EP0822574B1 - Tandem time-of-flight mass spectrometer with colission cell - Google Patents

Tandem time-of-flight mass spectrometer with colission cell Download PDF

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EP0822574B1
EP0822574B1 EP97112631A EP97112631A EP0822574B1 EP 0822574 B1 EP0822574 B1 EP 0822574B1 EP 97112631 A EP97112631 A EP 97112631A EP 97112631 A EP97112631 A EP 97112631A EP 0822574 B1 EP0822574 B1 EP 0822574B1
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chamber
mass spectrometer
collision
time
flight mass
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EP0822574A1 (en
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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
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/061—Ion deflecting means, e.g. ion gates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
    • H01J49/005—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by collision with gas, e.g. by introducing gas or by accelerating ions with an electric field
    • 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

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  • the invention relates to a time-of-flight time-of-flight mass spectrometer according to the preamble of claim 1.
  • time-of-flight mass spectrometers there is generally at least one two flight routes, on which ions by their different Flight times are separated according to their mass. Thereby always forms End location of the previous flight route the start location of the following one.
  • a specific ion mass is usually determined by means of the first flight route preselected, either before or after the selection of a is subjected to any interaction.
  • This interaction can e.g. the action of a laser beam, the crossing with a second ion beam or flying through a cell with collision gas his.
  • the fragments themselves can undergo further interaction be subjected to, after flying through the second Filter out the flight distance a certain ion mass, its fragments you then determine in the third flight route.
  • the maximum working pressure is 0.01 Pa (10 -4 mBar). Electrical discharges on high-voltage components can occur from a pressure of approx. 0.1 Pa (10 -3 mBar).
  • T.J. Cornish et al. can also suffice with helium as the collision gas Cause fragmentation in the ion masses to be examined.
  • This is achieved here by using a pulsed nozzle Let the high-density helium beam into the collision cell. By sufficient Waiting time until the next primary ion pulse becomes an increase in pressure Prevents electrical discharges in the time-of-flight mass spectrometer or cause damage to components of the instrument could.
  • a sufficient for fragmentation Pressure no discharges on the live parts of the mass spectrometer.
  • the device according to the invention which is in front of the chamber contains the reflector, another chamber, in the following scattering chamber called, arranged, which then contains the collision cell.
  • another chamber in the following scattering chamber called, arranged, which then contains the collision cell.
  • the collision cell Between Scattering chamber and reflector chamber are one or more Gas flow impedances, which in the collision cell a very high gas density can be achieved with only a slight increase in pressure in the reflector chamber.
  • the scattering chamber and the reflector chamber are separately pumped room areas arranged their each have their own pump nozzle, and that by a gas flow impedance are connected. So that the gas pressure in the reflector chamber is significantly lower than in the scattering chamber, the gas conductivity of the Connection between the two chambers may be significantly lower than that Pumping speed of the pump, which pumps on the reflector chamber.
  • it is a gas flow impedance around an opening of certain cross section in the partition between Areas of different pressure.
  • the cross-section of a gas flow impedance is always so small chosen that the ion beam is just not blocked. So achieved to get maximum sensitivity of the mass spectrometer with minimal Gas conductance of flow impedance.
  • the subclaims can therefore already exist components time-of-flight mass spectrometer as gas flow impedances used to have the greatest possible pressure difference between Reflector chamber or ion source chamber and the scattering chamber or the collision cell.
  • Fig. 1 shows a first embodiment of the arrangement according to the invention. Shown are the ion source chamber 1 with the ion source 21 and the withdrawal volume 11 contained therein.
  • the ion source chamber is connected to a pump 6 which generates a vacuum, preferably below 10 -4 Pa (10 -6 mBar).
  • the gas or ion beam 10 to be examined starts the ions to be detected on the detector 34 from the withdrawal volume on their path 12 into the time-of-flight mass spectrometer.
  • the scattering chamber 2 is arranged shortly behind the ion source chamber, connected via the connecting tube 4, which can simultaneously serve as flow impedance between the two chambers.
  • the collision cell 22 is located in the scattering chamber.
  • the collision gas is supplied via a gas line 24 and the metering valve 25.
  • the scattering chamber is connected to a pump 7, which generates a vacuum, preferably below 10 -3 Pa (10 -5 mBar).
  • An ion selector 23 can additionally be arranged within the collision cell.
  • the reflector chamber 3 is connected via the connecting tube 5.
  • a shielding plate 31 between the ion path and the detector or a shot tube 32 In order to shield the injected ions from stray fields of the detector 34, one can either use a shielding plate 31 between the ion path and the detector or a shot tube 32.
  • the bullet tube 32 cooperates with the connecting tube 5 as a gas flow impedance. As shown in FIG. 1, it can have a smaller cross section than the connecting pipe 5. However, a larger cross section can also be selected. By selecting a shot tube 32 with a predetermined cross section, the gas flow impedance can thus be set in a certain range.
  • the ions are deflected by 180 ° in the reflector 33 and hit a detector 34 which is located in relative proximity to the inlet opening of the reflector chamber.
  • the reflector chamber is connected to a pump 8 which generates a vacuum, preferably below 10 -4 Pa (10 -6 mBar).
  • the ion source is located in its own chamber, which has its own pump nozzle, which is connected to the scattering chamber via a connection with a small gas conductance. Since discharges can also occur at the ion source with its live electrodes at pressures of more than 10 -3 mbar, it may be necessary to reduce the residual gas pressure in the ion source chamber when the collision cell is charged with collision gas.
  • Fig. 2 shows a second embodiment of the arrangement according to the invention.
  • the ion source chamber and the scattering chamber are integrated in a vacuum chamber, which is separated by means of an orifice 26, which can also serve as an electrode of the ion source, into the two areas, which have their own pump stubs, and which only have a flow impedance of low gas conductance are connected.
  • This flow impedance can also be incorporated into an electrode of the ion source or into the diaphragm.
  • a pipe 35 is arranged within the connecting tube 5 from the scattering chamber 2 to the reflector chamber 3 or the bullet tube 32 in the reflector chamber.
  • This pipe is used for flow resistance between the scattering chamber and the reflector chamber.
  • it extends within both of the connecting tube 5 and the bullet tube 32 and consequently has a diameter that is smaller than the diameter of the two mentioned pipes.
  • the tube 35 can also only within one of the two pipes. The tube 35 thus offers another Possibility to adjust the gas flow impedance.
  • FIG. 3 shows an embodiment of a collision cell 22 with an integrated ion selector.
  • the ion selector 23 is shown here in the embodiment of an ion switching grid and is carried by the ceramic rings 27.
  • the collision cell itself consists of the two halves 22a, 22b, which can be held together with the ceramic rings of the ion selector by any device for clamping, which need not be shown here. Since the two halves of the collision cell can be made of metal, this entire unit can also be easily attached and positioned within the scattering chamber.
  • the collision gas is supplied via the gas line 24, which has its passage near the ion selector, which in the embodiment shown here is arranged in a plane perpendicular to the ion-optical axis, and divides the collision cell into two symmetrical halves. Because the collision gas is supplied near the center of the collision cell, the maximum possible pressure is generated in the center, at the same time with a minimal gas load on the scattering chamber.

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  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The mass spectrometer has an ion source (21), a reflector (33), and a detector (34). There is a collision cell (22) containing an impurity gas, in which primary ions are fractured to produce fragment ions by collision with the impurity atoms or molecules. Each of several different pressure regions of the mass spectrometer has a vacuum pump connection (6,7,8). The regions are connected via the gas flow impedances (4,5,32). One region is a reflector chamber (3) containing the reflector. A further region is a scattering chamber (2) containing the collision cell, which is arranged before the reflector chamber in the ion flight direction.

Description

Die Erfindung betrifft ein Flugzeit-Flugzeit-Massenspektrometer nach dem Oberbegriff des Anspruch 1.The invention relates to a time-of-flight time-of-flight mass spectrometer according to the preamble of claim 1.

Bei Flugzeit-Flugzeit-Massenspektrometern gibt es generell mindestens zwei Flugstrecken, auf welchen Ionen durch ihre unterschiedlichen Flugzeiten ihrer Masse nach aufgetrennt werden. Dabei bildet immer der Endort der vorangehenden Flugstrecke den Startort der folgenden.With time-of-flight mass spectrometers, there is generally at least one two flight routes, on which ions by their different Flight times are separated according to their mass. Thereby always forms End location of the previous flight route the start location of the following one.

Üblicherweise wird mittels der ersten Flugstrecke eine bestimmte Ionenmasse vorselektiert, welche entweder vor oder nach der Selektion einer beliebigen Wechselwirkung unterworfen wird. Diese Wechselwirkung kann z.B. die Einwirkung eines Laserstrahls sein, das Kreuzen mit einem zweiten Ionenstrahl oder auch das Durchfliegen einer Zelle mit Kollisionsgas sein.A specific ion mass is usually determined by means of the first flight route preselected, either before or after the selection of a is subjected to any interaction. This interaction can e.g. the action of a laser beam, the crossing with a second ion beam or flying through a cell with collision gas his.

Die Selektion bzw. Auswahl einer bestimmten Ionenmasse am Endort einer Flugstrecke kann nach dem Stand der Technik durch eine Reihe von Methoden bewirkt werden:

  • Sind die Flugstrecken orthogonal zueinander angeordnet, so kann die Selektion am Ende der einen bzw. am Anfang der folgenden Flugstrecke dadurch bewirkt werden, daß zum Ankunfts-Zeitpunkt einer bestimmten Ionenmasse die an diesem Ort plazierte lonenquelle des folgenden Flugzeit-Massenspektrometers angeschaltet wird, was die Ablenkung und den Einschuß genau dieser Ionenmasse in das folgende Flugzeit-Massenspektrometer bewirkt.
  • Sind die Flugstrecken kolinear zueinander angeordnet, so kann am Ende der einen bzw. am Anfang der folgenden Flugzstrecke eine Vorrichtung zum gepulsten Ablenken der Ionen vorgesehen werden:
  • a) Eine solche Vorrichtung kann z.B. aus zwei zueinander parallel angeordneten Platten bestehen, welche normalerweise auf unterschiedlichen Potentialen liegen, wodurch die hindurchfliegenden Ionen abgelenkt werden. Werden diese Platten nun kurzzeitig auf gleiches Potential gelegt, so kann nur die Ionenmasse passieren, welche sich gerade kurz vor den Platten befindet und während der Passage kein ablenkendes Feld spürt.
  • b) Eine solche Vorrichtung kann auch durch zwei kammartige Strukturen bewirkt werden, deren Zähne aus feinen Drähten bestehen, wobei die Zähne der einander gegenüberliegenden kammartigen Strukturen mittig ineinander greifen und alle zu jeweils einer kammartigen Struktur gehörenden Zähne elektrisch leitend miteinander verbunden sind. Werden diese beiden Strukturen auf Potentiale gelegt, die in ihrem Wert symmetrisch zum Potential der Driftstrecke sind, so heben sich die von den beiden kammartigen Strukturen erzeugten elektrischen Felder schon in sehr kurzem Abstand auf. Ein solches Ionenschaltgitter kann schon mit vergleichsweise geringen Spannungen durchtretende Ionen so stark ablenken, daß sie den Bahnbereich der Flugstrecken verlassen. Außerdem beeinflußt dieses Schaltgitter nur die Ionen in seiner allernächsten Nähe, was eine Selektion mit hoher Massenauflösung der gewünschten Ionenmasse bewirkt. Ein solches Ionenschaltgitter ist beispielsweise in der Veröffentlichung von D.J. Beussman et al. beschrieben. (Analytical Chemistry, Bd. 67, Seiten 3952 - 3957,1995)
According to the prior art, the selection or selection of a specific ion mass at the end point of a flight route can be effected by a number of methods:
  • If the flight paths are arranged orthogonally to one another, the selection at the end of the one or at the beginning of the following flight path can be brought about by switching on the ion source of the following time of flight mass spectrometer located at this point in time of arrival of a specific ion mass, which means that Deflection and the injection of precisely this ion mass into the following time-of-flight mass spectrometer.
  • If the flight paths are arranged colinearly to one another, a device for pulsed deflection of the ions can be provided at the end of the one or at the beginning of the following flight path:
  • a) Such a device can consist, for example, of two plates arranged parallel to one another, which are normally at different potentials, as a result of which the ions flying through are deflected. If these plates are briefly placed at the same potential, only the ion mass that is just in front of the plates and does not feel any distracting field during the passage can pass.
  • b) Such a device can also be brought about by two comb-like structures, the teeth of which consist of fine wires, the teeth of the opposing comb-like structures engaging in the center and all teeth belonging to a comb-like structure being connected to one another in an electrically conductive manner. If these two structures are placed on potentials whose value is symmetrical to the potential of the drift path, the electrical fields generated by the two comb-like structures cancel each other out at a very short distance. Such an ion switching grid can deflect ions passing through at comparatively low voltages to such an extent that they leave the rail area of the flight paths. In addition, this switching grid affects only the ions in its immediate vicinity, which results in a selection with high mass resolution of the desired ion mass. Such an ion switching grid is described, for example, in the publication by DJ Beussman et al. described. (Analytical Chemistry, vol. 67, pages 3952 - 3957, 1995)

Durch die nach oder vor der Selektion ausgeführte Wechselwirkung wird der innere Zustand der selektierten Ionenmasse geändert. Meist wird Energie zugeführt, um einen Zerfall dieser Ionenmasse in Bruchstücke zu bewirken. Die Massen dieser Bruchstücke lassen dann oft Rückschlüsse auf den Aufbau der ursprünglichen Ionenmasse zu und dienen so der Strukturaufklärung komplexer Moleküle. Die Massen dieser Bruchstücke werden nun durch Messen der Flugzeit in der zweiten Flugstrecke des Flugzeit-Flugzeit-Massenspektrometers bestimmt.Through the interaction performed after or before the selection the inner state of the selected ion mass is changed. Most of time energy is supplied to break up this ion mass into fragments to effect. The masses of these fragments then often drop Conclusions about the structure of the original ion mass and serve so the structure elucidation of complex molecules. The masses of these Fragments are now measured by measuring the flight time in the second flight route time-of-flight mass spectrometer.

Müssen noch mehr Einzelheiten als nur die Massen der Bruchstücke bestimmt werden, so können die Bruchstücke selbst einer weiteren Wechselwirkung unterworfen werden, man kann nach Durchfliegen der zweiten Flugstrecke eine bestimmte Ionenmasse herausfiltern, deren Bruchstücke man dann in der dritten Flugstrecke bestimmt.Need more details than just the mass of the fragments can be determined, the fragments themselves can undergo further interaction be subjected to, after flying through the second Filter out the flight distance a certain ion mass, its fragments you then determine in the third flight route.

Soll der selektierten Ionenmasse durch Wechselwirkung mit einem Kollisionsgas Energie zugeführt werden, so werden in den meisten Fällen die Gase Helium, Stickstoff, oder Argon verwendet, wobei sich in vielen Untersuchungen Helium als das günstigste Kollisionsgas erwiesen hat. Zum Stand der Technik finden sich zwei Anordnungen, welche Kollisionsgas in einem Flugzeit-Flugzeit-Massenspektrometer zur Erzeugung von Fragment-Ionen verwenden:

  • a) B. Spengler et al. (Journal of Physical Chemistry, Bd. 96, Seiten 9678 - 9684, 1992) untersuchen die Fragmentation des Moleküls Cytochrom C, indem sie verschiedene Gase bis zu einem Druck von 4 · 10-5 mbar in die Flugstrecke ihres Flugzeit-Flugzeit-Massenspektrometers einlassen.
  • b) T.J. Cornish et al. (Rapid Communications in Mass Spectrometry, Bd. 7, Seiten 1037 - 1040, 1993) untersuchen die Fragmentation von Molekülen in ihrem Flugzeit-Flugzeit-Massenspektrometer, indem sie mittels einer gepulsten Düse Argon oder Helium in eine Kollisionszelle einlassen, welche sich zwischen den beiden Flugstrecken ihrer Flugzeit-Flugzeit-Massenspektrometer-Anordnung befindet.
    • If the selected ion mass is to be supplied with energy by interaction with a collision gas, the gases helium, nitrogen or argon are used in most cases, whereby helium has proven to be the cheapest collision gas in many studies. The prior art has two arrangements which use collision gas in a time-of-flight time-of-flight mass spectrometer to generate fragment ions:
  • a) B. Spengler et al. (Journal of Physical Chemistry, vol. 96, pages 9678-9684, 1992) investigate the fragmentation of the molecule cytochrome C by letting various gases up to a pressure of 4 × 10 -5 mbar into the flight path of their time-of-flight time-of-flight mass spectrometer ,
  • b) TJ Cornish et al. (Rapid Communications in Mass Spectrometry, vol. 7, pages 1037-1040, 1993) investigate the fragmentation of molecules in their time-of-flight time-of-flight mass spectrometer by inserting argon or helium into a collision cell, which is located between the two, using a pulsed nozzle Flight routes of their time-of-flight mass spectrometer arrangement is located.

    • B. Spengler et al. haben hierbei die einfachste Ausführungsform gewählt. Das Kollisionsgas einfach in die Driftstrecke des Flugzeit-Massenspektrometers einzulassen, stellt die billigste, und am leichtesten zu realisierende Möglichkeit dar, Fragmente durch Stöße mit Gasmolekülen oder -Atomen zu erzeugen. Nachteilig ist allerdings, daß bei Helium, dem am häufigsten verwendeten Kollisionsgas nicht soviel Gas in die Driftstrecke eingelassen werden kann, so daß eine ausreichende Anzahl der Primärionen fragmentierbar wäre. Der Helium-Gasdruck, der notwendig für eine ausreichende Fragmentation wäre, würde elektrische Entladungen im Flugzeit-Massenspektrometer hervorrufen, welche seine Funktion beeinträchtigen würden, unter Umständen auch zur Zerstörung von Komponenten, insbesondere des Detektors führen könnten.B. Spengler et al. have chosen the simplest embodiment. The collision gas simply into the drift path of the time-of-flight mass spectrometer let in, represents the cheapest, and easiest to implement Possibility of fragments by collisions with gas molecules or To generate atoms. The disadvantage, however, is that with helium, the most often collision gas used not so much gas in the drift path can be let in, so that a sufficient number of Primary ions would be fragmentable. The helium gas pressure that is necessary for sufficient fragmentation would be electrical discharges in the time-of-flight mass spectrometer, which cause its function would impair, possibly also to the destruction of components, could lead in particular to the detector.

    Bei Vielkanalplatten, welche häufig in den Detektoren der Flugzeit-Massenspektrometer verwendet werden, wird als maximaler Arbeitsdruck 0.01 Pa (10-4 mBar) angegeben. Elektrische Entladungen an hochspannungsführenden Bauteilen können ab einem Druck von ca. 0.1 Pa (10-3 mBar) auftreten.For multi-channel plates, which are often used in the detectors of time-of-flight mass spectrometers, the maximum working pressure is 0.01 Pa (10 -4 mBar). Electrical discharges on high-voltage components can occur from a pressure of approx. 0.1 Pa (10 -3 mBar).

    T.J. Cornish et al. können auch mit Helium als Kollisionsgas ausreichende Fragmentation bei den zu untersuchenden Ionenmassen hervorrufen. Dies wird hier erreicht, indem sie mit einer gepulsten Düse einen Heliumstrahl hoher Dichte in die Kollisionszelle einlassen. Durch ausreichende Wartezeit bis zum nächsten Primärionenpuls wird ein Druckanstieg im Flugzeit-Massenspektrometer verhindert, der elektrische Entladungen bzw. Zerstörungen an Komponenten des Instruments hervorrufen könnte.T.J. Cornish et al. can also suffice with helium as the collision gas Cause fragmentation in the ion masses to be examined. This is achieved here by using a pulsed nozzle Let the high-density helium beam into the collision cell. By sufficient Waiting time until the next primary ion pulse becomes an increase in pressure Prevents electrical discharges in the time-of-flight mass spectrometer or cause damage to components of the instrument could.

    Insbesondere dadurch, daß T.J. Cornish et al. die Austrittsöffnung ihrer gepulsten Düse mit einer Hohl-Nadel bis zur Kollisionszelle verlängern (Analytical Chemistry, Bd. 65, Seiten 1043 - 1047, 1993), erreichen sie einen hohen Gasdruck im Bereich der Kollisionszelle, wobei gleichzeitig der Druckanstieg im restlichen Bereich des Massenspektrometers sich in zulässigen Grenzen hält.In particular that T.J. Cornish et al. the exit opening of their Extend the pulsed nozzle with a hollow needle to the collision cell (Analytical Chemistry, Vol. 65, pages 1043-1047, 1993) achieve this a high gas pressure in the area of the collision cell, at the same time the pressure increase in the remaining area of the mass spectrometer is in admissible limits.

    Trotzdem ist in jedem Falle, um einen unzulässigen Druckanstieg zu vermeiden, eine niedrige Repetitionsfrequenz der Düse notwendig, was infolge der langen Wartezeiten zwischen Primärionenpulsen jedoch die Empfindlichkeit des Flugzeit-Massenspektrometers in kaum vertretbarer Weise herabgesetzt. Außerdem stellt eine gepulste Düse ein Bauteil mit großem Verschleiß dar, d.h. es wird ein öfteres Auswechseln erforderlich sein.Nevertheless, in any case, an inadmissible increase in pressure avoid what a low repetition frequency of the nozzle necessary however, due to the long waiting times between primary ion pulses Sensitivity of the time-of-flight mass spectrometer in a hardly acceptable way Way belittled. A pulsed nozzle also creates a component great wear, i.e. more frequent replacement is required his.

    Dementsprechend ist es Aufgabe der Erfindung, ein Flugzeit-Flugzeit-Massenspektrometer anzugeben, bei welchem mit vertretbarem technischen Aufwand und ohne Einbußen bei der Massenauflösung oder Empfindlichkeit ein ausreichender Druck des Kollisionsgases für die verschiedenen Möglichkeiten der Fragmentation zur Verfügung steht. Insbesondere ist es Aufgabe der Erfindung, bei einem zur Fragmentation ausreichendem Druck, keine Entladungen an den spannungsführenden Teilen des Massenspektrometers entstehen zu lassen.Accordingly, it is an object of the invention to provide a time of flight time of flight mass spectrometer specify which one with reasonable technical Effort and without sacrificing mass resolution or sensitivity a sufficient pressure of the collision gas for the different Ways of fragmentation is available. In particular it is the object of the invention, with a sufficient for fragmentation Pressure, no discharges on the live parts of the mass spectrometer.

    Diese Aufgaben werden durch die kennzeichnenden Merkmale des Anspruchs 1 gelöst.These tasks are characterized by the distinctive features of the claim 1 solved.

    Bei der erfindungsgemäßen Vorrichtung wird vor der Kammer, welche den Reflektor enthält, eine weitere Kammer, im folgenden Streukammer genannt, angeordnet, welche dann die Kollisionszelle enthält. Zwischen Streukammer und Reflektorkammer befinden sich eine oder mehrere Gas-Strömungsimpedanzen, wodurch in der Kollisionszelle eine sehr hohe Gasdichte erzielbar ist, bei gleichzeitig nur geringfügigem Druckanstieg in der Reflektorkammer.In the device according to the invention, which is in front of the chamber contains the reflector, another chamber, in the following scattering chamber called, arranged, which then contains the collision cell. Between Scattering chamber and reflector chamber are one or more Gas flow impedances, which in the collision cell a very high gas density can be achieved with only a slight increase in pressure in the reflector chamber.

    Hierbei werden die Streukammer und die Reflektorkammer in verschiedenen, separat gepumpten Raumbereichen angeordnet, die ihre jeweils eigenen Pumpstutzen aufweisen, und die durch eine Gas-Strömungsimpedanz verbunden sind. Damit der Gasdruck in der Reflektorkammer deutlich niedriger als in der Streukammer ist, muß der Gas-Leitwert der Verbindung zwischen den beiden Kammern deutlich niedriger sein als das Saugvermögen der Pumpe, welche an der Reflektorkammer pumpt.The scattering chamber and the reflector chamber are separately pumped room areas arranged their each have their own pump nozzle, and that by a gas flow impedance are connected. So that the gas pressure in the reflector chamber is significantly lower than in the scattering chamber, the gas conductivity of the Connection between the two chambers may be significantly lower than that Pumping speed of the pump, which pumps on the reflector chamber.

    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. Vorteilhafterweise wird der Querschnitt einer Gas-Strömungsimpedanz immer so klein gewählt, daß der Ionenstrahl gerade eben nicht blockiert wird. So erzielt man maximale Empfindlichkeit des Massenspektrometers bei minimalem Gas-Leitwert der Strömungsimpedanz.In the simplest case, it is a gas flow impedance around an opening of certain cross section in the partition between Areas of different pressure. Have pipes or pipe-like structures but have a much lower gas conductance than openings Cross-section and are therefore preferable in many cases. advantageously, the cross-section of a gas flow impedance is always so small chosen that the ion beam is just not blocked. So achieved to get maximum sensitivity of the mass spectrometer with minimal Gas conductance of flow impedance.

    Es ist auch möglich, die Streukammer und die Reflektorkammer in einer gemeinsamen Vakuumkammer aufzubauen, und durch Trennwände solcherart voneinander zu trennen, daß sich Raumgebiete ergeben, welche nur durch Öffnungen mit kleinem Gas-Leitwert verbunden sind, und für jeden dieser Bereiche einen eigenen Pumpstutzen vorsehen.It is also possible to put the scattering chamber and the reflector chamber in to build a common vacuum chamber, and by partitions to be separated from each other in such a way that spatial areas arise which only connected through openings with small gas conductance, and for provide each of these areas with its own pump connection.

    Dadurch, daß die Kollisionszelle auf diese Weise nun vergleichbar nahe am Abzugsvolumen des Flugzeit-Massenspektrometers angeordnet ist, können auch bei großer Divergenz der Ionenbahnen die Querschnitte der Strömungsimpedanzen kleiner gewählt werden, ohne die Empfindlichkeit des Massenspektrometers herabzusetzen.The fact that the collision cell is now comparable in this way is arranged on the discharge volume of the time-of-flight mass spectrometer, can the cross sections of the Flow impedances can be chosen smaller without sensitivity of the mass spectrometer.

    Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen angegeben.Advantageous embodiments of the invention are in the subclaims specified.

    Als besonders vorteilhafte Ausführungsformen der Erfindung gemäß den Unteransprüchen können somit bereits vorhandene Komponenten des Flugzeit-Flugzeit-Massenspektrometers als Gas-Strömungsimpedanzen verwendet werden, um einen möglichst großen Druckunterschied zwischen Reflektorkammer bzw. Ionenquellenkammer und der Streukammer bzw. der Kollisionszelle hervorzurufen.According to particularly advantageous embodiments of the invention the subclaims can therefore already exist components time-of-flight mass spectrometer as gas flow impedances used to have the greatest possible pressure difference between Reflector chamber or ion source chamber and the scattering chamber or the collision cell.

    Im Folgenden wird nun anhand der in den Zeichnungen dargestellten Ausführungsbeispiele die Erfindung näher beschrieben und erläutert. Es zeigen:

  • Fig. 1 eine erste Ausführungsform der Erfindung.
  • Fig. 2 eine weitere Ausführungsform der Erfindung.
  • Fig. 3 eine Ausführungsform der Kollisionszelle mit integriertem Ionenselektor.
    • The invention will now be described and explained in more detail with reference to the exemplary embodiments illustrated in the drawings. Show it:
  • Fig. 1 shows a first embodiment of the invention.
  • Fig. 2 shows a further embodiment of the invention.
  • Fig. 3 shows an embodiment of the collision cell with an integrated ion selector.

    • Fig. 1 zeigt eine erste Ausführungsform der erfindungsgemäßen Anordnung. Gezeigt sind die Ionenquellenkammer 1 mit der Ionenquelle 21, und dem darin enthaltenen Abzugsvolumen 11. Die Ionenquellenkammer ist mit einer Pumpe 6 verbunden, die ein Vakuum, vorzugsweise unterhalb 10-4 Pa (10-6 mBar) erzeugt. Zum Start-Zeitpunkt der Massenanalyse werden von dem zu untersuchenden Gas- bzw. Ionenstrahl 10 die am Detektor 34 nachzuweisenden Ionen aus dem Abzugsvolumen heraus auf ihrer Bahn 12 ins Flugzeit-Massenspektrometer gestartet. Fig. 1 shows a first embodiment of the arrangement according to the invention. Shown are the ion source chamber 1 with the ion source 21 and the withdrawal volume 11 contained therein. The ion source chamber is connected to a pump 6 which generates a vacuum, preferably below 10 -4 Pa (10 -6 mBar). At the start of the mass analysis, the gas or ion beam 10 to be examined starts the ions to be detected on the detector 34 from the withdrawal volume on their path 12 into the time-of-flight mass spectrometer.

    Kurz hinter der Ionenquellenkammer ist die Streukammer 2 angeordnet, verbunden über das Verbindungsrohr 4, welches gleichzeitig als Strömungsimpedanz zwischen beiden Kammern dienen kann. In der Streukammer befindet sich die Kollisionszelle 22. Über eine Gasleitung 24 und das Dosierventil 25 wird das Kollisionsgas zugeführt. Die Streukammer ist mit einer Pumpe 7 verbunden, die ein Vakuum, vorzugsweise unterhalb 10-3 Pa (10-5 mBar) erzeugt. Innerhalb der Kollisionszelle kann zusätzlich ein Ionenselektor 23 angeordnet sein.The scattering chamber 2 is arranged shortly behind the ion source chamber, connected via the connecting tube 4, which can simultaneously serve as flow impedance between the two chambers. The collision cell 22 is located in the scattering chamber. The collision gas is supplied via a gas line 24 and the metering valve 25. The scattering chamber is connected to a pump 7, which generates a vacuum, preferably below 10 -3 Pa (10 -5 mBar). An ion selector 23 can additionally be arranged within the collision cell.

    Über das Verbindungsrohr 5 ist die Reflektorkammer 3 angeschlossen. Um die eingeschossenen Ionen gegenüber Streufeldern des Detektors 34 abzuschirmen, kann man entweder ein Abschirmblech 31 zwischen der Ionenbahn und dem Detektor oder ein Einschußrohr 32 verwenden. Das Einschußrohr 32 wirkt mit dem Verbindungsrohr 5 zusammen als Gasströmungsimpedanz. Es kann, wie in Fig. 1 dargestellt, einen geringeren Querschnitt als das Verbindungsrohr 5 aufweisen. Es kann aber auch ein größerer Querschnitt gewählt werden. Durch Auswahl eines Einschußrohrs 32 mit vorgegebenem Querschnitt kann somit die Gasströmungsimpedanz in einem gewissen Bereich eingestellt werden. Die Ionen werden im Reflektor 33 um 180° umgelenkt und treffen auf einen Detektor 34, der sich in relativer Nähe zur Eintrittsöffnung der Reflektorkammer befindet. Die Reflektorkammer ist mit einer Pumpe 8 verbunden, die ein Vakuum, vorzugsweise unterhalb 10-4 Pa (10-6 mBar) erzeugt.The reflector chamber 3 is connected via the connecting tube 5. In order to shield the injected ions from stray fields of the detector 34, one can either use a shielding plate 31 between the ion path and the detector or a shot tube 32. The bullet tube 32 cooperates with the connecting tube 5 as a gas flow impedance. As shown in FIG. 1, it can have a smaller cross section than the connecting pipe 5. However, a larger cross section can also be selected. By selecting a shot tube 32 with a predetermined cross section, the gas flow impedance can thus be set in a certain range. The ions are deflected by 180 ° in the reflector 33 and hit a detector 34 which is located in relative proximity to the inlet opening of the reflector chamber. The reflector chamber is connected to a pump 8 which generates a vacuum, preferably below 10 -4 Pa (10 -6 mBar).

    Diese Anordnung schützt den Detektor und Reflektor vor zu hohen Drücken, wobei insbesondere der Detektor mit seinen Vielkanalplatten ein empfindliches Bauteil darstellt, an welchem zuerst Probleme durch einen Druck von mehr als 0.01 Pa (10-4 mBar) entstehen würden. In dieser Ausführungsform befindet sich die Ionenquelle in einer eigenen Kammer, die einen eigenen Pumpstutzen aufweist, welche über eine Verbindung mit kleinem Gas-Leitwert an die Streukammer angeschlossen ist. Da auch an der Ionenquelle mit ihren spannungsführenden Elektroden bei Drücken von mehr als 10-3 mBar Entladungen auftreten können, kann es notwendig sein, den Restgasdruck in der Ionenquellenkammer zu reduzieren, wenn die Kollisionszelle mit Stoßgas beaufschlagt wird.This arrangement protects the detector and reflector from excessively high pressures, the detector in particular with its multi-channel plates being a sensitive component on which problems would first arise due to a pressure of more than 0.01 Pa (10 -4 mbar). In this embodiment, the ion source is located in its own chamber, which has its own pump nozzle, which is connected to the scattering chamber via a connection with a small gas conductance. Since discharges can also occur at the ion source with its live electrodes at pressures of more than 10 -3 mbar, it may be necessary to reduce the residual gas pressure in the ion source chamber when the collision cell is charged with collision gas.

    Fig. 2 zeigt eine zweite Ausführungsform der erfindungsgemäßen Anordnung. Hier sind die Ionenquellenkammer und die Streukammer in eine Vakummkammer integriert, die mittels einer Blende 26, die auch als Elektrode der Ionenquelle dienen kann, in die beiden Bereiche aufgetrennt wird, welche eigene Pumpstuzen aufweisen, und die nur durch eine Strömungsimpedanz von kleinem Gas-Leitwert verbunden sind. Diese Strömungsimpedanz kann auch in eine Elektrode der Ionenquelle bzw. in die Blende eingearbeitet sein. Fig. 2 shows a second embodiment of the arrangement according to the invention. Here, the ion source chamber and the scattering chamber are integrated in a vacuum chamber, which is separated by means of an orifice 26, which can also serve as an electrode of the ion source, into the two areas, which have their own pump stubs, and which only have a flow impedance of low gas conductance are connected. This flow impedance can also be incorporated into an electrode of the ion source or into the diaphragm.

    Innerhalb des Verbindungsrohrs 5 von der Streukammer 2 zur Reflektorkammer 3 bzw. des Einschußrohrs 32 in die Reflektorkammer ist ein Rohr 35 angeordnet. Dieses Rohr dient dazu, den Strömungswiderstand zwischen Streukammer und Reflektorkammer zu erhöhen. In der in Fig. 2 gezeigten Ausführungsform erstreckt es sich innerhalb sowohl des Verbindungsrohrs 5 als auch des Einschußrohrs 32 und hat demzufolge einen Durchmesser, der kleiner ist als die Durchmesser der beiden genannten Rohre. Das Rohr 35 kann sich aber auch nur innerhalb eines der beiden Rohre befinden. Das Rohr 35 bietet somit eine weitere Möglichkeit zur Einstellung der Gasströmungsimpedanz.Within the connecting tube 5 from the scattering chamber 2 to the reflector chamber 3 or the bullet tube 32 in the reflector chamber a pipe 35 is arranged. This pipe is used for flow resistance between the scattering chamber and the reflector chamber. In the in Fig. 2 embodiment it extends within both of the connecting tube 5 and the bullet tube 32 and consequently has a diameter that is smaller than the diameter of the two mentioned pipes. The tube 35 can also only within one of the two pipes. The tube 35 thus offers another Possibility to adjust the gas flow impedance.

    Fig. 3 zeigt eine Ausführungsform einer Kollisionszelle 22 mit integriertem Ionenselektor. Der Ionenselektor 23 ist hier in der Ausführungsform eines Ionenschaltgitters dargestellt und wird von den Keramikringen 27 getragen. Die Kollisionszelle selbst besteht aus den beiden Hälften 22a, 22b, welche durch eine beliebige Vorrichtung zum Klemmen, die hier nicht gezeigt werden muß, mit den Keramikringen des Ionenselektors zusammengehalten werden können. Da die beiden Hälften der Kollisionszelle aus Metall gefertigt werden können, läßt sich diese gesamte Einheit auch auf einfache Weise innerhalb der Streukammer befestigen und positionieren. Das Kollisionsgas wird über die Gasleitung 24 zugeführt, die ihren Durchtritt nahe des Ionenselektors hat, welcher in der hier gezeigten Ausführung in einer zur ionenoptischen Achse senkrechten Ebene angeordnet ist, und die Kollisionszelle in zwei symmetrische Hälften teilt. Dadurch, daß das Kollisionsgas nahe der Mitte der Kollisionszelle zugeführt wird, wird in der Mitte der maximal mögliche Druck erzeugt, gleichzeitig bei minimaler Gasbelastung der Streukammer. 3 shows an embodiment of a collision cell 22 with an integrated ion selector. The ion selector 23 is shown here in the embodiment of an ion switching grid and is carried by the ceramic rings 27. The collision cell itself consists of the two halves 22a, 22b, which can be held together with the ceramic rings of the ion selector by any device for clamping, which need not be shown here. Since the two halves of the collision cell can be made of metal, this entire unit can also be easily attached and positioned within the scattering chamber. The collision gas is supplied via the gas line 24, which has its passage near the ion selector, which in the embodiment shown here is arranged in a plane perpendicular to the ion-optical axis, and divides the collision cell into two symmetrical halves. Because the collision gas is supplied near the center of the collision cell, the maximum possible pressure is generated in the center, at the same time with a minimal gas load on the scattering chamber.

    Claims (14)

    1. An MS/MS time of flight mass spectrometer comprising an ion source (21), a reflector (33), a detector (34), and a collision cell (22), said collision cell containing a collision gas causing the decomposition of primary ions to fragment ions due to collision with collision gas atoms or molecules,
      characterized by
      said mass spectrometer being subdivided into regions of different gas pressure, each of said regions containing its own port for connection of a pump (6, 7, 8),
      said regions being connected via gas flow restrictions (4, 5, 32, 35),
      one of said regions forming the reflector chamber (3) containing the reflector (33),
      another one of said regions forming the collision chamber (2) containing the collision cell (22),
      said region forming the collision chamber (2) being positioned before the reflector chamber (3) with respect to the flight direction of the ions.
    2. An MS/MS time of flight mass spectrometer according to claim 1, characterized in that the ion source (21) is arranged in an ion source chamber (1) and the ion source chamber (1) and the collision chamber (2) each comprise its own port for connection of a pump (6, 7) and are connected via a gas flow restriction (4) such that the ion source chamber (1) comprises a lower gas pressure than the collision chamber (2) when collision gas is fed to the collision cell (22).
    3. An MS/MS time of flight mass spectrometer according to claim 1 or 2, characterized in that the reflector (33) and the detector (34) are contained within the same vacuum region.
    4. An MS/MS time of flight mass spectrometer according to one of the preceding claims, characterized in that the gas flow restriction (5, 32, 35) between the collision chamber (2) and the reflector chamber (3) is formed at least partially by a connecting tube (5) between both chambers.
    5. An MS/MS time of flight mass spectrometer according to claim 4, characterized in that the connecting tube (5) extends from an outlet port of the collision chamber (2) to an inlet port of the reflector chamber (3) and that at least one further part of the gas flow restriction is formed by an entrance tube (32) extending from the inlet port into the reflector chamber (3).
    6. An MS/MS time of flight mass spectrometer according to one or both of claims 4 and 5, characterized in that at least one further part of the gas flow restriction is formed by a tube (35), which
      comprises a smaller diameter than the connecting tube (5) and/or the entrance tube (32), and
      is arranged within one or both of the connecting tube (5) and the entrance tube (32).
    7. An MS/MS time of flight mass spectrometer according to one of the preceding claims, characterized in that the ion source (21) and collision cell (22) are housed in one and the same vacuum chamber, said vacuum chamber being divided into two parts (1, 2) by a vacuum separation wall (26) arranged within said vacuum chamber, wherein each of the parts (1, 2) comprises its own port for a vacuum pump (6, 7), and in that an opening in the separation wall (26) functions as a gas flow restriction between the parts (1, 2).
    8. An MS/MS time of flight mass spectrometer according to claim 7, characterized in that the ion source (21) contains electrodes and that at least a part of said separation wall (26) is integrated in one of said electrodes.
    9. An MS/MS time of flight mass spectrometer according to one of the preceding claims, characterized in that an ion selector (23) is arranged within said collision cell (22).
    10. An MS/MS time of flight mass spectrometer according to claim 9, characterized in that said collision cell (22) comprises one inlet flow restriction (22a) and one outlet flow restriction (22b) and said ion selector (23) is arranged between said both flow restrictions.
    11. An MS/MS time of flight mass spectrometer according to claim 9 or 10, characterized in that the attachment of said ion selector (23) is formed by said inlet or outlet flow restriction (22a, 22b) of the collision cell.
    12. An MS/MS time of flight mass spectrometer according to one of claims 9 to 11, characterized in that said ion selector (23) is arranged in a plane orthogonal to the ion optical axis and subdivides the collision cell (22) into two symmetrical halves.
    13. An MS/MS time of flight mass spectrometer according to one of claims 9 to 12, characterized in that said ion selector is a switching gate comprised of two comb-like, centrally interdigitating structures, the teeth of each of said comb-like structures are electrically connected with each other.
    14. An MS/MS time of flight mass spectrometer according to one of claims 9 to 12, characterized in that said ion selector is comprised of two opposing plates being arranged parallel to the ion optical axis.
    EP97112631A 1996-08-01 1997-07-23 Tandem time-of-flight mass spectrometer with colission cell Expired - Lifetime EP0822574B1 (en)

    Applications Claiming Priority (2)

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    DE19631161A DE19631161A1 (en) 1996-08-01 1996-08-01 Time of flight time of flight mass spectrometer with differentially pumped collision cell
    DE19631161 1996-08-01

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    US6331702B1 (en) * 1999-01-25 2001-12-18 University Of Manitoba Spectrometer provided with pulsed ion source and transmission device to damp ion motion and method of use
    USRE39099E1 (en) * 1998-01-23 2006-05-23 University Of Manitoba Spectrometer provided with pulsed ion source and transmission device to damp ion motion and method of use
    US6348688B1 (en) 1998-02-06 2002-02-19 Perseptive Biosystems Tandem time-of-flight mass spectrometer with delayed extraction and method for use
    DE19853189C1 (en) 1998-11-18 2000-04-13 Frech Oskar Gmbh & Co Hot chamber die casting machine has a ring inductor consisting of a bent pipe made of elastic material forming a one-part ring open at one point with connections for energy and for flowing cooling air
    US6781117B1 (en) 2002-05-30 2004-08-24 Ross C Willoughby Efficient direct current collision and reaction cell
    GB2390935A (en) 2002-07-16 2004-01-21 Anatoli Nicolai Verentchikov Time-nested mass analysis using a TOF-TOF tandem mass spectrometer
    US7196324B2 (en) * 2002-07-16 2007-03-27 Leco Corporation Tandem time of flight mass spectrometer and method of use
    KR100659261B1 (en) * 2006-02-07 2006-12-20 한국기초과학지원연구원 Tandem fourier transform ion cyclotron resonance mass spectrometer
    RU2769377C1 (en) * 2021-07-13 2022-03-30 Федеральное государственное бюджетное учреждение науки Физико-технический институт им. А.Ф. Иоффе Российской академии наук Tof mass spectrometer

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    DE3920566A1 (en) * 1989-06-23 1991-01-10 Bruker Franzen Analytik Gmbh MS-MS FLIGHT TIME MASS SPECTROMETER
    US5202563A (en) * 1991-05-16 1993-04-13 The Johns Hopkins University Tandem time-of-flight mass spectrometer
    DE4322102C2 (en) * 1993-07-02 1995-08-17 Bergmann Thorald Time-of-flight mass spectrometer with gas phase ion source
    US5464985A (en) * 1993-10-01 1995-11-07 The Johns Hopkins University Non-linear field reflectron

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    EP0822574A1 (en) 1998-02-04
    CA2209119A1 (en) 1998-02-01

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