EP0632482B1 - Gas phase ion source for high mass resolution, wide mass range time-of-flight mass spectrometer - Google Patents

Gas phase ion source for high mass resolution, wide mass range time-of-flight mass spectrometer Download PDF

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EP0632482B1
EP0632482B1 EP94110274A EP94110274A EP0632482B1 EP 0632482 B1 EP0632482 B1 EP 0632482B1 EP 94110274 A EP94110274 A EP 94110274A EP 94110274 A EP94110274 A EP 94110274A EP 0632482 B1 EP0632482 B1 EP 0632482B1
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electrodes
ion source
time
acceleration
field
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Thorald Dr. Bergmann
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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
    • H01J49/40—Time-of-flight spectrometers
    • H01J49/403—Time-of-flight spectrometers characterised by the acceleration optics and/or the extraction fields

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  • the invention relates to a gas phase ion source according to the preamble of claim 1.
  • time-of-flight mass analysis there is a start time from which started a group of ions in the time-of-flight mass spectrometer becomes. At the end of a flight route, the time is measured needed each incoming ion and from this the mass of the concerned Ions determined.
  • a gas phase ion source of a time-of-flight mass spectrometer is understood as the withdrawal volume the spatial area of the ion source, from which, starting from the start, ions on the surface of the time-of-flight mass spectrometer detector.
  • the Orbits on which the ions move are determined by the existing electrical fields and arise in a simple manner from the physical laws.
  • a transverse electric field is said to be an electric Field to be understood in the transverse direction, its direction and strength in the area of the ion orbits only slightly different from the Coordinates in the transverse direction.
  • This field is called Deflection field, and the electrodes for its production are called deflection electrodes.
  • the acceleration field and the deflection field are separate arranged from each other, i.e. the deflection field is arranged after the acceleration field.
  • the transverse electric field is created by a parallel plate capacitor generated.
  • the invention is accordingly based on the object of a gas phase ion source indicate with which a larger mass range of ions in the time-of-flight mass spectrometer can be accelerated into it.
  • the deflection field becomes the acceleration field directly superimposed so that the deflection field contains the speed components at the earliest possible time can compensate transverse to the direction of acceleration.
  • the deflection of the ion trajectories from the ion optical axis is kept small, which leads to The consequence of this is that particles with a larger mass still pass through apertures in the beam path can pass through.
  • the deflection field can be directly superimposed on the acceleration field by the electrodes producing the deflection field are integrated into the accelerating field. Usually this means that the electrodes generating the deflection field between the accelerating ones Field-generating electrodes must be arranged.
  • an electric field arises, which is a sum of a transverse electric field and an electric field with high cylindrical symmetry to the ion-optical axis.
  • 1a, 1b show the simplest embodiment of the invention according to claim 1.
  • Ions which are located at the start time in the withdrawal volume (11), are shown by the acceleration field generated by a repeller electrode (1) and an acceleration electrode (2) Paths (12) accelerated, which end on the detector of the time-of-flight mass spectrometer.
  • Known solutions exist for the further guidance of the ions after the ion source in the time-of-flight mass spectrometer, which is why they are not discussed in more detail here.
  • the deflection electrodes (20) are designed as flat deflection plates in this exemplary embodiment. As can be seen in FIG.
  • the deflection electrodes are arranged symmetrically to a normal plane of the gas or ion beam (10) to be examined, indicated by dashed lines ( B - B ' ).
  • the gas or ion beam (10) to be examined crosses the acceleration field through openings (21) in the two deflection electrodes (20).
  • the electrodes (1,2) which generate the accelerating electric field here the acceleration electrode (2) can also be used form the boundary of two areas of different gas pressure.
  • the opening (3) in the middle of the electrode (2) the function of a gas flow impedance.
  • Gas flow impedances are to be understood here as small openings Cross-section, which are large enough to keep the ions on their orbits to pass to the detector, but their conductance for gases is essential is lower than the pumping capacity of the pump in the area with the lower pressure. This latter area is usually seen in the direction of flight of the ions, behind the gas flow impedance.
  • Gas flow impedances thus have the advantage that through them with a high particle density in the discharge volume, the lowest possible residual gas pressure achieved in the remaining areas of the time-of-flight mass spectrometer can be. This is desirable to avoid collisions with the ions Atoms or molecules of the residual gas that cover the dynamic range of the Can minimize time-of-flight mass spectrometers.
  • the electrode arrangement in the exemplary embodiment according to FIGS. 1a, 1b creates a resultant electric field through the superimposition of an accelerating and a transverse field, by means of which the transverse speed components of the charged particles which are still present initially are largely canceled out already in the acceleration phase. In this way, ions of large masses can also be accelerated on orbits into the time-of-flight mass spectrometer.
  • FIGS. 1a, 1b The arrangement according to FIGS. 1a, 1b is not yet the optimal solution, since after deduction of the transverse field, ie after equating the potentials of the left and right deflection electrodes, the remaining electric field is not very homogeneous in the area of the discharge volume. This results in flight time errors that are difficult to compensate for. Flight time errors generally increase with the distance of an ion trajectory from the ion optical axis. If one has therefore decided on a certain limit below which flight time errors can be tolerated, an inhomogeneous electric field in the area of the withdrawal volume reduces the permissible distance of the ion trajectory from the ion-optical axis, ie the usable area in the withdrawal volume. This reduces the sensitivity of the time-of-flight mass spectrometer.
  • the ions are focused or defocused anisotropically with respect to the ion-optical axis when crossing the acceleration path. It follows that at least one further anisotropic lens element is required in the further course of the ion path.
  • Anisotropic lens elements are generally more complex, expensive and difficult to adjust than cylindrical symmetrical lens elements.
  • An electrical field with the required properties is by means of a To produce electrode construction in which the required cylinder symmetry of the remaining electric field can be achieved can, by making the deflection electrodes themselves cylindrical symmetrical Gives shape.
  • the gas flow impedance (3) on the acceleration electrode (2) is designed here as a tube which has a lower conductance for gases than a pinhole of the same cross section. However, as in FIG. 1a, a hole can be provided as the gas flow impedance.
  • the has cylindrical symmetry Training the deflection electrodes the further advantage that the Deflection electrodes can initially be manufactured as a turned part. In in a subsequent operation, they can then be broken down into two parts become.
  • 3a, 3b show an example of how two pairs of deflection electrodes (20, 25) can be arranged. This has the advantage that openings do not have to be provided either for the gas or ion beam (10) to be examined or for an ionizing laser beam. In addition, the volume of the acceleration section can be pumped out better. As shown in FIGS. 3a, 3b , the two pairs of deflection electrodes can also have different radii to the axis of the ion source.
  • the deflecting electrodes (20) can additionally be symmetrically divided along the plane which is defined by the direction of acceleration and the gas or ion beam (10) to be examined.
  • the quadrupole component must be zero due to symmetry considerations.
  • the remaining portion, which is not cylindrically symmetrical, then has octupole symmetry in this case, the strength of which in the lowest order is proportional to the fourth power of the distance to the axis of symmetry. If higher demands are placed on the imaging quality of the ion source, the symmetry of the electric field can be additionally increased in this way.

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  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

In order to achieve a high mass resolution in a time-of-flight mass spectrometer with gas phase ion source, the initial-speed components in the acceleration direction of the ions must be kept small. This can be achieved in that the gas or ion beam to be investigated traverses the ion source at right angles relative to the acceleration direction. If acceleration direction and flight direction of the gas or ion beam to be investigated are not parallel, then the flight path is loaded with less gas ballast, the dynamic range of the mass spectrometer being increased as a result. The mass range of such an ion source is limited by the fact that heavy ions can be deflected too far from the axis of the ion source and can get lost as a result. When the deflection field is already located in the acceleration path, the mass range of this ion source can be expanded significantly. <IMAGE>

Description

Die Erfindung betrifft eine Gasphasen-Ionenquelle nach dem Oberbegriff des Anspruch 1.The invention relates to a gas phase ion source according to the preamble of claim 1.

Bei der Flugzeit-Massenanalyse gibt es einen Start-Zeitpunkt, ab welchem eine Gruppe von Ionen im Flugzeit-Massenspektrometer gestartet wird. Am Ende einer Flugstrecke wird die Zeit gemessen, welche das jeweilige ankommende Ion benötigt hat und hieraus die Masse des betreffenden Ions ermittelt.In the time-of-flight mass analysis, there is a start time from which started a group of ions in the time-of-flight mass spectrometer becomes. At the end of a flight route, the time is measured needed each incoming ion and from this the mass of the concerned Ions determined.

In einer Gasphasen-Ionenquelle eines Flugzeit-Massenspektrometers wird als Abzugsvolumen der Raumbereich der Ionenquelle verstanden, aus welchem, beginnend ab dem Start-Zeitpunkt, Ionen auf die Oberfläche des Detektors des Flugzeit-Massenspektrometers gelangen können. Die Bahnen, auf welchen sich die Ionen dabei bewegen, sind bestimmt durch die vorhandenen elektrischen Felder und ergeben sich in einfacher Weise aus den physikalischen Gesetzen.In a gas phase ion source of a time-of-flight mass spectrometer is understood as the withdrawal volume the spatial area of the ion source, from which, starting from the start, ions on the surface of the time-of-flight mass spectrometer detector. The Orbits on which the ions move are determined by the existing electrical fields and arise in a simple manner from the physical laws.

Der Start-Zeitpunkt der Flugzeit-Analyse kann z.B. gegeben sein durch

  • den Zeitpunkt, in dem neutrale Teilchen eines im Abzugsvolumen befindlichen zu untersuchenden Gases durch den Puls einer das Abzugsvolumen durchstrahlenden Laserstrahl- oder Elektronenstrahlquelle ionisiert werden.
  • den Zeitpunkt des Anschaltens der Elektrodenspannungen der Ionenquelle. In diesem Fall handelt es sich meist darum, Ionen zu untersuchen, da Ionen nur dann in das Abzugsvolumen gelangen können, wenn an den Elektroden der Ionenquelle keine Spannungen anliegen.
The start time of the flight time analysis can be given, for example, by
  • the point in time at which neutral particles of a gas to be examined in the discharge volume are ionized by the pulse of a laser beam or electron beam source radiating through the discharge volume.
  • the time at which the electrode voltages of the ion source are switched on. In this case, it is usually a matter of examining ions, since ions can only get into the withdrawal volume if there are no voltages at the electrodes of the ion source.

Als ionenoptische Achse bezeichnet man bei Gasphasen-Ionenquellen diejenige Bahn eines Ions, welches zum Startzeitpunkt von einem geeignet gewählten Punkt nahe der geometrischen Mitte des Abzugsvolumens mit der Anfangsgeschwindigkeit υ = 0 aus startet. Ist der Aufbau der Ionenquelle zylindersymmetrisch, so wird als Startpunkt der ionenoptischen Achse üblicherweise ein Punkt auf der Symmetrieachse der Ionenquelle ausgewählt.In gas-phase ion sources, the ion-optical axis is the path of an ion that, at the starting time, starts from a suitably chosen point near the geometric center of the withdrawal volume at the initial speed υ = 0 off starts. If the structure of the ion source is cylindrically symmetrical, a point on the axis of symmetry of the ion source is usually selected as the starting point of the ion optical axis.

Um in einem Flugzeit-Massenspektrometer mit Gasphasen-Ionenquelle eine hohe Massenauflösung zu erzielen, müssen die Anfangs-Geschwindigkeitskomponenten in Beschleunigungsrichtung der Ionen klein gehalten werden. Dies läßt sich erreichen, indem der zu untersuchende Gas- bzw. Ionenstrahl in rechtem Winkel zur Beschleunigungsrichtung die Ionenquelle durchquert. In der Veröffentlichung von Bergmann et al. (Review of Scientific Instruments, Band 60(4), Seiten 792-793, 1989) ist gezeigt, warum der rechte Winkel nötig ist, und wie auf diese Weise eine Massenauflösung von 35000 (m/Δm) FWHM (Full Width at Half Maximum) erzielt wurde.In order to achieve a high mass resolution in a time-of-flight mass spectrometer with a gas-phase ion source, the initial velocity components in the direction of acceleration of the ions must be kept small. This can be achieved by the gas or ion beam to be examined crossing the ion source at a right angle to the direction of acceleration. In the publication by Bergmann et al. (Review of Scientific Instruments, Volume 60 (4), pages 792-793, 1989) shows why the right angle is necessary and how a mass resolution of 35000 ( m / Δ m ) FWHM (Full Width at Half Maximum) was achieved.

Es gibt zwei Arten von Ionenquellen, bei welchen der zu untersuchende Gas- bzw. Ionenstrahl nicht parallel zur Beschleunigungsrichtung der Ionenquelle ist.

  • Die geschwindigkeitsfokussierende Ionenquelle: Diese Ionenquelle ist gebräuchlich, falls die Geschwindigkeitsverteilung der Teilchen in dem zu untersuchenden Gas- bzw. Ionenstrahl breit ist. Bei dieser Ionenquelle sollen alle Ionen, unabhängig von ihren Anfangsgeschwindigkeiten in transversaler Richtung auf Bahnen, so parallel wie möglich zur ionenoptischen Achse, gezwungen werden. Diese Ionenquelle entspricht nicht dem Oberbegriff von Anspruch 1, und wird hier nicht weiter besprochen.
  • Die Ionenquelle mit Ablenkfeld: Diese Ionenquelle ist gebräuchlich, falls die Geschwindigkeitsverteilung der Teilchen in dem zu untersuchenden Gas- bzw. Ionenstrahl eng ist. Da dann bei allen Ionen die transversale Geschwindigkeit um einen sehr ähnlichen Betrag geändert werden soll, benötigt man ein von den transversalen Koordinaten unabhängiges elektrisches Feld in transversaler Richtung. Diese Ionenquelle entspricht dem Oberbegriff von Anspruch 1.
There are two types of ion sources in which the gas or ion beam to be examined is not parallel to the direction of acceleration of the ion source.
  • The speed-focusing ion source: This ion source is used if the speed distribution of the particles in the gas or ion beam to be examined is wide. With this ion source, all ions, regardless of their initial velocities in the transverse direction on orbits, should be forced as parallel as possible to the ion-optical axis. This ion source does not correspond to the preamble of claim 1 and is not discussed further here.
  • The ion source with deflection field: This ion source is used if the velocity distribution of the particles in the gas or ion beam to be examined is narrow. Since the transverse velocity should then be changed by a very similar amount for all ions, an electric field in the transverse direction which is independent of the transverse coordinates is required. This ion source corresponds to the preamble of claim 1.

Unter einem transversalen elektrischen Feld soll im folgenden ein elektrisches Feld in transversaler Richtung verstanden werden, dessen Richtung und Stärke im Bereich der Ionenbahnen nur geringfügig von den Koordinaten in transversaler Richtung abhängt. Dieses Feld nennt man Ablenkfeld, und die Elektroden zu seiner Erzeugung nennt man Ablenkelektroden.Below, a transverse electric field is said to be an electric Field to be understood in the transverse direction, its direction and strength in the area of the ion orbits only slightly different from the Coordinates in the transverse direction. This field is called Deflection field, and the electrodes for its production are called deflection electrodes.

Außer der Möglichkeit, eine höhere Massenauflösung zu erzielen, weisen Gasphasen-Ionenquellen nach dem Oberbegriff des Anspruch 1 noch eine weitere Reihe von Vorzügen auf:

  • In dem Kapitel "III. Results, A. Time-of-flight mass spectrometer" der Veröffentlichung von Dietz et al. (Journal of Chemical Physics, Band 73(10), Seite 4816-4821, 1980) wird diskutiert, welcher Mechanismus verhindert, daß ein unerwünschtes Signal durch Hintergrundgase im Massenspektrum erscheint. Hintergrundgase sind die Teilchen, welche aufgrund des unvermeidlichen, vakuumtechnischen Restgasdrucks in der Vakuumkammer der Ionenquelle vorhanden sind.
  • Der Massenbereich der von der Ionenquelle in das Flugzeit-Massenspektrometer beschleunigten Ionen läßt sich nach oben und unten begrenzen, indem man statische Spannungen an die Ablenkelektroden anlegt. Fig. 2 der Veröffentlichung von Rohlfing et al. (Journal of Physical Chemistry, Band 88, Seite 4497-4502, 1984) zeigt, wie durch Anlegen verschiedener Spannungen an die Ablenkplatten sich verschiedene Massenbereiche auswählen lassen.
  • Legt man eine zeitlich variable Spannung an die Ablenkplatten an, so kann die Ionenquelle Ionen eines wesentlich größeren Massenbereichs, nur noch begrenzt durch Blenden im Strahlengang, in das Flugseit-Massenspektrometer hinein beschleunigen. Diese Möglichkeit wird von Lubman und Jordan in ihrer Veröffentlichung (Review of Scientific Instruments, Band 56(3), Seite 373-376, 1985) diskutiert.
In addition to the possibility of achieving a higher mass resolution, gas phase ion sources have a further series of advantages according to the preamble of claim 1:
  • In the chapter "III. Results, A. Time-of-flight mass spectrometer" of the publication by Dietz et al. (Journal of Chemical Physics, Volume 73 (10), pages 4816-4821, 1980) discusses which mechanism prevents an unwanted signal from background gases from appearing in the mass spectrum. Background gases are the particles that are present in the vacuum chamber of the ion source due to the inevitable vacuum-technical residual gas pressure.
  • The mass range of the ions accelerated from the ion source into the time-of-flight mass spectrometer can be limited upwards and downwards by applying static voltages to the deflection electrodes. Fig. 2 of the publication by Rohlfing et al. (Journal of Physical Chemistry, Volume 88, pages 4497-4502, 1984) shows how different mass ranges can be selected by applying different voltages to the baffles.
  • If a voltage which is variable over time is applied to the deflection plates, the ion source can accelerate ions of a much larger mass range, limited only by apertures in the beam path, into the flight side mass spectrometer. This possibility is discussed by Lubman and Jordan in their publication (Review of Scientific Instruments, Volume 56 (3), pages 373-376, 1985).

Aus Review of Scientific Instruments, Band 60(6), Seiten 1065-1070 ist eine weitere Gasphasen-Ionenquelle für ein Flugzeit-Massenspektrometer bekannt.From Review of Scientific Instruments, Volume 60 (6), pages 1065-1070 is one known gas-phase ion source for a time-of-flight mass spectrometer.

Den Konstruktionen bisher bekannter Ionenquellen mit Ablenkfeld liegen folgende Tatsachen zugrunde:

  • Für Ionen, deren Anfangsgeschwindigkeit in Beschleunigungsrichtung Null ist, soll die Endgeschwindigkeit in Beschleunigigungsrichtung ausschließlich von der Ortskoordinate parallel zur Beschleunigungsrichtung abhängen. Die Endgeschwindigkeit in Beschleunigungsrichtung soll insbesondere unabhängig von den Ortskoordinaten und Anfangsgeschwindigkeiten in transversaler Richtung sein. Ein solches Verhalten läßt sich mit einem homogenen Beschleunigungsfeld erreichen.
  • Nach Durchlaufen eines homogenen Beschleunigungsfeldes sind die Geschwindigkeitskomponenten in transversaler Richtung unverändert geblieben. Die Geschwindigkeitskomponenten in transversaler Richtung sind unabhängig vom Startort der Ionen, und damit auch unabhängig von den Koordinaten ihrer Bahn nach dem Beschleunigungsfeld. Somit ist zur Änderung der Geschwindigkeitskomponenten in transversaler Richtung ein Ablenkfeld erforderlich, dessen Feldstärke in transversaler Richtung unabhängig von den transversalen Koordinaten ist.
The designs of previously known ion sources with a deflection field are based on the following facts:
  • For ions whose initial speed in the direction of acceleration is zero, the final speed in the direction of acceleration should depend exclusively on the position coordinate parallel to the direction of acceleration. The final speed in the direction of acceleration should in particular be independent of the location coordinates and initial speeds in the transverse direction. Such behavior can be achieved with a homogeneous acceleration field.
  • After passing through a homogeneous acceleration field, the speed components have remained unchanged in the transverse direction. The velocity components in the transverse direction are independent of the starting point of the ions and thus also independent of the coordinates of their orbit after the acceleration field. A deflection field is therefore required to change the speed components in the transverse direction, the field strength of which in the transverse direction is independent of the transverse coordinates.

Bei allen bisher bekannten Lösungen sind Beschleunigungsfeld und Ablenkfeld getrennt voneinander angeordnet, d.h. das Ablenkfeld ist nach dem Beschleunigungsfeld angeordnet. Üblicherweise wird das transversale elektrische Feld durch einen Parallelplatten-Kondensator erzeugt. Dadurch ist bei allen diesen Ionenquellen der Massenbereich nach oben begrenzt, da nämlich die schweren Ionen, bevor sie das Ablenkfeld spüren, sich zu weit von der ionenoptischen Achse, welche in Beschleunigungsrichtung der Ionenquelle weist, entfernt haben, und so z.B. an Blenden verloren gehen.In all previously known solutions, the acceleration field and the deflection field are separate arranged from each other, i.e. the deflection field is arranged after the acceleration field. Usually the transverse electric field is created by a parallel plate capacitor generated. As a result, the upper limit of the mass range is limited for all of these ion sources namely, the heavy ions, before they feel the deflection field, are too far from the ion optical Axis which points in the direction of acceleration of the ion source, and so e.g. get lost on panels.

Bei allen oben genannten Vorteilen, die sich ergeben, wenn die Richtung des zu untersuchenden Gas- bzw. Ionenstrahls senkrecht auf der Beschleunigungsrichtung der Ionenquelle steht, so ist doch die eben genannte Beschränkung des Massenbereichs ein entscheidender Nachteil.With all the advantages mentioned above, which result when the direction of the examined Gas or ion beam is perpendicular to the direction of acceleration of the ion source, the limitation of the mass range just mentioned is a decisive disadvantage.

Aus der Publikation von C.W.S. Conover et al. in Review of Scientific Instruments, Bd. 60, Nr.6, Juni 1989, Seiten 1065-1070, ist ein Flugzeit-Massenspektrometer bekannt, in welchem die Beschleunigungselektroden verdreht werden, sodaß die anfänglichen Transversalgeschwindigkeiten von zu untersuchenden Molekülclustern reduziert werden können.From the publication by C.W.S. Conover et al. in Review of Scientific Instruments, Vol. 60, No. 6, June 1989, pages 1065-1070, a time-of-flight mass spectrometer is known in which the acceleration electrodes are rotated so that the initial transverse speeds of molecular clusters to be examined can be reduced.

Der Erfindung liegt dementsprechend die Aufgabe zugrunde, eine Gasphasen-Ionenquelle anzugeben, mit welcher ein größerer Massenbereich von Ionen in das Flugzeit-Massenspektrometer hinein beschleunigt werden kann.The invention is accordingly based on the object of a gas phase ion source indicate with which a larger mass range of ions in the time-of-flight mass spectrometer can be accelerated into it.

Diese Aufgabe wird durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst.This object is achieved by the characterizing features of claim 1.

Bei der erfindungsgemäßen Vorrichtung wird das Ablenkfeld dem Beschleunigungsfeld direkt überlagert, so daß das Ablenkfeld zu dem frühestmöglichen Zeitpunkt die Geschwindigkeitskomponenten quer zur Beschleunigungsrichtung kompensieren kann. Auf diese Weise wird die Auslenkung der Ionenbahnen von der ionenoptischen Achse klein gehalten, was zur Folge hat, daß Teilchen mit größerer Masse noch durch im Strahlengang vorhandene Blenden hindurch passieren können.In the device according to the invention, the deflection field becomes the acceleration field directly superimposed so that the deflection field contains the speed components at the earliest possible time can compensate transverse to the direction of acceleration. In this way the deflection of the ion trajectories from the ion optical axis is kept small, which leads to The consequence of this is that particles with a larger mass still pass through apertures in the beam path can pass through.

In vielen Fällen laßt sich das Ablenkfeld dem Beschleunigungsfeld direkt überlagern, indem die das Ablenkfeld erzeugenden Elektroden in das beschleunigende Feld integriert werden. Üblicherweise bedeutet dies, daß die das Ablenkfeld erzeugenden Elektroden zwischen den das beschleunigende Feld erzeugenden Elektroden angeordnet werden müssen.In many cases, the deflection field can be directly superimposed on the acceleration field by the electrodes producing the deflection field are integrated into the accelerating field. Usually this means that the electrodes generating the deflection field between the accelerating ones Field-generating electrodes must be arranged.

Es ist ferner von besonderem Vorteil, wenn die Elektroden so angeordnet sind, daß ein elektrisches Feld entsteht, welches sich als Summe eines transversalen elektrischen Feldes und eines elektrischen Feldes mit hoher Zylindersymmetrie zur ionenoptischen Achse darstellen läßt.It is also of particular advantage if the electrodes are arranged in this way are that an electric field arises, which is a sum of a transverse electric field and an electric field with high cylindrical symmetry to the ion-optical axis.

Im Folgenden wird nun anhand der in den Zeichnungen dargestellten Ausführungsbeispielen die Erfindung näher beschrieben und erläutert.The following is now based on that shown in the drawings Embodiments described and explained the invention in more detail.

Fig. 1a,1b zeigen die einfachste Ausführungsform der Erfindung nach Anspruch 1. Ionen, die sich zum Start-Zeitpunkt im Abzugsvolumen(11) befinden, werden durch das von einer Repellerelektrode(1) und einer Beschleunigungselektrode(2) erzeugte Beschleunigungsfeld auf den gezeichneten Bahnen(12) beschleunigt, welche auf dem Detektor des Flugzeit-Massenspektrometers enden. Für die weitere Führung der Ionen nach der Ionenquelle im Flugzeit-Massenspektrometer gibt es bekannte Lösungen, weshalb hier nicht näher darauf eingegangen wird. Die Ablenkelektroden(20) sind in diesem Ausführungsbeispiel als ebene Ablenkplatten ausgeführt. Die Ablenkelektroden sind, wie in Fig. 1b zu sehen, symmetrisch zu einer gestrichelt mit ( B ― B' ) angedeuteten Normalebene des zu untersuchenden Gas- bzw. Ionenstrahls(10) angeordnet. Der zu untersuchende Gas- bzw. Ionenstrahl(10) kreuzt das Beschleunigungsfeld durch Öffnungen(21) in den beiden Ablenkelektroden(20). 1a, 1b show the simplest embodiment of the invention according to claim 1. Ions, which are located at the start time in the withdrawal volume (11), are shown by the acceleration field generated by a repeller electrode (1) and an acceleration electrode (2) Paths (12) accelerated, which end on the detector of the time-of-flight mass spectrometer. Known solutions exist for the further guidance of the ions after the ion source in the time-of-flight mass spectrometer, which is why they are not discussed in more detail here. The deflection electrodes (20) are designed as flat deflection plates in this exemplary embodiment. As can be seen in FIG. 1b, the deflection electrodes are arranged symmetrically to a normal plane of the gas or ion beam (10) to be examined, indicated by dashed lines ( B - B ' ). The gas or ion beam (10) to be examined crosses the acceleration field through openings (21) in the two deflection electrodes (20).

Die Elektroden(1,2), welche das beschleunigende elektrische Feld erzeugen, hier die Beschleunigungselektrode(2), können dabei auch zusätzlich die Begrenzung zweier Bereiche verschiedenen Gasdruckes bilden. Als Beispiel erfüllt dann die Öffnung(3) in der Mitte der Elektrode(2) die Funktion einer Gas-Strömungsimpedanz.The electrodes (1,2) which generate the accelerating electric field here the acceleration electrode (2) can also be used form the boundary of two areas of different gas pressure. As an example, the opening (3) in the middle of the electrode (2) the function of a gas flow impedance.

Gas-Strömungsimpedanzen sind hier zu verstehen als Öffnungen kleinen Querschnitts, welche groß genug sind, um die Ionen auf ihren Bahnen zum Detektor passieren zu lassen, deren Leitwert für Gase jedoch wesentlich niedriger ist als die Pumpleistung der Pumpe des Bereichs mit dem niedrigeren Druck. Dieser letztgenannte Bereich liegt für gewöhnlich, gesehen in Flugrichtung der Ionen, hinter der Gas-Strömungsimpedanz.Gas flow impedances are to be understood here as small openings Cross-section, which are large enough to keep the ions on their orbits to pass to the detector, but their conductance for gases is essential is lower than the pumping capacity of the pump in the area with the lower pressure. This latter area is usually seen in the direction of flight of the ions, behind the gas flow impedance.

Gas-Strömungsimpedanzen haben damit den Vorteil, daß durch sie bei hoher Teilchendichte im Abzugsvolumen ein möglichst niedriger Restgasdruck in den übrigen Bereichen des Flugzeit-Massenspektrometers erzielt werden kann. Dies ist wünschenswert, um Stöße der Ionen mit Atomen oder Molekülen des Restgases, die den dynamischen Bereich des Flugzeit-Massenspektrometers herabsetzen können, zu minimieren.Gas flow impedances thus have the advantage that through them with a high particle density in the discharge volume, the lowest possible residual gas pressure achieved in the remaining areas of the time-of-flight mass spectrometer can be. This is desirable to avoid collisions with the ions Atoms or molecules of the residual gas that cover the dynamic range of the Can minimize time-of-flight mass spectrometers.

Die kombinierte Verwendung von zwischen den Beschleunigungselektroden(1,2) angeordneten Ablenkelektroden und in die Beschleunigungselektroden(1,2) integrierten Gas-Strömungsimpedanzen bewirkt damit nicht nur, daß schwerere Ionen den Detektor erreichen können, sonden zusätzlich, daß diese durch Stöße auf ihrer Flugbahn weniger stark beeinträchtigt werden.The combined use of between the accelerating electrodes (1,2) arranged deflection electrodes and in the acceleration electrodes (1,2) integrated gas flow impedances not only that heavier ions can reach the detector in addition, that these are less affected by impacts on their trajectory become.

Durch die Elektrodenanordnung in dem Ausführungsbeispiel nach Fig. 1a,1b entsteht durch die Überlagerung eines beschleunigenden und eines transversalen Feldes ein resultierendes elektrisches Feld, durch welches die anfänglich noch vorhandenen transversalen Geschwindigkeitskomponenten der geladenen Teilchen bereits in der Beschleunigungsphase weitgehend aufgehoben werden. Auf diese Weise lassen sich mit dieser Anordnung auch Ionen großer Massen auf Bahnen ins Flugzeit-Massenspektrometer beschleunigen.The electrode arrangement in the exemplary embodiment according to FIGS. 1a, 1b creates a resultant electric field through the superimposition of an accelerating and a transverse field, by means of which the transverse speed components of the charged particles which are still present initially are largely canceled out already in the acceleration phase. In this way, ions of large masses can also be accelerated on orbits into the time-of-flight mass spectrometer.

Die Anordnung nach Fig. 1a,1b ist jedoch noch nicht die optimale Lösung, da nach Abzug des transversalen Feldes, d.h. nach Gleichsetzen der Potentiale der linken und rechten Ablenkelektroden, das verbleibende elektrische Feld im Bereich des Abzugsvolumens nicht sehr homogen ist. Hieraus resultieren schwer ausgleichbare Flugzeitfehler. Flugzeitfehler nehmen generell zu mit dem Abstand einer Ionenbahn zur ionenoptischen Achse. Hat man sich also auf eine gewisse Grenze festgelegt, unterhalb welcher Flugzeitfehler tolerierbar sind, so reduziert ein inhomogenes elektrisches Feld im Bereich des Abzugsvolumens den zulässigen Abstand der Ionenbahn zur ionenoptischen Achse, d.h. den nutzbaren Bereich im Abzugsvolumen. Dadurch nimmt die Empfindlichkeit des Flugzeit-Massenspektrometers ab.The arrangement according to FIGS. 1a, 1b is not yet the optimal solution, since after deduction of the transverse field, ie after equating the potentials of the left and right deflection electrodes, the remaining electric field is not very homogeneous in the area of the discharge volume. This results in flight time errors that are difficult to compensate for. Flight time errors generally increase with the distance of an ion trajectory from the ion optical axis. If one has therefore decided on a certain limit below which flight time errors can be tolerated, an inhomogeneous electric field in the area of the withdrawal volume reduces the permissible distance of the ion trajectory from the ion-optical axis, ie the usable area in the withdrawal volume. This reduces the sensitivity of the time-of-flight mass spectrometer.

Da die Anordnung nach Fig. 1a,1b anisotrop bezüglich der ionenoptischen Achse aufgebaut ist, werden die Ionen beim Durchqueren der Beschleunigungsstrecke anisotrop bezüglich der ionenoptischen Achse fokussiert bzw. defokussiert. Daraus folgt, daß im weiteren Verlauf der Ionenbahn mindestens ein weiteres anisotropes Linsenelement erforderlich ist. Anisotrope Linsenelemente sind generell aufwendiger, teurer und schwerer zu justieren als zylindersymmetrische Linsenelemente.Since the arrangement according to FIGS. 1a, 1b is constructed anisotropically with respect to the ion-optical axis, the ions are focused or defocused anisotropically with respect to the ion-optical axis when crossing the acceleration path. It follows that at least one further anisotropic lens element is required in the further course of the ion path. Anisotropic lens elements are generally more complex, expensive and difficult to adjust than cylindrical symmetrical lens elements.

Daraus kann man folgende Forderungen an das verbleibende elektrische Feld erkennen:

  • 1. Im Bereich des Abzugsvolumens muß es ausreichend homogen sein.
  • 2. Im gesamten Bereich der Ionenquelle soll es zylindersymmetrich sein.
    • Insbesondere die zweite Forderung stellt eine signifikante Erleichterung gegenüber der Forderung nach dem bisherigen Stand der Technik dar. Es ist also nicht notwendig, ein in dem gesamten Bereich der Beschleunigungsstrecke homogenes Beschleunigungsfeld mit einem transversalen Feld zu überlagern, sondern nur ein zylindersymmetrisches Beschleunigungsfeld und ein transversales Feld zu überlagern. Eine ausreichende Homogenität in dem kleinen Bereich des Abzugsvolumens läßt sich dann erzielen. From this one can see the following demands on the remaining electric field:
  • 1. It must be sufficiently homogeneous in the area of the discharge volume.
  • 2. It should be cylindrically symmetrical in the entire area of the ion source.
    • The second requirement in particular represents a significant relief compared to the requirement according to the prior art. It is therefore not necessary to overlay an acceleration field which is homogeneous in the entire area of the acceleration path with a transverse field, but only a cylinder-symmetrical acceleration field and a transverse field to overlay. Sufficient homogeneity in the small area of the draw volume can then be achieved.

    Ein elektrisches Feld mit den geforderten Eigenschaften ist mittels einer Elektrodenkonstruktion zu erzeugen, in der die geforderte Zylindersymmetrie des verbleibenden elektrischen Feldes dadurch erreicht werden kann, indem man den Ablenkelektroden selbst zylindersymmetrische Form verleiht.An electrical field with the required properties is by means of a To produce electrode construction in which the required cylinder symmetry of the remaining electric field can be achieved can, by making the deflection electrodes themselves cylindrical symmetrical Gives shape.

    Eine solche Ausführungsform wird beispielhaft in Fig. 2a,2b gezeigt. Wie in Fig. 2b zu sehen, sind die Ablenkelektroden(20) (schraffiert) zylindersymmetrisch zur ionenoptischen Achse der Ionenquelle angeordnet. Auf diese Weise läßt sich ein elektrisches Feld mit den geforderten Eigenschaften erzeugen. Dieses elektrische Feld läßt sich zerlegen in die beiden Anteile:

    • ein transversales elektrisches Feld, dessen Richtung und Stärke in transversaler Richtung im Bereich der Ionenbahnen vergleichsweise unabhängig von den Koordinaten in transversaler Richtung ist. Dieser Anteil des Feldes entsteht, wenn die linken und rechten Ablenkelektroden auf gegengleiche Potentiale, und die übrigen Elektroden auf Masse gelegt werden.
    • ein nahezu zylindersymmetrisches elektrisches Feld, welches im Bereich des Abzugsvolumens ausreichend homogen ist. Dieser Anteil des Feldes entsteht, wenn die linken und rechten Ablenkelektroden auf gleiche Potentiale gelegt werden.
    Der zu untersuchende Gas- bzw. Ionenstrahl(10) kreuzt das Beschleunigungsfeld durch Öffnungen(21) in den beiden Ablenkelektroden, für einen ionisierenden Elektronen- oder Laserstrahl sind Aussparungen(22) zwischen den beiden Ablenkelektroden vorgesehen.Such an embodiment is shown by way of example in FIGS. 2a, 2b . As can be seen in FIG. 2b , the deflection electrodes (20) (hatched) are arranged cylindrically symmetrically to the ion-optical axis of the ion source. In this way, an electric field with the required properties can be generated. This electric field can be broken down into two parts:
    • a transverse electric field, the direction and strength of which in the transverse direction in the region of the ion trajectories is comparatively independent of the coordinates in the transverse direction. This part of the field arises when the left and right deflection electrodes are connected to opposite potentials and the remaining electrodes are connected to ground.
    • an almost cylindrical symmetrical electric field, which is sufficiently homogeneous in the area of the discharge volume. This part of the field arises when the left and right deflection electrodes are connected to the same potential.
    The gas or ion beam (10) to be examined crosses the acceleration field through openings (21) in the two deflection electrodes, and recesses (22) are provided between the two deflection electrodes for an ionizing electron or laser beam.

    Die Gas-Strömungsimpedanz(3) an der Beschleunigungselektrode(2) ist hier als Rohr ausgebildet, das einen niedrigeren Leitwert für Gase als eine Lochblende gleichen Querschnitts aufweist. Es kann jedoch wie in Fig. 1a ein Loch als Gas-Strömungsimpedanz vorgesehen werden.The gas flow impedance (3) on the acceleration electrode (2) is designed here as a tube which has a lower conductance for gases than a pinhole of the same cross section. However, as in FIG. 1a, a hole can be provided as the gas flow impedance.

    Zusätzlich zu den optimalen Feldeigenschaften hat die zylindersymmetrische Ausbildung der Ablenkelektroden den weiteren Vorteil, daß die Ablenkelektroden zunächst als Drehteil hergestellt werden können. In einem anschließenden Arbeitsgang können sie dann in zwei Teile zerlegt werden.In addition to the optimal field properties, the has cylindrical symmetry Training the deflection electrodes the further advantage that the Deflection electrodes can initially be manufactured as a turned part. In in a subsequent operation, they can then be broken down into two parts become.

    Fig. 3a,3b zeigen beispielhaft, wie zwei Ablenkelektrodenpaare(20,25) angeordnet werden können. Dies hat den Vorteil, daß weder für den zu untersuchenden Gas- bzw. Ionenstrahl(10) noch für einen ionisierenden Laserstrahl Öffnungen vorgesehen werden müssen. Außerdem läßt sich das Volumen der Beschleunigungsstrecke so besser abpumpen. Wie in Fig. 3a,3b gezeigt, können die beiden Ablenkelektrodenpaare auch unterschiedliche Radien zur Achse der Ionenquelle haben. 3a, 3b show an example of how two pairs of deflection electrodes (20, 25) can be arranged. This has the advantage that openings do not have to be provided either for the gas or ion beam (10) to be examined or for an ionizing laser beam. In addition, the volume of the acceleration section can be pumped out better. As shown in FIGS. 3a, 3b , the two pairs of deflection electrodes can also have different radii to the axis of the ion source.

    In den Beispielen von Fig. 2a,2b und Fig. 3a,3b haben die Ablenkelektroden im wesentlichen zylindersymmetrische Form, außer daß sie in der Ebene, welche durch den Schnitt ( B ― B' ) definiert wird, geteilt sind. Dies bedeutet, daß nach Abzug der transversalen Anteile, das verbleibende elektrische Feld eine hohe Zylindersymmetrie aufweist. Außerdem verbleibt noch, bedingt durch die Schlitze zwischen den beiden Hälften, ein kleiner Feldanteil mit Quadrupolsymmetrie, dessen Stärke in niedrigster Ordnung proportional zum Quadrat des Abstandes zur Symmetrieachse ist. .. In the examples of Figures 2a, 2b and 3a, 3b have the deflection electrodes is substantially cylindrically symmetrical form, except that, in the plane defined by the interface - are defined, shared (B B '). This means that after deducting the transverse parts, the remaining electric field has a high cylindrical symmetry. In addition, due to the slits between the two halves, there remains a small field component with quadrupole symmetry, the strength of which in the lowest order is proportional to the square of the distance from the axis of symmetry.

    Fig. 4a,4b zeigen, wie die Ablenkelektroden(20) noch zusätzlich entlang der Ebene, welche durch die Beschleunigungsrichtung und den zu untersuchenden Gas- bzw. Ionenstrahl(10) definiert wird, symmetrisch geteilt werden können. Bei dieser Anordnung muß aufgrund von Symmetrieüberlegungen der Quadrupolanteil Null sein. Der verbleibende Anteil, welcher nicht zylindersymmetrisch ist, hat in diesem Fall dann Oktupolsymmetrie, dessen Stärke in niedrigster Ordnung proportional zur vierten Potenz des Abstandes zur Symmetrieachse ist. Werden höhere Anforderungen an die Abbildungsqualität der Ionenquelle gestellt, so läßt sich auf diese Weise die Symmetrie des elektrischen Feldes zusätzlich erhöhen. 4a, 4b show how the deflecting electrodes (20) can additionally be symmetrically divided along the plane which is defined by the direction of acceleration and the gas or ion beam (10) to be examined. In this arrangement, the quadrupole component must be zero due to symmetry considerations. The remaining portion, which is not cylindrically symmetrical, then has octupole symmetry in this case, the strength of which in the lowest order is proportional to the fourth power of the distance to the axis of symmetry. If higher demands are placed on the imaging quality of the ion source, the symmetry of the electric field can be additionally increased in this way.

    Claims (10)

    1. A gasphase ion source for time-of-flight mass-spectrometers
      where the gas or ion beam(10) to be analysed has velocity components orthogonal to the direction of acceleration within the ion source,
      in which a region of space called extraction volume(11) is defined, which contains at start time of the mass measurement the ions whose mass is to be determined,
      with accelerating electodes(1,2)
      with deflecting electrodes(20,25)
      said ion source posessing a region of space where the accelerating and the transverse electrical field is superposed,
      said region of space containing the extraction volume(11)
      characterized by deflecting electodes(20,25) that are separate from the accelerating electrodes(1,2).
    2. A gasphase ion source for time-of-flight mass-spectrometers according to claim 1, characterized by electrodes(20,25) generating a transverse field, said electrodes being arranged within the acceleration field.
    3. A gasphase ion source for time-of-flight mass-spectrometers according to claim 2, characterized by electrodes(20,25) capable of generating a transverse field, said electrodes being arranged between the electrodes(1,2) that generate the acceleration field.
    4. A gasphase ion source for time-of-flight mass-spectrometers according to one of the previous claims, characterized by electrodes(20,25) capable of generating a transverse field,
      said electrodes having for the main part rotationally symmetric form around the axis pointing in the direction of acceleration of said ion source,
      said electrodes being split along a plane( B ― B') into two symmetric half-parts, said plane being normal to the direction of flight of the analyte gas or ion beam.
    5. A gasphase ion source for time-of-flight mass-spectrometers according to one of the previous claims, characterized by electrodes(1,2) for generating the acceleration field and electrodes(20,25) for generating the transverse field, all said electrodes having constant voltages.
    6. A gasphase ion source for time-of-flight mass-spectrometers according to one of the claims 1 through 4, characterized by electrodes(1,2) for generating the acceleration field and electrodes(20,25) for generating the transverse field, one or several of said electrodes having constant voltages and one or several of said electrodes having time-dependent voltages.
    7. A gasphase ion source for time-of-flight mass-spectrometers according to one of the previous claims, characterized by electrodes(1,2) for generating the acceleration field and electrodes(20,25) for generating the transverse field, all said electrodes having time-dependent voltages.
    8. A gasphase ion source for time-of-flight mass-spectrometers according to one of the previous claims, characterized by electrodes(20,25) defining a transverse electrical field, said electrodes being additionally split symmetrically along a plane, said plane being defined by two vectors, one of said vectors being the direction of the analyte gas or ion beam, the other of said vectors being the direction of acceleration in the ion source.
    9. A gasphase ion source for time-of-flight mass-spectrometers according to one of the previous claims, characterized by electrodes(1,2), one or several of said electrodes representing a boundary between regions of different gas pressure within the time-of-flight mass-spectrometer, and gas flow restrictions(3) that are integrated into said electrodes.
    10. A time-of-flight mass spectrometer with a gasphase ion source according to one of the previous claims.
    EP94110274A 1993-07-02 1994-07-01 Gas phase ion source for high mass resolution, wide mass range time-of-flight mass spectrometer Expired - Lifetime EP0632482B1 (en)

    Applications Claiming Priority (2)

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    DE4322101 1993-07-02
    DE4322101A DE4322101C2 (en) 1993-07-02 1993-07-02 Ion source for time-of-flight mass spectrometers

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    DE19655304B8 (en) * 1995-12-14 2007-05-31 Micromass Uk Ltd. Mass spectrometers and methods for mass spectrometry
    GB9525507D0 (en) * 1995-12-14 1996-02-14 Fisons Plc Electrospray and atmospheric pressure chemical ionization mass spectrometer and ion source
    US6137112A (en) * 1998-09-10 2000-10-24 Eaton Corporation Time of flight energy measurement apparatus for an ion beam implanter
    US6831280B2 (en) * 2002-09-23 2004-12-14 Axcelis Technologies, Inc. Methods and apparatus for precise measurement of time delay between two signals
    JP4691712B2 (en) * 2005-03-17 2011-06-01 独立行政法人産業技術総合研究所 Time-of-flight mass spectrometer
    EP3306640B1 (en) * 2010-12-20 2024-04-10 Shimadzu Corporation Time-of-flight mass spectrometer

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    US3577165A (en) * 1968-05-31 1971-05-04 Perkin Elmer Corp Linear scanning arrangement for a cycloidal mass spectrometer
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    DE2242987B2 (en) * 1972-09-01 1980-06-12 Gesellschaft Fuer Strahlen- Und Umweltforschung Mbh, 8000 Muenchen Device for separating neutral particles and fast ions from slow ions
    DE2947542A1 (en) * 1979-11-26 1981-06-04 Leybold-Heraeus GmbH, 5000 Köln DEVICE FOR MONITORING AND / OR CONTROLLING PLASMA PROCESSES
    FR2514905A1 (en) * 1981-10-21 1983-04-22 Commissariat Energie Atomique DEVICE FOR MEASURING IONIC CURRENT PRODUCED BY ION BEAM
    JPH03503815A (en) * 1987-12-24 1991-08-22 ユニサーチ　リミテッド mass spectrometer
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    EP0632482A3 (en) 1995-11-29
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