EP0633602A2 - Spectromètre de masse à temps de vol pourvu d'une source d'ions en phase gaseuze présentant une sensibilité élevée ainsi qu'une large gamme dynamique - Google Patents

Spectromètre de masse à temps de vol pourvu d'une source d'ions en phase gaseuze présentant une sensibilité élevée ainsi qu'une large gamme dynamique Download PDF

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Publication number
EP0633602A2
EP0633602A2 EP94110273A EP94110273A EP0633602A2 EP 0633602 A2 EP0633602 A2 EP 0633602A2 EP 94110273 A EP94110273 A EP 94110273A EP 94110273 A EP94110273 A EP 94110273A EP 0633602 A2 EP0633602 A2 EP 0633602A2
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EP
European Patent Office
Prior art keywords
ion source
time
mass spectrometer
gas
flight mass
Prior art date
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Granted
Application number
EP94110273A
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German (de)
English (en)
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EP0633602B1 (fr
EP0633602A3 (fr
Inventor
Thorald Dr. Bergmann
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Individual
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Publication of EP0633602A3 publication Critical patent/EP0633602A3/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
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
    • 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
    • H01J49/403—Time-of-flight spectrometers characterised by the acceleration optics and/or the extraction fields

Definitions

  • the invention relates to a time-of-flight mass spectrometer with a gas-phase ion source according to the preamble of claim 1.
  • time-of-flight mass analysis there is a start time from which a group of ions is started in the time-of-flight mass spectrometer. At the end of a flight route, the time which the respective incoming ion needed was measured and from this the mass of the ion in question was determined.
  • the withdrawal volume is understood to be the spatial area of the ion source from which, starting from the start time, ion tracks lead to the surface of the detector of the time-of-flight mass spectrometer.
  • the generated electrons can also be detected in a time-of-flight mass spectrometer.
  • a withdrawal volume can also be defined for the electrons.
  • the withdrawal volume for the ions need not be congruent with the withdrawal volume for the electrons. However, these two volumes will at least be different partially overlap.
  • the electrons are withdrawn from the source in the opposite direction to the ions.
  • the first acceleration phase of the ions arriving at the detector takes place in the ion source.
  • the ions in the ion source are often accelerated to the final speed. It may be that the ion source still contains electrodes for focusing the ions arriving at the detector. However, it may also be the case that the electrodes for focusing are arranged separately, i.e. the ions arriving at the detector leave the source in a directional and spatial distribution which is unsuitable for further transport through the mass spectrometer and for which reason a separate focusing is still necessary.
  • a high particle density at the start time is advantageous in the withdrawal volume since the number of ions arriving at the detector is proportional to this density.
  • the size of the withdrawal volume and the density of the particles contained therein are a direct measure of the sensitivity of the time-of-flight mass spectrometer.
  • the dynamic range means the factor by which the signal of a certain mass may be smaller than the signal of other masses, without being covered by ions of these other masses arriving at wrong times.
  • the time-of-flight mass spectrometer is usually divided into different areas of different pressure, which depend on the sample introduction, that is, the generation of the gas or ion beam to be examined, up to the ion source and along the flight path in the time-of-flight mass spectrometer, are ordered according to decreasing pressure. Adjacent areas are connected by gas flow impedances so that neither the gas or ion beam to be examined nor the ions on their path from the discharge volume to the detector are obstructed. This procedure allows a high particle density in the discharge volume, and still a low residual gas pressure or low impact probability on the flight path of the time-of-flight mass spectrometer.
  • Gas flow impedances are to be understood here as openings of small cross-section which are large enough to allow the ions on their tracks to pass to the detector, but whose conductance for gases is significantly lower than the pumping capacity of the pump of the area with the lower pressure.
  • a gas flow impedance is an opening of a certain cross section in the partition between areas of different pressure.
  • pipes or pipe-like structures have a much lower gas conductance than openings of the same cross-section and are therefore preferable in many cases.
  • Skimmers are conical structures with an opening in the tip, which points towards the gas flow. Skimmers have a similar gas conductance to openings of the same cross-section and are preferable if the gas flow has a high density.
  • a large distance is therefore disadvantageous because there is a large gas load in the ion source area, and thus high residual gas pressure, can only achieve a lower particle density in the discharge volume. This results in reduced sensitivity and a lower dynamic range of the time-of-flight mass spectrometer.
  • the invention is accordingly based on the object of specifying a time-of-flight mass spectrometer with a gas-phase ion source, which likewise has a high sensitivity and a high dynamic range.
  • the device according to the invention is divided into two or more areas of different pressure, gas flow impedances each connecting two areas.
  • the gas flow impedance (s) are / are integrated directly into electrodes of the ion source in order to get as close as possible to the withdrawal volume. This has the advantage that a maximum particle density in the discharge volume can be achieved with a minimal impact probability in the flight path of the mass spectrometer.
  • the accelerating field will defined here by a repeller electrode (1) and an acceleration electrode (2).
  • these two electrodes define the accelerating field of the ion source.
  • a flow impedance (3) is only integrated into the acceleration electrode (2).
  • the acceleration electrode separates the area of the acceleration field with the higher pressure p 1 from the area of the flight path in the time-of-flight mass spectrometer with lower pressure p 2.
  • the gas flow impedance can, for example, as shown in FIG. 1 and in claim 2, to be a pinhole.
  • the gas or ion beam (10) to be examined can be shot into the ion source perpendicular to the direction of acceleration. Ionized particles, which are in the withdrawal volume (11) at the start time, are accelerated along the drawn paths (12) into the time-of-flight mass spectrometer.
  • the direction of acceleration is understood here to be the direction in which the ions are subsequently accelerated to the starting time.
  • the orbits (12) of the ions are divergent according to the gas flow impedance (3) and have to be focused afterwards. This can be achieved by already known lens designs and is therefore not described in more detail here.
  • Fig. 2 corresponds essentially to Fig. 1 , instead of a pinhole, the flow impedance (3) is formed by a tube.
  • a pipe has a much lower gas conductivity than a pinhole with the same cross-section.
  • the additional electrode (4) between the repeller electrode (1) and the acceleration electrode (2) serves to direct the ions on parallel tracks (12) through the flow impedance (3). Under certain circumstances, it may be advantageous to add further electrodes behind the gas flow impedance.
  • passage openings must be provided in the electrode (4). It is also possible to disassemble the electrode (4) into two parts, one closer to the repeller electrode (1) and one closer to the accelerating electrode (2). The beams can be aimed between these two parts.
  • Fig. 4 This arrangement is shown in Fig. 4 , which thus also gives an example according to claims 14 and 16, respectively.
  • the two electrodes (4, 5) between the repeller electrode (1) and the acceleration electrode (2) serve to direct the ions on crossing paths (12) through the flow impedance (3). Under certain circumstances, it may be advantageous to add further electrodes behind the gas flow impedance. It is also possible to choose different radii to the axis of the ion source for the two additional electrodes (4, 5).
  • a transverse electric field can be created , also called the deflection field. This deflection field can change the transverse velocity components of the charged particles.
  • the cylinder-symmetrical design of the deflection electrodes has the further advantage that the deflection electrodes can initially be produced as a turned part. In a subsequent step, they can then be broken down into two parts.
  • Fig. 5 shows an embodiment according to claim 20.
  • the generated electrons are withdrawn along the shown electron paths (13) by a gas flow impedance (6) in the repeller electrode (1). Due to the gas flow impedance (6) along the electron tracks (13), as seen in FIG. 5 , to the left of the repeller electrode (1), the pressure p 3 is lower than the pressure p 1 in the acceleration path.
  • the electron beam (13) is divergent according to the gas flow impedance (6) and must then be focused. This can be achieved by already known lens designs and is therefore not described in more detail here.
  • FIG. 6 shows an embodiment according to claim 10.
  • the gas or ion beam (10) to be examined is injected into the ion source parallel to the direction of acceleration by the skimmer (6).
  • the pressure p 3 in front of the skimmer is greater than the pressure p 1 in the acceleration section.
  • Electrodes which are also partitions between areas of different pressure, must be connected to the housing in order to be able to fulfill their function. If the electrode in question is at ground or housing potential, this is simple. If an electrode, which is also to be a partition between areas of different pressure, is not at ground potential, an insulator must be provided between this electrode and the housing. If this insulator is glued flat between the electrode and the housing, problems e.g. caused by outgassing of the adhesive, gas inclusions between the insulator and the electrode, etc.
  • FIG. 7 shows a possible solution if an electrode, which is also intended to represent a partition between areas of different pressure, is not at ground potential.
  • the electrode (2) and the housing wall (31) overlap, but do not touch.
  • the distance between the two, as shown here by way of example, is determined by a sapphire ball (32).
  • the gap between the electrode (2) and the housing wall (31) should be chosen so small that the conductance for gases is significantly smaller than the pumping capacity of the pump in the area with the lower pressure. It is understood that the electrode (2) against the Housing wall must be pressed. This can be brought about by already known methods, which is why it is not dealt with in more detail here.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
EP94110273A 1993-07-02 1994-07-01 Spectromètre de masse à temps de vol pourvu d'une source d'ions en phase gaseuze présentant une sensibilité élevée ainsi qu'une large gamme dynamique Expired - Lifetime EP0633602B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4322102A DE4322102C2 (de) 1993-07-02 1993-07-02 Flugzeit-Massenspektrometer mit Gasphasen-Ionenquelle
DE4322102 1993-07-02

Publications (3)

Publication Number Publication Date
EP0633602A2 true EP0633602A2 (fr) 1995-01-11
EP0633602A3 EP0633602A3 (fr) 1995-11-22
EP0633602B1 EP0633602B1 (fr) 2000-05-24

Family

ID=6491836

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94110273A Expired - Lifetime EP0633602B1 (fr) 1993-07-02 1994-07-01 Spectromètre de masse à temps de vol pourvu d'une source d'ions en phase gaseuze présentant une sensibilité élevée ainsi qu'une large gamme dynamique

Country Status (7)

Country Link
US (1) US5496998A (fr)
EP (1) EP0633602B1 (fr)
JP (1) JPH07176291A (fr)
AT (1) ATE193398T1 (fr)
AU (2) AU685113B2 (fr)
CA (1) CA2127183A1 (fr)
DE (2) DE4322102C2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005005333A1 (de) * 2005-01-28 2006-08-17 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Aerosol-Analyse, Sondenvorrichtung und Analysevorrichtung
DE19652021B4 (de) * 1995-12-14 2006-12-14 Micromass Uk Ltd. Ionen-Quelle und Ionisationsverfahren
DE19655304B4 (de) * 1995-12-14 2007-02-15 Micromass Uk Ltd. Massenspektrometer und Verfahren zur Massenspektrometrie
EP1726945A4 (fr) * 2004-03-16 2008-07-16 Idx Technologies Kk Spectroscope de masse a ionisation laser

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4441972C2 (de) * 1994-11-25 1996-12-05 Deutsche Forsch Luft Raumfahrt Verfahren und Vorrichtung zum Nachweis von Probenmolekülen in einem Trägergas
US5744797A (en) * 1995-11-22 1998-04-28 Bruker Analytical Instruments, Inc. Split-field interface
DE19631161A1 (de) * 1996-08-01 1998-02-12 Bergmann Thorald Flugzeit-Flugzeit-Massenspektrometer mit differentiell gepumpter Kollisionszelle
GB0021902D0 (en) * 2000-09-06 2000-10-25 Kratos Analytical Ltd Ion optics system for TOF mass spectrometer
US6675660B1 (en) * 2002-07-31 2004-01-13 Sandia National Laboratories Composition pulse time-of-flight mass flow sensor

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577165A (en) * 1968-05-31 1971-05-04 Perkin Elmer Corp Linear scanning arrangement for a cycloidal mass spectrometer
US3553452A (en) * 1969-02-17 1971-01-05 Us Air Force Time-of-flight mass spectrometer operative at elevated ion source pressures
GB1302193A (fr) * 1969-04-18 1973-01-04
GB8602463D0 (en) * 1986-01-31 1986-03-05 Vg Instr Group Mass spectrometer
JPH03503815A (ja) * 1987-12-24 1991-08-22 ユニサーチ　リミテッド 質量分析計
GB8813149D0 (en) * 1988-06-03 1988-07-06 Vg Instr Group Mass spectrometer
US5070240B1 (en) * 1990-08-29 1996-09-10 Univ Brigham Young Apparatus and methods for trace component analysis
DE4108462C2 (de) * 1991-03-13 1994-10-13 Bruker Franzen Analytik Gmbh Verfahren und Vorrichtung zum Erzeugen von Ionen aus thermisch instabilen, nichtflüchtigen großen Molekülen
JP2913924B2 (ja) * 1991-09-12 1999-06-28 株式会社日立製作所 質量分析の方法および装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19652021B4 (de) * 1995-12-14 2006-12-14 Micromass Uk Ltd. Ionen-Quelle und Ionisationsverfahren
DE19655304B4 (de) * 1995-12-14 2007-02-15 Micromass Uk Ltd. Massenspektrometer und Verfahren zur Massenspektrometrie
DE19655304B8 (de) * 1995-12-14 2007-05-31 Micromass Uk Ltd. Massenspektrometer und Verfahren zur Massenspektrometrie
EP1726945A4 (fr) * 2004-03-16 2008-07-16 Idx Technologies Kk Spectroscope de masse a ionisation laser
DE102005005333A1 (de) * 2005-01-28 2006-08-17 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Aerosol-Analyse, Sondenvorrichtung und Analysevorrichtung
DE102005005333B4 (de) * 2005-01-28 2008-07-31 Deutsches Zentrum für Luft- und Raumfahrt e.V. Verfahren zur Probennahme und Aerosol-Analyse

Also Published As

Publication number Publication date
DE59409371D1 (de) 2000-06-29
JPH07176291A (ja) 1995-07-14
CA2127183A1 (fr) 1995-01-03
AU6615394A (en) 1995-01-12
EP0633602B1 (fr) 2000-05-24
ATE193398T1 (de) 2000-06-15
EP0633602A3 (fr) 1995-11-22
US5496998A (en) 1996-03-05
AU685112B2 (en) 1998-01-15
AU685113B2 (en) 1998-01-15
DE4322102C2 (de) 1995-08-17
DE4322102A1 (de) 1995-01-19
AU6615294A (en) 1995-01-12

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