EP2355129B1 - Reflecteur pour un spectromètre de masse à temps de vol - Google Patents

Reflecteur pour un spectromètre de masse à temps de vol Download PDF

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Publication number
EP2355129B1
EP2355129B1 EP10152072A EP10152072A EP2355129B1 EP 2355129 B1 EP2355129 B1 EP 2355129B1 EP 10152072 A EP10152072 A EP 10152072A EP 10152072 A EP10152072 A EP 10152072A EP 2355129 B1 EP2355129 B1 EP 2355129B1
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Prior art keywords
reflector
electrode
ring
entry opening
ring electrodes
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Application number
EP10152072A
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German (de)
English (en)
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EP2355129A1 (fr
Inventor
Peter Bisling
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Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Priority to EP10152072A priority Critical patent/EP2355129B1/fr
Priority to US13/011,038 priority patent/US8314381B2/en
Publication of EP2355129A1 publication Critical patent/EP2355129A1/fr
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    • 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
    • H01J49/405—Time-of-flight spectrometers characterised by the reflectron, e.g. curved field, electrode shapes

Definitions

  • the present invention relates to a reflector for a time-of-flight mass spectrometer for reflection of ionized atoms and / or molecules having an inlet opening and an arrangement of ring electrodes arranged one behind the other along a longitudinal axis of the reflector and a shielding electrode on the side remote from the ring electrodes the inlet opening is provided and wherein the shielding electrode is at a potential which differs from that of the ring electrodes, preferably ground potential, and a time-of-flight mass spectrometer.
  • mass spectrometers with which the material of the sample is analyzed with regard to the atomic / molecular weight distribution.
  • time-of-flight mass spectrometers are frequently used in which the atoms / molecules of the material to be analyzed are first ionized and then accelerated by means of electric fields, whereby a predetermined kinetic energy is supplied to the ionized atoms / molecules.
  • the time of flight is measured, which the ions need to run from the point where they are ionized to a detector, wherein the ionization can not be continuous but pulsed, for example by means of laser pulses, so that a defined starting time is given for the transit time measurement.
  • the time of flight that the ionized atoms / molecules need for the given distance is a measure of their mass, because at a given fixed kinetic energy such atoms / molecules with a large mass take a longer time to travel the route than light.
  • reflectors are used with net-free ring electrodes, in which the electrodes are arranged along a common axis. In this way it is avoided that the ions in the reflector can come into contact with the electrodes, so that this leads to an increased transmission compared to mains electrodes and thus increased detection probability.
  • DE 35 24 536 A1 is a Time-of-flight mass spectrometer with such a reflector known.
  • a disadvantage of such reflectors is that in such a ring electrode arrangement, the drift paths along which the ions move are not field gradient free. However, it is precisely the assumption that ions with the same atomic / molecular weight outside the reflector are in a field gradient-free region and therefore their velocity is constant. An edge field which extends out of the reflector into this actually field gradient-free space has the consequence that the mass resolution of the time-of-flight mass spectrometer deteriorates.
  • the penetration of the field within the reflector to the field gradient-free drift path can also be minimized by keeping the diameter of the inlet opening or the first ring electrode very small.
  • this reduces the range of the acceptance angle for the ions to be detected and, in turn, results in a reduction in the number of ions entering the reflector and thus overall in the detection probability due to higher transmission losses.
  • the present invention is therefore an object of the invention to provide a reflector for a time-of-flight mass spectrometer or such a mass spectrometer, wherein at high detection probability an improved mass resolution is given.
  • the ring electrode next to the inlet opening is located on an opposite to the other ring electrodes electrical potential that is supplied by a power supply.
  • the drift paths for the ions outside the reflector are largely field gradient free, and in these regions the electric field within the reflector has no effect on the movement of the ions, thus neither accelerating nor ionizing the ions be slowed down.
  • This increases the mass dispersion due to the different speeds of the ions with different atomic / molecular weights and leads to an improvement of the mass resolution.
  • penetration of the field from the reflector into the field gradient-free region of the drift paths can also be achieved without reducing the size of the inlet opening.
  • the ions can also be incident at a larger angle relative to the longitudinal axis of the reflector and are nevertheless reflected without great losses. This means that the drift paths along which the ions move towards and away from the reflector can form a larger angle.
  • the dimensions of the ion source and the detector of the mass spectrometer perpendicular to the direction defined by the drift paths are substantially fixed, so that the minimum distance of these elements is given. If the maximum angle of incidence and / or the maximum angle which the drift paths can also include is greater because of the greater direction of incidence, the ion source and the detector can be arranged closer to the reflector, so that the size of the mass spectrometer can be reduced with improved mass resolution by the invention.
  • the magnitude of the electrical voltage with which the correction electrode is supplied is largely freely selectable, so that this parameter is still available in order to optimize the angular divergence of the reflector beam reflected ion beam on the detector geometry.
  • the voltage to supply the ring electrode next to the entrance opening is preferably between -1 kilovolt (kV) and -4 kV.
  • the influence of the electric fields generated in the reflector is further reduced to the drift paths.
  • the ring electrodes have a diaphragm opening, wherein the diaphragm opening of the ring electrode next to the inlet opening is larger than that of the remaining ring electrodes.
  • this is preferably formed annularly with an opening and extending in a plane which is perpendicular to the longitudinal axis of the reflector.
  • the passage opening the shielding electrode is preferably less than or equal to the aperture of the ring electrode, which is closest to the inlet opening in order to achieve a sufficiently large effect by the shielding electrode.
  • the distance between the shield electrode and the ring electrode closest to the entrance opening can be adjustable, thereby improving the focusing of the ion beam leaving the reflector.
  • a holder which surrounds the inlet opening, and the shield electrode is mounted on the holder, wherein such an arrangement is easy to assemble.
  • the holder can also be at ground potential.
  • a time-of-flight mass spectrometer having an ion source for ionizing atoms and / or molecules, with an electrode assembly, which may include a repeller electrode and a withdrawal electrode, for accelerating ionized atoms and / or molecules in a first direction electric fields, comprising an electrostatic reflector constructed in the manner described above, for reflecting the ionized atoms and / or molecules moving along the first direction in a second direction, the reflector being arranged such that the longitudinal axis of the reflector is the Angle bisector between the first and the second direction forms, and arranged along the second direction detector for detecting the impact of the ionized atoms and / or molecules.
  • an electrostatic reflector constructed in the manner described above, for reflecting the ionized atoms and / or molecules moving along the first direction in a second direction, the reflector being arranged such that the longitudinal axis of the reflector is the Angle bisector between the first and the second direction forms, and arranged along the second direction
  • FIG. 1 illustrated embodiment of a time-of-flight mass spectrometer according to the invention is arranged in a multi-chamber vacuum recipient 1, whose walls are shown in phantom in the drawing and which can be differentially evacuated by means of a pump device, not shown, so that the entire spectrometer is operated under vacuum.
  • the vacuum recipient 1 comprises a sample chamber 3, an ionization chamber 5 and a reflector chamber 7 with drift paths 53, 59 and the reflector 9. Finally, a detector chamber 11 is provided, which is formed as a tubular extension with a flange and in which the detector 55 for detecting the from Reflector 9 deflected ionized atoms and / or molecules is arranged.
  • the time-of-flight mass spectrometer has an ion source 13 for ionizing atoms or molecules, so that the components of a sample, which are first introduced into the sample chamber 3 and then transferred into the ionization chamber 5 by means of a gas jet, can be ionized.
  • the ionization is carried out with the aid of a pulsed laser (not shown), so that ions are generated only at the time points predetermined by the laser pulses.
  • the ion source 13 has an electrode arrangement comprising a repeller electrode 14 and a pull-off electrode 15, by means of which the ionized atoms / molecules are accelerated along a first direction 17 by means of an electric field.
  • an ion lens 19 follows along the first direction 17, with which the ion beam extracted from the ion source 13 by means of the repeller electrode 14 and the withdrawal electrode 15 can be suitably bundled To achieve the highest possible detection probability in the detector 55.
  • the ion lens 19 has a plurality of unspecified ion optical elements which are connected in operation with a power supply, not shown, so that electric fields act on the passing ions.
  • the time-of-flight mass spectrometer has an electrostatic reflector 9 extending along a longitudinal axis 21 for the reflection of ions, which is designed as a net-free ion reflector.
  • the term "grid-free” is to be understood as meaning that the reflector 9 has no nets formed as nets which extend through the path along which the ions move.
  • the reflector 9 is attached via a receiving ring 22 and support rods 23 to a flange which forms the wall of the reflector chamber 7, and has a circular inlet opening 25 which is formed in this preferred embodiment in an annular holder 27, but the holder is not must be mandatory.
  • the holder 27 is followed by an arrangement of mutually parallel ring electrodes 29, 31 with circular apertures 32, 32 'at.
  • the ring electrodes 29, 31 each have a ring holder 33 and an aperture electrode 35 secured thereto by screws, which are provided with the apertures 32 and 32 '.
  • the individual ring electrodes 29, 31 are arranged equidistantly in planes which run perpendicular to the longitudinal axis 21 of the reflector 9.
  • the diameter of the aperture 32 'of the inlet opening 25 in the holder 27 next annular electrode 31 is greater than that of the other ring electrodes 29.
  • the reflector 9 finally has at the end remote from the holder 27, a reflector electrode 37 and the receiving ring 22 for the support rods 23.
  • the ring electrode located closest to the inlet opening 25 is designed as a correction electrode 31, wherein it has the same shape as the other ring electrodes 29, but is provided with a larger aperture 32 '.
  • the correction electrode 31 is at a negative potential supplied by a first power supply 45 and may typically be between -1 kV and -4 kV for positively charged ions having a kinetic energy of 1 keV.
  • the ring electrodes 29 arranged behind in the direction of the reflector electrode 37 are designed as braking electrodes for the ions arriving in the reflector 9 and lie on a positive potential rising toward the reflector electrode 37.
  • the ring electrodes 29 may have an in FIG. 1 also shown schematically second Power supply 47 are placed on divergent positive potentials.
  • the correction electrode 31 can therefore be placed on an opposite to the other ring electrodes 29 arbitrary, opposite potential.
  • a likewise annular shielding electrode 41 is provided with a circular opening 42 at a distance from the holder 27, wherein spacers 43 are provided between the holder 27 and the shielding electrode 41.
  • the diameter of the passage opening 42 is smaller than that of the aperture 32 'formed in the correction electrode 31.
  • the shielding electrode 41 is at a potential that differs from that of the ring electrodes 29, 31, and in the present embodiment at the potential on which the drift paths are located in the vacuum recipient 1, namely at ground potential, as indicated by the ground connections 49, 51 is.
  • both the shielding electrode 41 and the drift paths 53 and 59 are set to a common potential which deviates from the potential of the vacuum recipient 1, that is to say preferably from the ground potential.
  • the distance of the shielding electrode 41 from the holder 27 and the diameter of the passage opening 42 of the shielding electrode 41 are adjusted so that on the one hand, the electric field of the correction electrode 31 is shielded for field gradient free region of the drift paths 53 and 59, but On the other hand, it does not occur that ions impinge on the shielding electrode 41, which would lead to a reduced detection probability due to transmission losses.
  • the through-opening 42 in the shielding electrode 41 is smaller than the aperture 32 'of the correction electrode 31.
  • the path between the ion lens 19 and the reflector 9 serves as a field gradient-free first drift path 53 for the ions, wherein the first drift path 53 runs along the first direction 17.
  • the time-of-flight mass spectrometer also has a detector 55 which, viewed from the reflector 9, is arranged in a second direction 57 at a distance from the reflector 9.
  • the detector 55 is configured to detect the impact of ions as a function of time.
  • a field-free second drift path 59 is formed, which extends along the second direction 57.
  • the ion source 13, the repeller electrode 14, the withdrawal electrode 15, the reflector 9 and the detector 55 are arranged in the vacuum recipient 1 such that the first direction 17, the longitudinal axis 21 of the reflector 9 and the second direction 57 in a common plane run.
  • the first and second directions 17, 57 are such that they meet at a point lying on the longitudinal axis 21 and in a range seen in the direction of movement of the ions emerging from the ion source 13, behind the entrance opening 25 of the reflector 9 lies.
  • the longitudinal axis 21 of the reflector 9 forms the bisecting line between the first direction 17 and the second direction 57.
  • the time-of-flight mass spectrometer is operated as follows.
  • the atoms and / or molecules supplied from the sample chamber 3 by means of a gas jet are preferably ionized by laser pulses.
  • the ionization is not continuous, but pulsed, so that a defined starting time for the transit time measurement is given.
  • Other methods of ionizing the atoms and / or molecules are possible, e.g. by matrix-assisted laser desorption / ionization (MALDI), electrospray ionization (ESI) and electron impact ionization.
  • the ions are accelerated by an electric field of the repeller electrode 14 and the exhaust electrode 15 along the first direction 17 and aligned with the aid of the ion lens 19 on the reflector 9.
  • the ions receive the same kinetic energy regardless of their mass, but then have different speeds due to the different masses.
  • the ions leave the ion source 13 and the ion lens 19 at their respective speeds and enter the first field gradient-free drift path 53, where they move at different speeds onto the reflector 9.
  • the ring electrodes 29 of the reflector 9 are at different positive potentials, wherein the following voltages at the individual, designated by B n diaphragms of the ring electrodes 29 have proven to be advantageous for ions with the related to ground kinetic energy of 1 keV: B 1 364 v B 2 514 V B 3 630 V B 4 727 V B 5 813 V B 6 891V B 7 962 V B 8 1029 V B 9 1091V B 10 1150V B 11 1206 V Reflector electrode 37 1260V
  • the incoming ions are decelerated in the reflector 9 and then accelerated in the opposite direction and leave the reflector again. In doing so, they fly along the second direction 57 oriented second drift path 59 onto the detector 55, where at the time of the impingement of an ion a signal is output, this signal having a time interval to the ionization triggering laser pulse.
  • This time interval is a measure of the mass of the ion that generated the signal. Larger mass ions later encounter the detector 55 as light ions due to their lower velocity.
  • the ions produced in the ion source 13 produce a plurality of signals, and a plot of the number of signals as a function of the time interval from the laser pulse represents a mass spectrum of the sample.
  • the first and second drift paths 53, 59 are in fact largely field gradient-free, and in these regions the electric field within the reflector 9 has no influence on the movement of the ions, so that the ions are neither accelerated nor decelerated become.
  • Behind the idea of the correction electrode 31 is the idea of suppressing field penetration of the drift paths 53, 59 without obstacles in the area of the ion trajectories. Instead, the disturbances are due to an electrical Field avoided.
  • the magnitude of the voltage with which the correction electrode 31 is supplied is largely freely selectable, so that this parameter is still available in order to adapt the angular divergence of the ion beam reflected in the reflector 9 to the detector geometry.
  • the mass resolution is represented as a function of the ratio (m / z) of mass (m) to charge (z) of the ions, once for the case with shielding and correction electrode (solid line) and once without using these electrodes (dashed line) is plotted.

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

Claims (8)

  1. Réflecteur pour un spectromètre de masse à temps de vol pour la réflexion d'atomes et/ou de molécules ionisés,
    avec une ouverture d'entrée (25) et
    avec un arrangement d'électrodes annulaires (31, 29) disposées les unes derrière les autres s'étendant le long d'un axe longitudinal (21) du réflecteur (9) dans la direction s'éloignant de l'ouverture d'entrée (25),
    une électrode écran (41) étant prévue du côté de l'ouverture d'entrée (25) détourné des électrodes annulaires (31, 29) et
    l'électrode écran (41) se trouvant à un potentiel qui diffère de celui des électrodes annulaires (31, 29), de préférence au potentiel de la terre,
    caractérisé en ce que
    l'électrode annulaire (31) la plus proche de l'ouverture d'entrée (25) se trouve en comparaison des autres électrodes annulaires (29) à un potentiel électrique opposé, qui est délivré par une alimentation en tension (45).
  2. Réflecteur selon la revendication 1, caractérisé en ce que les électrodes annulaires (31, 29) ont des ouvertures de diaphragme (32', 32) et
    en ce que l'ouverture de diaphragme (32') de l'électrode annulaire (31) la plus proche de l'ouverture d'entrée (25) est plus grande que celle des autres électrodes annulaires (29).
  3. Réflecteur selon la revendication 1 ou 2, caractérisé en ce que l'électrode écran (41) est configurée annulaire avec une ouverture (42) et s'étend dans un plan qui est perpendiculaire à l'axe longitudinal (21) du réflecteur (9).
  4. Réflecteur selon la revendication 3, caractérisé en ce que l'ouverture de passage (42) de l'électrode écran (41) est plus petite ou égale à l'ouverture de diaphragme (32') de l'électrode annulaire (31) qui est la plus proche de l'ouverture d'entrée (25).
  5. Réflecteur selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la distance entre l'électrode écran (41) et l'électrode annulaire (31) se trouvant le plus près de l'ouverture d'entrée (25) est réglable.
  6. Réflecteur selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'un support (27) est prévu, qui entoure l'ouverture d'entrée (25) et
    en ce que l'électrode écran (41) est montée sur le support (27).
  7. Réflecteur selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le potentiel de l'électrode annulaire (31) la plus proche de l'ouverture d'entrée (25) est compris entre -1 kilovolt et -4 kilovolts.
  8. Spectromètre de masse à temps de vol avec une source d'ions (13) pour l'ionisation d'atomes et/ou de molécules,
    avec une disposition d'électrodes (14, 15) pour accélérer des atomes et/ou des molécules ionisés dans une première direction (17) à l'aide de champs électriques,
    avec un réflecteur électrostatique (9) selon l'une quelconque des revendications 1 à 7 pour la réflexion des atomes et/ou des molécules ionisés se déplaçant le long de la première direction (17) dans une deuxième direction (57),
    le réflecteur (9) étant disposé de telle sorte que l'axe longitudinal (21) du réflecteur (9) forme la bissectrice entre la première et la deuxième direction (17, 57) et
    avec un détecteur (55) disposé le long de la deuxième direction (57) pour la détection des atomes et/ou des molécules ionisés.
EP10152072A 2010-01-29 2010-01-29 Reflecteur pour un spectromètre de masse à temps de vol Active EP2355129B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP10152072A EP2355129B1 (fr) 2010-01-29 2010-01-29 Reflecteur pour un spectromètre de masse à temps de vol
US13/011,038 US8314381B2 (en) 2010-01-29 2011-01-21 Reflector for a time-of-flight mass spectrometer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10152072A EP2355129B1 (fr) 2010-01-29 2010-01-29 Reflecteur pour un spectromètre de masse à temps de vol

Publications (2)

Publication Number Publication Date
EP2355129A1 EP2355129A1 (fr) 2011-08-10
EP2355129B1 true EP2355129B1 (fr) 2013-01-09

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EP10152072A Active EP2355129B1 (fr) 2010-01-29 2010-01-29 Reflecteur pour un spectromètre de masse à temps de vol

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EP (1) EP2355129B1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9490114B2 (en) * 2012-10-10 2016-11-08 Shimadzu Corporation Time-of-flight mass spectrometer
DE102014009900B4 (de) * 2014-07-03 2016-11-17 Bruker Daltonik Gmbh Reflektoren für Flugzeitmassenspektrometer
GB2533608B (en) * 2014-12-23 2019-08-28 Kratos Analytical Ltd A time of flight mass spectrometer
WO2019220554A1 (fr) * 2018-05-16 2019-11-21 株式会社島津製作所 Spectromètre de masse à temps de vol

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3524536A1 (de) * 1985-07-10 1987-01-22 Bruker Analytische Messtechnik Flugzeit-massenspektrometer mit einem ionenreflektor
DE3842044A1 (de) * 1988-12-14 1990-06-21 Forschungszentrum Juelich Gmbh Flugzeit(massen)spektrometer mit hoher aufloesung und transmission
US5017780A (en) 1989-09-20 1991-05-21 Roland Kutscher Ion reflector
US6924480B2 (en) * 2002-02-26 2005-08-02 The Regents Of The University Of California Apparatus and method for using a volume conductive electrode with ion optical elements for a time-of-flight mass spectrometer
GB2455977A (en) * 2007-12-21 2009-07-01 Thermo Fisher Scient Multi-reflectron time-of-flight mass spectrometer

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EP2355129A1 (fr) 2011-08-10
US8314381B2 (en) 2012-11-20
US20110186730A1 (en) 2011-08-04

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