EP0321819B2 - Method for the massspectrometric analysis of a gas mixture, and mass sprectrometer for carrying out the method - Google Patents
Method for the massspectrometric analysis of a gas mixture, and mass sprectrometer for carrying out the method Download PDFInfo
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- EP0321819B2 EP0321819B2 EP88120710A EP88120710A EP0321819B2 EP 0321819 B2 EP0321819 B2 EP 0321819B2 EP 88120710 A EP88120710 A EP 88120710A EP 88120710 A EP88120710 A EP 88120710A EP 0321819 B2 EP0321819 B2 EP 0321819B2
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- quistor
- annular electrode
- distance
- apex
- mass
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- 238000000034 method Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 title claims description 6
- 238000004949 mass spectrometry Methods 0.000 title description 3
- 150000002500 ions Chemical class 0.000 claims description 32
- 238000005040 ion trap Methods 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 5
- 238000011835 investigation Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000001228 spectrum Methods 0.000 description 13
- 238000013016 damping Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000006399 behavior Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 208000026139 Memory disease Diseases 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/4205—Device types
- H01J49/424—Three-dimensional ion traps, i.e. comprising end-cap and ring electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
- H01J49/426—Methods for controlling ions
- H01J49/427—Ejection and selection methods
- H01J49/429—Scanning an electric parameter, e.g. voltage amplitude or frequency
Definitions
- the invention relates to a method after the preamble of claim 1.
- the invention also relates to a mass spectrometer.
- a special property of the quistor is that the ions are in the center of the RF field are not exposed to any field strength that gives them a component of motion to leave the ion trap could issue.
- a collision gas is admitted into the ion trap Pressure is set so that the ions are sufficiently far from the center of the center by collisions Ion trap are driven to leave the ion trap. Because this gas passes through a Damping the ion movement transverse to the direction of expulsion causes an increase in the yield, it will also called "damping gas".
- the line shape is also affected by space charge effects if there are too many ions in the Quistor are located.
- space charge effects leads increasingly to scientific Misinterpretations.
- the invention has for its object in the method of the type mentioned in to develop in such a way that an improvement in the line shape and thus also an improvement of the resolving power in the mass spectroscopic analysis of gas mixtures using of such a mass spectrometer is achieved.
- the measure according to the invention not only shortens the time it takes for the ions to leave the trap need, but it also improves the line shape, sensitivity and that Detection ability increased by improving the signal / noise ratio and the influence of Space charge reduced.
- the reduction in the time it takes for the ions to leave the ion trap allows an increase in the number of spectra recordings per unit of time, which again increases the sensitivity can be achieved.
- the invention also relates to a mass spectrometer according to claim 2, which is used to examine a gas mixture is suitable by the method according to the invention.
- the distance r o of the apex of the ring electrode from the center of the quistor has a value which ensures that the greatest mass of interest is the amplitude of the RF voltage applied to the ring electrode is still captured by means of the memory field
- the values r o and Q which are particularly important for the behavior of the quistor, are preselected and the other values are determined in accordance with the specified rules, with the choice of R e and R r being free to take into account allow other influencing factors, especially in terms of manufacturing technology.
- the quistor shown in Fig. 1 has a ring electrode 4 and two, each on one side of the End electrodes 3, 5 arranged on the ring electrode, which define the chamber delimited by the ring electrode 4 seal on both sides of the ring electrode.
- the end electrodes 3 and 5 are on the ring electrode 4 each supported by annular insulators 7, 8.
- the ring-shaped insulators 7, 8 also form one tight connection between the outer sections of the ring electrode 4 and the end electrodes 3, 5.
- In one ring electrode 8 opens an inlet line 11, which allows a damping gas into the ion trap initiate.
- FIG. 1 has a central opening 10, which at the Outside of the end electrode 3, a hot cathode 1 for generating an electron beam and one for Control of the electron beam serving blocking lens 2 is opposite.
- the lower end electrode in FIG. 1 5 has a perforation 9 in the area of its center, through which ions can leave the quistor.
- a secondary electron multiplier 6 is arranged on the outside of the lower end electrode 5 and it makes it possible to detect the ions leaving the quistor through the perforation 9.
- Both the ring electrode 4 and the end electrodes 3 and 5 have strictly hyperbolic surfaces, which means that their contours are hyperbolas in the cross section shown in FIG. 1.
- the asymptotic angle of both the ring electrode 4 and the hyperbola producing the end electrodes 3, 5 is 1: 1.360.
- the end electrodes 3, 5 are at ground potential, an RF voltage with a frequency of 1.0 MHz is applied to the ring electrode 4, which can be varied in the range from 0 V to 7.5 kV.
- the range of the charge / mass ratio of the ions captured and stored by the quistor includes ions with mass numbers 1 to 500 ⁇ for simple ionization, where u is the atomic mass unit. Accordingly, by changing the RF voltage in the range from 0 V to 7.5 kV, a mass range from 1u to 500u can be covered in one scan.
- the device provided for the quistor of FIG. 1 for generating an electron beam allows the ions to be generated in the quistor itself by using their duration in the ionization phase of the blocking lens 2, an electron beam from the hot cathode 1 through the opening 10 is focused in the quistor.
- Typical ionization times for an electron beam of 100 ⁇ A strength are in the range from 10 ⁇ s to 100 ms, depending on the concentration of the substance to be examined.
- FIG. 3 illustrates the time it takes for ions to exit the quistor need and which is expressed as a line width, as a function of the distance-related circle ratio Q.
- the three curves of the diagram in FIG. 3 correspond to different scanning speeds, which are indicated at the bottom of Fig. 3. Damping gas was under each optimal printing conditions. It is readily apparent that for Q ⁇ 4,000 the triggering ability increases significantly.
- the quistors used had the dimensions shown in the following table (in cm): Q 3.6 4.0 4.4 r o 1 1 1 z o .7260 0.7071 .6905 R r .5269 0.5000 .4768 R e 1.3776 1.4142 1.4482
- Another advantage is that the influence of the space charge for values of Q ⁇ 4,000 is significantly reduced. Even if the signal strengths were reduced by a factor of 100, none could significant changes in line shape and line width can be observed.
- the reason for the observable improvements is the occurrence of a resonance of the secular movement of ions exactly at the instability limit, which is the increase in amplitude of the secular movement accelerates and thus increases the speed of ion ejection.
- the ejection therefore takes place only at Partly due to the instability of the railways and partly due to the additional energy consumption the ions from the storing RF field, which is made possible by the resonance.
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Description
Die Erfindung betrifft ein Verfahren nacht dem Oberbegriffs des Patentanspruches 1.The invention relates to a method after the preamble of claim 1.
Die Erfindung betrifft auch einen Massenspectrometer.The invention also relates to a mass spectrometer.
Grundlegende Ausführungen über die Verwendung eines Quistors bei der Massenspektrometrie finden sich in einem von P. H. Dawson herausgegebenen Buch mit dem Titel: "Quadrupol mass spectrometry and its applications", Amsterdam-Oxford-New York 1976, insbesondere Seiten 181 bis 190 und Seiten 203 bis 219. Das spezielle Verfahren, von dem die Erfindung ausgeht, ist in der EP-A-0 113 207 beschrieben. Bei diesem bekannten Verfahren werden durch Variation der Amplitude der HF-Spannung die Grenzen des Bereiches des Ladung/Massen-Verhaltnisses, für den im Quistor stabile Speicherbedingungen herrschen, verschoben, so daß nacheinander für Ionen mit zunehmender oder auch abnehmender Masse die Fangbedingungen verschwinden und die Ionen in die Lage versetzt werden, den Quistor in Richtung der Rotationsachse der Ringelektrode zu verlassen. Die den Quistor verlassenden Ionen werden mittels eines Elektronen-Vervielfachers registriert, um so das Spektrum der in dem Quistor enthaltenen Gasprobe zu gewinnen.Find basic explanations on the use of a quistor in mass spectrometry a book by P. H. Dawson entitled: "Quadrupol mass spectrometry and its applications ", Amsterdam-Oxford-New York 1976, especially pages 181 to 190 and pages 203 to 219. The specific method from which the invention is based is described in EP-A-0 113 207. at this known method, by varying the amplitude of the RF voltage, the limits of Area of the charge / mass ratio for which stable storage conditions prevail in the quistor, shifted so that the trapping conditions for ions with increasing or decreasing mass disappear and the ions are enabled to move the quistor towards the Leave axis of rotation of the ring electrode. The ions leaving the quistor are Electron multiplier registered so as to increase the spectrum of the gas sample contained in the quistor win.
Eine besondere Eigenschaft des Quistors besteht darin, daß die lonen im Zentrum des HF-Feldes keiner Feldstärke ausgesetzt sind, die ihnen eine Bewegungskomponente zum Verlassen der Ionenfalle erteilen könnte. Um diesem Mangel abzuhelfen, wird in die Ionenfalle ein Stoßgas eingelassen, dessen Druck so eingestellt ist, daß die Ionen durch Stöße optimaler Anzahl weit genug aus dem Zentrum der Ionenfalle getrieben werden, um die Ionenfalle verlassen zu können. Da dieses Gas gleichzeitig durch eine Dämpfung der Ionenbewegung quer zur Austreibungsrichtung einer Erhöhung der Ausbeute bewirkt, wird es auch "Dämpfungsgas" genannt.A special property of the quistor is that the ions are in the center of the RF field are not exposed to any field strength that gives them a component of motion to leave the ion trap could issue. To remedy this deficiency, a collision gas is admitted into the ion trap Pressure is set so that the ions are sufficiently far from the center of the center by collisions Ion trap are driven to leave the ion trap. Because this gas passes through a Damping the ion movement transverse to the direction of expulsion causes an increase in the yield, it will also called "damping gas".
Alle bekannt gewordenen Ausführungsformen der Ionenfalle folgen in ihrer Konstruktion dem sogenannten "idealen" Quistor. Die Konstruktion eines solchen "idealen" Quistors besteht aus einer Ringelektrode in Form eines hyperbolischen Toroids und zwei rotations-hyperbolischen Endelektroden, wobei der Asymptotenwinkel der Hyperbeln genau 1 : √2 ist. Ein Quistor mit diesem Aufbau zeichnet sich dadurch aus, daß die Ionenbahnen im Quistor durch Lösung der Matthieu'schen Differenzialgleichungen berechenbar sind. Die Ionenbahnen für andere Formen der Ionenfalle sind dagegen bisher nicht berechenbar. Es ist bis heute nicht einmal möglich, die exakte Potentialverteilung in anders geformten Ionenfallen so zu berechnen, daß eine erträglich schnelle Computer-Simulation der Bewegungen möglich wird.All known embodiments of the ion trap follow the so-called construction "ideal" quistor. The construction of such an "ideal" quistor consists of a ring electrode in Form of a hyperbolic toroid and two rotating hyperbolic end electrodes, the asymptotic angle the hyperbola is exactly 1: √2. A quistor with this structure is characterized in that the ion trajectories in the quistor can be calculated by solving the Matthieu differential equations. The ion trajectories for other forms of the ion trap, however, have so far not been predictable. It is still today not even possible to calculate the exact potential distribution in differently shaped ion traps in such a way that a tolerably fast computer simulation of the movements is possible.
Die Ergebnisse mit diesen "idealen" lonenfallen zeigen, daß die lonen während der Spektrenaufnahme unter optimalen Druckbedingungen des Dämpfungsgases und optimalen Scanbedingungen etwa 200 Perioden der HF-Spannung benötigen, um zu etwa 95% die lonenfalle verlassen zu können. Die Linienform zeigt daher nach einem steilen Anstieg zu einem Maximum ein langsames Auslaufen (tailing), was einer optimalen Auflösung des Spektrums entgegensteht.The results with these "ideal" ion traps show that the ions are in the process of spectra acquisition under optimal pressure conditions of the damping gas and optimal scanning conditions about 200 Periods of RF voltage need to be able to leave the ion trap to about 95%. The line shape therefore shows a slow tailing after a steep increase to a maximum, which is a optimal resolution of the spectrum stands in the way.
Die Linienform wird ferner durch Raumladungs-Effekte beeinträchtigt, wenn sich zu viele lonen in dem Quistor befinden. Wie einer Arbeit von J.W. Eichelberger et al in "Analytical Chemistry" 59, Seite 2732, 1987, entnommen werden kann, führt dieser Raumladungs-Effekt sogar zunehmend zu wissenschaftlichen Fehlinterpretationen.The line shape is also affected by space charge effects if there are too many ions in the Quistor are located. As a work by J.W. Eichelberger et al in "Analytical Chemistry" 59, page 2732, 1987, can be seen, this space charge effect leads increasingly to scientific Misinterpretations.
Demgemäß liegt der Erfindung die Aufgabe zugrunde, das Verfahren der eingangs genannten Art in solcher Weise weiterzuentwickeln, daß eine Verbesserung der Linienform und damit auch eine Verbesserung des Auflösungsvermögens bei der massenspektroskopischen Untersuchung von Gasgemischen mittels eines solchen Massenspektrometers erzielt wird.Accordingly, the invention has for its object in the method of the type mentioned in to develop in such a way that an improvement in the line shape and thus also an improvement of the resolving power in the mass spectroscopic analysis of gas mixtures using of such a mass spectrometer is achieved.
Diese Aufgabe wird nach der Erfindung gelöst durch das Verfahren gemäß Anspruch 1. Zur Durchführung
des Verfahrens wird ein Quistor verwendet, bei dem unter anderem das abstandsbezogene Verhältnis Q der Radien
der eingeschriebenen Elektroden-Scheitelkreise der Bedingung Q ≦ 3,990 genügt, wobei
- Re =
- Radius des Scheitelquerschnittes der Endelektroden
- Rr =
- Radius des Scheitelquerschnittes der Ringelektrode
- zo =
- Abstand der Scheitel der Endelektroden vom Zentrum des Quistors
- ro =
- Abstand des Scheitels der Ringelektrode vom Zentrum des Quistors.
- R e =
- Radius of the apex cross section of the end electrodes
- R r =
- Radius of the crown cross-section of the ring electrode
- z o =
- Distance of the apices of the end electrodes from the center of the quistor
- r o =
- Distance of the apex of the ring electrode from the center of the quistor.
Bei dem oben beschriebenen "idealen" Quistor hat das abstandsbezogene Verhältnis Q der Radien der eingeschriebenen Elektroden-Scheitelkreise genau den Wert Q = 4. Es ist überraschend, daß sich durch eine Verminderung des Verhältnisses Q auf einen Wert Q ≦ 3,990 die massenselektive Ejektion der Ionen durch sequentielles Instabilwerden der Ionenbahnen entscheidend verbessern läßt. Bisher wurde nämlich als selbstverständlich angenommen, daß sich der "ideale" Quistor nicht nur durch seine Berechenbarbeit auszeichnet, sondern auch in bezug auf seine Speichereigenschaften und sein sonstiges Verhalten als ideal erweisen würde. So ist es beispielsweise aus dem eingangs genannten Buch von Dawson bekannt, daß sogenannte Summen-Resonanzen der Ionenbewegungen im Quistor, die zu Speicherverlusten führen, auf außerordentlich geringfügige Abweichungen der Quistor-Konfiguration von der "idealen" Form zurückzuführen sind.In the "ideal" quistor described above, the distance-related ratio Q of the radii has the inscribed electrode vertexes exactly the value Q = 4. It is surprising that by a reduction in the ratio Q to a value Q ≦ 3.990 the mass-selective ejection of the ions can be decisively improved by sequentially unstable ion tracks. So far, namely taken for granted that the "ideal" quistor is not only due to its predictability distinguished, but also in terms of its storage properties and its other behavior as ideal would prove. For example, it is known from the Dawson book mentioned at the beginning that so-called sum resonances of the ion movements in the quistor, which lead to memory losses extremely small deviations of the quistor configuration from the "ideal" form are.
Durch die erfindungsgemäße Maßnahme wird nicht nur die Zeit verkürzt, die die Ionen zum Verlassen der Falle benötigen, sondern es werden auch die Linienform verbessert, die Empfindlichkeit und das Nachweisvermögen durch Verbesserung des Signal/Rausch-Verhältnisses gesteigert und der Einfluß der Raumladung vermindert. Die Verkürzung der Zeit, die die Ionen zum Verlassen der Ionenfalle benötigen, erlaubt eine Erhöhung der Anzahl der Spektrenaufnahmen pro Zeiteinheit, wodurch nochmals eine Steigerung der Empfindlichkeit erreicht werden kann.The measure according to the invention not only shortens the time it takes for the ions to leave the trap need, but it also improves the line shape, sensitivity and that Detection ability increased by improving the signal / noise ratio and the influence of Space charge reduced. The reduction in the time it takes for the ions to leave the ion trap allows an increase in the number of spectra recordings per unit of time, which again increases the sensitivity can be achieved.
Die Wirkung der erfindungsgemäßen Maßnahme läßt sich dadurch erklären, daß im Inneren des Quistors auf die Ionen das Potential am stärksten einwirkt, das sich an denjenigen Stellen auf den Elektroden befindet, die sich am nächsten zum Zentrum, also zum Speicherraum für die lonen, befinden. Diese Stellen sind die Scheitelpunkte der Endelektroden sowie die Scheitellinie der Ringelektrode. Bei hyperbolischen Elektroden weisen diese Stellen zugleich jeweils die stärkste Krümmung auf. Daher sind die Verhältnisse der Krümmungsradien der Elektroden an den Scheitelpunkten und die Abstände dieser Scheitelpunkte, wie es in dem oben definierten Verhältnis Q zum Ausdruck kommt, das kurz als abstandsbezogenes Kreisverhältnis bezeichnet werden kann, für das Verhalten des Quistors von entscheidender Bedeutung. Dabei sind schon relativ geringe Abweichungen von dem Verhältnis Q = 4,000, wie es bei dem idealen Quistor herrscht, von starkem Einfluß.The effect of the measure according to the invention can be explained in that inside the Quistors have the greatest effect on the potential of the ions that affect the There are electrodes that are closest to the center, i.e. to the storage space for the ions. These points are the apexes of the end electrodes and the apex line of the ring electrode. at Hyperbolic electrodes each have the strongest curvature. Therefore they are Ratios of the radii of curvature of the electrodes at the vertices and the distances between them Vertexes, as expressed in the ratio Q defined above, which is briefly referred to as distance Circular ratio can be called crucial for the behavior of the quistor Importance. There are relatively small deviations from the ratio Q = 4,000, as is the case with the ideal quistor prevails, of strong influence.
Gegenstand der Erfindung ist auch ein Massenspektrometer gemäß Patentanspruch 2, das zur Untersuchung eines Gasgemisches nach dem erfindungsgemäßen Verfahren geeignet ist. The invention also relates to a mass spectrometer according to claim 2, which is used to examine a gas mixture is suitable by the method according to the invention.
Die vorstehend angegebene Beziehung läßt viele Gestaltungsmöglichkeiten zu. Bei
der Erfindung hat von den das abstandsbezogene Verhältnis Q bestimmenden Abmessungen
des Quistors der Abstand ro des Scheitels der Ringelektrode vom Zentrum des Quistors einen Wert,
bei dem gewährleistet ist, daß bei der Amplitude der an der Ringelektrode anliegenden HF-Spannung die
größte interessierende Masse noch mittels des Speicherfeldes eingefangen wird, der Abstand Zo der
Scheitel der Endelektroden vom Zentrum des Quistors beträgt bei vorgegebenem Wert des Verhältnisses Q
Die Erfindung wird im folgenden anhand des in der Zeichnung dargestellten Ausführungsbeispieles näher beschrieben und erläutert. Die der Beschreibung und der Zeichnung zu entnehmenden Merkmale können bei anderen Ausführungsformen der Erfindung einzeln für sich oder zu mehreren in beliebiger Kombination Anwendung finden. Es zeigen
- Fig. 1
- einen Querschnitt durch einen nach der Erfindung ausgebildeten Quistor in schematischer Darstellung,
- Fig. 2
- das Stabilitätsdiagramm des Quistors nach Fig. 1,
- Fig. 3
- ein Diagramm, das die Zeit, welche die Ionen zum Verlassen des Quistors benötigen, als Funktion des Verhältnisses Q für drei verschiedene Scangeschwindigkeiten veranschaulicht, und
- Fig. 4
- die Wiedergabe von unter unterschiedlichen Bedingungen aufgenommenen Spektren.
- Fig. 1
- 3 shows a cross section through a quistor designed according to the invention in a schematic illustration,
- Fig. 2
- the stability diagram of the quistor of FIG. 1,
- Fig. 3
- a diagram illustrating the time it takes for the ions to exit the quistor as a function of the ratio Q for three different scanning speeds, and
- Fig. 4
- the reproduction of spectra recorded under different conditions.
Der in Fig. 1 dargestellte Quistor weist eine Ringelektrode 4 und zwei, jeweils zu einer Seite der Ringelektrode angeordnete Endelektroden 3, 5 auf, welche die von der Ringelektrode 4 begrenzte Kammer an den beiden Seiten der Ringelektrode abschließen. Die Endelektroden 3 und 5 sind an der Ringelektrode 4 jeweils durch ringförmige Isolatoren 7, 8 abgestützt. Die ringförmigen Isolatoren 7, 8 bilden zugleich eine dichte Verbindung zwischen den äußeren Abschnitten der Ringelektrode 4 und der Endelektroden 3, 5. In die eine Ringelektrode 8 mündet eine Einlaßleitung 11, die es ermöglicht, in die Ionenfalle ein Dämpfungsgas einzuleiten. Die in Fig. 1 obere Endelektrode 3 weist eine zentrale Öffnung 10 auf, der an der Außenseite der Endelektrode 3 eine Glühkathode 1 zum Erzeugen eines Elektronenstrahles und eine zur Steuerung des Elektronenstrahles dienende Sperrlinse 2 gegenübersteht. Die in Fig. 1 untere Endelektrode 5 weist im Bereich ihrer Mitte eine Perforation 9 auf, durch welche lonen den Quistor verlassen können. An der Außenseite der unteren Endelektrode 5 ist ein Sekundär-Elektronen-Vervielfacher6 angeordnet, der es ermöglicht, die den Quistor durch die Perforation 9 verlassenden Ionen nachzuweisen.The quistor shown in Fig. 1 has a ring electrode 4 and two, each on one side of the End electrodes 3, 5 arranged on the ring electrode, which define the chamber delimited by the ring electrode 4 seal on both sides of the ring electrode. The end electrodes 3 and 5 are on the ring electrode 4 each supported by annular insulators 7, 8. The ring-shaped insulators 7, 8 also form one tight connection between the outer sections of the ring electrode 4 and the end electrodes 3, 5. In one ring electrode 8 opens an inlet line 11, which allows a damping gas into the ion trap initiate. The upper end electrode 3 in FIG. 1 has a central opening 10, which at the Outside of the end electrode 3, a hot cathode 1 for generating an electron beam and one for Control of the electron beam serving blocking lens 2 is opposite. The lower end electrode in FIG. 1 5 has a perforation 9 in the area of its center, through which ions can leave the quistor. On A secondary electron multiplier 6 is arranged on the outside of the lower end electrode 5 and it makes it possible to detect the ions leaving the quistor through the perforation 9.
Sowohl die Ringelektrode 4 als auch die Endelektroden 3 und 5 haben streng hyperbolische Oberflächen, was bedeutet, daß ihre Konturen in dem in Fig. 1 dargestellten Querschnitt Hyperbeln sind. Der Asymptotenwinkel sowohl der die Ringelektrode 4 als auch der die Endelektroden 3, 5 erzeugenden Hyperbeln beträgt 1 : 1,360. Der innere Radius ro der Ringelektrode trägt 1,00 cm. Im übrigen sind die Abmessungen so gewählt, daß das oben definierte abstandsbezogene Verhältnis Q den Wert Q = 3,422 hat, also einen deutlich unter Q = 4,000 liegenden Wert. Während die Endelektroden 3, 5 auf Massepotential liegen, ist an die Ringelektrode 4 eine HF-Spannung mit einer Frequenz von 1,0 MHz angelegt, die im Bereich von 0 V bis 7,5 kV veränderbar ist. Bei einer Spannung von 7,5 kV umfaßt der Bereich des Ladungs/Massen-Verhältnissesder Ionen, die von dem Quistor gefangen und gespeichert werden, bei einer einfachen Ionisierung Ionen mit den Massenzahlen 1 bis 500 u, wobei u die atomare Masseneinheit bedeutet. Demgemäß kann durch Verändern der HF-Spannung im Bereich von 0 V bis 7,5 kV ein Massenbereich von 1u bis 500u in einem Scan überstrichen werden. Das hierfür charakteristische Stabilitätsdiagramm ist in Fig. 2 dargestellt. Darin sind sie Koordinatenwerte q der Feldstärke V/m des Wechselfeldes und die Koordinatenwerte a der Feldstärke U/m des Gleichfeldes proportional. Da bei dem als Ausführungsbeispiel dargestellten Quistor die Gleichspannung U den Wert U = 0 hat, wird durch Verändern der HF-Spannung der Stabilitätsbereich längs der Linie 21 durchlaufen.Both the ring electrode 4 and the end electrodes 3 and 5 have strictly hyperbolic surfaces, which means that their contours are hyperbolas in the cross section shown in FIG. 1. The asymptotic angle of both the ring electrode 4 and the hyperbola producing the end electrodes 3, 5 is 1: 1.360. The inner radius r o of the ring electrode is 1.00 cm. Otherwise, the dimensions are chosen so that the distance-related ratio Q defined above has the value Q = 3.422, that is to say a value which is significantly below Q = 4.000. While the end electrodes 3, 5 are at ground potential, an RF voltage with a frequency of 1.0 MHz is applied to the ring electrode 4, which can be varied in the range from 0 V to 7.5 kV. At a voltage of 7.5 kV, the range of the charge / mass ratio of the ions captured and stored by the quistor includes ions with mass numbers 1 to 500 µ for simple ionization, where u is the atomic mass unit. Accordingly, by changing the RF voltage in the range from 0 V to 7.5 kV, a mass range from 1u to 500u can be covered in one scan. The characteristic stability diagram for this is shown in FIG. 2. Therein they are coordinate values q of the field strength V / m of the alternating field and the coordinate values a of the field strength U / m of the constant field are proportional. Since the DC voltage U in the quistor shown as an exemplary embodiment has the value U = 0, the stability range is traversed along the line 21 by changing the RF voltage.
Die bei dem Quistor nach Fig. 1 vorgesehene Einrichtung zur Erzeugung eines Elektronenstrahles erlaubt es, die Ionen im Quistor selbst zu erzeugen, indem in der Ionisierungsphase, deren Dauer mittels der Sperrlinse 2 bestimmt werden kann, ein Elektronenstrahl von der Glühkathode 1 durch die Öffnung 10 in den Quistor fokussiert wird. Typische Ionisierungszeiten für einen Elektronenstrahl von 100 µA Stärke liegen im Bereich von 10 µs bis zu 100 ms, je nach der Konzentration der zu untersuchenden Substanz.The device provided for the quistor of FIG. 1 for generating an electron beam allows the ions to be generated in the quistor itself by using their duration in the ionization phase of the blocking lens 2, an electron beam from the hot cathode 1 through the opening 10 is focused in the quistor. Typical ionization times for an electron beam of 100 µA strength are in the range from 10 µs to 100 ms, depending on the concentration of the substance to be examined.
Das Diagramm nach Fig. 3 veranschaulicht die Zeit, welche Ionen für das Verlassen des Quistors benötigen und die sich demgemäß als Linienbreite äußert, als Funktion des abstandsbezogenen Kreisverhältnisses Q. Die drei Kurven des Diagrammes nach Fig. 3 entsprechen verschiedenen Scangeschwindigkeiten, die am unteren Rand von Fig. 3 angegeben sind. Dabei wurde Dämpfungsgas unter jeweils optimalen Druckbedingungen eingesetzt. Es ist ohne weiteres ersichtlich, daß für Q < 4,000 das Auslösungsvermögen beträchtlich zunimmt.3 illustrates the time it takes for ions to exit the quistor need and which is expressed as a line width, as a function of the distance-related circle ratio Q. The three curves of the diagram in FIG. 3 correspond to different scanning speeds, which are indicated at the bottom of Fig. 3. Damping gas was under each optimal printing conditions. It is readily apparent that for Q <4,000 the triggering ability increases significantly.
Fig. 4 zeigt das Spektrum der Gruppe der Molekülionen von Tetrachlorethen für verschiedene Werte
des abstandsbezogenen Kreisverhältnisses Q. Die Spektren wurden unter Verwendung von Luft mit einem
Druck von 4.10-4 mbar als Dampfungsgas mit verschiedenen Scangeschwindigkeiten über jeweils 300
Masseneinheiten aufgenommen. In den oberen Spektren a, c und e betrug die Scanzeit jeweils 100 ms,
während bei den unteren Spektren b, d, und f die Scanzeit jeweils 20 ms betrug. Die Spektren a und b
wurden in einem Quistor mit dem abstandsbezogenen Kreisverhältnis Q = 4,4, die mittleren Spektren c und
d in einem Quistor mit Q = 4,0 und endlich die rechten Spektren e und f in einem Quistor mit Q = 3,6
aufgenommen. Die verwendeten Quistoren hatten die sich aus der folgenden Tabelle ergebenden Abmessungen
(in cm):
Von diesen Abmessungen bestimmt der Abstand ro bei vorgegebener Amplitude der an der Ringelektrode
anliegenden HF-Spannung die Feldstärke V/m des Wechselfeldes und damit die höchste Masse, die mit
einem Scan erfaßt werden kann. Der unter diesem Gesichtspunkt für alle drei Quistoren gleich festgelegte
Wert von r0 = 1 cm ermöglichte den oben erwähnten Scan über jeweils 300 Masseneinheiten. Die Werte
von zo wurden zu
Die dramatische Verbesserung des Auflösungsvermögens und des Signal/Rausch-Verhältnisses zwischen den Spektren nach Fig. 4a und nach Fig. 4f unterstreicht den bedeutenden technischen Fortschritt. den die Erfindung bewirkt. Dabei ist besonders hervorzuheben, daß die Erhöhung der Scangeschwindigkeit, welche die Verminderung des abstandsbezogenen Kreisverhältnisses Q auf Werte Q < 4,000 ermöglicht, zugleich zu einem überproportionalen Anstieg des Signal/Rausch-Verhältnisses und damit zu dem bedeutend erhöhten Auflösungsvermögen führt.The dramatic improvement in resolution and signal-to-noise ratio between the spectra according to FIG. 4a and FIG. 4f underlines the significant technical progress. which the invention brings about. It should be emphasized in particular that the increase in the scanning speed, which enables the distance-related circular ratio Q to be reduced to values Q <4.000, at the same time to a disproportionate increase in the signal-to-noise ratio and thus to the significant leads to increased resolution.
Ein weiterer Vorteil besteht darin, daß auch der Einfluß der Raumladung für Werte von Q < 4,000 wesentlich verringert ist. Selbst bei einer Verringerung der Signalstärken um einen Faktor 100 konnte keine wesentliche Veränderung von Linienform und Linienbreite beobachtet werden.Another advantage is that the influence of the space charge for values of Q <4,000 is significantly reduced. Even if the signal strengths were reduced by a factor of 100, none could significant changes in line shape and line width can be observed.
Der Grund für die beobachtbaren Verbesserungen ist das Auftreten einer Resonanz der Sekularbewegung der lonen genau an der Instabilitätsgrenze, die die Amplitudenvergrößerung der Sekularbewegung beschleunigt und damit die Geschwindigkeit der lonen-Ejektion erhoht. Die Ejektion erfolgt daher nur zum Teil aufgrund des Instabilwerdens der Bahnen und zum anderen Teil durch die zusätzliche Energieaufnahme der lonen aus dem speichernden HF-Feld, die durch die Resonanz möglich wird.The reason for the observable improvements is the occurrence of a resonance of the secular movement of ions exactly at the instability limit, which is the increase in amplitude of the secular movement accelerates and thus increases the speed of ion ejection. The ejection therefore takes place only at Partly due to the instability of the railways and partly due to the additional energy consumption the ions from the storing RF field, which is made possible by the resonance.
Negative Einflüsse durch Resonanzphänomene konnten bisher nicht festgestellt werden, solange im wesentlichen ohne Anwendung eines Gleichspannungsfeldes gearbeitet wurde. Daher sieht eine bevorzugte Ausführungsform das Weglassen des Gleichspannungsfeldes vor. Grundsätzlich wäre es allerdings auch möglich, ein Gleichspannungsfeld anzuwenden und das Gleichspannungsfeld zur Veränderung des Stabilitätsbereiches zu variieren.So far, negative influences by resonance phenomena could not be determined, as long as in was worked essentially without using a DC voltage field. Therefore looks a preferred one Embodiment before omitting the DC voltage field. Basically, it would also be possible to apply a DC voltage field and the DC voltage field to change the stability range to vary.
Es versteht sich, daß die Erfindung nicht auf das dargestellte Ausführungsbeispiel beschränkt ist, sondern viele Abweichungen davon möglich sind, ohne den Rahmen der Patentansprüche zu verlassen.It goes without saying that the invention is not restricted to the exemplary embodiment shown, but many deviations from it are possible without leaving the scope of the claims.
Claims (2)
- Method for mass-spectroscopic investigation of a gas mixture by using a mass spectrometer having an ion trap which is constructed as a quistor with an annular electrode and two end electrodes which seal the chamber bounded by the annular electrode whereby the electrodes are formed as rotational hyperboloids and at least one of the electrodes is provided with a perforation arranged in an extension of the axis of rotation of the annular electrode, in which method the following steps are carried out:characterised in thatapplication of an RF voltage of such amplitude and frequency and, possibly, of such a direct voltage to the annular electrode that there is generated inside the ion trap a three-dimensional RF quadrupole field which is suitable for capturing ions, whose charge/mass ratio lies in a prescribed range, and storing them in the ion trap,introducing or generating ions of the gas mixture into or inside the ion trap, and storing in the ion trap ions whose charge/mass ratio lies in the prescribed range,varying at least one of the field parameters formed from the amplitude, the frequency and, possibly, the direct voltage in such a way that ions having a monotonically varying charge/mass ratio sequentially become unstable and leave the ion trap in the direction of the axis of rotation of its annular electrode through the said perforation in the end electrode andmeasuring and recording the intensity of the ion current leaving the ion trap as a function of the variation in the field parameters,
in order to carry out the method use is made of a quistor in which the distance-related ratio Q of the radii of the inscribed electrode apex circles satisfies the condition Q ≤ 3,990, it being the case that- Re =
- radius of the apex cross-section of the end electrodes
- Rr =
- radius of the apex cross-section of the annular electrode
- zo =
- distance of the apexes of the end electrodes from the centre of the quistor and
- ro =
- distance of the apex of the annular electrode from the centre of the quistor,
- Mass spectrometer having an ion trap which is constructed as a quistor with an annular electrode and two end electrodes sealing the chamber bounded by the annular electrode whereby the electrodes are formed as rotational hyperboloids and at least one of the electrodes is provided with a perforation arranged in an extension of the axis of rotation of the annular electrode, for investigating a gas mixture according to the method according to Claim 1,
characterised in that
the distance-related ratio Q of the radii of the inscribed electrode apex circles satisfies the condition Q ≤ 3,990, it being the case that- Re =
- radius of the apex cross-section of the end electrodes
- Rr =
- radius of the apex cross-section of the annular electrode
- zo =
- distance of the apexes of the end electrodes from the centre of the quistor and
- ro =
- distance of the apex of the annular electrode from the centre of the quistor,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3743718 | 1987-12-23 | ||
| DE3743718 | 1987-12-23 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0321819A2 EP0321819A2 (en) | 1989-06-28 |
| EP0321819A3 EP0321819A3 (en) | 1989-08-23 |
| EP0321819B1 EP0321819B1 (en) | 1993-04-21 |
| EP0321819B2 true EP0321819B2 (en) | 2002-06-19 |
Family
ID=6343365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88120710A Expired - Lifetime EP0321819B2 (en) | 1987-12-23 | 1988-12-12 | Method for the massspectrometric analysis of a gas mixture, and mass sprectrometer for carrying out the method |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5028777A (en) |
| EP (1) | EP0321819B2 (en) |
| DE (1) | DE3880456D1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225141A (en) * | 1988-07-11 | 1993-07-06 | Milad Limited Partnership | Process for injection molding a hollow plastic article |
| US5206506A (en) * | 1991-02-12 | 1993-04-27 | Kirchner Nicholas J | Ion processing: control and analysis |
| US5182451A (en) * | 1991-04-30 | 1993-01-26 | Finnigan Corporation | Method of operating an ion trap mass spectrometer in a high resolution mode |
| DE4142871C1 (en) * | 1991-12-23 | 1993-05-19 | Bruker - Franzen Analytik Gmbh, 2800 Bremen, De | |
| DE4142870C2 (en) * | 1991-12-23 | 1995-03-16 | Bruker Franzen Analytik Gmbh | Process for in-phase measurement of ions from ion trap mass spectrometers |
| DE4316738C2 (en) * | 1993-05-19 | 1996-10-17 | Bruker Franzen Analytik Gmbh | Ejection of ions from ion traps using combined electrical dipole and quadrupole fields |
| DE4324224C1 (en) * | 1993-07-20 | 1994-10-06 | Bruker Franzen Analytik Gmbh | Quadrupole ion traps with switchable multipole components |
| US5420425A (en) * | 1994-05-27 | 1995-05-30 | Finnigan Corporation | Ion trap mass spectrometer system and method |
| US5572025A (en) * | 1995-05-25 | 1996-11-05 | The Johns Hopkins University, School Of Medicine | Method and apparatus for scanning an ion trap mass spectrometer in the resonance ejection mode |
| JP3648906B2 (en) * | 1997-02-14 | 2005-05-18 | 株式会社日立製作所 | Analyzer using ion trap mass spectrometer |
| DE19733834C1 (en) * | 1997-08-05 | 1999-03-04 | Bruker Franzen Analytik Gmbh | Axially symmetric ion trap for mass spectrometric measurements |
| DE19751401B4 (en) | 1997-11-20 | 2007-03-01 | Bruker Daltonik Gmbh | Quadrupole radio frequency ion traps for mass spectrometers |
| US6124592A (en) * | 1998-03-18 | 2000-09-26 | Technispan Llc | Ion mobility storage trap and method |
| US6239429B1 (en) | 1998-10-26 | 2001-05-29 | Mks Instruments, Inc. | Quadrupole mass spectrometer assembly |
| US6469298B1 (en) * | 1999-09-20 | 2002-10-22 | Ut-Battelle, Llc | Microscale ion trap mass spectrometer |
| DE10028914C1 (en) * | 2000-06-10 | 2002-01-17 | Bruker Daltonik Gmbh | Mass spectrometer with HF quadrupole ion trap has ion detector incorporated in one of dome-shaped end electrodes of latter |
| US7019289B2 (en) * | 2003-01-31 | 2006-03-28 | Yang Wang | Ion trap mass spectrometry |
| US7034293B2 (en) * | 2004-05-26 | 2006-04-25 | Varian, Inc. | Linear ion trap apparatus and method utilizing an asymmetrical trapping field |
| US8334506B2 (en) | 2007-12-10 | 2012-12-18 | 1St Detect Corporation | End cap voltage control of ion traps |
| US7973277B2 (en) | 2008-05-27 | 2011-07-05 | 1St Detect Corporation | Driving a mass spectrometer ion trap or mass filter |
| US9171706B1 (en) * | 2014-11-06 | 2015-10-27 | Shimadzu Corporation | Mass analysis device and mass analysis method |
| CN110783165A (en) * | 2019-11-01 | 2020-02-11 | 上海裕达实业有限公司 | End cover electrode structure of ion introduction side of linear ion trap |
| CN115047259B (en) * | 2022-04-15 | 2022-12-06 | 安徽省太微量子科技有限公司 | Particle charge-to-mass ratio measuring method based on frequency-adjustable two-dimensional linear ion trap |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527939A (en) * | 1968-08-29 | 1970-09-08 | Gen Electric | Three-dimensional quadrupole mass spectrometer and gauge |
| US4540884A (en) * | 1982-12-29 | 1985-09-10 | Finnigan Corporation | Method of mass analyzing a sample by use of a quadrupole ion trap |
| US4650999A (en) * | 1984-10-22 | 1987-03-17 | Finnigan Corporation | Method of mass analyzing a sample over a wide mass range by use of a quadrupole ion trap |
| DE3650304T2 (en) * | 1985-05-24 | 1995-10-12 | Finnigan Corp | Operating method for an ion trap. |
| ATE99834T1 (en) * | 1988-04-13 | 1994-01-15 | Bruker Franzen Analytik Gmbh | METHOD FOR MASS ANALYSIS OF A SAMPLE USING A QUISTOR AND QUISTOR DEVELOPED FOR CARRYING OUT THIS PROCEDURE. |
-
1988
- 1988-12-12 EP EP88120710A patent/EP0321819B2/en not_active Expired - Lifetime
- 1988-12-12 DE DE8888120710T patent/DE3880456D1/en not_active Expired - Lifetime
- 1988-12-16 US US07/285,741 patent/US5028777A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3880456D1 (en) | 1993-05-27 |
| EP0321819A3 (en) | 1989-08-23 |
| EP0321819B1 (en) | 1993-04-21 |
| EP0321819A2 (en) | 1989-06-28 |
| US5028777A (en) | 1991-07-02 |
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