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WO2018015309A1 - Spectroscopie raman - Google Patents

Spectroscopie raman Download PDF

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Publication number
WO2018015309A1
WO2018015309A1 PCT/EP2017/067901 EP2017067901W WO2018015309A1 WO 2018015309 A1 WO2018015309 A1 WO 2018015309A1 EP 2017067901 W EP2017067901 W EP 2017067901W WO 2018015309 A1 WO2018015309 A1 WO 2018015309A1
Authority
WO
WIPO (PCT)
Prior art keywords
spectroscopic instrument
detector
time
raman
signal
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2017/067901
Other languages
English (en)
Inventor
Michael James FOSTER
Jonathan STOREY
Jon Lapington
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Is-Instruments Ltd
Original Assignee
Is-Instruments Ltd
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 Is-Instruments Ltd filed Critical Is-Instruments Ltd
Priority to EP17746406.2A priority Critical patent/EP3485245A1/fr
Publication of WO2018015309A1 publication Critical patent/WO2018015309A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/45—Interferometric spectrometry
    • G01J3/453—Interferometric spectrometry by correlation of the amplitudes
    • G01J3/4531—Devices without moving parts
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/2803—Investigating the spectrum using photoelectric array detector
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
    • G01J1/44—Electric circuits
    • G01J2001/4413—Type
    • G01J2001/442—Single-photon detection or photon counting

Definitions

  • the present invention relates to Raman spectroscopy, particularly to time-resolved Raman spectroscopy.
  • Raman spectrometry is an increasingly prominent tool in a variety of sectors, whereby all molecules provide a unique molecular signature that can be used as a finger print to identify the chemical composition of a substance. This has led the development of a variety of handheld systems that have been used for the identification of explosive materials, for example.
  • the present invention provides a Raman spectroscopic instrument comprising a time-resolved Raman spectrometer comprising a static Fourier transform spectrometer and a single-photon avalanche diode (SPAD) array detector comprising a plurality of detector pixels; wherein the detector provides a response in the form of an electronic signal for every pixel, which signal comprises precise information on the arrival time of an initial photon and, after detection of an initial photon, every pixel enters a recovery period during which it is disabled from further detection.
  • a Raman spectroscopic instrument comprising a time-resolved Raman spectrometer comprising a static Fourier transform spectrometer and a single-photon avalanche diode (SPAD) array detector comprising a plurality of detector pixels; wherein the detector provides a response in the form of an electronic signal for every pixel, which signal comprises precise information on the arrival time of an initial photon and, after detection of an initial photon, every pixel enters a recovery
  • the detector recovery period is more than Ins
  • the detector is triggered to provide accurate timing of the returns; the signal is recorded by read-out electronics that time stamps the returned response; and the signal observed in the first timing period is then separated to extract the Raman response.
  • all the pixels are used to provide and average of the time measurement, exploiting the response of the static Fourier transform spectrometer.
  • the spectroscopic instrument further comprises a trigger for the detector to respond at or before the short pulse source is activated.
  • the trigger signal is an electrical or photonic signal.
  • the detector is gated such that it is only on for a fixed period of time, in order to supress background light.
  • the period of time is greater than or equal to 10 ns and preferably the position of this gate is controlled by the trigger of the system, to coincide with the location of the target.
  • every detection element has an independent electronics channel capable of event timing. More preferably, the timing per electronics channel is better than 100 ps.
  • every timing electronics channel comprises a discriminator with threshold such that the discriminator logic contains event timing information to an accuracy of less than about lOOps.
  • every timing electronics channel performs time to digital conversion on the discriminator logic pulse to digitise the event time to better than 100 ps.
  • the detector array has more than one detection element.
  • a single detector element is used to precisely measure the distance to the target, allowing the trigger signal to be positioned for the extraction of the Raman signal.
  • the spectroscopic instrument provides an output signal corresponding to a Raman signal response.
  • the spectroscopic instrument further comprises an analysis function, preferably an analysis function adapted to record and analyse both Raman and fluorescent returns over a period of time.
  • the instrument further comprises a source for a short pulse of monochromatic light, or near monochromatic light.
  • the source is a laser source.
  • the source is arranged to excite a target sample and the assembly is further provided with an imaging or similar optical system to capture broadband continuum light emitted from the sample and pass the light to the detector.
  • the spectroscopic instrument provides an output signal corresponding to a Raman signal response.
  • the spectroscopic instrument includes an analysis function, more preferably, an analysis function adapted to record and analyse both Raman and fluorescent returns over a period of time.
  • Figure 1 is a schematic view of the overall measurement functionality of an embodiment of a Raman instrument in accordance with the present invention
  • Figure 2 is a schematic view of an embodiment of a spectroscopic instrument in accordance with the present invention.
  • Figure 3 is a schematic showing an embodiment of a spectroscopic instrument of the present invention comprising a static Fourier transform spectrometer
  • Figure 4 is a schematic of a typical electrical circuit used to read out the data from the detector and time the arrival time of the photon
  • a short pulse from a monochromatic or near monochromatic source is combined with a spectrometer and linear Geiger mode or single- photon avalanche diode (SPAD) array detector.
  • the light from the source causes the sample to radiate Raman light and fluorescence.
  • This broadband continuum light emitted from the sample is then captured via an imaging or similar optical system.
  • the light is passed via a spectrometer unto the detector.
  • the response of the detector is recorded by system electronics, with each pixel recording the time of arrival of the first photon detected to an accuracy of the order of 100 picoseconds or less.
  • the detector is triggered to respond at or before the laser pulse is fired. Once the photons have been recorded those observed in the first timing sector represent those emitted within 100 ps of the laser pulse starting to illuminate the sample, and are separated and identified as Raman signals by means of their recorded arrival times. Photons recorded in subsequent times are identified as fluorescence signals or unwanted signals. Once the signal photons have been recorded and converted into an electrical signal within the detector, fast timing electronics are then used to time stamp the photons with an accuracy of better than 100 ps. The time signature of each photon is thus used to identify them as either Raman or fluorescent/other photons.
  • the spectrometer used for the measurement is a static Fourier transform device. , (Fig 2) [Harlander. J., R. J Reynolds and F.
  • the trigger signal is suitably electrical in nature or may be photonic and may be generated by an external source or directly from the incident monochromatic light source.
  • a signal corresponding to a Raman signal response is output from the spectroscopic instrument.
  • the spectroscopic instrument includes an analytic function to record and analyse both the Raman and fluorescent returns.
  • the detector is gated such that it activates for a fixed period of time to supress background light.
  • the time is suitably greater than or equal to 10 ns, where the position of this gate is controlled by the trigger of the system, to coincide with the location of the target.
  • Figure 1 is a schematic view of the overall measurement functionality, where a laser pulse is shown in the left hand side of the image, which is followed by a "Raman" pulse from the sample.
  • the detector records the photon and enters the recovery period (of 1 to 50ns).
  • the final pulse is the fluorescent signal observed 200ps after the Raman pulse;
  • FIG. 2 is a schematic view of an embodiment of a spectrometer of the present invention.
  • the laser is incident on a sample that could be solid, liquid or gas in nature.
  • the scattered/ emitted light is captured by the receiving lens and passed through a filter to remove the laser light.
  • the light is then analysed in a spectrometer and focused onto the SPAD array;
  • Figure 3 is a schematic showing an embodiment of a static Fourier transform spectrometer of the present invention used to analyse the sample.
  • the incoming light is separated by a beam splitter, where the two paths strike a dispersive element (e.g a reflective diffraction grating). These reflective signals then interfere forming a fringe pattern which is observed at the detector.
  • a Fourier transform of the raw data is then applied to extract the spectral signal.
  • Figure 4 is a diagram of the timing electronics used on every pixel within the detector to time the incoming photons.
  • the signal from the SPAD array is passed to the event timing circuit that consists of a pre amp, discriminator and time to digital converter.
  • This property is in effect a perfect shutter and thus can be used to separate the Raman signal.
  • This invention while employing a detector similar to that discussed in US2013/0342835 [Jordana Blacksberg "Time resolved laser Raman spectroscopy using a single photon avalanche diode array"], uses an additional novel step whereby the timing of each photon is measured to an accuracy of 100 ps or less by means of fast electronics while the detector is gated on. Additionally, time gating as described in US2013/0342835 is used not for resolving short duration signals from longer duration signals but rather to provide additional information such as distance to the target etc.
  • the target instrument combines a high etendue static Fourier transform spectrometer (SFTS) and a linear array of greater than 100 pixels Geiger mode SPAD detector and electronic readout capable of time to digital conversion to provide a timing accuracy of ca. 100 ps.
  • SFTS static Fourier transform spectrometer
  • every pixel observes every wavelength of light simultaneously, unlike a classic dispersive system. Therefore, instead of a single pixel measurement being used to determine the timing, every pixel can be used no matter the nature of the signal. This provides a far greater statistical base for the timing measurement and hence improve the overall system accuracy.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

La présente invention concerne la spectroscopie Raman, en particulier la spectroscopie Raman à résolution temporelle. Elle concerne un instrument spectroscopique Raman comprenant un spectromètre Raman à résolution temporelle possédant un spectromètre statique à transformée de Fourier et un réseau de diodes à avalanche à photon unique (SPAD); le détecteur fournit une réponse sous la forme d'un signal électronique pour chaque pixel, lequel signal contient des informations précises sur le temps d'arrivée d'un photon initial et, après la détection d'un photon initial, chaque pixel entre dans une période de récupération pendant laquelle il ne peut effectuer d'autre détection.
PCT/EP2017/067901 2016-07-18 2017-07-14 Spectroscopie raman Ceased WO2018015309A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17746406.2A EP3485245A1 (fr) 2016-07-18 2017-07-14 Spectroscopie raman

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1612392.9 2016-07-18
GBGB1612392.9A GB201612392D0 (en) 2016-07-18 2016-07-18 Raman Spectroscopy

Publications (1)

Publication Number Publication Date
WO2018015309A1 true WO2018015309A1 (fr) 2018-01-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/067901 Ceased WO2018015309A1 (fr) 2016-07-18 2017-07-14 Spectroscopie raman

Country Status (3)

Country Link
EP (1) EP3485245A1 (fr)
GB (1) GB201612392D0 (fr)
WO (1) WO2018015309A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110836883A (zh) * 2018-08-17 2020-02-25 陈昊昌 基于spad的时间相关拉曼-荧光寿命光谱仪
CN111122541A (zh) * 2019-12-25 2020-05-08 桂林电子科技大学 一种区分拉曼信号和荧光信号的光纤探针系统

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130342835A1 (en) * 2012-06-25 2013-12-26 California Institute Of Technology Time resolved laser raman spectroscopy using a single photon avalanche diode array
WO2014018140A2 (fr) * 2012-04-23 2014-01-30 Wayne State University Interféromètre statique à élément réfléchissant de type en escalier
US8947659B1 (en) * 2013-02-26 2015-02-03 Optech Ventures, Llc Time correlated single photon counting by time to digital conversion
US20150285625A1 (en) * 2014-04-07 2015-10-08 Samsung Electronics Co., Ltd. High resolution, high frame rate, low power image sensor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014018140A2 (fr) * 2012-04-23 2014-01-30 Wayne State University Interféromètre statique à élément réfléchissant de type en escalier
US20130342835A1 (en) * 2012-06-25 2013-12-26 California Institute Of Technology Time resolved laser raman spectroscopy using a single photon avalanche diode array
US8947659B1 (en) * 2013-02-26 2015-02-03 Optech Ventures, Llc Time correlated single photon counting by time to digital conversion
US20150285625A1 (en) * 2014-04-07 2015-10-08 Samsung Electronics Co., Ltd. High resolution, high frame rate, low power image sensor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110836883A (zh) * 2018-08-17 2020-02-25 陈昊昌 基于spad的时间相关拉曼-荧光寿命光谱仪
CN111122541A (zh) * 2019-12-25 2020-05-08 桂林电子科技大学 一种区分拉曼信号和荧光信号的光纤探针系统

Also Published As

Publication number Publication date
EP3485245A1 (fr) 2019-05-22
GB201612392D0 (en) 2016-08-31

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