WO2003010519A1 - Dispositif de mesure d'absorption temporaire par resolution temporelle - Google Patents

Dispositif de mesure d'absorption temporaire par resolution temporelle Download PDF

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Publication number
WO2003010519A1
WO2003010519A1 PCT/JP2002/007394 JP0207394W WO03010519A1 WO 2003010519 A1 WO2003010519 A1 WO 2003010519A1 JP 0207394 W JP0207394 W JP 0207394W WO 03010519 A1 WO03010519 A1 WO 03010519A1
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WO
WIPO (PCT)
Prior art keywords
light
sample
optical system
optical
optical path
Prior art date
Application number
PCT/JP2002/007394
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English (en)
Japanese (ja)
Inventor
Haruhisa Saitoh
Motoyuki Watanabe
Original Assignee
Hamamatsu Photonics K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hamamatsu Photonics K.K. filed Critical Hamamatsu Photonics K.K.
Publication of WO2003010519A1 publication Critical patent/WO2003010519A1/fr

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Classifications

    • 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
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/636—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited using an arrangement of pump beam and probe beam; using the measurement of optical non-linear properties

Definitions

  • the present invention relates to a time-resolved transient absorption measuring device for measuring a temporal change of a transient absorption spectrum, and more particularly to a time-resolved transient absorption measuring device capable of measuring a femtosecond order transient absorption spectrum.
  • Time-resolved transient absorption measurement which measures transient absorption in a very short time range, is known as a method of tracking the irreversible reaction as well as the process of generating and annihilating reaction intermediates in photochemical reactions such as solutions, solids, and thin films.
  • a technique disclosed in Japanese Patent Publication No. 6-178686 is known.
  • This technique uses a probe light to irradiate a sample that has been photoexcited with pulsed light, and measures the temporal change in transmitted light intensity with a streak camera to measure the temporal change in the transient absorption spectrum.
  • the sample light and the reference light can be measured simultaneously by dividing the probe light and guiding one to the irradiation position of the pump light and the other to the other position.
  • the document states that the sample light and the reference light are emitted from the light source at the same time, so that the effects of the intensity of the probe light and the fluctuation of the spectrum can be eliminated. Disclosure of the invention
  • an object of the present invention is to provide a time-resolved transient absorption measuring device capable of measuring transient absorption with high accuracy and high time resolution in a time region from femtosecond to nanosecond.
  • a time-resolved transient absorption measuring apparatus comprises: a laser light source that emits pulse light including harmonics; and a white short pulse light generation that generates white short pulse light from an output pulse of the laser light source.
  • a first optical system that guides the harmonic component output from the laser light source to the sample and irradiates it as pump light, and a mirror, a shutter, a lens, and a half mirror.
  • the half-mirror splits the white short-pulse light output from the white short-pulse light generator into two optical paths with different optical path lengths, returns the same to the same optical path, combines the light with the half mirror, and guides the sample to the sample.
  • a second optical system that sequentially irradiates the sample before and after the pump light irradiation from a direction different from the light, and an extended light of the sample in the second optical system
  • a streaking camera that is disposed on the top and that spectrally outputs light transmitted through the sample and emitted from the sample, and a streak camera that records a temporal change in light intensity output from the spectral means.
  • the white single pulse is split into two by the second optical system, and the difference in the arrival time at the sample is generated according to the difference in the optical path length of the two split optical paths, and the white light is mixed with the pump light.
  • the light that has passed through the sample before irradiation with the pump light that is, the light that has passed through the sample after light excitation, ie, the light that has passed through the sample after light excitation, is measured as reference light. Since these two lights are obtained by dividing the same white single pulse, their components are the same, and the effect of the temporal fluctuation of the light source can be eliminated.
  • the first optical system and the second optical system each consist only of a mirror, a shutter, a lens, and a half mirror, and do not use an optical fiber.
  • the reference light and the data light are introduced on the same optical axis and can be detected by one detector, the effect of the fluctuation of the white light position can be avoided, and the measurement accuracy can be reduced. It is possible to improve the degree.
  • the influence of the non-uniformity due to the position of the sample can be eliminated.
  • the second optical system adjusts the difference in arrival time of light guided to the sample via both optical paths by changing the optical path length of at least one of the divided optical paths. This makes it possible to freely set the time interval between the reference light and the data light.
  • FIG. 1 is a configuration diagram showing a preferred embodiment of the time-resolved transient absorption measurement device according to the present invention.
  • FIG. 2 is a diagram for explaining the relationship among the sample arrival time of the reference light, the pump light, and the data light in the apparatus of FIG.
  • FIG. 3 is a flowchart showing a measurement procedure in the apparatus of FIG.
  • 4A and 4B are schematic diagrams each showing a streak image in the apparatus of FIG.
  • FIG. 1 is a configuration diagram showing a schematic configuration of a time-resolved transient absorption measurement device according to the present invention.
  • the optical system is shown in a simplified state.
  • This apparatus 100 is a device for measuring the time-resolved transient absorption of the sample 40 placed on the sample stage 4, and includes a laser light source 1, white short pulse light generating means 15, first and second optical devices.
  • the system consists of systems 2, 3, a sample table 4, a spectroscope 5 as a detection device, a streak camera 6, a television camera 7, a control and analysis device 8, and a monitor 9 for displaying analysis results.
  • the laser light source 1 is, for example, a femtosecond mode-locked pulse laser light source, and includes an output terminal 12 for outputting a fundamental wave component, and a harmonic that is a pump light for exciting the sample 40. And an output terminal 11 for outputting a component.
  • the first optical system 2 is configured by arranging a first shutter 21, mirrors 22, 23, and a lens 24 in order from the output terminal 11 side of the harmonic component.
  • the sample 40 is arranged so as to be irradiated from a predetermined direction.
  • the optical path length of the first optical system 2 from the output end 11 to the sample 40 is represented by 1 ⁇ .
  • the second optical system 3 three mirrors 31a to 31c and a half mirror 32a are arranged in order from the output end 12 side of the fundamental wave component, and on one of the branched optical paths 3A, In this order, a motorized reflector reflector 33 and mirrors 34a and 34b, which are arranged so as to be movable in the direction of arrow X by combining mirrors, are arranged at a position intersecting the other optical path 3B.
  • the half mirror 32b is placed on the surface and synthesized.
  • a second shutter 35, a sample stage 4, a slit 36, and a lens 37 are arranged in this order on the combined optical path 3C, and a spectroscope 5 is arranged on the extension of the optical path.
  • the white short-pulse light generating means 15 is arranged between the mirrors 31b and 31c of the second optical system 3, and is irradiated between the lenses 15a and 15c by irradiation of the fundamental wave component of the laser light.
  • a white short-pulse light generating material 41 b such as a nonlinear optical element for generating short-pulse light is arranged, and a filter 41 d for removing unnecessary light components is arranged at a subsequent stage.
  • the combined optical path 3C and the optical path of the first optical system are arranged so as to intersect at a predetermined angle on the sample 40.
  • the spectroscope 5 is, for example, an astigmatism correction type spectroscope that wavelength-decomposes incident light in a predetermined axial direction and outputs the light as output light.
  • the streak camera 6 time-resolves incident light with a direction orthogonal to the wavelength resolution direction of the spectrometer as a time axis direction, and outputs an image.
  • the television camera 7 has a function of acquiring this output image and converting it into an electric signal.
  • the control analysis device 8 is, for example, a personal computer, the laser light source 1, 1st shutter 2 1st, 2nd shutter 35, electric retro-reflector 33, spectroscope 5, streak camera 6, TV camera 7 Has the function of performing analysis.
  • the monitor 9 is a display device for displaying the analysis result and the like.
  • FIG. 2 is a diagram showing a temporal relationship of light guided to the sample by each optical path.
  • the light guided to the second optical system via the optical path 3B (hereinafter referred to as reference light L Ref ), the pump light L pump entering the sample 40 via the first optical system 1, and the light passing through the optical path 3A.
  • FIG. 2 is a diagram illustrating the relationship between the light guided to an optical system (hereinafter, referred to as data light L data ) and the arrival time at a sample 40.
  • the light reaches the sample 40 in the order of the reference light L Ref , the pump light L pump , and the data light L data , and also reaches the data light L data .
  • the time can be adjusted by adjusting the position of the motorized retroreflector 33.
  • FIG. 3 is a flowchart illustrating the measurement procedure
  • FIGS. 4A and 4B are schematic diagrams illustrating an example of a streak image acquired in the measurement.
  • the electric retroreflector 33 is driven to drive the optical path length L. 2.
  • step S2 any light emitted from the laser light source 1 reaches the sample stage 4 part, so that the streak image in the state where the laser light is not irradiated into the optical systems 2 and 3 of the apparatus 100 (Hereinafter, referred to as a dark current image) can be obtained (step S3).
  • the streak image of the output of the spectroscope 5 by the streak camera 6 is taken into the control analysis device 8 by the television camera 7.
  • step S4 a fundamental wave component is emitted from the output terminal 12 of the laser beam 11.
  • This light is guided to white short pulse light generating means 15 via mirrors 31a and 31b, and is incident on white short pulse light generating substance 15b via lens 15a.
  • the white short-pulse light-generating substance 15b emits a white light pulse with a pulse width of about 100 fmt in accordance with the incidence of the light (step S5).
  • the emitted white light pulse is output from the white short pulse light generating means 15 via the lens 41c and the filter 41d, is split into two by the half mirror 32a via the mirror 31c,
  • the light (reference light Lref) having passed through the optical path 3 B having a short optical path length reaches the sample stage 4 first through the half mirror 32 b and the second shutter 35. Then, the light transmitted through the sample 4 is guided to the spectroscope 5 by the slit 36 and the lens 37, wavelength-resolved, and introduced into the streak camera 6.
  • the other light (data light L data ) branched by the half mirror 32a is guided to the long optical path 3A, and the motorized retroreflector 33, the mirrors 34a and 34b are after it enters the half mirror 3 2 b, reaching the sample stage 4 portions at a Reference light L ref reaches after a predetermined time difference through the second shutter 35. Then, the light transmitted through the sample 4 is guided to the spectroscope 5 by the slit 36 and the lens 37, wavelength-resolved, and introduced into the streak camera 6.
  • the streak camera 6 time-resolves the wavelength-resolved light corresponding to the introduced reference light L ref and data light L data to output a strike image as shown in FIG. 4A. .
  • the output image is sent by the television camera 7 to the control analysis device 8 (step S6).
  • the sensitivity correction data at each wavelength (or wave number) position is calculated from the streak image corresponding to the reference light Lref and the data light L data thus obtained and the previously obtained dark current image (step S7).
  • the sample 40 is placed on the sample stage 4 (step S8), and the first shutter 21 is opened (step S9). As a result, both shutters 21 and 35 are opened. In this state, by outputting the harmonic component and the fundamental component of the laser light from the output terminals 11 and 12 of the laser light source 1, respectively, the sample is irradiated with the harmonic component and the white light pulse one after another ( Step S10).
  • the reference light L Re f having passed through the optical path 3 B of the second optical system 3 shines first input, the first pump light Lp Ump passing through the optical system 2 is incident from a different direction thereafter, Finally, the data light L data having passed through the optical path 3 A of the second optical system 3 enters. Then, the light emitted from the sample 40 and the light transmitted through the sample 40 in the meantime are wavelength-resolved by the spectroscope 5 and time-resolved by the streak camera 6, as shown in FIG. 4B. The image is captured as a streak image by the television camera 6 and sent to the control analysis device 8 (step S11).
  • the control analyzer calculates the transient absorption change of the sample 40 based on the acquired streak image data (step S12), and displays the result on the monitor 9 (step S13).
  • the measurement result may be printed using a printer.
  • the streak camera 6 by using the streak camera 6, the time position can be confirmed in the obtained streak image data, so that the measurement can be performed with high accuracy.
  • measurements with good time resolution can be performed from the femtosecond to the nanosecond level.
  • the present apparatus 100 uses the same pulse as the reference light and the data light, and further provides a time difference at the same position on the sample 40. In this case, the influence of light position intensity fluctuations and position fluctuations can be eliminated, and more accurate measurement can be performed.
  • the measurement system (spectrometer 5, streak camera 6, TV camera 7) can be configured as a single unit, the adjustment is easy, and unlike the case where reference light and data light are measured by separate measurement devices, It is possible to completely eliminate fluctuations in measurement ability due to instruments. Measurement can be performed with high accuracy.
  • the second optical system 3 is configured by a mirror / half mirror without using an optical member such as an optical fiber which may be accompanied by pulse width deformation, and by providing an optical path length difference, the pulse of the reference light and the data light is provided.
  • the width can be maintained at an extremely short pulse width, preventing its deformation and enabling measurement with a high time resolution of femtosecond level. Further, by making one optical path length of the second optical system 3 variable, the time change of transient absorption can be efficiently measured by one device.
  • white short-pulse light is generated from a fundamental wave component of laser light.
  • white short-pulse light may be generated from a harmonic component.
  • the arrangement of the white short-pulse light generating means 15 is not limited to the arrangement shown in FIG. 1, and may be arranged at any position on the laser light source 1 side from the optical path branching position in the second optical system. .
  • the time-resolved transient absorption measurement device can measure the resolved transient absorption characteristics with high accuracy and high time resolution in a time range from femtosecond to nanosecond, and can be used for biological, scientific, physical, and physical properties. It can be widely applied as a measurement device in basic science fields such as.

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Mechanical Light Control Or Optical Switches (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Selon l'invention, un premier système optique (2) est connecté au terminal de sortie d'onde de marée (11) d'une source lumineuse laser (1) et un second système optique (3) (comprenant un moyen de génération d'un faisceau blanc d'impulsions courtes (15)) est connecté à un terminal de sortie à composante d'onde de base (12). Le second système optique (3), qui présente deux parcours optiques (3A, 3B) ramifiés par un demi-miroir (32a), applique un faisceau de référence et un faisceau de données consécutivement à un échantillon (40) approximativement lorsqu'un faisceau de pompage est appliqué par l'intermédiaire du premier système optique afin de générer une image continue obtenue par exposition de la lumière fluorescente et de la lumière transmise de l'échantillon (40) à une résolution de longueur d'onde et à une résolution temporelle au moyen d'un spectroscope (5) et d'une caméra à image continue (6). L'image est ensuite envoyée à un analyseur de contrôle (8) par le biais d'une caméra de télévision (7).
PCT/JP2002/007394 2001-07-24 2002-07-22 Dispositif de mesure d'absorption temporaire par resolution temporelle WO2003010519A1 (fr)

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JP2001223439A JP2003035665A (ja) 2001-07-24 2001-07-24 時間分解過渡吸収測定装置

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Cited By (12)

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US7460453B2 (en) 2003-07-07 2008-12-02 Lg Electronics Inc. Recording medium, method of recording and/or reproducing speed information on a recording medium, and apparatus thereof
US7468936B2 (en) 2003-08-14 2008-12-23 Lg Electronics Co., Ltd. Recording and/or reproducing methods and apparatuses
US7650362B2 (en) 2003-08-14 2010-01-19 Lg Electronics Inc. Information recording medium, method of configuring version information thereof, recording and reproducing method using the same, and recording and reproducing apparatus thereof
US7652960B2 (en) 2003-08-14 2010-01-26 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7684292B2 (en) 2003-08-14 2010-03-23 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7706230B2 (en) 2004-05-13 2010-04-27 Lg Electronics, Inc. Recording medium, read/write method thereof and read/write apparatus thereof
US7817514B2 (en) 2003-07-07 2010-10-19 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and/or reproducing method using the same, and apparatus thereof
CN106644408A (zh) * 2016-12-13 2017-05-10 中国科学院西安光学精密机械研究所 同步扫描条纹相机时间分辨力测量装置及方法
CN108195761A (zh) * 2018-03-06 2018-06-22 南京信息工程大学 一种多维可调的分子准直实验***
CN112229804A (zh) * 2020-09-17 2021-01-15 中国科学院上海光学精密机械研究所 具有温场调控功能的非共轴透射式超快瞬态吸收***和测量方法
CN113686782A (zh) * 2021-07-09 2021-11-23 北京大学 一种可见瞬态吸收光谱测量***及方法
US11193825B2 (en) 2017-05-24 2021-12-07 The Penn State Research Foundation Short pulsewidth high repetition rate nanosecond transient absorption spectrometer

Families Citing this family (1)

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JP5865946B2 (ja) 2014-05-22 2016-02-17 株式会社ユニソク 過渡吸収測定方法及び過渡吸収測定装置

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Cited By (22)

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Publication number Priority date Publication date Assignee Title
US7460453B2 (en) 2003-07-07 2008-12-02 Lg Electronics Inc. Recording medium, method of recording and/or reproducing speed information on a recording medium, and apparatus thereof
US7468937B2 (en) 2003-07-07 2008-12-23 Lg Electronics Inc. Method of recording control information on a recording medium, and apparatus thereof
US8310907B2 (en) 2003-07-07 2012-11-13 Lg Electronics Inc. Recording medium, method of configuring control information thereof, recording and/or reproducing method using the same, and apparatus thereof
US7872955B2 (en) 2003-07-07 2011-01-18 Lg Electronics Inc. Recording medium, method of configuring control information thereof, recording and/or reproducing method using the same, and apparatus thereof
US7817514B2 (en) 2003-07-07 2010-10-19 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and/or reproducing method using the same, and apparatus thereof
US7652960B2 (en) 2003-08-14 2010-01-26 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7684292B2 (en) 2003-08-14 2010-03-23 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7701819B2 (en) 2003-08-14 2010-04-20 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7701817B2 (en) 2003-08-14 2010-04-20 Lg Electronics, Inc. Recording medium, method of configuring control information thereof, recording and reproducing method using the same, and apparatus thereof
US7650362B2 (en) 2003-08-14 2010-01-19 Lg Electronics Inc. Information recording medium, method of configuring version information thereof, recording and reproducing method using the same, and recording and reproducing apparatus thereof
US7542391B2 (en) 2003-08-14 2009-06-02 Lg Electronics Inc. Recording and/or reproducing methods and apparatuses
US7468936B2 (en) 2003-08-14 2008-12-23 Lg Electronics Co., Ltd. Recording and/or reproducing methods and apparatuses
US7706230B2 (en) 2004-05-13 2010-04-27 Lg Electronics, Inc. Recording medium, read/write method thereof and read/write apparatus thereof
US8279734B2 (en) 2004-05-13 2012-10-02 Lg Electronics Inc. Recording medium, read/write method thereof and read/write apparatus thereof
CN106644408A (zh) * 2016-12-13 2017-05-10 中国科学院西安光学精密机械研究所 同步扫描条纹相机时间分辨力测量装置及方法
CN106644408B (zh) * 2016-12-13 2023-01-06 中国科学院西安光学精密机械研究所 同步扫描条纹相机时间分辨力测量装置及方法
US11193825B2 (en) 2017-05-24 2021-12-07 The Penn State Research Foundation Short pulsewidth high repetition rate nanosecond transient absorption spectrometer
CN108195761A (zh) * 2018-03-06 2018-06-22 南京信息工程大学 一种多维可调的分子准直实验***
CN108195761B (zh) * 2018-03-06 2023-08-11 南京信息工程大学 一种多维可调的分子准直实验***
CN112229804A (zh) * 2020-09-17 2021-01-15 中国科学院上海光学精密机械研究所 具有温场调控功能的非共轴透射式超快瞬态吸收***和测量方法
CN112229804B (zh) * 2020-09-17 2021-07-06 中国科学院上海光学精密机械研究所 具有温场调控功能的非共轴透射式超快瞬态吸收***和测量方法
CN113686782A (zh) * 2021-07-09 2021-11-23 北京大学 一种可见瞬态吸收光谱测量***及方法

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