WO2015019460A1 - Spectromètre de masse à temps de vol - Google Patents

Spectromètre de masse à temps de vol Download PDF

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Publication number
WO2015019460A1
WO2015019460A1 PCT/JP2013/071465 JP2013071465W WO2015019460A1 WO 2015019460 A1 WO2015019460 A1 WO 2015019460A1 JP 2013071465 W JP2013071465 W JP 2013071465W WO 2015019460 A1 WO2015019460 A1 WO 2015019460A1
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WIPO (PCT)
Prior art keywords
ions
ion
deflection
unit
incident
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PCT/JP2013/071465
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English (en)
Japanese (ja)
Inventor
大輔 奥村
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株式会社島津製作所
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Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to JP2015530617A priority Critical patent/JP6044715B2/ja
Priority to PCT/JP2013/071465 priority patent/WO2015019460A1/fr
Publication of WO2015019460A1 publication Critical patent/WO2015019460A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/061—Ion deflecting means, e.g. ion gates
    • 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

  • the present invention relates to a time-of-flight mass spectrometer (Time-of-Flight Mass Spectrometer, hereinafter referred to as “TOFMS”), and more particularly to an orthogonal acceleration type TOFMS.
  • TOFMS Time-of-Flight Mass Spectrometer
  • an incident beam limiting mechanism composed of two or more slits arranged separated by a predetermined distance. Is used.
  • FIG. 5 is a schematic configuration diagram in the vicinity of the orthogonal acceleration unit of the orthogonal acceleration type TOFMS using such an incident beam limiting mechanism (see Non-Patent Document 1 and the like).
  • the orthogonal acceleration unit 4 includes a flat plate electrode 41 and a mesh electrode 42 in which a large number of openings through which ions can pass are formed.
  • An incident beam limiting mechanism 300 including two slit plates 301 and 302 arranged in parallel is arranged.
  • the initial beam direction of the ion beam incident on the acceleration region sandwiched between the plate electrode 41 and the mesh electrode 42 is the X-axis direction
  • the acceleration direction, that is, the time-of-flight analysis direction is the Z-axis orthogonal to the X-axis.
  • the electrodes 41 and 42 are at the same potential (for example, ground potential), and there is no electric field in the acceleration region.
  • a high voltage pulse having the same polarity as the ions is applied to the plate electrode 41 when a sufficient amount of ions are incident, an accelerating electric field is formed in the acceleration region, and the ions are given large kinetic energy, and the mesh electrode The flight starts through 42 openings.
  • E and ⁇ are the energy of the ion beam incident on the acceleration region and the angle formed with the X axis.
  • the greater the initial energy Ez the longer the flight time due to the turnaround time (the time it takes for an ion having a velocity component in the direction opposite to the time-of-flight analysis direction to start and return to the starting point).
  • the spread increases.
  • the incident beam limiting mechanism 300 is for limiting the angle ⁇ to be small. In the configuration shown in FIG.
  • the beam angle spread ⁇ with respect to the interval L between the two slit plates 301 and 302 and the opening width H of the slit plate 302. Is given by tan -1 (H / L). Therefore, by appropriately setting the distance L and the opening width H, the angle ⁇ of the ion beam can be suppressed, and variations in the initial energy of ions can be within an allowable range.
  • Non-Patent Document 1 an ion lens is arranged in a space between two slit plates, and the ion converging action by the ion lens is used, so that the ion transmittance is inferior, so the sensitivity is so high.
  • the difference in sensitivity between the high-sensitivity mode and the high-resolution mode is not so large, and the ion transmittance in the high-sensitivity mode is 1. It is only about 5 to 2 times.
  • the high-resolution mode is used for qualitative analysis, and the high-sensitivity mode is used for quantitative analysis.
  • the sensitivity difference is this level, for example, the content is very small, so it cannot be sufficiently observed in the high-resolution mode. Even if the component is observed by switching to the high sensitivity mode, it often happens that the component cannot be observed with sufficient sensitivity.
  • the present invention has been made to solve the above-described problems, and is an orthogonal acceleration method that can switch between a high-resolution mode that emphasizes mass resolution and a high-sensitivity mode that emphasizes measurement sensitivity in accordance with the purpose of analysis and the like.
  • the purpose of the time-of-flight mass spectrometer is to perform analysis with sufficiently high sensitivity and analysis with sufficiently high mass resolution.
  • the present invention made to solve the above problems comprises an orthogonal acceleration unit that accelerates incident ions in a direction orthogonal to the incident axis, and an ion optical system that sends ions to the orthogonal acceleration unit.
  • An orthogonal acceleration time-of-flight mass spectrometer The ion optical system is a) an incident beam restricting portion in which a plurality of slits for restricting the width of the ion beam in the acceleration direction in the orthogonal acceleration portion are provided in the acceleration direction, the two or more being arranged at predetermined intervals in the ion optical axis direction; b) Ions that are disposed between two adjacent incident beam restricting portions of the two or more incident beam restricting portions, and have passed through at least one of a plurality of slits provided in the incident beam restricting portion in the preceding stage.
  • a beam deflecting unit that deflects the ion beam so that the beam does not reach the slit provided in the incident beam regulating unit in the subsequent stage;
  • the ion beam when the ion beam is not deflected by the beam deflecting unit, for example, the same as the conventional incident beam restricting mechanism using a plurality of slit plates as shown in FIG.
  • an ion beam whose parallelism is increased by a plurality of incident beam restricting units arranged apart from each other in the ion optical axis direction is emitted from the ion optical system and introduced into the orthogonal acceleration unit.
  • the beam cross-sectional area (beam diameter) is large and the amount of ions is large. That is, since a large amount of ions are subjected to mass spectrometry, the measurement sensitivity is increased.
  • the ion beam that has passed through at least one of the plurality of slits provided in the preceding incident beam restricting unit passes through the slit provided in the subsequent incident beam restricting unit. Cannot pass.
  • the beam cross-sectional area is reduced accordingly. That is, since the width of the ion beam in the acceleration direction is narrowed, variations in the initial position of ions during acceleration are suppressed, and the spread of the flight time of the same ion species is suppressed, so that mass resolution is improved.
  • the time-of-flight mass spectrometer it is possible to switch between high-sensitivity measurement and high-resolution measurement depending on the presence or absence of deflection by the beam deflection unit.
  • a plurality of slits are provided, and all of these slits are used for high-sensitivity measurement, and part of the slits are not substantially used (no ions are allowed to pass) for high-resolution measurement. This amount can be changed greatly, and a sufficient sensitivity difference can be secured.
  • the beam deflection unit includes a deflection electrode disposed between two incident beam regulating units, and a deflection voltage generation unit that applies a deflection voltage to the deflection electrode. It is good to do.
  • the high resolution mode that prioritizes mass resolution and the high sensitivity mode that prioritizes sensitivity can be switched.
  • a deflection voltage is applied to the deflection electrode
  • time-of-flight mass spectrometer for example, when performing high-sensitivity measurement with an emphasis on measurement sensitivity, such as quantitative analysis of trace components, although the mass resolution is low, high-resolution measurement with an emphasis on mass resolution. Measurement can be performed with sufficiently high sensitivity.
  • high-sensitivity measurement with an emphasis on mass resolution such as qualitative analysis of components with a relatively high content
  • the sensitivity is low, but the measurement should be performed with sufficiently high mass resolution compared to high-sensitivity measurement.
  • it is possible to clearly switch the measurement with emphasis on sensitivity or mass resolution it is possible to obtain an accurate result according to the analysis purpose.
  • FIG. 1 is an overall configuration diagram of an orthogonal acceleration TOFMS that is an embodiment of the present invention.
  • FIG. The schematic block diagram of the ion optical system for beam shape adjustments in FIG.
  • the schematic perspective view of the ion incident part of the ion optical system for beam shape adjustments in FIG. The figure which shows the result of having simulated the ion orbit in the ion optical system for beam shape adjustments in FIG.
  • FIG. 1 is an overall configuration diagram of the orthogonal acceleration type TOFMS of the present embodiment.
  • FIG. 1 the same components as those already described with reference to FIG.
  • the orthogonal acceleration type TOFMS of this embodiment includes an ion source 1 that ionizes a target sample, a TOF analyzer 5 that includes a reflector 51, an orthogonal acceleration unit 4 that accelerates ions and sends them to the TOF analyzer 5, and an ion source.
  • a deflection voltage generator 12 that applies a predetermined voltage to the electrodes included in the ion optical system 3, and an orthogonal acceleration power supply unit 1 that applies a predetermined voltage to the electrodes 41 and 42 included in the orthogonal acceleration unit 4.
  • control unit 10 When provided with reflectors power unit 14 for applying a predetermined voltage to the reflector 51, a control unit 10 which controls the operation of each unit, and the analysis condition input unit 15 for a user to specify, the.
  • the control unit 10 includes an analysis mode switching unit 11 as a functional block.
  • the ionization method in the ion source 1 is not particularly limited.
  • an atmospheric pressure ionization method such as an electrospray ionization (ESI) method or an atmospheric pressure chemical ionization (APCI) method is used.
  • ESI electrospray ionization
  • APCI atmospheric pressure chemical ionization
  • MALDI matrix-assisted laser desorption ionization
  • the basic analysis operation in the orthogonal acceleration type TOFMS of the present embodiment is as follows. For example, various ions generated in the ion source 1 by the ESI method are introduced into the ion optical system 3 for beam shape adjustment through the ion guide 2 and introduced into the orthogonal acceleration unit 4 in the X-axis direction through the ion optical system 3 for beam shape adjustment. Is done.
  • an acceleration electric field is not formed in the orthogonal acceleration unit 4
  • the orthogonal acceleration power supply unit An accelerating electric field is formed by applying a predetermined voltage from 13 to the plate electrode 41 and the mesh electrode 42. Ions are given kinetic energy in the Z-axis direction by the action of this acceleration electric field, and are sent into the flight space of the TOF analyzer 5.
  • ions that have started flying from the acceleration region of the orthogonal acceleration unit 4 are folded back by an electric field formed by a voltage applied from the reflector power supply unit 14 to the reflector 51. Automatically reaches the detector 6.
  • the detector 6 sequentially generates a detection signal corresponding to the amount of ions that have reached with time.
  • the data processing unit 16 obtains a time-of-flight spectrum from this detection signal, and further obtains a mass spectrum by converting the flight time to a mass-to-charge ratio m / z.
  • FIG. 2 is a schematic configuration diagram of a beam shape adjusting ion optical system 3 disposed between the ion guide 2 and the orthogonal acceleration unit 4.
  • FIG. 2A schematically shows an ion trajectory in the high sensitivity mode
  • FIG. 2B schematically shows an ion trajectory in the high resolution mode.
  • FIG. 3 is a schematic perspective view of an ion incident portion of the ion optical system 3 for beam shape adjustment. The right side of the ion incident portion is shown by a cross section cut along a plane including the X axis and the Z axis.
  • the ion optical system 3 for beam shape adjustment includes two slit plates 31 and 32 arranged in parallel with being separated from each other by a predetermined distance in the X-axis direction which is the ion optical axis direction.
  • the slit plate 31 at the front stage has three slit openings 31a, 31b, 31c that are narrow in the Z-axis direction, which is the acceleration direction of ions in the orthogonal acceleration unit 4, and extend in the Y-axis direction orthogonal to the Z-axis. Are provided along the Z-axis direction.
  • the slit plate 32 at the rear stage is provided with three slit openings 32a, 32b, and 32c along the Z-axis direction.
  • a flat electrode 35 is disposed behind the upper edge of the slit opening 31a of the front slit plate 31 so as to face each other across the partition wall 33, and the lower edge of the slit opening 31c of the front slit plate 31 is also provided.
  • a flat plate electrode 36 is arranged behind the unit so as to face each other with the partition wall 34 interposed therebetween.
  • the partition wall 33 and the electrode 35 constitute a pair of deflection electrodes
  • the partition wall 34 and the electrode 36 constitute another pair of deflection electrodes.
  • the partition wall 33 and the partition wall 34 are grounded, and a predetermined DC deflection voltage is applied to the electrode 35 and the electrode 36 from the deflection voltage generator 12.
  • a high sensitivity mode and a high resolution mode are prepared as analysis modes.
  • measurement in any analysis mode is possible by an instruction from the analyst via the input unit 15. ing.
  • the analysis mode switching unit 11 instructs the deflection voltage generation unit 12 in the analysis mode.
  • the deflection voltage generation unit 12 does not generate the deflection voltage, and in the high resolution mode, the deflection voltage.
  • the generator 12 generates a predetermined deflection voltage.
  • the ion beam introduced into the orthogonal acceleration unit 4 is wide in the Z-axis direction. For this reason, the initial position variation when ions are accelerated by the orthogonal acceleration unit 4 is large, and this causes a decrease in the mass resolution. Therefore, the mass resolution is not so high.
  • the amount of ions blocked by the ion optical system 3 for adjusting the beam shape is small, and a larger amount of ions are introduced into the orthogonal acceleration unit 4 and used for mass analysis, so that high sensitivity can be realized.
  • a deflection voltage is applied to the two pairs of deflection electrodes, and a deflection electric field is formed between the partition wall 33 and the electrode 35 and between the partition wall 34 and the electrode 36, respectively.
  • ions that have reached the slit openings 31a to 31c on the surface of the previous slit plate 31 Passes through the slit openings 31a to 31c.
  • the ions that have passed through the slit opening 31b travel straight without being influenced by the deflection electric field, and pass through the slit opening 32b of the slit plate 32 at the subsequent stage and exit.
  • the ions that have passed through the upper and lower slit openings 31a and 31c receive a force in the Z-axis direction due to the deflection electric field immediately after that, and bend their trajectories as shown in FIG. As a result, the ions do not reach the slit openings 32a and 32c of the subsequent slit plate 32, and ions are not emitted from the slit openings 32a and 32c.
  • the ion beam introduced into the orthogonal acceleration unit 4 is narrow in the Z-axis direction. For this reason, variations in the initial position when ions are accelerated by the orthogonal acceleration unit 4 are reduced, and high mass resolution can be achieved.
  • the amount of ions blocked by the ion optical system 3 for beam shape adjustment is large, the amount of ions introduced into the orthogonal acceleration unit 4 and used for mass analysis is small, and the sensitivity is low.
  • FIG. 4 is a diagram showing a result of simulating ion trajectories in the ion optical system 3 for beam shape adjustment.
  • FIG. 4B in the high resolution mode, it can be confirmed that some orbits of ions that have passed through the front slit plate 31 are greatly bent and blocked by the rear slit plate 32.
  • the ion transmittance in each analysis mode is calculated, the ion transmittance in the high sensitivity mode is about 3.4 times that in the high resolution mode. This becomes a difference in sensitivity almost as it is. From this, it can be confirmed that the orthogonal acceleration method TOFMS of the present embodiment can sufficiently increase the sensitivity difference between the high sensitivity mode and the high resolution mode as compared with the case of using the conventional ion optical system for beam shape adjustment. It was.
  • the above embodiment is an example of the present invention, and it is obvious that any changes, modifications, additions, etc. within the scope of the present invention are included in the claims of the present application.
  • the number of slit plates, the number of slit openings formed in one slit plate, or the shape of the slit openings can be determined as appropriate.
  • the position and shape of the deflection electrode can be appropriately changed. It is also possible to deflect ions by a magnetic field instead of a deflection electric field.

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

Abstract

Selon la présente invention, un système optique de mise en forme de faisceau d'ions (3) envoyant des ions à une unité d'accélération orthogonale est pourvu de plaques à fentes (31, 32) présentant une pluralité d'ouvertures fendues (31a à 31c, 32a à 32c) dont la largeur est étroite dans la direction d'accélération (direction de l'axe Z) de l'unité d'accélération orthogonale, et, disposées dans l'étage suivant la plaque à fentes (31), d'une électrode de déviation comportant une partie paroi de séparation (33) et une électrode (35), et d'une électrode de déviation comportant une partie paroi de séparation (34) et une électrode (36). Dans un mode haute sensibilité, aucune tension n'est appliquée aux électrodes de déviation, et des ions passant par les ouvertures fendues (31a, 32a) et les ouvertures fendues (31c, 32c) sont émis. Bien qu'un écartement ionique dans la direction de l'axe Z devienne important, réduisant le pouvoir de résolution en masse, ceci permet une mesure à haute sensibilité par fourniture d'une grande quantité d'ions pour une spectrométrie de masse. Dans un mode haute résolution, une tension est appliquée aux électrodes de déviation et des ions passant par les ouvertures fendues (31a, 31c) sont déviés et bloqués. Bien que la sensibilité diminue, ceci permet d'atteindre un haut pouvoir de résolution en masse en limitant l'étalement des ions dans la direction de l'axe Z.
PCT/JP2013/071465 2013-08-08 2013-08-08 Spectromètre de masse à temps de vol WO2015019460A1 (fr)

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JP2015530617A JP6044715B2 (ja) 2013-08-08 2013-08-08 飛行時間型質量分析装置
PCT/JP2013/071465 WO2015019460A1 (fr) 2013-08-08 2013-08-08 Spectromètre de masse à temps de vol

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115828A1 (fr) * 2016-12-22 2018-06-28 Micromass Uk Limited Commande de transmission de sortie de guide d'ions
CN109817503A (zh) * 2017-11-22 2019-05-28 住友重机械离子科技株式会社 离子注入装置及离子注入装置的控制方法
GB2588462A (en) * 2019-10-25 2021-04-28 Spacetek Tech Ag Compact time-of-flight mass analyzer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5494092A (en) * 1978-01-06 1979-07-25 Hitachi Ltd Mass analyzer
JP2004362902A (ja) * 2003-06-04 2004-12-24 Jeol Ltd 飛行時間型質量分析装置
JP2005005022A (ja) * 2003-06-10 2005-01-06 Jeol Ltd 荷電粒子線装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5494092A (en) * 1978-01-06 1979-07-25 Hitachi Ltd Mass analyzer
JP2004362902A (ja) * 2003-06-04 2004-12-24 Jeol Ltd 飛行時間型質量分析装置
JP2005005022A (ja) * 2003-06-10 2005-01-06 Jeol Ltd 荷電粒子線装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MICHAEL UGAROV ET AL.: "New Method of Ion Beam Formation for Increased Sensitivity and Performance Stability of TOF MS", ASMS CONFERENCE ON MASS SPECTROMETRY AND ALLIED TOPICS, 59TH, 2011, POSTER PRESENTATION MP 097, 2011, Retrieved from the Internet <URL:http://www.chem.agilent.com/Library/posters/Public/ASMS_2011_MP_97.pdf> *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115828A1 (fr) * 2016-12-22 2018-06-28 Micromass Uk Limited Commande de transmission de sortie de guide d'ions
GB2558221A (en) * 2016-12-22 2018-07-11 Micromass Ltd Ion mobility separation exit transmission control
CN110326084A (zh) * 2016-12-22 2019-10-11 英国质谱公司 离子导向器出口传输控制
CN110326084B (zh) * 2016-12-22 2021-10-15 英国质谱公司 离子导向器出口传输控制
US11282690B2 (en) 2016-12-22 2022-03-22 Micromass Uk Limited Ion guide exit transmission control
GB2558221B (en) * 2016-12-22 2022-07-20 Micromass Ltd Ion mobility separation exit transmission control
CN109817503A (zh) * 2017-11-22 2019-05-28 住友重机械离子科技株式会社 离子注入装置及离子注入装置的控制方法
CN109817503B (zh) * 2017-11-22 2022-07-29 住友重机械离子科技株式会社 离子注入装置及离子注入装置的控制方法
GB2588462A (en) * 2019-10-25 2021-04-28 Spacetek Tech Ag Compact time-of-flight mass analyzer

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