EP0858674A1 - Time-of-flight mass spectrometer with position-sensitive detection - Google Patents
Time-of-flight mass spectrometer with position-sensitive detectionInfo
- Publication number
- EP0858674A1 EP0858674A1 EP96937307A EP96937307A EP0858674A1 EP 0858674 A1 EP0858674 A1 EP 0858674A1 EP 96937307 A EP96937307 A EP 96937307A EP 96937307 A EP96937307 A EP 96937307A EP 0858674 A1 EP0858674 A1 EP 0858674A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- time
- mass spectrometer
- flight mass
- electron
- anodes
- 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.)
- Granted
Links
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
- H01J49/40—Time-of-flight spectrometers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/025—Detectors specially adapted to particle spectrometers
Definitions
- the invention relates to a time-of-flight mass spectrometer with a position-sensitive detector, which has at least one electron multiplier and an anode arrangement for detecting the electrons released in the electron multiplier.
- Photoionized molecules usually decay into electrons and ions, which have to be detected simultaneously.
- the energy and momentum of these photodissociated fragments can be determined, for example, by means of a time-of-flight mass spectrometer with position-sensitive detector, with which the time of flight and the point of impact can be determined by the fragments.
- the position-sensitive detectors known in the prior art have various disadvantages. Detectors based on resistive anodes are relatively widespread, but generally have very long dead times, which limit the time resolution of the system.
- detectors consist of a matrix of crossed anodes, which are interconnected in rows and columns, as described, for example, in the publication by JHD Eland in Meas. Be. Technol. 5, 1501-1504 (1994). With these detectors too, the dead times are high due to the use of delay lines for indirect position determination from signal transit time measurements and digital circuits for time measurement. It is therefore an object of the present invention to provide a flight time mass spectrometer with a position sensitive detector with improved time and location resolution.
- the detector according to the invention consists of at least one electron multiplier and an anode matrix arranged behind each electron multiplier, in which anodes are connected to one another in rows or columns and each row or column is connected to an output connection.
- the anodes detect the electrons released in the electron multiplier in a position-sensitive manner.
- the time measurement is carried out in a device independent of the anode matrix.
- This device can be, for example, an analog circuit with which a time resolution of approximately 100 ps can be achieved. This represents an improvement in the time resolution by more than a factor of 10 compared to the prior art.
- FIG. 1 shows a schematic illustration of a first embodiment of the invention
- FIG. 3 shows a schematic representation of a further embodiment of the invention
- Fig. 4 is a block diagram of the embodiment of Fig. 3;
- FIG 5 shows an example of an anode pattern of an anode matrix.
- the basic mode of operation of the detector according to the invention is shown schematically and by way of example in FIG. 1.
- approximately monochromatic synchrotron radiation SR strikes the molecules of a molecular beam MB.
- the synchrotron radiation can, for example, be emitted by a synchrotron storage ring and guided through a wavelength-selective element such as a grating or crystal monochromator 1.
- a wavelength-selective element such as a grating or crystal monochromator 1.
- the measuring principle is shown schematically on the basis of the decay of a CO molecule. Based on the measured positions and times of the ions striking the detector 20, their energy and momentum can be determined shortly after the fragmentation.
- the detector 20 consists of two multi-channel plates 21, 22 arranged one behind the other and the anode matrix 23 which is arranged at such a distance from the second multi-channel plate 22 that an electron cloud triggered in the multi-channel plates hits at least one anode.
- the anode matrix consists of 900 flat anodes, which are regularly arranged in 30 rows and 30 columns. Overall, the anode matrix thus consists of 1800 partial anodes, two of which each form a flat anode.
- the anodes are arranged and dimensioned such that multi-channel plates or so-called microsphere plates with a diameter of 40 mm can be used.
- the anodes are at a potential 2800 V higher than the front side of the first multi-channel plate 21, which is at -4000 V with respect to ground. This voltage focuses the electron cloud in such a way that it hits at least one anode (two partial anodes).
- the partial anodes are connected to each other along each row (X) or each column (Y) and each row and each column is connected to an output connection, so that a total of 60 wires have to be led out of the vacuum chamber.
- An anode is struck at each event and a signal is generated on an X and a Y line. These signals are first fed to a position decoder 24 for determining the position.
- the position decoder 24 responds when two adjacent partial anodes have been hit by the electron wave at the same time.
- a feature of the present invention is that the time measurement is carried out by devices which are independent of the anode matrix and the other devices for determining the position.
- Fig. 1 the principle of time measurement is shown.
- a thin metal plate attached to the back of the second multi-channel plate 22 (see FIG. 2) or a metal coating applied to a carrier is used for the time measurement.
- the electrons released in the multi-channel plates pass through the metal plate essentially unhindered on their way to the anode.
- a pulse hereinafter referred to as ion signal IS
- the time of this pulse is considered to be representative of the time of the impact of the ions on the first multi-channel plate.
- the starting point of the ion analysis is taken as the reference point. In the present example, this is the time of ionization by the synchrotron radiation pulse entering the interaction zone.
- bunch marker (BM) signal a pulse derived from the high-frequency control of the synchrotron.
- TAC time-to-amplitude converter
- ADC analog-to-digital converter
- the next BM signal represents the stop time of the ion analysis and is therefore fed to the TACs as a stop signal, while the ion signals are fed to the TACs as start signals.
- the TACs have a dead time of 2.5 ⁇ s after the start signal, while the synchrotron period is 200-1000 ns.
- TAC-ADC time-to-digital converters
- FIG. 3 shows a further embodiment of the present invention, in which the electrons are additionally detected by an electron spectrometer 50.
- the electron spectrometer 50 contains a drift tube 51 and an electron detector 52, which, as shown, can be constructed in a manner similar to that of the ion detector, ie it can contain two multi-channel or microsphere plates and an anode, the anode of the electron detector can also be carried out over a large area.
- the signal of the electron detector hereinafter referred to as electron signal ES
- electron signal ES is used as a reference signal for the time measurement of the ion events, that is, it is supplied to the TACs as a start signal.
- the electron signal and the BM signal are fed to a TAC 4 (see FIG. 4).
- the electron signal is given to the TAC 4 as a start signal and the BM signal as a stop signal. So it always becomes Time period measured from the occurrence of the electron signal to that BM signal that follows the BM signal causing the electron signal.
- the analog signal of the TAC 4 is fed to an ADC 4 and its output signal is fed to the data coordination interface 25.
- the circuit diagram shown relates to the embodiment according to FIG. 3.
- the transit times of the ions detected by the ion detector are measured in TACs 0-3. They receive the start signal from the anode of the electron detector 52.
- the electron transit time is determined in the TAC 4, in which, as mentioned, the electron signal is supplied as the start signal and the BM signal taken from the synchrotron 70 of the subsequent cycle is supplied as a stop signal.
- the ion signals which arise on the metal plate at the rear of the second multi-channel plate are fed to a fast switch (MUX) 31 on a line, which has the task of subsequently distributing the signals to TACs 0-3 .
- MUX fast switch
- TACs In the example given, one electron and four ions can therefore be detected in one measurement cycle.
- the number of TACs is of course chosen arbitrarily and can be expanded very easily.
- An ADC is assigned to each TAC, which has a time dispersion of 0.1 ns per channel, which can also be selected to be smaller with a suitably fast rise time of the ion signals and can be reduced to 30 ps.
- the ion and electron signals are amplified by a factor of 50 to 100 by an amplifier (not shown) and then converted into standard pulses in a discriminator 32 (CFD, Constant Fraction Discriminator).
- CFD Constant Fraction Discriminator
- This ensures that for original pulses with a similar shape (rise time) but different levels, the time measurement in the TAC is started at comparable times.
- the exact mode of operation of this commercially available component is described in more detail in the literature, for example in the dissertation by B. Langer, TU Berlin, 1992.
- the MUX 31 is connected to the position decoder 24 and sends a gate trigger signal to it in order to enable the association of the measured time signals with the measured location signals.
- a pattern recognition system is therefore interposed as a fast unit, which loads the corresponding information of the position into a very fast memory when an electron cloud occurs. This memory can already be written with a new event position after 5 ns, so that the dead time for reading out depends only on the speed of the fast memory in this pattern recognition system.
- the pattern recognition system is part of the data acquisition interface 25 and also has the task of binary coding the position signals.
- the electron pulses are about 2 ns wide and have an amplitude of 20 mV.
- the dead time of the system according to FIGS. 3 and 4 after detection of an electron is determined by the width of the ion signals and the dead time of the MUX 31 and results in less than 7 ns.
- the widths of the signals and the dead time of the MUX can each be reduced to less than 1 ns.
- the system therefore has no fundamental limit of the smallest possible interval between two ion events, since the width of the signals is essentially decisive.
- FIG. 5 shows an example of a position-sensitive anode matrix used according to the invention (detail).
- the anode matrix is formed as a flat pattern, each anode comprising two partial anodes (A, B shown enlarged in the right part of the figure).
- the partial anodes A and B each correspond to the sub-pixels in the x and y directions.
- the partial anodes A and B are attached to an anode plate.
- the partial anodes A are each connected in rows by electrical connections (not shown) on the back of the anode plate.
- the partial anodes B are connected in columns by electrical connections on the front of the anode plate.
- Each row or column of partial anodes is assigned an output connection, which is connected to a fast preamplifier.
- a particular advantage of the invention is that the assignment of output connections to each row and each column enables a true position determination without signal delay measurements in delay lines. This significantly increases the speed of the position-sensitive detector according to the invention.
- Another advantage is that any enlargement of the anode matrix area to adapt to a specific measurement setup does not lead to a slowdown of the measurement processes. Furthermore, when the matrix area is increased by a certain factor, the number of lines is increased only by the square root of this factor.
- the position-sensitive detector according to the invention can be used in a variety of ways in all applications in which the occurrence of particles in particular is to be measured with a high time and location resolution.
- the invention has been described above with reference to a mass spectrometer.
- the detector according to the invention can also e.g. in an electron spectrometer or in an analyzer for neutral particles.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19541089 | 1995-11-03 | ||
DE19541089A DE19541089A1 (en) | 1995-11-03 | 1995-11-03 | Time-of-flight mass spectrometer with position-sensitive detection |
PCT/EP1996/004732 WO1997017718A1 (en) | 1995-11-03 | 1996-10-31 | Time-of-flight mass spectrometer with position-sensitive detection |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0858674A1 true EP0858674A1 (en) | 1998-08-19 |
EP0858674B1 EP0858674B1 (en) | 2001-05-30 |
Family
ID=7776590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96937307A Expired - Lifetime EP0858674B1 (en) | 1995-11-03 | 1996-10-31 | Time-of-flight mass spectrometer with position-sensitive detection |
Country Status (4)
Country | Link |
---|---|
US (1) | US6031227A (en) |
EP (1) | EP0858674B1 (en) |
DE (2) | DE19541089A1 (en) |
WO (1) | WO1997017718A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7019286B2 (en) * | 2001-05-25 | 2006-03-28 | Ionwerks, Inc. | Time-of-flight mass spectrometer for monitoring of fast processes |
AU2003291176A1 (en) | 2002-11-27 | 2004-06-23 | Ionwerks, Inc. | A time-of-flight mass spectrometer with improved data acquisition system |
US20040169885A1 (en) * | 2003-02-28 | 2004-09-02 | Mellor Douglas J. | Memory management |
US7388193B2 (en) * | 2005-06-22 | 2008-06-17 | Agilent Technologies, Inc. | Time-of-flight spectrometer with orthogonal pulsed ion detection |
FR2895833B1 (en) * | 2006-01-03 | 2008-02-29 | Phisikron Soc Par Actions Simp | METHOD AND SYSTEM FOR TANDEM MASS SPECTROMETRY WITHOUT PRIMARY MASS SELECTION AND FLIGHT TIME |
GB2540730B (en) * | 2015-05-11 | 2017-09-13 | Thermo Fisher Scient (Bremen) Gmbh | Time interval measurement |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5061850A (en) * | 1990-07-30 | 1991-10-29 | Wisconsin Alumni Research Foundation | High-repetition rate position sensitive atom probe |
JP2567736B2 (en) * | 1990-11-30 | 1996-12-25 | 理化学研究所 | Ion scattering analyzer |
US5619034A (en) * | 1995-11-15 | 1997-04-08 | Reed; David A. | Differentiating mass spectrometer |
US5777325A (en) * | 1996-05-06 | 1998-07-07 | Hewlett-Packard Company | Device for time lag focusing time-of-flight mass spectrometry |
US5777326A (en) * | 1996-11-15 | 1998-07-07 | Sensor Corporation | Multi-anode time to digital converter |
-
1995
- 1995-11-03 DE DE19541089A patent/DE19541089A1/en not_active Withdrawn
-
1996
- 1996-10-31 EP EP96937307A patent/EP0858674B1/en not_active Expired - Lifetime
- 1996-10-31 US US09/068,075 patent/US6031227A/en not_active Expired - Fee Related
- 1996-10-31 WO PCT/EP1996/004732 patent/WO1997017718A1/en active IP Right Grant
- 1996-10-31 DE DE59607015T patent/DE59607015D1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9717718A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19541089A1 (en) | 1997-05-07 |
WO1997017718A1 (en) | 1997-05-15 |
US6031227A (en) | 2000-02-29 |
DE59607015D1 (en) | 2001-07-05 |
EP0858674B1 (en) | 2001-05-30 |
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