Mass analyser

Abstract

A mass analyser comprises a pair of electrode arrays. Each array has a set of focusing electrodes which are supplied, in use, with voltage to create an electrostatic field in a space between the electrode arrays causing ions to undergo periodic, oscillatory motion in the space, ions passing between electrodes of the sets of focusing electrodes and being repeatedly focused at a center plane, mid-way between the electrode arrays. At least one electrode of each set of focusing electrodes has an electrode surface closer to the center plane than the electrode surfaces of other electrodes of the same set. The analyzer may be an ion trap mass analyser or a multi-turn ToF mass analyzer.

Claims

1. A mass analyser comprising a pair of electrode arrays, one electrode array of the pair being a mirror image of the other electrode array of the pair with respect to a centre plane mid-way between the electrode arrays, each array including a set of focusing electrodes and the electrode arrays being supplied, in use, with the same voltage pattern to create an electrostatic field in a space between the electrode arrays for causing ions to undergo periodic, oscillatory motion in said space whereby ions pass between electrodes of said sets of focusing electrodes and are repeatedly focused at the centre plane, wherein at least one electrode of each said set of focusing electrodes has an electrode surface that is closer to the centre plane than the electrode surfaces of other electrodes of the same set.

2. A mass analyser as claimed in claim 1 wherein said one electrode is positioned to face a region at the centre plane where electric field gradient has a maximum value.

3. A mass analyser as claimed in claim 1 wherein said one electrode and an immediately neighbouring electrode of the same set are supplied, in use, with voltage having opposite polarities.

4. A mass analyser as claimed in claim 3 wherein said one and immediately neighbouring electrodes have electrode surfaces that are closer to said centre plane than the electrode surfaces of other electrodes of the same set.

5. A mass analyser as claimed in claim 1 wherein said one electrode has a profiled electrode surface facing the centre plane.

6. A mass analyser as claimed in claim 4 wherein said one and immediately neighbouring electrodes both have profiled electrode surfaces.

7. A mass analyser as claimed in claim 5 wherein said profiled electrode surfaces have trapezoidal or hyperbolic cross-sections in a plane orthogonal to the centre plane and along a flight direction of ions.

8. A mass analyser as claimed in claim 1 wherein said one electrode of each said set of focusing electrodes is selected from the three outermost electrodes of the set.

9. A mass analyser as claimed in claim 1 wherein each said electrode array is mounted on a base member made from an electrically insulating material, said one electrode and or said base member being configured to increase surface tracking distance between said one and a said immediately neighbouring electrode.

10. A mass analyser as claimed in claim 9 wherein said base member is provided with a groove or recess between said one and said immediately neighbouring electrodes to increase surface tracking distance between said one and said immediately neighbouring electrodes.

11. A mass analyser as claimed in claim 9 wherein said one electrode is narrower at a lower part of the electrode, proximate the base member on which the electrode is mounted than at an upper part of the electrode further away from the base member to increase surface tracking distance between said one and a said immediately neighbouring electrode.

12. A mass analyser as claimed in claim 9 wherein said one electrode is mounted on the base member using an electrically insulating spacer to increase surface tracking distance between said one electrode and a said immediately neighbouring electrode.

13. A mass analyser as claimed in claim 12 wherein a said immediately neighbouring electrode is also mounted on said base member using an electrically insulating spacer.

14. A mass analyser as claimed in claim 9 wherein the electrodes of each electrode array are mounted on the base member by fixing members.

15. A mass analyser as claimed in claim 1 wherein the electrodes of each said set are concentric ring electrodes.

16. A mass analyser as claimed in claim 9 wherein the electrodes of each said electrode array are concentric ring electrodes, a ring electrode of an array including, and being mounted on the base member by, a plurality of electrically conductive fixing members that are angularly offset with respect to electrically conductive fixing members that mount a neighbouring ring electrode on the base member.

17. A mass analyser as claimed in claim 16 wherein the base member has grooves or slots configured to increase surface tracking distance between fixing members of neighbouring ring electrodes.

18. A mass analyser as claimed in claim 9 wherein the electrodes of each said array are mounted on the base member by brazing, soldering or adhesive bonding.

19. A mass analyser as claimed in claim 9 wherein electrodes of each electrode array are mounted on a said base member formed with a plurality of openings, at least two electrodes of the array are formed with a plurality of fixing members, a fixing member of one electrode and a fixing member of an immediately neighbouring electrode both being mounted in a respective opening in the base member with a gap between the fixing members to increase surface tracking distance between the one and immediately neighbouring electrodes.

20. A mass analyser as claimed in claim 19 wherein said fixing members are mounted on metalised edge surfaces of the openings.

21. A mass analyser comprising a pair of electrode arrays, one electrode array of the pair being a mirror image of the other electrode array of the pair with respect to a centre plane mid-way between the electrode arrays, each array including a set of focusing electrodes and the electrode arrays being supplied, in use, with the same voltage pattern to create an electrostatic field in a space between the electrode arrays for causing ions to undergo periodic, oscillatory motion in said space whereby ions pass between electrodes of said sets of focusing electrodes and are repeatedly focused at the centre plane, wherein each said electrode array is mounted on a base member made from an electrically insulating material at least one electrode of the array and or said base member being configured to increase surface tracking distance between said at least one and an immediately neighbouring electrode.

22. A mass analyser as claimed in claim 21 wherein said base member is provided with a groove or recess between said one and said immediately neighbouring electrodes to increase surface tracking distance between said one and said immediately neighbouring electrodes.

23. A mass analyser as claimed in claim 21 wherein said one electrode is narrower at a lower part of the electrode, proximate the base member on which the electrode is mounted, than at an upper part of the electrode further away from the base member to increase surface tracking distance between said one and a said immediately neighbouring electrode.

24. A mass analyser as claimed in claim 21 wherein said one electrode is mounted on the base member using an electrically insulating spacer to increase surface tracking distance between said one electrode and a said immediately neighbouring electrode.

25. A mass analyser as claimed in claim 24 wherein a said immediately neighbouring electrode is also mounted on said base member using an electrically insulating spacer.

26. A mass analyser as claimed in claim 21 wherein the electrodes of each electrode array are mounted on the base member by fixing members.

27. A mass analyser as claimed in claim 21 wherein the electrodes of each said set are concentric ring electrodes.

28. A mass analyser as claimed in claim 21 wherein the electrodes of each said electrode array are concentric ring electrodes, a ring electrode of an array including, and being mounted on the base member by, a plurality of electrically conductive fixing members that are angularly offset with respect to electrically conductive fixing members that mount a neighbouring ring electrode on the base member.

29. A mass analyser as claimed in claim 28 wherein the base member has grooves or slots configured to increase surface tracking distance between fixing members of neighbouring ring electrodes.

30. A mass analyser as claimed in claim 21 wherein electrodes of each electrode array are mounted on a said base member formed with a plurality of openings, at least two electrodes of the array are formed with a plurality of fixing members, a fixing member of one electrode and a fixing member of an immediately neighbouring electrode both being mounted in a respective opening in the base member with a gap between the fixing members to increase surface tracking distance between the one and immediately neighbouring electrodes.

31. A mass analyser as claimed in claim 30 wherein said fixing members are mounted on metalised edge surfaces of the openings.

32. A mass analyser as claimed in claim 14 wherein said fixing members are screws, pins, studs or rivets.

33. A mass analyser as claimed in claim 1 being an electrostatic ion trap mass analyser.

34. A mass analyser as claimed in claim 1 being a multi-turn ToF mass analyser.

35. A mass analyser as claimed in claim 1 being an analyzer switchable between a electrostatic ion trap analyser and a multi-turn ToF mass analyser.

Description

(1) Embodiments of the invention are now described, by way of example only, with reference to the accompanying drawings of which:

(2) FIGS. 1a and 1b are respectively plan and transverse sectional views of a known electrostatic ion trap mass analyser having a cylindrically symmetric configuration;

(3) FIG. 2a is a transverse sectional view of the trapping part only of the analyser shown in FIG. 1b, with each electrode array mounted on a respective electrically insulating base member;

(4) FIG. 2b is a transverse sectional view of the trapping part of an electrostatic ion trap mass analyser according to the present invention;

(5) FIGS. 3 and 4 are transverse sectional views of an outer part of one of the electrode arrays shown in FIG. 2b and further illustrate alternative arrangements for increasing surface tracking distance;

(6) FIG. 5 is a perspective view of part of the underside of an electrically insulating base member for supporting concentric ring electrodes using screws or alternative fixing members.

(7) FIG. 6 is a perspective view of the underside of part of an electrically insulating base member showing respective fixing members of two immediately neighbouring ring electrodes mounted on the base member.

(8) FIGS. 1a and 1b show an electrostatic ion trap mass analyser disclosed in WO 2012/116765 (Ding et al.). The electrostatic ion trap includes two arrays of concentric ring electrodes 1a, 1b, lying in mutually parallel planes. The two electrode arrays are arranged coaxially on the central axis (z) and are offset from one another to define a trapping space 16. One of the arrays is a mirror image of the other array with respect to the centre plane 12 and both arrays are supplied, in use, with the same voltage pattern. Ions produced by an ion source can be introduced into the trapping space 16 via a straight ion guide 14 and a curved ion guide 15. Ions pass along the straight ion guide 14 and then pass along the curved ion guide 15. While ions are travelling along the curved ion guide 15, a voltage pulse is applied to ion guide 15 causing ions to be injected radially inwards into the trapping space 16, where trapping electrostatic field is created by voltage supplied to the two arrays. Ions trapped in the trapping space 16 oscillate along an elliptical orbit 17 (in the x-y plane orthogonal to the z axis) with large aspect ratio and precess around the central axis z. Ion motion may have a component in the axial (z) direction and this is illustrated in the cross-sectional view in FIG. 1b. It is necessary to maintain an axial focusing force within the trapping space 16 so that ions will return to the centre plane 12 if there is an initial displacement from that plane or an initial velocity component in the axial direction; otherwise ion motion in the z direction will not be stable and ions will quickly collide with electrodes of one or other of the arrays. The focusing force in the z direction can be generated by provision of a voltage difference between the ring electrodes.

(9) The same situation arises in the multi-turn type ToF system, where ions can either be injected from the circumference of the outer ring electrode, such as in the case of above-described electrostatic ion trap, or generated in a central region of the ring electrodes, or injected from the central region using a deflector/bender. Ions will undergo many oscillations through similar orbits and arrive at a detector also located in the central region of the device. To avoid beam dispersion in the axial direction, it is, again, necessary to create an electric field that acts as a focusing force in the z direction.

(10) FIG. 2a is a transverse sectional view of the trapping part only of the electrostatic ion trap mass analyzer shown in FIG. 1a, but also shows supporting base members 10. Each electrode array has 8 concentric circular or ring electrodes. Of these, electrodes 1-7 constitute a set of focusing electrodes. Whereas electrodes 1a and b, 2a and b are responsible for time focusing to correct for an initial velocity spread in a tangential direction, electrodes 4a and b, 5a and b, 6a and b and 7a and b are responsible for spatial and time focusing to correct for a spread of initial position and initial velocity, respectively, in the axial z direction. On the other hand, the outermost electrodes 8a and 8b are gate/reflecting electrodes. Gate voltage is supplied to electrodes 8a and 8b allowing ions to enter the trapping space 16 between the electrode arrays, and this voltage is then switched to a higher potential to reflect ions undergoing oscillatory motion in the trapping space 16. Ions do not pass between electrodes 8 while ions are undergoing oscillatory motion in the trapping space and so electrodes 8 are not focusing electrodes. Each electrode array is attached to a respective base member 10 made from electrically insulating material before being assembled using screws 11. Focusing in the axial direction is mainly achieved by supplying negative voltage to the ring electrodes 5a, 5b, while keeping the immediately neighbouring ring electrodes 4a, 4b; 6a, 6b at a positive voltage or near ground potential. According to our calculation, ions having a radial flight energy as high as 4.6 kV, will require a focusing voltage on the flat ring electrodes 5a, 5b of about 11.4 kV and a voltage on the immediately neighbouring electrodes 6a, 6b of about 4.6 kV; that is, a voltage difference of 16 kV. With such a high voltage difference and, typically, a gap of only 2 mm between the electrodes electrical discharge might occur.

(11) FIG. 2b is substantially the same as FIG. 2a, but illustrates how the electrode structure has been modified, in accordance with the invention, with a view to at least alleviating this problem.

(12) FIGS. 2a and 2b both show equipotentials created by supplying voltage to the electrodes of the respective electrode structures. It has been found, by simulation, that it is possible to supply significantly reduced voltage to the modified electrodes (25a; 25b), and thereby reduce the voltage difference between those electrodes and the neighbouring electrodes in each array, without a significant reduction of field strength in the space between the electrode arrays. In this particular example, the geometry of electrodes (25a, 26a; 25b, 26b), including their surface profiles, was tailored to mimic the shape of the 6.4 keV equipotential line produced by the electrode structure of FIG. 2a. A comparison of FIGS. 2a and 2b shows that the shapes of the equipotential lines produced by the two electrode structures are substantially the same.

(13) Referring again to FIG. 2b, the ring electrodes 21a-27a; 21b-27b of each electrode array constitute a set of focusing electrodes. Each set of focusing electrodes and the outermost gate electrode 28a; 28b are mounted on a respective base member 10a; 10b made from electrically insulating material, such as a ceramic. The two electrode arrays are assembled coaxially, on the central axis z, and are axially offset from each other defining a trapping space between the electrode arrays. One electrode array is a mirror image of the other electrode array, with respect to the centre plane 12, mid-way between the two arrays, and both arrays are supplied in use with the same voltage pattern, whereby corresponding electrodes of the two arrays i.e. 21a, 21b; 22a, 22b etc are supplied with the same voltage.

(14) In contrast to the electrodes shown in FIG. 2a, the heights of selected electrodes shown in FIG. 2b have been increased in the axial direction so that their electrode surfaces are closer to the centre plane 12 and, in this embodiment, their surface profiles have also been changed. More specifically, electrodes 25a, 25b have electrode surfaces that are closer to the centre plane 12 than the electrode surfaces of the immediately neighbouring electrodes 24a, 24b; 26a, 26b, and they no longer have a flat surface profile.

(15) Similar changes are also made to electrodes 26a, 26b, and the gap between each pair of neighbouring electrodes 25a, 26a; 25b, 26b at the respective base member is also increased. As a result of these changes, voltages that need to be supplied to electrodes 25a, 26a; 25b, 26b to generate the same or very similar field near the centre plane 12 as that generated by the electrode structure of FIG. 2a are reduced to 6.4 kV and 4 kV respectively so that the voltage difference is reduced to 10.4 kV.

(16) The closer electrodes 25a and 25b are to the center plane, the greater will be the reduction of voltage supplied to those electrodes. Preferably, though, the distance of electrode 25a (and 25b) from the center plane is no less than the thickness of the ion beam (typically 2 mm), so that the gap between electrodes 25a and 25b is no less than twice the beam thickness. In this example, electrodes 25a and 25b have a trapezoidal cross-section in a plane along the flight direction, but orthogonal to the centre plane, although other surface profiles having hyperbolic, triangular or stepwise cross-sections could alternatively be used.

(17) The minimum tolerable gap between the electrodes supplied with voltages having opposite polarities is 3 mm. A gap of 3 mm in ultrahigh vacuum can normally withstand a voltage difference in excess of 12 kV, although good surface smoothness is required. As will be described in greater detail hereinafter, surface tracking distance between electrodes may also be increased and this should be larger than the arcing distance between the electrodes.

(18) Whereas one or more electrodes may have electrode surfaces that are closer to the centre plane, it might still be desirable that electrode surfaces of other electrodes are more distant thereby providing a wider trapping space, relatively free from obstacles with which ions following wider trajectories might otherwise collide.

(19) At the same time, a more distant field forming electrode requires simpler geometry and less accuracy in forming its surface profile; that is, because these more distant electrodes are further away from the ion trajectories, inaccuracies in their geometries will have less influence on the electrostatic field to which ions are exposed. Therefore, the electrode geometries will be a result of optimization, a compromise of achievable field strength and field accuracy.

(20) An electrode that is selected to have an electrode surface closer to the centre plane is preferably an electrode that is located in a region where a relatively high radial field gradient is needed. Often, this will be an electrode that is supplied with voltage of opposite polarity to voltages supplied to its immediately neighboring electrodes, such as in the case of electrodes 25a, 25b in FIG. 2b. As these electrodes are relatively large diameter electrodes, an electrode arranged to have an electrode surface closer to the centre plane will usually, but not necessarily, be located in an outer region (in the radial direction) of each electrode array.

(21) It is preferred to select a focusing electrode having a relatively large radius to be closer to the centre plane than a neighbouring ring electrode having a smaller radius. This means that at least one ring electrode near the gate/reflector ring electrode is closer to the center plane. A larger diameter electrode selected to be closer to the centre plane serves to screen an inner region of the trapping space from a varying electric field caused by the closing action of the gate electrode. Therefore, ions reaching an inner region of the trapping space will not be subjected to a mass-dependent acceleration due to a rising potential at the gate electrode.

(22) As already explained electrodes of each electrode array are mounted on an electrically insulating base member 10a; 10b. Surface tracking may occur at the electrically insulating surface of the base member if two neighbouring electrodes are supplied with voltage having a large voltage difference, even in a high vacuum environment. To increase the tracking distance on the insulating surface between neighbouring electrodes, each electrode 25a; 25b is designed to be narrower at a lower part of the electrode, proximate the base member on which it is mounted, than at an upper part of the electrode further away from the base member. In order to further increase the tracking distance between nearby electrodes at the surface of the base member, the following configurations are proposed in combination with the above electrode design.

(23) Referring to FIG. 3, ring electrodes 25b, 26b etc. are attached to the base member 10, made from electrically insulating material such as a ceramic, a macor or glass, using one of the bonding methods below at the bonding points 21. The methods can be: 1) Brazing the metal electrode to the ceramic which has been previously metalized on the bonding surface. Metallization of ceramic may be achieved by using any suitable thick film technology, such as screen printing and annealing or using physical or chemical vapor deposition. 2) Soldering the metal electrode to the ceramic which has previously been metalized on the bonding surface. 3) Using epoxy or other vacuum compatible adhesives.

(24) At locations below the electrodes, where high voltage difference occurs, the ceramic base is cut away with deep grooves or recesses so the surface distance between the bonding points 21 is increased. This effectively increases the surface tracking distance between the two electrodes.

(25) An alternative way to increase the surface tracking distance without cutting into the insulating base member is shown in the FIG. 4. With this approach the electrodes 24b, 25b and 26b are attached to the insulating base member 10 using screws 31, 32, 33. Electrically insulating spacers 35, 36, 37 are provided between the base member 10 and the electrodes 24b, 25b, and 26b to increase the surface tracking distances.

(26) The screws 31, 32, 33 can be made of metal or are preferably made of ceramic or other high tension plastic materials. The screws are only used for fastening purposes so they may be replaced with other kinds of fixing members, such as studs, pins or rivets as long as they hold the base member and electrodes together.

(27) In the case of electrically conductive fixing members, surface tracking may occur between the nearest fixing members of neighbouring electrodes, along an underside surface of the base member. There may need to be as many as 8 or more of these fixing members (e.g. screws) to hold each electrode firmly; however the angular distribution of the fixing members of the ring electrodes should be interleaved so as to achieve the maximum surface tracking distances between fixing members. As shown in FIG. 5, for example, screws 55 are used to fix one electrode (for example 5b) to the base member, whereas screws 56 are used to fix the neighbouring electrode (for example 6b). The angular distribution of the screws 55 is shifted by a certain angle relative to the angular distribution of screws 56, so that the two sets of screws are angularly offset with respect to each other so as to increase the surface tracking distance between adjacent screws. Likewise for other screw sets (e.g. 54) used to fix the other electrodes.

(28) If metal screws, pins, studs, or rivets are used there is an additional way to avoid shorting between these components. As shown in FIG. 5, multiple grooves 50 are cut between screw holes 55 and 56, so electric tracking cannot run directly from one screw to another and so the effective surface tracking distance is longer than the direct distance between the screws.

(29) With modern CNC machining, it is possible to produce ring electrodes having fixing members, such as legs, fingers or pads that project from their undersides. FIG. 6 shows part of the underside of a ceramic base plate 10 having a number of cut-out openings 60, of which only one is shown in FIG. 6. Each ring electrode 5b; 6b is mounted on the topside (not shown) of base plate 10b and has several connection pads which project from the underside of the electrode and are inserted into respective openings 60 of the base plate 10b.Only one such connection pad 75; 76 of each ring electrode 5b; 6b is shown in FIG. 6. Pads 75; 76 may be soldered to the ceramic base plate 10b along two edges of opening 60 having edge surfaces 61, 62 that have been metalized beforehand. A gap between the connection pads 75; 76 serves to increase surface tracking distance between the electrodes because electric tracking cannot run directly between the electrodes.

(30) Although the electrode structure according to this invention was described in embodiment of a planar electrostatic ion trap, it will be understood that mass analyzers according to the invention may also have the form of multi-turn ToF mass analyzer or, an analyzer that can be switched between the mode of planar electrostatic ion trap where image charge is detected and the mode of multi-turn ToF using a particle detector such as a MCP. The later configuration can be facilitated by using afore mentioned external ion injector and adding one MCP detector outside the circumference of the analyzer and keep the image charge detection circuitry coupled to some of the focusing electrodes. The ToF measurement may be activated by switching down the voltage on gate/reflecting electrode after several oscillatory flight of ions in the analyzer, so ions can be released from the trapping region to the detector and time of flight signal can be recorded. The configuration of the analyzer can either be in rectangular shape with straight strip electrodes or in circular shape with ring electrodes described in above embodiment.