This invention relates to an ion trap and to a method of ejecting ions from an ion trap, wherein the ions are ejected in an ejection direction E which is perpendicular or substantially perpendicular to the longitudinal direction L of the ion trap.
Ion traps could be used in order to provide a buffer for the incoming stream of ions and to prepare a packet with spatial, angular and temporal characteristics adequate for the specific mass analyser. Examples of pulsed mass analysers include time-of-flight (TOF), Fourier transform ion cyclotron resonance (FT ICR), Orbitrap® types (i.e. those using electrostatic only trapping), or a further ion trap.
Ion traps are storage devices that use RF fields for transporting or storing ions. Typically, they include a RF signal generator that provides a RF signal to the primary winding of a transformer. A secondary winding of the transformer is connected to the electrodes (typically four) of the storage device. Typically they comprise elongate electrodes extended in a longitudinal direction L and the electrodes are paired along axes perpendicular to the longitudinal direction. In a ion trap having e.g. 4 electrodes the electrodes are shaped to create a quadrupolar RF field with hyperbolic equi-potentials that contain ions entering or created in the ion trap. Trapping within the ion trap can be assisted by the use of a DC field. As can be seen from
In particular there are two types of ion traps having elongated electrodes: Linear ion traps comprise straight linear electrodes. Curved linear ion traps called C-trap comprise curved electrodes. An ion trap can have various number of of electrodes. In particular an ion trap has pairs of electrodes. Preferably on ion trap has 4 electrodes (quadrupole ion trap), 6 or 8 electrodes.
This invention is now to related to such ion traps, which are ejected ions which are trapped in the ion trap in an ejection direction E which is perpendicular or substantially perpendicular to the longitudinal direction L of the ion trap. Therefore the ion trap comprises one electrode, an ejection electrode, which has an opening in the ejection direction E. Preferably the opening is positioned in the middle of the ejection electrode or at least close to the middle of the electrode. The opening is in particular positioned in the middle of the ejection electrode in its longitudinal direction L or at least close to the middle of the ejection electrode in its longitudinal direction L.
To eject ions from the ion trap in the ejection direction E different approaches are known to apply a DC voltages to the electrodes, preferably after the RF voltage trapping the ions in the ion trap has been switched off or at least reduced.
Chien et al. are proposing in “Enhancement of resolution in Matrix-assisted Laser Desorption Using an Ion-trap Storage/Reflectron Tim-of-flight Mass Spectrometer”, Rapid. Comm. Mass Spectrom. Vol. 7, 837-844 (1993) to apply to an electrode, through which the ions are leaving the ion trap a DC voltage which is pulling the ions to the this ejection electrode. On the other hand Fountain et al. “Mass-selective Analysis of Ions in Time-of-flight Mass spectrometry Using an Ion-trap Storage Device”, Rapid. Comm. Mass Spectrom. Vol. 8, 487-494 (1994) to apply to electrode, which is opposite of the electrode, through which the ions are leaving the ion trap a DC voltage which is pushing the ions to the electrode, through which the ions are leaving the ion trap.
In U.S. Pat. No. 5,569,917 is disclosed to apply at the same time to apply to an electrode, through which the ions are leaving the ion trap a DC voltage which is pulling the ions to the this ejection electrode and to the electrode, which is opposite of this electrode, a DC voltage of opposite polarity which is pushing the ions to the electrode, through which the ions are leaving the ion trap.
A similar approach is also described in US 2011/0315873 A1 for an ion trap having elongated electrodes. The details, how to apply DC voltages to the electrodes to eject ions from the ion trap, are illustrated below. Also in this approach voltage difference is applied to the ejection electrodes and the electrode opposite of the ejection electrode. This approach requires a specific DC voltage supply for these two electrodes.
The efficiency of the ejection of the ions from ion trap using this approaches is limited. Not all ions stored in the ion trap can be extracted and transferred e.g. by the acceleration lens to a mass analyser. In particular the efficiency depends on the occurrence of space charges in an ion trap and the mass distribution of the stored ion population.
Further a lot of ions pushed to the ejection electrode get lost because they hit the edge of the opening of the ejection electrode. This results in an increased contamination of the edge which might further influence the behaviour of the ion trap, in particular during ion ejection.
Due to the mentioned problems further the dynamic range and linearity of mass analysers to which the ejected ions are transferred, is limited.
Another disadvantage of the known approaches to eject ions from ion traps is that to each electrode of a the ion trap a specific DC voltage has to be applied which is requiring a lot of DC supply devices and a detailed control of the application of different DC voltages to each DC electrode. It is an object of the invention to provide an improved ion trap having a higher efficiency of ion ejection.
It is an object of the invention to provide an improved ion trap, wherein the dependence of the efficiency of ion ejection on space charge is reduced.
It is an object of the invention to provide an improved ion trap, wherein the dependence of the efficiency of ion ejection on the mass distribution within the stored ion population is reduced.
It is an object of the invention to provide an improved ion trap, wherein during the ion ejection the contamination of the opening, through which the ions are ejected is reduced in comparison to ion traps of the prior art.
It is an object of the invention to provide an improved ion trap, by which the dynamic range of a mass analyser can increased, to which the ion trap is supplying the ejected ions.
It is an object of the invention to provide an improved ion trap, by which the linearity of a mass analyser can increased, to which the ion trap is supplying the ejected ions.
Another object of the invention is to provide an improved ion trap with a simplified voltage supply.
At least one and preferably all of the objects are solved by an ion trap of claim 1.
The inventive ion trap comprises for ion trapping one ejection electrode and further electrodes. The ejection electrode and the further electrodes are elongated in a longitudinal direction L. The ion trap may be a straight linear ion trap or a curved linear ion trap (C-trap). Also the ion trap might comprise electrodes with linear and curved portions. The ion trap may be a linear quadrupole ion trap, i.e. having four elongate electrodes. However, the invention may be applied in ion traps having more than four electrodes (e.g. six or eight electrodes). The electrodes of the ion trap, the ejection electrode and further electrodes, have preferably the same shape along the longitudinal direction L of the ion trap. So the longitudinal direction can be (the same direction along the whole ion trap) a straight line or a curved line or a partially straight and curved line.
In a specific embodiment, different electrodes of the ion trap can be used as ejection electrode at different instants of time.
The ejection electrode of the ion trap has an opening, through which ions in the ion trap 1 can be ejected in an ejection direction E. The ejection direction E of a package of ejected ions is defined as the average direction in which the ions of the package fly when leaving the opening of the ejection electrode. So for an ejected package of ions the ejection direction is typically defining the direction of the central ion beam of the ion package. The width of the ion beam perpendicular to the ejection direction E might still depend on experimental conditions. The ejection direction E of the ejected ions is at least nearly perpendicular to the longitudinal direction L of the electrodes. The angle α between the longitudinal direction L and the ejection direction E deviates from 90° typically not more than 15°, preferably not more than 10° and particularly preferably not more than 5°.
For the ion trapping in the ion trap the electrodes of the ion trap, the ejection electrode and the further electrodes, are supplied with a RF voltage. Some or all electrodes may be during ion trapping also supplied with a DC voltage e.g. to create potential walls.
The RF voltage applied to the electrodes is generated by transforming the RF voltage provided by a RF power supply. This RF power supply is providing the generated RF signal to a primary winding. Then is primary winding is inductively coupled with a secondary winding. The RF signal generated by transformation in this winding is then supplied to the ejection electrode. Further the primary winding is also inductively coupled with other secondary windings. The signal generated by transformation in these other windings is then supplied to the other electrodes of the ion trap.
The power supply of the ion trap is controlled by a controller, which may comprise various control means, for example: a processor, switches, and/or software to be executed by the processor and other software and hardware components.
With the RF voltages applied to the electrodes, the ions can be trapped in the ion trap. Optionally, the trapped ions are cooled or thermalised in the ion trap prior to ejection. For the ejection of the ions from the ion trap according to the invention also DC voltages have to be applied to the electrodes of the ion trap. Typically, they are applied, after the RF voltage provided to the electrodes has been switched off. The the inventive ion trap is comprising at least two DC supplies, providing DC voltages to the electrodes of the ion trap. The application of the DC voltages is controlled by the control of the ion trap.
For ejection of ions from the ion trap, a first DC voltage provided by first DC supply is applied to the ejection electrode. The first DC voltage is provided to the ejection electrode via the secondary winding, which is also supplying the RF signal to the ejection electrode. The first DC voltage is applied to the ejection electrode to pull the ions in the ion trap to the opening of the ejection electrode.
A second DC voltage is provided by second DC supply. The second DC voltage is provided to at least 70% of the further electrodes via the secondary windings which are also supplying the RF signal to the further electrodes. The second DC voltage pushes ions in the ion trap to the opening of the ejection electrode. Therefore, the DC voltage provided by second DC supply to the at least 70% of the further electrodes has the same polarity as most ions in the ion trap.
Preferably the number of further electrodes is 3, so that the ion trap is a quadrupole. But the number of the further electrodes could be also in other embodiments 5 (hexapole) or 7 (octopole).
In a preferred embodiment the ion trap comprises curved electrodes. In particular the inventive ion trap can be a curved ion trap.
In preferred embodiments of the inventive ion trap the angle α between the longitudinal direction L and the ejection direction E deviates from 90° not more than 7°, preferably not more than 3°.
In other preferred embodiment of the inventive ion trap the controller is applying in the time period the second DC voltage provided by the second DC supply via the secondary windings to the at least 80% of the further electrodes to push ions in the ion trap to the opening of the ejection electrode. In a more preferred embodiment of the inventive ion trap the controller is applying in the time period the second DC voltage provided by the second DC supply via the secondary windings to all further electrodes 3 to push ions in the ion trap to the opening of the ejection electrode.
The time period in which the controller is applying the first DC voltage to the ejection electrode and second DC voltage to the further electrodes, can be between 5 ms and 5000 ms, preferably between 10 ms and 2000 ms and particular preferably between 50 ms and 500 ms. In particular both DC voltages can be applied at the same time, but there might be a delay up to 5000 ns, preferably up 500 ns and in particular preferably up to 100 ns. Preferably the second voltage is at first applied to the further electrodes.
Typically, is voltage difference between the first DC voltage applied to the ejection electrode 2 and the second DC voltage applied to the further electrodes 3 between 50 V and 800 V, preferably between 100 V and 600 V and particular preferably between 200 V and 400 V.
The inventive ion trap comprises in a preferred embodiment a focusing lens, which is arranged for the ejected ions downstream of the of the opening of the ejection electrode and is focusing the ejected ions. Preferably the focusing lens has an opening into which the ejected ions are directed which is larger than the opening of the ejection electrode. The focusing lens 10 may be an electrostatic lens to which a DC voltage is applied. Typically is the voltage difference between the DC voltage of the focusing lens and the first DC voltage of the ejection electrode is between 250 V and 1,500 V, preferably between 400 V and 1,000 V and particular preferably between 600 V and 800 V. Typically the ratio of the voltage difference between the DC voltage of the focusing lens and the first DC voltage of the ejection electrode and the voltage difference between the first DC voltage applied to the ejection electrode and the second DC voltage applied to the further electrodes 3 is between 1.5 and 6, preferably between 2.0 and 4 and particular preferably between 2.2 and 3.
The inventive ion trap comprises in a preferred embodiment an acceleration lens, which is arranged for the ejected ions downstream of the focusing lens. The acceleration lens 12 has preferably an opening 13 into which the ejected ions are directed which is smaller than the opening of focusing lens, the acceleration lens 12 Preferably is the acceleration lens an electrostatic lens to which a DC voltage is applied. Typically the voltage difference between the DC voltage of the acceleration lens and the DC voltage of the focusing lens is between 800 V and 5,000 V, preferably between 1,500 V and 3,500 V and particular preferably between 2,000 V and 2,700 V. Typically is the ratio of the voltage difference between the voltage difference between the DC voltage of the acceleration lens and the first DC voltage of the ejection electrode and the voltage difference between the first DC voltage applied to the ejection electrode and the second DC voltage applied to the further electrodes between 2 and 12, preferably between 4 and 9 and particular preferably between 5 and 7. Typically is the ratio of the voltage difference between the first DC voltage applied to the ejection electrode and the second DC voltage applied to the further electrodes and the voltage difference between the voltage difference between the DC voltage of the acceleration lens and the second DC voltage applied to the further electrodes and is between 0.05 and 0.4, preferably between 0.1 and 0.25 and particular preferably between 0.12 and 0.2.
In a preferred embodiment of the ion trap the secondary winding supplying the transformed RF voltage to the ejection electrode and the secondary winding supplying the transformed RF voltage to one of the further electrodes are a pair of secondary windings connected in series.
In a preferred embodiment of the ion trap the secondary windings supplying the transformed RF voltage to two of the further electrodes 3 are a pair of secondary windings connected in series.
In preferred embodiment of the inventive ion trap further components of a mass spectrometer, in particular a HCD cell or a transport multipole, are supplied with a RF voltage, by tapping RF voltages from the RF supply of the ejection electrode 2 and further electrodes 3 of the ion trap. Preferably an inductance divider is used for tapping the RF voltage.
At least one and preferably all of the objects are solved by a method of electing ions from an ion trap of claim 23.
The ion trap comprises one ejection electrode and further electrodes elongated in a longitudinal direction L for ion trapping, wherein the ejection electrode comprises an opening, through which ions in the ion trap can be ejected in an ejection direction E, wherein an angle α between the longitudinal direction L and the ejection direction E deviates from 90° not more than 15°, wherein RF voltage is supplied to the ion trap by a primary winding connected to an RF power supply, a secondary winding coupling with the primary winding transforming the RF voltage of the RF power supply 6 and supplying the transformed RF voltages to the ejection electrode and secondary windings coupling with the primary winding transforming the RF voltage of the RF power supply and supplying the transformed RF voltages to the further electrodes, a first DC supply 8 and a second DC supply 9.
The methods comprises the first step of switching off the RF voltage supplied to the one ejection electrode and the further electrodes of the ion trap and then in a second step applying in a time period a first DC voltage via secondary winding provided by the first DC supply to the ejection electrode to pull ions in the ion trap to the opening of the ejection electrode and a second DC voltage provided by the second DC supply via the secondary windings to the at least 70% of the further electrodes to push ions in the ion trap to the opening 4 of the ejection electrode.
Further details of the inventive method can be derived from this specification.
When the trapped ions are to be ejected, the RF voltage and if present also the small DC voltage is switched off. Then an offset voltage Vacc is applied via an offset DC source which is positioned between the lower further electrode 3 and the acceleration lens 12, which is grounded. The same offset voltage Vacc (now shown) is also supplied to the upper further electrode 3. A typical value for the applied offset voltage is 2,200 V. Via a first DC supply 8 a first DC voltage Veject is applied to ejection electrode 2. This first DC voltage Veject is applied between the lower further electrode 3 and the ejection electrode 2 by the first DC supply 8. A typical value for the first DC voltage Veject is 300V, wherein the negative polarity is applied to the ejection electrode 2. Due to the ejection electrode 2 also being connected to the offset DC source that supplies voltage Vacc, relative to ground a voltage of 1,900 V is applied to the ejection electrode 2. Via a second DC supply 9 a second DC voltage is applied to left further electrode 3, which is arranged opposite to the ejection electrode 2 in the ion trap. In the shown example second DC voltage has the same value Veject as the first DC voltage. This second DC voltage is applied between the lower further electrode 3 and the left further electrode 3′ by the first DC supply 9. Then the value of the second DC voltage is also 300V, wherein the positive polarity is applied to the left further electrode 3′. Due to the ejection electrode 2 also being connected to the offset DC source that supplies voltage Vacc, relative to ground a voltage of 2,500 V is applied to the left further electrode 3. When these voltages are applied to the electrodes 2,3 of the ion trap, positively charged ions are pushed by the voltage applied to the left further electrode 3 in the direction of the ejection electrode 2 and pulled by the voltage applied to the ejection electrode 2 to the ejection electrode 2. This effect on the positively charged ions is created by the electric field in the ion trap, which is provided by the voltage difference between the left further electrode 3 and the ejection electrode 2. This electric field has in particular a component directed to the ejection electrode 2 and as shown by the ion beam 32 of the ions in the ion trap is directed to the opening 4 of the ejection electrode 2. But not all ions are ejected through the opening and are further accelerated by the acceleration lens 12. A portion of ions strike the edge of the opening 4. This leads to a reduced efficiency of the ion ejection and to a contamination of the ejection electrode 2 at the edge of its opening. Further, a small dotted circle shows the central region from which ions are ejected from the ion trap 1, when the DC voltages are applied as described before.
It is shown the ejection of ions stored in the ion trap 1 in ejection direction E The ion trap is comprising an ejection electrode 2 and the further electrodes 3, 3′. To facilitate ejection, a opening 4 is provided in the ejection electrode 2.
A RF power supply 6 is shown which is connected with a primary winding 5. Further three pairs of symmetrical secondary windings 7,7′ are shown, which are coupled with the primary winding 5. A RF switch 20 is shown to switch off the RF power supplied to secondary windings explained below. A first pair of secondary symmetrical windings 21 is shown which are connected to the full-wave rectifier 42 to rapidly reduce the RF voltage in the further secondary winding after the switch of the supplied RF voltage.
A first and a second winding 7′ of a second pair of secondary windings supplies the further electrodes 3, of the ion trap, which are above the middle and at the right side of the ion trap 1. A first winding 7′ of a third pair of secondary windings supplies the other further electrode 3 of the ion trap below the middle of the ion trap. The second winding 7 of a third pair of secondary windings supplies the other ejection electrode 2 of the ion trap. As can be seen from
With the circuit shown in
In this drawing further is shown the RF voltage supply to the electrodes 2,3 when ions are being trapped and the DC voltage supply to the electrodes 2,3 of the ion trap when ions are being ejected.
Normally at least an RF voltage of two opposite phases is applied to the four electrodes 2,3 of the ion trap, when ions are trapped. It is further possible to apply a small DC voltage to at least one of the electrodes 2,3 of the ion trap to improve the trapping by potential wells (supplied as the LO OFFSET voltage from supply 9).
An RF generator is shown as RF power supply 6, which is connected with a primary winding 5 of a transformer. This primary winding 5 in the transformer arrangement is coupled with two pairs of secondary windings 34, 35. The first pair of secondary windings 34 is supplying via the two windings 7′ a transformed RF voltage to the lower further electrode 3 and the left further electrode 3 arranged in the ion trap 1 opposite to the ejection electrode 2. The second pair of secondary windings 35 is supplying via the winding 7 a transformed RF voltage to the ejection electrode 2 and via the winding 7′ a transformed RF voltage to the upper further electrode 3. Further a low offset DC voltage is optionally applied to all electrodes 2, 3 when ions are trapped in the ion trap. In this situation a pull switch 26 is opened (lower switch position) and a push (offset) switch 27 is switched on to provide the low offset voltage (OFFSET_LO).
When the controller 50 of the ion trap is switching the voltage supply of the ion trap 1 to eject ions, the control is switching the RF switch 36, the pull switch 26 and the push switch 27. At first the RF switch 36 is activated so as to switch off the RF voltage supplied to all electrodes 2, 3 of the ion trap. Then with a very short delay of 0-1000 ns the push switch 27 is activated so as to provide a second DC voltage, a high push voltage (OFFSET_HI) to the further electrodes 3 and the ejection electrode 2 via the opened pull switch 26. The value of the push voltage is typically between 1,500 and 2,500 V, preferably between 1,800 V and 2,200 V. Then with a very short delay of 0-1000 ns the pull switch 26 is activated (upper switch position) so as to provide a first DC voltage (PULL_DC) to the ejection electrode 2 in addition to the high push voltage. Due to this DC voltage supply the ions in the ion trap 1 are ejected through the opening 4 of the ejection electrode. More details about the ion ejection are explained in
Normally at least an RF voltage is applied to the four electrodes 2,3 of the ion trap, when ions are trapped, for example in the manner shown in
When the trapped ions are to be ejected, the RF voltage and if present also the small DC voltage is switched off. Then a second DC voltage Vacc is applied via second DC supply 9 which is connected with the three further electrode 3 and the acceleration lens 12, which is grounded. The three further electrode 3 are connected with the second DC supply 9 via secondary windings 7′ of a transformer supplying the RF voltage to the three further electrodes 3. A typical value for the applied second voltage is 2,000 V. The second DC supply 9 is also connected to the ejection electrode 2 via a first DC supply 8, whereby a first DC voltage Veject is applied to ejection electrode 2. This first DC voltage Veject is applied between the further electrodes 3 and the ejection electrode 2 by the first DC supply 8. A typical value for the first DC voltage Veject is 300V, wherein the negative polarity is applied to the ejection electrode 2. Due to this, relative to ground, a voltage of 1,700 V is applied to the ejection electrode 2. When these voltages are applied to the electrodes 2,3 of the ion trap, positively charged ions are pushed by the voltage applied to the further electrodes 3 in direction of the ejection electrode 2 and pulled by the voltage applied to the ejection electrode 2 to the ejection electrode 2. This effect on the positively charged ions is created by the electric field in the ion trap, which is provided by the voltage difference between the further electrode 3 and the ejection electrode 2. This electric field has in particular an improved component directed to the ejection electrode 2 and in particular an improved component directed to the opening 4 of the ejection electrode 2. Providing only the ejection electrode 2 with a different voltage to the further electrodes 3 creates a more non-uniform electric field than in the prior art. Thus by the curcature of the equi-potentials of this electric field, stronger focusing of ions through the opening 4 of the ejection electrode 2 may be achieved. Such non-uniformity of the electric field within the volume of the ion trap creates a converging lens that may bring ions from a wide region (dashed circle) through the narrow ejection opening 4. Thus, advantages are that a higher amount of ions may be extracted from a region substantially wider that the ejection opening and contamination of the ejection electrode around the opening may be reduced. Accordingly, as shown in the Figure, the ion beam 32 of the ions in the ion trap is directed to the middle of opening 4 of the ejection electrode 2. At least nearly all ions are passing the opening 4 and are further accelerated by the grounded acceleration lens 12. In the inventive ion trap 1, preferably ions do not strike the edge of the opening 4 or only a small portion of ions do so. This leads to an improved efficiency of the ion ejection: a contamination of the ejection electrode 2 at the edge of its opening 4 can be avoided. Further the dotted circle shows the region from which ions are ejected from the ion trap 1, when the DC voltage is applied as described before. In comparison to
Several of the processes of the inventive method can be supported or implemented using one or more computers and processors, being stand alone or connected or in a cloud system, and by software to execute the processes.
The embodiments described in this application represent examples of the inventive ion traps and inventive methods. Accordingly, the invention can be realised by each embodiment alone or by a combination of several or all features of the described embodiments without any limitations.
Number | Date | Country | Kind |
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1907235.4 | May 2019 | GB | national |
This application claims priority to UK Patent Application 1907235.4, filed on May 22, 2019, and titled “Ion Trap with Elongated Electrodes,” by Jan Peter Hauschild et al, which is hereby incorporated herein by reference in its entirety. This application is further a divisional of U.S. patent application Ser. No. 16/878,722, filed on May 20, 2020, and titled “Ion Trap with Elongated Electrodes,” by Jan Peter Hauschild et al.
Number | Date | Country | |
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Parent | 16878722 | May 2020 | US |
Child | 18112138 | US |