CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from and the benefit of United Kingdom patent application No. 1901411.7, which was filed on 1 February 2019. The entire content of this applications are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to an electrode assembly for generating electrical fields to manipulate charged particles, such as ions, and to corresponding methods of using such an electrode assembly to manipulate charged particles.

Embodiments of the present disclosure include mass or mobility spectrometers comprising the electrode assembly, and corresponding methods of mass or mobility spectrometry.

BACKGROUND

In order to provide miniaturised and/or accurate instruments, it is necessary to provide ion optical devices having relatively small and/or precise electrode structures. Technologies such as Micro-Electro-Mechanical Systems (MEMS) and printed circuit boards have been used to achieve this.

Printed circuit boards (PCBs) having an electrically insulating substrate and electrodes deposited thereon have previously been used to form electrode structures in mass spectrometry, e.g. see US 6607414. However, charged particles such as ions impact on the insulating substrate in the areas between the electrodes, causing those areas to become electrically charged and hence affecting the electrical potential profile in the vicinity of those areas. In order to avoid this problem, it is known to cut out the insulating substrate in the areas between the electrodes so as to form gaps, so that electrical charge cannot build up in these areas. However, external electrical fields are then able to penetrate through such gaps and into the ion optical device, which is generally undesirable. In order to mitigate this, the width of the gap can be made relatively small, as compared to the depth of the gap in the direction through the substrate. It is desirable to make the width of the gap 2.5 to 3 times smaller than the depth of the gap. However, the depth of the gap is set by the thickness of the insulating substrate and is relatively small. It is not always possible to make the width of the gap 2.5 to 3 times smaller than this, for example, as the potential difference between electrodes on the PCB either side of the gap can be high and doing so may lead to electrical breakdown and arcing between the electrodes.

Another known approach is to provide grooves in the substrate surface such that the charged particles enter into the groves, rather than charge building up on the outer surface, such as in US 9653273. As the groove does not extend entirely through the substrate this technique prevents external electric fields penetrating into the ion-optical device. However, in order to function well, the depth of the groove is required to be relatively large as compared to its width. For example, it is desirable for the depth of the groove to exceed its width by factor of three or more. However, as the depth of the groove is limited by the thickness of the substrate, the width of the groove and hence the spacing between electrodes on the PCB is also limited to being relatively small. This again places limitations on the voltages that can be applied to the electrodes either side of the groove.

Another known approach is to coat the spaces between the electrodes with a resistive layer that transfers charge to the electrodes, as described in Austin et al JASMS 19, 1435-1441 , 2008. However, it is difficult to support the desired electric field accuracy when using such resistive coatings. Also, only moderate electric fields are able to be used with such techniques so as to avoid surface discharges.

SUMMARY

The present invention provides an electrode assembly comprising:

a first layer having a plurality of electrodes that are separated by one or more gaps; at least one second layer arranged to cover said one or more gaps and prevent electric fields passing through said one or more gaps, said at least one second layer having electrically conductive material located to be coincident with said one or more gaps in the first layer.

As gaps are provided between the electrodes of the first layer, any charged particles, such as ions, that are directed towards the first layer either impact on the electrodes or pass through the gaps between the electrodes. As such, unwanted electrical charge is unable to build up on the inner surface of the first layer and does not affect the electric field generated by the electrodes of the first layer. The second layer prevents electric fields passing through the gaps, in either direction, which may be undesirable. The conductive material of the second layer may also prevent unwanted electrical charge from building up and affecting the electric field generated by the electrodes of the first layer.

The conductive material of the second layer may overlay the one or more gaps in the first layer.

Optionally, no solid material is provided in the gaps in the first layer.

The plurality of electrodes may be elongated electrodes and the gaps may be elongated slots.

The first layer may comprise only electrode material, such as spaced apart electrodes.

Alternatively, the first layer may comprise a printed circuit board (PCB) having an electrically insulating substrate, wherein said plurality of electrodes are deposited on, etched on, printed on, laminated to, or otherwise formed on said substrate; and wherein the substrate may have one or more apertures therethrough that are respectively coincident with said one or more gaps.

Relative to machined electrodes, PCBs allow the production of finer, more accurate features. For example, in the context of the electrode assembly being used in an ion mirror, the electrode assembly is able to produce relatively high ion focussing at the edge of the mirror.

The PCB substrate may be made of a vacuum-compatible material such as ceramic.

As the substrate includes one or more apertures coincident with said one or more gaps, charged particles that enter the gaps are able to pass through the substrate and away from the first layer.

The electrodes of the first layer may extend so as to cover side edges of the apertures in the substrate.

A single said second layer may cover multiple gaps, or all gaps, in the first layer.

A separate one of said second layers may cover each gap in the first layer.

The at least one second layer may comprise a printed circuit board (PCB) having an electrically insulating substrate, wherein said electrically conductive material is deposited on, etched on, printed on, laminated to, or otherwise formed on said substrate.

The use of PCBs for the first and second layers (and any intermediate layers), allows manufacturing ease, low cost, and allows electrode layers to be accurately aligned easily.

The first layer may be a plurality of spaced apart sheet metal or plate metal electrodes; and/or said second layer may be at least one sheet metal or plate metal electrode.

The electrically conductive material may be at least on the side of the second layer facing towards the first layer.

This may be used to prevent charge building up on the second layer that may otherwise affect the electric fields from the plurality of electrodes on the first layer.

Alternatively, the electrically conductive material may be on the side of the second layer facing away from the first layer, which may be arranged to prevent electric fields passing through the gap. It is also contemplated that the entirety of the second layer may be conductive.

The conductive material may be electrically grounded or connected to a voltage source so as to be maintained at an electrical potential, in use.

The first layer may comprise first and second electrodes on opposite sides of each gap in the first layer and that are connected to voltage sources so as to be maintained at different electrical potentials in use, and the conductive material in the second layer at a location coinciding with that gap may be connected to a voltage source so as to be maintained at an electrical potential between said different electrical potentials, in use.

The conductive material may be connected to a voltage source so as to be maintained at an electrical potential substantially midway between said different electrical potentials, in use.

The electrode assembly may comprise at least one intermediate layer arranged between the first and second layers for spacing the first layer away from the at least one second layer; optionally wherein the at least one intermediate layer is a PCB. The first, second and intermediate layers may be substantially parallel and may each be substantially planar.

The at least one intermediate layer may be at least one electrically insulating layer.

If the at least one intermediate layer is a PCB layer, it may comprise conductive material on one or more of its surfaces or may only be the PCB substrate material.

Each of the at least one intermediate layers may comprise a plurality of apertures therein, wherein each aperture is located to be coincident with both one of the gaps in the first layer and the conductive material on the second layer.

The apertures may be slotted apertures.

Each of the at least one intermediate layer may comprise a plurality of ribs between the apertures. The ribs may be located to be coincident with the electrodes in the first layer, and optionally between the spaced apart conductive material on the second layer.

The first layer, second layer, and any intermediate layer(s) present may be adhered or otherwise joined together to provide a composite layered structure. This composite layered structure may be adhered or otherwise joined to a rigid support, for example, to provide the composite layered structure an accurate shape and/or flatness.

The first layer and/or second layer (and/or any intermediate layers present) may be formed by 3D printing.

One or more electrical components, such as resistors or capacitors etc., may connect the electrodes in the first layer or the electrodes in the second layer (or any electrodes in any intermediate layers present). For example, one or more electrical components, such as resistors may connect the electrodes on either side of each gap in the first layer. The electrodes in the first layer may be connected to each other by such electrical components such that, when connected to a voltage supply, these electrodes generate the desired electrical field (e.g. an ion reflecting field when the electrode assembly is used in an ion mirror). Additionally, or alternatively, the electrodes in the second layer may be connected to each other by resistors.

The electrode assembly may comprise a gas conduit from the outside of the second layer to the one or more gaps in the first layer, for pumping gas from the gaps to the outside of the second layer. Embodiments may therefore include a gas pump arranged to perform such gas pumping. This, for example, enables the electrode assembly to be used in an ion-optical device that is required to be evacuated.

The second layer (and any intermediate layers that may be present) may comprise apertures in fluid communication with the gaps in the first layer, so that gas can be pumped through the apertures and out to the outside of the second layer.

The present invention also provides an ion-optical element comprising:

a first electrode assembly of the form described hereinabove; and

a second electrode assembly of the form described hereinabove;

wherein the first and second electrode assemblies are spaced apart so as to define an ion receiving region therebetween.

The first and second electrode assemblies may be planar and/or parallel to each other. The first layer of the first electrode assembly may face the first layer of the second electrode assembly.

The ion-optical element may be an ion mirror comprising voltage supplies connected to the plurality of electrodes in each of the first and second electrode

assemblies for applying different voltages to these electrode for reflecting ions within the ion mirror. Alternatively, the ion-optical element may be an ion lens, ion deflector, ion reflector, ion accelerator, orthogonal ion accelerator or ion detector.

The first and second electrode assemblies may be connected to each other by one or more additional electrode or insulator layer. All of the layers in such an assembly may be PCB layer, for example, so as to for a hollow multilayer PCB device. For example, the ion optical device may be an ion mass or mobility analyser and the whole analyser (optionally except for any ion detector present) may be formed from a multilayer PCB structure.

The ion-optical element may comprise one or more metal electrode extending between and/or joined to the first and second electrode assemblies.

The one or more metal electrode may be a sheet metal or plate metal electrode.

The present invention also provides a Time of Flight (TOF) mass analyser, multi- reflecting TOF mass analyser, electrostatic trap, mass spectrometer or mobility

spectrometer comprising an electrode assembly or ion-optical element as described hereinabove.

In less preferred embodiments it is contemplated that the at least one second layer does not have electrically conductive material located to be coincident with said one or more gaps in the first layer.

Accordingly, from a second aspect the present invention provides an electrode assembly comprising:

a first layer having a plurality of electrodes that are separated by one or more gaps; and at least one second layer arranged and configured to cover said one or more gaps and prevent electric fields passing through said one or more gaps.

BRIEF DESCRIPTION OF THE DRAWINGS

Various embodiments will now be described, by way of example only, and with reference to the accompanying drawings in which:

Figs. 1A and 1 B show schematics of MRTOF mass analysers according to embodiments of the present invention;

Fig. 2 shows a perspective view of a portion of an MRTOF mass analyser according to an embodiment of the present invention;

Fig. 3A shows a section through an embodiment of an MRTOF mass analyser, illustrating the structure of the ion mirrors and orthogonal accelerator, Fig. 3B shows four different types of layer for forming each ion mirror, and Fig. 3C shows a portion of the ion mirror structure; Fig. 4 shows a Simion (RTM) plot of an embodiment of the orthogonal accelerator and deflector shown in Fig. 2;

Fig. 5 shows a Simion (RTM) plot of the ion deflector 12 in the cross-sectional view illustrated as view B in Fig. 2; and

Fig. 6 shows another embodiment of an ion mirror.

DETAILED DESCRIPTION

Although the present invention may be used to form electrode structures in any ion- optical device, such as for or in a mass spectrometer or ion mobility spectrometer, embodiments will now be described in which the electrode structures form part of a Time of Flight (TOF) mass analyser. In particular, embodiments will now be described in which the electrode structures form part of a Multi-Reflecting Time of Flight (MRTOF) mass analyser.

Fig. 1A shows a schematic of an MRTOF mass analyser according to an embodiment of the present invention. The instrument comprises two gridless ion mirrors 2 that are separated in the X-dimension by a field-free region 3. Each ion mirror 2 comprises multiple electrodes arranged so that different voltages may be applied to the different electrodes to cause the ions to be reflected in the X-dimension. The electrodes are elongated in the Z-dimension, which allows the ions to be reflected multiple times by each mirror 2 as they pass through the device, as will be described in more detail below. Each ion mirror 2 may form a two-dimensional electrostatic field in the X-Y plane. The drift space 3 arranged between the ion mirrors 2 may be substantially electric field-free such that when the ions are reflected and travel in the space between the ion mirrors 2 they travel through a substantially field-free region 3. An ion accelerator 6, such as an orthogonal accelerator for example, may be arranged at one end of the mass analyser (in the Z-dimension) and an ion detector 8 may be arranged at the other end of the analyser.

In embodiments, an ion source delivers ions 9 along the Z-dimension to the orthogonal ion accelerator 6, which pulses packets of ions 10 towards a first of the ion mirrors. The ions therefore have a velocity in the X-dimension and also a drift velocity in the Z-dimension. The ions enter into the first ion mirror and are reflected back towards the second of the ion mirrors. The ions pass through the field-free region 3 between the mirrors 2 as they travel towards the second ion mirror and they separate according to their mass to charge ratios in the known manner that occurs in field-free regions. The ions then enter the second mirror and are reflected back to the first ion mirror, again passing through the field-free region 3 between the mirrors as they travel towards the first ion mirror. The first ion mirror then reflects the ions back to the second ion mirror. This continues and the ions are continually reflected between the two ion mirrors 2 as they drift along the device in the Z-dimension until the ions impact upon ion detector 8. The ions therefore follow a substantially sinusoidal mean trajectory within the X-Z plane between the orthogonal accelerator and the ion detector 8.

The MRTOF mass analyser may use the duration of time that has elapsed between a given ion being pulsed from the orthogonal accelerator 6 to the time at which that ion is detected, along with the knowledge of its flight path length, to calculate the mass to charge ratio of that ion.

Fig. 1 B shows a schematic of an MRTOF mass analyser according to another embodiment of the present invention. This embodiment is the same as that shown in Fig. 1A, except that the ion receiving axis of the orthogonal accelerator 6 is tilted with respect to the Z-dimension. Additionally, or alternatively, an ion deflector 12 is provided for deflecting the ions that have been pulsed by the orthogonal accelerator 6 in the Z-dimension. This deflector 12 reduces the velocity of the ions in the Z-dimension and hence increases the number of ion mirror reflections before the ions impact on the detector 8. The deflector 12 may be arranged so as to deflect ions at the exit of the orthogonal accelerator 6, before the ions have passed into any ion mirrors 2.

In order for such MRTOF instruments to attain high mass resolution and mass accuracy it is important that the electrodes of the ion mirrors 2 are formed and aligned to a relatively high precision. Conventionally, ion mirrors in TOF mass analysers are assembled using bulk metal plate electrodes. For relatively high quality MRTOF ion mirrors that can focus ions having a relatively wide spread of kinetic energies, it is advantageous to provide precisely positioned and relatively narrow electrodes in the vicinity of ion reflection area. For example, some electrodes may be required to be only as wide as 2-3 mm in the X-dimension. The electrodes may be elongated in the drift (Z-) dimension and may need to have high parallelism in the drift (Z-) dimension, such as to a higher accuracy than 50 microns. Such electrode structures are difficult to provide using conventional mechanical treatments of bulk metal or using sheet metals. For example, conventional ion mirror electrodes are made of stacked parallel plate electrodes, each of which has a large aperture therein to form the ion reflecting path through it. The stacked plates are separated by spacers formed from electrically insulating material. However, it is difficult to make the electrodes precisely flat unless they are relatively thick. Also, the insulators between the plates need to be relatively far from the ion inlet to the mirror interior so as to prevent electric fields penetrating through the regions between the plates, and also to minimize spurious electric fields that would otherwise be caused by ions impacting on and electrically charging the insulating spacers. This renders the ion mirror assembly relatively large and heavy.

Embodiments of the present invention may use a printed circuit board (PCB) to provide multiple electrodes of an ion-optical device. The PCB may be slotted or otherwise apertured the entire way therethrough so as to provide a gap between different electrodes. A layer may be provided behind that gap in the PCB so as to prevent electric fields passing through the gap. The layer is desirably spaced apart from the apertured PCB, although it is contemplated that it may be directly adjacent to it. The layer may be a conductive sheet, Alternatively the layer may be a conductive material coated on the surface of a substrate that faces the electrodes of the PCB, the coating being at least in the regions coinciding with the gaps in the apertured PCB. The conductive sheet or material coinciding with any given gap may be grounded or another electrical potential applied thereto, such as a potential intermediate the potentials of the electrodes on either side of the gap. This prevents charge building up on the layer and affecting the electric field inside the ion-optical device.

Fig. 2 shows a schematic illustration of part of an MRTOF mass analyser of the type shown in Figs. 1A-1 B and according to an embodiment of the present invention.

Portions of the ion mirrors 2 are shown with the orthogonal accelerator 6 and deflector 12 arranged therebetween. As shown by the arrows, in use, ions are delivered to the orthogonal ion accelerator 6 and are orthogonally ejected therefrom into one of the ion mirrors 2. The ions are then reflected between the ion mirrors multiple times, as described above in relation to Figs. 1A-1 B.

In order to reflect the ions in the X-dimension, each ion mirror 2 comprises a plurality of electrodes 14 that are spaced apart in the X-dimension and which are elongated in the Z-dimension. Different voltages are applied to the different electrodes so as to generate an electric field within the ion mirror for reflecting the ions. As can be seen from Fig. 2, slotted gaps 16 are provided between adjacent electrodes 14 of the ion mirror 2. These slotted gaps 16 are open and are not filled with any solid material. For example, an electrically insulating material is not present in these gaps 16. An electrically conductive layer 18 is arranged on the outer side of the ion mirror 2 at a location coinciding with (and overlaying) each gap 16 so as to cover the gap 16. A separate layer may be provided for each gap 16, as shown, or a single layer may be provided to cover multiple gaps or all gaps. Each layer 18 may prevent or inhibit electric fields passing through the gap(s) 16 that it covers so as to prevent or inhibit such fields entering the ion mirror 2. The layer 18 may be spaced apart in the Y-dimension from the electrodes 14 or may be directly adjacent to it. Additionally, or alternatively, the layer 18 may be a coating of conductive material on the surface of a substrate that faces the electrodes 14, the coating being at least in the regions coinciding with the gaps 16. For example, the layer 18 may be a conductive pattern formed on an electrically insulating substrate (in other words, formed by a PCB). The conductive layer coinciding with any given gap may be grounded or another electrical potential applied thereto, such as a potential intermediate the potentials of the electrodes on either side of the gap. This prevents charge building up on the layer and affecting the electric field inside the ion mirror.

The electrodes 14 may be formed by sheet metal electrodes, plate metal electrodes or PCBs. Additionally, or alternatively, the layer(s) 18 may be may be formed by sheet metal electrodes, plate metal electrodes or PCBs. In embodiments where the layer(s) 18 are in direct contact with the electrodes 14 that form the inner surface of the ion mirror 2, and in which the layer(s) are electrically conductive on the inner surface, the layer(s) 18 are electrically insulated from the electrodes 14 that form the inner surface.

Embodiments are contemplated wherein both the electrodes that form the inner surface of the ion mirror and the layer(s) covering the gaps are formed from a composite layered PCB structure.

Fig. 3A shows a section through an embodiment of an MRTOF mass analyser, which illustrates part of the structure of the ion mirrors 2 and the orthogonal accelerator 6. Each ion mirror 2 comprises two multi-layered PCB assemblies 20 that are each arranged in the X-Z plane and that are spaced apart in the Y-dimension so as to define an ion receiving region therebetween for reflecting ions. Each assembly 20 comprises a plurality of electrodes 14 that are each elongated in the Z-direction and that are spaced apart in the X-direction by gaps 16 between the electrodes. Voltages are applied to these electrodes for reflecting ions in the ion mirror. The structure of each assembly will be described in more detail below in relation to Figs. 3B-3C. Each ion mirror 2 may also comprise an end cap 22 at the X-dimensional end of the ion mirror at which the ions are turned around, and may comprise side walls at the Z-dimensional ends of the ion mirror (not shown). These structures may be formed by a stack of PCBs, sheet metal electrodes or plate metal electrodes, as will be described below.

Fig. 3B shows four different types of PCB sheets for forming the ion mirror shown on the right side (in the X-dimension) of Fig. 3A. As described above, each of the ion mirrors comprises two PCB assemblies 20 that are each arranged in the X-Z plane. Each PCB assembly comprises a first PCB sheet 24 at the inner surface of the ion mirror 2. This first PCB sheet 24 comprises the above-described plurality of different electrodes 14. The portions of the insulating substrate of the first PCB sheet 24 between the electrodes have been removed so as to form slotted gaps 16 between the electrodes 14 that extend through the first PCB sheet 24. A second PCB sheet 26 is arranged against the outer surface of the first PCB sheet 24. The second PCB sheet 26 has a plurality of slotted gaps 28 arranged therein that are spaced apart in the X-dimension and separated by ribs 30 of the PCB, such as ribs of the insulating substrate. The majority (or all) of the second PCB sheet 26, or at least the ribs 30 thereof, may not be coated with electrically conductive material. The second PCB sheet 26 acts as a spacer layer and is arranged against the outer side of the first PCB sheet 24 such that the slotted gaps 28 of the second PCB sheet 26 are coincident with the slotted gaps 16 in the first PCB sheet 24, and the ribs 30 of the second PCB sheet 26 are against the portions of the first PCB sheet 24 on which the electrodes 14 are located. A third PCB sheet 32 is arranged against the outer surface of the second PCB sheet 26. The third PCB sheet 32 has a plurality of different electrodes 34 arranged thereon (which may correspond to layer 18 in previous embodiments) that are spaced apart in the X-dimension and separated by insulating substrate 36 between the electrodes 34. The third PCB sheet 32 is arranged against the second PCB sheet 26 such that the slotted gaps 28 of the second PCB sheet are coincident with the electrodes 34 of the third PCB sheet 32, and the ribs 30 of the second PCB sheet 26 may be against insulating substrate portions 36 of the third PCB sheet 32. In other words, in the X-Z plane, the electrodes 34 of the third PCB sheet 32 are arranged within the gaps 16 in the first PCB sheet 24. A portion of the PCB assembly 20 is shown in Fig. 3C.

It is also contemplated that additional PCB sheets could be provided between the first and third PCB sheets 24,32 so as to increase the spacing between the electrodes 14 and electrodes 34. Alternatively, it is contemplated that the second PCB sheet 26 may be omitted, although it must still be ensured that the electrodes 14 on the first PCB sheet 24 are arranged so as to be electrically isolated from any electrodes 34 on the third PCB sheet 32. Fig. 3B also illustrates a fourth type of PCB 40, a plurality of which may be stacked together and arranged between opposing PCB assemblies 20 in each ion mirror 2, thereby forming the end cap 22 and Z-dimension side walls of the ion mirror 2. This is shown in Fig. 3A, except that this sectional view does not show the Z-dimensional side walls of the ion mirror. This fourth PCB type 40 corresponds to the first PCB type 24, except that its central portion and one of the X-dimensional side walls are not present. The fourth PCB type 40 consists of a first elongated strip portion 42 for forming the end cap wall 22 of the ion mirror and an orthogonally arranged elongated strip portion 44 at either longitudinal end of the first elongated strip portion 42, for forming the Z-dimensional side walls of the ion mirror. In other words, the fourth PCB 40 is substantially C-shaped. The first elongated strip portion 42 comprises an electrode 46 arranged on the insulating substrate, to which the end cap voltage may be applied. Each of the orthogonally arranged elongated strip portions 44 has a plurality of electrodes 48 arranged thereon that are spaced apart in the X-dimension and separated by insulating substrate between the electrodes. These electrodes 48 may be arranged such that when the fourth PCBs40 are located in the ion mirror, these electrodes are at the same locations (in the X-dimension) as the electrodes 14 on the first PCB 24. The voltage applied to any given one of the electrodes 48 on the fourth PCB40 may be the same as the voltage applied to the electrode 14 on the first PCB 24 at the same location in the X-dimension.

It will be appreciated that mirror images of the PCB layers shown in Fig. 3B are used to form the ion mirror shown on the left side (in the X-dimension) of Fig. 3A.

In use, various different voltages are applied to the electrodes of the first PCB 24 and fourth PCB 40 of the ion mirror to generate an electric field for reflecting ions in the ion mirror. As gaps 16 are provided between the electrodes 14 on the first PCB, any ions (or other charged particles) that are scattered towards the first PCB either impact on the electrodes 14 or pass through the gaps 16 between the electrodes. As such, unwanted electrical charge is unable to build up on the inner surface of the first PCB 24. The third PCB 32, that is located outwardly of the first PCB 24, overlays and covers the gaps 16 in the first PCB. This third PCB 32 may be configured to prevent electric fields from passing from the outside of the ion mirror 2 to the inside of the ion mirror, through the gaps 16 in the first PCB 24. For example, the third PCB 32 may have electrical

conductors/electrodes 34 arranged at locations that coincide (in the X-Z plane) with the gaps 16 in the first PCB 24. Electric potentials may be applied to these electrodes 34 on the third PCB 32. For example, the potential applied to any given electrode 34 on the third PCB 32 may be between the two potentials applied to the two respective electrodes 34 on opposite sides of the gap 16 with which that electrode on the third PCB is coincident. For example, the potential applied to any given electrode on the third PCB may be substantially midway between the two potentials applied to the two electrodes on opposite sides of the gap with which that electrode on the third PCB is coincident. This may reduce the impact on the electric fields within the ion mirror that are generated by the electrodes on the first PCB layer. It is advantageous to minimize the exposure of the PCB insulating substrate to scattered ions. For this purpose, the electrodes 14 of the first PCB 24 may extend down the edge walls 50 of the gaps 16 in the first PCB 24 (as shown in Fig. 3C). Alternatively, the edges may be cut such that the walls 50 of the gaps are not orthogonal to the inner surface of the first layer, but are instead angled such that the edge walls 50 are hidden below the first layer.

The second PCB 26 enables the third PCB 32 to be spaced apart from the first PCB 24. As electrodes 14 of the first PCB 24 may extend down the edge walls 50 of the gaps 16 in the first PCB 24 (as shown in Fig. 3C), the use of the second PCB 26 enables the electrodes 34 on the third PCB 32 to be spaced apart and therefore electrically isolated from the first electrodes 14 (particularly at the edges 50 of the gaps 16). The second PCB 26 may have substantially no conductive material thereon and may be substantially only an insulating substrate sheet.

In alternative embodiments to those described above, rather than providing a second PCB sheet 26, a sheet other than a PCB may be used or individual spacer members may be used to space the first and third PCBs 24 and 32) apart.

Fig. 3A also shows an embodiment of the structure of the gridless orthogonal accelerator 6. The orthogonal accelerator comprises two PCB assemblies 20’ that are each arranged in the X-Z plane and that are spaced apart in the Y-dimension so as to define an ion receiving region therebetween. Each assembly 20’ comprises a plurality of electrodes that are each elongated in the Z-direction and that are spaced apart in the X- direction by gaps between the electrodes. Voltages are applied to these electrodes for accelerating ions into one of the ion mirrors. The structure of each PCB assembly may be formed in the same manner as the PCB assemblies in the ion mirror. An additional PCB layer 52 may be provided on part of the inner surface of each first PCB sheet so as to provide a restricted aperture in the Y-Z plane through which the ions are pulsed. The orthogonal accelerator 6 also comprises a pushing electrode wall 54 at the X-dimensional end from which the ions are pulsed, and may also comprises Z-dimensional side walls (not shown). These may be formed using the fourth type of PCB 40 shown in Fig. 3B, in the same way that the end cap 22 and side walls of the ion mirror 2 are formed. Alternatively, these may be formed by sheet metal electrodes or plate metal electrodes.

In use, various different voltages are applied to the electrodes at the inner surfaces of the orthogonal accelerator to generate an electric field that orthogonally accelerates ions entering the orthogonal accelerator.

As shown in Fig. 3A, it is contemplated that rigid walls 56 of the housing of the mass analyser may be used to provide flatness and precise positioning of the PCB electrodes. The ion mirror PCB assemblies 20 and orthogonal accelerator 6 may therefore be fully formed by PCB assemblies that are sandwiched between the rigid walls 56.

Optionally, the ion mirror PCB assemblies 20 and orthogonal accelerator 6 may be sandwiched between further PCB sheets (not shown), which themselves are sandwiched between the rigid walls 56. As described above, it is contemplated that conventional electrodes may be used in combination with the PCB electrode assemblies, particularly for example where good flatness of surfaces is needed in a direction orthogonal or inclined to the PCB layered surfaces. For example, a conventional metal sheet or metal plate electrode may be used for the ion mirror end cap, each ion mirror side wall, the orthogonal accelerator pushing electrode wall, or for other electrodes of the orthogonal accelerator. These electrodes may be soldered or otherwise secured between the opposing PCB assemblies, optionally being jigged before being secured in place. These conventional electrodes may serve as spacers between the PCB electrode assemblies.

Fig. 2 shows an example of an orthogonal accelerator 6 having a combination of conventional metal sheet or metal plate electrodes for orthogonally accelerating the ions, and PCB electrodes for deflecting the ions in the Z-dimension. The conventional electrodes may be soldered or otherwise secured between the PCB layers.

Fig. 4 shows a Simion (RTM) plot of an embodiment of the orthogonal accelerator 6 and deflector 12 shown in Fig. 2, illustrating the electric potentials and ion trajectories of the ions. Fig. 4 corresponds to the cross-sectional view illustrated as view A in Fig. 2. The orthogonal accelerator 6 may comprise opposing PCB sheets 60 that are spaced apart in the Y-dimension and a plurality of electrodes 62 that extend in the Y-Z plane arranged therebetween. Some or all of the electrodes 62 arranged in the Y-Z plane may be sheet metal or plate metal electrodes that are secured to the PCB sheets 60, for example by soldering. Voltages may be applied to these electrodes 62 so as to control the motion of the ions in the X-dimension. As described in relation to Fig. 1 B, an ion deflector 12 may also be provided for deflecting ions in the Z-dimension. This deflector 12 may comprise electrodes 64 of the PCB sheets 60, i.e. electrodes deposited on the PCB substrate.

Fig. 5 shows a Simion (RTM) plot of the ion deflector 12 in the cross-sectional view illustrated as view B in Fig. 2. The electric potentials within the ion deflector are illustrated. As can be seen from this view, the deflector 12 may comprise a plurality of electrodes 64 spaced apart in the Z-dimension along each PCB sheet 60. Different voltages may be applied to different electrodes 64 as a function of their location in the Z-dimension so as to generate a nearly homogeneous electric field that substantially evenly deflects ions in the Z-dimension. The deflector 12 may comprise opposing side wall electrodes 66 arranged in the X-Y plane. These electrodes 66 may be plate metal or sheet metal electrodes and may be secured to and between the PCB sheets 60, for example, by soldering.

It is contemplated that at least the deflector electrodes 64 that are spaced in the Z- dimension may comprise opposing PCB assemblies with the layers of thin electrodes of the type described above in relation to the ion mirrors.

Fig. 6 shows another embodiment of an ion mirror 2, with a fine electrode structure in the region where ions are turned around, without the Z-dimensional side walls being illustrated. As in some of the previously described embodiments, the ion mirror may comprise two PCB assemblies that are each arranged in the X-Z plane and that are spaced apart in the Y-dimension so as to define an ion receiving region therebetween. The end cap electrode 22 may be formed by sheet metal, plate metal, or orthogonally mounted metal-plated board (such as a PCB). The end cap electrode 22 may be soldered between or to the ends of the PCB assemblies. The external surfaces of the PCB assemblies may be electrically grounded for their safe mounting between the rigid support walls 56 (shown in Fig. 3A). The slots may be made through the external layers to enable gas to be pumped through the electrode assemblies so as to evacuate the interior of the mass analyser.

Although the present invention has been described with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the scope of the invention as set forth in the accompanying claims.

For example, although embodiments of an MRTOF mass analyser have been described in which the ions drift along a linear Z-axis whilst they are reflected between the ion mirrors, it is alternatively contemplated that each ion mirrors may define a cylindrical ion receiving region such that the ions drift in a circumferential direction around the cylindrical mirrors. Such embodiments do not require the Z-dimensional end walls described above.

Although embodiments of ion mirrors, gridless orthogonal accelerators and ion deflectors have been described in relation to ion-optical components for MRTOF mass analysers, the ion-optical components may be for single reflection TOF mass analysers. Moreover, the layered structures described herein may be used for electrode structures in other types of ion-optical components to those described herein, such as ion lenses, or for ion-optical components other than those in mass or mobility spectrometers. The layered structures described herein may be used, for example, in any device where a fine/precise electrode structure or electric field is required.

A PCB as used herein may refer to a component comprising electrodes (such as conductive tracks, pads and other features) etched from, printed on, deposited on, or laminated to a non-conductive substrate.

The electrically non-conductive substrates described herein may be sheet or bulk material, or may be 3D-printed or deposited on another substrate by any other method.