EP0321819B2 - 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
EP0321819B2
EP0321819B2 EP88120710A EP88120710A EP0321819B2 EP 0321819 B2 EP0321819 B2 EP 0321819B2 EP 88120710 A EP88120710 A EP 88120710A EP 88120710 A EP88120710 A EP 88120710A EP 0321819 B2 EP0321819 B2 EP 0321819B2
Authority
EP
European Patent Office
Prior art keywords
quistor
annular electrode
distance
apex
mass
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.)
Expired - Lifetime
Application number
EP88120710A
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German (de)
English (en)
Other versions
EP0321819A3 (en
EP0321819B1 (fr
EP0321819A2 (fr
Inventor
Jochen Dr. Franzen
Reemt-Holger Dr. Gabling
Gerhard Heinen
Gerhard Weiss
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Bruker Daltonics GmbH and Co KG
Original Assignee
Bruker Daltonik GmbH
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Filing date
Publication date
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Application filed by Bruker Daltonik GmbH filed Critical Bruker Daltonik GmbH
Publication of EP0321819A2 publication Critical patent/EP0321819A2/fr
Publication of EP0321819A3 publication Critical patent/EP0321819A3/de
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Publication of EP0321819B1 publication Critical patent/EP0321819B1/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
    • H01J49/42—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 after the preamble of claim 1.
  • the invention also relates to a mass spectrometer.
  • a special property of the quistor is that the ions are in the center of the RF field are not exposed to any field strength that gives them a component of motion to leave the ion trap could issue.
  • a collision gas is admitted into the ion trap Pressure is set so that the ions are sufficiently far from the center of the center by collisions Ion trap are driven to leave the ion trap. Because this gas passes through a Damping the ion movement transverse to the direction of expulsion causes an increase in the yield, it will also called "damping gas".
  • the line shape is also affected by space charge effects if there are too many ions in the Quistor are located.
  • space charge effects leads increasingly to scientific Misinterpretations.
  • the invention has for its object in the method of the type mentioned in to develop in such a way that an improvement in the line shape and thus also an improvement of the resolving power in the mass spectroscopic analysis of gas mixtures using of such a mass spectrometer is achieved.
  • the measure according to the invention not only shortens the time it takes for the ions to leave the trap need, but it also improves the line shape, sensitivity and that Detection ability increased by improving the signal / noise ratio and the influence of Space charge reduced.
  • the reduction in the time it takes for the ions to leave the ion trap allows an increase in the number of spectra recordings per unit of time, which again increases the sensitivity can be achieved.
  • the invention also relates to a mass spectrometer according to claim 2, which is used to examine a gas mixture is suitable by the method according to the invention.
  • the distance r o of the apex of the ring electrode from the center of the quistor has a value which ensures that the greatest mass of interest is the amplitude of the RF voltage applied to the ring electrode is still captured by means of the memory 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 the choice of R e and R r being free to take into account allow other influencing factors, especially in terms of manufacturing technology.
  • the quistor shown in Fig. 1 has a ring electrode 4 and two, each on one side of the End electrodes 3, 5 arranged on the ring electrode, which define the chamber delimited by the ring electrode 4 seal on both sides of the ring electrode.
  • the end electrodes 3 and 5 are on the ring electrode 4 each supported by annular insulators 7, 8.
  • the ring-shaped insulators 7, 8 also form one tight connection between the outer sections of the ring electrode 4 and the end electrodes 3, 5.
  • In one ring electrode 8 opens an inlet line 11, which allows a damping gas into the ion trap initiate.
  • FIG. 1 has a central opening 10, which at the Outside of the end electrode 3, a hot cathode 1 for generating an electron beam and one for Control of the electron beam serving blocking lens 2 is opposite.
  • the lower end electrode in FIG. 1 5 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 it 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 captured and stored by the quistor includes ions with mass numbers 1 to 500 ⁇ for simple ionization, 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 provided for the quistor of FIG. 1 for generating an electron beam allows the ions to be generated in the quistor itself by using their duration in the ionization phase 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.
  • FIG. 3 illustrates the time it takes for ions to exit the quistor need and which is expressed as a line width, as a function of the distance-related circle ratio Q.
  • the three curves of the diagram in FIG. 3 correspond to different scanning speeds, which are indicated at the bottom of Fig. 3. Damping gas was under each optimal printing conditions. It is readily apparent that for Q ⁇ 4,000 the triggering ability increases significantly.
  • the quistors used had the dimensions shown in the following table (in cm): Q 3.6 4.0 4.4 r o 1 1 1 z o .7260 0.7071 .6905 R r .5269 0.5000 .4768 R e 1.3776 1.4142 1.4482
  • Another advantage is that the influence of the space charge for values of Q ⁇ 4,000 is significantly reduced. Even if the signal strengths were reduced by a factor of 100, none could significant changes in line shape and line width can be observed.
  • the reason for the observable improvements is the occurrence of a resonance of the secular movement of ions exactly at the instability limit, which is the increase in amplitude of the secular movement accelerates and thus increases the speed of ion ejection.
  • the ejection therefore takes place only at Partly due to the instability of the railways and partly due to the additional energy consumption the ions from the storing RF field, which is made possible by the resonance.

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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)

Claims (2)

  1. Procédé d'examen par spectroscopie de masse d'un mélange de gaz, en utilisant un spectromètre de masse avec un piège à ions, réalisé sous forme de quistor, avec une électrode annulaire et deux électrodes d'extrémité, fermant les chambres délimitées par l'électrode annulaire, les électrodes étant formées par des hyperboloides de rotation et des électrodes d'extrémité dont au moins l'une est pourvue d'une perforation disposée dans le prolongement de l'axe de rotation de l'électrode annulaire, procédé dans lequel sont effectuées les étapes suivantes :
    application à l'électrode annulaire d'une tension H.F. d'une amplitude et d'une fréquence telles, ainsi que, le cas échéant d'une tension continue telle, qu'un champ de quadripôlaire H.F. tridimensionnel est produit à 1' intérieur du piège à ions et convient pour capter les ions dont le rapport charge/masse est situé dans une plage déterminée et les stocker dans le piège à ions,
    introduction ou production d'ions du mélange de gaz dans, respectivement à l'intérieur du piège à ions et stockage des ions dans le piège à ions dont le rapport charge/masse est situé dans la plage déterminée,
    modification d'au moins un paramètre de champ formé par l'amplitude, la fréquence et, le cas échéant, la tension continue, de manière telle que des ions ayant un rapport charge/masse variant de façon monotone deviennent les uns après les autres instables et quittent le piège à ions en direction de l'axe de rotation de leur électrode annulaire, à travers ladite perforation ménagée dans l'électrode d'extrémité, et
    mesure et enregistrement de l'intensité du courant ionique quittant le piège à ions, à titre de fonction de la modification des paramètres de champ, caractérisé en ce que
       pour mettre en oeuvre le procédé est utilisé un quistor, pour lequel le rapport Q, lié aux espacements, entre les rayons des cercles inscrits passant par les sommets des électrodes satisfait à la condition Q ≤ 3,990, où Q = Re zo × ro Rr , avec
    Re =
    rayon de cercle de la section transversale passant par le sommet de chaque électrode d'extrémité,
    Rr =
    rayon de cercle de la section transversale passant par le sommet de l'électrode annulaire,
    zo =
    distance entre les sommets des électrodes d'extrémité et le centre du quistor,
    ro =
    distance entre les sommets de l'électrode annulaire et le centre du quistor,
    en ce qu'à partir des dimensions, déterminant le rapport Q lié aux espacements, du quistor, la distance ro entre le sommet de l'électrode annulaire et le centre du quistor a une valeur pour laquelle il est assuré que, pour l'amplitude de la tension H.F. appliquée à l'électrode annulaire, on a encore capté au moyen du champ de stockage la plus grande masse intéressante, pour une valeur prédéterminée du rapport Q entre la distance zo du sommet des électrodes d'extrémité et le centre du quistor zo = ro/4 Q et, enfin, les rayons Re et Rr des sections transversales de sommet sont choisis telles que l'on a Re x Rr = ro x zo.
  2. Spectromètre de masse avec un piège à ion, réalisé sous forme de quistor, avec une électrode annulaire et deux électrodes d'extrémité, délimitant les chambres délimitées par l'électrode annulaire, les électrodes étant formées par des hyperboloides de rotation et des électrodes d'extrémité dont au moins l'une est pourvue d'une perforation disposée dans le prolongement de l'axe de rotation de l'électrode annulaire, destiné à l'examen d'un mélange de gaz suivant le procédé selon la revendication 1, caractérisé en ce que le rapport Q, lié aux espacements, entre les rayons des cercles inscrits passant par les sommets des électrodes satisfait à la condition Q ≤ 3,990, où Q = Re zo × ro Rr , avec
    Re =
    rayon de cercle de la section transversale passant par le sommet de chaque électrode d'extrémité,
    Rr =
    rayon de cercle de la section transversale passant par le sommet de l'électrode annulaire,
    zo =
    distance entre les sommets des électrodes d'extrémité et le centre du quistor,
    ro =
    distance entre les sommets de l'électrode annulaire et
    le centre du quistor, et en ce qu'à partir des dimensions, déterminant le rapport Q lié aux espacements, du quistor, la distance ro entre le sommet de l'électrode annulaire et le centre du quistor a une valeur pour laquelle il est assuré que, pour l'amplitude de la tension H.F. appliquée à l'électrode annulaire, on a encore capté au moyen du champ de stockage la plus qrande masse intéressante, pour une valeur prédéterminée du rapport Q entre la distance zo du sommet des électrodes d'extrémité et le centre du quistor zo = ro/4 Q et, enfin, les rayons Re et Rr des sections transversales de sommet sont choisis telles que l'on a Re x Rr = ro x zo.
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 EP0321819A2 (fr) 1989-06-28
EP0321819A3 EP0321819A3 (en) 1989-08-23
EP0321819B1 EP0321819B1 (fr) 1993-04-21
EP0321819B2 true EP0321819B2 (fr) 2002-06-19

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ID=6343365

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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)

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

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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
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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
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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
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Publication number Publication date
US5028777A (en) 1991-07-02
EP0321819A3 (en) 1989-08-23
DE3880456D1 (de) 1993-05-27
EP0321819B1 (fr) 1993-04-21
EP0321819A2 (fr) 1989-06-28

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