JP2009175026A

JP2009175026A - Detector for ultraviolet-visible near infrared spectrophotometer

Info

Publication number: JP2009175026A
Application number: JP2008014735A
Authority: JP
Inventors: Kasumi Yokota; 佳澄横田
Original assignee: Shimadzu Corp
Current assignee: Shimadzu Corp
Priority date: 2008-01-25
Filing date: 2008-01-25
Publication date: 2009-08-06

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detector for a spectrophotometer having sufficient sensitivity over a wide range of ultraviolet region, visible region, near infrared region, and solving a problem caused by a photo-conduction type. <P>SOLUTION: Instead of a conventional PbS detector for covering the near infrared region, an InAs detector is employed, three detectors of a photomultiplier detector 20, an InGaAs detector 24, and an InAs detector 25 are used, the detectors are switched in response to the measurement wavelength by moving control of a movable mirror 15 and a switching mechanism 23. Thus, all detectors are of electromotive force type and unified into current output type, so that the application of bias voltage is not required and high-speed response can also be attained. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲（おおよそ１５０nm〜３５００nm）を測定対象とする汎用分光光度計の検出装置に関する。 The present invention relates to a detection apparatus for a general-purpose spectrophotometer that uses a wavelength range (approximately 150 nm to 3500 nm) over an ultraviolet region, a visible region, and a near infrared region as a measurement target.

紫外領域から近赤外領域までの広い波長範囲をカバーするような汎用分光光度計においては、単一の検出器で全ての波長を検出することは不可能である。そのため、従来の汎用分光光度計では、上記のような広い波長範囲を適宜の波長で２乃至３程度の領域に分割し、各領域毎にそれに合った波長特性を持つ検出器を用いるようにしている。一般的には、紫外領域及び可視領域では光電子増倍管（ＰＭＴ）検出器やＳｉ（シリコン）検出器が用いられ、それよりも長波長の近赤外領域ではＰｂＳ（硫化鉛）検出器が用いられることが多い。 In a general-purpose spectrophotometer that covers a wide wavelength range from the ultraviolet region to the near infrared region, it is impossible to detect all wavelengths with a single detector. Therefore, in the conventional general-purpose spectrophotometer, the above-mentioned wide wavelength range is divided into about 2 to 3 regions with appropriate wavelengths, and a detector having a wavelength characteristic suitable for each region is used. Yes. Generally, a photomultiplier tube (PMT) detector or a Si (silicon) detector is used in the ultraviolet region and the visible region, and a PbS (lead sulfide) detector is used in the near-infrared region having a longer wavelength. Often used.

例えば、特許文献１、２に記載の分光光度計用検出装置では、８００nm付近を切替波長とし、それよりも短波長領域ではＰＭＴ検出器、長波長領域ではＰｂＳ検出器が使用されている。また、特許文献３に記載の分光光度計用検出装置では、ＰＭＴ検出器による検出波長領域とＰｂＳ検出器による検出波長領域との境目にあたる８００〜９００nm付近の波長領域を担うＩｎＧａＡｓ検出器を設けている。 For example, in the detection apparatus for spectrophotometers described in Patent Documents 1 and 2, a switching wavelength is around 800 nm, and a PMT detector is used in a shorter wavelength region and a PbS detector is used in a longer wavelength region. In addition, the spectrophotometer detection device described in Patent Document 3 is provided with an InGaAs detector that bears a wavelength region in the vicinity of 800 to 900 nm, which is the boundary between the detection wavelength region by the PMT detector and the detection wavelength region by the PbS detector. Yes.

このように一般的に汎用分光光度計においては、近赤外波長領域の検出器としてＰｂＳ検出器が使用されている。これは、素子が比較的安価で且つ大きな受光面積が得やすいことが主な理由である。しかしながら、ＰｂＳ検出器には次のようないくつかの問題がある。即ち、ＰｂＳ検出器は光導電型の検出器であるためバイアス電圧を印加する必要があるが、暗抵抗値が容易に変動してしまうため、例えば一定のバイアス電圧を印加してもバイアス電流が変化してしまう。それにより、みかけ上、検出感度が変動し、検出動作の安定性が乏しい。また、ＰｂＳ検出器は応答速度が比較的遅い。例えば典型的なＰｂＳ検出器における６３％上昇時間は６００μ秒程度もあり、これはＰＭＴ検出器やＳｉ検出器と比較すると格段に遅い。そのため、波長走査の際にも走査速度を低くする必要があり、分析時間が掛かる大きな要因となっている。 Thus, generally, in a general-purpose spectrophotometer, a PbS detector is used as a detector in the near infrared wavelength region. This is mainly because the element is relatively inexpensive and it is easy to obtain a large light receiving area. However, the PbS detector has several problems as follows. That is, since the PbS detector is a photoconductive detector, it is necessary to apply a bias voltage. However, since the dark resistance value easily fluctuates, for example, even if a constant bias voltage is applied, the bias current does not change. It will change. As a result, the detection sensitivity fluctuates and the stability of the detection operation is poor. Moreover, the response speed of the PbS detector is relatively slow. For example, the 63% rise time in a typical PbS detector is about 600 μs, which is much slower than a PMT detector or a Si detector. For this reason, it is necessary to reduce the scanning speed even during wavelength scanning, which is a major factor in taking analysis time.

上記のようなＰｂＳ検出器の問題を回避するために、特許文献２には、Ｓｉ検出器とＩｎＧａＡｓ検出器とを組み合わせた構成も記載されているが、ＩｎＧａＡｓ検出器では近赤外領域の検出感度が不足し、３５００nm近辺までの測定を行う汎用分光光度計としては満足できない。 In order to avoid the problems of the PbS detector as described above, Patent Document 2 also describes a configuration in which a Si detector and an InGaAs detector are combined, but the InGaAs detector detects the near infrared region. Insufficient sensitivity makes it unsatisfactory as a general-purpose spectrophotometer that performs measurements up to around 3500 nm.

特開平8-184495号公報Japanese Patent Laid-Open No. 8-184495 特開2002-62189号公報JP 2002-62189 A 特開2006-23284号公報JP 2006-23284 A

本発明は上記課題を解決するために成されたものであり、紫外領域・可視領域・近赤外領域の全体に亘って十分な感度を有し、十分に速い応答速度を確保しつつ、ＰｂＳ検出器のような光導電型であることに起因する問題をも解消することができる分光光度計用検出装置を提供することである。 The present invention has been made to solve the above-described problems, and has sufficient sensitivity over the entire ultraviolet region, visible region, and near-infrared region, and ensures a sufficiently high response speed while maintaining PbS. It is an object of the present invention to provide a spectrophotometer detection device that can solve the problems caused by the photoconductive type such as a detector.

上記課題を解決するために成された第１発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)光電子増倍管検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記３個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴としている。 In order to solve the above problems, the first invention is a spectrophotometer detection device for detecting light in a wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors which are a photomultiplier tube detector, an InGaAs detector, and an InAs detector;
b) switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into any of the three detectors according to the measurement wavelength;
It is characterized by having.

上記課題を解決するために成された第２発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)光電子増倍管検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記３個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記３個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴としている。 The second invention made to solve the above problems is a detection apparatus for a spectrophotometer that detects light in a wavelength range over an ultraviolet region, a visible region, and a near infrared region,
a) three detectors which are a photomultiplier tube detector, an InGaAs detector, and an InAs detector;
b) a single integrating sphere equipped with the three detectors so that measurement light obtained from the sample is introduced in parallel;
c) a switching means that selectively adopts one of the outputs from the three detectors according to the measurement wavelength;
It is characterized by having.

上記課題を解決するために成された第３発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器及びＩｎＡｓ検出器である２個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記２個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴としている。 The third invention made to solve the above problems is a detection apparatus for a spectrophotometer that detects light in a wavelength range over an ultraviolet region, a visible region, and a near infrared region,
a) two detectors, a Si detector and an InAs detector;
b) a switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into one of the two detectors according to the measurement wavelength;
It is characterized by having.

上記課題を解決するために成された第４発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、及びＩｎＡｓ検出器の２個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記２個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記２個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴としている。 A fourth invention made to solve the above problems is a detection apparatus for a spectrophotometer that detects light in a wavelength range over an ultraviolet region, a visible region, and a near infrared region,
a) two detectors, a Si detector and an InAs detector;
b) a single integrating sphere equipped with the two detectors so that the measurement light obtained from the sample is introduced in parallel;
c) switching means that selectively adopts one of the outputs from the two detectors according to the measurement wavelength;
It is characterized by having.

上記課題を解決するために成された第５発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記３個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴としている。 In order to solve the above problems, the fifth invention is a spectrophotometer detection device for detecting light in a wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors, a Si detector, an InGaAs detector, and an InAs detector;
b) switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into any of the three detectors according to the measurement wavelength;
It is characterized by having.

上記課題を解決するために成された第６発明は、紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記３個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記３個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴としている。 A sixth invention made to solve the above problems is a spectrophotometer detection device for detecting light in a wavelength range over an ultraviolet region, a visible region, and a near infrared region,
a) three detectors, a Si detector, an InGaAs detector, and an InAs detector;
b) a single integrating sphere equipped with the three detectors so that measurement light obtained from the sample is introduced in parallel;
c) a switching means that selectively adopts one of the outputs from the three detectors according to the measurement wavelength;
It is characterized by having.

第１及び第２発明に係る分光光度計用検出装置では、光電子増倍管検出器は対象とするおおよそ１５０〜３５００nmの波長範囲のうちの８００nm程度以下の短波長の紫外・可視領域をカバーし、ＩｎＧａＡｓ検出器はそれよりも長波長側の領域、例えば８００〜１６００nm程度の領域（近赤外領域の一部）をカバーする。一方、第３及び第４発明に係る分光光度計用検出装置では、１５０〜１０００nm程度の波長範囲をＳｉ検出器でカバーする。さらにまた、第５及び第６発明に係る分光光度計用検出装置では、第１及び第２発明に係る分光光度計用検出装置において光電子増倍管検出器がカバーする波長範囲をＳｉ検出器でカバーする。そして、第１乃至第６発明に係る分光光度計用検出装置のいずれにおいても、さらにそれよりも長波長側の近赤外領域については、従来のＰｂＳ検出器に代えてＩｎＡｓ検出器でカバーする。 In the detection apparatus for spectrophotometers according to the first and second inventions, the photomultiplier tube detector covers a short wavelength ultraviolet / visible region of about 800 nm or less in a target wavelength range of about 150 to 3500 nm. The InGaAs detector covers a region on the longer wavelength side, for example, a region of about 800 to 1600 nm (part of the near infrared region). On the other hand, in the detection apparatus for a spectrophotometer according to the third and fourth inventions, a wavelength range of about 150 to 1000 nm is covered with a Si detector. Furthermore, in the detection apparatus for a spectrophotometer according to the fifth and sixth inventions, the wavelength range covered by the photomultiplier detector in the detection apparatus for the spectrophotometer according to the first and second inventions is defined by an Si detector. Cover. In any of the spectrophotometer detection devices according to the first to sixth inventions, the near-infrared region on the longer wavelength side is covered with an InAs detector instead of the conventional PbS detector. .

ＩｎＡｓ検出器の標準的な波長範囲は１０００〜３５００nm程度であり、ＰｂＳ検出器の波長範囲とほぼ同じで、波長範囲についてはそのまま置き換えが可能である。したがって、本発明に係る分光光度計用検出装置によれば、紫外領域、可視領域、及び近赤外領域の測定範囲全体に亘って、感度低下の少ない、Ｓ／Ｎ比の高い検出を行うことができる。 The standard wavelength range of the InAs detector is about 1000 to 3500 nm, which is almost the same as the wavelength range of the PbS detector, and the wavelength range can be replaced as it is. Therefore, according to the detection apparatus for a spectrophotometer according to the present invention, it is possible to perform detection with a low S / N ratio and a low sensitivity reduction over the entire measurement range in the ultraviolet region, the visible region, and the near infrared region. Can do.

また、ＩｎＡｓ検出器は光導線型ではなく光起電力型のフォトダイオードであるため、検出器が飽和しない範囲での直線性に関し、ＰｂＳ検出器よりも原理的に有利である。また、光起電力型であるため、ＰｂＳ検出器で問題となる暗抵抗の変化やバイアス電流・電圧に関する問題も生じない。これにより、みかけ上の感度変化が抑えられ、検出データの再現性が向上するとともに、バイアス電圧を印加するための電源回路などが不要になる。 Further, since the InAs detector is a photovoltaic type photodiode rather than an optical linear type, it is theoretically advantageous over the PbS detector in terms of linearity within a range where the detector is not saturated. In addition, since it is of the photovoltaic type, there is no problem with respect to the change of dark resistance and the bias current / voltage, which are problems in the PbS detector. This suppresses an apparent change in sensitivity, improves the reproducibility of detection data, and eliminates the need for a power supply circuit for applying a bias voltage.

また、代表的な受光面１ｍｍφのＩｎＡｓ検出器における６３％上昇時間は０．４５μ秒程度であって、応答速度はＰｂＳ検出器よりも格段に速い。さらに、複数の検出器を光起動力型として、電流出力型に統一できるという利点もある。一般的に、微小電圧と微小電流との取扱い、例えばノイズ混入の防止などに関しては電流のほうが容易であるため、電流出力型に統一されることでそうした対策が採り易い。 Further, the 63% rise time in a typical InAs detector having a 1 mmφ light receiving surface is about 0.45 μsec, and the response speed is much faster than that of a PbS detector. Further, there is an advantage that a plurality of detectors can be unified into a current output type as a light starting force type. In general, since current is easier in handling minute voltages and minute currents, for example, prevention of noise mixing, it is easy to take such measures by unifying the current output type.

［第１実施例］
以下、本発明に係る分光光度計用検出装置の一実施例（第１実施例）を図面を参照して説明する。図１は第１実施例による検出装置を中心とする分光光度計の要部の構成図である。この実施例は、本発明に係る検出装置を回転セクタ鏡を用いたダブルビーム方式の透過光測定分光光度計に適用したものである。 [First embodiment]
Hereinafter, an embodiment (first embodiment) of a spectrophotometer detection device according to the present invention will be described with reference to the drawings. FIG. 1 is a block diagram of the main part of a spectrophotometer centering on the detection apparatus according to the first embodiment. In this embodiment, the detection apparatus according to the present invention is applied to a double beam type transmitted light measuring spectrophotometer using a rotating sector mirror.

図示しない分光器により分光された光（波長分散光）は出口スリット１０を通過した後、回転セクタ鏡１１により、反射鏡１２、１６の２方向に交互に送られる。したがって、サンプルセル１７及び参照セル１３に交互に光が入射されて、それぞれのセル１７、１３を通過する。参照セル１３を通過した光は反射鏡１４で反射され、サンプルセル１７を通過した光は反射鏡１８、１９で反射され、いずれも可動鏡１５が光路中に挿入された状態ではＩｎＡｓ／ＩｎＧａＡｓ切替器２３の方向に送られる。この場合、両セル１７、１３からの光は、ＩｎＡｓ／ＩｎＧａＡｓ切替器２３に設けられた窓２３ａ、２３ｂを通過し、各凹面鏡２１、２２によりＩｎＡｓ／ＩｎＧａＡｓ切替器２３上の１点に集束される。 Light (wavelength-dispersed light) dispersed by a spectroscope (not shown) passes through the exit slit 10 and is then sent alternately by the rotating sector mirror 11 in the two directions of the reflecting mirrors 12 and 16. Accordingly, light alternately enters the sample cell 17 and the reference cell 13 and passes through the respective cells 17 and 13. The light that has passed through the reference cell 13 is reflected by the reflecting mirror 14, the light that has passed through the sample cell 17 is reflected by the reflecting mirrors 18 and 19, and both are switched between InAs / InGaAs when the movable mirror 15 is inserted in the optical path. It is sent in the direction of the vessel 23. In this case, light from both the cells 17 and 13 passes through windows 23a and 23b provided in the InAs / InGaAs switch 23, and is converged to one point on the InAs / InGaAs switch 23 by the concave mirrors 21 and 22. The

ＩｎＡｓ／ＩｎＧａＡｓ切替器２３は、図１中の矢印の方向に移動することにより、ＩｎＡｓ検出器２５又はＩｎＧａＡｓ検出器２４を択一的にその集光点に位置させる。即ち、可動鏡１５が光路中に挿入された状態では、ＩｎＡｓ検出器２５又はＩｎＧａＡｓ検出器２４のいずれかによる透過光測定が可能である。一方、可動鏡１５が光路から外れるように移動されたときは、各セル１３、１７からの透過光はいずれもＰＭＴ（光電子増倍管）検出器２０に入射する。 The InAs / InGaAs switch 23 moves in the direction of the arrow in FIG. 1 to selectively position the InAs detector 25 or the InGaAs detector 24 at the condensing point. That is, in a state where the movable mirror 15 is inserted in the optical path, the transmitted light can be measured by either the InAs detector 25 or the InGaAs detector 24. On the other hand, when the movable mirror 15 is moved out of the optical path, the transmitted light from each of the cells 13 and 17 is incident on the PMT (photomultiplier tube) detector 20.

このようにして、図示しない可動鏡１５の位置及びＩｎＡｓ／ＩｎＧａＡｓ切替器２３の位置をそれぞれ適宜制御することにより、ＰＭＴ検出器２０、ＩｎＧａＡｓ検出器２４又はＩｎＡｓ検出器２５のいずれかに択一的に、セル１３、１７からの透過光を入射させることができる。上記位置の制御は、例えばＣＰＵを中心に構成される図示しない制御部により行われる。また、上記のような測定光を入射する検出器の切替えに同期して、３つの検出器の出力の切替えが行われ、測定光の強度信号がデータ処理部に入力される。 In this manner, the position of the movable mirror 15 (not shown) and the position of the InAs / InGaAs switch 23 are appropriately controlled, so that the PMT detector 20, the InGaAs detector 24, or the InAs detector 25 can be alternatively selected. In addition, the transmitted light from the cells 13 and 17 can be made incident. The control of the position is performed by a control unit (not shown) configured mainly with the CPU, for example. In addition, the outputs of the three detectors are switched in synchronism with the switching of the detector that receives the measurement light as described above, and the intensity signal of the measurement light is input to the data processing unit.

図２はＰＭＴ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器の感度特性を示すグラフである。ＰＭＴ検出器はおおよそ１５０〜８００nmの紫外・可視波長領域、ＩｎＧａＡｓ検出器はおおよそ８００〜１６００nmの近赤外波長領域の一部、ＩｎＡｓ検出器はおおよそ１６００〜３５００nmの近赤外波長領域の一部、をそれぞれカバーし、それらにより１５０〜３５００nmの幅広い波長範囲を高い感度でカバーすることができる。 FIG. 2 is a graph showing sensitivity characteristics of the PMT detector, InGaAs detector, and InAs detector. The PMT detector is in the ultraviolet / visible wavelength region of approximately 150 to 800 nm, the InGaAs detector is part of the near infrared wavelength region of approximately 800 to 1600 nm, and the InAs detector is part of the near infrared wavelength region of approximately 1600 to 3500 nm. , Thereby covering a wide wavelength range of 150 to 3500 nm with high sensitivity.

したがって、上記装置において、或る１つの測定波長の透過測定を行う場合、所定の波長範囲内を所定の波長ステップ幅で変化させながらスキャン測定を行う場合のいずれにおいても、その測定対象波長に応じて、ＰＭＴ検出器２０、ＩｎＧａＡｓ検出器２４、及びＩｎＡｓ検出器２５のいずれかに測定光が入射するように可動鏡１５及びＩｎＡｓ／ＩｎＧａＡｓ切替器２３の移動を制御することで、セル１３、１７の溶液の透過特性を反映した測定光の強度検出を高感度で行うことができる。例えば、検出器切替えの波長としては、ＰＭＴ検出器２０／ＩｎＧａＡｓ検出器２４の切替波長を８３０nm、ＩｎＧａＡｓ検出器２４／ＩｎＡｓ検出器２５の切替波長を１６５０nmとするとよい。 Therefore, in the above-mentioned apparatus, when performing transmission measurement at a certain measurement wavelength, whether performing scan measurement while changing within a predetermined wavelength range with a predetermined wavelength step width, it depends on the wavelength to be measured. By controlling the movement of the movable mirror 15 and the InAs / InGaAs switch 23 so that the measurement light is incident on any one of the PMT detector 20, the InGaAs detector 24, and the InAs detector 25, the cells 13, 17 Intensity detection of the measurement light reflecting the transmission characteristics of the solution can be performed with high sensitivity. For example, as the wavelength for switching the detector, the switching wavelength of the PMT detector 20 / InGaAs detector 24 may be 830 nm, and the switching wavelength of the InGaAs detector 24 / InAs detector 25 may be 1650 nm.

なお、図１に記載のＩｎＡｓ／ＩｎＧａＡｓ切替器２３の移動機構は直線的なものであるが、例えば回転機構等、適宜に変形することができる。
［第２実施例］ The moving mechanism of the InAs / InGaAs switch 23 shown in FIG. 1 is linear, but can be appropriately modified, for example, a rotating mechanism.
[Second Embodiment]

図３は本発明に係る分光光度計用検出装置の他の実施例（第２実施例）の概略構成を示す図である。第１実施例で説明した構成要素と同じものには同一の符号を付している。この第２実施例は、積分球を用いて３つの検出器の切り替えを行うものである。 FIG. 3 is a diagram showing a schematic configuration of another embodiment (second embodiment) of the spectrophotometer detection apparatus according to the present invention. The same components as those described in the first embodiment are denoted by the same reference numerals. In the second embodiment, three detectors are switched using an integrating sphere.

ＰＭＴ検出器２０、ＩｎＧａＡｓ検出器２４、及びＩｎＡｓ検出器２５は、それぞれの入射面が積分球３０の内壁面に面するように配置されている。各検出器２０、２４、２５は図示しないサンプルセル及び参照セルからの入射光の入射口３１、３２に直接対向しない位置に置かれているので、入射光は直接各検出器２０、２４、２５には入射せず、積分球３０の内面で１乃至複数回反射した光がそれら入射面に並行的に入射するようになっている。この場合には、測定光の波長に拘わらず全検出器に測定光が入射するので、制御部はその測定波長に応じてデータ処理部に入力する検出器の出力を切り替えることで、第１実施例における波長切替を行う。このように積分球３０を用いることにより、装置を小型化することができるとともに、可動部分を伴わないため装置の信頼性を高めることができる。 The PMT detector 20, the InGaAs detector 24, and the InAs detector 25 are arranged so that the respective incident surfaces face the inner wall surface of the integrating sphere 30. Since each detector 20, 24, 25 is placed at a position not directly facing the incident ports 31, 32 for incident light from a sample cell and a reference cell (not shown), the incident light is directly applied to each detector 20, 24, 25. The light reflected from the inner surface of the integrating sphere 30 one or more times enters the incident surfaces in parallel. In this case, since the measurement light is incident on all the detectors regardless of the wavelength of the measurement light, the control unit switches the output of the detector input to the data processing unit according to the measurement wavelength, so that the first implementation is performed. Perform wavelength switching in the example. By using the integrating sphere 30 as described above, the apparatus can be reduced in size, and the reliability of the apparatus can be improved because there is no moving part.

図３に記載の積分球３０では３個の検出器を別個の位置に配したが、図４に示すように、パッケージ４０内にＩｎＡｓ検出器２５とＩｎＧａＡｓ検出器２４とを横に並べて設け、一体化した検出器として積分球３０の壁面に配してもよい。これにより、積分球３０の開口部分（非反射面部分）を少なくして、測定光の減衰を抑制することができ、感度の向上を実現することができる。 In the integrating sphere 30 shown in FIG. 3, three detectors are arranged at separate positions. However, as shown in FIG. 4, an InAs detector 25 and an InGaAs detector 24 are provided side by side in a package 40. You may distribute | arrange on the wall surface of the integrating sphere 30 as an integrated detector. Thereby, the opening part (non-reflective surface part) of the integrating sphere 30 can be decreased, attenuation | damping of measurement light can be suppressed, and the improvement of a sensitivity can be implement | achieved.

［第３実施例］
図５は本発明に係る分光光度計用検出装置の他の実施例（第３実施例）による検出装置を中心とする分光光度計の要部の構成図である。この実施例は、第１実施例の検出装置におけるＰＭＴ検出器２０とＩｎＧａＡｓ検出器２４との機能を１個のＳｉ検出器２６で達成したものである。 [Third embodiment]
FIG. 5 is a configuration diagram of a main part of a spectrophotometer centering on a detection apparatus according to another embodiment (third embodiment) of the spectrophotometer detection apparatus according to the present invention. In this embodiment, the functions of the PMT detector 20 and the InGaAs detector 24 in the detection apparatus of the first embodiment are achieved by one Si detector 26.

図６はＳｉ検出器及びＩｎＡｓ検出器の感度特性を示すグラフである。紫外領域、可視領域及び近赤外領域のごく一部（おおよそ１５０〜１０５０nm）をＳｉ検出器２６でカバーし、近赤外領域の大部分（１０５０〜３０５０nm）をＩｎＡｓ検出器２５でカバーしている。この場合、可動鏡１５の移動のみで２つの検出器２５、２６の切替えが行われる。 FIG. 6 is a graph showing sensitivity characteristics of the Si detector and the InAs detector. A small part (approximately 150 to 1050 nm) of the ultraviolet region, visible region and near infrared region is covered with the Si detector 26, and most of the near infrared region (1050 to 3050 nm) is covered with the InAs detector 25. Yes. In this case, the two detectors 25 and 26 are switched only by moving the movable mirror 15.

［第４実施例］
図７は本発明に係る分光光度計用検出装置の第４実施例の概略構成図である。この第４実施例は、第２実施例に示した積分球３０を用いた構成に、第３実施例に示したＳｉ検出器２６及びＩｎＡｓ検出器２５の２つの検出器の切り替えを適用したものである。 [Fourth embodiment]
FIG. 7 is a schematic configuration diagram of a fourth embodiment of the spectrophotometer detection device according to the present invention. In the fourth embodiment, switching between the two detectors of the Si detector 26 and the InAs detector 25 shown in the third embodiment is applied to the configuration using the integrating sphere 30 shown in the second embodiment. It is.

図６を見れば分かるように、Ｓｉ検出器とＩｎＡｓ検出器の２つの検出器だけでは、１１００〜１５００nm程度の波長範囲の感度が低くなる傾向にある。そこで、第１及び第２実施例における光電子増倍管検出器の代わりにＳｉ検出器を用い、Ｓｉ検出器、ＩｎＧａＡｓ検出器及びＩｎＡｓ検出器の３個の検出器で紫外〜近赤外の幅広い波長範囲をカバーする構成としてもよい。図８はＳｉ検出器、ＩｎＧａＡｓ検出器及びＩｎＡｓ検出器の感度特性を示すグラフである。 As can be seen from FIG. 6, with only two detectors, the Si detector and the InAs detector, the sensitivity in the wavelength range of about 1100 to 1500 nm tends to be low. Therefore, a Si detector is used in place of the photomultiplier tube detector in the first and second embodiments, and a wide range from ultraviolet to near infrared is obtained with three detectors: a Si detector, an InGaAs detector, and an InAs detector. It is good also as a structure which covers a wavelength range. FIG. 8 is a graph showing sensitivity characteristics of the Si detector, InGaAs detector, and InAs detector.

なお、上記実施例は本発明の一例であり、本発明の趣旨の範囲で適宜変形、修正、追加を行っても本願特許請求の範囲に包含されることは当然である。 The above-described embodiment is an example of the present invention, and it is a matter of course that modifications, corrections, and additions may be appropriately made within the scope of the present invention, and included in the scope of the claims of the present application.

本発明の一実施例（第１実施例）による検出装置を中心とする分光光度計の要部の構成図。The block diagram of the principal part of the spectrophotometer centering on the detection apparatus by one Example (1st Example) of this invention. ＰＭＴ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器の感度特性を示すグラフ。The graph which shows the sensitivity characteristic of a PMT detector, an InGaAs detector, and an InAs detector. 本発明に係る分光光度計用検出装置の第２実施例の概略構成図。The schematic block diagram of 2nd Example of the detection apparatus for spectrophotometers which concerns on this invention. 第２実施例の変形例におけるパッケージされた検出器の概略構成図。The schematic block diagram of the packaged detector in the modification of 2nd Example. 本発明の第３実施例による検出装置を中心とする分光光度計の要部の構成図。The block diagram of the principal part of the spectrophotometer centering on the detection apparatus by 3rd Example of this invention. Ｓｉ検出器及びＩｎＡｓ検出器の感度特性を示すグラフ。The graph which shows the sensitivity characteristic of Si detector and InAs detector. 本発明に係る分光光度計用検出装置の第４実施例の概略構成図。The schematic block diagram of 4th Example of the detection apparatus for spectrophotometers which concerns on this invention. Ｓｉ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器の感度特性を示すグラフ。The graph which shows the sensitivity characteristic of Si detector, InGaAs detector, and InAs detector.

符号の説明Explanation of symbols

１０…出口スリット
１１…回転セクタ鏡
１２、１４、１８…反射鏡
１３…参照セル
１５…可動鏡
１７…サンプルセル
２０…ＰＭＴ検出器
２１、２２…凹面鏡
２３…ＩｎＡｓ／ＩｎＧａＡｓ切替器
２３ａ、２３ｂ…窓
２４…ＩｎＧａＡｓ検出器
２５…ＩｎＡｓ検出器
２６…Ｓｉ検出器
３０…積分球
３１、３２…入射口
４０…パッケージ DESCRIPTION OF SYMBOLS 10 ... Exit slit 11 ... Rotating sector mirror 12, 14, 18 ... Reflector mirror 13 ... Reference cell 15 ... Movable mirror 17 ... Sample cell 20 ... PMT detector 21, 22 ... Concave mirror 23 ... InAs / InGaAs switch 23a, 23b ... Window 24 ... InGaAs detector 25 ... InAs detector 26 ... Si detector 30 ... Integrating sphere 31, 32 ... Entrance 40 ... Package

Claims

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)光電子増倍管検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記３個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors which are a photomultiplier tube detector, an InGaAs detector, and an InAs detector;
b) switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into any of the three detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising:

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)光電子増倍管検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記３個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記３個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors which are a photomultiplier tube detector, an InGaAs detector, and an InAs detector;
b) a single integrating sphere equipped with the three detectors so that measurement light obtained from the sample is introduced in parallel;
c) a switching means that selectively adopts one of the outputs from the three detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising:

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器及びＩｎＡｓ検出器である２個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記２個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) two detectors, a Si detector and an InAs detector;
b) a switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into one of the two detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising:

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、及びＩｎＡｓ検出器の２個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記２個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記２個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) two detectors, a Si detector and an InAs detector;
b) a single integrating sphere equipped with the two detectors so that the measurement light obtained from the sample is introduced in parallel;
c) switching means that selectively adopts one of the outputs from the two detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising:

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)測定波長に応じて、試料から得られた測定光を前記３個の検出器のいずれかに択一的に導入するように光路又は検出器の位置を切り替える切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors, a Si detector, an InGaAs detector, and an InAs detector;
b) switching means for switching the optical path or the position of the detector so as to selectively introduce the measurement light obtained from the sample into any of the three detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising:

紫外領域、可視領域、及び近赤外領域に亘る波長範囲の光を検出対象とする分光光度計用検出装置において、
a)Ｓｉ検出器、ＩｎＧａＡｓ検出器、及びＩｎＡｓ検出器である３個の検出器と、
b)試料から得られた測定光が並行して導入されるように前記３個の検出器が装着された単一の積分球と、
c)測定波長に応じて、前記３個の検出器による出力のいずれかを択一的に採用する切替手段と、
を備えることを特徴とする紫外可視近赤外分光光度計用検出装置。 In the spectrophotometer detection device for detecting light in the wavelength range over the ultraviolet region, visible region, and near infrared region,
a) three detectors, a Si detector, an InGaAs detector, and an InAs detector;
b) a single integrating sphere equipped with the three detectors so that measurement light obtained from the sample is introduced in parallel;
c) a switching means that selectively adopts one of the outputs from the three detectors according to the measurement wavelength;
An ultraviolet-visible near-infrared spectrophotometer detection apparatus comprising: