1. Field of the Invention
This invention relates to radio frequency (RF) ion guides for use in mass spectrometry.
2. Description of the Related Art
Ion guides are commonly used in a mass spectrometer (MS) to transport ions between the ion source and the mass analyzer and commonly consist of a number of elongate, parallel conductive rods that are placed around a common axis. Various embodiments of ion guides are known in the art. An example of a prior art multipole ion guide is illustrated in
As shown in
As shown, ion source 204 and ion detector may generally be provided at opposing ends of the ion path in the mass spectrometer. Due to the particular path settings in the example shown, the ion source 204 and the ion detector can be located immediately adjacent to one another, separated only by intermediate walls 208 (dashed lines) bordering the two vacuum stages 202A, 202B. Deviating from the example shown, it would be likewise possible to replace the curved assemblies Q0 and Q2 by straight equivalents, whereby a linear configuration would result.
An ultra-high (turbo) vacuum pump, not shown, may be disposed in the housing 200 to maintain the two vacuum stages 202A, 202B evacuated. Evacuation holes, not shown in
At the center of the ion path along the quadrupole ion guide Q0, a gas inlet may be provided for introducing an interaction gas, such as helium, nitrogen or methane, into the quadrupole ion guide Q0 which can be configured, for example, like the one described in U.S. Pat. No. 8,525,106 B2 to Muntean.
In the example shown in
Because of the proximity to the source region, ion guides are generally exposed to contamination in the form of deposits on the ion guide electrodes. Deposits can be brought about by either neutral molecules that condense on the electrodes, or by large amounts of ions that are rejected by the ion guide, hit the electrodes as a result thereof and lose the charge so that the underlying neutral substrate molecules condense on the electrodes. A combined effect of the aforementioned may also be that neutral molecules condense on the electrodes and then react with rejected ions that hit the electrodes and decompose into stable solid structures that “grow” on the electrode surfaces, such as carbon deposits originating from hydrocarbon analyte molecules that have decomposed.
Such deposits in mass spectrometers are described in the literature, for example, by Girard et al. (Journal of Chromatography Science, 2010 October, 48 (9), 778-779) and Kenneth L. Busch (“Ion Burn and the Dirt of Mass Spectrometry”, online publication, Sep. 1, 2010).
The formation of deposits on the ion guide electrodes is undesired, because the deposited layer may be dielectric and charges up when hit by rejected ions. In such a case, the deposits can lead to undesired electric potential barriers which deflect and distort ion motion and deteriorate the MS performance.
A remedy for the above-mentioned deposition problem could be to heat the ion guide electrodes during operation so that they are less prone to accepting contaminating deposits. Another remedy would be to periodically clean the ion guide electrodes in order to restore the MS performance when the deposits have grown too large. The first solution, heating, adds complexity to the mass spectrometer design, both because it requires additional hardware for heating and because it requires adding a heat barrier to prevent the hot ion guide from affecting the performance of the mass analyzer that follows. The second solution, cleaning, is generally not desired at high frequency, because it reduces the uptime of the instrument and is thereby detrimental to the productivity of the MS. Furthermore, it may also create performance problems if disassembly, cleaning, and reassembly are not carried out correctly (for instance by ill-trained staff).
D. L. Swingler, International Journal of Mass Spectrometry and Ion Processes, 54 (1983) 225-230, suggested to provide for longitudinal or transverse slots in the pole electrodes of a quadrupole mass filter. Although such structural modification of the electrodes might mitigate the contamination issue, the electrodes retain material directly at their front ends which are particularly susceptible to ion impingement and hence deposit forming. It can be shown from ion trajectory simulations that the electrode surfaces at the entrance area of an ion guide are exposed to the highest ion current, because most ions rejected by the RF confinement fields (that is, not stably transmitted) will be ejected at this point.
In view of the foregoing, there is a need to provide ion guides that are less susceptible to contamination on the electrode surfaces.
The disclosure presents an ion guide construction that naturally minimizes contamination by generally allowing rejected ions to fly through and away from the ion guide electrodes and preventing them from hitting the sensitive electric potential defining surfaces of the ion guide electrodes.
In a first aspect, the invention relates to a radio frequency ion guide having a plurality of electrodes arranged about an axis and a radio frequency voltage generator applying radio frequency voltages to the plurality of electrodes for radially confining ions, wherein the ions are received at an entrance end of the ion guide, and further wherein each electrode of the plurality of electrodes has a forked front end which is located at the entrance end of the ion guide.
The forked front end may comprise two or more teeth.
In various embodiments, a conductive mesh may cover an intermediate gap between the teeth and thereby at least partially restore an electric potential defining inwardly facing surface of each electrode.
A thickness of the teeth may decrease in a direction away from the axis, such that the gap obtains substantially a V-profile, for instance.
The teeth may extend along the axis over about one centimeter (from the front end).
In various embodiments, a width of a gap between the teeth may amount to up to half of the total width of the electrode. Further, a width of a gap between the teeth may taper in a direction along the axis.
The front end may be one of bifurcated (two teeth) and further multi-furcated (four or more teeth).
In various embodiments, the plurality of electrodes may comprise four or more rod electrodes, such as six, eight, etc.
In various embodiments, the plurality of electrodes may comprise one of straight (or linear) electrodes and curved electrodes, such as curved by 90° or 180°, for example.
In various embodiments, the assembly may further comprise an ion source, such as an El or Cl source, located upstream of the ion guide so that ions originating therefrom are transmitted to the entrance end, and may yet further comprise a mass analyzer, such as a triple quadrupole mass analyzer, time-of-flight analyzer, Fourier Transform analyzer, etc., located downstream from the ion guide so that ions having traversed the ion guide are further transmitted thereto.
A first portion at the entrance end of each electrode may be materially detached from a subsequent second portion of each electrode.
In various embodiments, the detached portion may be located in a first pressure regime, such as in an ion source, and the subsequent second portion may be located in a second, lower pressure regime, such as in a vacuum stage.
In various embodiments, the radio frequency voltage applied to the detached portion may be different to that applied to the subsequent second portion.
The voltage generator may also be capable of providing direct current voltage(s) to the plurality of electrodes, such as to establish an offset potential at the electrodes or to operate the ion guide as a (narrow) band-pass filter for ions of a limited mass-to-charge ratio range, for instance.
The disclosure also presents an ion guide construction that generally allows rejected ions to impinge on surfaces of the pole electrodes offset from the ion guide axis compared to integral pole electrodes, thereby minimizing any detrimental influence deposits on such surfaces might have on the electric fields in the interior of the ion guide.
In a second aspect, the invention relates to a radio frequency ion guide having a plurality of electrodes arranged about an axis and a radio frequency voltage generator applying radio frequency voltages to the plurality of electrodes for radially confining ions, wherein the ions are received at an entrance end of the ion guide, and further wherein each electrode of the plurality of electrodes has a recessed feature at a surface facing an interior of the ion guide, the recessed feature being located at the entrance end of the ion guide.
In various embodiments, the assembly further comprises a conductive mesh which may cover at least a portion of the recessed feature and thereby at least partially restores the electric potential defining surface facing the interior of the ion guide of each electrode.
The recessed feature may comprise an elongate groove or pocket.
The invention can be better understood by referring to the following figures. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention (often schematically).
While the invention has been shown and described with reference to a number of embodiments thereof, it will be recognized by those skilled in the art that various changes in form and detail may be made herein without departing from the scope of the invention as defined by the appended claims.
Radio frequency ion guides can be operated with very large transmission efficiency, close to 100% for a wide mass range. Nevertheless, the mass range is limited at the low end (low mass cut-off) such that all ions having a mass to charge ratio m/z lower than this cut-off value will not be transmitted and end up hitting the ion guide electrodes (if they do not pass through the gaps between the electrodes). Ion trajectory simulations show that most of these ions are rejected and hit the entrance section of the ion guide, which is also supported by the observation that most of ion guide contamination occurs in the entrance region of the ion guide, as shown in
One idea of this invention, according to a first aspect, is to open up a central section of the electrode structure at the ion guide entrance such that most of the rejected ions can escape through and away from the electrodes. In this manner, the rejected ions can be pumped away without running the risk of them hitting a part of the sensitive, electric potential defining electrode surfaces which face the interior and/or axis of the ion guide. The open section is subject to a size restriction in that the electric fields in the central part of the ion guide that are responsible for the radial confinement of ions meeting the stability criteria must not be significantly perturbed. When observing these requirements, the ion transmission of the useful ions, or ions of interest, is not significantly affected.
A first exemplary way of doing it is presented in
At an entrance end 415, as shown in
As becomes apparent from the illustration of
A variation of the embodiment shown in
The square electrode profile of
Other embodiments include the teeth of the forked front end of the pole electrodes being materially detached from the remaining portion of the pole electrodes, as shown in
Yet further embodiments include the teeth of the forked front end having a tapering side wall such that a gap or slit width is small at the side facing the interior and/or axis of the ion guide and wider compared thereto at the outside, as shown in
It will be acknowledged further by a practitioner in the field that the square profile of the rods 405 in the previous figures is shown merely by way of example. It is possible to implement features according to the invention also in pole electrodes of other configuration, for instance circular round (as shown in the front view of the entrance end in
Moreover,
The teeth and/or gaps generally can have straight or (slightly) rounded edges. The wealth of usable shapes is generally not restricted. It is further possible to provide for the gap width to taper in a direction along the axis of the ion guide, as illustrated by way of example in
Ion trajectory simulations using the tool SIMION™ show that transmission of useful ions is largely unaffected by cutting out these open longitudinal slits at the entrance end of the ion guide as shown in
As can be seen, by using the forked entrance end the transmission rate is not significantly impaired compared to integral square electrodes. This can be explained by the fact that, at the initial part of the ion guide, the useful ions travel close to the center, or in other words close to the axis, where the electric fields are largely unaffected by the cut-outs through the electrodes. Electric field calculations with the SIMION™ program further show that the electric equi-potential lines are largely consistent with a hyperbolic field and unperturbed at the center of the ion guide and only affected close to the electrodes which is, however, not crucial for the overall performance.
Simulated curves of ion transmission for other embodiments of the modified ion guide electrodes show a similar good match between integral pole electrode and modified pole electrode, and are not shown here for the sake of conciseness.
With the aforementioned modification of the ion guide electrodes, it becomes possible to significantly prolong the uptime of the correspondingly configured ion guide without the need to clean the electrodes at high frequency or heat the electrodes during operation.
The width of the central gaps can be up to substantially half of the effective electrode surface width facing the interior and/or axis of the ion guide. Even with such pronounced modification compared to an integral electrode, the ion transmission remains largely unaffected, less than 5%.
A preferred longitudinal dimension of the gaps and/or teeth would be about one centimeter from the electrode front end and is expected to vary, that is, being longer or shorter, depending in particular on the RF voltage frequency and the axial energy of the ion beam. In some instances, it might be possible to extend the longitudinal dimension to more than one centimeter.
According to another aspect of the invention, as evident from
The variant with the recessed feature may be advantageous when there are particularly high requirements on pressure control, because the pole electrodes may be used as gas-tight elements and this configuration could simplify the establishing of a regulated pressure level in the channel between the electrodes.
Variations discussed above for the longitudinal end slit embodiments may also be used with the recessed feature embodiments. It is likewise possible, for example, to cover the recessed feature with a conductive mesh (in analogy to
The invention has been described with reference to a number of different embodiments thereof. It will be understood, however, that various aspects or details of the invention may be changed, or various aspects or details of different embodiments may be arbitrarily combined, if practicable, without departing from the scope of the invention. Generally, the foregoing description is for the purpose of illustration only, and not for the purpose of limiting the invention which is defined solely by the appended claims.
Number | Name | Date | Kind |
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8525106 | Muntean | Sep 2013 | B2 |
20060027745 | Rebettge et al. | Feb 2006 | A1 |
20090321624 | Fang | Dec 2009 | A1 |
20110016700 | Egley et al. | Jan 2011 | A1 |
20150097115 | Schwartz | Apr 2015 | A1 |
Entry |
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Girard et al., Determination of Quadrupole Charging in MS/MS Instruments, Journal of Chromatography Science, Oct. 2010, 778-779, vol. 48 (9). |
Busch, Kenneth L., Ion Burn and the Dirt of Mass Spectrometry, Advanstar Communications, Sep. 1, 2010, http://license.icopyright.net/user/viewFreeUse.act?fuid=MTg0NTU5Njk%3D. |
Swingler, D. L., The Use of Slotted Poles in a Quadrupole Mass Filter, International Journal of Mass Spectrometry and Ion Processes, 1983, 225-230, vol. 54. |