JP2007218632A - Analyzer, refractive index measuring instrument and analysis method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an analyzer capable of calculating the concentration of components in a sample, without relying on the light path length in the sample and reducing the volume of a measuring cell to analyze the sample. <P>SOLUTION: The analyzer 1 is equipped with a refractive index measuring part 18 for measuring the wavelength dependence of the refractive index of the sample and an analysis operation part for calculating the absorption coefficient of the sample, on the basis of the wavelength dependence of the refractive index and analyzing the sample, on the basis of the absorption coefficient. Furthermore, the refractive index measuring part 18 is equipped with a diffraction lattice for diffracting measuring light of a predetermined wavelength region to branch the same at each wavelength; a measuring cell for holding the sample and refracting the measuring light entering on the held sample to deflect the same at each wavelength; a condensing lens for condensing the respective beams of measuring light branched by the diffraction lattice and deflected by the measuring cell; a light-detecting element for detecting the respective beams of measuring light, condensed by the condensing lens and a refractive index operation part for calculating the refractive indexes at each wavelength of the sample, on the basis of the light detecting positions of the respective beams of measuring light detected by the light-detecting element. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an analyzer and an analysis method for measuring an optical characteristic of a sample and analyzing the sample based on the measured optical characteristic, and a refractive index measuring apparatus suitable for application to the analyzer and the analysis method. .

  Conventionally, a sample in which a specimen such as blood or urine and a reagent are mixed is stored in a measurement cell, light is irradiated and transmitted through the stored sample, and the absorbance of the sample is measured based on the amount of transmitted light. An analyzer for performing component analysis of a sample is known (see, for example, Patent Document 1).

Japanese Patent Publication No. 1-30100 JP-A-2005-98743

  By the way, in biochemical, immunological or genetic analyses, there are cases where multi-item analysis is performed on a small amount of specimen, and there is a demand for a small amount of sample. However, in the above-described conventional analyzer, in order to measure the absorbance of the sample with high accuracy, it is necessary to ensure the optical path length of the light transmitted through the sample to be a predetermined length or more, thereby reducing the capacity of the measurement cell. It was difficult. Further, in calculating the component concentration of the sample based on the measured absorbance, there is a problem that an accurate calculation result cannot be obtained unless the optical path length in the sample is strictly determined.

  The present invention has been made in view of the above, and can determine the component concentration of the sample regardless of the optical path length in the sample, and can analyze the sample by reducing the volume of the measurement cell. It is an object of the present invention to provide an analysis apparatus and an analysis method, and a refractive index measurement apparatus suitable for application to the analysis apparatus and the analysis method.

  In order to solve the above-described problems and achieve the object, an analyzer according to claim 1 is configured to measure an optical characteristic of a sample and analyze the sample based on the measured optical characteristic. Refractive index measuring means for measuring the wavelength dependence of the refractive index of the sample, and an analytical calculation means for calculating the absorption coefficient of the sample based on the wavelength dependence of the refractive index and analyzing the sample based on the absorption coefficient And.

  Further, in the analysis apparatus according to claim 2, in the above invention, the refractive index measurement unit includes a light source that emits measurement light in a predetermined wavelength region, a diffraction element that diffracts the measurement light and branches the wavelength. A deflecting container that holds the sample and refracts the measurement light incident on the held sample and deflects it for each wavelength; and each measuring light branched by the diffraction element and deflected by the deflecting container Based on a condensing optical system for condensing, a two-dimensional light receiving element for receiving each measurement light collected by the condensing optical system, and a light receiving position of each measurement light received by the two-dimensional light receiving element, And a refractive index calculating means for calculating a refractive index for each wavelength of the sample.

  According to a third aspect of the present invention, in the above invention, the diffraction element is a one-dimensional diffraction grating, the deflection container holds the sample in a prism shape, and the diffraction of the one-dimensional diffraction grating. The measurement light is deflected in a deflection direction orthogonal to the direction, and the refractive index calculation means calculates the wavelength of each measurement light based on the light reception position in the diffraction direction, and determines the light reception position in the deflection direction. Based on the calculated wavelength and the deflection angle, the refractive index for each wavelength of the sample is calculated based on the calculated deflection angle of the measurement light.

  According to a fourth aspect of the present invention, in the above invention, the refractive index measuring means adjusts at least one of an incident angle and an incident position of the measurement light incident on the sample held by the deflection container. Adjusting means, wherein the incident light adjusting means converts the principal ray of the measurement light, which is the 0th-order diffracted light of the one-dimensional diffraction grating and has a predetermined reference wavelength in the wavelength range, to the light of the condensing optical system. It is characterized by matching with the axis.

  The analyzer according to claim 5 is characterized in that, in the above invention, the predetermined reference wavelength is a longest wavelength in the wavelength range.

  According to a sixth aspect of the present invention, in the above invention, the deflecting container holds the sample in a right-angle prism shape.

  According to a seventh aspect of the present invention, in the above invention, the diffraction element is a two-dimensional diffraction grating, and the condensing optical system is a one-dimensional that condenses the measurement light in a predetermined direction. A condensing optical system, wherein the deflection container holds the sample in a cylindrical lens shape, deflects and condenses the measurement light in a deflection direction orthogonal to the predetermined one direction, and calculates the refractive index. Calculates the wavelength of each measurement light based on the light receiving position in the predetermined light collection direction, and the focal length of the deflection container corresponding to each measurement light based on the light reception position in the deflection direction And the refractive index for each wavelength of the sample is calculated based on the calculated wavelength and focal length.

  According to an eighth aspect of the present invention, in the above invention, the principal ray of the measurement light as the zero-order diffracted light of the two-dimensional diffraction grating coincides with each optical axis of the condensing optical system and the deflection container. It is characterized by doing.

  According to a ninth aspect of the present invention, in the above invention, the deflection container holds the sample having a refractive index smaller than the refractive index of the deflection container in the shape of a concave lens cylindrical lens. The sample having a refractive index larger than the refractive index is held in a cylindrical shape of a convex lens type.

  According to a tenth aspect of the present invention, there is provided the analyzer according to the above invention, wherein the condensing optical system condenses the respective measurement lights using telecentricity.

  The analyzer according to claim 11 is characterized in that, in the above invention, the condensing optical system is an optical system having no chromatic aberration.

  According to a twelfth aspect of the present invention, in the above invention, the condensing optical system is an achromatic lens system or a concave reflecting optical system.

  A refractive index measuring apparatus according to a thirteenth aspect is a refractive index measuring apparatus that measures the wavelength dependence of a refractive index of a sample, and diffracts the measurement light with a light source that emits measurement light in a predetermined wavelength range. A diffraction element that branches for each wavelength, a deflection container that holds the sample, refracts the measurement light incident on the held sample and deflects the measurement light for each wavelength, and is branched by the diffraction element, the deflection container A condensing optical system for condensing each measurement light deflected by the light, a two-dimensional light receiving element for receiving each measurement light condensed by the condensing optical system, and each of the two-dimensional light receiving elements received by the two-dimensional light receiving element And a refractive index calculating means for calculating a refractive index for each wavelength of the sample based on a light receiving position of the measurement light.

  The refractive index measurement apparatus according to claim 14 is the above invention, wherein the diffraction element is a one-dimensional diffraction grating, and the deflection container holds the sample in a prism shape, and the one-dimensional diffraction grating. The measurement light is deflected in a deflection direction orthogonal to the diffraction direction of the light, and the refractive index calculating means calculates the wavelength of each measurement light based on the light reception position in the diffraction direction, and the light reception in the deflection direction. A deviation angle of each measurement light by the deflection container is calculated based on the position, and a refractive index for each wavelength of the sample is calculated based on the calculated wavelength and deviation angle.

  In the refractive index measuring apparatus according to claim 15, in the above invention, the diffractive element is a two-dimensional diffraction grating, and the condensing optical system condenses each measurement light in a predetermined direction. A one-dimensional condensing optical system, wherein the deflection container holds the sample in a cylindrical lens shape, deflects and condenses the measurement light in a deflection direction orthogonal to the predetermined one direction, and the refractive index The computing means calculates the wavelength of each measurement light based on the light receiving position in the predetermined condensing direction, and calculates the wavelength of the deflection container corresponding to each measurement light based on the light receiving position in the deflection direction. A focal length is calculated, and a refractive index for each wavelength of the sample is calculated based on the calculated wavelength and focal length.

  The analysis method according to claim 16 is a refractive index for measuring the wavelength dependence of the refractive index of the sample in the analysis method for measuring the optical property of the sample and analyzing the sample based on the measured optical property. A measurement step; and an analysis calculation step of calculating an absorption coefficient of the sample based on the wavelength dependence of the refractive index and analyzing the sample based on the absorption coefficient.

  In the analysis method according to claim 17, in the above invention, the refractive index measurement step includes a diffraction step of diffracting measurement light in a predetermined wavelength region and branching the measurement light for each wavelength, and the measurement incident on the sample. A deflection step for refracting light and deflecting it for each wavelength; a condensing step for condensing each measurement light branched by the diffraction step and deflected by the deflection step; A light receiving step for receiving measurement light; and a refractive index calculation step for calculating a refractive index for each wavelength of the sample based on a light receiving position of each measurement light in the light receiving step.

  According to the analyzer and the analysis method of the present invention, the wavelength dependency of the refractive index of the sample is measured, the absorption coefficient of the sample is calculated based on the wavelength dependency of the measured refractive index, and the calculated absorption coefficient is calculated. Therefore, the sample component concentration, etc. can be obtained regardless of the optical path length in the sample, and the sample can be analyzed by reducing the volume of the measurement cell. it can. Moreover, according to the refractive index measuring apparatus concerning this invention, the refractive index for every wavelength of a sample can be measured collectively, and the wavelength dependence of the refractive index of a sample can be calculated | required in a short time.

  Exemplary embodiments of an analyzer, a refractive index measuring device, and an analysis method according to the present invention will be described below in detail with reference to the accompanying drawings. Note that the present invention is not limited to the embodiments. In the description of the drawings, the same parts are denoted by the same reference numerals.

(Embodiment 1)
First, an analysis apparatus, a refractive index measurement apparatus, and an analysis method according to the first embodiment of the present invention will be described. FIG. 1 is a diagram illustrating a main configuration of the analyzer 1 according to the first embodiment. As shown in FIG. 1, the analyzer 1 dispenses a sample and a reagent as an analysis target into a measurement cell as a sample, and optically measures a reaction occurring in the dispensed measurement cell, A control analysis mechanism 21 that controls the entire analysis apparatus 1 including the measurement mechanism 11 and analyzes a measurement result in the measurement mechanism 11 is provided. The analyzer 1 automatically performs biochemical, immunological or genetic analysis of a plurality of specimens by linking these mechanisms.

  The measurement mechanism 11 roughly includes a sample transfer unit 12, a sample dispensing unit 13, reagent tables 14A and 14B, reagent dispensing units 15A and 15B, a reaction table 16, a refractive index measuring unit 18, and a cleaning unit 19. The control analysis mechanism 21 includes a control unit 22, an input unit 23, an output unit 24, and a storage unit 25. These units included in the measurement mechanism 11 and the control analysis mechanism 21 are electrically connected to the control unit 22.

  The sample transfer unit 12 includes a plurality of sample racks 12b that hold a plurality of sample containers 12a containing liquid samples such as blood and urine and sequentially transfer them in the direction of the arrows in the figure. The sample in the sample container 12a transferred to a predetermined position on the sample transfer unit 12 is dispensed by the sample dispensing unit 13 to the measurement cell 17 that is arranged and conveyed on the reaction table 16. The sample dispensing unit 13 includes an arm 13a that pivots in the horizontal direction and a pipette-like probe that is attached to the pivoting tip of the arm 13a in the vertical direction. The sample accommodated in the sample container 12a is aspirated by the probe. Dispensing is performed by discharging into the measurement cell 17 transported to a predetermined position on the reaction table 16.

  Each of the reagent tables 14A and 14B is formed in a circular shape in the horizontal plane, and is rotated in the circumferential direction by a driving mechanism (not shown) to hold a plurality of reagent containers 14Aa and 14Ba held along the circumferential portion. Rotate and move. As with the sample dispensing unit 13, each of the reagent dispensing units 15A and 15B includes arms 15Aa and 15Ba that pivot in the horizontal direction, and pipette-like probes that are vertically attached to the pivoting tip of each arm. The measuring cell 17 is aspirated by the probe with the reagent in the reagent containers 14Aa and 14Ba moved to a predetermined position on the reagent tables 14A and 14B and conveyed to the predetermined position on the reaction table 16. Dispense into.

  The reaction table 16 is formed in a circular shape in the horizontal plane, is rotated in the circumferential direction by a drive mechanism (not shown), is arranged along the circumferential portion, and rotates and conveys the plurality of measurement cells 17 in the circumferential direction. The reaction table 16 normally rotates and conveys the measurement cell 17 continuously in the clockwise direction in the drawing at a predetermined rotation speed, but the rotation speed and the rotation direction can be changed based on an instruction from the control unit 22.

  The refractive index measurement unit 18 irradiates the sample in the measurement cell 17 with measurement light in a predetermined wavelength region, receives the measurement light transmitted through the sample, and measures the wavelength dependence of the refractive index of the sample. The measurement result is output to the control unit 22 and analyzed. Details of the mechanism and operation of the refractive index measuring unit 18 will be described later.

  The cleaning unit 19 sucks and discharges the sample in the measurement cell 17 that has been measured by the refractive index measuring unit 18 by a nozzle (not shown), and performs cleaning by injecting and sucking a cleaning liquid such as a detergent or cleaning water. Do.

  The control unit 22 is configured using a CPU or the like, and controls processing and operation of each unit of the analyzer 1. In particular, the control unit 22 includes an analysis calculation unit 22a. The analysis calculation unit 22a calculates an absorption coefficient of the sample based on the measurement result acquired from the refractive index measurement unit 18, and the sample is calculated based on the calculated absorption coefficient. That is, component analysis of the specimen is performed. The control unit 22 acquires various information necessary for sample analysis, analysis operation instruction information, and the like from the outside through the input unit 23 configured using a keyboard, a mouse, and the like. In addition, the control unit 22 outputs various information including the analysis result of the sample to the output unit 24 configured using a display, a printer, a communication mechanism, and the like, and also stores data configured using a ROM, a RAM, and the like. Record in section 25.

  In the analyzer 1 configured as described above, the sample dispensing unit 13 dispenses the sample in the sample container 12a to the plurality of measurement cells 17 that are sequentially conveyed in a row, and the reagent dispensing unit. After 15A and 15B dispense the reagents in the reagent containers 14Aa and 14Ba, respectively, the refractive index measurement unit 18 measures the wavelength dependence of the refractive index of the sample in a state where the specimen and the reagent are reacted, and this measurement result Is analyzed automatically by the control unit 22. Further, the cleaning unit 19 cleans the measurement cell 17 that is transported after the measurement by the refractive index measuring unit 18 while transporting it, so that a series of analysis operations are continuously repeated.

  The analyzer 1 includes two sets of the reagent table and the reagent dispensing unit, but may include one set or three or more sets depending on the analysis item or the like. Moreover, the reagent accommodated in each reagent container 14Aa, 14Ba is selected according to an analysis item etc., and may be the same or different. Furthermore, the analyzer 1 can also include a stirring mechanism (not shown) that stirs the measurement cell 17 when the sample and the reagent are dispensed. Note that the sample and reagent dispensing order for each measurement cell 17, the number of reagents dispensed to the same measurement cell 17, and the like can vary depending on the analysis item, reagent type, analysis protocol, and the like.

  Next, the refractive index measuring unit 18 will be described in detail. 2-4 is a figure which shows the principal part structure of the refractive index measurement part 18, FIG. 2 is a perspective view, FIG. 3 is a side view, FIG. 4 is a top view. As shown in FIGS. 2 to 4, the refractive index measuring unit 18 includes a collimated light source unit 31, mirrors 32 and 33, a diffraction grating 35, a condensing lens 36, a light receiving element 37, a processing circuit 38, and a refractive index calculating unit 39. Prepare. Each part from the collimating light source unit 31 to the diffraction grating 35 is provided inside the circular row of the measurement cells 17 arranged on the reaction table 16, and the condensing lens 36 and the light receiving element 37 are circular in the measurement cell 17. It is provided outside the row. The measurement cell 17 is supported on the reaction table 16 by the cell holding mechanism HL. In the drawing showing the configuration of the refractive index measuring unit 18, an xyz coordinate system set for convenience is also shown.

  The collimated light source unit 31 includes a light source 31a that emits measurement light in a predetermined wavelength region, a lens 31b that forms a light source image, a lens 31c that collimates measurement light from the light source image, and a beam diameter of the collimated measurement light. And a measurement light L1 as parallel light having a predetermined light beam diameter is emitted in the z-axis direction. Here, an incandescent bulb such as a halogen lamp or a discharge lamp such as a mercury lamp can be used as the light source 31a. The diaphragm 31d may be capable of changing or replacing the diaphragm diameter.

  The mirror 33 is held by the mirror holding unit 34, and reflects the measurement light L 1 emitted from the collimated light source unit 31 and reflected by the mirror 32 toward the diffraction grating 35 and the measurement cell 17. The mirror holding part 34 is comprised using the drive part 34a and the support | pillar part 34b. The drive unit 34a holds the mirror 33 so that it can move up and down along the support column 34b and can rotate along the yz plane. Thereby, the mirror 33 and the mirror holding unit 34 can adjust the incident angle and the incident position of the measuring light L1 with respect to the diffraction grating 35 and the measuring cell 17 along the yz plane as incident light adjusting means.

  The diffraction grating 35 is a flat one-dimensional diffraction grating arranged to diffract incident light in a direction perpendicular to the yz plane, and is made parallel to the incident surface of the measurement cell 17 by a holding mechanism (not shown). It is arranged in the vicinity of this incident surface. The diffraction grating 35 diffracts incident measurement light L1 and branches it for each wavelength. That is, the measurement light L1 is diffracted into 0th-order diffracted light, + 1st-order diffracted light, and −1st-order diffracted light, and the + 1st-order diffracted light and −1st-order diffracted light are branched for each wavelength. Specifically, the wavelength range of the measurement light emitted from the light source 31a is λ1 to λ5 (λ1 <λ5), and the representative wavelengths in this wavelength range are λ2, λ3, and λ4 (λ1 <λ2 <λ3 <λ4 <λ5). In this case, as shown in FIG. 5A, the diffraction grating 35 diffracts the measurement light having a longer wavelength in the + 1st order and −1st order diffracted light at a larger diffraction angle, and branches outward with the 0th order diffracted light as the center. .

  As shown in FIGS. 5A and 5B, the measurement cell 17 holds the sample SP in the accommodating portion 17a formed in a right-angle prism shape, and refracts the measurement light incident on the held sample SP. Deflection for each wavelength. Here, FIG. 5B is a diagram illustrating a cross section of the measurement cell 17 parallel to the yz plane. The measurement cell 17 is arranged with the ridge line 17b of the accommodating portion 17a parallel to the y-axis, and refracts measurement light incident through the diffraction grating 35 in the y-axis direction and deflects it for each wavelength. Specifically, as shown in FIG. 5B, the measurement cell 17 refracts each measurement light, which is each diffraction light from the diffraction grating 35, as the wavelength is shorter, and deflects the measurement light with a larger deflection angle.

  Each measurement light branched for each wavelength by the diffraction grating 35 and deflected for each wavelength by the measurement cell 17 enters the condenser lens 36 as the measurement light L2. Among these, the principal ray of the measurement light that is the 0th-order diffracted light of the diffraction grating 35 and has the longest wavelength in a predetermined wavelength range is set to coincide with the optical axis OA of the condenser lens 36. This setting is performed by adjusting the incident angle and the incident position of the measurement light L1 in advance by changing the vertical position and the inclination angle of the mirror 33 by the drive unit 34a.

  FIG. 5-2 exemplifies the case where the sample SP having a refractive index larger than that of the member of the measurement cell 17 is accommodated in the accommodating portion 17a, and the measurement light incident on the y axis in the minus direction. L1 is diffracted by the diffraction grating 35 and then refracted by the measurement cell 17 in the positive direction of the y-axis. On the contrary, when a sample having a refractive index smaller than that of the member of the measurement cell 17 is accommodated in the accommodating portion 17a, the position and angle of the mirror 33 are adjusted by the driving portion 34a, and the measurement light L1 is emitted. It is good to make it incline in the positive direction of the y-axis. In this case, the measurement light L1 is diffracted by the diffraction grating 35 and then refracted by the measurement cell 17 in the negative direction of the y axis.

  Here, the measurement cell 17 is formed of a member whose wavelength dependency of the refractive index is known. As such a member, for example, a glass member such as quartz glass is used. Further, the two inclined surfaces 17c and 17d, which are the inner walls of the accommodating portion 17a, are optically polished, and the sample SP is held in contact with both the polished inclined surfaces 17c and 17d. In addition, the front and rear side surfaces that are the incident surface and the exit surface of the measurement light in the measurement cell 17 are each formed in parallel with the ridge line 17b and arranged perpendicular to the z-axis.

  The condensing lens 36 as a condensing optical system is an optical system having no chromatic aberration, and is configured as an optical system (achromatic lens system) using an achromatic lens. 2 to 4, the condensing lens 36 is illustrated as a single lens in order to avoid complication, but is actually configured using a plurality of lenses or lens groups. As shown in FIGS. 2 to 4, the condensing lens 36 condenses each measurement light L <b> 2 branched by the diffraction grating 35 and deflected by the measurement cell 17 on the focal plane by making it telecentric on the rear side. To do.

  The light receiving element 37 as a two-dimensional light receiving element is realized by using an image pickup element such as a CCD or a CMOS, and is arranged so that the image pickup surface thereof coincides with the focal plane of the condenser lens 36. The light receiving element 37 collectively receives the measurement lights L2 collected by the condenser lens 36. The light receiving element 37 outputs an intensity signal obtained by photoelectrically converting each received measurement light L2 to the processing circuit 38, and the processing circuit 38 performs A / D conversion on the intensity signal and then outputs the intensity signal to the refractive index calculating unit 39 as image information. Output.

  The refractive index calculator 39 calculates the refractive index for each wavelength of the sample SP as the wavelength dependence of the refractive index based on the light receiving position of each measurement light L2 received by the light receiving element 37. Specifically, the refractive index calculation unit 39 calculates the wavelength of each measurement light L2 based on the light receiving position of each measurement light L2 in the diffraction direction of the diffraction grating 35, and performs each measurement in the deflection direction of the measurement cell 17. Based on the light receiving position of the light L2, the deflection angle of each measurement light L2 by the measurement cell 17 is calculated, and the refractive index for each wavelength of the sample SP is calculated based on the calculated wavelength and the deflection angle.

  Here, with reference to FIG. 6, the calculation for the refractive index calculation unit 39 to calculate the refractive index for each wavelength will be described in more detail. FIG. 6 is a diagram showing each measurement light L2 collected on the light receiving surface of the light receiving element 37. In particular, each measurement light having wavelengths λ1 to λ5 corresponding to FIGS. 5-1 and 5-2. It is a figure which shows typically the light reception position of L2.

  As shown in FIG. 6, among the measurement lights L <b> 2 collected by the condenser lens 36, the 0th order diffracted light, the + 1st order diffracted light, and the −1st order diffracted light by the diffraction grating 35 are received by the light receiving element 37. On the surface, the light is collected for each wavelength on the y-axis, the curve C1, and the curve C2. At this time, in the x-axis direction, in the + 1st-order and −1st-order diffracted light, the measurement light L2 having a longer wavelength is collected outward with the y-axis as the center, and the measurement light L2 having a shorter wavelength in the y-axis direction is on the plus side. It is focused on. Specifically, the measurement light L2 which is + 1st order or −1st order diffracted light and has a wavelength λ5 is collected on the outermost side in the x-axis direction, and the measurement light L2 having the wavelength λ1 regardless of the diffraction order is y It is condensed on the most positive side in the axial direction.

  This is because the diffraction direction in the diffraction grating 35 is set parallel to the x-axis, and the refraction direction, that is, the deflection direction in the measurement cell 17 is set parallel to the y-axis. That is, each measurement light L2 is not affected by refraction by the measurement cell 17 in the x-axis direction, and is branched and condensed for each wavelength according to the diffraction action by the diffraction grating 35, and is diffracted in the y-axis direction. This is because the light is deflected and condensed for each wavelength according to the refraction action by the measurement cell 17 without being affected by diffraction by the grating 35.

In the condensing pattern of the + 1st order and −1st order diffracted lights collected in this way, the x coordinate x (λ) at the light receiving position for each wavelength λ of the measurement light L2 is the diffraction angle θx (λ) by the diffraction grating 35. Using the focal length f of the condenser lens 36, it is determined by the following equation (1).
x (λ) = f · tan θx (λ) (1)
Further, the diffraction angle θx (λ) is determined by the following equation (2) using the grating constant d of the diffraction grating 35.
θx (λ) = sin ⁻¹ (λ / d) (2)

On the other hand, the y coordinate y (λ) of the light receiving position is determined by the following equation (3) using the relative deflection angle θy (λ) in the measurement cell 17 and the focal length f of the condenser lens 36. However, the relative declination angle θy (λ) is a declination angle based on the optical axis OA of the condenser lens 36, and in the case shown in FIG. 6, is a declination angle based on the 0th-order diffracted light of wavelength λ5.
y (λ) = f · tan θy (λ) (3)
Further, the relative declination angle θy (λ) has a predetermined relationship with the refractive index n (λ) of the sample SP and is uniquely determined from each other.

  From the above relationship, the refractive index calculation unit 39 determines the sample SP based on the x-coordinate x (λ) and the y-coordinate y (λ) as the light receiving position of the measurement light L2 that is + 1st order or −1st order diffracted light. The refractive index n (λ) for each wavelength is calculated.

Here, the relationship between the relative deflection angle θy (λ) and the refractive index n (λ) is derived as follows with reference to FIG. FIG. 7 is a cross-sectional view showing a state in which the measurement light L (λ) incident on the measurement cell 17 is refracted by the sample SP. The incident angle θ ₁ (λ) and the refraction angle θ ₂ (λ) of the measurement light L (λ) on the inclined surface 17c are Snell's law using the refractive index n ₀ (λ) of the member of the measurement cell 17. Are in a relationship represented by the following formula (4).
sin θ ₂ (λ) = n ₀ (λ) · sin θ ₁ (λ) / n (λ) (4)
Similarly, the incident angle θ ₃ (λ) and the refraction angle θ ₄ (λ) of the measurement light L (λ) on the inclined surface 17d have a relationship represented by the following equation (5).
sin θ ₃ (λ) = n ₀ (λ) · sin θ ₄ (λ) / n (λ) (5)
In addition, the refraction angle θ ₄ (λ) is expressed by the following equation (6) using the included angle ψ formed by the normal line of the inclined surface 17d and the optical axis OA.
θ ₄ (λ) = ψ + θy (λ) (6)

この式（８）において、入射角θ₁（λ）と挟角ψとは、ミラー３３および測定セル１７の配置に応じて予め求められる角度であるため、屈折率演算部３９は、相対偏角θy（λ）をもとに、試料ＳＰの屈折率ｎ（λ）を算出することができる。 On the other hand, from the geometrical relationship with respect to the apex angle α of the accommodating portion 17a, it is clear that θ ₂ (λ) = α + θ ₃ (λ), and the apex angle α = 90 degrees and the sine of both sides of this equation Is calculated, the following equation (7) is obtained.
sin ² θ ₂ (λ) = 1−sin ² θ ₃ (λ) (7)
By substituting the equations (4) to (6) into this equation (7) and rearranging, the following equation (8) is obtained as a relational expression between the relative declination angle θy (λ) and the refractive index n (λ). Derived.

In this equation (8), the incident angle θ ₁ (λ) and the included angle ψ are angles determined in advance according to the arrangement of the mirror 33 and the measurement cell 17, so that the refractive index calculator 39 calculates the relative declination angle. Based on θy (λ), the refractive index n (λ) of the sample SP can be calculated.

  Since the measurement light L (λ) is refracted at the incident surface and the exit surface of the measurement cell 17, strictly speaking, the relative declination θy (λ ) And the refractive index n (λ) of the sample SP.

  Here, more specifically, the result of simulating the refractive index measurement by the refractive index measuring unit 18 is shown in FIGS. 8 and 9-1 to 9-3. FIG. 8 shows the refractive index measurement results for each wavelength for a plurality of samples, and FIGS. 9-1 to 9-3 show the condensing pattern of the measurement light L2 for each of the plurality of samples shown in FIG.

  In this simulation, S-BSL7, S-BSM2 (hereinafter, optical glass manufactured by OHARA INC.) And water are used as the sample SP, and the grating constant d of the diffraction grating 35 is 0.1 mm (spatial frequency is equivalent to 10 lines / mm). ), The focal length f of the condenser lens 36 is 200 mm. The member of the measurement cell 17 is quartz glass, the apex angle α is 90 degrees, and the included angle ψ is 45 degrees. In addition, the refractive index for every wavelength of quartz glass is known, and is shown in FIG. 8 together with the simulation result. FIG. 8 shows the incident angle when the measuring light L2 having a wavelength of 800 nm, which is zero-order diffracted light, is parallel to the optical axis OA as the incident angle θin of the measuring light L1 with respect to the diffraction grating 35. When the incident angle θin> 0, the measurement light L1 is incident with an inclination in the positive direction of the y axis, and when the incident angle θin <0, the measurement light L1 is incident with an inclination in the negative direction of the y axis.

  When the sample SP is water, the refractive index is lower than that of quartz glass. Therefore, the measurement cell 17 refracts incident measurement light that is inclined in the positive direction of the y axis in the negative direction of the y axis. As a result, the measurement light L2 forms a condensing pattern in the negative region in the y-axis direction as shown in FIG. On the other hand, when the sample SP is S-BSL7 or S-BSM2, the refractive index is higher than that of quartz glass, so that the measurement cell 17 injects the measurement light incident on the y-axis in the minus direction. Refract in the positive direction of the axis. As a result, the measurement light L2 forms a condensing pattern in the positive region in the y-axis direction, as shown in FIGS. 9-2 and 9-3.

  As described above, the refractive index measurement unit 18 diffracts the measurement light in a predetermined wavelength region by the diffraction grating 35 and branches it for each wavelength, and this sample SP by the measurement cell 17 holding the sample SP in a prism shape. Is refracted and deflected for each wavelength. The condensing lens 36 condenses the measurement light deflected by the diffraction grating 35 and deflected by the measurement cell 17. The light receiving element 37 condenses the measurement light. The measurement light collected by the lens 36 is received, and the refractive index calculation unit 39 calculates the refractive index for each wavelength of the sample SP based on the light receiving position of each measurement light in the light receiving element 37. Thereby, the refractive index measuring unit 18 can collectively measure the refractive index for each wavelength of the sample SP in a predetermined wavelength region.

  Conventionally, in order to measure the wavelength dependence of the refractive index of a sample over a wide wavelength range, for example, using the refractive index measurement technique disclosed in Patent Document 2, the refractive index is changed for each wavelength while sequentially changing the wavelength of measurement light. There has been a problem that measurement requires a lot of labor and time. However, according to the refractive index measuring unit 18 as a refractive index measuring device, it is not necessary to sequentially change the wavelength of the measurement light, and the refractive index for each wavelength can be measured collectively for a wide range of wavelengths. Therefore, the wavelength dependence of the refractive index of the sample SP can be measured easily and in a short time.

  Heretofore, the diffraction grating 35 has been arranged on the light source side of the measurement cell 17, and the measurement cell 17 has been described as refracting each diffracted light diffracted by the diffraction grating 35 and deflecting it for each wavelength. The arrangement order may be changed, and the diffraction grating 35 may diffract and branch each measurement light refracted by the measurement cell 17 and deflected for each wavelength.

On the other hand, in the analyzer 1, the analysis calculation unit 22a acquires the wavelength dependency n (λ) of the refractive index of the sample SP measured by the refractive index measurement unit 18, and the wavelength dependency n (λ of the acquired refractive index. ), The absorption coefficient of the sample SP is calculated, and the sample SP is analyzed based on the calculated absorption coefficient. At this time, the analysis calculation unit 22a, for example, based on the Kramers-Kronig relational expression represented by the following formula (9), the absorption coefficient ε ( λ) is calculated. Here, the coefficient P means taking the main value of Cauthy.

  In this way, in the analyzer 1, the refractive index measurement unit 18 measures the wavelength dependence n (λ) of the refractive index of the sample SP regardless of the optical path length in the sample SP in the measurement cell 17, and this refraction. Based on the wavelength dependence n (λ) of the rate, the analysis calculation unit 22a calculates the absorption coefficient ε (λ), and the sample SP is analyzed based on the absorption coefficient ε (λ). Therefore, analysis can be performed regardless of the optical path length in the sample SP. Therefore, it is possible to perform the analysis with high accuracy without having to strictly measure the optical path length in the sample SP. Further, since the measurement of the wavelength dependency n (λ) of the refractive index does not depend on the optical path length of the sample SP, the analysis can be performed by reducing the volume of the measurement cell 17 and reducing the volume of the sample SP.

  In the refractive index measuring unit 18 described above, the condensing lens 36 as the condensing optical system has been described as an achromatic lens system. However, as an optical system free from chromatic aberration, for example, concave reflection optics configured using a concave reflecting mirror. It may be a system. In this case, it is preferable to use an off-axis parabolic mirror as the concave reflecting mirror.

  Further, in the refractive index measuring unit 18, the shape of the accommodating portion 17a holding the sample SP has been described as a right-angle prism shape, but the apex angle α of the prism shape is not limited to a right angle (90 degrees). Any angle can be used as long as the measurement light incident on the beam can be deflected and emitted for each wavelength.

  Furthermore, although the refractive index measurement unit 18 has been described as making the measurement light L2 having the longest wavelength in a predetermined wavelength region coincide with the optical axis OA of the condenser lens 36, the measurement light L2 having the reference wavelength is measured on the optical axis OA. The wavelength of the measurement light L2 to be matched is not limited to the longest wavelength, and may be any wavelength in a predetermined wavelength range.

(Embodiment 2)
Next, an analysis apparatus, a refractive index measurement apparatus, and an analysis method according to the second embodiment of the present invention will be described. 10 to 12 are diagrams showing a main configuration of the refractive index measuring unit 118 as a refractive index measuring unit included in the analyzer according to the second embodiment, and FIG. 10 is a perspective view. Is a plan view, and FIG. 12 is a side view. The analyzing apparatus according to the second embodiment includes a measuring cell 117 and a refractive index measuring unit 118 instead of the measuring cell 17 and the refractive index measuring unit 18 based on the analyzing apparatus 1. Other configurations are the same as those of the analyzer 1. However, the control unit 22 has a function of controlling the refractive index measuring unit 118 instead of the refractive index measuring unit 18.

  As shown in FIGS. 10 to 12, the refractive index measuring unit 118 includes a collimated light source unit 41, a diffraction grating 42, a condenser lens 43, a light receiving element 44, a processing circuit 45, and a refractive index calculating unit 46. Each part from the collimating light source unit 41 to the condensing lens 43 is arranged inside the circular row of the measurement cells 117 arranged on the reaction table 16, and the light receiving element 44 is arranged outside the circular row. Yes. The measurement cell 117 is supported on the reaction table 16 by a holding mechanism (not shown). In the drawing showing the configuration of the refractive index measuring unit 118, an xyz coordinate system set for convenience is also shown.

  The collimated light source unit 41 includes a light source 41a that emits measurement light in a predetermined wavelength region, lenses 41b and 41c that cooperate to form a light source image, a pinhole 41d that defines the size of the light source image, and a light source image. The measurement light L11 as parallel light having a predetermined light beam diameter is formed by using a lens 41e that collimates the measurement light and a stop 41f that shapes the light beam diameter of the collimated measurement light. To ejaculate. Here, the light source 41a and the diaphragm 41f are the same as the light source 31a and the diaphragm 31d.

  The diffraction grating 42 is a flat plate-like two-dimensional diffraction grating having a two-dimensional grating pattern as shown in FIG. 13, and is arranged perpendicular to the z-axis, and two-dimensionally measures the measurement light incident in the z-axis direction. And divides into each wavelength. The diffraction grating 42 diffracts the incident measurement light L11 in four directions of the x-axis direction, the y-axis direction, the D1-axis direction, and the D2-axis direction, and diffracts the first-order diffracted light diffracted to the plus side and the minus side in each direction. Each is branched for each wavelength. Specifically, when the wavelength range of the measurement light emitted from the light source 41a is λa to λc and the center wavelength in this wavelength range is λb (λa <λb <λc), the diffraction grating 42 is shown in FIGS. As shown in the figure, the measurement light having a longer wavelength is diffracted at a larger diffraction angle, and is branched to the outer side centering on the 0th-order diffracted light.

  Note that the D1 axis and the D2 axis shown in FIG. 13 are axes set in an oblique direction in the xy coordinate system, and the lattice constant dx in the x-axis direction and the lattice constant dy in the y-axis direction of the diffraction grating 42 are used. , And xy coordinate system, the axes are set in the directions represented by dy / dx and -dy / dx, respectively. The diffraction grating 42 functions as a diffraction grating having a grating constant dxy in the D1 axis direction and the D2 axis direction.

  The condensing lens 43 as the condensing optical system is an achromatic lens system configured as a cylindrical lens having a positive refractive power in the y-axis direction, and the optical axis is zero-order diffracted light of the measuring light L11 and the diffraction grating 42. Are arranged to match. 10 to 12, the condensing lens 43 is illustrated as a single lens in order to avoid complication, but actually, the condensing lens 43 is configured using a plurality of lenses or lens groups. As shown in FIG. 12, the condensing lens 43 condenses each measurement light L12 diffracted by the diffraction grating 42 and branched for each wavelength on the focal plane in a telecentric manner in the y-axis direction.

  As shown in FIGS. 10 to 12, the measurement cell 117 is configured as a cylindrical lens that holds the sample SP in a housing portion 117 a formed in a concave lens type cylindrical lens shape and has a positive refractive power in the x-axis direction. ing. The measurement cell 117 is arranged so that the optical axis thereof coincides with the optical axis of the condenser lens 43, and refracts and deflects each measurement light L12 from the condenser lens 43 incident on the sample SP for each wavelength, Each beam is focused on the focal plane by telecentricity in the x-axis direction. At this time, the measurement cell 117 shows a different focal length according to the wavelength of the incident measurement light L12, and the shorter the wavelength, the smaller the focal length, that is, the greater the refractive power, the light is condensed.

  10 to 12 exemplify the case where the sample SP having a refractive index smaller than that of the member of the measurement cell 117 is accommodated in the accommodating portion 117a. Therefore, the accommodating portion 117a has a concave lens type cylindrical lens shape. It is said that. On the contrary, when a sample having a refractive index larger than that of the member of the measurement cell 117 is accommodated in the accommodating portion 117a, the accommodating portion may be a convex lens type cylindrical lens. Here, the measurement cell 117 is formed of a member whose wavelength dependency of the refractive index is known. As such a member, for example, a glass member such as quartz glass is used.

  The light receiving element 44 as a two-dimensional light receiving element is realized by using an image pickup element such as a CCD or a CMOS, and is arranged so that the image pickup surface thereof coincides with the focal plane of the condenser lens 43. The light receiving element 44 collectively receives the measurement lights L12 collected by the condenser lens 43 and the measurement cell 117, respectively. The light receiving element 44 photoelectrically converts the intensity signal of each received measurement light L12 and outputs it to the processing circuit 45. The processing circuit 45 performs A / D conversion or the like on the intensity signal, and then performs a refractive index calculation unit 46 as image information. Output to.

  The refractive index calculation unit 46 calculates the refractive index for each wavelength of the sample SP as the wavelength dependence of the refractive index based on the light receiving position of each measurement light L12 received by the light receiving element 44. Specifically, the refractive index calculation unit 46 calculates the wavelength of each measurement light L12 based on the light receiving position of each measurement light L12 in the y-axis direction as the light collection direction of the condenser lens 43, and the measurement cell. Based on the light receiving position of each measurement light L12 in the x-axis direction as the deflection direction of 117, the focal length of the measurement cell 117 corresponding to each measurement light L12 is calculated, and based on the calculated wavelength and focal length, The refractive index for each wavelength of the sample SP is calculated.

  Here, with reference to FIG. 14, the calculation for the refractive index calculation unit 46 to calculate the refractive index for each wavelength will be described in more detail. FIG. 14 is a diagram showing each measurement light L12 collected on the light receiving surface of the light receiving element 44, and in particular, is a diagram representatively showing the light receiving position of each measurement light L12 having wavelengths λa to λc.

  As shown in FIG. 14, among the measurement lights L12 collected by the condenser lens 43 and the measurement cell 117, the 0th-order diffracted light by the diffraction grating 42, the first-order diffracted light in the D1 axis direction, and the D2 axis direction First-order diffracted light means that the measurement cell 117 has a different focal length depending on the wavelength, and therefore, on the light-receiving surface of the light-receiving element 44, on the y-axis, on the curve C3, and on the curve C4, for each wavelength. Focused. At this time, in the first-order diffracted light, the measurement light L12 having a longer wavelength is condensed outward in each of the x-axis direction and the y-axis direction. Specifically, the measurement light L12 that is the first-order diffracted light and has the wavelength λc is collected on the outermost side.

  When the measurement cell 117 has a constant focal length regardless of the wavelength, the first-order diffracted light in the D1 axis direction is the D1 ′ axis corresponding to the projection image of the D1 axis by the condenser lens 43 and the measurement cell 117. Condensed linearly above. Similarly, the first-order diffracted light in the D2 axis direction is linearly collected on the D2 ′ axis corresponding to the projected image of the D2 axis. However, actually, since the measurement cell 117 has a different focal length for each wavelength, the first-order diffracted light in the D1 axis direction and the D2 axis direction is condensed nonlinearly on the curve C3 and the curve C4, respectively.

In the condensing pattern of the first-order diffracted light thus collected, the y coordinate y (λ) at the light receiving position for each wavelength λ of the measuring light L12 is the diffraction angle φy (λ) in the y-axis direction by the diffraction grating 42. Using the focal length fy of the condensing lens 43, it is determined by the following equation (10).
y (λ) = fy · tanφy (λ) (10)
The diffraction angle φy (λ) is determined by the following equation (11) using the grating constant dy of the diffraction grating 42.
φy (λ) = sin ⁻¹ (λ / dy) (11)

On the other hand, the x coordinate x (λ) of the light receiving position is expressed by the following equation using the diffraction angle φx (λ) in the x-axis direction by the diffraction grating 42 and the focal length fx (λ) for each wavelength of the measurement cell 117: 12).
x (λ) = fx (λ) · tan θx (λ) (12)
The diffraction angle φx (λ) is determined by the following equation (13) using the grating constant dx of the diffraction grating 42.
φx (λ) = sin ⁻¹ (λ / dx) (13)

この式（１４）は、屈折率ｎ（λ）について解くと、次式（１５）〜式（１９）によって表すことができる。

Further, the focal length fx (λ) is the refractive index n (λ) of the sample SP, the refractive index n ₀ (λ) of the member of the measurement cell 117, and the radius of curvature r ₁ of the first surface of the cylindrical lens-shaped accommodation portion 117a. Using the curvature radius r _{2 of} the second surface and the surface interval t between the first surface and the second surface, it is determined by the following equation (14).

When this equation (14) is solved for the refractive index n (λ), it can be expressed by the following equations (15) to (19).

  From the above relationship, the refractive index calculation unit 46 is based on the x coordinate x (λ) and the y coordinate y (λ) as the light receiving position of the measurement light L12 that is the first-order diffracted light in the D1 axis direction or the D2 axis direction. The refractive index n (λ) for each wavelength of the sample SP is calculated.

During the calculation of the refractive index n (λ), the refractive index calculator 46 calculates the x-coordinate x1 (λ) of the first-order diffracted light in the D1-axis direction and the x-coordinate x2 (λ of the first-order diffracted light in the D2-axis direction. ), The focal length fx (λ) can be calculated by the following equation (20) instead of the equation (12). In this case, the focal length fx (λ) can be calculated with twice the sensitivity compared to the calculation using Expression (12), and as a result, the refractive index n (λ) can be calculated with higher accuracy. it can.
(X1 (λ) −x2 (λ)) = 2fx (λ) · tan θx (λ) (20)

  As described above, the refractive index measurement unit 118 diffracts the measurement light in a predetermined wavelength range by the diffraction grating 42 and branches the measurement light for each wavelength, and the measurement light branched by the diffraction grating 42 by the condenser lens 43 is predetermined. The measurement light incident on the sample SP is refracted in a direction orthogonal to the light collection direction of the condenser lens 43 by the measurement cell 117 that collects the light in one direction and holds the sample SP in the shape of a cylindrical lens. And the light receiving element 44 receives the measurement light collected by the condenser lens 43 and the measurement cell 117, and the refractive index calculation unit 46 sets the measurement light at the light receiving position of each measurement light. Based on this, the refractive index for each wavelength of the sample SP is calculated. As a result, the refractive index measuring unit 118 can collectively measure the refractive index for each wavelength of the sample SP in a predetermined wavelength region, similarly to the refractive index measuring unit 18 in the first embodiment. The wavelength dependence of the refractive index can be measured easily and in a short time.

  Heretofore, the measurement cell 117 has been described as being disposed on the light receiving element side of the condensing lens 43, and the condensing lens 43 condenses each measurement light condensed in the y-axis direction in the x-axis direction. The arrangement order of these may be changed so that the measurement lens 117 condenses the measurement light in the x-axis direction and the condensing lens 43 condenses in the y-axis direction. Further, although the condenser lens 43 has been described as an achromatic lens system, an optical system free from chromatic aberration may be a concave reflecting optical system configured by using, for example, a concave reflecting mirror.

  In the analysis apparatus according to the second embodiment described above, the analysis calculation unit 22a is the wavelength of the refractive index of the sample SP measured by the refractive index measurement unit 118, as in the case of the analysis apparatus 1 according to the first embodiment. The dependence n (λ) is obtained, and the absorption coefficient of the sample SP is obtained using the Kramers-Kronig relational expression shown in the formula (9) based on the wavelength dependence n (λ) of the obtained refractive index. And the sample SP is analyzed based on the calculated absorption coefficient.

  As described above, in the analyzer according to the second embodiment, similarly to the analyzer 1, analysis can be performed with high accuracy regardless of the optical path length in the sample SP, and the volume of the measurement cell 117 can be reduced. In addition, the analysis can be performed by reducing the volume of the sample SP.

  Up to this point, the best mode for carrying out the present invention has been described as the first and second embodiments. However, the present invention is not limited to the first and second embodiments and is within the scope of the present invention. Various modifications are possible. For example, in the first and second embodiments described above, the refractive index measuring units 18 and 118 have been described as the refractive index measuring means in the analyzer according to the present invention, but the refractive index measuring units 18 and 118 are independently used as the refractive index measuring device. Can be used as

  In this case, it is not limited to a liquid sample such as the sample SP, and the wavelength dependency of the refractive index can be measured using an individual such as glass as a sample. Also, for example, the wavelength dependence of the refractive index of various substances, the condensing pattern of the measurement light in the light receiving element, etc. are stored in advance as a database, and the refractive index or condensing pattern of the sample to be measured is collated with this database. By doing so, the substance which comprises a sample can be specified. When the refractive index measuring units 18 and 118 are used as a refractive index measuring device as described above, it is preferable to newly provide a control mechanism for controlling the entire device.

It is a figure which shows the structure of the analyzer concerning Embodiment 1 of this invention. It is a perspective view which shows the structure of the refractive index measurement part shown in FIG. It is a side view which shows the structure of the refractive index measurement part shown in FIG. It is a top view which shows the structure of the refractive index measurement part shown in FIG. It is a top view explaining the effect | action of a diffraction grating and a measurement cell. It is a longitudinal cross-sectional view explaining the effect | action of a diffraction grating and a measurement cell. It is a figure which shows the condensing pattern of the measurement light condensed on a light receiving element. It is a figure explaining the refractive action in a measurement cell. It is a figure which shows the measurement result of the refractive index by simulation. It is a figure which shows the condensing pattern of the measurement light by simulation. It is a figure which shows the condensing pattern of the measurement light by simulation. It is a figure which shows the condensing pattern of the measurement light by simulation. It is a perspective view which shows the structure of the refractive index measurement part with which the analyzer concerning Embodiment 2 of this invention is provided. It is a top view which shows the structure of the refractive index measurement part with which the analyzer concerning Embodiment 2 of this invention is provided. It is a side view which shows the structure of the refractive index measurement part with which the analyzer concerning Embodiment 2 of this invention is provided. It is a figure which shows the grating pattern of a diffraction grating. It is a figure which shows the condensing pattern of the measurement light condensed on a light receiving element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Analyzer 11 Measurement mechanism 12 Sample transport part 12a Sample container 12b Sample rack 13 Sample dispensing part 13a Arm 14A, 14B Reagent table 14Aa, 14Ba Reagent container 15A, 15B Reagent dispensing part 15Aa, 15Ba arm 16 Reaction table 17, 117 Measurement cell 17a, 117a Storage unit 17b Ridge line 17c, 17d Slope 18, 118 Refractive index measurement unit 19 Cleaning unit 21 Control analysis mechanism 22 Control unit 22a Analysis operation unit 23 Input unit 24 Output unit 25 Storage unit 31 Collimated light source unit 31a Light source 31b , 31 c Lens 31 d Aperture 32, 33 Mirror 34 Mirror holding mechanism 34 a Drive unit 34 b Column 35, 42 Diffraction grating 36, 43 Condensing lens 37, 44 Light receiving element 38, 45 Processing circuit 39, 46 Refractive index calculation unit 41 Collimator The light source unit 41a light source 41b, 41c, 41e lens 41d pinhole 41f aperture C1~C4 curves L1, L2, L11, L12, L (λ) measurement light OA optical axis SP samples

Claims (17)

In an analyzer for measuring the optical properties of a sample and analyzing the sample based on the measured optical properties,
Refractive index measuring means for measuring the wavelength dependence of the refractive index of the sample;
Calculating an absorption coefficient of the sample based on the wavelength dependence of the refractive index, and an analysis calculation means for analyzing the sample based on the absorption coefficient;
An analyzer characterized by comprising: The refractive index measuring means includes
A light source that emits measurement light in a predetermined wavelength range;
A diffractive element that diffracts the measurement light and branches it for each wavelength;
A deflecting container that holds the sample and refracts the measurement light incident on the held sample and deflects it for each wavelength;
A condensing optical system for condensing each measurement light branched by the diffraction element and deflected by the deflection container;
A two-dimensional light receiving element for receiving each measurement light condensed by the condensing optical system;
A refractive index calculating means for calculating a refractive index for each wavelength of the sample based on a light receiving position of each measurement light received by the two-dimensional light receiving element;
The analyzer according to claim 1, further comprising: The diffraction element is a one-dimensional diffraction grating,
The deflection container holds the sample in a prism shape and deflects the measurement light in a deflection direction orthogonal to a diffraction direction of the one-dimensional diffraction grating,
The refractive index calculation means calculates the wavelength of each measurement light based on the light receiving position in the diffraction direction, and the deflection angle of the measurement light by the deflection container based on the light reception position in the deflection direction. The analyzer according to claim 2, wherein the refractive index for each wavelength of the sample is calculated based on the calculated wavelength and deviation angle. The refractive index measuring means includes incident light adjusting means for adjusting at least one of an incident angle and an incident position of the measurement light incident on a sample held by the deflection container,
The incident light adjusting means matches the principal ray of the measurement light, which is the zero-order diffracted light of the one-dimensional diffraction grating and has a predetermined reference wavelength in the wavelength range, with the optical axis of the condensing optical system. The analyzer according to claim 3.   The analyzer according to claim 4, wherein the predetermined reference wavelength is a longest wavelength in the wavelength range.   The analyzer according to claim 3, wherein the deflection container holds the sample in a right prism shape. The diffraction element is a two-dimensional diffraction grating,
The condensing optical system is a one-dimensional condensing optical system that condenses the measurement lights in a predetermined direction,
The deflection container holds the sample in a cylindrical lens shape, deflects and condenses the measurement light in a deflection direction orthogonal to the predetermined one direction,
The refractive index calculating means calculates the wavelength of each measurement light based on the light receiving position in the predetermined light collecting direction, and corresponds to each measurement light based on the light receiving position in the deflection direction. The analyzer according to claim 2, wherein a focal length of the deflection container is calculated, and a refractive index for each wavelength of the sample is calculated based on the calculated wavelength and focal length.   The analyzer according to claim 7, wherein a principal ray of the measurement light as zero-order diffracted light of the two-dimensional diffraction grating coincides with each optical axis of the condensing optical system and the deflection container.   The deflection container holds the sample having a refractive index smaller than the refractive index of the deflection container in the shape of a concave lens type cylindrical lens, and the sample having a refractive index larger than the refractive index of the deflection container is a convex lens type cylindrical lens. The analyzer according to claim 7 or 8, wherein the analyzer is held in a shape.   The analyzer according to claim 2, wherein the condensing optical system condenses the respective measurement lights by telecentric.   The analysis apparatus according to claim 2, wherein the condensing optical system is an optical system having no chromatic aberration.   The analyzer according to claim 11, wherein the condensing optical system is an achromatic lens system or a concave reflecting optical system. A refractive index measuring device for measuring the wavelength dependence of the refractive index of a sample,
A light source that emits measurement light in a predetermined wavelength range;
A diffractive element that diffracts the measurement light and branches it for each wavelength;
A deflecting container that holds the sample and refracts the measurement light incident on the held sample and deflects it for each wavelength;
A condensing optical system for condensing each measurement light branched by the diffraction element and deflected by the deflection container;
A two-dimensional light receiving element for receiving each measurement light condensed by the condensing optical system;
A refractive index calculating means for calculating a refractive index for each wavelength of the sample based on a light receiving position of each measurement light received by the two-dimensional light receiving element;
A refractive index measuring device comprising: The diffraction element is a one-dimensional diffraction grating,
The deflection container holds the sample in a prism shape and deflects the measurement light in a deflection direction orthogonal to a diffraction direction of the one-dimensional diffraction grating,
The refractive index calculation means calculates the wavelength of each measurement light based on the light receiving position in the diffraction direction, and the deflection angle of the measurement light by the deflection container based on the light reception position in the deflection direction. The refractive index measurement apparatus according to claim 13, wherein the refractive index for each wavelength of the sample is calculated based on the calculated wavelength and declination. The diffraction element is a two-dimensional diffraction grating,
The condensing optical system is a one-dimensional condensing optical system that condenses the measurement lights in a predetermined direction,
The deflection container holds the sample in a cylindrical lens shape, deflects and condenses the measurement light in a deflection direction orthogonal to the predetermined one direction,
The refractive index calculating means calculates the wavelength of each measurement light based on the light receiving position in the predetermined light collecting direction, and corresponds to each measurement light based on the light receiving position in the deflection direction. The refractive index measuring apparatus according to claim 13, wherein a focal length of the deflection container is calculated, and a refractive index for each wavelength of the sample is calculated based on the calculated wavelength and focal length. In an analysis method for measuring optical characteristics of a sample and analyzing the sample based on the measured optical characteristics,
A refractive index measurement step for measuring the wavelength dependence of the refractive index of the sample;
Calculating the absorption coefficient of the sample based on the wavelength dependence of the refractive index, and analyzing the sample based on the absorption coefficient;
The analysis method characterized by including. The refractive index measurement step includes
A diffraction step for diffracting the measurement light in a predetermined wavelength region and branching it for each wavelength;
A deflection step for refracting the measurement light incident on the sample and deflecting it for each wavelength;
A condensing step for condensing each measurement light branched by the diffraction step and deflected by the deflection step;
A light receiving step for receiving each of the measurement lights collected by the light collecting step;
Based on the light receiving position of each measurement light in the light receiving step, a refractive index calculation step for calculating a refractive index for each wavelength of the sample;
The analysis method according to claim 16, further comprising:

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