EP0633602A2 - High sensitivity, wide dynamic range time-of-flight mass spectrometer provided with a gas phase ion source - Google Patents
High sensitivity, wide dynamic range time-of-flight mass spectrometer provided with a gas phase ion source Download PDFInfo
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- 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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- 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
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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 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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Abstract
Description
Die Erfindung betrifft ein Flugzeit-Massenspektrometer mit Gasphasen-Ionenquelle nach dem Oberbegriff des Anspruch 1.The invention relates to a time-of-flight mass spectrometer with a gas-phase ion source according to the preamble of
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 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.
In einer Gasphasen-Ionenquelle eines Flugzeit-Massenspektrometers wird als Abzugsvolumen der Raumbereich der Ionenquelle verstanden, aus welchem, beginnend ab dem Start-Zeitpunkt, Ionenbahnen auf die Oberfläche des Detektors des Flugzeit-Massenspektrometers führen.In a gas phase ion source of a time-of-flight mass spectrometer, 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.
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 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 Nebenfunktion können in einem Flugzeit-Massenspektrometer auch die erzeugten Elektronen nachgewiesen werden. Für die Elektronen kann man in Analogie auch ein Abzugsvolumen definieren. Das Abzugsvolumen für die Ionen muß nicht mit dem Abzugsvolumen für die Elektronen deckungsgleich sein. Diese beide Volumina werden aber zumindest sich teilweise überlappen. Üblicherweise werden die Elektronen in der entgegengesetzten Richtung zu den Ionen aus der Quelle abgezogen.As a side function, the generated electrons can also be detected in a time-of-flight mass spectrometer. In analogy, 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. Typically, the electrons are withdrawn from the source in the opposite direction to the ions.
Da der wesentlich häufigere Fall der Nachweis von Ionen ist, wird im Folgenden hauptsächlich darauf eingegangen. Wenn allerdings im Folgenden Ionen und deren Bahnen diskutiert werden, so trifft in entsprechender Analogie dasselbe für Elektronen und deren Bahnen zu.Since the much more common case is the detection of ions, this is mainly dealt with in the following. However, if ions and their orbits are discussed below, the same applies analogously to electrons and their orbits.
In jedem Fall findet in der Ionenquelle, anschließend an den Start-Zeitpunkt, die erste Beschleunigungsphase der am Detektor ankommenden Ionen statt. Oft werden die Ionen in der Ionenquelle auch bis auf die Endgeschwindigkeit beschleunigt. Es kann sein, daß die Ionenquelle noch Elektroden zur Fokussierung der am Detektor ankommenden Ionen enthält. Es kann aber auch sein, daß die Elektroden zur Fokussierung separat angeordnet sind, d.h. die am Detektor ankommenden Ionen die Quelle in einer Richtungs- und Ortsverteilung verlassen, welche für den weiteren Transport durch das Massenspektrometer ungeeignet ist, und aus diesem Grunde noch eine separate Fokussierung nötig ist.In any case, after the start time, 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.
Im Abzugsvolumen ist eine hohe Teilchendichte zum Startzeitpunkt vorteilhaft, da die am Detektor ankommende Anzahl von Ionen proportional zu dieser Dichte ist. Somit ist die Größe des Abzugsvolumens und die Dichte der darin enthaltenen Teilchen ein direktes Maß für die Empfindlichkeit des Flugzeit-Massenspektrometers.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. Thus, 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.
Ein weiteres wichtiges Qualitätsmerkmal eines Flugzeit-Massenspektrometers ist sein dynamischer Bereich. Als dynamischer Bereich ist hier der Faktor gemeint, um welchen das Signal einer bestimmten Masse kleiner als das Signal anderer Massen sein darf, ohne durch zu falschen Zeiten ankommende Ionen dieser anderen Massen zugedeckt zu werden.Another important quality feature of a time-of-flight mass spectrometer is its dynamic range. The dynamic range here 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.
Diese beiden Qualitätsmerkmale werden durch Stöße der Ionen mit Molekülen oder Atomen auf ihrer Bahn zum Detektor beeinträchtigt. Hierbei müssen zwei Arten von Stößen auseinandergehalten werden:
- 1. Stöße, welche die Geschwindigkeit oder Richtung der Ionen derart ändern, daß sie nicht mehr am Detektor ankommen. Sofern diese Art von Stoß nur bei einem geringen Anteil der Ionen auftritt, wird hierdurch der dynamische Bereich und die Empfindlichkeit des Massenspektrometers nicht wesentlich verringert.
- 2. Stöße, welche die Geschwindigkeit oder Richtung der Ionen nur geringfügig verändern, so daß sie immer noch am Detektor ankommen, jedoch zu falschen Zeiten. Diese Stöße verringern zwar die Empfindlichkeit nur in ebenso geringem Maße wie Stöße der ersten Sorte. Da der dynamische Bereich proportional zum Quotient (richtig ankommende)/(falsch ankommende) Ionen ist, und die Anzahl der falsch ankommenden Ionen hier im Nenner steht, ist der Einfluß dieser Art Stöße auf den dynamischen Bereich des Flugzeit-Massenspektrometers sehr groß.
- 1. collisions which change the speed or direction of the ions in such a way that they no longer reach the detector. If this type of collision occurs only with a small proportion of the ions, the dynamic range and the sensitivity of the mass spectrometer are not significantly reduced.
- 2. Collisions that change the speed or direction of the ions only slightly so that they still arrive at the detector, but at wrong times. These impacts only reduce the sensitivity to the same extent as impacts of the first kind. Since the dynamic range is proportional to the quotient (correctly arriving) / (incorrectly arriving) ions, and the number of incorrectly arriving ions is in the denominator here, the impact of this type of impact on the dynamic range of the time-of-flight mass spectrometer is very great.
Um eine hohe Empfindlichkeit des Flugzeit-Massenspektrometers zu erreichen, ist es also notwendig, eine hohe Teilchendichte im Abzugsvolumen zu erreichen. Um einen hohen dynamischen Bereich des Flugzeit-Massenspektrometers zu bewirken, muß ein möglichst niedriger Restgasdruck erzielt werden. Sollen beide Qualitätsmerkmale optimiert werden, so entsteht in vielen Anwendungsfällen der Flugzeit-Massenspektrometrie an Gasphasenteilchen das Problem, daß eine hohe Teilchendichte im Abzugsvolumen auch eine hohe Belastung mit unerwünschtem Gasballast, welcher den Restgasdruck erhöht, bedeutet.In order to achieve a high sensitivity of the time-of-flight mass spectrometer, it is therefore necessary to achieve a high particle density in the withdrawal volume. In order to achieve a high dynamic range of the time-of-flight mass spectrometer, the lowest possible residual gas pressure must be achieved. If both quality features are to be optimized, the problem arises in many applications of time-of-flight mass spectrometry on gas phase particles that a high particle density in the discharge volume also means a high load of undesired gas ballast, which increases the residual gas pressure.
Üblicherweise wird das Flugzeit-Massenspektrometer in verschiedene Bereiche unterschiedlichen Druckes aufgeteilt, welche von der Probeneinführung, d.h. der Erzeugung des zu untersuchenden Gas- bzw. Ionenstrahls, bis zur Ionenquelle und entlang der Flugstrecke im Flugzeit-Massenspektrometers nach absteigendem Druck geordnet sind. Damit weder der zu untersuchende Gas bzw. Ionenstrahl, noch die Ionen auf ihrer Bahn vom Abzugsvolumen zum Detektor, behindert werden, werden angrenzende Bereiche durch Gas-Strömungsimpedanzen verbunden. Dieses Vorgehen erlaubt eine hohe Teilchendichte im Abzugsvolumen, und dennoch einen niedrigen Restgasdruck bzw. niedrige Stoßwahrscheinlichkeit auf der Flugstrecke des Flugzeit-Massenspektrometers.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-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.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.
Im einfachsten Fall handelt es sich bei einer Gas-Strömungsimpedanz um eine Öffnung bestimmten Querschnitts in der Trennwand zwischen Bereichen verschiedenen Druckes. Rohre oder rohrähnliche Gebilde haben jedoch einen wesentlich kleineren Gasleitwert als Öffnungen gleichen Querschnitts und sind darum in vielen Fällen vorzuziehen.In the simplest case, a gas flow impedance is an opening of a certain cross section in the partition between areas of different pressure. However, 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.
Skimmer sind kegelige Gebilde mit Öffnung in der Spitze, welche dem Gasstrom entgegen weist. Skimmer haben ähnlichen Gasleitwert wie Öffnungen gleichen Querschnitts und sind vorzuziehen, falls der Gasstrom eine hohe Dichte aufweist.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.
Der Veröffentlichung von Michael et al. (Review of Scientific Instruments, Band 63(10), Seiten 4277-4284, 1992) kann man entnehmen, daß das Flugzeit-Massenspektrometer in mehrere Bereiche mit verschiedenem Druck aufgeteilt ist, wobei der Bereich, in welchem sich das Abzugsvolumen befindet, einen höheren Restgasdruck aufweist als Teile der Ionenflugbahn. Jedoch sind, wie man Kapitel "C. TOF operation" entnehmen kann, die Ionenquelle, eine Gas-Strömungsimpedanz ("A restriction of 1 in. tubing is placed between the flight tube and the main chamber"), und die Fokussierungselektroden einzeln und getrennt angeordnete Einheiten.The publication by Michael et al. (Review of Scientific Instruments, volume 63 (10), pages 4277-4284, 1992) it can be seen that the time-of-flight mass spectrometer is divided into several areas with different pressures, the area in which the withdrawal volume is located being higher Has residual gas pressure as parts of the ion trajectory. However, how to take chapter "C. TOF operation" can, the ion source, a gas flow impedance ("A restriction of 1 in. tubing is placed between the flight tube and the main chamber"), and the focusing electrodes individually and separately arranged units.
Der Nachteil dieser separaten Anordnung von Ionenquelle und Gas-Strömungsimpedanz ist, daß die Ionen eine relativ lange Strecke noch sich durch das dichte Gas in der Ionenquelle bewegen müssen und dadurch eine große Stoßwahrscheinlichkeit für Ionen mit Restgasteilchen besteht. Im Übrigen scheint bei der oben genannten Gas-Strömungsimpedanz der Durchmesser zu groß oder die Länge zu klein gewählt zu sein, da der Druckunterschied der beiden Bereiche weniger als einen Faktor 4 ausmacht (2 × 10⁻⁶ bzw. 6 × 10⁻⁷).The disadvantage of this separate arrangement of the ion source and the gas flow impedance is that the ions still have to travel a relatively long distance through the dense gas in the ion source and there is therefore a high probability of collision for ions with residual gas particles. Incidentally, with the gas flow impedance mentioned above, the diameter seems to be too large or the length is too small, since the pressure difference between the two areas is less than a factor of 4 (2 × 10⁻⁶ or 6 × 10⁻⁷).
Die Offenlegungsschrift DE 41 08 462 A1 und die Veröffentlichung von Rohwer et al. (Zeitschrift für Naturforschung, Band 43a, Seiten 1151-1153, 1988) zeigen, wie ein Skimmer getrennt von der Ionenquelle vor der Ionenquelle angeordnet ist. Hier ist die Strecke zwischen Skimmeröffnung und Abzugsvolumen relativ groß.The published patent application DE 41 08 462 A1 and the publication by Rohwer et al. (Zeitschrift für Naturforschung, volume 43a, pages 1151-1153, 1988) show how a skimmer is arranged separately from the ion source in front of the ion source. The distance between the opening of the skimmer and the extraction volume is relatively large.
Dies ist aus folgenden Gründen von Nachteil: Man möchte, daß der zu untersuchende Gas bzw. Ionenstrahl das Abzugsvolumen durchquert, da von hier aus die Ionen auf ihrer Flugbahn ins Massenspektrometer gestartet werden. Wenn Teile des zu untersuchenden Gas bzw. Ionenstrahls das Abzugsvolumen nicht durchqueren, so tragen diese Teile nicht zur Erhöhung der Empfindlichkeit bei, sie erhöhen lediglich den Restgasdruck und verringern damit den dynamischen Bereich des Flugzeit-Massenspektrometers. Da der zu untersuchende Gas bzw. Ionenstrahl immer mehr oder weniger divergent ist, sind die Anteile, welche das Abzugsvolumen nicht durchqueren umso größer, je größer der Abstand Skimmer/Abzugsvolumen ist. Ein großer Abstand ist also von Nachteil, da sich bei großer Gasbelastung des Ionenquellen-Bereichs, und damit hohem Restgasdruck, nur eine geringere Teilchendichte im Abzugsvolumen erzielen läßt. Dies hat eine verringerte Empfindlichkeit und einen niedrigeren dynamischen Bereich des Flugzeit-Massenspektrometers zur Folge.This is disadvantageous for the following reasons: You want the gas or ion beam to be examined to cross the withdrawal volume, since from here the ions are started on their trajectory into the mass spectrometer. If parts of the gas or ion beam to be examined do not cross the discharge volume, these parts do not contribute to increasing the sensitivity, they merely increase the residual gas pressure and thus reduce the dynamic range of the time-of-flight mass spectrometer. Since the gas or ion beam to be examined is always more or less divergent, the greater the distance between the skimmer and the discharge volume, the greater the proportions which do not cross the discharge volume. 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.
Der Erfindung liegt dementsprechend die Aufgabe zugrunde, ein Flugzeit-Massenspektrometer mit Gasphasen-Ionenquelle anzugeben, welches gleichermaßen eine hohe Empfindlichkeit sowie einen hohen dynamischen Bereich aufweist.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.
Insbesondere ist es Aufgabe dieser Erfindung, ein Flugzeit-Massenspektrometer mit Gasphasen-Ionenquelle anzugeben, welches eine hohe Teilchendichte im Abzugsvolumen zuläßt, gleichzeitig aber einen niedrigen Restgasdruck auf der Flugstrecke der Ionen vom Abzugsvolumen zum Detektor aufweist.In particular, it is an object of this invention to provide a time-of-flight mass spectrometer with a gas-phase ion source which allows a high particle density in the withdrawal volume, but at the same time has a low residual gas pressure on the flight path of the ions from the withdrawal volume to the detector.
Diese Aufgabe wird durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst.This object is achieved by the characterizing features of
Die erfindungsgemäße Vorrichtung ist in zwei oder mehr Bereiche unterschiedlichen Druckes aufgeteilt, wobei Gas-Strömungsimpedanzen jeweils zwei Bereiche miteinander verbinden. Dabei wird/werden die Gas-Strömungimpedanz(en), um möglichst nah an das Abzugsvolumen heranzukommen, direkt in Elektroden der Ionenquelle integriert. Dies hat den Vorteil, daß eine maximale Teilchendichte im Abzugsvolumen bei gleichzeitig minimaler Stoßwahrscheinlichkeit in der Flugstrecke des Massenspektrometers erreicht werden kann.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.
Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen angegeben.Advantageous embodiments of the invention are specified in the subclaims.
Im Folgenden wird nun anhand der in den Zeichnungen dargestellten Ausführungsbeispiele die Erfindung näher beschrieben und erläutert.The invention will now be described and explained in more detail below on the basis of the exemplary embodiments illustrated in the drawings.
Fig. 1 zeigt die einfachste Möglichkeit, die Gas-Strömungsimpedanz in eine der Elektroden zu integrieren. Das beschleunigende Feld wird hier definiert durch eine Repellerelektrode(1) und eine Beschleunigungselektrode(2). Diese beiden Elektroden definieren in diesem Beispiel das beschleunigende Feld der Ionenquelle. 1 shows the simplest possibility of integrating the gas flow impedance into one of the electrodes. The accelerating field will defined here by a repeller electrode (1) and an acceleration electrode (2). In this example, these two electrodes define the accelerating field of the ion source.
Bei dieser Ausführungsform ist nur in die Beschleunigungselektrode(2) eine Strömungsimpedanz(3) integriert. Die Beschleunigungselektrode trennt den Bereich des Beschleunigungsfeldes mit dem höheren Druck p1 von dem Bereich der Flugstrecke im Flugzeit-Massenspektrometer mit niedrigerem Druck p2. Bei der Gas-Strömungsimpedanz kann es sich z.B., wie in Fig. 1 gezeigt und in Anspruch 2 ausgeführt, um eine Lochblende handeln.In this embodiment, a flow impedance (3) is only integrated into the acceleration electrode (2). The acceleration electrode separates the area of the acceleration field with the
Wie in Fig. 1 gezeigt, kann der zu untersuchende Gas- bzw. Ionenstrahl(10), entsprechend Anspruch 12, senkrecht zur Beschleunigungsrichtung in die Ionenquelle eingeschossen werden. Ionisierte Teilchen, welche sich zum Start-Zeitpunkt im Abzugsvolumen(11) befinden, werden entlang der gezeichneten Bahnen(12) ins Flugzeit-Massenspektrometer beschleunigt.As shown in FIG. 1 , 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.
Als Beschleunigungsrichtung wird hier die Richtung verstanden, in welche die Ionen anschließend an den Startzeitpunkt beschleunigt werden.The direction of acceleration is understood here to be the direction in which the ions are subsequently accelerated to the starting time.
Bei der Ausführungsform von Fig. 1 sind die Bahnen(12) der Ionen nach der Gas-Strömungsimpedanz(3) divergent und müssen anschließend noch fokussiert werden. Dies kann durch bereits bekannte Linsenkonstruktionen erreicht werden, und wird deshalb hier nicht näher beschrieben.In the embodiment of FIG. 1 , 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 entspricht im wesentlichen Fig. 1, statt einer Lochblende wird die Strömungsimpedanz(3) durch ein Rohr gebildet. Ein Rohr hat einen wesentlich geringeren Gas-Leitwert als eine Lochblende gleichen Querschnitts. 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.
Fig. 3 zeigt beispielhaft eine Ausführungsform nach Anspruch 14 bzw. 16. Hierbei dient die zusätzliche Elektrode(4) zwischen der Repellerelektrode(1) und der Beschleunigungselektrode(2) dazu, die Ionen auf parallelen Bahnen(12) durch die Strömungsimpedanz(3) zu lenken. Unter Umständen kann es vorteilhaft sein, hinter der Gas-Strömungsimpedanz weitere Elektroden anzubringen. 3 shows an example of an embodiment according to claim 14 or 16. Here, 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.
Soll ein Laser- oder Elektronenstrahl zur Ionisierung durch das Abzugsvolumen geschossen werden, so müssen dafür Durchtrittsöffnungen in der Elektrode(4) vorgesehen werden. Es ist auch möglich, die Elektrode(4) in zwei Teile zu zerlegen, wovon eine näher zur Repellerelektrode(1), und eine näher zur Beschleunigungselektrode(2) gelegen ist. Die Strahlen können zwischen diesen beiden Teilen hindurch gezielt werden.If a laser or electron beam is to be shot through the discharge volume for ionization, 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.
Diese Anordnung wird in Fig. 4 gezeigt, welche damit auch ein Beispiel, entsprechend den Ansprüchen 14 bzw. 16 angibt. Hierbei dienen die beiden Elektroden(4,5) zwischen der Repellerelektrode(1) und der Beschleunigungselektrode(2) dazu, die Ionen auf sich kreuzenden Bahnen(12) durch die Strömungsimpedanz(3) zu lenken. Unter Umständen kann es vorteilhaft sein, hinter der Gas-Strömungsimpedanz weitere Elektroden anzubringen. Ebenso ist es möglich, für die beiden zusätzlichen Elektroden(4,5) unterschiedliche Radii zur Achse der Ionenquelle zu wählen.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).
Teilt man die Elektroden(4,5) entlang einer, in Fig. 4 gestrichelt mit ( B - B' ) markierten, Normalebene des zu untersuchenden Gas- bzw. Ionenstrahls(10) in zwei symmetrische Hälften, so kann man ein transversales elektrisches Feld, auch genannt Ablenkfeld, erzeugen. Dieses Ablenkfeld kann die transversalen Geschwindigkeitskomponenten der geladenen Teilchen ändern.If the electrodes ( 4 , 5) are divided into two symmetrical halves along a normal plane of the gas or ion beam (10) to be examined, which is marked with a dash ( B - B ' ) in FIG. 4 , 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.
Außer einem notwendigen, kleinen Spalt zwischen den beiden Hälften, behalten dann die Elektroden(4,5) ihre zylindersymmetrische Form. Dies hat folgende Vorteile:
- Zieht man die zylindersymmetrischen Anteile des Feldes von dem gesamten elektrischen Feld ab, d.h. setzt man die linken und rechten Hälften der geteilten Elektroden(4,5) auf gegengleiche Potentiale, und die übrigen, ungeteilten Elektroden(1,2) auf Massepotential, so entsteht in einem großen Bereich entlang der Achse ein elektrisches Feld, dessen Feldstärke in transversaler Richtung nur schwach von den transversalen Koordinaten abhängt.
- Zieht man die transversalen Anteile des Feldes von dem gesamten elektrischen Feld ab, d.h. setzt man die linken und rechten Hälften der geteilten Elektroden(4,5) auf gleiche Potentiale, so verbleibt als Rest ein nahezu zylindersymmetrisches elektrisches Feld. In einem zylindersymmetrischen Feld werden die Ionen isotrop fokussiert bzw. defokussiert, und somit sind dann nach der Ionenquelle keine anisotropen Linsenelemente nötig. Anisotrope Linsenelemente sind generell aufwendiger, teurer und schwerer zu justieren als zylindersymmetrische Linsenelemente.
- Subtracting the cylindrically symmetrical portions of the field from the total electric field, ie if the left and right halves of the divided electrodes (4, 5) are set to opposite potentials, and the remaining undivided electrodes (1, 2) are set to ground potential in a large area along the axis there is an electric field whose field strength in the transverse direction depends only weakly on the transverse coordinates.
- If the transverse portions of the field are subtracted from the total electric field, ie if the left and right halves of the divided electrodes (4, 5) are set to the same potential, the remainder remains an almost cylindrically symmetrical electric field. The ions are isotropically focused or defocused in a cylindrically symmetrical field, and thus no anisotropic lens elements are then necessary after the ion source. Anisotropic lens elements are generally more complex, expensive and difficult to adjust than cylindrical symmetrical lens elements.
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 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 zeigt eine Ausführungsform nach Anspruch 20. Hierbei werden die erzeugten Elektronen entlang der gezeigten Elektronenbahnen(13) durch eine Gas-Strömungsimpedanz(6) in der Repellerelektrode(1) abgezogen. Durch die Gas-Strömungsimpedanz(6) entlang der Elektronenbahnen(13) ist, gesehen in Fig. 5, links von der Repellerelektrode(1) der Druck p3 niedriger als der Druck p1 in der Beschleunigungsstrecke. Fig. 5 shows an embodiment according to claim 20. Here, 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
Bei der Ausführungsform von Fig. 5 ist der Elektronenstrahl(13) nach der Gas-Strömungsimpedanz(6) divergent und muß anschließend noch fokussiert werden. Dies kann durch bereits bekannte Linsenkonstruktionen erreicht werden, und wird deshalb hier nicht näher beschrieben.In the embodiment of FIG. 5 , 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 zeigt eine Ausführungsform nach Anspruch 10. Hierbei wird der zu untersuchende Gas- bzw. Ionenstrahl(10) parallel zur Beschleunigungsrichtung durch den Skimmer(6) in die Ionenquelle eingeschossen. Für diese Ausführungsform der Erfindung ist der Druck p3 vor dem Skimmer größer als der Druck p1 in der Beschleunigungsstrecke. 6 shows an embodiment according to
Elektroden, welche gleichzeitig Trennwände zwischen Bereichen verschieden Drucks darstellen, müssen mit dem Gehäuse verbunden werden, um ihre Funktion erfüllen zu können. Falls die betreffende Elektrode auf Masse- bzw. Gehäusepotential liegt, ist dies einfach. Falls eine Elektrode, die gleichzeitig eine Trennwand zwischen Bereichen verschiedenen Drucks darstellen soll, sich nicht auf Massepotential befindet, muß zwischen dieser Elektrode und dem Gehäuse ein Isolator vorgesehen werden. Wenn dieser Isolator flächig zwischen Elektrode und Gehäuse geklebt wird, können dadurch Probleme z.B. durch Ausgasen des Klebers, Gaseinschlüsse zwischen Isolator und Elektrode, usw. entstehen.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 zeigt eine mögliche Lösung, falls eine Elektrode, die gleichzeitig eine Trennwand zwischen Bereichen verschiedenen Drucks darstellen soll, sich nicht auf Massepotential befindet. Wie gezeigt, überlappen sich die Elektrode(2) und die Gehäusewand(31), berühren sich aber nicht. Der Abstand zwischen beiden wird, wie hier beispielhaft gezeigt, durch eine Saphirkugel(32) festgelegt. Der Spalt zwischen der Elektrode(2) und der Gehäusewand(31) soll so klein gewählt werden, daß der Leitwert für Gase deutlich kleiner ist als die Pumpleistung der Pumpe des Bereichs mit dem niedrigeren Druck. Es versteht sich, daß die Elektrode(2) gegen die Gehäusewand gedrückt werden muß. Dies kann durch bereits bekannte Methoden bewirkt werden, weshalb hier nicht näher darauf eingegangen wird. 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. As shown, 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.
Claims (21)
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DE4322102A DE4322102C2 (en) | 1993-07-02 | 1993-07-02 | Time-of-flight mass spectrometer with gas phase ion source |
DE4322102 | 1993-07-02 |
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EP0633602A2 true EP0633602A2 (en) | 1995-01-11 |
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US (1) | US5496998A (en) |
EP (1) | EP0633602B1 (en) |
JP (1) | JPH07176291A (en) |
AT (1) | ATE193398T1 (en) |
AU (2) | AU685112B2 (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102005005333A1 (en) * | 2005-01-28 | 2006-08-17 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Method for aerosol analysis especially concerning particle size and particle mass involves transferring aerosol sample to measuring instrument, whereby aerosol measurement current with reduced aerosol concentration |
EP1726945A1 (en) * | 2004-03-16 | 2006-11-29 | Kabushiki Kaisha IDX Technologies | Laser ionization mass spectroscope |
DE19652021B4 (en) * | 1995-12-14 | 2006-12-14 | Micromass Uk Ltd. | Ion source and ionization process |
DE19655304B4 (en) * | 1995-12-14 | 2007-02-15 | Micromass Uk Ltd. | Electro-spray ion source for ionisation of esp. high molecular weight thermally labile samples for mass spectrometry - has particle generator disposed w.r.t. extraction chamber entrance orifice such that most particles in generated stream have velocity whose component parallel to linear deflected trajectory is smaller than perpendicular component |
Families Citing this family (5)
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DE4441972C2 (en) * | 1994-11-25 | 1996-12-05 | Deutsche Forsch Luft Raumfahrt | Method and device for the detection of sample molecules in a carrier gas |
US5744797A (en) * | 1995-11-22 | 1998-04-28 | Bruker Analytical Instruments, Inc. | Split-field interface |
DE19631161A1 (en) * | 1996-08-01 | 1998-02-12 | Bergmann Thorald | Time of flight time of flight mass spectrometer with differentially pumped collision cell |
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 |
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JP2913924B2 (en) * | 1991-09-12 | 1999-06-28 | 株式会社日立製作所 | Method and apparatus for mass spectrometry |
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- 1993-07-02 DE DE4322102A patent/DE4322102C2/en not_active Expired - Fee Related
-
1994
- 1994-06-30 CA CA002127183A patent/CA2127183A1/en not_active Abandoned
- 1994-07-01 AU AU66152/94A patent/AU685112B2/en not_active Ceased
- 1994-07-01 US US08/269,544 patent/US5496998A/en not_active Expired - Fee Related
- 1994-07-01 DE DE59409371T patent/DE59409371D1/en not_active Expired - Fee Related
- 1994-07-01 EP EP94110273A patent/EP0633602B1/en not_active Expired - Lifetime
- 1994-07-01 AU AU66153/94A patent/AU685113B2/en not_active Ceased
- 1994-07-01 AT AT94110273T patent/ATE193398T1/en active
- 1994-07-04 JP JP6152489A patent/JPH07176291A/en active Pending
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Cited By (7)
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DE19652021B4 (en) * | 1995-12-14 | 2006-12-14 | Micromass Uk Ltd. | Ion source and ionization process |
DE19655304B4 (en) * | 1995-12-14 | 2007-02-15 | Micromass Uk Ltd. | Electro-spray ion source for ionisation of esp. high molecular weight thermally labile samples for mass spectrometry - has particle generator disposed w.r.t. extraction chamber entrance orifice such that most particles in generated stream have velocity whose component parallel to linear deflected trajectory is smaller than perpendicular component |
DE19655304B8 (en) * | 1995-12-14 | 2007-05-31 | Micromass Uk Ltd. | Mass spectrometers and methods for mass spectrometry |
EP1726945A1 (en) * | 2004-03-16 | 2006-11-29 | Kabushiki Kaisha IDX Technologies | Laser ionization mass spectroscope |
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DE102005005333A1 (en) * | 2005-01-28 | 2006-08-17 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Method for aerosol analysis especially concerning particle size and particle mass involves transferring aerosol sample to measuring instrument, whereby aerosol measurement current with reduced aerosol concentration |
DE102005005333B4 (en) * | 2005-01-28 | 2008-07-31 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Method for sampling and aerosol analysis |
Also Published As
Publication number | Publication date |
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EP0633602A3 (en) | 1995-11-22 |
CA2127183A1 (en) | 1995-01-03 |
US5496998A (en) | 1996-03-05 |
EP0633602B1 (en) | 2000-05-24 |
AU6615394A (en) | 1995-01-12 |
AU685112B2 (en) | 1998-01-15 |
DE4322102A1 (en) | 1995-01-19 |
DE59409371D1 (en) | 2000-06-29 |
AU685113B2 (en) | 1998-01-15 |
ATE193398T1 (en) | 2000-06-15 |
AU6615294A (en) | 1995-01-12 |
JPH07176291A (en) | 1995-07-14 |
DE4322102C2 (en) | 1995-08-17 |
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