EP0633601B1 - Détecteur pour spectromètre de masse à temps de vol présentant des distorsions réduites des temps de vols à ouverture élevée - Google Patents
Détecteur pour spectromètre de masse à temps de vol présentant des distorsions réduites des temps de vols à ouverture élevée Download PDFInfo
- Publication number
- EP0633601B1 EP0633601B1 EP94110272A EP94110272A EP0633601B1 EP 0633601 B1 EP0633601 B1 EP 0633601B1 EP 94110272 A EP94110272 A EP 94110272A EP 94110272 A EP94110272 A EP 94110272A EP 0633601 B1 EP0633601 B1 EP 0633601B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ion
- conversion surface
- time
- detector
- flight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
-
- 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
Definitions
- the invention relates to detectors for time-of-flight mass spectrometers the preamble of claim 1.
- Detectors for time-of-flight mass spectrometers are said to be incident Oppose the largest possible area of the ion beam, and yet have small flight time errors.
- Each detector has an ion-electron conversion surface, at which time an ion hits a certain Probability one or more electrons are generated that are in one or several downstream electron multipliers will. This gives an electrical impulse, which with the impact of the ion on the conversion surface in a temporal context stands.
- the ion-optical axis of a detector means one selected path in or near the center of the incident ion beam. If the detector has a cylindrical symmetry, you usually choose the axis of symmetry.
- the flight time along the ion-optical axis from the reference plane to the ion-electron conversion surface can be selected as the reference flight time.
- Flight time errors can be specified as a function of the starting location on the reference level. In the most general case, the flight time errors are depending on the two variables that parameterize the reference level. If the detector has a cylindrical symmetry, then these are Flight time error is a function of the distance of the orbit in question the ion-optical axis in the reference plane.
- Ions can within a detector with inhomogeneous electrical Field focused or scattered on a smaller or larger area will. For this reason, the usable area is suitable the ion-electron conversion area is not a measure of the sensitivity of the detector.
- the content of the surface on the reference level is appropriate, from which consists of ions with acceptably small time-of-flight errors in the detector can be started into it.
- the probability with which an ion hits the Ion-electron conversion surface electrons are triggered, i.e. the electron yield depends very much on the speed at Impact. Because the speed of the ions is inversely proportional to the square root of their mass, the probability of detection increases with ions of large mass.
- a detector If a detector is to detect ions of larger mass, the ions must therefore be accelerated before being on the ion-electron conversion surface to hit with sufficient probability to release electrons from the conversion surface upon impact. Of the detector must therefore be designed so that a strong, accelerating electric field in front of the conversion surface. Through this post-acceleration field flight time errors can occur.
- the flight time errors are kept small by keeps the post-acceleration field homogeneous.
- Has a homogeneous field a location-independent direction and strength of the electric field, whereby the time of flight from the reference plane in a detector with homogeneous fields independent of the ion-electron conversion surface from the starting point at reference level or regardless of the point of entry into the Post-acceleration field is.
- the post-acceleration field is necessarily inhomogeneous, whereby ions on different orbits with different from each other Flight times get to the ion-electron conversion surface.
- the size of the flight time error is a function the distance of the trajectory from the ion-optical axis. It is the distance to the ion-optical axis as a variable in this function on the reference level, not on the conversion surface. in the best case, i.e. when the conversion surface is movably suspended the size of this flight time error is proportional to the square of the Distance from the ion-optical axis.
- the detector in order to keep the flight time errors small, to load the detector only near the ion-optical axis.
- the measure of the sensitivity of the detector is the content of that Area on the reference plane from which ion trajectories are acceptable small time-of-flight errors can be started into the detector can.
- the invention is accordingly based on the object Specify detector for time-of-flight mass spectrometer, which alike ensures high sensitivity and high mass resolution.
- the object of the present invention is a detector for time-of-flight mass spectrometers, in which despite large usable area opposed to the incident beam on the reference level, the flight time errors are kept small.
- the inhomogeneous ones prevailing in the detector electric field generated or occurring in front of the detector Flight time errors between ions with different trajectories compensated by the detector itself.
- the curvature causes that occurring in each trajectory Flight time depending on the lateral position on the ion beam varies so, i.e. is either lengthened or shortened by that caused the inhomogeneous field or those occurring in front of the detector Flight time errors can be compensated or at least minimized.
- lanes can also be used use that with initial conditions corresponding to the actual Operation of the time-of-flight mass spectrometer started from the ion source will. That means that in principle such flight time errors, as in the ion source and in the remaining parts of the time-of-flight mass spectrometer arise in determining the curvature of the Ion-electron conversion area can be included.
- the end face (20) At the determination of the end face (20) one must take into account that the space of the initial conditions in this case 6 coordinates, so 3 for initial speeds and 3 for initial coordinates. Because the end face is a 2-parameter area in 3-dimensional space is, the end face (20) must be adapted to the end points of the tracks (11) in this way be the average distance of the web endpoints to the end face (20) is minimal.
- the method can also be designed in such a way that first on a design of the detector electrodes including one determines the curvature of the ion-electron conversion surface, and then the voltages varied until the flight time error fall below a predetermined limit. This procedure corresponds Process claim 10.
- FIG. 3 shows the simplest embodiment of a detector according to the invention.
- the time-of-flight errors of off-axis paths are compensated for by a curved conversion surface (3).
- the only ring electrode (1) is at the potential of the drift path.
- This embodiment also corresponds to claim 7.
- tilting a movably mounted bracket it is possible to certain in the detector Flight time errors of the ion source, the reflector and / or the drift path of the time-of-flight mass spectrometer.
- Fig. 4 shows a detector design in which the field of the post-acceleration path can be adjusted by additional ring electrodes (4). In this way, the necessary curvature of the conversion surface (3) can be kept smaller at a certain voltage than in the design of FIG. 3 . Alternatively, a higher post-acceleration voltage can be set with the same curvature of the ion-electron conversion surface (3).
- the additional ring electrodes (4) reduce the flight time errors off-axis Trajectories by moving the areas of greater field curvature through them Areas are placed where the speed of the ions is already is bigger.
- the ring electrodes are placed on potentials, their values between the drift path potential and the potential of the ion-electron conversion surface (3) lie. Instead of two or more Ring electrodes (4) would also be a single additional ring electrode conceivable.
- the flight time errors become of off-axis orbits larger.
- the ion orbits also bent more towards the ion-optical axis. Both require that the curvature of the ion-electron conversion surface increases Post-acceleration potential must increase. If the ion orbits are so strongly bent towards the ion-optical axis that they all hitting a point on the conversion surface, it is no longer so possible to correct the flight time errors by curving the conversion surface compensate. This is only with even greater post-acceleration potential possible if the ion trajectories are in front of the conversion surface cross.
- a detector If a detector is to be operated with a large post-acceleration potential, it is advantageous, as shown in FIG. 5 , to operate it according to method claim 8.
- arbitrarily high post-acceleration voltages can be achieved with a comparatively small curvature of the ion-electron conversion surface (3) by ensuring that the ion paths (11) cross in front of the conversion surface by suitable arrangement of the electrodes and suitable adjustment of the voltages. Since a number of possibilities are known for arranging electrodes or adjusting voltages in such a way that an electric field with the required properties results, the electrodes are not shown here.
- FIG. 6 shows a detector design according to claim 6, in which the electrons generated on the curved ion-electron conversion surface (3) are withdrawn transversely to the detector axis by a field superimposed on the post-acceleration field.
- the electron tracks (15) are shown in dashed lines.
- the ion trajectories (11) are shown twice in the middle part of the post-acceleration section, since here, similar to Fig. 5 , it is possible to cause crossing (11a) ion trajectories, or the ion trajectories essentially parallel (11b) to the ion Lead electron conversion surface (3).
- the generated electrons can be scanned using a multi-channel plate or scintillator or similar be effected.
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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)
Claims (11)
- Détecteur pour spectromètre de masse à durée de vol, comportantune ou plusieurs électrodes (1, 2, 4) pour la post-accéleration des ions, etune surface de conversion (3) ions-électrons,
- Détecteur suivant la revendication 1 caractérisé en ce que la surface de conversion (3) ions-électrons est formée en métal.
- Détecteur suivant la revendication 1 comportant une galette de microcanaux servant comme surface de conversion (3) ions-électrons.
- Détecteur suivant l'une quelconque des revendications précédentes caractérisé en ce que les électrodes (1, 2, 4) pour la post-accéleration des ions et la surface de conversion (3) ions-électrons sont en forme cylindrosymétrique.
- Détecteur suivant l'une quelconque des revendications 1 à 3 caractérisé en ce que les électrodes (1, 2, 4) pour la post-accéleration des ions et/ou la surface de conversion (3) ions-électrons ne sont pas en forme cylindrosymétrique.
- Détecteur suivant l'une quelconque des revendications précédentes caractérisé en ce que le champ de post-accélération des ions est superposé par un champ extracteur des ions produits à la surface de conversion (3) ions-électrons.
- Détecteur suivant l'une quelconque des revendications précédentes caractérisé en ce qu'il est possible d'incliner la surface de conversion (3) ions-électrons autour un ou plusieurs axes.
- Spectromètre de masse à durée de vol comportant un détecteur suivant l'une quelconque des revendications précédentes.
- Procédé d'opération d'un détecteur pour un spectromètre de masse à durée de vol comportantune ou plusieurs électrodes (1, 2, 4) pour la post-accéleration des ions, etune surface de conversion (3) ions-électrons,la surface de conversion (3) ions-électrons n'etant pas planla courbure de la surface de conversion (3) ions-élections servant à réduir les erreurs de durée de vol, etles électrodes (1, 2, 4) et les tensions appliquées à ceux-ci ayant l'effect de courber des trajectoires extraaxiales (11) à un tel degrée qu'ils sont incidentes sur le côté opposé de l'axe.
- Procédé de détermination de la courbure de la surface de conversion (3) ions-électrons d'un détecteur comportant plusieurs électrodes (1, 2, 4) caractérisé en ce quea) on destine toutes les formes des électrodes (1, 2, 4) à l'avance, à l'exception de la courbure de la surface de conversion (3) ions-électrons,b) on choisit une forme arbitraire pour la surface de conversion (3) ions-électrons.c) on détermine les tensions de toutes les électrodes (1, 2, 4),d) on détermine le potentiel des formes et des tensions données des électrodes,e) on détermine une groupe de trajectoires (11), soità partir d'une surface (12) verticale à l'axe optique des ions du détecteur, étant orientées vers l'intérieur du détecteur, parallèles à l'axe optique des ions et possédant la même vitesse initiale, ou soità partir de la source des ions du spectromètre de masse à durée de vol, les trajéctoires étant choisies tel qu'elles possedent des lieux, des vitesses et des directions initials qui correspondent aux conditions normales d'utilisation du spectromètre de masse à durée de vol,f) la surface (20), laquelleen cas de conditions initiales à deux dimensions, est definie par les points d'extremité des trajectoires ainsi déterminées, ou respectivementen cas de conditions initiales à plus de deux dimensions, est une approximation optimalisée des points d'extremité des trajectoires ainsi déterminéesg) la surface détermine au pas f) est. soitprise directement comme nouvelle forme de la surface de conversion (3) ions-électrons, ou soitadaptée optimal par une surface à nombre fini de paramètres,
- Procédé de détermination des tensions des électrodes d'un détecteur comportant une surface de conversion (3) ions-électrons courbée caractérisé en ce quea) on détermine toutes les formes des électrodes (1, 2, 3, 4) à l'avance,b) on choisit un jeu de tensions pour toutes les électrodes,c) on calcule le potentiel à partir des formes et tensions données des électrodes,d) on détermine une groupe de trajectoires (11), soità partir d'une surface (12) verticale à l'axe optique des ions du détecteur, étant orientées vers l'intérieur du étecteur, parallèles à l'axe optique des ions et possédant la même vitesse initiale, ou soità partir de la source des ions du spectromètre de masse à durée de vol, les trajéctoires étant choisies tel qu'elles possedent des lieux, des vitesses et des directions initials qui correspondent aux conditions normales d'utilisation du spectromètre de masse à durée de vol,e) on varie les tensions de toutes les électrodes jusqu'à ce que l'écart moyen entre les points d'extremité déterminés des trajectoires (1 1) des ions au pas d) et la surface de conversion (3) ions-électrons atteint un minimum.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4322104 | 1993-07-02 | ||
DE4322104A DE4322104A1 (de) | 1993-07-02 | 1993-07-02 | Detektor für Flugzeit-Massenspektrometer mit geringen Flugzeitfehlern bei gleichzeitig großer Öffnung |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0633601A2 EP0633601A2 (fr) | 1995-01-11 |
EP0633601A3 EP0633601A3 (fr) | 1995-11-22 |
EP0633601B1 true EP0633601B1 (fr) | 1998-10-14 |
Family
ID=6491838
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94110272A Expired - Lifetime EP0633601B1 (fr) | 1993-07-02 | 1994-07-01 | Détecteur pour spectromètre de masse à temps de vol présentant des distorsions réduites des temps de vols à ouverture élevée |
Country Status (7)
Country | Link |
---|---|
US (1) | US5637869A (fr) |
EP (1) | EP0633601B1 (fr) |
JP (1) | JPH0831372A (fr) |
AT (1) | ATE172323T1 (fr) |
AU (1) | AU685114B2 (fr) |
CA (1) | CA2127184A1 (fr) |
DE (2) | DE4322104A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10188881A (ja) * | 1996-12-26 | 1998-07-21 | Yokogawa Analytical Syst Kk | 飛行時間型質量分析装置及びイオンビーム用収束レンズ |
US6013913A (en) * | 1998-02-06 | 2000-01-11 | The University Of Northern Iowa | Multi-pass reflectron time-of-flight mass spectrometer |
US6891712B2 (en) * | 2001-10-18 | 2005-05-10 | Pst Associates, Llc | Field converter |
US20050099761A1 (en) * | 2001-10-18 | 2005-05-12 | Pst Associates, Llc | Field converter for thrust generation |
GB2399677C (en) * | 2003-02-13 | 2007-03-06 | Micromass Ltd | Ion detector |
US7141785B2 (en) | 2003-02-13 | 2006-11-28 | Micromass Uk Limited | Ion detector |
CN103745908B (zh) * | 2014-01-10 | 2016-06-22 | 清华大学深圳研究生院 | 一种时间补偿离子检测器及弯曲型离子迁移谱仪 |
US9666423B2 (en) | 2014-05-22 | 2017-05-30 | W Henry Benner | Instruments for measuring ion size distribution and concentration |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2534796C3 (de) * | 1975-08-04 | 1979-07-05 | Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V., 3400 Goettingen | Rotationssymetrischer Ionen-Elektronen-Konverter |
US4472631A (en) * | 1982-06-04 | 1984-09-18 | Research Corporation | Combination of time resolution and mass dispersive techniques in mass spectrometry |
SU1274547A2 (ru) * | 1984-08-10 | 1988-04-30 | Институт Аналитического Приборостроения Научно-Технического Объединения Ан Ссср | Устройство дл масс-спектрометрического анализа |
US5300774A (en) * | 1991-04-25 | 1994-04-05 | Applied Biosystems, Inc. | Time-of-flight mass spectrometer with an aperture enabling tradeoff of transmission efficiency and resolution |
US5160840A (en) * | 1991-10-25 | 1992-11-03 | Vestal Marvin L | Time-of-flight analyzer and method |
-
1993
- 1993-07-02 DE DE4322104A patent/DE4322104A1/de not_active Withdrawn
-
1994
- 1994-06-30 CA CA002127184A patent/CA2127184A1/fr not_active Abandoned
- 1994-07-01 AT AT94110272T patent/ATE172323T1/de not_active IP Right Cessation
- 1994-07-01 AU AU66154/94A patent/AU685114B2/en not_active Ceased
- 1994-07-01 DE DE59407075T patent/DE59407075D1/de not_active Expired - Fee Related
- 1994-07-01 US US08/269,545 patent/US5637869A/en not_active Expired - Fee Related
- 1994-07-01 EP EP94110272A patent/EP0633601B1/fr not_active Expired - Lifetime
- 1994-07-04 JP JP6152490A patent/JPH0831372A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
DE59407075D1 (de) | 1998-11-19 |
CA2127184A1 (fr) | 1995-01-03 |
EP0633601A2 (fr) | 1995-01-11 |
JPH0831372A (ja) | 1996-02-02 |
EP0633601A3 (fr) | 1995-11-22 |
ATE172323T1 (de) | 1998-10-15 |
AU6615494A (en) | 1995-01-12 |
DE4322104A1 (de) | 1995-01-19 |
AU685114B2 (en) | 1998-01-15 |
US5637869A (en) | 1997-06-10 |
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