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WO2001011660A1 - Spectrometre de masse a temps de vol comportant un accelerateur orthogonal - Google Patents

Spectrometre de masse a temps de vol comportant un accelerateur orthogonal Download PDF

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Publication number
WO2001011660A1
WO2001011660A1 PCT/AU2000/000922 AU0000922W WO0111660A1 WO 2001011660 A1 WO2001011660 A1 WO 2001011660A1 AU 0000922 W AU0000922 W AU 0000922W WO 0111660 A1 WO0111660 A1 WO 0111660A1
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WO
WIPO (PCT)
Prior art keywords
electrode
ions
ion
electrodes
slot
Prior art date
Application number
PCT/AU2000/000922
Other languages
English (en)
Inventor
Alexander A. Makarov
Original Assignee
Gbc Scientific Equipment Pty 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 Gbc Scientific Equipment Pty Ltd filed Critical Gbc Scientific Equipment Pty Ltd
Priority to AU61411/00A priority Critical patent/AU6141100A/en
Publication of WO2001011660A1 publication Critical patent/WO2001011660A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/40—Time-of-flight spectrometers
    • H01J49/401—Time-of-flight spectrometers characterised by orthogonal acceleration, e.g. focusing or selecting the ions, pusher electrode

Definitions

  • This invention relates to a time of flight mass spectrometer including an orthogonal accelerator.
  • Time of flight mass spectrometers generally include an ion source for producing a continuous or pulsed beam of ions which are directed in a first direction.
  • the ions generally pass through various electric focusing optics so as to collimate the beam and to direct the beam to an orthogonal accelerator.
  • the orthogonal accelerator pushes ions in the ion beam out of the beam in a direction transverse to the first direction into a flight tube so that the ions travel along the tube and eventually arrive at a detector.
  • the time taken to travel along the tube and arrive at the detector is dependant on the mass of the ions and therefore the detection of ions at different time intervals can provide an indication of the mass of the ions in the ion beam and therefore the material in the sample substance which is being analysed and from which the ion beam is formed.
  • Conventional orthogonal accelerators generally comprise a number of electrodes at least some of which are in the nature of grids. Electric potentials are applied to the various electrodes so as to force the ions to travel in the direction transverse to the first direction.
  • the grid electrodes enables some of the ions to pass through the grid and therefore into the tube for detection at the detector.
  • the grids in conventional orthogonal accelerators produce a number of disadvantages including the fact that the grids become covered by deposits and may start charging up thus reducing mass peak stability, grids reduce sensitivity by absorbing part of the beam and scattering transmitted ions, and grids are difficult to mount reproducably.
  • the present inventor has found that the main problem which grids cause is associated with the grid closest to the ion beam which enters the orthogonal accelerator. Ions have the lowest energy during accumulation in the acceleration stage and therefore even small voltages induced by charge contamination is enough to ruin the integrity of the beam entering the orthogonal accelerator. This charge contamination can result in an angular divergence of ions out of the beam as the beam enters into the orthogonal accelerator. The angular divergence induced by contamination results in greatly increased time of flight and geometrical aberrations which reduces a resolution of the spectrometer. The influence of deposits on further grids is orders of magnitude lower as those grids are shielded by the first grid and also ions possess much higher energies when they finally pass through those grids during the extraction process from the orthogonal accelerator.
  • the present invention may be said to reside in a time of flight mass spectrometer including: means for producing a beam of ions and for directing the beam of ions in a first direction; an orthogonal accelerator for receiving the beam of ions and for accelerating ions in the beam in a direction transverse to the first direction into a time of flight cavity; a detector for detecting the ions after travel from the orthogonal accelerator through the time of flight cavity; and wherein said orthogonal accelerator has; a plurality of electrodes for receiving electric potentials, and for extracting ions in a direction transverse to the first direction, one of the electrodes being the first electrode through which ions are transported during extraction of the ions in the transverse direction by the orthogonal accelerator; and wherein the first electrode is a gridless electrode including a slot which is elongated in the said first direction.
  • the orthogonal accelerator can operate in two modes.
  • the first of the two modes being an accumulation mode, in which inevitable stray and scattered ions are prevented from bleeding into the time of flight cavity by the field between the first electrode and another of the pluralities of electrodes while the beam stays far enough from the first electrode not to be perturbed by the electric field created by the first electrode; and the second mode being an extraction mode when fields on both sides of the first electrode change in such a way that the difference in field gradients is not high enough to introduce noticeable time of flight aberrations and angular scattering.
  • the width of the slot in the first electrode does not exceed the largest distance from the slot to any ion within the ion beam during the accumulation mode when ions are accumulated in the orthogonal accelerator prior to extraction in the transverse direction.
  • said first electrode forms together with further electrodes of the plurality of electrodes, a retarding field during the ion accumulation mode, and an extraction field during the ion extraction mode in such a way that minimum size of an ion packet of a given mass to charge ratio both in space and time of flight is achieved at the detector.
  • the orthogonal accelerator comprises; a flat back plate electrode; a thin plate electrode which forms said first electrode, the flat back plate electrode and the thin plate electrode defining a space for receiving the ion beam which is directed in the first direction; a thin-plate second electrode having a slot parallel to the slot in the first electrode; a third electrode with a slot parallel to the slot in the first electrode; and wherein electric potentials on all electrodes are variable independently, so that during the accumulation mode the voltage between the first and second electrodes is retarding for ions and during the extraction mode all voltages are changed in such a way that an extraction field is formed for accelerating the ions in the transverse direction.
  • the widths of the slots in the first and second electrodes are equal, and the gap between the back plate electrode and the first electrode is equal to the gap between the second and third electrodes, and the gap between the first and second electrodes being three times smaller than the gap between the thin plate second and third electrodes and two times bigger than the width of the slots in the first and second electrodes.
  • the time of flight spectrometer includes ion gating means, a reflectron and a lens, and wherein; voltages applied during the extraction mode are chosen in such a way that non uniform electric fields provides both spacial and first or second order time of flight focusing exactly in the plane of the ion gating means; the lens is elongated along the first direction and has voltages applied to it in such a way that minimum spacial size of ion packets is achieved at the detector; and voltages on the reflectron are adjusted in such a way that minimum time of flights spread of ion packets is achieved at the detector.
  • the ion beam in the first direction is directed into the space between the back plate electrode and the first electrode a minimum distance from the back plate electrode.
  • Figure 1 is a schematic diagram of a time of flight mass spectrometer
  • Figure 2 is a schematic diagram showing the orthogonal accelerator according to the preferred embodiment of the invention.
  • Figures 3 and 4 are graph showing the application of electric potentials during the accumulation mode and extraction mode respectively for the embodiments shown in Figure 2;
  • Figure 5 is a view of a second embodiment of the invention.
  • Figure 6 and Figure 7 are graphs showing a graph of electric potential during an accumulation mode and extraction mode applicable to the embodiment shown in Figure 5;
  • Figure 8 is a schematic perspective view of the orthogonal accelerator.
  • time of flight mass spectrometers are well known and therefore the schematic representation shown in Figure 1 is merely to provide a basic outline of the position of the orthogonal accelerator in the time of flight spectrometer.
  • the spectrometer generally comprises an ion source 10 which may be an inductively coupled plasma ion source, an electro spray or the like.
  • Generally focusing optics and beam creating optics 12 are provided for focusing and directing an ion beam 14 from the source 10 in a first direction x.
  • An orthogonal accelerator 20 is provided for accelerating the ion packets from the beam in a second direction y transverse to the direction x into a time of pulse tube or cavity.
  • the ion packets accelerated from the orthogonal accelerator 20 may be received directly by a detector 22 or, as in the case of Figure 1, a reflection 24 may be provided for turning the ion packets 16 before they arrives at the detector 22.
  • An ion gate 17 is disposed in the path of the ions for selectively filtering unwanted ions and a lens 18 is provided for focusing of the ions 16.
  • the orthogonal accelerator 20 most preferably comprises a flat back electrode 30 which is held at a static potential TJO .
  • a first electrode 32 forms a compensation electrode which is approximately 0.2 mm thick and which is spaced from the back electrode 30 by a distance of about 6 mm.
  • a potential Ul is applied to the electrode 32.
  • a second electrode 34 forms a pull out and electrode is spaced from the electrode
  • the electrodes 32, 34 and 36 are gridless solid plate electrodes which have a slot 38, 40 and 42 respectively which is elongated in the direction of the beam 14 (i.e. direction x) from the ion source 10.
  • the slot 38 has a width w (see Figure 8) of about 4 mm, and the slot 40 has a width of Wi of about 3 mm.
  • the exit electrode 36 is also preferably gridless and has slot 42 which is also elongated in the direction of the ion beam 14.
  • the width W 2 of the slot 42 is about 3 mm.
  • (U2-U1) is > (U0-U3)/100, so that virtually no fieled is experienced by ions moving near the back electrode 30, while ions penetrating through the slot 38 of the compensation electrode 32 experience a retarding field. This field stops ions bleeding into the time of flight tube or cavity 23 thus drastically reducing ion background.
  • a positive pulse Pi is applied to the back electrode 30 and a negative pulse of amplitude P2 is applied to the pull out electrode 34 less than 20 ns later.
  • the electrode 32 provides as low as possible electric fields in the region of ion beam 14 during accumulation, absorbs some scattered ions and also serves as a filed- sustaining and focusing electrode during ion extraction.
  • a second embodiment is shown in Figures 5 to 7 in which the only difference to that described with reference to Figure 2 is a grid as attached to the pull out electrode 34 and thus the arrangement shown in Figure 5 may be regarded as inferior to that shown in Figure 2.
  • the arrangement shown in Figure 5 allows the use of lower static voltages (U2-U1) > (U0-U3) /300 and allows easier tuning. In all modes and constructions, potential Ul is variable; I U1-U0 I >0.001x(U0-U3) .
  • the acceleration stage of the orthogonal accelerator in both Figures 1 and Figure 2 may also be combined with ion gating (eg. flat deflection plates activated by short electric pulses) at the plane of the time of flight focusing.
  • potentials PI, P2 and Ul could be tuned to provide simultaneous second- order focusing on the time of flight as well as spacial focusing.
  • the later allows to improve mass resolution of the ion gating means .
  • the deflection of the ion beam during the accumulation mode is minimised by choosing the width of the slot in the compensation electrode 32 small compared to the distance from the slot 2 ions in the beam 14.
  • this slot 38 should be big enough to allow all ions of the beam to pass through during the subsequent extraction mode. It has been found experimentally that in such a construction contamination from the ion beam is absorbed mainly by electrodes downstream of the compensation electrode 32 and therefore influences of contamination on the ion beam is greatly reduced.
  • Electrodes 30, 32, 34 and 36 are formed from non-magnetic stainless steel.
  • the speedometer may include ion trapping or collisional cooling or additional focusing/deflecting ion optics before the orthogonal accelerator.
  • the slots in the electrodes 32, 34 and 36 could be formed by electroetching, electroforming or laser cutting
  • a slotted plated electrode is located between the first electrode 32 and the back electrode 30 to assist in confining the electric fields produced by the electrodes 32, 34 and 36.
  • This plate electrode does not play any part in the ion beam formation and is usually at the potential of the back plate electrode 30 or another electrode to which it is connected.
  • first interfaces may be utilised between the ion source and the orthogonal accelerator 20 including collisional cooling or chemical reactions in RF multipoles at elevated pressures, MS-MS stages and additional ionoptics. More than one reflectron or additional lenses may also be utilised within the time of flight cavity 23.
  • the orthogonal accelerator 20 could omit the electrode 36 (and therefore be a two- stage orthogonal accelerator, or electrode 32 may be pulsed (e.g. instead of the electrode 34) .
  • Ion sources include the ICP electrode as described, or ES, APCI, EI-CI-MALDI sources.

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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 spectromètre de masse à temps de vol comprenant une source (10) d'ions, un accélérateur (20) orthogonal, un réflectron (24) et un détecteur (22). L'accélérateur (20) orthogonal possède une première électrode (32) qui est une électrode sans grille et qui comprend une fente allongée dans la direction d'un faisceau d'ions fourni à l'accélérateur orthogonal par la source (10). L'accélérateur (20) orthogonal possède une deuxième électrode à plaque mince dotée d'une fente parallèle à la fente de la première électrode, et une troisième électrode dotée d'une fente parallèle à la fente dans la première électrode. Les électrodes créent un champ retardateur en mode d'accumulation d'ions et un champ d'extraction en mode d'extraction d'ions.
PCT/AU2000/000922 1999-08-10 2000-08-04 Spectrometre de masse a temps de vol comportant un accelerateur orthogonal WO2001011660A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61411/00A AU6141100A (en) 1999-08-10 2000-08-04 A time of flight mass spectrometer including an orthogonal accelerator

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPQ2131A AUPQ213199A0 (en) 1999-08-10 1999-08-10 A time of flight mass spectrometer including an orthogonal accelerator
AUPQ2131 1999-08-10

Publications (1)

Publication Number Publication Date
WO2001011660A1 true WO2001011660A1 (fr) 2001-02-15

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Country Status (2)

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AU (1) AUPQ213199A0 (fr)
WO (1) WO2001011660A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10158924A1 (de) * 2001-11-30 2003-06-12 Bruker Daltonik Gmbh Pulser für Flugzeitmassenspektrometer mit orthogonalem Ioneneinschuss
WO2004047141A3 (fr) * 2002-11-20 2004-07-29 Amersham Biosciences Ab Reflectron
GB2402262A (en) * 2003-05-02 2004-12-01 Micromass Ltd Mass Spectrometer
US7157698B2 (en) 2003-03-19 2007-01-02 Thermo Finnigan, Llc Obtaining tandem mass spectrometry data for multiple parent ions in an ion population
DE10005698B4 (de) * 2000-02-09 2007-03-01 Bruker Daltonik Gmbh Gitterloses Reflektor-Flugzeitmassenspektrometer für orthogonalen Ioneneinschuss
DE102004049918B4 (de) * 2003-10-14 2010-11-25 Micromass Uk Ltd. Verfahren zur Massenspektrometrie
WO2012175517A2 (fr) 2011-06-23 2012-12-27 Thermo Fisher Scientific (Bremen) Gmbh Analyse ciblée pour une spectrométrie de masse tandem
WO2013093114A2 (fr) 2011-12-22 2013-06-27 Thermo Fisher Scientific (Bremen) Gmbh Procédé de spectrométrie de masse en tandem
RU2564443C2 (ru) * 2013-11-06 2015-10-10 Общество с ограниченной ответственностью "Биотехнологические аналитические приборы" (ООО "БиАП") Устройство ортогонального ввода ионов во времяпролетный масс-спектрометр
CN105225918A (zh) * 2014-06-13 2016-01-06 中国科学院大连化学物理研究所 用于飞行时间质谱中离子束整形的静电透镜
DE102014009900A1 (de) * 2014-07-03 2016-01-07 Bruker Daltonik Gmbh Reflektoren für Flugzeitmassenspektrometer
US9373490B1 (en) 2015-06-19 2016-06-21 Shimadzu Corporation Time-of-flight mass spectrometer
DE102016008230A1 (de) 2015-07-27 2017-02-02 Thermo Fisher Scientific (Bremen) Gmbh Elementaranalyse von organischen Proben

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464985A (en) * 1993-10-01 1995-11-07 The Johns Hopkins University Non-linear field reflectron
WO1997048120A1 (fr) * 1996-06-10 1997-12-18 Hd Technologies Limited Spectrometre de masse a temps de vol

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5464985A (en) * 1993-10-01 1995-11-07 The Johns Hopkins University Non-linear field reflectron
WO1997048120A1 (fr) * 1996-06-10 1997-12-18 Hd Technologies Limited Spectrometre de masse a temps de vol

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10005698B4 (de) * 2000-02-09 2007-03-01 Bruker Daltonik Gmbh Gitterloses Reflektor-Flugzeitmassenspektrometer für orthogonalen Ioneneinschuss
US6903332B2 (en) 2001-11-30 2005-06-07 Bruker Daltonik Gmbh Pulsers for time-of-flight mass spectrometers with orthogonal ion injection
GB2386751B (en) * 2001-11-30 2005-03-23 Bruker Daltonik Gmbh Pulsers for time-of-flight mass spectrometers with orthogonal ion injection
DE10158924B4 (de) * 2001-11-30 2006-04-20 Bruker Daltonik Gmbh Pulser für Flugzeitmassenspektrometer mit orthogonalem Ioneneinschuss
GB2386751A (en) * 2001-11-30 2003-09-24 Bruker Daltonik Gmbh Pulser for a time-of-flight mass spectrometer with orthogonal ion injection
DE10158924A1 (de) * 2001-11-30 2003-06-12 Bruker Daltonik Gmbh Pulser für Flugzeitmassenspektrometer mit orthogonalem Ioneneinschuss
WO2004047141A3 (fr) * 2002-11-20 2004-07-29 Amersham Biosciences Ab Reflectron
US7312443B2 (en) 2002-11-20 2007-12-25 Ge Healthcare Bio-Sciences Ab Reflectron
DE112004000453B4 (de) 2003-03-19 2021-08-12 Thermo Finnigan Llc Erlangen von Tandem-Massenspektrometriedaten für Mehrfachstammionen in einer Ionenpopulation
US7157698B2 (en) 2003-03-19 2007-01-02 Thermo Finnigan, Llc Obtaining tandem mass spectrometry data for multiple parent ions in an ion population
GB2402262A (en) * 2003-05-02 2004-12-01 Micromass Ltd Mass Spectrometer
GB2402262B (en) * 2003-05-02 2005-03-16 Micromass Ltd Mass spectrometer
DE102004049918B4 (de) * 2003-10-14 2010-11-25 Micromass Uk Ltd. Verfahren zur Massenspektrometrie
WO2012175517A2 (fr) 2011-06-23 2012-12-27 Thermo Fisher Scientific (Bremen) Gmbh Analyse ciblée pour une spectrométrie de masse tandem
DE112012002568B4 (de) * 2011-06-23 2019-11-07 Thermo Fisher Scientific (Bremen) Gmbh Gezielte Analyse für Tandem-Massenspektrometrie
DE112012005396B4 (de) 2011-12-22 2019-03-14 Thermo Fisher Scientific (Bremen) Gmbh Verfahren zur Tandem-Massenspektrometrie und Tandem-Massenspektrometer
WO2013093114A2 (fr) 2011-12-22 2013-06-27 Thermo Fisher Scientific (Bremen) Gmbh Procédé de spectrométrie de masse en tandem
RU2564443C2 (ru) * 2013-11-06 2015-10-10 Общество с ограниченной ответственностью "Биотехнологические аналитические приборы" (ООО "БиАП") Устройство ортогонального ввода ионов во времяпролетный масс-спектрометр
CN105225918A (zh) * 2014-06-13 2016-01-06 中国科学院大连化学物理研究所 用于飞行时间质谱中离子束整形的静电透镜
CN105225918B (zh) * 2014-06-13 2017-04-05 中国科学院大连化学物理研究所 用于飞行时间质谱中离子束整形的静电透镜
DE102014009900A1 (de) * 2014-07-03 2016-01-07 Bruker Daltonik Gmbh Reflektoren für Flugzeitmassenspektrometer
DE102014009900B4 (de) * 2014-07-03 2016-11-17 Bruker Daltonik Gmbh Reflektoren für Flugzeitmassenspektrometer
US10026601B2 (en) 2014-07-03 2018-07-17 Bruker Daltonik Gmbh Reflectors for time-of-flight mass spectrometers having plates with symmetric shielding edges
US9373490B1 (en) 2015-06-19 2016-06-21 Shimadzu Corporation Time-of-flight mass spectrometer
DE102016008230A1 (de) 2015-07-27 2017-02-02 Thermo Fisher Scientific (Bremen) Gmbh Elementaranalyse von organischen Proben
DE102016008230B4 (de) 2015-07-27 2024-05-08 Thermo Fisher Scientific (Bremen) Gmbh Elementaranalyse von organischen Proben

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