EP0321819B1 - 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
EP0321819B1
EP0321819B1 EP88120710A EP88120710A EP0321819B1 EP 0321819 B1 EP0321819 B1 EP 0321819B1 EP 88120710 A EP88120710 A EP 88120710A EP 88120710 A EP88120710 A EP 88120710A EP 0321819 B1 EP0321819 B1 EP 0321819B1
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Prior art keywords
quistor
annular electrode
distance
apex
ion trap
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EP88120710A
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German (de)
English (en)
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EP0321819B2 (fr
EP0321819A2 (fr
EP0321819A3 (en
Inventor
Jochen Dr. Franzen
Reemt-Holger Dr. Gabling
Gerhard Heinen
Gerhard Weiss
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Bruker Daltonics GmbH and Co KG
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Bruken Franzen Analytik GmbH
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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, in which method the following steps are carried out:
  • the invention also relates to a mass spectrometer.
  • 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 the optimal number of impacts that they can 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 seen, this space charge effect even leads increasingly to scientific misinterpretations.
  • the invention has for its object to further develop the method of the type mentioned in such a way that an improvement in the line shape and thus an improvement tion of the resolving power is achieved in the mass spectrometric examination of gas mixtures using such a mass spectrometer.
  • the measure according to the invention not only shortens the time which 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 the space charge.
  • the shortening of 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.
  • 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 taking into account the rules given, whereby for the choice of R e and R r there are freedoms that take into account other influencing factors, especially
  • 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 and 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 that are captured and stored by the quistor, with a simple ionization includes ions with mass numbers 1 to 500 ⁇ , 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 1 to 500 ⁇ 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 according to FIG. 3 illustrates the time it takes for ions to leave the quistor and accordingly manifests itself as a line width as a function of the distance-related circular ratio Q.
  • the three curves of the diagram according to FIG. 3 correspond to different scanning speeds speeds indicated at the bottom of Fig. 3. 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 molecular ion group of tetrachloroethene for different values of the distance-related ratio circuit Q.
  • the spectra were recorded as Dampfungsgas mbar with different scanning speeds over each 300 mass units using air at a pressure of 4.10- 4.
  • the scan time was 100 ms each, while in the lower spectra b, d, and f the scan time was 20 ms each.
  • the quistors used had the dimensions shown in the following table (in cm):
  • 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)

Claims (3)

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, 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 l'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
Figure imgb0008
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,
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, 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
Figure imgb0009
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,
3. Spectromètre de masse selon la revendication 2, caractérisé 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
Figure imgb0010
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.
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

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

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DE4142870C2 (de) * 1991-12-23 1995-03-16 Bruker Franzen Analytik Gmbh Verfahren für phasenrichtiges Messen der Ionen aus Ionenfallen-Massenspektrometern
DE4142871C1 (fr) * 1991-12-23 1993-05-19 Bruker - Franzen Analytik Gmbh, 2800 Bremen, De
DE4316738C2 (de) * 1993-05-19 1996-10-17 Bruker Franzen Analytik Gmbh Auswurf von Ionen aus Ionenfallen durch kombinierte elektrische Dipol- und Quadrupolfelder
US5420425A (en) * 1994-05-27 1995-05-30 Finnigan Corporation Ion trap mass spectrometer system and method
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
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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

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US5028777A (en) 1991-07-02
EP0321819B2 (fr) 2002-06-19
EP0321819A2 (fr) 1989-06-28
EP0321819A3 (en) 1989-08-23
DE3880456D1 (de) 1993-05-27

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