WO2016067373A1 - Dispositif de spectrométrie de masse - Google Patents

Dispositif de spectrométrie de masse Download PDF

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Publication number
WO2016067373A1
WO2016067373A1 PCT/JP2014/078680 JP2014078680W WO2016067373A1 WO 2016067373 A1 WO2016067373 A1 WO 2016067373A1 JP 2014078680 W JP2014078680 W JP 2014078680W WO 2016067373 A1 WO2016067373 A1 WO 2016067373A1
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WO
WIPO (PCT)
Prior art keywords
electrode
ions
ion guide
mass spectrometer
ion
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PCT/JP2014/078680
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English (en)
Japanese (ja)
Inventor
益之 杉山
橋本　雄一郎
和茂 西村
長谷川　英樹
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株式会社日立製作所
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Priority to PCT/JP2014/078680 priority Critical patent/WO2016067373A1/fr
Publication of WO2016067373A1 publication Critical patent/WO2016067373A1/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
    • 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
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons

Definitions

  • the present invention relates to a mass spectrometer.
  • Patent Document 1 discloses a multipole ion guide composed of parallel rod electrodes of multipoles (quadrupole, hexapole, octupole, etc.).
  • Patent Document 2 discloses an ion guide for holding ions by arranging a plurality of plate electrodes having circular holes through which ions pass in the center, and applying alternating reverse-phase RF voltages to these plate electrodes.
  • Patent Document 3 discloses an ion guide that holds ions by applying an RF voltage and a DC voltage between a cylindrical electrode and an internal electrode at the center of the cylindrical electrode.
  • An object of the present invention is to realize an ion guide that can separate airflow and ions and has high ion transmission efficiency.
  • Patent Documents 1 and 2 are both complicated in structure and expensive to manufacture. Further, ions are held using a pseudopotential formed by an RF voltage in a direction perpendicular to the central axis of the ion guide through which ions pass. When the pressure in the ion guide is high, the force that the ions receive from the pseudopotential is weaker than the force received from the airflow. For this reason, the methods of Patent Documents 1 and 2 cannot be separated from the air current without losing ions.
  • Patent Document 3 does not describe the operation under conditions where airflow exists. Patent Document 3 only describes a method in which ions are made incident on the potential minimum point of the ion guide and taken out from the same potential minimum point at the outlet.
  • one of the representative mass spectrometers of the present invention includes an ion source that generates ions, an ion guide that transports ions, and a mass analyzer that detects and separates the mass of ions.
  • the ion guide is composed of an electrostatic voltage acting on the first electrode and the second electrode, at least one of the first electrode and the second electrode in a direction to attract ions to the first electrode, A power supply having a distribution in which the density of the force applied to the ions between the first electrode and the second electrode is sparse to dense by applying an RF voltage in a direction away from the electrodes
  • the ion source has an inlet that introduces an airflow containing ions generated by the ion source between the first electrode and the second electrode, and the ion distribution at the outlet of the ion guide and the neutrality contained in the airflow The particle distribution is different. .
  • an ion guide capable of separating airflow and ions and having high ion transmission efficiency is realized.
  • FIG. 1 is a configuration diagram of a mass spectrometer using the present ion guide.
  • Ions generated by an ion source 14 operating at atmospheric pressure or low vacuum such as an electrospray ion source, atmospheric pressure chemical ion source, atmospheric pressure photoion source, atmospheric pressure matrix assisted laser desorption ion source, etc. Passed through and introduced into the differential exhaust section 12.
  • the differential exhaust unit 12 is provided with the ion guide of the present invention and exhausted by the pump 15.
  • the ions 100 separated from the airflow 101 by this ion guide pass through the pores 11 and are introduced into the mass analysis unit 13 exhausted by the pump 16.
  • the pressure at which this ion guide operates is about 10,000 Pa to 1E-3 Pa. In particular, at 10000 Pa to 100 Pa, since the kinetic energy of ions is cooled by collision with neutral gas molecules, ions can be converged efficiently.
  • Examples of the structure of the ion guide include an introduction port, a wire electrode 2 as a first electrode, a cylindrical electrode 1 as a second electrode, a lead electrode 4, a wire electrode terminal column 3, and an ion guide power supply 300. It is done.
  • FIG. 2A is an overall view of the ion guide
  • FIG. 2B is an axial sectional view
  • FIG. 2C is a radial apparatus sectional view.
  • the axial direction is the direction of the central axis of the wire electrode
  • the radial direction is the direction perpendicular to the central axis of the wire electrode.
  • An example of the wire electrode 2 and the cylindrical electrode 1 is a wire and a cylinder surrounding the wire electrode.
  • the present invention is applicable if the density of the force related to the charged particles has a sparse to dense distribution between the electrodes.
  • a form in which the two electrodes approximately form concentric circles is desirable.
  • an AC voltage and a DC voltage static voltage
  • the AC voltage and the DC voltage may be applied to either the wire electrode or the cylindrical electrode.
  • the wire electrode 2 is held by the wire electrode start end fulcrum 5 and the wire electrode end support column 3.
  • the shape of the wire electrode terminal column 3 may be a cylinder (FIG. 3A), a plate (FIG. 3B), or the like.
  • the width of the wire electrode terminal column is preferably 1 mm or less.
  • the wire electrode terminal column is preferably made of a conductor in order to prevent the potential of the wire electrode terminal column from fluctuating due to charge-up and losing ions.
  • a wire electrode terminal column may be formed of an insulator, and a conductor may be plated on the surface of the wire electrode terminal column to apply a voltage.
  • Fig. 4 shows the configuration of the extraction electrode 4.
  • the extraction electrode As the extraction electrode, a configuration in which a flat surface (FIG. 4 (A)) or a taper (FIG. 4 (B)) has a pore 11 at the center is conceivable.
  • the extraction electrode may serve as a vacuum partition wall with the vacuum chamber on the mass analysis unit side.
  • a DC voltage lower than the DC voltage of the wire electrode is applied to the extraction electrode in order to extract ions near the wire electrode terminal column.
  • a DC voltage higher than the DC voltage of the wire electrode is applied to the extraction electrode.
  • the introduction port 6 has a shape of a fine hole or a small tube, and introduces an air flow containing ions into the ion guide.
  • the pore diameter of the introduction port or the narrow tube is sufficiently smaller than the diameter of the cylindrical electrode of the ion trap, and is typically 1 ⁇ 4 or less.
  • the inlet may serve as the pore 10 of the vacuum partition.
  • the position of the inlet 6 and the direction of air flow introduction may be provided at a position where the distribution of ions at the outlet of the ion guide is different from the distribution of neutral molecules contained in the air flow.
  • a method of transmitting ions with this ion guide will be described.
  • an ion guide composed of a cylindrical electrode (radius: r2) and a wire electrode (radius: r1) arranged coaxially will be described.
  • a DC-grounded high-frequency voltage (amplitude Vrf, frequency: ⁇ / 2 ⁇ ) and a DC voltage (Udc) are applied to the cylindrical electrode.
  • amplitude Vrf, frequency: ⁇ / 2 ⁇ amplitude
  • Udc DC voltage
  • a high frequency voltage of several hundred kHz to 10 MHz is used as the AC voltage.
  • the potential formed between the two electrodes is given by the following equation depending on the distance r from the central axis.
  • This equation consists of two parts, the first term on the right side is the pseudopotential due to high frequency, and the second term is the potential due to static voltage.
  • the pseudopotential is a potential that applies an outward force from the central axis to the ion and does not affect the polarity of the ion.
  • the static voltage is a potential that can give the ion a force that directs the ion in the direction of the central axis.
  • Udc is positive when transmitting positive ions
  • Udc is negative when transmitting negative ions.
  • FIG. 5 also shows the potential obtained by adding both, that is, the total potential given by (Equation 3). As can be seen from this, the potential of this ion guide has a minimum value, and the position where the minimum value is given from (Equation 3) is given by Equation 4 below.
  • the polarity of Udc is determined with respect to the polarity of ions as described above.
  • FIG. 6 shows the result of simulating the ion trajectory in the ion guide as shown in FIG. 6A shows the axial direction
  • FIG. 6B shows the radial direction.
  • the simulation configuration is a cylindrical electrode (radius: 10 mm, axial length 50 mm) and wire electrode (radius: 0.1 mm).
  • the DC voltage of the wire electrode is 0V
  • the RF voltage of the cylindrical electrode is 250 V 0p , 586 kHz
  • DC voltage is 20V.
  • the pressure was 130 Pa and the flow in the wire electrode axial direction was 200 m / s.
  • Ions (m / z 600) introduced from a position offset by 0.3 to 9.9 mm in the radial direction from the central axis of the wire electrode converged to the potential minimum point in the vicinity of the wire electrode.
  • this ion guide it was found that even ions incident from a position offset in the radial direction from the wire electrode can converge to the potential minimum point near the wire electrode.
  • FIG. 7 describes the airflow introduced into the ion guide.
  • FIG. 7A shows a schematic diagram of an air flow introduced from the chamber 208 at the pressure p0 into the chamber 209 at the pressure p1 through the inlet when the introduction port is the pore 203 having a sufficiently small thickness with respect to the hole diameter.
  • the Mach disk 201 and the barrel shock 200 are formed according to the pressure difference before and after the pores, and the airflow goes straight with the same diameter as the Mach disk after the Mach disk.
  • the diameter of the Mach disk is given by:
  • the air flow direction 202 is perpendicular to the plane of the pores.
  • FIG. 7 (B) shows a schematic diagram of an air flow introduced from the chamber 208 at the pressure p0 to the chamber 209 at the pressure p1 through the inlet when the introduction port is a thin tube 204 having a sufficiently large thickness with respect to the hole diameter.
  • the introduction port is a narrow tube
  • the Mach disk 201 and the barrel shock 200 are formed in the same manner as in the case of the fine holes, and after the Mach disk, the airflow goes straight with substantially the same diameter as the Mach disk.
  • the air flow direction 202 is the direction of the thin tube central axis.
  • an air stream containing ions is introduced between the cylindrical electrode and the wire electrode, that is, from the introduction port at a position offset in the radial direction from the wire electrode on the side surface of the cylindrical electrode.
  • the ions are coaxial with the airflow. The greater the offset from the wire electrode at the inlet, the better the separation of airflow and ions, but the higher the initial energy of ions, the easier it is for ions to dissociate and lose.
  • the angle at which the airflow enters the ion guide is substantially parallel to the central axis of the wire electrode, the force of the airflow acts in the direction of transmitting ions (axial direction), and high ion transmission efficiency is obtained.
  • the separation of the air current from the ion is improved, but the force of the air current also acts in the direction away from the wire electrode.
  • the ion transmission efficiency is lower than when the airflow is incident substantially parallel to the wire electrode.
  • the ions are attracted to the vicinity of the wire electrode by the potential of Formula 3 as shown by the arrow. Since the kinetic energy of ions decreases due to collision with surrounding neutral molecules, the ions converge near the potential minimum point of Equation 4. Ions move in the vicinity of the potential minimum point in the axial direction, and are extracted from the vicinity of the wire terminal column by the voltage of the extraction electrode.
  • the “ion guide outlet” is defined as the radial plane at the end of the cylindrical electrode in the axial direction.
  • Neutral particles contained in the air stream go straight in the direction of the arrow 101 in the figure with a diameter of about Mach disk (Equation 5) from the inlet, so “neutral particles contained in the air stream” are in the direction of the air stream at the inlet. It has a distribution of about Mach disk (Formula 5) centering on the position where the extension line of the vector intersects the plane of the “exit guide exit”.
  • ions are distributed at potential minimum points around the planar wire electrode at the “exit of the ion guide”. For this reason, as shown in FIG. 2 (C), in this ion guide, the “distribution 90 of neutral particles contained in the air current” and the “ion distribution 91” do not overlap each other at the “exit of the ion guide”. Can be separated.
  • This ion guide realizes an ion guide that can separate airflow and ions and has high ion transmission efficiency.
  • the air flow and the ion distribution can be separated and only the components in the ion distribution range can be introduced into the mass spectrometer, the flow rate of the gas introduced to the mass analyzer side is reduced and the load on the vacuum pump is reduced. To do.
  • This makes it possible to use a small and inexpensive pump with a low exhaust speed. Further, neutral molecules contained in the air stream and droplets contained in the air stream are prevented from entering the ion path of the mass analysis unit, and the robustness of the apparatus is improved.
  • FIG. 8A is a configuration diagram of this embodiment
  • FIG. 8B is a cross-sectional view seen from the axial direction
  • FIG. 8C is a potential on a line indicated by an arrow in FIG. 8B.
  • An RF voltage having the same phase is applied to the first cylindrical electrode 31 and the second cylindrical electrode 32.
  • the phase of the RF voltage is shifted, the effective RF voltage is lowered at the boundary surface of the cylindrical electrode, and the pseudopotential that keeps the ions away from the wire electrode in the equation becomes shallow at the boundary surface of the cylindrical electrode, causing an ion loss.
  • the depth of the minimum point of the potential can be changed by changing the offset of the DC voltage applied to the first cylindrical electrode 31 and the second cylindrical electrode 32.
  • FIG. 8C shows the potential depth.
  • 112 is the position of the second cylindrical electrode
  • 113 is the position of the first cylindrical electrode
  • 114 is the position of the central axis of the wire electrode.
  • the potential minimum point 111 on the second cylindrical electrode side is the first cylindrical electrode as shown in FIG. It becomes lower than the minimum point 110 of the potential on the one cylindrical electrode side.
  • the ions converge near the potential minimum point on the second cylindrical electrode side among the potential minimum points around the wire.
  • ions can be converged in a narrower range than in the first embodiment.
  • the mass analyzer can introduce the ions with higher efficiency, thereby improving the sensitivity of the mass spectrometer.
  • the case where it is divided into two has been described as an example, but the same applies to the case where it is divided into three or more.
  • FIG. 9A shows a configuration diagram in the case of division into two
  • FIG. 9B shows a plot of the minimum point of the potential in the radial direction with respect to the position in the axial direction.
  • An RF voltage having the same phase is applied to the first cylindrical electrode 33 and the second cylindrical electrode 34.
  • the potential is minimized within the range surrounded by the first cylindrical electrode 33 and the range surrounded by the second cylindrical electrode 34. Differences in point depth.
  • FIG. 11 shows a configuration diagram of this embodiment.
  • a DC voltage lower than the DC voltage of the wire electrode is applied to the quadrupole ion guide in order to extract ions near the wire electrode terminal column 3.
  • a DC voltage higher than the DC voltage of the wire electrode is applied to the quadrupole ion guide.
  • the wire electrode terminal column 3 is always arranged in the gap of the quadrupole rod where the RF electric field of the quadrupole rod electrode is zero as shown in FIG. 11 (B). With this arrangement, the influence of the quadrupole ion guide on the electric field can be reduced and high ion transmittance can be obtained.
  • the wire electrode terminal column 3 may be inserted into the quadrupole rod 40.
  • diffusion of ions at the end of the wire electrode can be prevented by the pseudopotential of the quadrupole ion guide, so that the efficiency of introducing ions into the quadrupole ion guide is improved.
  • the quadrupole ion guide can focus the ions on the central axis of the ion guide, the ions are converged by the quadrupole ion guide after being separated from the air flow by the present ion guide, so that the ions are more narrowly cut than in the first embodiment. Can converge to the area.
  • FIG. 12 shows a configuration in which two ion guides are connected in the radial direction.
  • a DC voltage is applied to each wire electrode so that the potential of the first wire electrode 50 is higher than the potential of the second wire electrode 51.
  • the RF voltage may be set to the same phase.
  • the ions incident from the introduction port first converge once near the potential minimum point near the first wire electrode 50.
  • the potential minimum point around the first wire electrode is changed from the potential minimum point around the first wire electrode to the potential minimum point around the second wire electrode by the difference in the DC voltage potential between the first wire electrode and the second wire electrode.
  • the airflow traveling direction 101 After that, it moves along the potential minimum point of the second wire electrode and is drawn out by the voltage of the lead electrode in the vicinity of the terminal pillar of the second wire electrode.
  • a reflection plate or the like is provided at the tip of the airflow traveling direction 101, the airflow can be prevented from going in the ion traveling direction.
  • FIG. 13 shows a configuration in which the radius of the cylindrical electrode is different in the axial direction in a tapered shape.
  • the force works more strongly when ions are converged with a large potential gradient.
  • the ions are efficiently transferred to the potential minimum point around the wire electrode by making the airflow obliquely incident on the axis so as to pass through the vicinity of the wire in the range where the radial radius of the cylindrical electrode is small.
  • the direction of the airflow at the exit of the ion guide can be separated from the ion distribution in terms of distance.
  • the ions that pass through the ion guide are given an M / Z region that can pass through the ion guide stably depending on the values of the high-frequency voltage and the static voltage. This is derived from the condition that “the stable point of the ion given by (Equation 3) must exist between the inner and outer electrodes. Otherwise, the ion collides with the electrode”.
  • the upper limit of m / z is

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Abstract

L'invention concerne un dispositif de spectrométrie de masse caractérisé par ce qui suit: le dispositif comporte un orifice d'introduction (10) pour introduire un courant d'air provenant d'une source d'ions (14) entre une première électrode (2) et une seconde électrode (1) configurant un guide d'ions, et, au moins sur l'une de la première électrode et de la seconde électrode, une source d'alimentation électrique (300) pour appliquer une tension électrostatique agissant dans le sens dans lequel les ions sont attirés vers la première électrode et une tension RF agissant dans le sens dans lequel les ions sont envoyés à l'opposé de la première électrode de manière à amener la densité des forces exercées sur les ions à suivre une distribution allant d'éparse à dense entre la première électrode et la seconde électrode; et la distribution des ions (100) dans l'orifice de sortie du guide d'ions et la distribution des particules neutres contenues dans le courant d'air (101) introduit en provenance du guide d'ions sont différentes. Ceci permet d'obtenir un dispositif de spectrométrie de masse équipé d'un guide d'ions qui sépare un courant d'air et des ions et présente une grande efficacité de transmission des ions.
PCT/JP2014/078680 2014-10-29 2014-10-29 Dispositif de spectrométrie de masse WO2016067373A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019000699A1 (fr) * 2017-06-28 2019-01-03 中国地质科学院水文地质环境地质研究所 Nouveau spectromètre de masse isotopique chlore/brome et son procédé d'analyse
JP2019510350A (ja) * 2016-04-25 2019-04-11 株式会社島津製作所 イオン光学デバイス
EP4117018A4 (fr) * 2020-03-05 2024-04-24 Hitachi High-Tech Corporation Spectromètre de masse

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008524788A (ja) * 2004-12-17 2008-07-10 マイクロマス ユーケー リミテッド 質量分析計
JP2009266656A (ja) * 2008-04-25 2009-11-12 Agilent Technol Inc プラズマイオン源質量分析装置
JP2010157499A (ja) * 2008-12-03 2010-07-15 Shimadzu Corp イオン輸送装置、イオン分析装置、及び、超音速分子ジェット法を用いた分析装置
JP2011108569A (ja) * 2009-11-20 2011-06-02 Shimadzu Corp 質量分析装置
WO2012081122A1 (fr) * 2010-12-17 2012-06-21 株式会社島津製作所 Guide d'ions et spectromètre de masse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008524788A (ja) * 2004-12-17 2008-07-10 マイクロマス ユーケー リミテッド 質量分析計
JP2009266656A (ja) * 2008-04-25 2009-11-12 Agilent Technol Inc プラズマイオン源質量分析装置
JP2010157499A (ja) * 2008-12-03 2010-07-15 Shimadzu Corp イオン輸送装置、イオン分析装置、及び、超音速分子ジェット法を用いた分析装置
JP2011108569A (ja) * 2009-11-20 2011-06-02 Shimadzu Corp 質量分析装置
WO2012081122A1 (fr) * 2010-12-17 2012-06-21 株式会社島津製作所 Guide d'ions et spectromètre de masse

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019510350A (ja) * 2016-04-25 2019-04-11 株式会社島津製作所 イオン光学デバイス
WO2019000699A1 (fr) * 2017-06-28 2019-01-03 中国地质科学院水文地质环境地质研究所 Nouveau spectromètre de masse isotopique chlore/brome et son procédé d'analyse
EP4117018A4 (fr) * 2020-03-05 2024-04-24 Hitachi High-Tech Corporation Spectromètre de masse

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