodetection device according to an embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a view showing a cross section along the excitation light optical axis L of the photodetecting device 1 of the present embodiment. FIG. 2 is a cross-sectional view taken along the excitation light optical axis L and perpendicular to the cross-section shown in FIG. FIG. 1 shows a case where the light detection device 1 is set up so that the excitation light optical axis L is along the vertical line, and the sample held in the sample holder 40 (second sample holder) is measured. On the other hand, FIG. 2 shows a case where the light detection apparatus 1 is laid so that the excitation light optical axis L is along the horizontal line and the sample held in the sample holder 60 (first sample holder) is measured.

  The light detection apparatus 1 includes an integrating sphere 20 that observes light to be measured generated by irradiating a sample with excitation light, sample holders 40 and 60 that are detachably attached to the integrating sphere 20, and are used for excitation. An L-shaped optical fiber holder 30 for introducing light into the integrating sphere 20, an optical fiber holder 50 for detecting light for acquiring light to be measured, and two mounting surfaces 10a and 10b. A gantry 10 is provided. The integrating sphere 20 is attached to the gantry 10 with a mounting screw 102.

First, referring to FIG. 1, a sample held by the sample holder 40 with the photodetecting device 1 placed upright with the mounting surface 10 a of the gantry 10 facing down so that the excitation light optical axis L is along the vertical line. The configuration of the photodetecting device 1 when measuring the above will be described.
Here, the sample holder 40 is mainly used for measurement of a solid sample, a powder sample, etc., and these samples may be held by the sample holder 40 in a form applied to a substrate such as glass, or a container such as a petri dish. May be held by the sample holder 40 in a form housed in the container.

  The integrating sphere 20 is formed with an excitation light introduction hole 201, a sample introduction hole 202 (second sample introduction hole), and a photodetector introduction hole 203. The excitation light introduction hole 201 is formed in one of the poles (upper pole in FIG. 1) where the integrating sphere 20 and the vertical line (vertical line in the state of FIG. 1) intersect. The sample introduction hole 202 is formed at the pole opposite to the excitation light introduction hole 201 (the lower pole in FIG. 1). The photodetector introduction hole 203 is on a meridian having both the position where the excitation light introduction hole 201 is formed and the position where the sample introduction hole 202 is formed, and is equidistant from both the poles. Is formed. The light shielding plate 204 is formed between the sample introduction hole 202 and the photodetector introduction hole 203.

  An excitation light optical fiber holder 30 is attached to the excitation light introduction hole 201, a sample holder 40 is attached to the sample introduction hole 202, and a light detection optical fiber holder 50 is attached to the photodetector introduction hole 203.

  An optical fiber (not shown) attached to the fiber holder 301 of the excitation light optical fiber holder 30 is connected to an excitation light source (not shown). Excitation light emitted from an excitation light source (not shown) is guided to the lens 302 of the excitation light optical fiber holder 30 through an optical fiber (not shown). The excitation light is guided into the integrating sphere 20 along the optical axis L, and is applied to the sample S placed on the sample holder 40 disposed opposite to the excitation light optical fiber holder 30.

  When the sample S is irradiated with excitation light, light to be measured is generated that includes a reflection component of the excitation light and a component generated from the sample S that has absorbed the excitation light. The light to be measured from the sample S irradiated with the excitation light is subjected to multiple diffuse reflection by a diffuse reflector such as barium sulfate coated on the inner wall of the integrating sphere 20. The diffusely reflected measurement light is incident on an optical fiber 501 attached to the optical fiber holder 50 for light detection. The optical fiber 501 is connected to a photodetector, for example, but not limited to, a multichannel photodetector (not shown). Therefore, the light to be measured incident on the optical fiber 501 is guided to a multichannel photodetector (not shown) through the optical fiber 501. Measurement data detected by a multi-channel photodetector (not shown) is output to a data processing device (not shown) for data processing, and the intensity of the light under measurement is measured. In this embodiment, the photodetector is used by being connected to the optical fiber 501, but a configuration in which a photodetector such as a photoelectric conversion element is directly attached to the light detection introduction hole 203 may be used. In this specification, a photodetector is used as including both forms.

  The light shielding plate 204 is provided to prevent the light to be measured from the sample S from directly entering the optical fiber 501. This is because when the light to be measured is directly incident on the optical fiber 501, a significant error occurs in the intensity data of the light to be measured. The light shielding plate 204 is preferably a meridian that passes through the photodetector introduction hole 203 when the position where the excitation light introduction hole 201 is formed and the position where the sample introduction hole 202 is formed are both poles. It is formed at a position on the upper side that is substantially equidistant from the photodetector introduction hole 203 and the sample introduction hole 202.

  Next, the sample holder 40 will be described with reference to FIGS. FIG. 3 is an enlarged cross-sectional view of the vicinity of the sample holder 40 in FIG. FIG. 4 is an enlarged cross-sectional view of the vicinity of the sample holder 40 in FIG.

  The sample holder 40 includes a sample stage 41, a handling knob 42, a holder main body 43, and an attachment flange 44 (locking portion). A sample S is placed on the placement surface 411 of the sample stage 41. The mounting surface 411 exposed inside the integrating sphere is preferably coated with a diffuse reflector such as barium sulfate, which will be described later. As shown in FIG. 3, the mounting surface 411 is formed so as to be inclined from a plane perpendicular to the optical axis L of the excitation light. The sample stage 41 is held between the holder main body 43 and the handling knob 42. The holder main body 43 to which the sample stage 41 and the handling knob 42 are attached is inserted into the attachment flange 44. As shown in FIG. 4, a fixing projection 101 extending from the gantry 10 is inserted into the mounting flange 44, and a fixing screw 45 is provided on the side opposite to the inserted portion. When the fixing screw 45 is tightened, the holder main body 43 is sandwiched and fixed between the fixing protrusion 101 and the fixing screw 45.

  The sample holder 40 will be described in more detail. FIG. 5 is an exploded perspective view of the sample holder 40. The holder main body 43 includes a cylindrical tube portion 431 and a flange portion 432 provided at one end of the tube portion 431. A positioning notch 432a is formed in the collar portion 432. The flange portion 432 is also formed with a screw hole 432b for attaching the handling knob 42. Folded portions (not shown) are formed at the multi-ends of the cylindrical portion 431, and the sample table 41 is sandwiched and fixed with the handling knob 42.

  The handling knob 42 includes a first collar part 421, a second collar part 422, a small diameter part 423, and a large diameter part 424. The small diameter portion 423 has a cylindrical shape and is formed between the first flange portion 421 and the second flange portion 422. The large diameter portion 424 has a cylindrical shape and is formed to extend from the second flange portion 422 to the opposite side to the small diameter portion 423. The first flange 421 is a part for fixing the sample table 41 with the holder main body 43 therebetween. The second flange 422 is provided with a hole 422 a at a position corresponding to the screw hole 432 of the holder main body 43. Accordingly, when the sample base 41 is sandwiched and the holder main body 43 and the handling knob 42 are screwed together, the sample base 41, the holder main body 43, and the handling knob 42 can be fixed to each other. In addition, since the O-ring 46 is disposed between the sample stage 41 and the handling knob 42, the sample stage 41 can be prevented from rotating with respect to the handling knob 42.

  The mounting flange 44 has a flange main body 441 and a fixing screw 45. The flange body 441 is provided with positioning pins 441b. The positioning pin 441 b is provided at a position corresponding to the positioning notch 432 a of the holder main body 43. Therefore, when the cylindrical portion 431 of the holder main body 43 is inserted into the flange main body 441, the positioning pins 441b are inserted into the positioning notches 432a, and the holder main body 43 is positioned with respect to the flange main body 441. A fixing hole 441a is formed on the side opposite to the position where the fixing screw 45 is provided. The fixing hole 441a is a hole into which the above-described fixing protrusion 101 is inserted.

  The sample stage 41 will be described with reference to FIG. FIG. 6 is a plan view of the sample stage 41 as viewed from the placement surface 411 side. In FIG. 6, it is assumed that the upper side of the drawing is a portion where the placement surface 411 is high, and the lower side of the drawing is a portion where the placement surface 411 is low. On the mounting surface 411, positioning portions 412 are formed at four locations. Concave portions 413 are formed on the mounting surface 411 inside the positioning portions 412 formed at the four locations.

  The positioning portions 412 are arranged in the vicinity of the outer periphery of the circular mounting surface 441 so as to be equidistant from each other. Each positioning part 412 has a convex part 412a and a concave part 412b surrounded by the convex part 412a. The positioning portion 412 is formed by forming a prismatic protrusion, making a cylindrical hole in the center of the prismatic protrusion, and cutting out one corner of the prismatic protrusion. A portion cut out in each positioning portion 412 is formed so as to face the center direction of the placement surface 411.

  Therefore, when the sample S has a rectangular shape as illustrated, the four corners of the sample S enter the concave portions 412b of the positioning portions 412 and are held by the convex portions 412a. Further, when the sample is put in the holding member S2 such as a circular petri dish, the sample is held by the positioning portions 412 formed at four places, like the rectangular sample.

  When the sample S is a rectangular glass substrate coated with a light emitting material, a part of the photons emitted from the light emitting material propagates through the glass substrate as an optical waveguide and is emitted from the end face. Therefore, when the form of the positioning portion 412 as in the present embodiment is adopted, the contact portion between the sample S and the positioning portion 412 can be reduced, and the photons emitted from the end surface of the sample S can be more accurately detected. Can be measured.

  Even if the light emitting material is attached to the mounting surface 411 side of the sample S, the concave portion 413 is formed on the mounting surface 411, so that the light emitting material is attached to the mounting surface 411. Can be suppressed. Moreover, since the positioning part 412 is also provided with the recessed part 412b, adhesion of the luminescent material to the positioning part 412 can also be suppressed.

  A modification of the positioning portion 412 is shown in FIG. In the sample table 71 shown in FIG. 7A, a pair of positioning portions 412 are formed on the placement surface 711, and one protrusion 712 is formed. The pair of positioning portions 412 and the protrusions 712 are arranged in the vicinity of the outer periphery of the circular mounting surface 441 so as to be equidistant from each other.

  A sample table 72 shown in FIG. 7B has a pair of positioning portions 412 formed on the mounting surface 721. The pair of positioning portions 412 are provided at positions corresponding to the lower two locations of the four positioning portions 412 in FIG. Since the mounting surface 721 is inclined so that the upper side in the drawing is high and the lower side in the drawing is low, the sample S (holding member S2) can be held by the two positioning portions 412.

  Further, as described with reference to FIG. 6, the sample S can be prevented from coming into contact with the mounting surface 411 other than the mode in which the concave portion 413 is formed on the mounting surface 411. One example will be described with reference to FIG. FIG. 8 is a cross-sectional view of a sample stage for showing an example thereof.

  The example shown in FIG. 8A shows a sample table 81 in which the shapes of the four positioning portions 412 of the sample table 41 described with reference to FIG. 6 are changed. 8A is a cross-sectional view of the vicinity of the positioning portion 812 formed on the mounting surface 811 of the sample table 81. FIG. As shown to (a) of FIG. 8, the positioning part 812 has the convex part 812a and the recessed part 812b enclosed by the convex part 812a. The concave portion 812b is in a state of being recessed with respect to the convex portion 812a, but is protruding from the placement surface 811. Therefore, when the sample S is arranged so as to be placed on each positioning portion 812, the sample S is held in a state where it rides on the concave portion 812 b of each positioning portion 812, and a gap is formed between the placement surface 811.

  The example shown in FIG. 8B shows a sample stage 82 in which the shapes of the positioning portion 412 and the protrusion 712 of the sample stage 71 described with reference to FIG. 8B is a cross-sectional view of the vicinity of the protrusion 813 (near the center of the sample table 81) formed on the mounting surface 821 of the sample table 81. FIG. As shown in FIG. 8B, the positioning portion 812 has the same shape as that described with reference to FIG. Further, the protrusion 813 is formed to have the same height as the concave portion 812b of the positioning portion 812 with reference to the mounting surface 821. Accordingly, when the sample S is disposed so as to be placed on each positioning portion 812 and is disposed so as to ride on the protrusion 813, the sample S is held and placed on the recess 812b and the protrusion 813 of each positioning portion 812. A gap is formed between the surface 811.

  The sample holder 40 of the present embodiment includes a sample stage 41 having a mounting surface 411 formed so as to be inclined from a surface perpendicular to the optical axis L of the excitation light, and the mounting surface 411 is directed in a predetermined direction. Since the mounting flange 44 that is engaged with the integrating sphere 20 is provided, the sample S placed on the placement surface 411 can be arranged at a predetermined angle with respect to the optical axis L of the excitation light. . Therefore, the excitation light is incident on the sample S obliquely, and the reflected measurement light does not return to the excitation light introduction hole 201. Further, since the predetermined angle depends on the inclination of the mounting surface 411, for example, when measuring a plurality of types of samples by changing the predetermined angle, it is possible to cope with the problem by changing the sample stage 41. In addition, since the sample holder 40 is fixed by the mounting flange 44 so that the mounting surface 411 is oriented in a predetermined direction, the light to be measured reflected by the sample S is always directed to a predetermined portion in the integrating sphere 20. Irradiation is performed, and errors in measurement values can be reduced.

Subsequently, with reference to FIG. 2, the light detection device 1 is laid down (sideways) with the mounting surface 10 b of the gantry 10 facing down so that the excitation light optical axis L is along the horizontal line, and the sample holder 60. The structure of the photodetection device 1 when measuring the sample held in the above will be described.
Here, the sample holder 60 is mainly used for measurement of a liquid sample in which a dye or the like is dissolved, and the sample is held by the sample holder 60 in a form accommodated in a container such as an optical cell.

  The positional relationship between the excitation light introduction hole 201, the sample introduction hole 202, and the photodetector introduction hole 203 is as described above. The sample introduction hole 205 (first sample introduction hole) is the center of each of the integrating sphere 20 and the vertical line (vertical line, excitation light introduction hole 201, sample introduction hole 202, and photodetector introduction hole 203 in the state of FIG. It is formed on one of the poles (vertical line on the plane passing through) (upper pole in FIG. 2). A sample holder 60 is attached to the sample introduction hole 205.

  As described above, the pumping light emitted from the pumping light source (not shown) is guided to the lens 302 of the pumping light optical fiber holder 30 through the optical fiber (not shown). The excitation light is guided into the integrating sphere 20 along the optical axis L, and is applied to the solution sample in the cell C held by the sample holder 60. The cell C is made of glass, and includes a prism portion and a branch pipe connected to the prism portion. In this embodiment, the cell C is a glass square cell having an optical path length of 10 mm.

  When the excitation light is irradiated onto the solution sample accommodated in the cell C, light to be measured is generated that includes a reflection component of the excitation light and a component emitted from the solution sample that has absorbed the excitation light. The light to be measured from the solution sample in the cell C irradiated with the excitation light is subjected to multiple diffuse reflection by the high diffuse reflector applied to the inner wall of the integrating sphere 20. The diffusely reflected measurement light is incident on an optical fiber 501 attached to the optical fiber holder 50 for light detection. As described above, the light to be measured that has entered the optical fiber 501 passes through the optical fiber 501 and is guided to a photodetector, for example, but not limited to, a multichannel photodetector (not shown). Measurement data detected by a multi-channel photodetector (not shown) is output to a data processing device (not shown) for data processing, and the intensity of the light under measurement is measured.

  The sample holder 60 is detachably attached to the integrating sphere 20 by an attachment flange 75 and a fixing screw 70. The mounting flange 75 and the integrating sphere 20 have a mutual positional relationship defined by locking means such as positioning pins. In addition, the mounting flange 75 and the sample holder 60 have a mutual positional relationship determined by locking means such as positioning pins (locking portions, positioning means). The mounting flange 75 is a ring-shaped flange. When the sample holder 60 is inserted into the ring and a fixing screw 70 screwed into a screw hole provided in the ring-shaped side surface portion is tightened, the sample holder 60 is sandwiched between the integrating sphere 20 and engaged. It is possible to stop.

  A cover 80 is attached to the attachment flange 75 by a fixing screw 85. The cover 80 is provided so as to cover the mounting flange 75, the sample holder 60, and the cell C held by the sample holder 60, and prevents external light from entering the integrating sphere from the outside.

  Next, the sample holder 60 will be described more specifically with reference to FIG. FIG. 9 is a perspective view of the sample holder 60. The sample holder 60 is composed of two parts 62 and parts 64 having substantially the same shape.

  Each of the parts 62 and 64 includes cylindrical portions 621 and 641 (holding portions) having a substantially cylindrical shape, and flat plate portions 622 and 642 having a shape obtained by partially cutting a substantially semicircular shape. The flat plate portion 622 is provided at one end of the cylindrical portion 621 via a recess 623. Similarly, the flat plate portion 642 is provided at one end of the cylindrical portion 641 via a recess 643. The concave portions 623 and 643 are provided along the outer circumferences of the cylindrical portions 621 and 641, respectively.

  A concave portion 624 (gripping portion) and a concave portion 644 (gripping portion) each having a semicircular cross section are formed at portions facing when the component 62 and the component 64 are assembled as the sample holder 60. The concave portion 624 is formed from the flat plate portion 622 to the other end of the cylindrical portion 621 opposite to the flat plate portion 622. Similarly, the concave portion 644 is formed from the flat plate portion 642 to the other end of the cylindrical portion 641 on the opposite side to the flat plate portion 642 provided. Therefore, when the component 62 and the component 64 are assembled, the cell C can be inserted into the cylindrical hole formed by the recess 624 and the recess 644. When the cell C is sandwiched between the component 62 and the component 64, a buffer member (not explicitly shown in FIG. 3) is provided at a portion where the recess 624 and the recess 644 come into contact with the cell C.

  The flat plate portion 622 of the component 62 is provided with a notch 622a. The cutout portion 622a is formed on the outer periphery of the flat plate portion 622 and at a substantially central portion. The notch 622a is used for positioning with a positioning pin (not shown) formed in the mounting flange 75 when the mounting flange 75 is mounted.

  When the sample holder 60 is attached to the sample introduction hole 30, the end faces 625 and 645 of the cylindrical portions 621 and 641 exposed to the inside of the integrating sphere are preferably coated with a diffuse reflector such as barium sulfate. .

  In the above embodiment, the optical measurement in which the sample is individually held in the sample holders 40 and 60 according to the sample form has been described. When the sample holder 40 holds the sample, that is, as shown in FIG. 1, the photodetecting device 1 is placed with the placement surface 10 a of the gantry 10 facing downward (vertically placed), and the sample on the placement surface 411 is placed. When measuring, the sample holder 60 that does not hold the cell C is attached to the sample introduction hole 205, and the end surfaces 625 and 645 coated with the reflective agent of the sample holder 60 receive the light to be measured as part of the inner wall of the integrating sphere. Diffuse reflection. When the sample holder 60 holds the sample, that is, as shown in FIG. 2, the photodetection device 1 is placed with the mounting surface 10 b of the gantry 10 on the downside (sideways), and the sample in the cell C is measured. In this case, the sample holder 40 that does not hold the sample is attached to the sample introduction hole 202, and the mounting surface 411 coated with the reflective agent of the sample holder 40 diffuses and reflects the light to be measured as a part of the inner wall of the integrating sphere. To do. Therefore, since the light detection apparatus according to the present invention can use the sample holder properly according to the sample form, there is no trouble of changing the integrating sphere. Moreover, since the area | region (end surface 625 and 645, mounting surface 411) exposed to the inside of the integrating sphere of each sample holder is coated with the light diffuse reflection agent, highly accurate measurement is attained.

  Note that a sample introduction hole that is not used for measurement may be provided with a cap (not shown) that prevents external light from entering the integrating sphere from the outside, instead of the sample holder according to the present invention. The inside of the cap exposed inside the integrating sphere is preferably coated with a diffuse reflector to act as part of the inner wall of the integrating sphere.

  Subsequently, the specimen holder jig will be described. The jig for the sample holder is inserted into the cell C introduced into the integrating sphere 20 for observing the light to be measured generated by irradiating the sample with excitation light, and the sample introducing hole 205 provided in the integrating sphere 20. It is a jig for a sample holder for adjusting a relative positional relationship with a sample holder 60 that is detachably attached and holds a cell C. This sample holder jig is illustrated in FIG.

  As shown in FIG. 10, the sample holder jig 9 includes a main body portion 92 extending along the cell C, a holder holding portion 922 formed on the main body portion 92 for holding the sample holder 60, and a main body portion 92. And a cell holding portion 91 having a hole 911 (angling means) for directing the incident surface when the excitation light is incident on the cell C in a predetermined direction with respect to the sample holder 60.

  The main body 92 is a semi-cylindrical portion extending along the cell C. A holder holding groove 922 (holder holding part) extending from the end surface 923 and a recess 921 extending to the cell holding part 91 connected to the holder holding groove 922 are formed inside the main body 92.

  The holder holding groove 922 is a groove for holding the sample holder 60, and its cross-sectional shape is semicircular, and is formed along the outer periphery of the cylindrical portions 621 and 641 of the sample holder 60.

  The cross-sectional shape of the recess 921 is also semicircular, and its radius is smaller than the radius of the holder holding groove 922 and is set to a radius that can accommodate the cell C. Therefore, when the cylindrical portions 621 and 641 of the sample holder 60 are stored in the holder holding groove 922, the flat plate portions 622 and 642 abut against the end surface 923, and the tips of the cylindrical portions 621 and 641 are formed between the holder holding groove 922 and the concave portion 921. Abuts on the stepped part between.

  The cell holding portion 91 is a semicircular flat plate portion extending so as to intersect with the main body portion 92. A hole 911 is formed in a substantially central portion of the cell holding portion 91. The hole 911 has substantially the same shape as the cross-sectional shape of the cell C, and is formed so that the cell C can be inserted.

  Here, a state in which the sample holder 60 and the cell C are held in the sample holder jig 9 is shown in FIG. A method of using the sample holder jig 9 will be described with reference to FIG.

  First, the branch pipe C1 of the cell C is held between the parts 62 and 64 of the sample holder 60, and the parts 62 and 64 are temporarily fixed with screws. At this time, the branch pipe C <b> 1 is sandwiched between the recess 624 of the component 62 and the recess 644 of the component 64.

  Subsequently, the assembly including the sample holder 60 and the cell C temporarily fixed in this manner is attached to the sample holder jig 9. Specifically, the prismatic part C <b> 2 of the cell C is stored in the recess 921 formed in the cell holding part 91. Further, the sample holder 60 is accommodated in the holder holding portion 922, and the positioning pin 924 of the sample holder jig 9 is disposed so as to be inserted into the notch portion 622a of the sample holder 60.

  Subsequently, the screw temporarily fixing the component 62 and the component 64 is loosened, the vertical position of the cell C is adjusted, and the prismatic portion C2 of the cell C is inserted into the hole 911. Since the hole 911 in which the prismatic part C2 of the cell C is inserted has substantially the same shape as the cross-sectional shape of the prismatic part C2, the cell C can move up and down.

  Further, when arranged as shown in FIG. 11, a hole 911 is formed so that the cell C forms an appropriate angle with respect to the sample holder 60. In the case of this embodiment, when the sample holder 60 holding the cell C is attached to the integrating sphere 20, the angle formed by the optical axis L of the excitation light and the incident surface of the prism C2 of the cell C is 15 It is set to be °.

  When the positioning is completed, the component 62 and the component 64 are fixed with screws. The cell C and the sample holder 60 fixed to each other in this way are attached to the light detection apparatus 1 as shown in FIG. 2 and irradiated with excitation light.

  Here, FIG. 12 shows a state in which the screw fixing the part 62 and the part 64 is removed from the state of FIG. 11 and the part 64 and the cell C are removed. As shown in FIG. 12, a buffer member 624a is disposed in the concave portion 624 of the component 62 in which the branch pipe C1 of the cell C is held. Therefore, even when the component 62 and the component 64 are screwed in a state where the branch pipe C1 of the cell C is sandwiched, it is possible to suppress the damage to the cell C due to the action of the buffer member 624a, and the sliding of the cell C Movement can be suppressed.

  In addition, it is also preferable that a reflecting material is applied to the tip surface 621a of the component 62 and the tip surface 641a of the component 64 constituting the sample holder 60, respectively.

  A modification of this embodiment is shown in FIGS. The modification shown in FIG. 13 shows a sample holder jig 9a in which marks M1 are provided in two places on the cell holding portion 91 in place of the hole 911 as the angling means. The mark M1 is provided at a predetermined position where the cell C can be seen.

  In the same manner as described above, first, the cell C and the sample holder 60 are temporarily attached to the sample holder jig 9a. Subsequently, the screw temporarily fixing the component 62 and the component 64 is loosened, and the cell C is rotated so that the corner of the prism portion C2 of the cell C matches the mark M1. The mark M <b> 1 is formed so that the cell C forms an appropriate angle with respect to the sample holder 60. When the positioning of the cell C is completed, the part 62 and the part 64 are screwed and fixed.

  In the modification shown in FIG. 13, a mark M2 as a height adjusting means is also provided. This mark M2 is for aligning the position of the optical axis L of the excitation light in the integrating sphere 20 with the incident position of the excitation light in the cell C. The height adjustment is performed in this way because the measurement with the reference sample is performed at the time of the quantum yield measurement, and the height, angle, liquid level, and the like must match between the reference sample and the measurement sample. Because.

  The modification shown in FIG. 14 is a sample holder jig 9b having a main body formed in a columnar shape. When the sample holder jig 9b is used, the positional relationship with the sample holder 60 can be adjusted while the cell C is covered.

  In addition to the prismatic cell described above, the present invention can be suitably applied as long as the incident surface and the exit surface of the excitation light are parallel. A cell such as a tube cell or a cylindrical cell can also be used.

  The effect of this embodiment is demonstrated. The prism C2 of the cell C can be attached to the sample holder 60 in a predetermined direction. When the sample holder 60 and the cell C assembled in this way are attached to the integrating sphere 20, the optical axis L of the excitation light and the incident surface of the cell C can be attached at a predetermined angle (for example, 15 °). Since the reproducibility of the mounting angle can also be improved, the measurement accuracy when performing reference measurement and sample measurement can be improved more effectively.

  By the way, since the incident surface of the cell C is a glass plate, it is optically flat, and a part of light incident on the incident surface is reflected to the side opposite to the incident direction. If it is arranged so as to be perpendicular to the axis L, the light reflected by the incident surface returns to the excitation light introduction hole 201, and the intensity of the light to be measured cannot be measured accurately. Therefore, by arranging the cell C so as to form a predetermined angle with respect to the optical axis L of the excitation light as in this embodiment, the reflected light is prevented from returning to the excitation light introduction hole 201, It can be applied to the inner wall of the integrating sphere 20.

  Further, when the cell C is held by the sample holder 60 as in the present embodiment, only the branch pipe portion of the cell C is held, so that the influence on the measured light can be reduced.

  Further, since it is possible to selectively measure both the sample holder 40 suitable for a sample such as a powder or a thin film, and the sample holder 60 and the cell C suitable for a solution sample, various samples can be obtained with one integrating sphere 20. Can be measured.

It is sectional drawing which shows the photon detection apparatus which concerns on this embodiment. It is sectional drawing which shows the photon detection apparatus which concerns on this embodiment. It is an expanded sectional view of FIG. It is an expanded sectional view of FIG. It is a disassembled perspective view of a sample holder. It is a top view which shows the mounting surface of a sample holder. It is a top view which shows the modification of a mounting surface. It is sectional drawing which shows the modification of a sample stand. It is a perspective view of the sample holder in FIG. It is a perspective view of the jig for sample holders concerning this embodiment. It is a figure for demonstrating the usage method of the jig | tool for sample holders of FIG. It is a figure for demonstrating the sample holder jig | tool and sample holder jig | tool of this embodiment. It is a perspective view of the jig for sample holders which is a modification of this embodiment. It is a perspective view of the jig for sample holders which is a modification of this embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Photodetection device, 10 ... Mounting stand, 20 ... Integrating sphere, 30 ... Optical fiber holder for excitation light, 40, 60 ... Sample holder, 50 ... Optical fiber holder for light detection.

Claims (7)

A photodetecting device comprising an integrating sphere for observing light to be measured generated by irradiating a sample with excitation light, and a sample holder detachably attached to the integrating sphere,
The integrating sphere has an excitation light introduction hole for introducing the excitation light and a sample introduction hole for introducing a cell held by the sample holder,
The cell is composed of a prism portion and a branch pipe connected to the prism portion,
Together with the sample holder is locked to the sample introducing hole, and a holding portion for holding the branch pipes of the cell for accommodating the sample, the incident surface when the excitation light is incident on the cell, And positioning for arranging the cells in a state in which the prism portion is angled about the branch pipe so that an exit surface parallel to the incident surface is inclined from a plane perpendicular to the optical axis of the excitation light. And a light detection device.   The photodetecting device according to claim 1, wherein the holding unit includes a gripping unit that grips the cell, and the gripping unit includes a buffer member at a portion that contacts the cell.   The light detection apparatus according to claim 1, wherein the positioning unit is a locking portion for locking the sample holder to the integrating sphere. A body portion extending along the front SL cells,
A holder holding part formed on the main body part for holding the sample holder;
And angling means for directing a predetermined direction with respect to the formed in the body portion, the sample holder to the incident surface at the time of the excitation light is incident on the cell,
The light detection according to claim 1 , further comprising a sample holder jig for adjusting a relative positional relationship between the cell and the sample holder. Equipment . The angling means, formed in said cell holding part extending so as to intersect the body portion, Ri hole der sectional shape and substantially the same shape of the cell, said by inserting the cell into the hole light detecting device according to claim 4, characterized in Rukoto direct the incident surface in the predetermined direction. The position of the optical axis of the excitation light within the integrating sphere, light as claimed in claim 4 or 5, characterized in that it comprises a height adjusting means for matching, and the incident position of the excitation light in the cell Detection device .   The integrating sphere has a photodetector introduction hole for guiding the light to be measured to a photodetector,
  The cell is inserted from the sample introduction hole into the integrating sphere to a point where an optical axis of the excitation light and a central axis of the photodetector introduction hole intersect. The photodetector of any one of -6.

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