EP0321819A2 - Méthode d'analyse d'un mélange de gaz par spectrométrie de masse et spectromètre de masse utilisé dans ce but - Google Patents

Méthode d'analyse d'un mélange de gaz par spectrométrie de masse et spectromètre de masse utilisé dans ce but Download PDF

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Publication number
EP0321819A2
EP0321819A2 EP88120710A EP88120710A EP0321819A2 EP 0321819 A2 EP0321819 A2 EP 0321819A2 EP 88120710 A EP88120710 A EP 88120710A EP 88120710 A EP88120710 A EP 88120710A EP 0321819 A2 EP0321819 A2 EP 0321819A2
Authority
EP
European Patent Office
Prior art keywords
quistor
ring electrode
distance
ion trap
end electrodes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88120710A
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German (de)
English (en)
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EP0321819A3 (en
EP0321819B2 (fr
EP0321819B1 (fr
Inventor
Jochen Dr. Franzen
Reemt-Holger Dr. Gabling
Gerhard Heinen
Gerhard Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bruker Daltonics GmbH and Co KG
Original Assignee
Bruken Franzen Analytik GmbH
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Publication date
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Application filed by Bruken Franzen Analytik GmbH filed Critical Bruken Franzen Analytik GmbH
Publication of EP0321819A2 publication Critical patent/EP0321819A2/fr
Publication of EP0321819A3 publication Critical patent/EP0321819A3/de
Application granted granted Critical
Publication of EP0321819B1 publication Critical patent/EP0321819B1/fr
Publication of EP0321819B2 publication Critical patent/EP0321819B2/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
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes
    • 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
    • H01J49/426—Methods for controlling ions
    • H01J49/427—Ejection and selection methods
    • H01J49/429—Scanning an electric parameter, e.g. voltage amplitude or frequency

Definitions

  • the invention relates to a method for mass spectroscopic examination of a gas mixture using a mass spectrometer with an ion trap, which is designed as a quistor with a ring electrode and two end electrodes closing the chamber delimited by the ring electrode, of which end electrodes at least one with an extension of the axis of rotation of the ring electrode arranged perforation ver you can see which procedure performs the following steps: Applying an RF voltage of such amplitude and frequency and possibly such a DC voltage to the ring electrode that a three-dimensional RF quadrupole field is generated within the ion trap, which is suitable for ions whose charge / mass ratio is in a predetermined range, to catch and store in the ion trap Introducing or generating ions of the gas mixture into or within the ion trap and storing those ions in the ion trap whose charge / mass ratio is in the predetermined range, Changing at least one of the field parameters formed by the amplitude, the frequency and possibly the DC voltage in such
  • a special property of the quistor is that the ions in the center of the RF field are not exposed to any field strength that could give them a movement component to leave the ion trap.
  • a collision gas is admitted into the ion trap, the pressure of which is set in such a way that the ions are driven far enough from the center of the ion trap by shocks to leave the ion trap. Since this gas simultaneously increases the yield by damping the ion movement transverse to the direction of expulsion, it is also called "damping gas".
  • the line shape is also affected by space charge effects if there are too many ions in the quistor. As a work by J.W. Eichelberger et al in "Analytical Chemistry" 59, page 2732, 1987, can be taken, this space charge effect even leads to scientific misinterpretation.
  • the invention is based on the object of further developing the method of the type mentioned in such a way that an improvement in the line shape and thus also an improvement in the resolving power is achieved in the mass spectroscopic examination of gas mixtures by means of such a mass spectrometer.
  • the measure according to the invention not only shortens the time that the ions need to leave the trap, but also improves the line shape, increases sensitivity and detection capacity by improving the signal / noise ratio and reduces the influence of space charge.
  • the shortening of the time that the ions need to leave the ion trap allows an increase in the Number of spectra recordings per unit of time, which can further increase sensitivity.
  • the invention also relates to a mass spectrometer which is suitable for examining a gas mixture according to the method according to the invention and has an ion trap which is designed as a quistor with a ring electrode and two end electrodes closing the chamber delimited by the ring electrode, of which end electrodes at least one with one perforation arranged in the extension of the axis of rotation of the ring electrode.
  • the distance r o of the apex of the ring electrode from the center of the quistor has a value which ensures that the amplitude of the RF voltage applied to the ring electrode has the value largest mass of interest is still captured by means of the storage field
  • the values r o and Q which are particularly important for the behavior of the quistor, are preselected and the other values are determined in accordance with the specified rules, with freedom to take R e and R r into account allow other influencing factors, especially in terms of manufacturing technology. It goes without saying. that the stated relationships represent only one guideline, compliance with which is expedient, but is not essential for the success of the invention, so that it is also possible to deviate from the given guideline.
  • the quistor shown in FIG. 1 has a ring electrode 4 and two end electrodes 3, 5, each arranged on one side of the ring electrode, which terminate the chamber delimited by the ring electrode 4 on both sides of the ring electrode.
  • the end electrodes 3 and 5 are each supported on the ring electrode 4 by ring-shaped insulators 7, 8.
  • the ring-shaped insulators 7, 8 also form a tight connection between the outer sections of the ring electrode 4 and the end electrodes 3, 5.
  • An inlet line 11 opens into the ring electrode 8, which makes it possible to introduce a damping gas into the ion trap.
  • the lower end electrode 5 in FIG. 1 has a perforation 9 in the area of its center, through which ions can leave the quistor.
  • a secondary electron multiplier 6 is arranged on the outside of the lower end electrode 5 and makes it possible to detect the ions leaving the quistor through the perforation 9.
  • Both the ring electrode 4 and the end electrodes 3 and 5 have strictly hyperbolic surfaces, which means that their contours are hyperbolas in the cross section shown in FIG. 1.
  • the asymptotic angle of both the ring electrode 4 and the hyperbola producing the end electrodes 3, 5 is 1: 1.360.
  • the end electrodes 3, 5 are at ground potential, an RF voltage with a frequency of 1.0 MHz is applied to the ring electrode 4, which can be varied in the range from 0 V to 7.5 kV.
  • the range of the charge / mass ratio of the ions which are captured and stored by the quistor in the case of a simple ionization, comprises ions with the mass numbers 1 to 500 u, where u is the atomic mass unit. Accordingly, by changing the RF voltage in the range from 0 V to 7.5 kV, a mass range from 1u to 500u can be covered in one scan.
  • the device for generating an electron beam provided in the quistor according to FIG. 1 allows the ions to be generated in the quistor itself by in the ionization phase, the duration of which can be determined by means of the blocking lens 2, an electron beam from the hot cathode 1 through the opening 10 is focused in the quistor.
  • Typical ionization times for an electron beam of 100 ⁇ A strength are in the range from 10 ⁇ s to 100 ms, depending on the concentration of the substance to be examined.
  • the diagram in FIG. 3 illustrates the time it takes for ions to leave the quistor and which is accordingly expressed as a line width as a function of the distance-related circular ratio Q.
  • the three curves in the diagram in FIG. 3 correspond to different scanning speeds, which are at the bottom of Fig. 3 are given. Damping gas was used under optimal pressure conditions. It is readily apparent that the release capability increases significantly for Q ⁇ 4,000.
  • Fig. 4 shows the spectrum of the group of molecular ions of tetrachloroethene for different values of the distance-related circular ratio Q.
  • the spectra were recorded using air with a pressure of 4.10 ⁇ 4 mbar as a steaming gas with different scanning speeds over 300 mass units each.
  • the scan time was 100 ms each, while in the lower spectra b, d, and f the scan time was 20 ms each.
  • Another advantage is that the influence of the space charge is significantly reduced for values of Q ⁇ 4.000. Even if the signal strengths were reduced by a factor of 100, no significant change in line shape and line width could be observed.
  • the reason for the observable improvements is the occurrence of a resonance of the secular movement of the ions exactly at the instability limit, which accelerates the increase in the amplitude of the secular movement and thus increases the speed of the ion ejection.
  • the ejection is therefore only partly due to the instability of the orbits and partly due to the additional energy absorption of the ions from the storing HF field, which is made possible by the resonance.
  • a preferred embodiment therefore provides for the omission of the DC voltage field. In principle, however, it would also be possible to use a DC voltage field and to vary the DC voltage field in order to change the stability range.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
EP88120710A 1987-12-23 1988-12-12 Méthode d'analyse d'un mélange de gaz par spectrométrie de masse et spectromètre de masse utilisé dans ce but Expired - Lifetime EP0321819B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3743718 1987-12-23
DE3743718 1987-12-23

Publications (4)

Publication Number Publication Date
EP0321819A2 true EP0321819A2 (fr) 1989-06-28
EP0321819A3 EP0321819A3 (en) 1989-08-23
EP0321819B1 EP0321819B1 (fr) 1993-04-21
EP0321819B2 EP0321819B2 (fr) 2002-06-19

Family

ID=6343365

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88120710A Expired - Lifetime EP0321819B2 (fr) 1987-12-23 1988-12-12 Méthode d'analyse d'un mélange de gaz par spectrométrie de masse et spectromètre de masse utilisé dans ce but

Country Status (3)

Country Link
US (1) US5028777A (fr)
EP (1) EP0321819B2 (fr)
DE (1) DE3880456D1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0512700A1 (fr) * 1991-04-30 1992-11-11 Finnigan Corporation Méthode d'opération d'un spectromètre de masse de type piège ionique en mode haute résolution
US5206506A (en) * 1991-02-12 1993-04-27 Kirchner Nicholas J Ion processing: control and analysis
EP0684628A1 (fr) * 1994-05-27 1995-11-29 Finnigan Corporation Spectromètre de masse du type piège à ions et méthode de mise en oeuvre de celui-ci
US6297500B1 (en) 1997-11-20 2001-10-02 Bruker Daltonik Gmbh Quadrupole RF ion traps for mass spectrometers
DE10028914C1 (de) * 2000-06-10 2002-01-17 Bruker Daltonik Gmbh Interne Detektion von Ionen in Quadrupol-Ionenfallen

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5225141A (en) * 1988-07-11 1993-07-06 Milad Limited Partnership Process for injection molding a hollow plastic article
DE4142871C1 (fr) * 1991-12-23 1993-05-19 Bruker - Franzen Analytik Gmbh, 2800 Bremen, De
DE4142870C2 (de) * 1991-12-23 1995-03-16 Bruker Franzen Analytik Gmbh Verfahren für phasenrichtiges Messen der Ionen aus Ionenfallen-Massenspektrometern
DE4316738C2 (de) * 1993-05-19 1996-10-17 Bruker Franzen Analytik Gmbh Auswurf von Ionen aus Ionenfallen durch kombinierte elektrische Dipol- und Quadrupolfelder
DE4324224C1 (de) * 1993-07-20 1994-10-06 Bruker Franzen Analytik Gmbh Quadrupol-Ionenfallen mit schaltbaren Multipol-Anteilen
US5572025A (en) * 1995-05-25 1996-11-05 The Johns Hopkins University, School Of Medicine Method and apparatus for scanning an ion trap mass spectrometer in the resonance ejection mode
JP3648906B2 (ja) * 1997-02-14 2005-05-18 株式会社日立製作所 イオントラップ質量分析計を用いた分析装置
DE19733834C1 (de) * 1997-08-05 1999-03-04 Bruker Franzen Analytik Gmbh Axialsymmetrische Ionenfalle für massenspektrometrische Messungen
US6124592A (en) * 1998-03-18 2000-09-26 Technispan Llc Ion mobility storage trap and method
US6239429B1 (en) 1998-10-26 2001-05-29 Mks Instruments, Inc. Quadrupole mass spectrometer assembly
US6469298B1 (en) * 1999-09-20 2002-10-22 Ut-Battelle, Llc Microscale ion trap mass spectrometer
US7019289B2 (en) * 2003-01-31 2006-03-28 Yang Wang Ion trap mass spectrometry
US7034293B2 (en) * 2004-05-26 2006-04-25 Varian, Inc. Linear ion trap apparatus and method utilizing an asymmetrical trapping field
US8334506B2 (en) 2007-12-10 2012-12-18 1St Detect Corporation End cap voltage control of ion traps
US7973277B2 (en) 2008-05-27 2011-07-05 1St Detect Corporation Driving a mass spectrometer ion trap or mass filter
US9171706B1 (en) * 2014-11-06 2015-10-27 Shimadzu Corporation Mass analysis device and mass analysis method
CN110783165A (zh) * 2019-11-01 2020-02-11 上海裕达实业有限公司 线性离子阱离子引入侧的端盖电极结构
CN115047259B (zh) * 2022-04-15 2022-12-06 安徽省太微量子科技有限公司 基于频率可调二维线性离子阱的颗粒荷质比测量方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3527939A (en) * 1968-08-29 1970-09-08 Gen Electric Three-dimensional quadrupole mass spectrometer and gauge
US4540884A (en) * 1982-12-29 1985-09-10 Finnigan Corporation Method of mass analyzing a sample by use of a quadrupole ion trap
US4650999A (en) * 1984-10-22 1987-03-17 Finnigan Corporation Method of mass analyzing a sample over a wide mass range by use of a quadrupole ion trap
DE3650304T2 (de) * 1985-05-24 1995-10-12 Finnigan Corp Betriebsverfahren für eine Ionenfalle.
ATE99834T1 (de) * 1988-04-13 1994-01-15 Bruker Franzen Analytik Gmbh Methode zur massenanalyse einer probe mittels eines quistors und zur durchfuehrung dieses verfahrens entwickelter quistor.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5206506A (en) * 1991-02-12 1993-04-27 Kirchner Nicholas J Ion processing: control and analysis
EP0512700A1 (fr) * 1991-04-30 1992-11-11 Finnigan Corporation Méthode d'opération d'un spectromètre de masse de type piège ionique en mode haute résolution
EP0684628A1 (fr) * 1994-05-27 1995-11-29 Finnigan Corporation Spectromètre de masse du type piège à ions et méthode de mise en oeuvre de celui-ci
US6297500B1 (en) 1997-11-20 2001-10-02 Bruker Daltonik Gmbh Quadrupole RF ion traps for mass spectrometers
DE19751401B4 (de) * 1997-11-20 2007-03-01 Bruker Daltonik Gmbh Quadrupol-Hochfrequenz-Ionenfallen für Massenspektrometer
DE10028914C1 (de) * 2000-06-10 2002-01-17 Bruker Daltonik Gmbh Interne Detektion von Ionen in Quadrupol-Ionenfallen

Also Published As

Publication number Publication date
DE3880456D1 (de) 1993-05-27
EP0321819A3 (en) 1989-08-23
EP0321819B2 (fr) 2002-06-19
EP0321819B1 (fr) 1993-04-21
US5028777A (en) 1991-07-02

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