WO2017115591A1 - Photothermal conversion analysis apparatus and liquid cell - Google Patents

Photothermal conversion analysis apparatus and liquid cell Download PDF

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Publication number
WO2017115591A1
WO2017115591A1 PCT/JP2016/084884 JP2016084884W WO2017115591A1 WO 2017115591 A1 WO2017115591 A1 WO 2017115591A1 JP 2016084884 W JP2016084884 W JP 2016084884W WO 2017115591 A1 WO2017115591 A1 WO 2017115591A1
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detection light
photothermal conversion
excitation light
liquid cell
sample
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PCT/JP2016/084884
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French (fr)
Japanese (ja)
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滋郎 橋爪
青野　宇紀
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株式会社日立製作所
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/16—Investigating or analyzing materials by the use of thermal means by investigating thermal coefficient of expansion

Definitions

  • the present invention relates to a photothermal conversion analysis apparatus using a thermal lens effect and a liquid cell used in the apparatus.
  • a photothermal conversion analyzer is known as an apparatus that actively utilizes this effect and measures the concentration of a sample of a non-fluorescent substance with high sensitivity. As the photothermal conversion analyzer, there are a transmission type device and a reflection type device.
  • a detector is disposed in an optical path opposite to a light source with respect to a sample, and detects detection light transmitted through the sample.
  • the detector is disposed in the optical path on the light source side with respect to the sample, and detects the detection light reflected in the space opposite to the light source with respect to the sample.
  • the detection light passes through the sample that causes the thermal lens effect twice, so that the detection sensitivity can be improved.
  • Patent Document 1 discloses a photothermal conversion analysis apparatus using a reflection optical system in which laser light that has passed through a sample is turned back by a mirror, the sample is allowed to pass again, and analysis is performed using the reflected light.
  • the lower concentration limit of the sample that can be analyzed by the photothermal conversion analyzer is determined by the noise inherent in the device.
  • Excitation light emitted from the excitation light source is slightly absorbed by optical elements such as a sample cell and an objective lens other than the sample. Thereby, each optical element generates heat, and a thermal lens effect is generated. Since the detection light passes through these optical elements that have caused the thermal lens effect, noise due to the thermal lens effect of each optical element is generated in the detection signal. In particular, in the reflection type apparatus, the detection light passes through the sample cell and the optical element twice, and thus noise due to the thermal lens effect generated outside the sample is a major cause of a decrease in analysis sensitivity.
  • the present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a reflection type photothermal conversion analyzer capable of highly sensitive analysis of a sample and a liquid cell used therefor.
  • a photothermal conversion analyzer of the present invention includes an excitation light source that emits excitation light, a detection light source that emits detection light having a wavelength different from that of the excitation light, and the detection light that receives the detection light.
  • a detector for detecting the intensity of the sample a liquid cell for storing the sample to be measured, and a reflecting member for reflecting at least a part of the detection light transmitted through the sample to be measured. The reflectance is greater than the reflectance of the reflecting member with respect to the excitation light.
  • a sample can be analyzed with high sensitivity in a reflection type photothermal conversion analyzer.
  • FIG. 6 is an explanatory diagram in the vicinity of a sample cell in Example 2. Explanatory drawing of the structure of the reflection member in Example 3, and the wavelength dependence of a reflectance.
  • the photothermal conversion analyzer of this embodiment can detect trace components in a sample without using fluorescence, it can be used not only for general-purpose devices but also for clinical applications such as biochemical automatic analyzers, immune automatic analyzers, etc. It can also be used for inspection automatic analyzers.
  • sample to be measured is referred to as a sample solution.
  • FIG. 1 is a configuration diagram showing the photothermal conversion analyzer of the present embodiment.
  • the photothermal conversion analyzer of FIG. 1 includes an excitation light source 101 that is a laser that generates excitation light, a detection light source 102 that is a laser that generates detection light, a filter, a wavelength plate, and a focusing lens. It has a converging optical system, a detector 111 that receives detection light and detects its intensity, and a control unit that controls each component such as a light source and a detector.
  • the light beam of the excitation light L1 is indicated by a one-dot chain line
  • the light beam of the detection light L2 is indicated by a solid line.
  • the optical system focuses the first filter 103 and the second filter 104 that transmit the excitation light and reflect the detection light, the quarter-wave plate 105, the excitation light and the detection light at predetermined positions.
  • a first focusing lens 106 is included.
  • the operations of the excitation light source 101 and the detection light source 102 are controlled by drive circuits 202 and 204, respectively.
  • the detector 111 includes a pinhole 115, a second condenser lens 118 that focuses the detection light into the pinhole 115, and a light receiving element 116 that detects the light that has passed through the pinhole 115.
  • the detector 111 is not limited to a general detector configured by only the pinhole 115 and the light receiving element 116, and may be a detector using an astigmatism method, a knife edge method, or the like. Moreover, you may provide the 3rd filter 110 which interrupts
  • An electric signal detected by the light receiving element 16 is input to a computer 205 as a control unit via a current-voltage conversion circuit 201 and a lock-in amplifier 203.
  • the control unit of the photothermal conversion analyzer may be configured as hardware by a dedicated circuit board, or may be configured by software executed by a computer connected to the photothermal conversion analyzer as shown in FIG. .
  • When configured by hardware it can be realized by integrating a plurality of arithmetic units for executing processing on a wiring board or in a semiconductor chip or package.
  • When configured by software it can be realized by mounting a high-speed general-purpose CPU on a computer and executing a program for executing desired arithmetic processing.
  • the excitation light L ⁇ b> 1 whose intensity is modulated at the specific frequency f ⁇ b> 0 is emitted from the excitation light source 101 and passes through the first filter 103.
  • the detection light L2 is emitted from the detection light source 102 as a continuous wave based on a signal from the drive circuit 204 set by the computer 205, reflected by the first filter 103, and passed through the first filter 103. Aligned on the same optical axis as L1.
  • the combined light passes through the second filter 104 and the first quarter wave plate 105.
  • the excitation light L1 and the detection light L2 that have passed through the first quarter-wave plate 105 are condensed in the sample liquid 109 stored in the liquid cell 107 by the first condenser lens 106.
  • FIG. 2 is a schematic diagram of the optical paths of the excitation light L1 and the detection light L2 in the vicinity of the liquid cell 107.
  • the excitation light L1 is collected at a certain point in the sample liquid 109 in the liquid cell 107.
  • the detection light L ⁇ b> 2 passes through the sample liquid 109 in the liquid cell 107 and is then collected on the reflection member 108 provided in the liquid cell 107.
  • the reflection member 108 is provided on the inner wall of the liquid cell 107.
  • the reflection member 108 may be provided on the outer wall of the liquid cell or may be provided outside the liquid cell.
  • the reflecting member 108 may be provided in the liquid cell. preferable. At least a part of the collected detection light is reflected by the reflecting member 108.
  • FIG. 3A and 3B are examples of the wavelength dependence of the reflectance of the reflecting member 108.
  • the reflectance of the reflecting member 108 with respect to the detection light L2 is larger than the reflectance with respect to the excitation light L1. Most of the light that is not reflected passes through the reflecting member 108 and is emitted to the outside of the liquid cell 107.
  • the reflecting member 108 for example, a dielectric multilayer film reflecting mirror in which a plurality of dielectrics having different refractive indexes are stacked and the thickness or material of each layer is changed may be used.
  • the detection light L2 that has passed through the sample liquid 109 is reflected by the reflecting member 108, passes through the first condenser lens 106 and the first quarter-wave plate 105 again, and then passes through the second filter.
  • the light is reflected at 104, passes through the third filter 110, the second condensing lens 118, and the pinhole 115, and then irradiates the light receiving element 116.
  • the excitation light L1 that has passed through the second filter 104 and the first quarter-wave plate 105 is condensed by the first condenser lens 106 and applied to the sample liquid 109.
  • FIG. 4A is a diagram illustrating the optical path of the detection light L2 in the liquid cell 107 when a thermal lens is generated in the sample liquid 109.
  • FIG. 4B is a diagram for explaining an optical path until the detector 111 is irradiated with the detection light L ⁇ b> 2 when a thermal lens is generated in the sample liquid 109.
  • trajectory of the light beam of the detection light L2 when a thermal lens arises is described with the broken line in the figure.
  • the sample liquid 109 contains a sample that absorbs the excitation light L1
  • the sample liquid 109 absorbs a part of the excitation light L1 and generates heat according to the concentration of the sample, thereby forming a thermal lens.
  • a thermal lens is formed inside the sample liquid 109 by the excitation light L1
  • the condensing angle of the detection light L2 that has passed through the thermal lens becomes small as indicated by the broken light beam in FIG.
  • the detection light L2 reflected by the reflecting member 108 passes through the thermal lens again, passes through the first condenser lens 106 shown in FIG. 4A, passes through the first quarter-wave plate 105 as weakly diverging light. Passes and is reflected by the second filter 104.
  • the detection light L ⁇ b> 2 reflected by the second filter 104 passes through the third filter 110 and is collected by the second condenser lens 118.
  • the pinhole 115 is disposed in the vicinity of the condensing point of the detection light L2 when no thermal lens is generated. For this reason, the detection light L2 that has passed through the second condenser lens 118 as weakly diverging light is not sufficiently condensed at the position of the pinhole 115, and a part of the light flux is lost at the pinhole 115 and received. Irradiation is performed on the element 116.
  • the light amount of the detection light L2 that passes through the pinhole 115 and is detected by the light receiving element 116 changes in proportion to the light amount that the excitation light L1 is absorbed by the sample liquid 109. That is, when a part of the excitation light L1 is absorbed by the sample, a thermal lens is generated, and the detection light L2 detected by the detector 111 becomes weak.
  • Current signal of a specific frequency f 0 in the intensity-modulated detection light L2 received by the detector 111 is a current shown in FIG. 1 - is converted into a voltage signal by the voltage conversion circuit 201 is input to the lock-in amplifier 203 .
  • Lock-in amplifier 203 by further receives the modulation frequency f 0 of the excitation light L1 from the drive circuit 202 of the pumping light source 101 as a reference signal, a signal included in the detection light L2 received by the detector 111 with high precision
  • the extracted signal is output to the computer 205.
  • the sample concentration of the measurement target contained in the sample liquid 109 is analyzed by these procedures.
  • the excitation light source 101 is a light source such as a gas laser that cannot be directly modulated at high speed
  • a device capable of modulating the light intensity of the excitation light L1 output from the excitation light source 101 at high speed such as a chopper, is used as the excitation light source 101 and the first You may arrange
  • the lock-in amplifier 203 uses the reference signal from the chopper controller instead of the reference signal from the drive circuit 202.
  • the reflecting member 108 has wavelength selectivity, and most of the excitation light L1 is transmitted through the reflecting member 108. Therefore, the amount of reflected light of the excitation light L1 from the reflecting member 108, which has been a conventional problem, is small. Thereby, the thermal lens effect produced in each optical element by reflected excitation light L1 can be reduced, and background noise can be reduced as a result.
  • FIG. 5 is a diagram for explaining the vicinity of the sample cell in the second embodiment. The installation position of the reflection member 108 is demonstrated using this.
  • FIG. 5A shows a configuration having a heat insulating member 112 between the reflecting member 108 and the sample liquid 109.
  • the reflecting member 108 absorbs part of the excitation light L1 and generates heat.
  • the sample liquid 109 in contact with the reflecting member 108 is warmed, and a thermal lens effect that causes background noise is generated. Therefore, in the second embodiment, the heat insulating member 112 is sandwiched between the reflecting member 108 and the sample liquid 109.
  • the heat insulating member 112 By inserting the heat insulating member 112 into the interface between the reflective member 108 and the sample liquid 109, heat due to the excitation light L1 absorbed by the reflective member 108 becomes difficult to be transmitted from the reflective member 108 to the sample liquid 109, so that background noise is reduced.
  • the detection sensitivity can be further improved.
  • a structure in which the heat radiating member 114 is fixed to the back surface of the reflecting member 108 may be used.
  • the heat of the reflecting member 108 generated by the excitation light L1 is transmitted to the heat radiating member 114 fixed on the back surface and is not easily transmitted to the sample liquid 109, so that background noise is reduced and detection sensitivity can be further improved.
  • a variable wavelength excitation light source capable of changing the wavelength of excitation light is used as the excitation light source
  • a reflection member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is used as the reflection member.
  • the wavelength of the excitation light L1 that is easily absorbed by the sample liquid 109 is different. Therefore, in this embodiment, a variable wavelength excitation light source that can be changed to the wavelength of the excitation light matched to the sample to be measured included in the sample liquid 109 analyzed by the photothermal conversion analyzer is used.
  • the reflectance of the wavelength of the specific detection light L2 is designed high. Therefore, with respect to the wavelength of the different excitation light L1, the reflectance increases, and the noise increases accordingly, so that the detection sensitivity decreases.
  • the reflecting member 108 the reflecting member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is used.
  • FIG. 6A illustrates the structure of the reflecting member 113 in this embodiment.
  • FIG. 6B is a diagram for explaining the wavelength dependence of the reflectance of the reflecting member 113.
  • the reflection member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is, for example, a reflection member 113b fixed to the liquid cell 107 and a reflection member 113a whose position can be adjusted in the optical axis direction. These two members are laminated. There is a gap between the reflecting member 113a and the reflecting member 113b. A larger gap between the reflecting member 113a and the reflecting member 113b, the wavelength of the excitation light L1 transmitted through the reflecting member 113 is wavelength becomes longer in lambda 2 from lambda 1. Therefore, this gap may be adjusted so that the reflectance of the excitation light L1 is low and the reflectance of the detection light L2 is high.
  • the liquid cell of this embodiment is provided with a position adjusting mechanism that makes at least one of the reflecting members 113a and 113b movable in the stacking direction (a direction perpendicular to the plane of the reflecting member).
  • a MEMS actuator using a semiconductor processing technique may be used as a mechanism for adjusting the interval between the reflecting members.
  • the gap between the reflecting member 113a and the reflecting member 113b may be filled with a liquid or the like.
  • 101 excitation light source
  • 102 detection light source
  • 103 first filter
  • 104 second filter
  • 105 first quarter-wave plate
  • 106 first condenser lens
  • 107 liquid cell
  • 108 reflecting member
  • 109 sample liquid
  • 110 third filter
  • 111 detector
  • 112 heat insulating member
  • 113 reflecting member
  • 115 pinhole
  • 116 light receiving element
  • 118 second condenser lens
  • 201 current-voltage conversion circuit
  • 202 excitation light source drive circuit
  • 203 lock-in amplifier
  • 204 detection light source drive circuit
  • 205 computer
  • L1 excitation light
  • L2 detection light
  • 300 photothermal conversion analysis apparatus

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  • Life Sciences & Earth Sciences (AREA)
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  • Analytical Chemistry (AREA)
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Abstract

A reflective photothermal conversion analysis apparatus has a problem in that excitation light is absorbed slightly even by a part through which the excitation light passes, which causes deterioration in optical characteristics and signal noise. Accordingly, the purpose of the present invention is to provide a reflective photothermal conversion analysis apparatus which is capable of analyzing a small sized sample included in a sample fluid with high sensitivity. A liquid cell used in this photothermal conversion analysis apparatus, which is provided with an excitation light source that emits excitation light, a detection light source that emits detection light, and a detector that receives the detection light and detects the intensity of the detection light, is provided with a reflection member that reflects at least a part of the detection light which has passed through the sample to be measured. The reflection member is arranged to have a higher reflectivity for the detection light than for the excitation light.

Description

光熱変換分析装置および液体セルPhotothermal conversion analyzer and liquid cell
本発明は、熱レンズ効果を用いた光熱変換分析装置および当該装置に用いられる液体セルに関するものである。 The present invention relates to a photothermal conversion analysis apparatus using a thermal lens effect and a liquid cell used in the apparatus.
　測定対象の試料を混ぜたサンプルに特定の波長の光を集光して照射すると、そのサンプルは光を吸収し、温度が局所的に上昇する。この温度上昇に応じてサンプルの屈折率が変化する。多くの物質では、温度上昇により屈折率は低下するため、光の集光部近傍のサンプル液は凹レンズが生じたような光学効果が起こる。この効果は一般的に熱レンズ効果と言われている。この効果を積極的に利用し、非蛍光物質の試料の濃度を高感度に測定する装置として光熱変換分析装置が知られている。光熱変換分析装置としては、透過型装置と反射型装置がある。透過型装置は、検出器がサンプルに対して光源と反対側の光路に配置され、サンプルを透過した検出光を検出するものである。一方、反射型装置は、検出器がサンプルに対して光源側の光路に配置され、サンプルに対して光源と反対側の空間で反射した検出光を検出するものである。反射型装置では、熱レンズ効果を生じるサンプルを検出光が二度通過するため、検出感度を向上させることが可能である。 ¡When light of a specific wavelength is collected and irradiated to a sample mixed with the sample to be measured, the sample absorbs light and the temperature rises locally. The refractive index of the sample changes according to this temperature rise. For many substances, the refractive index decreases with increasing temperature, so that the sample solution near the light condensing part has an optical effect like a concave lens. This effect is generally referred to as a thermal lens effect. A photothermal conversion analyzer is known as an apparatus that actively utilizes this effect and measures the concentration of a sample of a non-fluorescent substance with high sensitivity. As the photothermal conversion analyzer, there are a transmission type device and a reflection type device. In the transmission type device, a detector is disposed in an optical path opposite to a light source with respect to a sample, and detects detection light transmitted through the sample. On the other hand, in the reflection type device, the detector is disposed in the optical path on the light source side with respect to the sample, and detects the detection light reflected in the space opposite to the light source with respect to the sample. In the reflection type apparatus, the detection light passes through the sample that causes the thermal lens effect twice, so that the detection sensitivity can be improved.
　特許文献１には、試料を通過したレーザ光をミラーで折り返し、再び試料を通過させ、その反射光を用いて分析する反射光学系を用いた光熱変換分析装置が開示されている。 Patent Document 1 discloses a photothermal conversion analysis apparatus using a reflection optical system in which laser light that has passed through a sample is turned back by a mirror, the sample is allowed to pass again, and analysis is performed using the reflected light.
特開平０４－３６９４６７号公報Japanese Patent Laid-Open No. 04-369467
　光熱変換分析装置で分析可能な試料の濃度下限は、装置の固有のノイズで決まる。励起光源から出射した励起光はサンプル以外の試料セルや対物レンズなどの光学素子にも僅かに吸収される。それにより、各光学素子は発熱し、熱レンズ効果が生じる。これら熱レンズ効果を生じた光学素子を検出光が透過するため、検出信号に各光学素子の熱レンズ効果に起因したノイズが発生する。特に反射型装置では、検出光が試料セルや光学素子を２度通るため、このようにサンプル以外で発生する熱レンズ効果に起因するノイズが分析感度低下の大きな原因となる。 The lower concentration limit of the sample that can be analyzed by the photothermal conversion analyzer is determined by the noise inherent in the device. Excitation light emitted from the excitation light source is slightly absorbed by optical elements such as a sample cell and an objective lens other than the sample. Thereby, each optical element generates heat, and a thermal lens effect is generated. Since the detection light passes through these optical elements that have caused the thermal lens effect, noise due to the thermal lens effect of each optical element is generated in the detection signal. In particular, in the reflection type apparatus, the detection light passes through the sample cell and the optical element twice, and thus noise due to the thermal lens effect generated outside the sample is a major cause of a decrease in analysis sensitivity.
　本発明は上記従来技術の課題を踏まえなされたものであり、試料の高感度分析が可能である反射型光熱変換分析装置およびこれに用いられる液体セルを提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a reflection type photothermal conversion analyzer capable of highly sensitive analysis of a sample and a liquid cell used therefor.
　上記課題を解決するために本発明の光熱変換分析装置は、励起光を発する励起光源と、前記励起光とは異なる波長の検出光を発する検出光源と、前記検出光を受光して当該検出光の強度を検知する検出器と、測定対象試料を格納する液体セルと、前記測定対象試料を透過した検出光の少なくとも一部を反射する反射部材と、を備え、前記反射部材の前記検出光に対する反射率は、前記反射部材の前記励起光に対する反射率より大きいことを特徴とする。 In order to solve the above problems, a photothermal conversion analyzer of the present invention includes an excitation light source that emits excitation light, a detection light source that emits detection light having a wavelength different from that of the excitation light, and the detection light that receives the detection light. A detector for detecting the intensity of the sample, a liquid cell for storing the sample to be measured, and a reflecting member for reflecting at least a part of the detection light transmitted through the sample to be measured. The reflectance is greater than the reflectance of the reflecting member with respect to the excitation light.
　本発明によれば、反射型光熱変換分析装置において、サンプルを高感度に分析することが可能となる。上記した以外の課題、構成及び効果は、以下の実施形態の説明により明らかにされる。 According to the present invention, a sample can be analyzed with high sensitivity in a reflection type photothermal conversion analyzer. Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.
光熱変換分析装置の全体概略構成図。The whole schematic block diagram of a photothermal conversion analyzer. 液体セル近傍の励起光と検出光の光路の説明図。Explanatory drawing of the optical path of the excitation light and detection light of the liquid cell vicinity. 反射部材の反射率の波長依存性を示す図。The figure which shows the wavelength dependence of the reflectance of a reflection member. サンプル内に熱レンズ効果が発生した状態の検出光の光路を説明する図。The figure explaining the optical path of the detection light in the state where the thermal lens effect has occurred in the sample. 実施例２における試料セル近傍の説明図。FIG. 6 is an explanatory diagram in the vicinity of a sample cell in Example 2. 実施例３における反射部材の構造と、反射率の波長依存性の説明図。Explanatory drawing of the structure of the reflection member in Example 3, and the wavelength dependence of a reflectance.
　以下、図面を参照し、本発明の実施例について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
　本実施例の光熱変換分析装置は、蛍光を使わずにサンプル内の微量成分を検出することができるため、汎用の装置のみならず、例えば生化学自動分析装置、免疫自動分析装置、などの臨床検査用自動分析装置にも用いることができる。 Since the photothermal conversion analyzer of this embodiment can detect trace components in a sample without using fluorescence, it can be used not only for general-purpose devices but also for clinical applications such as biochemical automatic analyzers, immune automatic analyzers, etc. It can also be used for inspection automatic analyzers.
　なお、以下では測定対象となる試料をサンプル液と称する。 In the following, the sample to be measured is referred to as a sample solution.
　図１は、本実施例の光熱変換分析装置を示す構成図である。図１の光熱変換分析装置は、励起光を発生するレーザである励起光源１０１、検出光を発生するレーザである検出光源１０２、フィルタや波長板や集束レンズからなり励起光や検出光を選択または集束する光学系、検出光を受光してその強度を検出する検出器１１１、および光源や検出器などの各部品を制御する制御部を有する。ここで、励起光と検出光の波長は異なるものとし、図中、励起光Ｌ１の光線を一点鎖線、検出光Ｌ２の光線を実線で記載している。 FIG. 1 is a configuration diagram showing the photothermal conversion analyzer of the present embodiment. The photothermal conversion analyzer of FIG. 1 includes an excitation light source 101 that is a laser that generates excitation light, a detection light source 102 that is a laser that generates detection light, a filter, a wavelength plate, and a focusing lens. It has a converging optical system, a detector 111 that receives detection light and detects its intensity, and a control unit that controls each component such as a light source and a detector. Here, it is assumed that the wavelengths of the excitation light and the detection light are different, and in the drawing, the light beam of the excitation light L1 is indicated by a one-dot chain line, and the light beam of the detection light L2 is indicated by a solid line.
　より具体的には、光学系は、励起光を透過し検出光を反射する第一フィルタ１０３および第二フィルタ１０４、４分の１波長板１０５、励起光および検出光を所定の位置に集束させる第１の集束レンズ１０６を含む。励起光源１０１、検出光源１０２はそれぞれ駆動回路２０２，２０４によって動作制御される。また、検出器１１１は、ピンホール１１５、検出光をピンホール１１５に集束させる第２の集光レンズ１１８、ピンホール１１５を通過した光を検出する受光素子１１６を含む。なお、検出器１１１は、ピンホール１１５と受光素子１１６だけで構成する一般的な検出器に限らず、非点収差法やナイフエッジ法などを用いた検出器でも良い。また、図１のように検出器１１１の前に励起光を遮断する第三のフィルタ１１０を備えてもよい。受光素子１６で検出された電気信号は電流―電圧変換回路２０１、ロックインアンプ２０３を介して制御部であるコンピュータ２０５に入力される。 More specifically, the optical system focuses the first filter 103 and the second filter 104 that transmit the excitation light and reflect the detection light, the quarter-wave plate 105, the excitation light and the detection light at predetermined positions. A first focusing lens 106 is included. The operations of the excitation light source 101 and the detection light source 102 are controlled by drive circuits 202 and 204, respectively. The detector 111 includes a pinhole 115, a second condenser lens 118 that focuses the detection light into the pinhole 115, and a light receiving element 116 that detects the light that has passed through the pinhole 115. The detector 111 is not limited to a general detector configured by only the pinhole 115 and the light receiving element 116, and may be a detector using an astigmatism method, a knife edge method, or the like. Moreover, you may provide the 3rd filter 110 which interrupts | blocks excitation light before the detector 111 like FIG. An electric signal detected by the light receiving element 16 is input to a computer 205 as a control unit via a current-voltage conversion circuit 201 and a lock-in amplifier 203.
　光熱変換分析装置の制御部は、専用の回路基板によってハードウェアとして構成されていてもよいし、図１のように光熱変換分析装置に接続されたコンピュータで実行されるソフトウェアによって構成されてもよい。ハードウェアにより構成する場合には、処理を実行する複数の演算器を配線基板上、または半導体チップまたはパッケージ内に集積することにより実現できる。ソフトウェアにより構成する場合には、コンピュータに高速な汎用ＣＰＵを搭載して、所望の演算処理を実行するプログラムを実行することで実現できる。 The control unit of the photothermal conversion analyzer may be configured as hardware by a dedicated circuit board, or may be configured by software executed by a computer connected to the photothermal conversion analyzer as shown in FIG. . When configured by hardware, it can be realized by integrating a plurality of arithmetic units for executing processing on a wiring board or in a semiconductor chip or package. When configured by software, it can be realized by mounting a high-speed general-purpose CPU on a computer and executing a program for executing desired arithmetic processing.
　光熱変換分析装置の動作を説明する。 The operation of the photothermal conversion analyzer will be described.
　コンピュータ２０５で設定された駆動回路２０２からの信号に基づき、励起光源１０１から特定周波数ｆ０で強度変調された励起光Ｌ１が出射し、第一のフィルタ１０３を通過する。一方、検出光Ｌ２はコンピュータ２０５で設定された駆動回路２０４からの信号に基づき、検出光源１０２から連続波として出射され、第一のフィルタ１０３で反射し、第一のフィルタ１０３を通過した励起光Ｌ１と同一光軸上に合わされる。合わされた光は第二のフィルタ１０４と第一の４分の１波長板１０５を通過する。第一の４分の１波長板１０５を通過した励起光Ｌ１と検出光Ｌ２は第一の集光レンズ１０６で液体セル１０７内に格納されたサンプル液１０９中に集光される。 Based on the signal from the drive circuit 202 set by the computer 205, the excitation light L <b> 1 whose intensity is modulated at the specific frequency f <b> 0 is emitted from the excitation light source 101 and passes through the first filter 103. On the other hand, the detection light L2 is emitted from the detection light source 102 as a continuous wave based on a signal from the drive circuit 204 set by the computer 205, reflected by the first filter 103, and passed through the first filter 103. Aligned on the same optical axis as L1. The combined light passes through the second filter 104 and the first quarter wave plate 105. The excitation light L1 and the detection light L2 that have passed through the first quarter-wave plate 105 are condensed in the sample liquid 109 stored in the liquid cell 107 by the first condenser lens 106.
　図２は、液体セル１０７近傍の励起光Ｌ１と検出光Ｌ２の光路の概略図である。 FIG. 2 is a schematic diagram of the optical paths of the excitation light L1 and the detection light L2 in the vicinity of the liquid cell 107.
　励起光Ｌ１は、液体セル１０７内のサンプル液１０９中のある一点に集光される。検出光Ｌ２は、液体セル１０７内のサンプル液１０９を通過後、液体セル１０７に設けた反射部材１０８に集光される。反射部材１０８は液体セル１０７の内壁に設けられている。また、別の例として、液体セルが透明であれば反射部材１０８は液体セルの外壁に設けられてもよいし、液体セル外部に設けられてもよい。ただし、この場合には励起光Ｌ１が液体セルを通過することになるため液体セル自体で励起光Ｌ１を吸収し発熱する可能性があるため、反射部材１０８は液体セルの中に設けられることが好ましい。集光された検出光の少なくとも一部は反射部材１０８によって反射される。 The excitation light L1 is collected at a certain point in the sample liquid 109 in the liquid cell 107. The detection light L <b> 2 passes through the sample liquid 109 in the liquid cell 107 and is then collected on the reflection member 108 provided in the liquid cell 107. The reflection member 108 is provided on the inner wall of the liquid cell 107. As another example, if the liquid cell is transparent, the reflection member 108 may be provided on the outer wall of the liquid cell or may be provided outside the liquid cell. However, in this case, since the excitation light L1 passes through the liquid cell, the liquid cell itself may absorb the excitation light L1 and generate heat. Therefore, the reflecting member 108 may be provided in the liquid cell. preferable. At least a part of the collected detection light is reflected by the reflecting member 108.
　図３（ａ）と図３（ｂ）は、反射部材１０８の反射率の波長依存性の例である。 3A and 3B are examples of the wavelength dependence of the reflectance of the reflecting member 108. FIG.
　図３（ａ）と図３（ｂ）に示すように反射部材１０８の検出光Ｌ２に対する反射率は、励起光Ｌ１に対する反射率より大きい。反射しない光の大半は反射部材１０８を透過し、液体セル１０７外部に放出される。反射部材１０８は、例えば屈折率の異なる複数の誘電体を積層し、各層の厚みや材料を変えた誘電体多層膜反射鏡を用いてもよい。 3A and 3B, the reflectance of the reflecting member 108 with respect to the detection light L2 is larger than the reflectance with respect to the excitation light L1. Most of the light that is not reflected passes through the reflecting member 108 and is emitted to the outside of the liquid cell 107. As the reflecting member 108, for example, a dielectric multilayer film reflecting mirror in which a plurality of dielectrics having different refractive indexes are stacked and the thickness or material of each layer is changed may be used.
　サンプル液１０９を透過した検出光Ｌ２の大半は、反射部材１０８で反射され、再び第一の集光レンズ１０６と第一の４分の１波長板１０５を通過した後、今度は第二のフィルタ１０４で反射され、第三のフィルタ１１０と第二の集光レンズ１１８とピンホール１１５を通過後、受光素子１１６に照射される。 Most of the detection light L2 that has passed through the sample liquid 109 is reflected by the reflecting member 108, passes through the first condenser lens 106 and the first quarter-wave plate 105 again, and then passes through the second filter. The light is reflected at 104, passes through the third filter 110, the second condensing lens 118, and the pinhole 115, and then irradiates the light receiving element 116.
　次に、サンプル液１０９に含有する試料の濃度の測定方法について説明する。 Next, a method for measuring the concentration of the sample contained in the sample liquid 109 will be described.
　第二のフィルタ１０４と第一の４分の１波長板１０５を通過した励起光Ｌ１は第一の集光レンズ１０６で集光され、サンプル液１０９に照射される。 The excitation light L1 that has passed through the second filter 104 and the first quarter-wave plate 105 is condensed by the first condenser lens 106 and applied to the sample liquid 109.
　図４（ａ）は、サンプル液１０９内に熱レンズが発生しているときの液体セル１０７内での検出光Ｌ２の光路を説明する図である。図４（ｂ）は、サンプル液１０９内に熱レンズが発生しているときの、検出光Ｌ２が検出器１１１に照射されるまでの光路を説明する図である。なお、熱レンズが生じた時の検出光Ｌ２の光線の軌跡を図中破線で表記している。 FIG. 4A is a diagram illustrating the optical path of the detection light L2 in the liquid cell 107 when a thermal lens is generated in the sample liquid 109. FIG. FIG. 4B is a diagram for explaining an optical path until the detector 111 is irradiated with the detection light L <b> 2 when a thermal lens is generated in the sample liquid 109. In addition, the locus | trajectory of the light beam of the detection light L2 when a thermal lens arises is described with the broken line in the figure.
　サンプル液１０９に励起光Ｌ１を吸収する試料を含有する場合、試料の濃度に応じてサンプル液１０９は励起光Ｌ１の一部を吸収して発熱し、熱レンズが形成される。励起光Ｌ１によりサンプル液１０９内部に熱レンズが形成される場合、図４（ａ）の破線の光線で示すように熱レンズを通過した検出光Ｌ２の集光角度が小さくなる。反射部材１０８で反射された検出光Ｌ２は再び熱レンズを通過し、図４（ａ）に示す第一の集光レンズ１０６を通過し弱発散光として第一の４分の１波長板１０５を通過し、第二のフィルタ１０４で反射される。第二のフィルタ１０４で反射された検出光Ｌ２は第三のフィルタ１１０を通過し第二の集光レンズ１１８で集光される。ピンホール１１５は熱レンズが生じない時の検出光Ｌ２の集光点近傍に配置されている。そのため、弱発散光として第二の集光レンズ１１８を通過した検出光Ｌ２はピンホール１１５の位置で光束が十分に集光されておらず、光束の一部がピンホール１１５で欠損され、受光素子１１６上に照射される。つまり、ピンホール１１５を通過し、受光素子１１６で検出される検出光Ｌ２の光量は、励起光Ｌ１がサンプル液１０９に吸収される光量に比例した変化を生じる。つまり、試料に励起光Ｌ１の一部が吸収されると熱レンズが生じこれによって、検出器１１１で検出される検出光Ｌ２は弱くなる。 When the sample liquid 109 contains a sample that absorbs the excitation light L1, the sample liquid 109 absorbs a part of the excitation light L1 and generates heat according to the concentration of the sample, thereby forming a thermal lens. When a thermal lens is formed inside the sample liquid 109 by the excitation light L1, the condensing angle of the detection light L2 that has passed through the thermal lens becomes small as indicated by the broken light beam in FIG. The detection light L2 reflected by the reflecting member 108 passes through the thermal lens again, passes through the first condenser lens 106 shown in FIG. 4A, passes through the first quarter-wave plate 105 as weakly diverging light. Passes and is reflected by the second filter 104. The detection light L <b> 2 reflected by the second filter 104 passes through the third filter 110 and is collected by the second condenser lens 118. The pinhole 115 is disposed in the vicinity of the condensing point of the detection light L2 when no thermal lens is generated. For this reason, the detection light L2 that has passed through the second condenser lens 118 as weakly diverging light is not sufficiently condensed at the position of the pinhole 115, and a part of the light flux is lost at the pinhole 115 and received. Irradiation is performed on the element 116. That is, the light amount of the detection light L2 that passes through the pinhole 115 and is detected by the light receiving element 116 changes in proportion to the light amount that the excitation light L1 is absorbed by the sample liquid 109. That is, when a part of the excitation light L1 is absorbed by the sample, a thermal lens is generated, and the detection light L2 detected by the detector 111 becomes weak.
　検出器１１１で受光された特定周波数ｆ０で強度変調された検出光Ｌ２の電流信号は図１に示す電流―電圧変換回路２０１で電圧信号に変換された後、ロックインアンプ２０３に入力される。ロックインアンプ２０３は、さらに励起光源１０１の駆動回路２０２から励起光Ｌ１の変調周波数ｆ０をリファレンス信号として入力することで、検出器１１１で受光された検出光Ｌ２に含まれる信号を高精度に抽出し、その信号をコンピュータ２０５に出力する。これらの手順によりサンプル液１０９に含まれる測定対象の試料濃度を分析する。 Current signal of a specific frequency f 0 in the intensity-modulated detection light L2 received by the detector 111 is a current shown in FIG. 1 - is converted into a voltage signal by the voltage conversion circuit 201 is input to the lock-in amplifier 203 . Lock-in amplifier 203, by further receives the modulation frequency f 0 of the excitation light L1 from the drive circuit 202 of the pumping light source 101 as a reference signal, a signal included in the detection light L2 received by the detector 111 with high precision The extracted signal is output to the computer 205. The sample concentration of the measurement target contained in the sample liquid 109 is analyzed by these procedures.
　なお、励起光源１０１がガスレーザなどの直接高速に変調できない光源の場合は、励起光源１０１から出力された励起光Ｌ１をチョッパ等の光強度を高速に変調可能な装置を励起光源１０１と第一のフィルタ１０３との間に配置しても良い。この時、ロックインアンプ２０３には駆動回路２０２からのリファレンス信号の代わりにチョッパ制御装置からのリファレンス信号を用いる。 In the case where the excitation light source 101 is a light source such as a gas laser that cannot be directly modulated at high speed, a device capable of modulating the light intensity of the excitation light L1 output from the excitation light source 101 at high speed, such as a chopper, is used as the excitation light source 101 and the first You may arrange | position between the filters 103. At this time, the lock-in amplifier 203 uses the reference signal from the chopper controller instead of the reference signal from the drive circuit 202.
　本実施例１においては、反射部材１０８が波長選択性を持っており、励起光Ｌ１の大部分が反射部材１０８を透過する。そのため、従来課題であった反射部材１０８からの励起光Ｌ１の反射光量が少ない。それにより、反射した励起光Ｌ１により各光学素子に生じる熱レンズ効果を低減でき、結果として背景ノイズを低減できる。 In the first embodiment, the reflecting member 108 has wavelength selectivity, and most of the excitation light L1 is transmitted through the reflecting member 108. Therefore, the amount of reflected light of the excitation light L1 from the reflecting member 108, which has been a conventional problem, is small. Thereby, the thermal lens effect produced in each optical element by reflected excitation light L1 can be reduced, and background noise can be reduced as a result.
　次に、反射部材１０８からの熱を断熱または放熱することによって背景ノイズを低減する例について説明する。実施例２の基本構成は実施例１と同様であるため、以下では、実施例１と同様の部分については説明を省略する。 Next, an example in which background noise is reduced by insulating or dissipating heat from the reflecting member 108 will be described. Since the basic configuration of the second embodiment is the same as that of the first embodiment, the description of the same parts as those of the first embodiment will be omitted below.
　図５は実施例２における試料セル近傍の説明する図である。これを用いて反射部材１０８の設置位置について説明する。 FIG. 5 is a diagram for explaining the vicinity of the sample cell in the second embodiment. The installation position of the reflection member 108 is demonstrated using this.
　図５（ａ）では、反射部材１０８とサンプル液１０９の間に断熱部材１１２を有する構成である。図５（ａ）において、反射部材１０８は励起光Ｌ１の一部を吸収し、発熱する。それにより、反射部材１０８に接するサンプル液１０９が温められ、背景ノイズとなる熱レンズ効果を生じる。そこで、本実施例２では反射部材１０８とサンプル液１０９の間に断熱部材１１２を挟む。断熱部材１１２を反射部材１０８とサンプル液１０９の界面に挿入することで、反射部材１０８が吸収した励起光Ｌ１による熱が反射部材１０８からサンプル液１０９に伝わり難くなるため、背景ノイズが低減し、検出感度をさらに向上することができる。 FIG. 5A shows a configuration having a heat insulating member 112 between the reflecting member 108 and the sample liquid 109. In FIG. 5A, the reflecting member 108 absorbs part of the excitation light L1 and generates heat. Thereby, the sample liquid 109 in contact with the reflecting member 108 is warmed, and a thermal lens effect that causes background noise is generated. Therefore, in the second embodiment, the heat insulating member 112 is sandwiched between the reflecting member 108 and the sample liquid 109. By inserting the heat insulating member 112 into the interface between the reflective member 108 and the sample liquid 109, heat due to the excitation light L1 absorbed by the reflective member 108 becomes difficult to be transmitted from the reflective member 108 to the sample liquid 109, so that background noise is reduced. The detection sensitivity can be further improved.
　また、図５（ｂ）に示すように、反射部材１０８の背面に放熱部材１１４を固定した構造でもよい。これにより、励起光Ｌ１により発熱した反射部材１０８の熱は、背面固定した放熱部材１１４に伝わり、サンプル液１０９に伝わり難くなるため、背景ノイズが低減し、検出感度をさらに向上することができる。 Further, as shown in FIG. 5B, a structure in which the heat radiating member 114 is fixed to the back surface of the reflecting member 108 may be used. As a result, the heat of the reflecting member 108 generated by the excitation light L1 is transmitted to the heat radiating member 114 fixed on the back surface and is not easily transmitted to the sample liquid 109, so that background noise is reduced and detection sensitivity can be further improved.
　なお、図５（ａ）の断熱部材１１２と図５（ｂ）の放熱部材１１４を合わせて用いてもよい。 In addition, you may use together the heat insulation member 112 of Fig.5 (a), and the thermal radiation member 114 of FIG.5 (b).
　次に、測定対象試料の種類によって励起光の波長を変える例について説明する。実施例３の基本構成は実施例１と同様であるため、以下では、実施例１と同様の部分については説明を省略する。 Next, an example in which the wavelength of excitation light is changed depending on the type of sample to be measured will be described. Since the basic configuration of the third embodiment is the same as that of the first embodiment, the description of the same parts as those of the first embodiment will be omitted below.
　本実施例では、励起光源として励起光の波長が変更可能な波長可変励起光源を用い、また、反射部材として、反射率の波長依存性を任意に調整可能な反射部材１１３を用いる。 In this embodiment, a variable wavelength excitation light source capable of changing the wavelength of excitation light is used as the excitation light source, and a reflection member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is used as the reflection member.
　サンプル液１０９に含まれる測定対象の試料が異なると、サンプル液１０９に吸収され易い励起光Ｌ１の波長が異なる。そこで、本実施例では、光熱変換分析装置で分析するサンプル液１０９に含まれる測定対象の試料に合わせた励起光の波長に変更可能な波長可変励起光源を用いる。 When the sample to be measured contained in the sample liquid 109 is different, the wavelength of the excitation light L1 that is easily absorbed by the sample liquid 109 is different. Therefore, in this embodiment, a variable wavelength excitation light source that can be changed to the wavelength of the excitation light matched to the sample to be measured included in the sample liquid 109 analyzed by the photothermal conversion analyzer is used.
　また、実施例１や実施例２で説明した図２に示す誘電体多層膜反射鏡を用いた反射部材１０８は、特定の励起光Ｌ１の波長の反射率が低く（＝透過率が高く）、特定の検出光Ｌ２の波長の反射率が高く設計されている。そのため、異なる励起光Ｌ１の波長に対しては、反射率が増加し、それに伴ってノイズが増加することで検出感度が低下する。 Further, the reflecting member 108 using the dielectric multilayer film reflecting mirror shown in FIG. 2 described in the first and second embodiments has a low reflectance of the wavelength of the specific excitation light L1 (= high transmittance). The reflectance of the wavelength of the specific detection light L2 is designed high. Therefore, with respect to the wavelength of the different excitation light L1, the reflectance increases, and the noise increases accordingly, so that the detection sensitivity decreases.
　そこで本実施例では、反射部材１０８として、反射率の波長依存性を任意に調整可能な反射部材１１３を用いる。 Therefore, in this embodiment, as the reflecting member 108, the reflecting member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is used.
　図６（ａ）は本実施例における反射部材１１３の構造を説明する図である。図６（ｂ）は反射部材１１３の反射率の波長依存性を説明する図である。 FIG. 6A illustrates the structure of the reflecting member 113 in this embodiment. FIG. 6B is a diagram for explaining the wavelength dependence of the reflectance of the reflecting member 113.
　図６（ａ）に示すように、反射率の波長依存性を任意に調整可能な反射部材１１３は、例えば液体セル１０７に固定された反射部材１１３ｂと光軸方向に位置調整可能な反射部材１１３ａの２つの部材が積層されて構成されている。反射部材１１３ａと反射部材１１３ｂとの間には間隙がある。反射部材１１３ａと反射部材１１３ｂとの間隙を広げると、反射部材１１３を透過する励起光Ｌ１の波長はλ１からλ２に波長が長くなる。したがって、この間隙を調整して、励起光Ｌ１の反射率が低く、検出光Ｌ２の反射率が高くなるようにすればよい。本実施例の液体セルは、反射部材１１３ａ、１１３ｂの少なくともいずれかを積層方向（反射部材の平面に垂直な方向）に可動とする位置調整機構を設ける。 As shown in FIG. 6A, the reflection member 113 capable of arbitrarily adjusting the wavelength dependency of the reflectance is, for example, a reflection member 113b fixed to the liquid cell 107 and a reflection member 113a whose position can be adjusted in the optical axis direction. These two members are laminated. There is a gap between the reflecting member 113a and the reflecting member 113b. A larger gap between the reflecting member 113a and the reflecting member 113b, the wavelength of the excitation light L1 transmitted through the reflecting member 113 is wavelength becomes longer in lambda 2 from lambda 1. Therefore, this gap may be adjusted so that the reflectance of the excitation light L1 is low and the reflectance of the detection light L2 is high. The liquid cell of this embodiment is provided with a position adjusting mechanism that makes at least one of the reflecting members 113a and 113b movable in the stacking direction (a direction perpendicular to the plane of the reflecting member).
　なお、反射部材の間隔を調整する機構は例えば半導体加工技術を用いたＭＥＭＳアクチュエータを用いても良い。また、位置調整可能な反射部材１１３ａは複数あって、位置調整可能な反射部材が多段になっていても良い。また、反射部材１１３ａと反射部材１１３ｂとの間の間隙には液体などが満たされていても良い。 Note that, for example, a MEMS actuator using a semiconductor processing technique may be used as a mechanism for adjusting the interval between the reflecting members. Further, there may be a plurality of position-adjustable reflecting members 113a, and the position-adjustable reflecting members may be multi-staged. Further, the gap between the reflecting member 113a and the reflecting member 113b may be filled with a liquid or the like.
　このように、サンプル液１０９に含まれる測定対象の試料の吸収スペクトルにあわせた励起光Ｌ１と反射部材１１３を用いることで、幅広い種類の試料を高感度に検出できる。 Thus, a wide variety of samples can be detected with high sensitivity by using the excitation light L1 and the reflecting member 113 that match the absorption spectrum of the sample to be measured contained in the sample liquid 109.
１０１：励起光源、１０２：検出光源、１０３：第一のフィルタ、１０４：第二のフィルタ、１０５：第一の４分の１波長板、１０６：第一の集光レンズ、１０７：液体セル、１０８：反射部材、１０９：サンプル液、１１０：第三のフィルタ、１１１：検出器、１１２：断熱部材、１１３：反射部材、１１５：ピンホール、１１６：受光素子、１１８：第二の集光レンズ、２０１：電流‐電圧変換回路、２０２：励起光源の駆動回路、２０３：ロックインアンプ、２０４：検出光源の駆動回路、２０５：コンピュータ、Ｌ１：励起光、Ｌ２：検出光、３００：光熱変換分析装置 101: excitation light source, 102: detection light source, 103: first filter, 104: second filter, 105: first quarter-wave plate, 106: first condenser lens, 107: liquid cell, 108: reflecting member, 109: sample liquid, 110: third filter, 111: detector, 112: heat insulating member, 113: reflecting member, 115: pinhole, 116: light receiving element, 118: second condenser lens 201: current-voltage conversion circuit, 202: excitation light source drive circuit, 203: lock-in amplifier, 204: detection light source drive circuit, 205: computer, L1: excitation light, L2: detection light, 300: photothermal conversion analysis apparatus

Claims (11)

  1. 　励起光を発する励起光源と、
    　前記励起光とは異なる波長の検出光を発する検出光源と、
    　前記検出光を受光して当該検出光の強度を検知する検出器と、
    　測定対象試料を格納する液体セルと、
    　前記測定対象試料を透過した検出光の少なくとも一部を反射する反射部材と、を備え、
    　前記反射部材の前記検出光に対する反射率は、前記反射部材の前記励起光に対する反射率より大きいことを特徴とする光熱変換分析装置。     An excitation light source that emits excitation light;
    A detection light source that emits detection light having a wavelength different from that of the excitation light;
    A detector that receives the detection light and detects the intensity of the detection light;
    A liquid cell for storing a sample to be measured;
    A reflection member that reflects at least a part of the detection light transmitted through the measurement target sample,
    The photothermal conversion analyzer according to claim 1, wherein a reflectance of the reflecting member with respect to the detection light is greater than a reflectance of the reflecting member with respect to the excitation light.
  2. 　請求項１に記載の光熱変換分析装置において、
    　前記反射部材は前記液体セルに設けられていることを特徴とする光熱変換分析装置。     In the photothermal conversion analyzer according to claim 1,
    The photothermal conversion analyzer, wherein the reflecting member is provided in the liquid cell.
  3. 　請求項１に記載の光熱変換分析装置において、
    　前記反射部材は前記液体セルの内壁に設けられ、
    　前記測定対象試料と前記反射部材の間に断熱部材を備えることを特徴とする光熱変換分析装置。     In the photothermal conversion analyzer according to claim 1,
    The reflecting member is provided on an inner wall of the liquid cell;
    A photothermal conversion analyzer comprising a heat insulating member between the measurement target sample and the reflecting member.
  4. 　請求項１に記載の光熱変換分析装置において、さらに、
    　前記反射部材の背面に設けられた放熱部材を備えることを特徴とする光熱変換分析装置。     The photothermal conversion analyzer according to claim 1, further comprising:
    A photothermal conversion analyzer comprising a heat radiating member provided on the back surface of the reflecting member.
  5. 　請求項１に記載の光熱変換分析装置において、
    　前記反射部材は反射率の波長依存性が可変であることを特徴とする光熱変換分析装置。     In the photothermal conversion analyzer according to claim 1,
    The photothermal conversion analyzer according to claim 1, wherein the reflective member has a variable wavelength dependency of reflectance.
  6. 　請求項５に記載の光熱変換分析装置において、
    　前記反射部材は、複数の反射部材が積層された構造であり、
    　前記複数の反射部材の少なくとも１つを積層方向に可動とする位置調整機構を備えることを特徴とする光熱変換分析装置。     In the photothermal conversion analyzer according to claim 5,
    The reflective member has a structure in which a plurality of reflective members are laminated,
    A photothermal conversion analyzer, comprising: a position adjustment mechanism that moves at least one of the plurality of reflecting members in the stacking direction.
  7. 　励起光を発する励起光源と、前記励起光とは異なる波長の検出光を発する検出光源と、前記検出光を受光して当該検出光の強度を検知する検出器と、を備える光熱変換分析装置で用いられる、測定対象試料を格納する液体セルであって、
    　当該液体セルは、前記測定対象試料を透過した検出光の少なくとも一部を反射する反射部材と、を備え、
    　前記反射部材の前記検出光に対する反射率は、前記反射部材の前記励起光に対する反射率より大きいことを特徴とする液体セル。     A photothermal conversion analyzer comprising: an excitation light source that emits excitation light; a detection light source that emits detection light having a wavelength different from that of the excitation light; and a detector that receives the detection light and detects the intensity of the detection light. A liquid cell for storing a sample to be measured, which is used,
    The liquid cell includes a reflective member that reflects at least a part of the detection light transmitted through the measurement target sample,
    The liquid cell, wherein the reflectance of the reflection member with respect to the detection light is greater than the reflectance of the reflection member with respect to the excitation light.
  8. 　請求項７に記載の液体セルにおいて、
    　前記反射部材は前記液体セルの内壁に設けられ、
    　前記測定対象試料と前記反射部材の間に断熱部材を備えることを特徴とする液体セル。     The liquid cell according to claim 7, wherein
    The reflecting member is provided on an inner wall of the liquid cell;
    A liquid cell comprising a heat insulating member between the sample to be measured and the reflecting member.
  9. 　請求項７に記載の液体セルにおいて、さらに、
    　前記反射部材の背面に設けられた放熱部材を備えることを特徴とする液体セル。     The liquid cell according to claim 7, further comprising:
    A liquid cell comprising a heat dissipating member provided on a back surface of the reflecting member.
  10. 　請求項７に記載の液体セルにおいて、
    　前記反射部材は反射率の波長依存性が可変であることを特徴とする液体セル。     The liquid cell according to claim 7, wherein
    The reflective cell is characterized in that the wavelength dependency of reflectance is variable.
  11. 　請求項１０に記載の液体セルにおいて、
    　前記反射部材は、複数の反射部材が積層された構造であり、
    　前記複数の反射部材の少なくとも１つを積層方向に可動とする位置調整機構を備えることを特徴とする液体セル。     The liquid cell according to claim 10.
    The reflective member has a structure in which a plurality of reflective members are laminated,
    A liquid cell comprising: a position adjusting mechanism for moving at least one of the plurality of reflecting members in the stacking direction.
PCT/JP2016/084884 2015-12-28 2016-11-25 Photothermal conversion analysis apparatus and liquid cell WO2017115591A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113514967A (en) * 2021-05-11 2021-10-19 岭南师范学院 Controllable stealthy device based on thermal lens effect

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004286578A (en) * 2003-03-20 2004-10-14 Asahi Kasei Corp Reflection type spectrum analyzer for hot lens
JP2006084431A (en) * 2004-09-17 2006-03-30 Kobe Steel Ltd Photothermal conversion measuring device, and its method
JP2008128942A (en) * 2006-11-24 2008-06-05 Kobe Steel Ltd Device for measuring photothermal conversion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004286578A (en) * 2003-03-20 2004-10-14 Asahi Kasei Corp Reflection type spectrum analyzer for hot lens
JP2006084431A (en) * 2004-09-17 2006-03-30 Kobe Steel Ltd Photothermal conversion measuring device, and its method
JP2008128942A (en) * 2006-11-24 2008-06-05 Kobe Steel Ltd Device for measuring photothermal conversion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113514967A (en) * 2021-05-11 2021-10-19 岭南师范学院 Controllable stealthy device based on thermal lens effect

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