WO1999067801A2 - Detecteur a anodes multiples offrant un gamme dynamique plus etendue pour les spectrometres de masse a mesure de temps de vol avec acquisition des donnees par comptage - Google Patents

Detecteur a anodes multiples offrant un gamme dynamique plus etendue pour les spectrometres de masse a mesure de temps de vol avec acquisition des donnees par comptage Download PDF

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Publication number
WO1999067801A2
WO1999067801A2 PCT/US1999/013965 US9913965W WO9967801A2 WO 1999067801 A2 WO1999067801 A2 WO 1999067801A2 US 9913965 W US9913965 W US 9913965W WO 9967801 A2 WO9967801 A2 WO 9967801A2
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WO
WIPO (PCT)
Prior art keywords
anode
anodes
histogram
fraction
incoming
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/US1999/013965
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English (en)
Other versions
WO1999067801A3 (fr
Inventor
Marc Gonin
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.)
Ionwerks Inc
Original Assignee
Ionwerks Inc
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 Ionwerks Inc filed Critical Ionwerks Inc
Priority to US09/720,182 priority Critical patent/US6646252B1/en
Priority to AU45806/99A priority patent/AU4580699A/en
Publication of WO1999067801A2 publication Critical patent/WO1999067801A2/fr
Anticipated expiration legal-status Critical
Priority to US10/957,897 priority patent/US7060973B2/en
Publication of WO1999067801A3 publication Critical patent/WO1999067801A3/fr
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/025—Detectors specially adapted to particle spectrometers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers
    • H01J49/0036—Step by step routines describing the handling of the data generated during a measurement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/40—Time-of-flight spectrometers

Definitions

  • TITLE A MULTI-ANODE DETECTOR WITH INCREASED
  • the present invention is useful in time-of-flight mass spectrometry (TOFMS), a method for qualitative and quantitative chemical analysis.
  • TOFMS time-of-flight mass spectrometry
  • Many TOFMS work with counting techniques, in which case the dynamic range of the analysis is strongly limited by the measuring time and the cycle repetition rate.
  • This invention describes a detection method to increase the dynamic range of elemental-, isotopic-, or molecular analysis with counting techniques.
  • Anode The part of a particle detector, which receives the electrons from the electron multiplier.
  • Anode Fraction The fraction of the total amount of particles, which is detected by a specific anode.
  • Single Signal The signal pulse produced by a detector when a single particle hits the detector.
  • a counting electronics counts the single signals and their arrival.
  • Signal A superposition of single signals, caused by particles of one specie hitting the detector within a very short time.
  • Time-of-flight mass spectrometers allow the acquisition of wide-range mass spectra at high speeds because all masses are recorded simultaneously. Most TOFMS work in a cyclic mode. In each cycle, a certain number of particles (up to several thousand) are extracted and traverse a flight section towards a detector. Each particle's time-of-flight is recorded to deliver information about its mass. Thus, in each cycle, a complete time spectrum is recorded and added to a histogram. The repetition rate of this cycle is commonly in the range of 1 to 50 kHz.
  • the present invention uses multiple anodes wherein each anode has a different anode fraction.
  • saturation can be eliminated.
  • One method for achieving a different anode fraction is through use of anodes of different sizes as shown in Figure 4 at 46 and 47.
  • the example in Figure 4 uses two unequal size anodes with a size ratio of approximately 1:9.
  • the small anode only detects one particle 8 per cycle, just on the edge of saturation for N 2 .
  • Figure 1 is a schematic diagram showing a time-of-flight mass spectrometer to which the invention can be advantageously applied;
  • Figure 2 is a schematic diagram showing a single anode detector of the prior art
  • Figure 3 is a schematic diagram showing a multiple anode detector of the prior art
  • Figure 4 is a schematic diagram showing a detector with multiple, unequal- sized anodes in accordance with the present invention
  • Figure 5 is a graph showing a generic spectrum including an 80% component and a 1 ppm component to depict the saturation effects suffered by prior art detectors and the spectrums generated by a detector of the present invention
  • Figure 6 is a schematic diagram showing an alternate embodiment of the detector of the present invention with two large anodes and one small anode;
  • Figure 7 is a schematic diagram showing numerical simulations of two electron paths of the detector of Figure 6 achieved by varying the electrical field within the detector;
  • Figure 8 is a flowchart showing a method for evaluating the spectra taken with a 2-anode detector with unequal-sized anodes.
  • Figure 9 is a graph showing a sample spectrum of air with two saturated peaks (N 2 and 0 2 ).
  • TOFMS gaseous particles are ionized and accelerated into a flight tube from an extraction chamber 20.
  • Some TOFMS such as the one illustrated, use reflectors to increase the apparent length of the flight tube and, hence, the resolution of the
  • TOFMS TOFMS.
  • ions 6 impinge an electron multiplier 41 causing an emission of electrons.
  • Anodes 44 detect the electrons from the electron multiplier 41 and the signal is then processed through a preamplifier 58, a CFD
  • a histogram that reflects the composition of the sample is generated either in the TDC 60 or in a digital computer
  • FIG. 4 One preferred embodiment of the present invention is shown in Figure 4.
  • unequal-sized anodes 46 and 47 are used in the detector.
  • the detection fraction of the small anode is small enough so that on average it detects only one particle 8 out of the ten incoming particles 6 of the specie.
  • the embodiment shown in Figure 4 uses two unequal size anodes with a size ratio of approximately 1:9.
  • the small anode only detects one particle 8 per cycle, just on the edge of saturation for N 2 .
  • 2 anodes of unequal size it is possible to increase the dynamic range by a factor often or more.
  • Figure 5 shows the results achieved by using the detector of Figure 4.
  • the top graph of Figure 5 is in logarithmic scale, while the bottom graph is linear.
  • the spectrum recorded by the large anode is shown as a solid line, while the smaller anode's spectrum is shown as a dashed line.
  • the large anode becomes saturated in the area of an abundant specie (shown between 2000 and 2060 nanoseconds TOF). However, less abundant specie are recorded accurately by the large anode.
  • the anode with the smaller anode fraction records the abundant specie without becoming saturated.
  • minor species e.g., 1 ppm
  • Figure 6 shows an alternate embodiment of the present invention.
  • the electrical potential applied to the small anode 47 is variable, which gives a method for adjusting the small anode's 47 anode fraction.
  • the lower potential on the small anode 47 is less attractive to the electrons 8 and 9 resulting in detection of a smaller fraction of particles 8 and 9 by the small anode 47.
  • Alternative methods for changing the fractions detected by an anode include the application of magnetic fields and physically constructing the instrument in a way such that the ion beam hits the various anodes with different intensities. In most cases, a mixture of these three methods will be used.
  • the detector shown in Figure 7 varies each anode's anode fraction through a combination of size differences, geometry, and electrical potential.
  • Figure 8 is a flowchart showing a preferred method for evaluating the spectra taken with a 2-anode detector with unequal anode sizes. The additional procedures are encapsulated in the dashed box. As can be seen from the flowchart, upon creating anode histograms, the histograms are analyzed to detect which spectrum regions reflect large anode saturation. In many cases, certain spectrum regions will theoretically be assumed to be saturated and will be treated as such by the method. However, saturation can also be detected by comparing the large anode histogram to the small anode histogram. The small anode histogram, which is not saturated, will accurately reflect the ratio between counts for various regions.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

L'invention concerne un nouveau système de détection applicable aux spectromètres de masse qui mesurent le temps de vol. Le système en question permet d'étendre la gamme dynamique des spectromètres fonctionnant avec une technique de comptage (conversion temporelle-numérique). L'extension de la gamme dynamique résulte de l'élaboration d'un détecteur à anodes multiples dans lequel les anodes individuelles détectent différentes fractions des particules entrantes. On obtient ces fractions différentes en faisant varier la taille, l'emplacement physique et les champs électriques/magnétiques des anodes individuelles. Une anode à petite fraction d'anode évite la saturation et permet à un détecteur d'ions de fournir un décompte précis des ions, même pour des espèces abondantes.
PCT/US1999/013965 1998-06-22 1999-06-21 Detecteur a anodes multiples offrant un gamme dynamique plus etendue pour les spectrometres de masse a mesure de temps de vol avec acquisition des donnees par comptage Ceased WO1999067801A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/720,182 US6646252B1 (en) 1998-06-22 1999-06-21 Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition
AU45806/99A AU4580699A (en) 1998-06-22 1999-06-21 A multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition
US10/957,897 US7060973B2 (en) 1999-06-21 2004-10-04 Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1328/98 1998-06-22
CH132898 1998-06-22

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US09720182 A-371-Of-International 1999-06-21
US09/720,182 A-371-Of-International US6646252B1 (en) 1998-06-22 1999-06-21 Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition
US10/628,145 Continuation US6812454B2 (en) 1998-06-22 2003-07-28 Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition

Publications (2)

Publication Number Publication Date
WO1999067801A2 true WO1999067801A2 (fr) 1999-12-29
WO1999067801A3 WO1999067801A3 (fr) 2006-05-18

Family

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Family Applications (1)

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PCT/US1999/013965 Ceased WO1999067801A2 (fr) 1998-06-22 1999-06-21 Detecteur a anodes multiples offrant un gamme dynamique plus etendue pour les spectrometres de masse a mesure de temps de vol avec acquisition des donnees par comptage

Country Status (2)

Country Link
AU (1) AU4580699A (fr)
WO (1) WO1999067801A2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002097856A3 (fr) * 2001-05-29 2003-03-13 Thermo Finnigan Llc Spectrometre de masse a temps de vol et capteur multiple associe
US6647347B1 (en) 2000-07-26 2003-11-11 Agilent Technologies, Inc. Phase-shifted data acquisition system and method
US6683299B2 (en) * 2001-05-25 2004-01-27 Ionwerks Time-of-flight mass spectrometer for monitoring of fast processes
US6747271B2 (en) 2001-12-19 2004-06-08 Ionwerks Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition
US6864479B1 (en) 1999-09-03 2005-03-08 Thermo Finnigan, Llc High dynamic range mass spectrometer
US6878931B1 (en) 2000-07-26 2005-04-12 Agilent Technologies, Inc. Multipath data acquisition system and method
WO2005043575A2 (fr) 2003-10-20 2005-05-12 Ionwerks, Inc. Spectrometre de masse de mesure de temps de vol destine a controler des processus rapide
US7019286B2 (en) 2001-05-25 2006-03-28 Ionwerks, Inc. Time-of-flight mass spectrometer for monitoring of fast processes
US7372022B2 (en) 2000-07-26 2008-05-13 Agilent Technologies, Inc. Multipath data acquisition system and method
DE102010011974A1 (de) * 2010-03-19 2011-09-22 Bruker Daltonik Gmbh Sättigungskorrektur für Ionensignale in Flugzeitmassenspektrometern
GB2480148A (en) * 2010-05-07 2011-11-09 Bruker Daltonik Gmbh Mass Spectrometric Detection of Microbes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5777326A (en) * 1996-11-15 1998-07-07 Sensor Corporation Multi-anode time to digital converter

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6864479B1 (en) 1999-09-03 2005-03-08 Thermo Finnigan, Llc High dynamic range mass spectrometer
US7372022B2 (en) 2000-07-26 2008-05-13 Agilent Technologies, Inc. Multipath data acquisition system and method
US6647347B1 (en) 2000-07-26 2003-11-11 Agilent Technologies, Inc. Phase-shifted data acquisition system and method
US6878931B1 (en) 2000-07-26 2005-04-12 Agilent Technologies, Inc. Multipath data acquisition system and method
US7129480B2 (en) 2000-07-26 2006-10-31 Agilent Technologies, Inc. Multipath data acquisition system and method
US6683299B2 (en) * 2001-05-25 2004-01-27 Ionwerks Time-of-flight mass spectrometer for monitoring of fast processes
US7084395B2 (en) 2001-05-25 2006-08-01 Ionwerks, Inc. Time-of-flight mass spectrometer for monitoring of fast processes
US7019286B2 (en) 2001-05-25 2006-03-28 Ionwerks, Inc. Time-of-flight mass spectrometer for monitoring of fast processes
DE10296885B4 (de) * 2001-05-29 2010-09-16 Thermo Finnigan Llc, San Jose Flugzeit-Massenspektrometer und Verfahren zum Detektieren der Flugzeit von Ionen
WO2002097856A3 (fr) * 2001-05-29 2003-03-13 Thermo Finnigan Llc Spectrometre de masse a temps de vol et capteur multiple associe
US6940066B2 (en) 2001-05-29 2005-09-06 Thermo Finnigan Llc Time of flight mass spectrometer and multiple detector therefor
US7145134B2 (en) 2001-12-19 2006-12-05 Ionwerks, Inc. Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisitions
EP1464068A4 (fr) * 2001-12-19 2007-06-13 Ionwerks Inc Detecteurs multi-anodes presentant une plage dynamique accrue pour des spectrometres de masse a temps de vol presentant des acquisitions de donnees de comptage
US6909090B2 (en) 2001-12-19 2005-06-21 Ionwerks Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisitions
US7291834B2 (en) 2001-12-19 2007-11-06 Ionwerks, Inc. Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisitions
US6747271B2 (en) 2001-12-19 2004-06-08 Ionwerks Multi-anode detector with increased dynamic range for time-of-flight mass spectrometers with counting data acquisition
WO2005043575A2 (fr) 2003-10-20 2005-05-12 Ionwerks, Inc. Spectrometre de masse de mesure de temps de vol destine a controler des processus rapide
DE102010011974A1 (de) * 2010-03-19 2011-09-22 Bruker Daltonik Gmbh Sättigungskorrektur für Ionensignale in Flugzeitmassenspektrometern
DE102010011974B4 (de) * 2010-03-19 2016-09-15 Bruker Daltonik Gmbh Sättigungskorrektur für Ionensignale in Flugzeitmassenspektrometern
GB2480148A (en) * 2010-05-07 2011-11-09 Bruker Daltonik Gmbh Mass Spectrometric Detection of Microbes
DE102010019870A1 (de) * 2010-05-07 2011-11-10 Bruker Daltonik Gmbh Massenspektrometrischer Mikrobennachweis
GB2480148B (en) * 2010-05-07 2016-02-17 Bruker Daltonik Gmbh Mass spectrometric detection of microbes
DE102010019870B4 (de) 2010-05-07 2024-06-20 Bruker Daltonics GmbH & Co. KG Massenspektrometrischer Mikrobennachweis

Also Published As

Publication number Publication date
WO1999067801A3 (fr) 2006-05-18
AU4580699A (en) 2000-01-10

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